Tribology

TRIBOLOGY
FUNDAMENTALS
AND ADVANCEMENTS
Edited by Jürgen Gegner

Tribology: Fundamentals and Advancements
Edited by Jürgen Gegner
Contributors
Maciej Paszkowski, Giuseppe Pintaude, Mohammad Tauviqirrahman, Rifky Ismail, J
Jamari, Dirk J. Schipper, Manfred Mauntz, Jürgen Gegner, Ulrich Kuipers, Stefan Klingauf,
Nehal Ahmed, Amal Nassar, Masataka Nosaka, Virginia Sáenz De Viteri, Elena Fuentes,
Remigiusz Michalczewski, Marek Kalbarczyk, Michal Pawel Michalak, Witold Piekoszewski,
Marian Szczerek, Waldemar Tuszynski, Jan Wulczyński, Xana Fernandez, Amaya Igartua,
Erik Kuhn, Walter Holweger
Copyright © 2016 Second Edition
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and not necessarily those of the editors or publisher. No responsibility is accepted for the
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materials, instructions, methods or ideas contained in the book.
First published May, 2013 second - 2016
ISBN-10: 953-51-1135-3
ISBN-13: 978-953-51-1135-1
Contents
Preface VII
Section 1 Lubrication and Properties of Lubricants 1
Chapter 1 Fundamentals of Lubricants and Lubrication 3

Walter Holweger
Chapter 2 Lubrication and Lubricants 55

Nehal S. Ahmed and Amal M. Nassar
Chapter 3 Some Aspects of Grease Flow in Lubrication Systems and

Friction Nodes 77
Maciej Paszkowski
Section 2 Boundary Lubrication Applications 107
Chapter 4 Cryogenic Tribology in High-Speed Bearings and Shaft Seals of

Rocket Turbopumps 109
Masataka Nosaka and Takahisa Kato
Chapter 5 Titanium and Titanium Alloys as Biomaterials 155

Virginia Sáenz de Viteri and Elena Fuentes
Section 3 Testing and Modeling 183
Chapter 6 New Scuffing Test Methods for the Determination of the

Scuffing Resistance of Coated Gears 185
Remigiusz Michalczewski, Marek Kalbarczyk, Michal Michalak,
Witold Piekoszewski, Marian Szczerek, Waldemar Tuszynski and Jan
Wulczynski
VI Contents
Chapter 7 Introduction of the Ratio of the Hardness to the Reduced

Elastic Modulus for Abrasion 217
Giuseppe Pintaude
Chapter 8 Artificial Slip Surface: Potential Application in

Lubricated MEMS 231
M. Tauviqirrahman, R. Ismail, J. Jamari and D.J. Schipper
Chapter 9 Friction and Wear of a Grease Lubricated Contact — An

Energetic Approach 251
Erik Kuhn
Section 4 Sustainability of Tribosystems 273
Chapter 10 Innovative “Green” Tribological Solutions for Clean

Small Engines 275
Xana Fernández-Pérez, Amaya Igartua, Roman Nevshupa, Patricio
Zabala, Borja Zabala, Rolf Luther, Flavia Gili and Claudio Genovesio
Chapter 11 A Sensor System for Online Oil Condition Monitoring of

Operating Components 305
Manfred R. Mauntz, Jürgen Gegner, Ulrich Kuipers and Stefan
Klingau
Preface
As the subject of tribology comprises lubrication, friction and wear of contact components
highly relevant to practical applications, it challenges scientists from chemistry, physics and
materials engineering around the world on today’s sophisticated experimental and theoreti‐
cal foundation to complex interdisciplinary research. Recent results and developments are
preferably presented and evaluated in the context of established knowledge. Consisting of
eleven chapters divided into the four parts of Lubrication and Properties of Lubricants,
Boundary Lubrication Applications, Testing and Modeling, and Sustainability of Tribosys‐
tems, this textbook therefore merges basic concepts with new findings and approaches. Tri‐
bology – Fundamentals and Advancements, supported by competent authors, aims to
convey current research trends in the light of the state of the art to students, scientists and
practitioners and help them solve their problems.
The undesirable loss of energy and material by friction and wear cause damage amounting
to several ten billion dollars. The high economical relevance of the demand for durable
products has been driving the development and continuous refinement of the scientific and
engineering discipline of tribology since the middle of the last century.
The excellent invited Chapter 1 on Fundamentals of Lubricants and Lubrication opens the book
by providing an expert introduction to the chemistry and basic properties of oils, additives
and greases on the advanced level of a standard reference guide. The two following contri‐
butions complete the general background of the Part 1. Chapter 2 on Lubrication and Lubricat‐
ing Oil outlines the regimes of lubrication and deals with liquid, solid and gaseous
lubricants. Oils take up the most space of this paper. Chapter 3 on Some Aspects of Grease
Flow in Lubrication Systems and Friction Nodes extends the discussion of grease lubrication
and covers structural as well as rheologic properties.
Part 2 turns the reader’s attention to applications under adverse operating conditions. Chap‐
ter 4 on Cryogenic High-Speed Bearings and Shaft Seals of Rocket Turbopumps reviews promising
approaches for reliable machine elements in future space transportation systems. A crucial
material issue in aerospace engineering is associated with this task, for instance, due to the
differences in the thermal alteration of the mechanical behavior. The optional use of ceram‐
ics in hybrid bearings at extremely low service temperatures and boundary lubrication indi‐
cates the importance of innovative materials for tribologically loaded components. Chapter
5 on Titanium and Titanium Alloys as Biomaterials makes this conclusion even more meaning‐
ful and extents it to mixed friction oriented surface engineering. Recent attempts to increase
the wear resistance of orthopedic implants are discussed. Titanium and its alloys provide
excellent biocompatibility and corrosion protection but the poor tribological properties are
detrimental.
VIII Preface
Part 3 of the book is dedicated to laboratory testing, modeling approaches and mathematical
simulation. The New Scuffing Test Methods for the Determination of the Scuffing Resistance of
Coated Gears, proposed in Chapter 6, is applied to evaluate the performance of coatings. The
examination of new lubricants requires gear testing as well. The prediction of the abrasion
response of a tribosystem involves material characteristics of the counterbodies. It is an of‐
ten raised question what relationship holds between wear and hardness? Introducing the Ra‐
tio of the Hardness to the Reduced Elastic Modulus for Abrasion in Chapter 7 serves the purpose
of modeling the wear coefficient. The suitability is demonstrated on the examples of the
well-known tribosystems of glass‒bearing steel and alumina‒hard metal. The characteriza‐
tion of the cutting efficiency is particularly relevant to machining processes. Chapter 8, enti‐
tled Artificial Slip Surface: Potential Application in Lubricated MEMS, is another highlight of the
book. It presents a novel lubrication model for moving parts in micro electro-mechanical
systems, based on the numerical solution of a modified Reynolds equation, to improve the
tribological performance of lubricated contacts. Chapter 9 on Friction and Wear of a Grease
Lubricated Contact ‒ An Energetical Approach instructively specializes the discussion of Chap‐
ter 3. It elaborates an advanced energy balance model and includes rheometer tests. Grease
degradation is correlated with the energetics of a tribosystem.
Part 4 finally addresses the emerging sustainability topic from the two essential aspects of
environmentally friendly tribology and early failure detection. Chapter 10 on Innovative
“Green” Tribological Solutions for Clean Small Engines considers the practical problems with
biodegradable lubricants, such as abrasive wear, in this demanding operating environment.
It investigates new biofuel-compatible eco-oils and materials or coatings that promote their
use. Chapter 11 introduces A Sensor System for Online Oil Condition Monitoring of Operating
Components with up-to-date web-based accessibility. The electrical oil sensor assists with in‐
creasing the level of machine availability, e.g., of off-shore wind turbines and can also be
used to measure the percentage of biodiesel in a fuel blend.
The editor especially would like to thank the authors for their valuable work. The support of
the publisher is also highly appreciated.
Jürgen Gegner
University of Siegen,
Germany
Section 1
Lubrication and Properties of Lubricants

Chapter 1
Fundamentals of Lubricants and Lubrication
Walter Holweger
Additional information is available at the end of the chapter
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1. Introduction
Literature about lubricants is available in all public domains. Readers should search at those
platforms in the case of special interests. Citations given here do not represent the full scale
but reflect an overview from a today’s perspective. [1-7]
Part of this chapter will be the basic chemical structure of lubricants including some property
descriptions. Since literature in tribology is innumerous, the reader should check his special
area of interest.
Lubricants play a key role in machinery element safety. Their main tasks are
• to keep moving parts apart from each other,
• to take heat out of the contact by their through pass,
• to keep surfaces clean,
• to transport functional additives toward the surface and
• to transfer power in the application (hydraulic, automatic transmission, breaks). [6, 8]
Functionality of lubricants is defined by their chemical structure and their physical properties.
Basics of lubrication are covered by organic chemistry to a major and inorganic chemistry to
a minor extent. [2, 3]
Lubricants are regulated internationally and locally, e. g. by ASTM (American Standard of

Testing Materials) or DIN (Deutsche Industrienorm). Regulation covers the physical, chemical
and toxicological description of lubricants including safety guide lines and others. [2, 3]
4 Tribology - Fundamentals and Advancements
2. Some basics
The spatial structure of carbon chemistry defines all activities of the lubricants derived
from them. The spatial structure of organic carbon chemicals is given by the binding state
of carbon. [10]
Three main types are discussed. Two are essential for lubrication: single and double bonds.
2.1. Single bonds: Tetrahedral binding
In the tetrahedral binding state, reflecting the status of single bonds, carbon is placed in the
centre of a pyramid with bindings into space from the centre to the corner (Figure 1).
Figure 1. Tetrahedral binding of carbon
Carbon is placed in the centre of the tetrahedral with four attached valences. Within chemical
convention in order to abbreviate the structure denotation the atom symbols are neglected.
Carbon may bind to another one by corner to corner. (Figure 2)
Figure 2. Corner to corner binding state
Corner to corner binding leads to zigzag chains, where the angle of carbon to the hydrogen
atoms is 108°. In general the hydrogen is neglected, leading to a skeleton drawing of the
structure.
Beyond the fixed angle of 108° and the zigzag shape of such hydrocarbon structures, a high
variety of structures arise due to the fact that those bindings may branch or bind to cyclic
structures. (Figure 3 and Figure 4)
Figure 3. Branched structures by carbon to carbon binding

Fundamentals of Lubricants and Lubrication 5
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Figure 4. Cyclic Structures by carbon-carbon binding
Single bonds in hydrocarbons are free to rotate (Figure 5). Rotation leads to the situation that
hydrogen atoms within the chain get close to each other. As a consequence the energy of the
molecule rises.
Ground State - low in energy Rotated State - Higher energy
Figure 5. Energy rise in rotated structures
Similar to internal rotation, molecular energy rises if molecules get under stress by moving
them closely together without giving time to relax. (Figure 6)
Figure 6. Excitation by pushing molecules to one another by shear stress
Also the fact of putting or pressing molecules toward a surface may lead to a steep increase in
internal molecular energy, sometimes high enough to cut them.
2.2. Double bonds
Carbon may also bind to others by double bonds, such that two of the four bindings attach to
the other as double, whereas the remaining bonding stays single. (Figure 7)
Figure 7. Double bonding
Double bond shows a 120° neighborhood angle to the carbon. This angle is kept constant and
will lead toward different structures in the double bond chemistry. (Figure 8)
Figure 8. E and Z structures in double bond
Both structures differ in their energy. Double bonds are part of biodegradable additives (native
oils) but also additives and thickeners in the case of greases. Z-Structures are dominant in
native oils.
2.3. Triple bonds
Triple bonds are seldom found in tribology. They represent a high energy state in molecules
with very high reactivity. As such, they are part of catalytic degradation processes in lubricants.
Within a triple bond carbons attach to each other by a linear principle (Figure 9):
Figure 9. Triple bond present in a hydrocarbon
3. Base oils in lubrication: General comments about specie and groups
Hydrocarbon Base Oils for Lubrication derive from organic chemistry. Different categories are
given by their chemical composition and structure. [2]
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Hydrocarbons, e.g. Structures that contain solely Hydrogen and Carbon (H, C)
Ester Oils, e.g. Structures containing Hydrogen, Carbon and Oxygen. Some Esters are derived
from other precursors, such as phosphoric acid esters.
Polyglycoles: Structure containing Hydrogen, Carbon and Oxygen but being different in
binding state compared to Esters.
Within a general scheme, base oils are identified as Groups.
Group I: Those lubricants are built from saturated hydrocarbons, e.g. hydrocarbons without
alkenes (hydrocarbons with double bonds)) (> 90%), obtained by solvent extraction processes
and catalytic hydrogenation. Sulfur may part in amount of > 0.03%. Viscosity index (VI) is in
between 80 and 120.
Group I+: Oils that are in a VI range of 103-108.
Group II: Hydrogenated (saturated) hydrocarbons (> 90%) and sulfur below 0.03% per weight
with viscosity index (VI) of 80 till 120.
Group II+: Oils in the VI range of 113-119.
The base oil within this group is manufactured by hydrocracking, solvent extraction or
catalytic dewaxing processes. Those oils are pale or water like colored.
Group III: Oils with a saturation > 90%, sulfur < 0.03% and a viscosity index > 120. Those oils
are produced by catalytic procedures with a concurrent rearrangement of the carbon backbone
during hydrogenation.
Group III+: Oils providing a VI at least of 140.
Group IV: Poly-α-Olefins with sulfur content approximately 0, viscosity index 140–170, being
produced by catalytic polymerization of low molecular weight end terminated olefins.
Group V: All other oils, e.g. esters, polyglycoles, phosphate esters.
North America states Group III, IV and V as synthesized hydrocarbons (SHC) while in Europe
Group IV and V is declared as synthetic oil.
4. Saturated natural hydrocarbons
Saturated hydrocarbons are those who do not contain double bonds in their structure. They
derive from the tetrahedral binding of carbon (bindings that point into corners of tetrahedron).
The simplest structure is given by methane, ethane, propane, butane with carbons attached at
the corners of the tetrahedral. These representatives are present in the natural gases, while
methane is found in enormous quantities as methane-ice cluster. The gases themselves are not
in use as lubricants but are components of fuels. (Figure 10)
H H H H H
H H H
H H
H H H
H HH H H H H H H
H H
H H H H
Methane Ethane Propane Butane
Figure 10. Methane, Ethane, Propane, Butane
Starting from pentane the hydrocarbons get liquid and are the principal components of fuels,
solvents, and raw materials for the chemical industry. To facilitate reading and drawing only
the carbon backbone is drawn without explicitly showing hydrogen. (Figure 11)
Figure 11. Pentane, Hexane, Heptane
Binding of carbon to carbon may be realized in chains, but also in branched chains and different
cycles (Figure 12).
Figure 12. Methylbutane (Isopentane), 2,2-Dimethylpropane (Neopentane), Cyclohexane
Hydrocarbons from C10 on till C14 are in use as solvents for cleaning (C11-C13 isoparaffines)
(Figure 13):
Figure 13. C11-C13 Iso paraffines
From C16 on, hydrocarbons represent typical structures present in lubricants. As the linear
hydrocarbons, beginning at C18 are solids, they are common in waxes and thickeners for liquid
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hydrocarbons. Due to their high solidification point they are a threat if present in Diesel fuels
by blocking filters.
Apart from their function as hydrocarbon waxes they are not suitable as lubricants for machine
oil circuits.
Suitable lubricants are derived from C16–C70 hydrocarbons with branched chains. Branching
leads to low pour points (the point where the lubricant starts to get solid). Machine oils with
low pour point, suitable for low temperature applications are branched in their carbon chain.
(Figure 14)
Figure 14. Representatives of saturated hydrocarbons as typical lubricants
In general, the viscosity of a lubricant - as a measure for the ability to move across - increases
with the molecular weight, e.g. the number of carbon atoms attached. Viscosity is measured
by different techniques. Basically the lubricant is pushed or moved in between plates or by
moving it in the gravity field. International convention states 16 classes of viscosity as an ISO
Standard (ISO VG classes): ISO VG 5, 7, 10, 15, 22, 32, 46, 68, 100, 150, 220, 320, 460, 680, 1000
and 1500. Low numbers indicate low viscosity, higher numbers high viscosity. Since viscosity
is strictly related to temperature, the ISO VG classification refers to 40°C as a standard
temperature. The nature of measuring the viscosity leads to the physical value of an area per
time: mm2/s. Hence, ISO VG 68 for example denotes a viscosity of the lubricant, measured at
40°C within 68 mm2/s within a range of roughly 10% below and 10% beyond the given 68mm2/s.
Low molecular weight, branched hydrocarbons are often used in pneumatic spraying, due to their
viscosity range, starting at 2 (water-like), 5, 10 and 15.
Low viscous hydrocarbons from ISO VG 10, 15, 22, 32, 46, 68 and 100 are in use as hydraulic oils.
Common hydraulic oil viscosity is around ISO VG 32, 46 and 68.
Hydrocarbons with higher viscosities are part of machine oils, carrying out the ordinary lubrication
functions. Machine oil viscosities are in the range of ISO VG 68, 100, 150, 220, 320, 460. The
number of carbons is in the range of 30–80 in the chain.
Some applications in heavy duty processes demand viscosities even higher in the range of ISO
VG 680, 1000 and 1500.
4.1. Cyclic hydrocarbons (Naphtenes)
Naphtenic hydrocarbons are derived from hydrocarbon cycles with more or less long chains
attached to the cycle. Due to their high branching they are very common in low temperature
applications (below -30°C) for hydraulics; low temperature greases. (Figure 15)
Figure 15. Principal Structure of Napthenic Hydrocarbons
4.2. Aromatic hydrocarbons (Alkyl aromats)
Aromatic Hydrocarbons (Alkyl Aromats) derive from the six-membered benzene ring system,
attached by hydrocarbon chains. Aromatic hydrocarbons are in use for low temperature
applications.
Alkyl Naphthalenes are a modern group of aromatic hydrocarbons. They may act as solvent
improvers for synthetic oils, facilitators in generating greases, low temperature applications
and much more (Figure 16):
Figure 16. Alkyl Aromats and Naphtalenes
Aromats and aromat-containing hydrocarbons are very vulnerable toward oxygen. Oxidation
of aromats starts at the attached hydrocarbon chain, proximate to the aromat nucleus by a
radical attack. This position is always very sensitive in similar structure, due to the fact, that
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the intermediate carbon radical is stabilized by the aromat and thus starts to stay persistent.
As a fact, aromats may strongly boost oxidation of hydrocarbons if present in the mixture due
to the mentioned persistency of the reactive intermediates. (Figure 17)
Aromats and naphtenics (containing unsaturated hydrocarbons and aromats) should be

stabilized against oxidation.
Metal (Iron)
O-O
Stabilization
Further Attack
.
Figure 17. Oxygen attack in the oxidation mechanism of Alkylaromats
5. Synthetic hydrocarbons
5.1. Poly-α-Olefins (PAO)
PAO is dominating all synthetic hydrocarbons by amount of production and worldwide

turnover. Syntheses start from Dec-1-ene, a linear C10 hydrocarbon with a double bond at the
beginning of the molecule. Polymerization and hydrogenation leads to PAO, as a highly
branched and fully saturated hydrocarbon (Figure 18). [2, 4]
Modern PAO may also start from a variety of hydrocarbons (C8-C12) by the same processes.
PAO are the most prominent worldwide used hydrocarbons and found in all important
applications, e.g. gear oils, circuit oil, hydraulic oil, base stock for automotive applications and
others. [2, 3, 6, 7]
Dec-1-ene
Catalyst
Polymerisation
Remove PAO
precursors
Figure 18. Principle of PAO formation
The extraordinary importance of PAO is due to its applicability at very low temperatures (pour
points below –30°C) and, in the case of suitable antioxidant prevention also at higher temper‐
atures (> 120°C). While PAO is, by its structure, very common in low temperature applications,
it is very poor in the contact with metal surfaces beyond 120°C if not properly additivated by
antioxidants.
Principal antioxidants for PAO are Phenyl-α-Naphtylamine (PAN) and octyldiphenylamines

(see antioxidants (AO)).
5.2. Polyisobutenes (PIB)
PIB are a sub class of polymerized olefins. They are widely used to boost low viscous oils to
higher ISO VG grades or as functional additives to improve the viscosity index (VI): the attitude
of the lubricant to lower its viscosity strongly by temperature is reduced by addition of PIB.
Synthesis is carried out starting from isobutene by catalytic oxidation processes (Figure 19):
Isobutene Polyisobutene
Figure 19. PIB formation by catalytic polymerization of Isobutene

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Sulfurization with activated sulfur precursors lead toward sulfurized isobutenes (SIB) widely
used as extreme pressure (see also section about EP/AW additives).
6. Ester oils
6.1. General
Esters are in general reaction products between alcohols and acids. Their formation is also
possible by means of other techniques, e.g. specific oxidation reactions, rearrangements in
organic molecules or different reactions. [10]
Carboxylic Acid esters are created by the reaction of alcohols and carboxylic acids [A] and their
derivatives, by trans–esterification (B), or catalytic reactions, e.g. epoxides with carbon dioxide
(C) (Figure 20). [10]
6.2. Esters in lubrication technology
Despite their high variety in structure esters are used in different categories: [1, 2, 4]
6.3. Mono-esters
Mono-Esters derive from a monocarboxylic acid (Carboxylic Acid that contains only one acidic
centre) and monofunctional alcohols (Alcohole with only one OH group). [10]
Esters derived from this structure are seldom used as pure lubricants, more as solvents or
dispersants. For example alcohol ethoxylates, formed by addition of alcohols to epoxides may
be esterified by a monocarboxylic acid leading toward a dispersant or self-emulsifying solvent.
(Figure 21)
6.4. Di-esters
Di-Esters are synthesized by use of dicarboxylic acids, mainly adipaic or sebacaic acid and two
molecules of an alcohole. 2-Ethylhexylalcohole (Iso Octanole), leading to Di-isooctyladipate
(DOA) or Di-isooctylsebacate (DOS, DEHS = Di-ethylhexylsebacate). (Figure 22)
They constitute an important group of oils, with either the function of base oil by themselves
but also as adjuvant to mineral oil or PAO formulations.
For Di-Esters the reaction of alcohols (A) with two hydroxyl groups and a monofunctional
carboxylic acid (B, B’) is also applicable. (Figure 23)
For technical purposes the reaction product of Neo Pentylgylcole (3.3 Dimethyl-propane-1.4-
diol) with oleic acid is important in lubrication technologies for use as a friction reducer and
in minimal lubrication systems. (Figure 24)
Figure 20. Examples for creation of esters. (A) Reaction of Carboxylic Acids with Alcohols, (B) Transesterfication, (C)
Reaction of Expoxide to cyclic Esters.
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O O
O O
Figure 21. Mono Ester Formation with the specialty of esterified alcohole ethoxilates
O CH3
H3C O DOA
O CH3
H3C O
H3C
O CH3
DOS
H3C O DEHS
O CH3
O
Figure 22. DOA and DOS
B A
B'
O
+ OH HO CH3
H3C OH HO +
O
O
O CH3
H3C O
O
Figure 23. Formation of Di-Esters by Di-Alcoholes (A) reacted with Monocarboxylic Acids (B, B’)
6.5. Tri-esters
Tri-Esters are mainly created by the reaction of trivalent alcohols with monocarboxylic acids.
They are mainly represented by to major groups:
6.5.1. Glycerol esters
Esters derived from glycerol as a trivalent alcohole leads to tri-Esters. (Figure 25)
OCH2
CH2O
Figure 24. Neopentylgylcoledioleate (NPG-Dioleate)
HO
OH O
OH HO
+
O
OH
HO
Glycerole Carboxylic Acid
O
Glycerole Triester
O O
O O
Figure 25. Esterification of Glycerole to tri-Esters
Glycerol Tri-Esters represent the huge group of natural oils. Sunflower, rapseed oil are
prominent representatives. A mixture of short chain carboxylic acids with unsaturated long
chain acids is used.
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As a fact of the presence of short chain carboxylic acids those esters are nutrients, biological
degradable and widely used as natural, biodegradable oils.
As a special glycerol ester, important for lubrication, ricinoleic acid esters have to be men‐
tioned.
Within this group ricinoleic acid represents the group of 12-hydroxy substituted C18 carbox‐
ylic acids.
Hence, alkaline cleavage of ricinoleic acid glycerol esters lead to 12-Hydroxi-oleic acid on the
one hand and to sebacaic acid on the other hand by degradation of the double bond.
Catalytic hydrogenation of 12-Hydroxioleic acid results in the formation of 12-Hydroxistearic
acid, which is important for modern grease concepts. Sebacaic Acid on the other hand is a raw
material for DOS (see above) but also for the production of complex greases. (Figure 26) [1, 2, 4]
Octan-2-ole OH
H
OH O
Alkalines OH
O O
O
12-Hydroxioleic Acid
O
OH O
O
HO
OH
Glycerol-Ricinoleic Acid Ester O
Sebacaic Acid
H2 OH O
H
O OH
OH 12-Hydroxi Stearic Acid
O
Figure 26. Cleavage of Glycerol – Ricinioleic Acid and hydrogenation to 12-Hydroxistearic Acid, Sebacaic Acid and Oc‐
tan-2-ole [10].
Glycerole Esters with long chain carboxylic acids only, e.g. Glycerole Tristearate, are no longer
nutrients and sparingly biodegradable. They are used as emulsifiers, consistency givers.
Glycerole Trioleate is a powerful friction reducer in tribological applications.
6.5.2. Triesters, derived from alcohols else than glycerole
6.5.2.1. Trimethylolpropane esters (TMP-esters)
TMP-Esters are created out of Trimethylolpropane (TMP) by reaction with short chain
carboxylic acids, e.g. the range from C6 to C10. (Figure 27)
O
H3C
O
O
Figure 27. TMP Esters
TMP Trioleate is created by reaction of TMP with oleic acid or by trans-esterification.and

commonly used as lubricant in minimal lubrication.
6.5.2.2. Trimellitic esters (TM-esters)
Apart from the described structures where trivalent alcohols get reacted with monocarboxylic
acids, trimellitic Esters (TM-Esters) are products from Trimellitic Acid Anhydride with Mono
alcohols. (Figure 28)
Due to the aromatic core those esters are high in thermal stability and widely used in high
temperature applications.
6.6. Tetra esters (Pentaerythrolesters, PE-esters)
Pentaerythrole acts as a four-valent alcohole which may be esterified by four carboxylic acids.
(Figure 29)
Carboxylic acids are in the range from C6 to C10.
Dipentaerythrol Esters (Di PE Esters) are formed starting from Dipentaerythrole as a six- valent
alcohole reacted by six monocarboxylic acids in a Carbon Chain length from 6 to 10. (Figure 30)
6.7. Polyesters
In the past 20 years new groups of esters have been created by reaction of polycarboxylic
polymers with alcohols. Those are reaction products of maleic acid anhydride (MSA) by Ene-
Reaction with PAO precursors, leading to the PAO-backbone MSA addition product that
might be esterified by butanole, leading to carboxylic complex esters (Figure 31).
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COOH HO
COOH
HO
+
COOH
HO
O O
O
O
O
Figure 28. TM Esters by reaction of trimellitic acid with branched alcohole
O
O O
O
O
O
O
O
Figure 29. PE Esters

O O O
O
O
O
O
O O
O
O
Figure 30. Di PE Esters
O
H O
O
n O
O
O n
ROH
O
O O
O
O O RO OR
O OR
O RO O
O
Figure 31. Complex Ester Formation by Ene-Reaction Sequences
Complex Esters from those structures are widely used to improve the additive solubility and
performance. Their structure with shielding the carboxylic groups causes less aggressiveness
toward sealings.
7. Structure activity relationship in esters
Esters are prominent representatives of lubricants where the chemical structure promptly
leads to a specific tribological activity. However, if a tribological acitivity is demanded, the
specific construction of esters may offer the solution.
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7.1. Polar acitivity
Esters are polar by their nature due to the central element where a carboxylic acid tail binds
toward an alcohol. Polarity gives some advantage but also disadvantage in the case esters are
used. In general, esters enhance the solubility of functional additives and keep them away
from fall-out. Esters also enhance the cleaning of metal surfaces in operation, preventing a
formulation by creation of sludge. Esters are, as a fact of their polarity, aggressive toward
sealings with a general tendency to shrink them. Plastics and elastomers under bending are
susceptible toward stress corrosion cracking if attacked by esters. Hence, stress-corrosion
cracking has to be considered explicitly in the case if esters are used. Since hydrocarbons, like
PAO have a tendency to swell elastomers, the addition of esters may counteract such that the
effect is neutralized. As a fact synthetic oils based on PAO are additivated by addition of 10
or 20 % esters per weight to create this effect.
7.2. Low temperature (Pour point) properties
Di-Esters, e.g. DOA, DOS are very useful in temperature ranges that undergo -40°C. This effect
might be explained by the lack of hydroxyl groups that might associate at low temperature via
hydrogen bridging, but also as a consequence of the crystallization hindrance due to the spatial
structure of esters which does not allow a dense crystal packing. In contrast, esters may be
designed such that their low temperature properties are lost, just by changing their structure.
Also, if the number of polar groups increase the tendency to molecular association increases,
and hence the pour point rises.
7.3. High temperature properties
High temperature applications in the use of esters are achieved by

• Sterical hindrance of the ß-Position in the Alcohol
• Use of Aromatic Nuclei in the Ester structure

As a specialty esters may rearrange within their structure via a preferred six-membered
cyclic intermediate that creates an alkene on one side and a carboxylic acid on the other
side (Figure 32).
O
a
O ß
H
OH
Figure 32. Decomposition of esters via cyclic rearrangement

Degradation of esters via such mechanisms takes place at ambient temperatures, e.g. by copper
activation even at 70°C. The formation of carboxylic acids and alkenes may lead to corrosion
and unfavorable deposits on metals. In the case of blocking the ß-position, as in the NPG and
TMP esters, the cyclic rearrangement is blocked and the ester does not undergo the thermal
degradation. Such oils are commonly used as turbine oils.
7.4. Side reactions
7.4.1. Hydrolysis
Ester Oils generally hydrolyze by interaction with water. The hydrolytic process is somehow
the reverse reaction how esters form. The attack of water is enhanced if alkalinity is present
but also acids may catalyze the hydrolysis. Common understanding states the attack of so
called nucleophiles, like water at the carbonyl C-atom, followed by rearrangement sequences,
leading to carboxylic acid and alcohols. (Figure 33)
OH
O
O
O
OH
OH2
Figure 33. water-based cleavage of Esters toward carboxylic acids and alcohols.
Catalytic hydrolysis of ester oils also take place at metal surfaces, e.g. under tribological
conditions. Formation of carboxylic acids may lead to corrosion as a consequence.
7.4.2. Biodegradation
Esters may decline under the interaction of bacteria and combust. Biodegradation is observed
in the case of vegetable oils, e.g. glycerol esters, seldom on technical esters. In principal
biodegradation cleaves esters, like water does to carboxylic acids. Biodegradation as a complex
process does not stop there but lead to further products. Esters may oxidize as described in
mineral oils and PAO at the organic tail. As a specialty they may undergo hydroxylation at a
side position followed by trans-esterification to lactones. The lactone sequence is described
already in the mineral oil section. Lactones are observed if esters, but also PAO are decomposed
on iron at higher temperature. Infrared Spectra show absorption at 1800 -1760 cm-1 caused by
lactone formation (see also chapter of antioxidants). (Figure 34)
7.5. Other esters
Esters may be created, as already mentioned by reaction of acids, in a different way as

carboxylic ones. Prominent representatives are esters derived from phosphoric acid. Phos‐
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Fe/O2
OH
O
O HO
O
Lactone
Figure 34. Lactone formation by side-chain oxidation of esters
phorous offers two main oxidation states (+III and +V) from which acids are derived. Depend‐
ing on the oxidation state and the alcohols, phosphoric esters are different in use. Also
phosphorous overtakes the role of anti-wear activity in such substances. [9]
A common representative is Trilaurylphosphite (Figure 35).
O
P O
O
Figure 35. Trilaurylphosphite as a representative of Phosphinic Acid Esters
7.5.1. Phosphoric acid esters
Phosphorus in the oxidation state (+V) creates a plenty of variant Acids, such as Orthophos‐
phoric Acid, Diphosphoric Acid, Triphosphoric Acids switching into each other. (Figure 36)
Phosphoric Acids are created by reaction of either phosphoric acid anhydride with alcohols
or phosphoric acid derivatives, e.g. POCl3 (Phosphorous-Oxi-Chloride) with alcohols. Ali‐
phatic alcohols are in use, but also Phenols [10].
O O
OH
HO HO OH
HO P O P-O-P OH HO P-O-P-O-P
HO OH OH
OH
O O
O
Figure 36. Representation of Phosphoric Acid Ester
7.5.1. Formation of phosphoric acid ester
Reaction of aliphatic alcohols, e.g. hexanole, with phosphorous pentoxide leads to hexylphos‐
phate. In general some acidity remains due to insufficient esterifications. As a consequence
those esters are often neutralized with amines to give amine phosphates. [10] (Figure 37)
Amine phosphates are widely used as anti-wear and anti-corrosion additives in all kinds of
applications. Phosphoric Acid Esters derived from Phenoles are shown below. (Figure 38).
In a different reaction Scheme Phosphoroxichloride reacts with alcohols. Those reactions are
convenient to come to aryl phosphoric acid esters. Arylphosphates are somehow used to come
to non-flammable high temperature lubricants at temperatures beyond 200°C.
Apart from the use as base oil phosphoric esters like Tricresylphosphates, based on the reaction
from Phosphorous Oxichloride with Cresol (Methylphenols) are common additives for
lubricants in bearing industry.
Whilst TCP with the methyl group in the para-position is seen as hazardous, TCP isomers in
the ortho is registered to be highly toxic. Also mixtures of TCP isomers, due to the content of
the highly toxic ortho isomer are registered as highly toxic. TCP, despite its superior behavior
as AW additive for bearing lubrication is restricted for use (Figure 39).
Use of Thiophosphorylchloride as precursor, the reaction with Phenole leads to EP/AW
additives like Triphenylphosphorothionate (TPPT) and its derivatives. (Figure 40)
TPPT is widely used as non metal EP Additive as a substitute for Zn and Molybdenum
Dithiophosphates. Due to its thermal stability, TPPT undergoes reactions at higher tempera‐
tures (>100°C). As to the fact that TPPT is ashless and starts to react at higher temperatures, it
is a preferred additive in high temperature lubrication in combination with sterically hindered
esters and PAO. In contrast to TCP, TPPT is not registered to be toxic, even more, the use of
TPPT is allowed at level of 0.5% per weight for incidental food contact.
8. Polyglycoles (PG)
8.1. General
Synthesis of Polyglycoles starts from Epoxides, obtained by catalytic oxidation of Alkenes from
Petrol- or hydrocarbon chemistry. Polymerization catalysed either by acids or alkaline result
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P
O O
O
P OH O
O P n
O O
P O P O
O O O
O
Phosphor (V) Oxide
O Phosphoric Acid Ester

P Alcoholes
O O
O
P OH O
O P n
O O
P O P O
O O OH
O
NH Amine Phosphate
Amines O
O P O
O
NH2+
Figure 37. Phosphate Esters and Amine phosphates
in the formation of polyglycoles. In the case of alkaline catalyst, e.g. alkoxides on half of the
PG contains a hydroxyl group while the end is capped by an ether function. (Figure 41) [1, 2,
7, 10]
Cresol
Cl OH O
Cl P=O + O P=O Tricresylphosphate
Cl TCP
Phosphorousoxichloride
Figure 38. Arylphosphates derived from Phosphor Oxide Chloride Reactions
O O
O
O P=O O P=O
O P=O
O O
O
meta - Tricresylphosphate para- Tricresylphosphate

ortho Tricresylphosphate hazardous
highly toxic hazardous
Figure 39. TCP and some isomers
Phenol
Cl OH O
Cl +
P=S O P=S Triphenylphosphorothionate
Cl TPPT
Phosphorousoxichloride
Figure 40. Synthesis of TPPT

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R R R
R'OH O OH
R'O O O n
O
R
Figure 41. General Formation of Polyglycoles by alkaline catalytic polymerization of Alkene Epoxides
The choice of either different alkenes (Group R) or alkoxides (R’) leads toward a huge variety
of PG, all of them with different chemical and physical properties.
Polyglycoles PEG PPG-PEG PPG PBG

Mixed
Polymers
Ethylene/ Prop Butyleneoxid
ylene Proyleneoxide e
Description Ethyleneoxide Polymer Oxide Polymers Polymers
Chemical Data
Physical Data Density approx. 1 0.95-0.98 0.95-0.98 0.95-0.98

Flashpoint approx.
Pourpoint approx.
Water miscible(%) 100 partially
Hydrocarbons non miscible partially partially partially
Ester Oils partially- full partially-full partially-full partially-full
Other PG PPG partially- full partially-full partially-full partially-full
PBG partially- full partially-full partially-full partially-full
Tribological Data Viscosity, 40°C Range 32 - 46 32- 100 32- 100 32- 100
VT Coefficient Range 180-..> 200 180-..> 200 180-..> 200 180-..> 200
VP Coefficient Range
Others Seals NBR compatible
ABS compatible
Paintings not compatible
Table 1. PG and their data and applicability
Technically only a couple of variances are produced in a larger scale, such as:
• Polyethylenglycoles (PEG) where Ethylene Oxide is the starter

• Polypropyleneglycoles (PPG) where Propylene Oxide is the starter
• Polyethylene- Polypropylene Oxide Mixtures started from mixtures or Ethylene and Propylene
Oxide
Table 1 offers an overview across the most common PG their data and applicability.
Single addition of long chain alcohols lead to the formation of fatty alcohol ethoxilates, for use
as non-ionic detergants and dispersants in lubricant formulations, as silicone free defoaming
and emulsifiers for lubricant formulae.
In general PG are not thermally stable by themselves and tend to decompose by emission of
volatile degradation products, e.g. low boiling compounds, such as aldehydes, ketones, acids
and others. Due to this behavior PG are used in high temperature applications where the
formation of polymers and lacquers due to heat induced degradation of lubricants is not
convenient, for example high temperature chain lubrication.
Presence of alkalines, such as overbased sulphonates, widely used in motor oils, as corrosion
inhibitor lead to multiple cross-reactions with the decomposition products of PG (aldol
reactions): Results of the aldole reaction are tars, sludge and slurries in the system. In conse‐
quence corrosion resistance of PG should always be carried out by acidic corrosion inhibitors,
such as succinic-esters, Zinc-Naphtenates or Phosphoric partial esters. (Figure 42)
Polyglycole
R R
R'O O OH
O O n
H
Heat Aldehydes
Catalysis Ketones
O
H
n Aldol Products
O
O
HO
n
HO OH
Figure 42. Aldole sludge formation in PG by use of alkaline
It has to be considered that PG are poorly soluble even amongst themselves and should be
carefully checked. In general their solubility in mineral oils is poor, better in esters (depending
on the structure). However, PG needs to be stabilized by antioxidants in order to prevent the
early thermal degradation. By doing so, the application of PG are enhanced significantly, such,
that even applications temperatures > 160°C are approached.
Convenient stabilizers are Phenyl-α-Naphtylamine, Phenothiazines or Alkyldiphenylamines.

The amount should be adapted to the application.
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In general PG offer very high viscosity indices, mainly above 160 (compared to mineraloils at
ranges from 20 (alkylnaphtalenes), napthenics (70), paraffine base solvates (110), Poly-α-
Olefines (140).
This high VI allows reducing the calculated viscosity in a given tribological application down
to one or two levels. For example, if in a given application ISO VG 320 (320 mm2/s, at 40°C) is
calculated for a mineral oil with a VI of 100, this viscosity maybe reduced by use of a PG down
to 220 mm2/s or even 150 mm2/s. Pour points are low in the case of PG, very often in the range
of -30.. – 40 °C even. Reaching the Pour point, PG tend to form highly viscous liquid, however,
crystallization-inhibited. As a fact of this huge increase, PG is not for use even at temperatures
above the pour point. Realistically PG is not suitable in the vicinity of their pour point.
Therefore they are not very good low temperature base oils compared, for instance, with esters
or PAO fluids. Due to their chemical structure PG are somehow strong solvents, e.g. paintings.
In the case PG is used, the system has to be checked whether the paintings of the tank, the
machine housing or others are affected. Dissolved painting from the tank may cause severe
problems in the oil circuit by blocking filters. Additive response, known from standard
applications, may change seriously by use of PG due to their different solvent capability.
Extreme Pressure Additives have to be checked in their performance if used in PG. Normally
anti-wear and anti-friction additives may be decreased in their content.
As a fact of the presence of epoxides in PG and due to their cancerogenic potential, the use of
PG formulations drops down.
8.2. Polyethylene Glycols (PEG)

Polyethylene Glycols are made from ethylene oxide by polymerization (Figure 43).
HO O OH
O O O n
Figure 43. PEG formation and structure
PEG, apart from its wide use in cosmetic industry is completely water miscible. Due to its water
miscibility PEG is only or sparingly soluble in hydrocarbons. Compatibility of the PEG with
a given fluid has to be checked before use. PEG, as facts of its water miscibility will uptake
water without separation. In case of the use of PEG in applications within water environment
the water ingress should be checked carefully. Effects of water ingress are increasing threat of
corrosion and thinning due to the mixture.
8.2.1. Use of PEG

Water miscibility is of use in non-flammable hydraulics in coal mining industries, but also in
applications of pharmacy and food processing. In general PEG is allowed within the FDA
regulation to be safe for incidental food contact. Due to the positive effect of sliding especially
in worm gears PEG is somehow recommended for use in such applications. [2, 6, 7, 9]
8.3. Polypropylene Glycoles (PPG)
Polypropylene Glycols are made from Proplyene Oxide by polymerization by use of butoxides
leading to a half ether structure (Figure 44):
H3C CH3 CH3

R'OH O OH
R'O O O n
O
CH3 CH3
Figure 44. PPG Structure
Due to the additional methyl group in the structure water miscibility drops down (contrast to
PEG) while the oil miscibility promotes. Also by choosing longer alkyl chain butoxides, PPG
structures may be obtained with enhanced oil solubility.
While PEG is highly dissolved in water, PPG forms droplets immersed in the water. Due to
this fact water separation out of PPG is difficult to achieve.
The partial solubility and immersion of PPG in water causes a very high fish toxicity. PPG
should never be used in the case of its break out-in free lands or water
8.3.1. Use of PPG
PPG is commonly used as high temperature circuit oil, e.g. calandars, compressors, high
temperature chain lubrication. All over PPG has to be stabilized by acid corrosion inhibitors,
e.g. phosphoric partial esters and antioxidants like Phenyl-α-Naphtylamine [2] [3] [5] [8].
8.4. Polybutylene Glycoles (PBG)
PBG are seldom in use and made consequentially from Butylene Oxide polymerization by use
of alkoxides, leading to half esters (Figure 45)
C2H5 C2H5 C2H5

R'OH O OH
R'O O O n
O
C2H5 C2H5
Figure 45. PBG Structure
8.4.1. Use of PBG
PBG is useful for enhancing the solubility of additives, boosting the viscosity index of mineral
oil variants.
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8.5. Alcohole Ethoxilates
Alcohole Ethoxilates are formed by a cross reaction of epoxides with alcohols. (Figure 46)
OH
O
O OH
Figure 46. Alcohole Ethoxilates
The use of long chain alcohols leads to alcohole ethoxilates being used as non-ionic surfactants,
emulsifiers and dispersants in multiple applications, e.g. hydraulic oils with dispersant
capability, cutting fluids, and dispersants for applications where sludge is expected.
Due to their non ionic nature alcohole ethoxilates are widely compatible in lubricant formu‐
lations.
9. Siloxanes
Siloxanes (Silicone Oils) are common lubricants in multiple applications, such as food and
pharmacy, but also in applications where special low friction properties are demanded [2, 3, 8]
In general silicones are the result of alkylchlorosilane hydrolyses [10] (Figure 47).
Si OH2 Si Si Si
O O O O O
n
Cl Cl
Figure 47. Scheme of Silicone Oil formation
Side groups are methyl, but also phenyl groups leading to polydimethylsiloxanes or polyar‐
ylsiloxanes. Mixtures of methyl and arylsiloxanes are in use with different spreading between
in the side chain (Figure 48).
Si Si Si
O O O O O
n
Figure 48. Polymethyl-Aryl Siloxanes

Siloxanes with different structures are not generally miscible amongst each other. Miscibility
has to be checked carefully. As mentioned, siloxanes are widely used in lubrication technology
due their exceptional properties concerning low friction capability, high temperature stability
and low toxicity in various applications. Prominent applications are starter components in
cars, valves in food industry, slow speed bearings and high temperature applications where
arylsiloxanes are in use. Siloxanes creep widely across surfaces and may cause problems in
coatings, lacquering and paintings.
10. Polyfluorinated Polyether (PFPE) base oil
PFPE Base Oil is created by polymerization of Perfluoroepoxids. Structure of PFPE is similar

to polyglycoles but with overall substitution of hydrogen by fluorine [2] [3] (Figure 49)
CF3 CF3
F F
CF2 O CF2 O
* O CF2 O n *
F F
CF3 CF3
Figure 49. PFPE Base Oil
Due to the effective shielding of the C-O-C backbone in the structure of PFPE by the trifluor‐
omethyl side chain group PFPE are completely insoluble in water, inert toward alkaline and
acids and even oxygen.
PFPE Base oil is used for high temperature purposes and in the presence of aggressive media,
mentioned above in junction with PTFE thickener. (Figure 50)
CF2 CF2 CF2

CF2 CF2
n
Figure 50. PTFE as thickener for PFPE
PFPE sparingly adheres to metal surfaces due to droplet formation. The low adhesion
causes creeping across surfaces and mal-lubrication if the surfaces are not cleaned thor‐
oughly. Creeping and low adhesion may cause low friction in certain applications. PFPE
is insoluble in most of the common base oils. Use of PFPE hence is restricted to the fluo‐
rine group of base oil.
Inertness of PFPE and PTFE make greases suitable for incidental food contact lubrication.
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High temperature combustion of PFPE may cause the emission of hydrogen fluoride and
fluoro phosgene which makes PFPE formulations somehow corrosive, especially on steel alloy
compositions. Due to this fact, the high temperature corrosiveness should be carefully taken
into account in the case of PFPE use.
11. Additives
Additives in lubricants enhance base oil functionalities. Additive technology is in broad scale
based on organic chemistry syntheses. From their origin they are found by chance, less than
by a real scientific approach. Nevertheless, literature about their reactions is innumerous from
the very beginning. [2, 3, 9]
Modern additive technology commenced in the early 20th century and has progressed contin‐
uously due to advanced organic chemistry syntheses. Upcoming modern spectrometry has
been used to clarify their structures and their reaction at different metal sites. [2, 3, 9]
Beyond the basic and industrial reaction mechanism studies, mixtures of additives have been
studied extensively by industry and science over the years. Such studies reveal the mechanisms
of compatibility and incompatibility of additives acting together at a given application. [9]
For example a functional mismatch is caused by diverse demanding addressed to additives,

e.g.: additives acting against corrosion may interfere with additives that have to prevent metal
surfaces against fretting or welding.
Modern additive technology is inevitable to reach the “for-life” goal of modern technologies.
As “for-life” might be understood in a different manner by users, additive packages are
developed during the decades adapted to a given customer demanding. For example, the
demanding to get automatic transmission gear oil performances is achieved by additive
packages that may not fit for wind turbine or paper mill applications. Hence, additives and
their mixtures have to be selected carefully for each purpose. [2, 3, 8, 9]
In general there are no rules up to now to predict additive performances at a given technical
application. As a consequence formulations have to be tested in forecast extensively to assure
its functionality. Such testing is addressed by international and national regulations.
Additives may cover a distinct structure-property relationship. Since there are no scientific
rules declaring on how a chemical structure of an additive causes a function all variations in
additives have to be validated by tests.
Additive technologies have been revised many times during their history, either due to a
change in demanding or due to their toxicity. Toxicity is a severe problem in additive tech‐
nology, since no one knows their real long term biological and ecological effects. [9]
Since the validation of those different chemical additive structures causes tremendous costs,
it is a fact, that additive free technologies or additive technologies with marginal content level
are favored as future solutions.
The following chapter addresses additive technologies concerning extreme pressure, anti-wear
functions and also corrosion-protecting and antioxidants.
11.1. Extreme Pressure (EP) and Anti-Wear (AW) additives
11.1.1. General
Extreme Pressure (EP) and Anti-Wear(AW) Additives are functional chemicals in lubricants
with the task to separate metal surfaces in the case of heavy loading and to improve their
resistance toward wear in the case of oil film break in the contact [9].
Machinery elements that start to run or stop due to emergency show pronounced loading due
to a lack of lubrication, e.g. the oil does not separate the metal surfaces and the protection of
the oil film drops down. At that point EP and AW additives are supposed to jump into the
arena by causing reaction layers preventing the metal from direct rupture or welding.
Their chemical structures are found by chance. For example observations during drilling and
maching show that tools perform better if lubrication is carried out by use of sulfurized oils
derived from vegetables, mixed and heated with sulfur.
Later on intense research the nature and reaction started including modern surface spectrom‐
etry techniques. The transformation of EP/AW additives as a function of the nature of the
surfaces, their loading, contact geometry, temperature and their structure shows a clear picture
of structure-activity relationship. Also additives perform as a function of their chemical
structure, but also as a function of their solubility in base oil and as a function of other additives
being present. In that sense, it is shown that additives either may prolong service life but are
also capable to shrink life.
11.1.2. Sulfur additives
Sulfur acts as a powerful extreme pressure additive. The high reactivity, especially toward
copper makes it unlike to use sulfur as element in tribology.
Sulfur embedded in organic framework acts as a powerful Extreme Pressure additive.

Choosing appropriate organic structures the activity toward copper drops down. However,
using sulfurized additives copper deactivation should be present anyhow.
Sulfur is added either by reaction of reactive organic precursors like alkenes and their
derivatives by heating up with the element, or by polymerization sequences with activated
sulfur precursors such as di-sulfur dichloride. Doing so, all kinds of unsaturated specie gives
reaction products leading to sulfurized specie. Prominent representatives are reaction
products of Isobutene with Disulfur Dichloride, or reaction products with terpenes (Figure
51) but also unsaturated carboxylic acid esters, like rapseed oil:
Sulfurized Additives (S-Additives) are often used together with phosphoric acid esters, since
the synergistic between those additives are known from the past. Doing so, gear oils may
contain S-Additives with amine phosphate esters. Also extreme pressure additives containing
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Figure 51. Didodecyltrisulfide as polysulfide representative
Dialkyl-Thiophosphoricacidesters are prominent representatives in sulfur additive chemistry.

(Figure 52).
Figure 52. Thiophosphoric Acid Ester
11.1.3. Dithiophosphates
Zinc- and Molybdenum dithio phosphates (ZndtP- ModtP)
Zincdithiophosphate (ZndtP) represent a prominent group of EP/AW additives. They derive

from the neutralization of Thiophosphoric Acids, obtained by ring opening of Phosphorous
pentasulfide with alcohols, with Zn-Carbonate or Hydroxides. As a fact, the ZndtP differ
strongly by their carbon-chain length. A couple of variants are achieved by choosing different
alcohols in the ring opening sequence of Phosphorous (V) sulfide. From the structural
perspective, ZndtP may be regarded as chelate complexes rather than a salt (Figure 53).
Molybdenumdithiophosphates contains a Molybdenum [µ-oxo] Core, distinct compared to

ZndtP (Figure 54).
11.1.4. Dithiocarbamates
Similar to Dithiophosphates, Chelat Complexes from Zinc, Molybdenum but also Bismuth and
others may be formed by reaction of Thiocarbamic Acid with the metal precursors. Dithiocar‐
bamic Acid is synthesized via addition of amines to Carbondisulfide. By varying the chain
length of the amine different dithiocarbamates are achieved (Figure 55 and Figure 56):
S
Various alcohols
P
S HO
S
O
S
S P +
P S P
S SH
P O
S
S
S
Thiophosphoric Acid
Phosphorous (V) Sulfide
Zn Carbonate
O S S O
P Zn P
S S O
O
ZndtP
Figure 53. ZndtP from neutralization of Thiophosphoric Acid with Zn Carbonate
O
O S S O
O
P Mo Mo P
O S O O
S
O
Figure 54. Molybdenumdithiophosphate
11.2. Corrosion protection
11.2.1. General
Within this chapter only iron as a chief element in technical application is considered.
Generally metal surfaces tend to corrosion if water, oxygen and probably salts, like sodium
chloride are present. Corrosion may take place either by cathodic reduction of oxygen or by
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S=C=S
S
+ N SH
H
NH2
R-CHO
Metal-Carbonate
NH
H
S N S
S
S R
Metal
S S S
S
N HN
H
Figure 55. Syntheses of dithiocarbamates
ZndtC
S S
N C Zn C N
H H
S S
O
S O S
N C Mo Mo C N
H O H
S S
O
ModtC
Figure 56. Zincdithiocarbamate (ZndtC) and Molybdenumdithiocarbamate (ModtC)
anodic oxidation of the metal. Charges, either positive (anode) or negative (cathode) pass the
surface layer. [2, 3, 9]
Charge transport from the metal toward the outer region is hindered by the surface potential
(over potential). Thus, corrosion processes have to overcome this potential and start after a
certain induction period. Once, if this potential has been overcome the corrosion starts without
hindrances by successive material transport. Materials transport ends up in a drastic change
of the surface, mainly accompanied by a loss.
For iron as metal, the transport of the metal ends up in a flaky layer (Rust) that permits water
and oxygen to penetrate. Due to this effect the rust process ends up in a total damage of the
metal, especially in an environment that boosts corrosive processes.
Counteracting corrosion, the initial processes of charge transportation have to be blocked.

Doing so, the over potential, e.g. the natural barrier of charges passing the surface has to be
increased by creating additional layers on the metal surface (Passivation) or by creation of
stable, insoluble complexes, formed by interaction of the surface atoms with a complex builder.
Passivation of iron surfaces and enhancing the over potential is achieved by deposition of
chromium layers that cause a thin and gas-dense closed layer on the metal. Thus, chromium
is a powerful inhibitor toward corrosion processes. As the charge transport phenomena
occurring on iron surfaces are cathodic or anodic and vice versa, this process could also be
stopped by offering an anodic victim like a zinc coating.
Additives that create a corrosion protection are in general dissolved in a carrier base-oil that
spreads over the surface. Due to their adapted functional groups a physical binding toward
the surface starts to create a layer. In order to create an appropriate corrosion protection this
layer has to be packed dense to avoid the penetration of water and oxygen. This is realized by
strong dipolar groups and oil soluble tails with a marginal demand in lateral spacing, e.g. long,
- unbranched alkyl chains.
Else, passivation also is achieved by placing insoluble complex builders onto the iron surface,
like phosphates are. Iron phosphate builds up a close dense insoluble layer on the surface.
Restriction of iron phosphate is indicated by the fact that, under certain conditions, phosphates
start to get reduced forming posphanes. Phosph4anes strongly affect metals due to segregation
of phosphorous at grain boundaries and releasing hydrogen into the metal. Hydrogen is
detrimental to the microstructure by inducing, e.g. hydrogen enhanced local plasticit (HELP)
or hydrogen induced cracking (HIC). Presence of phosphanes by reduction of phosphates takes
place in acidic and reducing environment, e.g. presence of hydrogen sulfide, chlorides and
others.
The following chapter will show some of the most prominent representatives of corrosion
protectors.
11.2.2. Sulfonate-chemistry
General
Sulfonates derive from sulfonic acids by neutralization with alkali, earth alkali –metals but
also with metals from the transition group, for example zinc. Principally each sulfonic acid
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may be neutralized. In technical applications mainly alkyl benze sulfonic acids and dodecyl‐
sulfonic acid are neutralized. Production starts from alkenes out of petrol chemistry by
addition sulfuric acid or SO3.
Neutralization with either sodiumhydroxide, Calciumcarbonate, Magnesiumcarbonate or

Bariumcarbonate leads to sulfonates: A = Sodiumsulfonate, B = Calciumsulfonate and with
excess Carbonate to over based Calciumsulfonate (B’), Magnesiumsulfonate (C) and Barium‐
sulfonate (D) (Figure 57).
Catalysts
Dodecylbenzene
SO3/H2SO4
HO3S
Dodecylbenezesulfonic Acid
NaOH
A BaCO3
CaCO3 MgCO3 SO3-
D Ba++
SO3-
SO3-
+
Na SO3-
C Mg++
SO3-
SO3-
B Ca++
SO3-
SO3-
B'
Ca++
X
X = Carbonate, Hydroxide
Figure 57. Sulfonic Acids and their Salts

11.2.3. Carboxylic acids and derivatives
Carboxylic Acid and their derivatives, e.g. esters may act as metal corrosion protectors. While
carboxylic acids are supposed to cause corrosion, some of them prevent. Rust preventing
carboxylic acids are derivatives from α-Aminoacids, like N-Oleylglycine. (Figure 58)
N-Oleyl Glycine N
H COOH
Figure 58. N-Oleylglycine
N-Oleylgylcine acts as powerful emulsifier, even at low dosage. Rust protecting is due to the
spread of water in the formulation over a big volume. N-Oleylglycine, even at low percentages
also counteracts with EP/AW additives, driving their activity down.
Carboxylic Acids, derived from Phenoles such as Nonyl-phenoxiaceticacid is a non emulsify‐

ing corrosion protector but under prohibition, due to its irritating effects (Figure 59).
O
CH 2COOH
Nonyl Phenoxy Acetic Acid
Figure 59. Nonylphenoxyaceticacid
Succinic Acid Derivatives, such as Succinic Half Ester of Octanole are powerful metal protec‐
tors, but also strong counteracting with EP/AW additives. Synthesis is carried out by reacting
succinic acid anhydride with alcoholes (Figure 60).
Carboxylates, derived from neutralizing carboxylic acids with transition metals like Zinc,
Lead, Bismuth lead to corrosion protection. Common acids are Napthenic acids or medium
chain carboxylic acids like octanoic acid (Figure 61).
11.2.4. Amine phosphate esters
Amine Phosphate Esters may act as anti-corrosion additives in addition to their anti-wear
properties. Due to their synergistic properties and due to the fact, that certain amine phos‐
phates are allowed as additives for incidental food contact, they are often found in all kind of
lubricants (Figure 62).
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O
HO
O +
O
O
OH Succinic Half Esters
Figure 60. Succinic Half Ester
ZnCO3
n COOH
COO-
Zn++
n
COO-
Zinc Naphtenates
Figure 61. Zn (Bi) Carboxylates (Napthenate and Octoate)
Am ine Phosphate
O
NH 2+ O
O P
O
Figure 62. Amine Phosphate Structure

Amine Phosphates are powerful activators of copper and zinc and cause leaching of those
metals from brass cages in bearings. Adding Amine Phosphates copper deactivators like
benzotriazoles have to be present (Figure 63).
N N
N N
N N
H
Benzotriazole N-Alkylated Benzotriazoles
Figure 63. Benzotriazole and N-Alkylbenzotriazoles as Cooper Passivators
11.3. Antioxidants (AO)
AO prevent lubricants from oxygen attack. Oxygen is, by nature, a diradical that undergoes
several transitions. Electron uptake from metal surfaces by a cathodic transfer, leads to
varieties of activated oxygen specie, powerful attacking hydrocarbon sites by abstraction of
hydrogen, leading to peroxides, and carbon radicals. The carbon radical itself starts to stabilize
by abstraction of hydrogen leaving an alkene as new product [10]. (Figure 64)
Due to radical stabilization the new formed alkene starts to continue the oxidation by sequen‐
tial abstraction of hydrogen, forming di-, tri- and polyalkenes, but also benzene rings. Apart
from the hydrogen abstraction, also oxidation takes place by attacking carbon radicals by
oxygen. At least the products created by such this procedures are carbonyl compounds, e.g.
alcohols, ketones, aldehydes, carboxylic acids and sometimes esters. PAO oxidation at metal
surfaces, e.g. iron beyond 120°C results in the formation of lactones (esters that come up by
internal reaction between an alcohol group and terminal carboxylic group) (Figure 65).
Hence oxidation sequences dramatically change the original hydrocarbon chain. If once started
it is self accelerating till new, different and stable products are reached. Oxidation is unselective
and takes place everywhere in the chain. Hence, plenty of products are formed by radical
oxygen assisted processes.
Antioxidants in general prevent the base oil, quenching the oxygen attack by formation of
stable radicals. Stabilization of the radicals is realized by a delocalization of the persistent AO
radical, created by oxygen attack due to the presence of aromats in the structure (Figure 66).
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.O-O.
electron transfer
Metal .O-O-
Reactive O-intermediate
attacks
creates
.
Hydrocarbon Hydrocarbon Radical
abstracts hydrogen new attack
Creates Alkenes
abstracts
. hydrogen
Di-Ene
Allyl Radical
Repetitive Sequnece
Tri-Ene Poly-Enes
Graphite like Structures
Figure 64. Oxygen – Hydrocarbon Attack sequence
The AO radical subsequently stabilizes to form new products like quinones. The quinone
structure may form a dark colored charge transfer complex with the original antioxidant.
Very often this causes strong discoloration of AO stabilized lubricants since the charge
transfer complexes are very intense in color. Sometimes, for example in the case of poly‐
urea greases, such charge transfer complexes may interfere with the grease structure in
terms of solidification.
Persistent radicals formed by AO are dangerous in some cases. In the case of their accumulation
in the system they are able to boost oxidation rather than to prevent. Dosage of AO hence
activated oxygen
. O-O
.
Hydrocarbon Radical
O-OH
Peroxides
Alcoholes Ketones
Aldehydes
O
O H
O
H
Lactones
O O
Figure 65. Oxidation sequence of Hydrocarbons toward carbonyl compounds
should be carefully tested. Formation of either charge transfer complexes or oxidation products
by the presence of AO may cause increased formation of sludge in the lubricant if the dosage
balance is not appropriate.
Nearly all AO contain aromats as a base principle. Prominent AO candidates are Butylhy‐
droxitoluene (BHT) (A), Alkyldiphenylamine ), Phenyl-α-Naphtylamine (PAN) (C) and
various others (Figure 67).
12. Greases
12.1. General remarks

Greases are defined apart from their chemical composition by the manufacturing processes.
Thickener and oil, getting heated by stirring, start to dissolve. Getting cold, the process of
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Activated O H
N
H
. N
H Formation of persistant
N=
. radicals due to delocalisation
N= O Quinone Structure
Figure 66. Principal delocalization of radicals created by oxygen attack.
OH
NH
NH
A B C
Phenyl--Naphtylamine
Butylhydroxitoluene Octyldiphenylamine PAN
BHT
Figure 67. Structures of AO: (A): BHT, (B) Alkyldiphenylamine, (C) PAN
stirring leads to a raw material where amorphous and crystalline structures are merged. The
amount of crystals and amorphous materials depends on the nature of the raw materials on
the one side and on the rate of heating and cooling on the other side. Rapid cooling causes
homogeneous and amorphous structure, as particles are not able to grow to a large size. The
raw grease, as effect of the mixture of solid structures has to be homogenized carefully.
Homogenization leads to a smoothened appearance of the grease with a scale distribution of
thickener particles as effect of the cooling process. Slow cooling generally leads to material
with large sized particles as an effect of nucleation and crystal growth. Oil embedding in such
structures is different due to the solid structure of the thickener. Stiffness and flowing
capability may change as an effect of the merged structure. Greases, even in the case of identical
chemical composition may differ significantly by their manufacturing process. Stiffness of
greases is defined by the NLGI grade declaration, measured by penetration of standard cone
into the grease. The deeper it’s penetration the more liquid the grease will be. To get a constant
value, the grease is worked by 60 strokes, then tempered to 25 °C and measured by cone
penetration. NLGI grades are presented in table 2: [3]
NLGI Grade Cone Penetration in 1/10 mm

OOO 445 - 475
OO 400 - 430
O 355 - 385
1 310 - 340
2 265 - 295
3 220 - 250
4 175 - 205
5 130 - 160
6 85 - 115
Table 2. NLGI Grades of Greases
12.1.1. Oil bleeding
Within grease the base oil is bound in different states. Some oil is weakly bound to the thickener
nuclei and gets easy released. Oil, bound in micelles and large structures with van-der-Waals
and dipolar bonding releases less. Oil release takes place due to centrifugal effects in speeding
machinery elements, e.g. bearings, creeping across walls e.g. sealings enhanced by tempera‐
ture. Successive loss of oil in grease may lead to its change in performance, accompanied by a
malfunction. Oil bleeding is measured with different techniques. Within the most popular one
the grease is sat on a sieve and pressed by a static load through it a given temperature. Bleeding
is measured as a function of time. For bearings the long term bleeding rate should be less than
5 % per weight in 7 days. [3]
12.1.2. Dropping point
Greases - if heated - start to get liquid at a certain point. Molten grease will leak out at sealing
edges and may cause a malfunction of the grease. For bearings the thumb rule is given by
dropping point minus 50 °C as the upper point of applicability. [3]
12.2. Soap based greases
Greases are soft solids, created by a thickener that gelates in suitable base oils. Gelling takes
place by intense mixing of thickeners with the base oil, often accompanied by heating till the
gelation is reached [3]. (Figure 68):
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COO- Li+
H3C
Lithiumstearate
OH
COO- Li+
H3C
Lithium-12-hydroxystearate
O
Li+ O-
O- Li+
O Lithium Acelate
H3C COO- Ca++ -OOC CH3
Calciumacetate
Figure 68. Prominent representatives of thickeners for grease production
Thickeners are all substances where gelling in the base oil is achievable. Prominent represen‐
tatives are lithium and calcium salts of carboxylic acids, for example Lithium Stearate,
Lithium-12-hydroxistearate, Calciumstearate, Calcium-12-hydroxistearate but also Calciuma‐
cetate. Lithium Complex Greases are created by the co-existence of lithium-12-hydroxistearate
with dicarboxylic acids like Acelaic or sebacaic acid.
Calcium Complex Greases are composed by calcium acetate, Calcium Stearate and calcium-12-
hydoxistearate as thickeners.
Salts of magnesium, barium and alumina are used for grease production but to minor extent.
12.3. Di and Polyurea greases (PU-greases)
Urea Greases are often called PU-Greases in technical language.
Urea structures are realized by adding amines to isocyanates (Figure 69):
-N=C=O + -HN-R -NH-CO-NH-R
Isocyanate Amine Urea
Figure 69. Urea Formation

Di-Urea grease production take aromatic Isocyanates, like Diphenylmethane Isocyanate

(Methylenbisdi-isocyanate, MDI) reacted with various aliphatic amines, like Cyclohexyla‐
mine, Alkylamines from C8 to C18 chain length.
Synthesis of the thickeners and grease formation is carried out simultaneously. Ester Oils, like
trimellitic acid esters facilitate the synthesis by solving the precursors before the reaction takes
place (Figure 70):
O=C=N N=C=O
Diisocyanate
H2N + NH2
Amine
Ester as Solvent
NHCONH
NHCONH
Di-Urea Thickener
Figure 70. Formation of Di-Urea Grease
Tetra- and polyurea Greases are created by mixing Di-Isocyanates like MDI or Toluenediiso‐
cyanates (TDI) with diamines, like ethylene diamine and monoamines, like Octadecylamine
in suitable base oils (Figure 71):
Urea Greases offer plenty nitrogen-hydrogen bridges within their structures. Concordant with
the presence of temperature resistant aromatic nuclei and in junction with high temperature
resistant base oils, they represent the group of high temperature grease “per se”. As to the high
variability of taking precursor amines, PU greases offer the possibility to adapt the grease to
a given application, much more than soap greases do.
Polyurea Greases that start from tallow amine, tolyenediisocyanate and ethylene di-amine are
in accordance with the US FDA regulations H1 (incidental food contact) if H1 base oil (like
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Diisocyanate
Diamine
N=C=O
H2N
NH2
N=C=O
+
NH2
Monoamine
NHCON NHCONH
NHCONH
NHCONH
Tetra Urea (idealised)
Figure 71. Formation of Tetra-and Polyurea Greases
white mineral oil or PAO) is used. Also the modern EU REACH regulations are valid for
polymeric structure.
As the polymeric degree increase, the thickeners may get insoluble and crystalline. Greases
are no longer available due to this because a lack of gelling. Due to this fact, variances of PU
Greases are restricted.
MDI and especially TDI are ought to be highly toxic by inhalation. Production of PU greases
have to take care, than none of the precursors are free in air, nor present in the grease.
Some isocyanates tend to polymerize during production, rather than to react with the amine,
especially at the end of the syntheses. Polymeric Isocyanates may remain in the grease and
cause severe toxicitiy, especially if the greases are up -heated.
PU Greases are very sensitive toward ingress of OH – groups (e.g. alkalines, water, polygly‐
coles) as the nitrogen-hydrogen bridging is disturbed. Ingress of such pollutants may cause a
change in consistency. Polyglycoles, if heated emit aldehydes that interfere with the NH
groups in PU greases. This reaction may end up in making the solid PU liquid! PU greases
thus should be monitored to those facts (Figure 72):
HO R'
R'-CHO
-HN-CO-NH-R -HN-CO-N-R
+
Figure 72. Reaction of PU Grease and Aldehydes
Other incompatibilities of PU Greases arise from mixtures with clay thickeners due to the
presence of either OH (Si-OH) or NH functional groups if the clay is modified by organic
amines.
12.4. Other thickeners
12.4.1. Clay greases-structure and use
Clay Thickeners derive from Alumina-Silicates. Due to their high surface and modification
they are suitable for gelling base oils, e.g. Esters, Napthenic Base Oils, sometimes Silicones and
Phosphoric Acid Esters. Clay Structure is generated by tetrahedral arrangement of Silica with
insertion of alumina (see figure) in layers of approximately 1-2 nm distance. Water and other
cations may be inserted in the space in between the two layers. Other cations, e.g. magnesium,
may also be inserted in between. [3] (Figure 73).
Gelling takes place by adhesion and insertion of organic molecules in the structure, assisted
by polar additives like propylene carbonate. Clay grease is produced by multiple milling the
clay with appropriate base oil by addition of water suppliers like glycerol or Propylene
carbonate at temperatures below 100°C. If water is lost the structure may break down during
the manufacturing. Doing so, the grease produced is a buttery solid with no dropping point.
12.4.2. Use of clay greases
Clay greases are used for applications where the grease should not move out and for special
high temperature applications, e.g. cement industry in slow motion bearings. Due to the
inertness of the inorganic structure toward alkaline and acids, clay greases are preferred in
applications where water, alkaline and acids are present, e.g. chain or bearing lubrication with
such ingress. Clay is declared as safe for incidental food contact and allowed for lubricants in
food industry (USDA H1 regulated) in junction with base oils like white mineral oil, PAO or
esters that are allowed for this purpose.
12.4.3. Restrictions in the use of clay greases
Restrictions for the use of clay greases are the presence of Lithium, - Calcium or Polyurea
Greases that may interfere with the hydrogen bonding of the clay structure. Mixtures of clay
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O O O O O O
Si Si Si Si Si Si Si
O O HO O OH OH O
O O O
Al Al Al Al Al Al
O O O
OH O HO O O OH O
Si Si Si Si Si Si
O O Si
O O O O
1-2 nm
Distance OH2 Metal Cations
OH2
OH2
O O O O O O
Si Si Si Si Si Si Si
O O O OH O
OH O O OH O
Al Al Al Al Al Al
O O O
OH O O O OH O
OH
Si Si Si Si Si Si
O O Si
O O O O
Figure 73. Estimated basic structure of clay
and conventional greases should be evaluated very carefully. Clay greases are restricted in
bearing lubrication strictly due to over rolling speed. In general the speed factor is limited to
ndm (Average of outer and inner diameter of the bearing times the speed (revolution per
minute)) of 100.000. Only slow moving bearings could bear clay lubrication.
13. Silica
Silica is in use for thickeners as amorphous material, obtained by flame decomposition of Silica
Tetrachloride (Figure 74):
Silica, due to its powerful surface activity may be used as powerful thickener in low percentage
for each kind of base oil. Greases obtained by mixing silica with base oils are transparent. The
inorganic structure causes no dropping point for such greases. Silica Thickened greases cause
steep and irreversible thickening by heating up due to the increase of internal hydrogen
bonding. They never should be in use for high speed and high temperature rotating bearings,
SiCl4
Flame
O O
O O
Si O O
Si O O
Si O
O Si
O
O
O
n
Figure 74. Principal formation of amorphous SiO2 by flame combustion
since they block their motion. The ndm (Average of Bearing Size times revolution per minute)
is restricted to 100.000, hence slow motion. Due to the possible entrance of water, silica
thickened grease is poorly water stable and should not be in use in applications where water
(especially hot water) and alkalines are present. Alkalines react with silica to silicates, starting
its degradation.
14. Polytetrafluoroethylene (PTFE)
PTFE is a convenient thickener in base oils for the purpose of incidental food contact, low
friction properties and high temperature. The fluorine entity causes low activity toward
oxygen. PTFE Grease is used in oxygen application (valves under oxygen impact), especially
with PFPE.
15. Conclusion
Tribology is highly guided by physics and chemistry of the lubricants. Functionality of lu‐
bricants is given by their physics and their chemical structure. Modern understanding of
lubrication hence allows the construction of lubricants appropriate to a given application
to a certain extent. Under the conditions of full lubrication their physical properties, e.g.
viscosity, viscosity-temperature and viscosity –pressure properties dominate over the
chemical structure. Under such circumstances, the lubricant takes away heat (cooling
function) from the mating contacts, but also wear and debris (cleaning function). Within a
running – in period some reaction layers of lubricant constituents (additives) may be cre‐
ated. Basically those layers stay constant over time and do not change. On the other
hand, if lubrication undermines the given roughness’s of the mating partners, or over‐
takes the natural temperature limit given by the restrictions of organic chemistry (e.g.
temperatures beyond 150°C), chemistry starts to perform reaction scenario highly related
to the nature of the chemical structure of the ingredients in the lubricant. The basic reac‐
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tions found here are radical reactions, as a fact of the presence of oxygen and iron. With‐
in such radical reaction sequences hydrogen is abstracted, alkenes and alkynes are formed
and their oxidation products (aldehydes, ketones, carboxylic acids and their derivatives).
Additives, in general improve the lubricants by expanding their limits.
In general, lubrication fundamentals in tribology have overcome the alchemy of the past by
numerous efforts taken by the scientific community.
Author details
Walter Holweger*
Schaeffler Technologies AG & Co.KG, R&D Central Materials, Germany
References
[1] Rudnik L.R., editor. Synthetics, Mineral Oils, and Bio-Based Lubricants. Boca Raton:
CRC Press; 2005.
[2] Dresel W., Mang T., editors: Lubricants and Lubrication. 2nd Edition. Weinheim: Wi‐
ley-VCH; 2007.
[3] Klamann D. Schmierstoff und verwandte Produkte. Weinheim: VCH-Verlag; 1982.
[4] Mortier R.M., Fox M.F., Orszullik T.M., editors. Chemistry and Technology of Lubri‐
cants Dordrecht: Springer; 2010. http://link.springer.com/book/
10.1007/978-1-4020-8662-5/page/1 (accessed 27 December 2012).
[5] Dowson D., Taylor C., Childs T., Dalmaz G. editors. Lubricants and Lubrication. In:
Tribology Series 30 : Proceedings of the 21st Leeds-Lyon Symposium on Tribology.
Amsterdam : Elsevier; 1995.
[6] Bloch, H.P., Practical Lubrication for Industrial Facilities. Lilburn: Fairmont Press;
2000.
[7] Stepina V., Vesely V. Lubricants and Special Fluids. Amsterdam: Elsevier; 1992.
[8] Lansdown A.R., Lubrication and lubricant selection: a practical guide. 3rd Edition.
John Wiley & Sons; 2004.
[9] Rudnick L. R., editor. Lubricant Additives: Chemistry and Applications, 1st Edition.
New York:Marcel Dekker, 2003.
[10] March, J., Advanced Organic Chemistry: Reactions, mechanisms, Structure. New
York: Wiley-VCH; 1992.
Chapter 2
Lubrication and Lubricants
Nehal S. Ahmed and

Amal M. Nassar
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1. Introduction
1.1. Lubrication
The primary purpose of lubrication is to reduce wear and heat between contacting surfaces in
relative motion. While wear and heat cannot be completely eliminated, they can be reduced
to negligible or acceptable levels. Because heat and wear are associated with friction, both
effects can be minimized by reducing the coefficient of friction between the contacting surfaces.
Lubrication is also used to reduce oxidation and prevent rust; to provide insulation in
transformer applications; to transmit mechanical power in hydraulic fluid power applications;
and to seal against dust, dirt, and water.
1.1.1. The lubrication regimes
The modern period of lubrication began with the work of Osborne Reynolds (1842-1912).
Reynold's research was concerned with shafts rotating in bearings and cases this show in Fig.
1. When a lubricant was applied to the shaft, Reynolds found that a rotating shaft pulled a
converging wedge of lubricant between the shaft and the bearing. He also noted that as the
shaft gained velocity, the liquid flowed between the two surfaces at a greater rate. This, because
the lubricant is viscous, produces a liquid pressure in the lubricant wedge that is sufficient to
keep the two surfaces separated. Under ideal conditions, Reynolds showed that this liquid
pressure was great enough to prevent direct contact between the metal surfaces. Fig.2 taking
a plain journal bearing as example, Fig.3 which is known as Stribeck curve summarizes the
lubrication regimes by describing the relationship between speed, load, oil viscosity, oil film
thickness, and friction.
Figure 1. Three positions of shaft in a bearing
Figure 2. Plain Journal bearing
In this graph, the coefficient of friction is plotted against the expression ZN/P (sometimes
referred to as the Hersey number)
oil viscosity×shaft speed

Where ZN/P =
bearing pressure
(1)
Lubrication and Lubricants 57
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Zone 1 Zone 3
Zone 2
ZN/P
B
Fig. (2) Stribeck curve
ZN/P
Figure 3. Stribeck curve
Figure 3. Stribeck curve
In this graph, the coefficient of friction is plotted against the expression ZN/P (sometimes referred to as the Hersey
number)
Where ZN/P = (1)
As shown there are three distinct zones separated by points A and B. At B the oil film is just thick enough to
ensure that there is no contact between asperities on the shaft and bearing surfaces. Smoother surfaces shift B to
the left, while at point A the oil film thickness reduces virtually to nil. Zone 2, between A and B is known as the
zone of mixed lubrication. Mixed-film lubrication is unstable at which increase in lubrication temperature causes
further increases in lubrication temperature .
Scheme 1. Mixed-film lubrication
As shown there are three distinct zones separated by points A and B. At B the oil film is just
thick enough to ensure that there is no contact between asperities on the shaft and bearing
Mixed-film lubrication
surfaces. Smoother surfaces shift B to the left, while at point A the oil film thickness reduces
virtually to nil. Zone 2, between A and B is known as the zone of mixed lubrication. Mixed-
film lubrication1.1.1
is unstable
HydrodynamicatLubrication.
which increase in lubrication temperature causes further
increases in lubrication temperature.
Basically, lubrication is governed by one of two principles: hydrodynamic lubrication and boundary lubrication. In
1.1.2. Hydrodynamic lubrication

the former, a continuous full-fluid film separates the sliding surfaces. In the latter, the oil film is not sufficient to
prevent metal-to-metal contact. Hydrodynamic lubrication is the more common, and it is applicable to nearly all
Basically, lubrication is governed
types of continuous by one
sliding action whereof twopressures
extreme principles: hydrodynamic
are not involved. lubrication
Whether the sliding and
occurs on flat
boundary lubrication. In the former, a continuous full-fluid film separates the sliding surfaces.
In the latter, the oil film is not sufficient to prevent metal-to-metal contact. Hydrodynamic
lubrication is the more common, and it is applicable 2to nearly all types of continuous sliding
action where extreme pressures are not involved. Whether the sliding occurs on flat surfaces,
as it does in most thrust bearings, or whether the surfaces are cylindrical, as in the case of
journal (plain or sleeve) bearings, the principle is essentially the same.
It would be reasonable to suppose that, when one part slides on another, the protective oil film
between them would be scraped away. Except under some conditions of reciprocating motion,
this is not necessarily true at all. With the proper design, in fact, this very sliding motion
constitutes the means of creating and maintaining that film.
In zone 3 is the zone of hydrodynamic or fluid film lubrication where there is no wear because
there is no contact between the surfaces. Hydrodynamic Lubrication is often referred to as
stable lubrication. There are four essential elements in hydrodynamic lubrication, a liquid,
relative motion, the viscous properties of the liquid, and the geometry of the surfaces between
which the convergent wedge of fluid is produced. Only friction present in a hydrodynamic
lubrication system is the friction of the lubricant itself, it would make sense to have a less
viscous fluid in order to minimize friction: the less viscous a liquid the lower the friction. Too
low of a viscosity jeopardizes our system though. We have to be very careful that the distance
between the two surfaces is greater than the largest surface defect. The distance between the
two surfaces decreases with higher loads on the bearing, less viscous fluids, and lower speeds.
The surface geometry is also very important. The surfaces have to be such that a converging
wedge of fluid can develop between the surfaces, allowing the hydrodynamic pressure of the
lubricant to support the load of the shaft or moving surface. Hydrodynamic lubrication is an
excellent method of lubrication since it is possible to achieve coefficients of friction as low as
0.001, and there is no wear between the moving parts. Special attention must be paid to the
heating of the lubricant by the frictional force since viscosity is temperature dependent. One
method of accomplishing this is to cycle the lubricant through a cooling reservoir in order to
maintain the desired viscosity of the fluid. Another way of handling the heat dissipation is to
use commercially available additives to decrease the viscosity's temperature dependence
which are known as viscosity index improvers.
The formation of fluid film is influenced by the following factors:
• The contact surfaces must meet at a slight angle to allow formation of the lubricant wedge.
• The fluid viscosity must be high to maintain adequate film thickness to separate the
contacting surfaces at operating speeds.
• The fluid must be adhering to the contact surfaces for conveyance into the pressure area to
support the load.
• The fluid must be distributing itself completely within the bearing clearance area.
• The operating speed must be sufficient to allow formation and maintenance of the fluid film.
• The contact surfaces of bearings and journals must be smooth and free from sharp surfaces
that will disrupt the fluid film.
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Scheme 2. Hydrodynamic lubrication
1.1.3. Boundary lubrication
The oil film has become so thin in Zone 1 that there is no hydrodynamic contribution and only
boundary lubrication which is defined by Campbell in 1969 as the lubrication by a liquid under
conditions where the solid surfaces are so close together that appreciable contact between
opposing asperities is possible. The friction and wear in boundary lubrication are determined
predominantly by interaction between the solids and between the solids and the liquid. The
bulk flow properties of the liquid play little or no part in the friction and wear behavior.
As mentioned, boundary lubrication is effective when a complete fluid film does not develop
between potentially rubbing surfaces, the film thickness may be reduced to permit momentary
dry contact between wear surface high points or asperities. Boundary lubrication occurs
whenever any of the essential factors that influence formation of a full fluid film are missing.
The most common example of boundary lubrication includes bearings, which normally
operate with fluid film lubrication but experience boundary lubricating conditions during
routine starting and stopping of equipment. Other examples include gear tooth contacts and
reciprocating equipment.
A brief explanation of what needs to be added to basic mineral oil in order to create an effective
boundary lubricant. Generally, the best additives are active organic compounds with long
chain molecules and active end groups. These compounds bind tightly and intricately with
each other, forming a film that builds up on the surface of the metal itself. This results in a thin
film that is very difficult to penetrate. When two surfaces, each covered with a boundary layer,
come in contact with each other they tend to slide along their outermost surfaces, with the
actual faces of the surfaces rarely making contact with each other. Liquids are rarely good
boundary lubricants. The best boundary lubricants are solids with long chains of high inter-
chain attraction, low shear resistance so as to slip easily, and a high temperature tolerance. The
Scheme 3. Boundary lubrication
boundary lubricant should also, obviously, be able to maintain a strong attachment to the
surfaces under high temperatures and load pressures.
The most common boundary lubricants are probably greases. Greases are so widely used
because they have the most desirable properties of a boundary lubricant. They not only shear
easily, they flow. They also dissipate heat easily; form a protective barrier for the surfaces,
preventing dust, dirt, and corrosive agents from harming the surfaces
1.2. Base stock
Petroleum is one of the naturally occurring hydrocarbons that frequently include natural gas,
natural bitumen, and natural wax. The name ‘‘petroleum’’ is derived from the Latin petra (rock)
and oleum (oil). According to the most generally accepted theory today, petroleum was formed
by the decomposition of organic refuse, aided by high temperatures and pressures, over a vast
period of geological time.
Although petroleum occurs, as its name indicates, among rocks in the earth, it sometimes seeps
to the surface through fissures or is exposed by erosion. The existence of petroleum was known
to primitive man, since surface seepage, often sticky and thick, was obvious to anyone passing
by prehistoric animals were sometimes mired in it, but few human bones have been recovered
from these tar pits. Early man evidently knew enough about the danger of surface seepage to
avoid it.
The petroleum remaining from the distillation is thick like pitch; if the distillation has been
pushed far, the residuum will flow only languidly in the retort, and in cold weather it becomes
a soft solid, resembling much the maltha or mineral pitch Fig. 4 shows that the distillation of
crude oil.
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Figure 4. Schematic View of Crude Oil Distillation
Base stocks are refined from crude oil to obtain products with the best lubricating properties.
Base stocks generally make up 80-95% of a typical engine oil and 5% additives [1]. Base stock
is used to describe plain mineral oil. The physical properties of an oil depend on its base stock.
In most cases it is chemically inert there are three sources of base stock: biological, mineral and
synthetic. The oils manufactured from these sources exhibit different properties and they are
suitable for different applications. For example:
a. Biological oils are suitable in applications where the risk of contamination must be
reduced to a minimum, for example, in the food or pharmaceutical industry. They are
usually applied to lubricate kilns, bakery ovens, etc. There can be two sources of this type
of oil: vegetable and animal. Examples of vegetable oils are: castor, palm and rape-seed
oils while the examples of animal oils are: sperm, fish and wool oils from sheep (lanolin).
b. Mineral oils are the most commonly used lubricants throughout industry. They are
petroleum based and are used in applications where temperature requirements are
moderate. Typical applications of mineral oils are to gears, bearings, engines, turbines,
etc.
c. Synthetic oils are artificially developed substitutes for mineral oils. They are specifical‐
ly developed to provide lubricants with superior properties to mineral oils. For
example, temperature resistant synthetic oils are used in high performance machi‐
nery operating at high temperatures. Synthetic oils for very low temperature applica‐
tions are also available [2].
1.3. Lubricants
All liquids will provide lubrication of a sort, but some do it a great deal bettor than others. The
difference between one lubricating material and another is often the difference between
successful operation of a machine and failure. For almost every situation, petroleum products
have been found to excel as lubricants. Petroleum lubricants stand high in metal-wetting
ability, and they possess the body, or viscosity characteristics, that a substantial film requires,
these oils have many additional properties that are essential to modern lubrication, such as
good water resistance, inherent rust-preventive characteristics, natural adhesiveness, relative‐
ly good thermal stability, and the ability to transfer frictional heat away from lubricated parts.
What is more, nearly all of these properties can be modified during manufacture to produce
a suitable lubricant for each of a wide variety of applications. Oils have been developed hand-
in- hand with the modern machinery that they lubricate; indeed, the efficiency, if not the
existence, of many of today’s industries and transportation facilities is dependent upon
petroleum lubricants as well as petroleum fuels.
The basic petroleum lubricant is lubricating oil, which is often referred to simply as “oil.” This
complex mixture of hydrocarbon molecules represents one of the important classifications of
products derived from the refining of crude petroleum oils, and is readily available in a great
variety of types and grades.
Any description of lubricating oils would be incomplete without consideration of oils for
vehicle engines. These oils are used in greater quantity than all other lubricants combined, and
are of interest to more people than any other lubricants. Engine oils are generally recommend‐
ed by automotive builder according to the Society American of Automotive Engineers (SAE)
viscosity classification.
Engine oil lubricants make up nearly one half of the lubricant market and therefore attract a
lot of interest. The principal function of the engine oil lubricant is to extend the life of moving
parts operating under many different conditions of speed, temperature, and pressure. At low
temperatures the lubricant is expected to flow sufficiently in order that moving parts are not
starved of oil. At higher temperatures they are expected to keep the moving parts apart to
minimize wear. The lubricants reduce friction and removing heat from moving parts.
1.3.1. General classification of the lubricating oils
The term lubricating oil is generally used to include all those classes of lubricating materials
that are applied as fluids [3]. Lubricating oils are made from the more viscous portion of the
crude oil which remains after removal by distillation of the gas oil and lighter fraction [4-8].
Although crude oils from various parts of the world differ widely in properties and appear‐
ance, there is relatively little difference in their elemental analysis. Thus, crude oil samples will
generally show carbon content ranging from 83% to 87 %, and hydrogen content from 11% to
14%. The remainder is composed of elements such as oxygen, nitrogen, and sulfur, and various
metallic compounds. An elemental analysis, therefore, gives little indication of the extreme
range of physical and chemical properties that actually exists, or of the nature of the lubricating
base stocks that can be produced from a particular crude oil.
An idea of the complexity of the lubricating oil-refining problem can obtained from a consid‐
eration of the variations that can exist in a single hydrocarbon molecule with a specific number
of carbon atoms. For example, the paraffinic molecule containing 25 carbon atoms has 52
hydrogen atoms. This compound can have about 37,000,000 different molecular arrangements
[3]. The hydrocarbons of the crude oils are:
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1.3.1.1. Paraffinic components
The paraffinic components, show in Fig. 5 (a, b), which determine the pour point, contain not
only linear but also branched paraffins. The straight chain paraffins of high molecular weights
raise the pour point of oils (waxy compounds) and should be removed by dewaxing processes.
The branched paraffins are chemically interesting hydrocarbons and they are found in large
quantities in lubricating oil fractions from paraffinic crudes. Oil rich in paraffinic hydrocarbons
have relatively low density and viscosity for their molecular weight and boiling range. Also,
they have good viscosity/ temperature characteristics. In general, paraffinic components are
reasonably resistant to oxidation and have particularly good response to oxidation inhibitors
[9, 10].
1.3.1.2. Naphthenic components
They have rather higher density and viscosity for their molecular weight compared to the
paraffinic components. An advantage which naphthenic components have over the paraffinic
ones is that they tend to have low pour point and so do not contribute to wax. However, one
disadvantage is that they have inferior viscosity/ temperature characteristics. Single ring
alicyclics with long paraffinic side chains, however, share many properties with branched
paraffins and can in fact be highly desirable components for lubricant base oils. Naphthenic
components, Fig. 5 (c), tend to have better solvency power for additives than paraffinic
components but their stability to oxidative processes is inferior [9, 10].
1.3.1.3. Aromatic components
They have densities and viscosities which are still higher viscosity/ temperature characteristics
are in general poor but pour point is low, although they have the best solvency power for
additives, their stability to oxidation is poor. As for alicyclics, single ring aromatics with long
paraffinic side chain may be very desirable base oil components, Fig. 5 (d). The classifying of
hydrocarbon as paraffinic, naphthenic and aromatic groups which are generally used for
characterizing the base oil should not be taken as absolute but as an expression of the pre‐
dominating chemical tendencies of the base stocks [11].
1.3.1.4. Non hydrocarbon components
The non hydrocarbons in lubricating oil are analogous in many ways to the hydrocarbons.
Sulfur and nitrogen compounds are found almost entirely in ring structures such as sulfides,
thiophene, pyridine and pyrrol types. More complex molecules are also thought to exist in
lubricating oil in which nitrogen and sulfur atoms are found in the same molecule. As in the
case of hydrocarbons, these compounds will probably also have paraffinic side chains and
possibly be condensed with naphthenic and aromatic ring structures [11]
Although these non hydrocarbons may be present in only trace amounts, they often play a
major role in controlling the properties of lubricating oils. In general they are chemically more
active than the hydrocarbon, and hence they may markedly affect properties such as oxidation
Figure 5. Chemical Structure of Lubricating oil
stability, thermal stability and deposit forming tendencies. In refining the general tendency is
to reduce the non hydrocarbons content to a minimum.
Naphthenic acid account for most of the oxygenated compounds found in petroleum. These
are removed in the refining processes by neutralization and distillation. The naphthenates are
retained in the residue from the distillation and can be removed by deasphalting process.
Modern refining methods generally remove most of resins, asphaltenes, polycyclic aromatic,
di aromatic and their analogous non hydrocarbons, so that the final lubricant consists chiefly
of saturated and monocyclic aromatic fraction [12].
1.3.2. Main properties of lubricating oils

The main properties which a lubricating oil must posses to full performance are :
1.3.2.1. Physical properties of lubricating oil

a. Viscosity
Viscosity is the measure of the internal friction within a liquid; the way the molecules interact
to resist motion. It is a vital property of a lubricant because it influences the ability of the oil
to form a lubricating film or to minimize friction [8]. Newton defined the absolute viscosity of
a liquid as the ratio between the applied shear stress and the resulting shear rate.
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b. Viscosity index
The most frequently used method for comparing the variation of viscosity with temperature
between different oils by calculation of dimensionless numbers, known as the viscosity index
(VI). The kinematic viscosity of the sample is measured at two different temperatures (40°C,
100°C) and the viscosity compared with an empirical reference scale. VI is used as a convenient
measure of the degree of aromatics removal during the base oil manufacturing process, but
comparison of VI of different oil samples is only realistic if they are derived from the same
distillate feedstock [8].
c. Low temperature properties.
When a sample of oil is cooled, its viscosity increases in a predictable manner until wax crystals
start to form. The matrix of wax crystals becomes sufficiently dense with further cooling to
cause an apparent solidification of the oil. Although the solidified oil does not pour under the
influence of gravity, it can move if sufficient force is applied. Further decrease in temperature
cause more wax to form, increasing the complexity of the wax/oil matrix. Many lubricating
oils have to be capable of flow at low temperatures and a number of properties should be
measured.
• cloud point
It is the temperature at which the first sign of wax formation can be detected. A sample of
oil is warmed sufficiently to be fluid and clear. It is then cooled at a specified rate. The tem‐
perature at which haziness is first observed is recorded as the cloud point, the ASTM D
2500/IP 219 test. The oil sample must be free of water because it interferers with the test.
• pour point
It is the lowest temperature at which the sample of the sample of oil can make to flow by
gravity alone. The oil is warmed and then cooled at a specified rate. The test jar is removed
from the cooling bath at intervals to see if the sample is still mobile. The procedure is repeat‐
ed until movement of the oil doesnot occur, ASTM D 97/IP 15. the pour point is the last tem‐
perature before the movement ceases, not the temperature at which solidification occurs.
This is an important property of diesel fuels as well as lubricant base oils. High- Viscosity
oils may cease to flow at low temperatures because their viscosity becomes too high rather
than because of wax formation. In these cases, the pour point will be higher than the cloud
point.
d. High temperature properties.
The high temperature properties of oil are governed by distillation or boiling range charac‐
teristics of the oil.
• volatility
It is important because it is an indication of the tendency of oil to be lost in service by vapor‐
ization.
• flash point
It is important for oil from a safety point of view because it is the lowest temperature at which
auto-ignition of the vapour occur above the heated oil sample. Different methods are used,
ASTM D 92, D93, and it is essential to know which equipment has been used when comparing
results.
e. Other physical properties
Various other physical properties may be measured, most of them relating to specialized
lubricant applications. Some of the more important measurements are:
• density
Important, because oils may be formulated by weight, but measured by volume.
• demulsification
Ability of oil and water to separate.
• foam characteristics
Tendency to foam formation and stability of the foam that results.
• pressure/viscosity characteristics
• thermal conductivity
Important for heat transfer fluid.
• electrical properties
Resistively, dielectric constant.
• surface properties
As surface tension, air separation.
1.3.2.2. Chemical properties of lubricating oils
a. Ease of starting rapidity of warming up.
The ease of starting depends chiefly on the cranking speed which is influenced by oil viscosity
at the temperature of the crankcase. The major factor in the usage of a lubricant is its viscosity.
It's not enough that the lubricants should have the proper viscosity but also they should
maintain the little viscosity change within the temperature range during and after the apper‐
tain. So, viscosity controls not only frictional and thermal effect but also oil flow as a function
of the load speed, temperature and design of the device lubricated. In other words, if the
equipment will often have no make a cold start, it's also important that the viscosity at starting
temperature is not so high that the machine can not be started. The rapidity with which an
engine can be put to work is dependent on the speed of circulation and supply of oil to vital
components, all forms of wear and even the safety of the engine are influenced by rapidity of
circulation of the lubricants.
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b. Low Carbon Forming Tendency.
This property is important for high compression ratio petro engine where carbon deposit will
adversely affect combustion quality. The extent and also the composition of such formed
deposits are causing noisy and rough burning which subjects the engine to high thermal and
mechanical stresses resulting in lowering of performance and reduction of engine life. The
typical symptoms will be knocking, preignition and surface ignition. These call higher octane
fuels which are more expensive and do not eliminate the need for ultimate decarbonizing.
Carbon residue test methods.
Provide with some indication about the relative coke forming tendency of the oil in some
application and quality-controlled lubricants. So, the test can be helpful in selecting oils for
certain industrial applications such as heat treating, lubrication of bearing subjected to high
temperature and air compressors. It is claimed that the presence of viscous oil (bright stock)
in the base oils plays an important role in the formation of carbon deposits.
c. High Oxidation Stability.
One of the most important requirement of the lubricant is that its properties are not changed
during use [5-10]. The lubricant is often subjected to several oxidizing conditions which are
primarily due to the oxidative changes of the oil. While the temperature of the oil, engine parts
presence of oxygen, nature by products of fuel composition contribute to the oxidative change
the properties of the lubricant during use. Therefore, It's essential that the lubricating oil; when
exposed to high temperature; doesn't contribute to the forming of deposits even after a long
period of continuous engine running. So, the lubricant resistance to the oxidative depends
mainly on the nature of the lubricant and the presence of anti-oxidant additives.
d. Wear Reduction.
Wear occurs in lubricated systems by three mechanisms (abrasion, corrosion and metal-to-
metal contact. i.e adhesion). The lubricant play an important role in combating each type of
wear.
i. Abrasive wear
It is caused by solid particles entering into the area between the lubricated surfaces and
physically eroding these surfaces and may contaminate wear fragments. To cause wear, the
solid particles must be larger than the oil-film thickness and harder than the lubricated
surfaces. The flushing action of the lubricant, especially in forced feed or once through systems,
severs to remove potentially harmful solid particles from the area of lubricated surfaces.
ii. Corrosive wear
Corrosive wear is generally caused by the products of oxidation of lubricants. The high sulfur
content of the fuel helps the corrosive attack. In other words, corrosion is the principal cause
of wear in the internal combustion engines because the products of combustion are highly
acidic and contaminate the lubrication oil, lubricants function to minimize corrosive wear is
in two ways: proper refinement plus the use of oxidation inhibitors which reduces lubricant
deterioration and keeps the level of corrosive oxidation products low.
iii. Adhesive wear
This type of wear can significaly affect certain parts of the engine where metal-to-metal contact
takes place. Adhesive wear takes place also if power was increased without corresponding
modification is design, finishing and composition of the metal parts. Wear of this type also
results form breakdown of lubricant film. It can also be the result of excessive surface rough‐
ness or interruption of the lubricant supply. A plentiful supply of the proper viscosity of oil is
often the best way to avoid these conditions. The composition of the base oil and addition of
certain chemical additives are also the important factors in protection of engine parts compo‐
nents against adhesive wear.
e. Detergency and Dispersancy.
With the exception of detergency and dispersancy in the combustion chamber, deposit in
the oil are controlled by its detergent power.The source of the deposits found in engines
are many and their volume depends mainly on the used, the quality of combustion, the
temperature of lubricating oil and coolant, and on the gas sealing of the ring in the cylin‐
der. It these deposits are not removed with the oil when it is drained, their accumulation
in the engine would drastically shorten the engine life. The role of the detergent addi‐
tives is to reduce the amount of deposits formed and their removal easy. The detergent
property imparted to oils by additives seems to perform differently depending upon
whether deposits result from high low temperature, low temperature deposits are mainly
yielded from the fuel combustion and the detergency function is to keep them in suspen‐
sion or solution in the lubricating oil. However, high temperature deposits are mainly re‐
lated to the oxidized fraction of the oil.
The role of detergency here is not only to maintain these products in suspension, but also to
stop the development of those chain reaction which promote the formation of varnishes and
lacquers. The physical and functional properties of the lube oil will depend on the properties
of carbon atoms in the various ring structures and aliphatic side chain
f. Seal compatibility
Lubricants are often used in machines where they come into contact with rubber or plastic
seal. The strength and degree of swell of these seals may be affected by interaction with the
oil. Various tests have been devised to measure the effect of base oils different seals and under
different test conditions [13]. The strength and degree of swell of these seals may be affected
by interaction with the oil. Various tests measure the effects of base oils on different seals and
under different test conditions.
1.3.3. Required performance characteristics for lubricating oils
Selection and application of lubricating oil are determined by the functions which are expected
for performance. In one application, such as delicate instrument bearing, the reduction friction
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is paramount and in another, such as metal cutting, the temperature control may be most
important. A lubricating oil performance or requirement for a modern high speed engine
should fulfill the following five important functions:
1. Reduction of the frictional resistance:
The reduction of engine resistance to minimum is necessary to ensure maximum mechanical

efficiency (running costs of a vehicle or engines are influenced by the lubricant viscosity)
2. Protection of the engine against all types of wear:
All users wants minimum maintenance costs, longer engine life and increased usefulness.
Modern oil has allowed longer intervals between engines over hauls.
3. Reduction of gas and oil leakages:
The reduction of gas and oil leakages in an efficient and lasting manner is necessary to maintain
engine performance and to prevent the combustions products from adulterating the oil.
4. Contributing the thermal equilibrium of the engine:
In modern engines, the oil functions and more as a heat exchange medium, dissipating the
heat is not converted into work. This is often associated with the first function in this list where
the viscous oil give greater frictional resistance and its slow internal circulation leads to a rapid
temperature raise of some vital part of the engine to cool efficiency, the oil must be able to
circulated quickly.
5. Removal of all injurious impurities:
The lubricant give the function of protecting the engine against corrosive and mechanical wear
which caused by all injurious impurities. So, the removal of these impurities by lubricants is
very important for engine. The function and the corresponding qualities required for engine
lubricating oils are summarized in Table (1).
1.3.4. Types of lubricants
1.3.4.1. Gaseous lubricants
Gaseous lubricants belong to the simplest, lowest viscosity lubricants known and include air,
nitrogen, oxygen, and helium. They are applied in aerodynamic and aerostatic bearings. Since
the chemical properties and the aggregate state of most gases remain unchanged over a wide
temperature range, gaseous lubricants offer several advantages over liquid lubricants. First,
they can be applied at both very high and very low temperatures. Their chemical stability
eliminates any risk of contamination of the bearing by the lubricant, important for the
machinery used in many branches of industry, primarily in the food, pharmaceutical and
electronic industries.
A useful property of gases is that their viscosities increase with temperature, wheras the
opposite is true of liquids, resulting in load – carrying capacity of gas – lubricated bearings
Main functions required Qualities required
Reduce frictional resistance • Viscosity not too high to provide good pumpability or to cause undue
cracking resistance.
• Minimum viscosity without risk of metal to metal contact under the
varying condition of temperatures, speed and load.
• Sufficiently high viscosity a high temperature; good lubrication property
outside the hydrodynamic condition.
• Anti-seizure properties, especially during the run-in period.
Protect against corrosion and wear • Must protect metallic surface against corrosive action of fuel
decomposition product (wear, So2, HBr, HCl, etec.)
• Must resist degradation (resist oxidation and have a good thermal
stability).
• Must counteract action of fuel and lubricant decomposition product at
high temperatures, especially on non-ferrous metals.
• By intervention in the friction mechanism, must reduce the consequences
of unavoidable metal-to-metal contact.
• Must resist deposit formations which would affect lubrication
(detergency or dispersancy action).
• Must contribute to the elimination of dust and other pollutants
(dispersancy action).
Assist sealing • Must have sufficient viscosity at high temperature and low volatility.
• Must limit wear.
• Must not contribute to formation of deposits and fight against such
formation.
Contribute to cooling • Must good and thermal stability and oxidation resistance.
• Must have low volatility.
• Viscosity must not be too high.
Facilitate the suspension and • Must be able to maintain in fine solid material whatever the temperature
eliminate undesirable products and physical and chemical condition.
Table 1. Function and qualities required for engine oils.
increasing with temperature. However, the relatively low viscosity of gases generally limits
the load-carrying capacity of self-acting, aerodynamic bearings to 15-20kPa. It is possible to
achieve better bearing performance with gaseous lubricants than with liquid lubricants due
to the very low viscosity of the gases which results in smaller heat generation by internal
friction. In some cases, such as in foil air bearings, sliding contact occurs during stops and
starts [14], therefore solid lubricants such as PTFE are used to reduce friction.
1.3.4.2. Liquid lubricants
Mineral oils: As the hydrodynamic behaviour of plain bearings of plain bearings is totally
dependent on the viscosity characteristics of the lubricant, typical liquid bearing lubricants are
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straight mineral oil raffinates of various viscosity grades. The viscosity grade required is
dependent upon bearing speed, oil temperature and load. table (2) provides a general guideline
to selecting the correct ISO viscosity grade. The ISO grade number indicated is the preferred
grade for the speed and temperature range. ISO 68- and 100- Grade oils are commonly used
in indoor, heated applications, with32- grade oils being used for high-speed, 10.000 rpm, units
and some outdoor low temperature applications. The higher the bearing speed, the lower the
oil viscosity required and also that the higher the unit operating temperature, the higher the
oil viscosity required. If vibration or minor shock loading is possible, a higher grade of oil than
the one indicated in table (2) should be considered.
Bearing Speed (rpm) Bearing / Oil Temperature (oC)
0-50 60 75 90
300-1,500 - 68 100-150 -
1,800 32 32 - 46 68 -100 100
3,600 32 32 46 - 68 68 -100
10,000 32 32 32 32-46
Table 2. Plain Bearing ISO viscosity grade selection
Other methods for determining the viscosity grade required in an application are to apply
minimum and optimum viscosity criteria to a viscosity – temperature plot. A third and more
complex method is to calculate the oil viscosity needed to obtain a satisfactory oil film
thickness.
The lubrication of bearings for machine tools usually requires mineral oils of ISO VG 46 or 68.
for fast – running grinding spindles with plain bearings, mineral oils of ISO VG 5 or 7 are
required, dependent on bearing clearance and speed. Bearings operating under high loads
need lubricants of ISO VG 68 or 100. the service life of the bearing can be increased if the
viscosity of the selected liquid lubricant at operating temperature exceeds the calculated
optimum viscosity.
On the other hand, increased viscosity also increases operating temperature. In practice,
therefore, the extent to which lubrication can be improved in this way is often limited. The
chemical compositions of these oils differ from typical base oils in that they contain somewhat
more aromatic hydrocarbons and heterocyclic compounds, which act as natural oxidation
inhibitors. An increased viscosity for oils derived from the same crude oil does not significantly
change their chemical composition; the difference generally lies with the increasing chain
length of the paraffinic hydrocarbons, mostly isoparaffins, and in the aliphatic substituents of
naphthenic and aromatic rings, together with a slight increase in the number of naphthenic
and aromatic rings. More highly refined mineral oils and oxidation inhibitors are used for
applications where higher temperatures or longer service periods require better ageing
stabilites.
Synthetic lubricants: in practice, every synthetic oil of adequate viscosity and good viscosity-
temperature behavior can be used as a bearing lubricant, e.g. polyglycols are very good bearing
lubricants for mills and calenders in the rubber, plastics, textile and paper industries. However,
in most cases the synthetic oils specifically developed for lubricating particular equipment are
also used to lubricate its bearings. Although synthetic oils do not form a lubricant film under
pressure as well as mineral oils and may not be effective bearing lubricants despite their higher
temperature viscosity.
Biodegradable products: Biodegradable products of vegetable or animal origin are also
considered for liquid lubrication, e.g. the effects of sunflower oil added to base oil on the
performance of journal bearings. The use of vegetable oils as lubricants is likely to increase
due to environmental and government requirements and is becoming increasingly important.
1.3.4.3. Solid lubricants

General description: bearings used under vacuum, at very high temperatures or under very
high radiation cannot be lubricated by liquid lubricants or greases. For these and many other
cases, solid lubricants are used, deemed to be any solid material used to reduce friction and
wear between two moving surfaces.
In general, the solid material is interposed as a film between sliding and /or rolling surfaces.
Simply stated, an adequate solid material is required for the special lubrication requirements
of extreme operating conditions, such as very high or very low temperatures over a wide range,
e.g. -200 to 850oC, and corrosive atmospheres. Such materials normally have a layered
crystalline structure which ensures low shear strength, thereby minimizing friction. The shear
strength between the crystalline layers is weak and sets up a low and sets up a low friction
mechanism by slippage of the crystalline layers under low shearing forces. Examples of layer-
lattice solids are molybdenum disulphide, graphite, boron nitride, cadmium iodide and borax.
Solid lubricants are used mainly in the form of powders or as bonded solid films.
A good solid film lubricant has strong adhesion to the bearing substrate material, full surface
coverage and good malleability. It should also be chemically stable and prevent corrosion,
taking into account operational and environmental conditions. Many solid film lubricants have
poor wear resistance, since any breaks in the film are not self-healing, in contrast to the surface
coating formed by a liquid lubricant. Advanced solid film lubricants perform reliably in many
specific applications and much experience has been gained to better understand their limita‐
tions. The most commonly used disulphide, graphite, polytetrafluroethylene propylene.
Another group of materials, the self-lubricated materials, are related to solid lubricants and
are particulary important for bearings. Their self-lubricating characteristics eliminate the need
of grease or other lubrication and gove improved performance under high temperature
conditions. Graphalloy (Graphite/matal) alloys make use of special properties of graphite, the
structure of which can be compared to a deck of cards with individual layers able to easily
slide off. This phenomenon gives the material a self lubricating ability matched by few other
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materials and allows for the elimination of grease or oil that would evaporate, congeal or
solidify, causing premature failure. The graphite matrix can be filled with a variety of embed‐
ded lubricants to enhance chemical, mechanical and tribological properties to give a constant,
low friction coefficient rather than just a surface layer, helping to protect against catastrophic
failure. Lubrication is maintained during linear motion where lubricant is not frawn out and
dust is not pulled in.
A recent development in solid bearing lubricants is micro –porous polymeric lubricants, MPL,
where a polymer containing a continous microporous network has oil contained within the
pores, which may include appropriate additives [14]. The oil content in the polymer can be
more than 50% by weight and the microporous polymer acts as a sponage, releasing and
absorbing oil when necessary.
1.3.5. Lubricant impurities and contaminants
• Water Content
Water content (ASTM D95, D1744, D1533, and D96) is the amount of water present in the
lubricant. It can be expressed as parts per million, percent by volume or percent by weight. It
can be measured by centrifuging, distillation and voltametry. The most popular, although least
accurate, method of water content assessment is the centrifuge test. In this method a 50%
mixture of oil and solvent is centrifuged at a specified speed until the volumes of water and
sediment observed are stable. Apart from water, solids and other solubles are also separated
and the results obtained do not correlate well with those obtained by the other two methods.
The distillation method is a little more accurate and involves distillation of oil mixed with
xylene. Any water present in the sample condenses in a graduated receiver. Voltametry
method is the most accurate. It employs electrometric titration, giving the water concentration
in parts per million.
Corrosion and oxidation behaviour of lubricants is critically related to water content. An oil
mixed with water gives an emulsion. An emulsion has a much lower load carrying capacity
than pure oil and lubricant failure followed by damage to the operating surfaces can result. In
general, in applications such as turbine oil systems, the limit on water content is 0.2% and for
hydraulic systems 0.1%. In dielectric systems excessive water content has a significant effect
on dielectric breakdown. Usually the water content in such systems should be kept below 35
[ppm].
• Sulphur Content
Sulphur content (ASTM D1266, D129, D1662) is the amount of sulphur present in an oil. It can
have some beneficial, as well as some detrimental, effects on operating machinery. Sulphur is
a very good boundary agent, which can effectively operate under extreme conditions of
pressure and temperature. On the other hand, it is very corrosive. A commonly used technique
for the determination of sulphur content is the bomb oxidation technique. It involves the
ignition and combustion of a small oil sample under pressurised oxygen. The sulphur from
the products of combustion is extracted and weighed.
• Ash Content
There is some quantity of noncombustible material present in a lubricant which can be

determined by measuring the amount of ash remaining after combustion of the oil (ASTM
D482, D874). The contaminants may be wear products, solid decomposition products from a
fuel or lubricant, atmospheric dust entering through a filter, etc. Some of these contaminants
are removed by an oil filter but some settle into the oil. To determine the amount of contami‐
nant, the oil sample is burned in a specially designed vessel. The residue that remains is then
ashed in a high temperature muffle furnace and the result displayed as a percentage of the
original sample. The ash content is used as a means of monitoring oils for undesirable
impurities and sometimes additives. In used oils it can also indicate contaminants such as dirt,
wear products, etc.
• Chlorine Content
The amount of chlorine in a lubricant should be at an optimum level. Excess chlorine causes
corrosion whereas an insufficient amount of chlorine may cause wear and frictional losses to
increase. Chlorine content (ASTM D808, D1317) can be determined either by a bomb test which
provides the gravimetric evaluation or by a volumetric test which gives chlorine content, after
reacting with sodium metal to produce sodium chloride, then titrating with silver nitride [14].
2. Conclusion
1. The technology of lubrication has been used from the ancient times, from the pyramid
building where massive rock slabs are moved, up to present modern times.
2. The main purpose of lubrication is to reduce friction and wear in bearings or sliding
components to prevent premature failure.
3. Adequate lubrication also helps to prevent foreign material from entering the bearings
and guards against corrosion and rusting. Satisfactory bearing performance can be
achieved by adopting the lubricating method that is most suitable for the particular
application and operating conditions
4. A lubricant prevents the direct contact of rubbing surfaces and thus reduces wear. It keeps
the surface of metals clean.Lubricants can also act as coolants by removing heat effects
and also prevent rusting and deposition of solids on close fitting parts.
5. lubricant is consisting of either oil or grease. Most grease is from animal fats or vegetable
lard.
6. Lubricating oils are made from the more viscous portion of the crude oil which remains
after removal by distillation of the gas oil and lighter fraction
7. There are three major types of lubricants: Gaseous lubricants e.g. air, helium, Liquid
lubricants e.g. oils, water and Solid lubricants e.g. graphite, grease, teflon, molybdenum
disulphide etc. Liquid lubricant is the most commonly used lubricant because of its wide
http://dx.doi.org/10.5772/56043
range of possible applications while gaseous and solid lubricants are recommended in
special applications.
8. Lubricants do not persist working without additives.
9. Additives are chemical compounds added to lubricating oils to impart specific properties
to the finished oils. Some additives impart new and useful properties to the lubricant;
some enhance properties already present, while some act to reduce the rate at which
undesirable changes take place in product during its service.
Author details
Nehal S. Ahmed and Amal M. Nassar
Additives lab., Department of Petroleum Applications, Egyptian Petroleum Research Insti‐

tute, Nasr City, Cairo, Egypt
References
[1] Rudnick Leslie R., Ewa A. Bardasz, and Gordon D. Lamb; "Lubricant Additives:
Chemistry and Applications", Marcel Dekker, pages 387-427, (2003).
[2] Stachowiak Gwidon W.,and Andrew W. Batchelor; Engineering Tribology", third ed‐
ition, Amsterdam: Elsevier, pages 2,12,-22,52,62-67,77, (2005).
[3] Geore J.W.; "Lubrication Fundamentals", (1980).
[4] Dowson D.; History of Tribology, 2nd Edition, Professional Engineering Publishing,
London (1998).
[5] Pirro D.M. and Wessol A.A.; "Lubrication fundamentals"; Marcel Dekker, Inc. New
York and Basel 3, 37 (2001).
[6] Spikes H.; Tribology International 34, 789 (2001).
[7] Stachowiak G. W. and Batchelor A.w.; Engineering Tribology, 2nd Edition, Butter‐
worth-Heinemann, Boston,(2001).
[8] Pawlak Z., “Tribochemistry of Lubricating Oils”; Elsevier, UK, 45, 17 (2003).
[9] Avilino S.Jr.,“Lubricant Base Oil and Wax Processing”, Morcel Dekker,Inc.,New
York, Chapter (2),pp.17-36,(1994).
[10] Mortier R.M. and Orszulik S.T.; “Chemistry and Technology of Lubricant”, Blackie
Academic and Professional Publications, Chapter (1), pp.2-12,(1993).
[11] O’Connar J.J., Boyd J. and Auallane E.A.; “Standard Hand Book of Lubrication Engi‐
neering”, McGrow Hill, New York, 14-2 (1968).
[12] Allyson M., Keith D., Vincent R. and Thibon A.; Tribology International 34, 389-395
(2001).
[13] Anon, Machinery and Production, 19 July 24 (1996).
[14] Roy M. M., Malcolm F. F., and Stefan T. Orszulik; Chemistry and Technology of Lu‐
bricants, 3rd Edition, 12-13,( 2010).
Chapter 3
Some Aspects of Grease Flow in

Lubrication Systems and Friction Nodes
Maciej Paszkowski
http://dx.doi.org/10.5772/55929
1. Introduction
An optimally designed lubrication system should reliably distribute a lubricant to particular

reception points. The distribution must be precise and preferably fully automated. It is
particularly difficult to design such a system if it is to supply a lubricant to heavily loaded
machines, featuring a considerable (even up to a few hundred) number of different kinds of
friction nodes distributed in a non-linear way, with long distances between each other. An
additional problem might be hard conditions of the environment in which the system is
expected to work (high or low temperature, high air humidity, etc.). All the conditions make
the task of the designing of a reliable central lubrication system a real challenge, even for an
experienced designer specialising in that particular field. While building a lubrication system
it is important to define fundamental parameters which will determine its reliable operation.
One of the crucial things is to select an appropriate grease that ought to reduce friction
resistance and wear of the friction nodes, to protect them against the influence of the environ‐
ment, as well as to guarantee the lowest possible flow resistance during its distribution (mainly
through the lubricating conduits). An inappropriately selected grease, in terms of its rheolog‐
ical and tribological properties, and also the dynamically changing working conditions, may
lead to a considerable increase in the opearting costs of the machine.
The chapter contains the most important information on the structure of greases along with
the discussion of the influence of the thickener's microstructure on the behaviour of the
lubrication formula mainly in lubrication systems, but also in reception points, namely in the
friction nodes (including roller bearings). It also refers to the problems of the influence of the
mechanical stability of a thickener's microstructure on the quality of lubricating the roller
bearings and their service life. Additionally, the chapter presents works on generating the
lubrication film on the friction nodes working surface. Also, the fundamental problems
connected with the grease rheology (the grease performance in the fixed flow rate conditions
and the notion of the linear and the non-linear viscoelasticity) have been discussed in the text.
The state of the art knowledge on the fundamental phenomena observed in the lubrication
systems, including the mechanisms of the thixotropic changes in the grease microstructure at
shearing and relaxation, as well as the forming of the boundary layer at the grease flowing
through the conduits in the main line of the lubrication system have been presented.
2. Microstructure of the lubricating greases
Lubricating greases are rheologically complex two-phase non-Newtonian fluids. They are
chemically and physically heterogeneous. The dispersive phase is normally a mineral oil, a
synthetic oil or a vegetable oil, whereas the dispersed phase is a thickener and, depending on
the needs, solid additives. The particles of the thickeners can vary in their dimensions. Soaps,
for instance, do not normally exceed 100 µm in length, and their diameter is not shorter than
0.1 µm and not longer than 0.5 µm [1-3]. The lithium and calcium soaps particles are definitely
bigger than the sodium soaps particles. The isometric aggregates of bentonite clay and mica
are approximately 0.5 µm in width and 0.1 µm in thickness [1]. The solid additives have similar
dimensions. Due to the size of the thickener particles, the greases acquire the characteristics
of the mechanically dispersed (suspension) or the colloidal system. The thickener particles size
depends primarily on the process of the grease production [4,5], as well as on the conditions
in the friction node. During the shearing of a grease in the friction node, the size of the particles
can change considerably. According to Boner [5], in order to achieve the optimum tribological
and rheological properties of a lubricating compound, greases containing variously dispersed
thickener particles ought to be mixed. It concerns particularly the lubricants thickened with
metal soaps. Too high particles dispersion of the thickener in the grease can negatively
influence its lubricating properties. Such particles do not present enough capability of making
spatial, three-dimensional structures resulting from the physicochemical interactions. Too
long particles of the thickener cause too high an increase of the consistency of the lubricating
grease and lead to its easy breaking both in the lubrication systems and the tribological pairs.
Microstructure of the lubricating greases with soap thickeners can be compared to a sponge
with a lubricating oil (Figure 1). It makes a three-dimensional, coherent network of intercon‐
nected particles (flow units), in the literature referred to as floccules. The oil is locked in the free
spaces of the microstructure through the mechanical occlusion, the capillary phenomena as
well as the molecular attraction between the thickener and the polar components of oil [6]. It
is estimated that the amount of the oil locked in the microstructure of the soap greases can
amount even to 75%. The soap particles making the microstructure, from the chemical
viewpoint, are associated molecules [7], namely groups of identical molecules generated as a
result of the dipol-dipol type of interaction or the hydrogen bonds [8]. The final skeleton of
the microstructure – shaped in the dispersion center – is made in situ in the process of
crystallization of the soap particles and/or through nucleation, namely making crystallite
nucleuses and their further growth [5]. The shape of the thickener particles and their surface
topography can be different, depending on the kind of soap used and the particles' size. If they
Some Aspects of Grease Flow in Lubrication Systems and Friction Nodes 79
http://dx.doi.org/10.5772/55929
exceed the size of 1 µm, their structure is rough and resembles twisted ropes. The crystallites
of the colloidal size are definitely smoother and less twisted [3]. The microscope photographs
also show a clear difference in the surface structure of the lithium, sodium and calcium
thickener floccules [7,9]. The calcium soap particles are rougher than the particles of the lithium
and sodium soaps, independently of their length [5]. In the case of the non-organic thickeners,
the grease microstructure is made of numerous individual aggregates popularly called open
card-house [10], for instance bentonite (Figure 2), mica or vermiculite. Such particles have a
skeleton structure which resembles heterogeneous, fuzzy-edged, curled flakes or straight
plates piled one on the top of the other [11].
The shape of the soap particles and other organic or non-organic thickeners, their anisometry
(in reference to their length and lateral dimensions), as well as their dispersivity and the
percentage in the full volume of the grease, greatly influence the physical properties of the
ultimate lubricating compound [7,12-14]. The last two factors are critical for the easiness of the
making of different energy connection types between the elements of the microstructure. Apart
from providing the appropriate consistency, thickeners influence the way the lubricating
grease flows, changes its shape or the type of flow resistance (pumpability) it presents. It is
particularly important in the central lubrication systems where the lubricant is often trans‐
ported in long conduits to particular receiving points.
Figure 1. Floccules of the lithium thickener with particles of polytetrafluoroethylene (PTFE) improving the tribological
properties of the lubricant. The microphotograph was taken by means of a scanning electron microscope (SEM) in sec‐
ondary electron imaging (SEI) mode at the magnification of 12 500 times.
Figure 2. Bentonite clay aggregates making the open card-house structure.The microphotograph was taken by the
scanning electron microscope (SEM) in secondary electron imaging (SEI) mode at the magnification of 12 000 times.
The mechanical durability and the stability of the microstructure of the thickener in a lubri‐
cating grease determines the friction reduction, the protection of the lubricated surfaces as well
as the grease performance during the mechanical loading in the friction node and work at
ultimately high temperatures. Cann [15] analyzed thin layers of the lithium lubricants without
the solid additives on treadmill roller bearings with the use of attenuated total reflectance –
Fourier transform infrared (ATR-FTIR) spectroscopy. The research showed that the oil gets
out of the lubricated roller bearing as a result of damage in the thickener's microstructure. In
the case of the untouched microstructure, the oil is connected with the thickener by means of
the capillary forces. When the microstructure is damaged, it gets out of the bearing, washing
out individual soap crystallites. Such an oil undergoes oxidation and evaporation easier, which
lowers its lubrication quality. Additionally, its rheological properties are much worse than the
properties of the base oil, and its kinematic viscosity is significantly reduced [16]. Similar
conclusions were drawn by Farcas and Gafitanu [17]. Based on experimental research, Farcas
and Gafitanu presented a mathematical model correlating the degree of the thickener micro‐
structure destruction with the service life of the roller bearing. Their SEM photographs of the
lubricating greases subjected to shearing in the roller bearing showed a damaged microstruc‐
ture of the grease with the base oil bled out of it. According to the researchers, a crucial role
in the process of the microstructure destruction is played by temperature. Above 60-70 oC,
along with its increase by each 10-15 oC, the service life of the bearing falls by half. Above 70
o
C, the bearing's failures are most frequently caused not by the contact fatigue, but predomi‐
http://dx.doi.org/10.5772/55929
nantly by the degradation of the thickener's microstructure and worsening of the grease's
properties. Vinogradov et al. proved that interactions between the thickener particles and the
microstructure state may influence the increase of the friction moment in the roller bearing [18].
The thickener in the lubricating grease is responsible also for the thickness of the lubrication
film on the working surfaces of the friction joints. Spikes, Cann, Wiliamson and Kendal in their
works [19,20] presented results of the research on the interaction of the thickener's particles
with the treadmill sprinkled with titanium oxide. They observed an increase in the thickness
of the lubricating film in the elastohydrodynamic conditions of the collaboration of a steel ball
with the treadmill. The measurement was done by means of Alström's method. In the case of
the lubricants thickened with metal soaps, the biggest capability of making the lubrication film
was recorded in the lithium grease. The thickness of the generated grease layer, apart from the
kind of thickener, was also determined by the flow speed of the lubricant between the treadmill
of the roller bearing and the rolling element. The thickness of the observed thickener's layer
was 100 up to approximately 250 nm, depending on the kind of the lubricating grease. Long-
lasting tests showed that the lubrication film's thickness generated on the bearing's treadmill,
at a constant load, falls with time up to the stabilization at the level from 20 to 50 nm.
Apart from the thickener, the lubricating grease microstructure can also contain solid addi‐
tives. Their main function is to improve the tribological properties of the lubricant. The solid
additives are normally graphite, molybdenum disulfide (MoS2), polytetrafluoroethylene
(PTFE) as well as metal powders. The percentage of the solid additives in the grease usually
does not exceed 5%. Research results indicate the benefits of the increase of the percentage of
the solid additives in the lubricating greases. Of course, there are also works which show the
advantages of the synergism of the powdered PTFE as well as tin and copper in the lubricating
compounds [21,22].
Solid additives significantly influence the rheological properties of the lubrication compound
[23,24]. The lubricants thickened with the polar lithium soap without the solid additives show
quite high values of the structural viscosity and of the shear stress. After the enriching the
lubricants with the graphite thickeners and MoS2 the lowering of the parameters' values occurs.
The additives reduce the shear stress both in the bulk of the grease as well as in the boundary
layer. Research show that PTFE does not influence the change of the values of the parameters
in the lithium soap. In the case of the lubricants thickened with the bentonite clay, solid
additives cause the increase of the yield stress both close to the wall and in the bulk of the
grease. The most influential determinant of the values increase is the graphite thickener.
Adding the PTFE in this case does not significantly determine the structural changes thus
generated lubrication compound.
3. The basic rheological properties of the lubricating greases
3.1. Behaviour of the lubricating greases in the steady flow conditions

Greases, depending on their characteristic structure, are shear-thinning (pseudoplastic) and
rheounstable fluids having a yield point. They show very complex rheological properties.
Lubricating greases, at very low shear rates behave like a Newtonian fluid of a constant
viscosity η0, being a slope of a tangent to the flow curve, equal to the shear rate going to zero
(η0 = limγ̇→0η(γ̇)). At the shear rate going to infinity, lubricating greases also behave like
Newtonian fluids, but of viscosity η∞ close to the dispersion phase, namely of the base oil
(η∞ = limγ̇→∞ η(γ̇)). The viscosity η∞ is a slope of a straight line being a flow curve asymptote.
In the bracket of the indirect shear rates, the curve of the lubricating grease flow curve is
described with the following equation:
t
h= , (1)
g&
where: η - dynamic viscosity, τ - shear stress, γ̇ - shear rate.
Figure 3 illustrates results of the rheological measurements made on the lithium greases of a
various thickener percentage, showing the shear stress changes and of the structural viscosity
as a function of the shear rate. Additionally, the theoretical curves generated from the Herschel-
Bulkley's [25] and Carreau-Yasuda's [26] dependences have been presented. Values of the
parameters defining the theoretical curves traced according to the abovementioned depend‐
ences for the greases of a various thickener percentage have been presented in Table 1. The
greases were thickened with lithium 12-hydroxystearate, and the oil base was ORLEN OIL
SN-400 (ORLEN OIL, Cracow, Poland) mineral oil. The flow curves were defined at temper‐
ature of 25 oC. The tests were repeated five times, and their results were statistically elaborated
at the confidence level p = 0.95, using t-Student test. Additionally, correlation coefficient values
were calculated. The experiment was carried out by means of Physica Anton-Paar MCR 101
rotational rheometer. The rheometer was working in the cone-and-plate system (CP-25-1, 25
mm, 1o) at a constant measuring gap height of 49 µm.
Thickener Herschel-Bulkley model Carreau-Yasuda model

content τ kC η0– η∞ η∞ λ
m Rxy a n Rxy
(%) (Pa) (Pas) (Pas) (Pas) (s)
4.0 120.27 5.826 0.66964 0.99983 1852.4 0.38843 47.456 2 0.20073 0.99600
5.0 190.52 83.155 0.37458 0.99958 4189.5 0.20014 47.457 2 0.23465 0.99668
6.0 216.00 83.867 0.38633 0.99973 4742.5 0.26093 47.939 2 0.22985 0.99811
6.5 241.47 212.430 0.29112 0.99982 9090.5 0.18576 47.940 2 0.20100 0.99919
7.0 672.60 148.930 0.35189 0.99750 15225.0 0.26328 47.455 2 0.17468 0.99696
8.0 712.54 285.550 0.28687 0.99592 21453.0 0.25487 47.423 2 0.16048 0.99944
9.0 785.29 230.630 0.37532 0.99956 16023.0 0.54032 47.458 2 0.21285 0.99743
Table 1. Values of the parameters determining the theoretical curves traces, defined according to dependences (1)
and (2) for the greases of the thickener content 4-9%.
http://dx.doi.org/10.5772/55929
a)
b)
Figure 3. Dependences of the shear stress (a) and the structural viscosity (b) in a function of the shear rate for the
lithium greases based on the mineral oil, with a various thickener percentage. The diagrams, in order to achieve a
greater clarity, do not contain the confidence intervals.
The Herschel-Bulkley (2) dependence takes into account the existence of a yield stress τ0 value,
namely such a value of the shear stress above which the lubricating grease starts flowing:
1
t = t 0 + ( kC × g& ) m , (2)
where: τ0 –yield stress, kC – consistency factor of the thickener in the grease, m – nondimen‐
sional index exponent. Carreau-Yasuda (3) dependence enables approximation of the course
of changes in the structural viscosity as a function of the shear rate with viscosity η∞ and η0
included:
n -1
h (g& ) = h¥ + (h0 - h¥ ) × [1 + (l × g& )a ] a , (3)
where: η∞ = limγ̇→∞ η(γ̇), η0 = limγ̇→0η(γ̇), λ – time-constant, a and n – nondimensionalparame‐

ters. For the shear-thinning fluids, a parameter normally equals 2 [27].
The flow curves clearly illustrate the fact that the greases have the pseudoplastic proper‐
ties. It results from the degradation of the lubricating greases' microstructure as well as
from the further orientation of the dispersed particles of the thickener. During relaxation
of the stress in the lubricating grease, a considerable entanglement of the thickener particles
is observed. However, during shearing of the grease, one can record straightening and
untangling of the particles which are directed along the current line. With the increase of
the shear rate, the effect is more and more visible. The reduction of the internal friction
resulting from a smaller size of the particles and a limited activity between them is
observed. At very high shear rates, the total orientation of the particles in the grease is
achieved. The internal friction remains constant at a low level. The structural viscosity of
the grease then gets close to the viscosity of the base oil.
Figure 3 shows that at a large enough percentage of the dispersion, the interaction between
the thickener particles may cause formation of the spatial microstructure resistant to the shear
stress which does not exceed certain value. Below the value, the lubricating grease behaves
like an elastic solid. When yield stress τ0 (yield point) is reached, the microstructure gets
damaged and the grease starts behaving as a viscous liquid. When the shear stress in lubri‐
cating grease becomes lower than the limit value, the immediate reconstruction of the
microstructure takes place.The determination of the yield stress value in the lubricating grease
is very important because it enables the determining of its usefulness for the application in the
central lubrication systems of machines [9,28] or in the friction nodes [7].
3.2. Linear and non-linear viscoelasticity
When a lubricating grease undergoes the periodic stress oscillation, its response in a form of
a relative deformation will be shifted in the phase by δ angle. The angle, called the phase angle
shift, falls in the range from 0o to 90o. The response of the lubricating grease determined by the
extortion is influenced primarily by: complex modulus | G ∗ | and complex viscosity |η ∗|.
The complex modulus is defined as a sum of the real and the imaginary part:
G* = G¢ + iG¢¢, (4)
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where: G ′ - storage modulus (elastic component in the phase with the stress), G ″ - loss modulus
(viscous component shifted in the phase in relation to the stress). Components G ′, G ″ are equal:
s0
G¢ = cos d , (5)
g0
s0
G¢¢ = sin d . (6)
g0
Storage modulus G ′ is a measure of the energy stored and recovered per each deformation
cycle, whereas loss modulus G ″ is a measure of the energy lost per a sinusoidal deformation
cycle. What results from equations (5) and (6) is that phase angle shift δ can be defined as:
G¢¢
tan d = . (7)
G¢
The dispersion effects can also be described by means of complex viscosity η ∗. The complex
viscosity, similarly to the complex modulus can be formulated as:
h * = h ¢ - ih ¢¢, (8)
where:
G0
h¢ = sin d , (9)
g 0w
G0
h ¢¢ = cos d . (10)
g 0w
The real part of complex viscosity η ′ is called the viscous component or, less frequently, the
dynamic viscosity, whereas imaginary part η ″ is called the elastic component. The measure‐
ment of quantities G ′, G ″ and η ′, η ″ enables the rheological characteristics of the greases in
terms of their viscoelastic properties.
Figure 4 illustrates example results of a strain sweep test of Nanolubricant 2010 (Orapi, Saint-
Vulbas, France) commercialgrease, thickened with the lithium 12-hydroxystearate, based on
a synthetic oil with the addition of tungsten disulfide nanoparticles. The deformation range
of the grease was 0 to 100% at 1 Hz oscillation frequency. The measurements were done at 25
o
C. The oscillation measurements made it possible to determine the limit of the linear viscoe‐
lasticity (marked in the diagram with the vertical line). The reasearch showed that plateau
modulus G0N for Nanolubricant 2010 was 75 743 Pa at deformation γC equal 0.336%. The review
of the methods used for the determining of the linear viscoelasticity limit (the critical point)
on the basis of the dynamic-oscillation tests is widely discussed in [29].
Figure 4. The storage and loss moduli and the phase angle shiftas a function ofNanolubricant 2010 grease strain.
Figure 5 illustrates the influence of the soap thickener (lithium 12-hydroxystearate) percentage
in the lubricating grease based on the mineral oil on (a) value of critical strain γC and (b) of
shear stress τ in the critical point, as a function of the percentage of the thickener. The diagrams
show that the range of the linear viscoelasticity depends on the percentage of the thickener in
the grease – the smaller percentage of the thickener, the wider range of the linear viscoelasticity.
In the case of the shear stress in the critical point, there is an adverse situation. The research
was carried out by means of a stress/strain controlled rotational rheometerPhysica Anton-Paar
MCR 101. The rheometer was working in the cone-and-plate system (CP-25-1, 25 mm, 1o) at a
constant measuring gap of 49 µm.
The rheological dynamic-oscillation research (which is a combination of the creep and

relaxation experiments) are currently the basic tool at evaluating the structure of dispersion
and its mechanical stability as well as the behaviour of the lubricating grease in the start phase
of the flow. At high frequencies and amplitudes, the dynamic-oscillation tests can be used for
the determining of the speed at which the microstructure is created and damaged under the
http://dx.doi.org/10.5772/55929
a)
b)
Figure 5. Critical strain γC (a) and shear stress τ in the critical point (b),as a function of the percentage of the lithium
thickener in the lubricating grease
influence of oscillation. Carrying out such research is important for the evaluation of the
lubricating greases' behaviour at the start-up phase of the friction nodes and of the flow in the
lubrication systems conduits. The dynamic-oscillation research on the lubricating greases has
been, among others, conducted by Yeong et al. [14] as well as Delgado [12], Martín-Alfonso et
al. [30,31].
4. Mechanism of thixotropic changes in the microstructure of the

lubricating grease during its shearing and relaxation
The term 'thixotropy' comes from the Greek words thixis (mix, shake) and trepo (revolve,
change), and it was first suggested by Péterfi [32] (the original name – thixitropy) [33]. The
phenomenon is defined as an isothermal decrease in structural viscosity during shearing

followed by an increase in the viscosity and the re-solidification of the substance once shearing
ends [34]. The phenomenon of thixotropy concerns suspensions of the internal microstructure
made of particles which undergo aggregation or flocculation. In such systems, there are
physical interactions between particles, which, during relaxation of a substance, determine the
creation of a spatial, cross-linked microstructure. They are primarily the Van der Waals-
London attractive forces, the electrostatic repulsive forces (particularly important when the
dispersed phase particles are anisometric in shape) as well as the steric forces. Also, the
Brownian motion may have an important part to play in the process, but their appearance is
limited only to colloids. A wide description of the intermolecular interactions which are
common in thixotropic systems can be found in the publications of Efremov et al. [35,36] as
well as of Sonntag's [37] and Scheludko's [38]. During shearing, the microstructure made of
the dispersed phase particles, as a consequence of their mutual interaction, gets disintegrated
forming bigger aggregates and individual particles, floccules, suspended freely in the disper‐
sion medium. The review of the references concerning the thixotropy of suspensions can be
found, for instance, in the publications of Mewis and Barnes [10,39].
The lubricating greases also show thixotropy. The structural viscosity of the lubricating grease
decreases systematically during its shearing in the tribological node or during its flow through
lubrication system conduits. The standstill of the grease leads to its re-solidification and a little
increase in its structural viscosity. The decrease of viscosity during flowing of the grease is
reduced to a certain minimum value, primarily depending on the viscosity of the base oil, a
kind and amount of the thickener as well as the shear rate. At high shear rates, the structural
viscosity of the grease reaches the value close to the base oil viscosity. According to Czarny [1]
“Both in the slide bearings and in the roller bearings, the high-speed ones in particular, the
rheological properties of the lubricant, so its hydrodynamic lift force, are determined mainly
by the base oil. The thickener influences the force at the start-up and at the stopping of the
bearing.”. Due to the complexity of the processes of degradation and reconstruction of the
thickener's microstructure in the lubricating greases, scientific works which would thoroughly
explain the processes have not been published so far.
The first publications on thixotropy of the lubricating greases appeared at the beginning of the
1950s. In 1951, Moore and Cravathpusblished their work [13] on the mechanical process of the
soap fibre disruption in the lubricating greases caused by the shearing force and on the
influence of the disruption on the change of the consistency of the greases. The research
concerned the lubricants thickened with the barium, sodium, lithium and calcium soaps. The
degradation of the soap fibre consisted in the working of the samples in a penetration appa‐
ratus, as well as on their long-lasting disintegration in a rolling apparatus. During shearing,
at different intervals, the measuring of the greases micropenetration level was performed. The
tests showed that the biggest differences in the consistency of the greases were observed in the
commercial grease thickened with the barium soap, whereas the smallest differences were
recorded for the lithium grease. Additionally, a series of photographs of single soap fibres by
means of an electron microscope was taken. The photographs showed a considerable differ‐
ence in the fibre length before and after shearing for most of the tested samples. Moore and
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a)
b)
Figure 6. Microstructure of the lithium thickener in the paraffin oil [40]: (a) fresh grease, (b) grease sheared at 120 oC
for 10 hours at γ̇ = 0.01 s-1 shear rate. The microphotograph taken by means of the atomic force microscope (AFM).
Scanning area 20 µm x 20 µm.
Cravath proposed a soap fibre disruption intensity model at different times of the external
shearing force activity.
A similar analysis to the one conducted by Moore and Cravath was carried out by Renshaw
[41]. He was particularly interested in the lithium thickened greases based on the ester oil,
which showed high shear resistance. The measuring of the micropenetration was done directly
before and after the 9-hour long shearing of the grease in a bearing at the speed of 10 000 rev/
min and after 100 000 double strokes of the piston in the penetration apparatus. In the first
case, Renshaw observed in the electron microscope, a considerable shortening of the lithium
thickener's fibre and slight changes in the micropenetration values. After the working of the
grease in the penetration apparatus, the situation was exactly reverse, namely the changes in
the micropenetration were remarkable but the particles were shortened only to a minor extent.
The research showed that the intensity of degradation in the thickener's microstructure
depends not only on the mechanical strength of individual fibres, but mainly on the shearing
way and on the direction of the fibres at the flow of the grease.
Sirianni et al. [42] investigated the question of the influence of size of the calcium and barium
soaps and their concentration on the change of the lubricating greases thixotropy coefficient. For
the experiment, they used a theory proposed earlier by Goodeveand Whitfield [43] which was
aimed at the determination of the thixotropy of the black suspension in the mineral oil [44].
According to the theory, the speed of the microstructure reconstruction (proportional to the
thickener's concentration) equals the speed of its degradation. The thickener's concentration,
however, is proportional to the difference between apparent viscosity η and grease equillibri‐
um viscosity η0 following the total degradation of the cross-linked microstructure of the
thickener at the infinitely high shear rate.
q FT
h - h0 = = , (11)
g& g&
where: η – apparent viscosity, η0 – equillibrium viscosity, γ̇ – shear rate, θ – thixotropy

coefficient, F T – momentum generated by the intermolecular forces transmitted by the unit of
surface in the unit of time.
The theory assumes that at the increase of 1 / γ̇ expression, apparent viscosity η rises until it
reaches the plateau. According to Goodeve and Whitfield, the thixotropy coefficient is a source
of the non-Newtonian effects, which is directly correlated with the intermolecular bonds
disruption effects, the average life span of the bonds and the change of size of the interacting
molecules in the thixotropic process. In order to calculate the thixotropy coefficient, Goodeve
assumed that the bonds between the molecules of the dispersed phase are subject to Hooke's
law.
Moses and Puddington [45], using the same theory, determined the influence of the thickener's
percentage (10%, 14% and 19.7%), the shear rate (from 1 400 s-1 to 250 000 s-1), temperature
(from 35 oC up to the value at which a visible sedimentation occurs) as well as the size-reduction
of the thickener particles, on the change of the thixotropy coefficient of the lithium, sodium and
aluminium greases. Different sizes of the soap fibre were generated by means of the colloid
mill. For determining equillibrium viscosity η0 a metal capillary was used.
Hahn, Ree and Eyring [46], while observing behaviour of the macromolecular polymers
suspensions, formulated a theory (later called sinh law) which ultimately was widely used for
the quantity description of the phenomena of the lubricating greases microstructure degrada‐
tion and reconstruction, where the soap is a thickener. They took into account the fact that the
thickener's structure contains the so called entangled particles (aggregates which create a three-
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dimensional network and make the solution acquire the non-Newtonian fluid properties) and
the not entangled particles (single floccules which make the solution acquire the Newtonian
fluid properties). The number of the former and the latter depends on the temporary shear
stress. The flow curve equation used by Hahn et al. was:
c 1b1 c
t= g& + 2 sinh -1 ( b 2g& ), (12)
1 2
where: χ1 – share of the not entangled particles, χ2– share of the entangled particles, 1/α1 – the
not entangled particles shear stress, 1/α2 – the entangled particles shear stress, 1/β1 – shear
intensity for the not entangled particles, 1/β2 – shear intensity for the entangled particles, γ̇ –
shear rate.
Hahn and the collaborators assumed that at the increase, and next at the decrease of the shear
rate, the free energy of the soap particles changes, and it is directly dependent on their strain
energy. The cross-linked particles aggregates featuring the non-Newtonian characteristics get
untangled making individual floccules, freely suspended in the dispersion medium, featuring
the Newtonian characteristics. The process is reversible. Two years later, the scientists
presented the equation of the changes kinetics [47]:
h0 w 2 -(1-h0 )( w ¢)2
dc (13)
- 2 = c2k f e kT - c 1 kb e kT ,
dt
where: kf – parameter determining the time of the entangled particles → not entangled particles
reaction; kb – parameter determining the time of the not entangled → entangled particles; w –
elastic strain energy of the entangled particles, w ′ – elastic strain energy of the not entangled
particles, η0 – viscosity of the entire thixotropy system at zero shear rate, k – Boltzman constant,
T – temperature.
Thus, Hahn et al. elaborated theoretical flow curves for the lubricating greases during the
disruption and reinforcenment of the thickener's structure. The models have been widely
applied for the determination of the thixotropic properties of, for instance, motor oils [48].
Validity of the assumptions made at the making of the mathematical dependences was proven
by the experimentally developed curves. The mathematical model proposed by Hahn was also
used by Utsugi et al. [49]. They analyzed the thixotropy of the calcium greases and the silica
gel thickened greases. At the determining of the thixotropic hysteresis loop, Utsugi used the
rotational rheometer. Bair [50] proved that the models proposed in the 1960s by Hahn and
Eyring were still true. During the verification of the models, Bair used more technologically
advanced rotational rheometers. He drew particular attention to the possibility of the depend‐
ences application for describing the thixotropy phenomenon of the lubricants working at the
friction contact, in the elastohydrodynamic conditions.
Vinogradov, Deinega and Verbitsky [18] investigated the correlation between the changes of
the friction momentum in the ball bearings and the thixotropic properties of the calcium and
the lithium greases. At the research, they observed that the shape of the dispersed phase
particles considerably influences the behaviour of the lubricating greases during their further
deformation and shear-thinning. On the turn of the 1960s and 1970s, Vinogradov also inves‐
tigated the lubricating greases using the polarimetry and other optical methods. It enabled the
quantity evaluation of the level of the thickener microstructure reconstruction. He also
conducted research on the thixotropic hysteresis loop for the calcium and lithium greases with
the use of the rotational coaxial cylinder rheometers. His works are widely discussed by
Froischteter in [7].
Sacchettini, Magnin, Piau and Pierrard [51] published in the Journal of Theoretical and Applied
Mechanics a paper on the thixotropic properties of commercial greases: Shell Alvania, ELF
Multi and ELF EL series (8305-8308 and 9309) of NLGI (National Lubricating Grease Institute)
2 consistency class. The analyzed lubricating greases showed a different fibre length of the
soap thickener (lithium 12-hydroxystearate). The oil base in the greases was the mineral oil.
Sacchettini et al. focused mainly on the research of change in the shear stress as a function of
shearing time. They analyzed changes in the lithium thickener microstructure at the cyclic
shearing lasting a few seconds at different shear rates (from 0.018 s-1 to 18 s-1) and different
grease relaxation time (from 2 minutes to 38 hours). They did not analyzed the structural
viscosity increase of the greases at their relaxation, however. Apart from the thixotropy,
Sacchettini et al. investigated the wall effects.
Czarny, in his paper [52], presented results of the research on the process of degradation and
reconstruction of the thickener microstructure in the commercial calcium greases (STP) and
the lithium greases (ŁT-4S2). He used the method of cyclic shearing of the lubricating grease
at specified time intervals, at a constant shear rate. The research on the grease was carried out
without removing it from the rheometer head. He thus simulated the conditions observed in
the conduits of lubrication system. In 1990, Czarny investigated the influence of temperature
on the thixotropy of the lubricating greases [53]. He proposed a mathematical description of
the energetic changes which take place in the microstructure of the thickener during its
shearing at various temperatures. Czarny observed that along with the temperature increase,
the structural viscosity of the lubricating grease is reduced, and the activity of the thickener
particles increases. According to Czarny, the motion of the particles along with the increase in
the lubricant temperature, a certain energetic barrier, which Czarny called the activation
energy, must be overcome. Czarny also carried out the research on the degradation of the
thickener microstructure by means of the Couette rotational rheometer, and on the influence
of temperature on the process. He investigated the bentonite greases, the calcium greases (STP,
Kalton EP1), the lithium greases (Shell Alvania EP2, ŁT4-S2) as well as the lithium-calcium
greases. In accordance with the experimental research and the theory proposed by Czarny,
when temperature increases, the thickener intermolecular bonds get weakened, making a
cross-linked, compact microstructure, and the activity of single crystallites freely suspended
in the base oil increases. As a result, the lubricating greases, in the process of long-lasting
shearing, take on the Newtonian fluid characteristics.
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Figure 7. Dependence of the shear stress as a function of shearing time at constant shear rate γ̇ = 8.1 s-1 (p = 0.95) for
the greases with the thickener percentage: (a) 6%, (b) 7%, (c) 8%. 1 – the first stage of shearing, 2 – the second stage
of shearing, 3 – resolidification process of the grease in its relaxation phase.
Figure 7 illustrates the thixotropy curves for the lubricating greases thickened with the lithi‐
um 12-hydroxystearate based on the mineral oil, received by means of the measuring meth‐
od proposed by Czarny. The grease shearing time in two cycles was 120 minutes in total.
The grease relaxation time between the shearing cycles was 24 hours. The research was repe‐
aed five times. The experiment was carried out with the use of Rheotest 2.1 rotational co‐
axial cylinder rheometer working at 2 mm measuring gap. For the measurements, a right
handed helix shaped grooved polytetrafluoroethylene internal cylinder, with 95 0.5 mm-
deep grooves was used. Such a surface structure enabled a visible reduction of the Weissen‐
berg effect and of the slip effect at the cylinder wall, which could have negatively influenced
the measurements.
The energetic interpretation of the lubricating greases thixotropy was presented by Kuhn [54].
He focused primarily on those cases of thixotropy of the lubricating greases which occur during
the hydrodynamic lubrication of the slide bearing. According to Kuhn, the energy loss during
the friction shearing of the grease is a function of the lubricant's qualities and the conditions
it is sheared in. If the lubricant's qualities change in the process of the fluid friction, the energy
density (energy/volume) also changes:
æ d ö
erh = hg& ç e* ÷, (14)
e çh ÷
è 0 ø
where: er h e – rheological density of energy in the microcontact region (J/mm3), η –dynamic

viscosity (Pas), γ̇ – shear rate (s-1), de – average diameter of the microcontact (mm), h o * – average
lubrication film thickness (mm).
Using the dependence presented above, Kuhn estimated friction coefficient μ which was:
erh
m= i , (15)
pr rh
where: erh – sum of the rheological energy densities in the region of all microcontacts (J/mm3),
irh – friction intensity (non-dimensional value), pr – pressure (MPa).
Kuhn also observed a similarity between the curve of changes in the rheological energy density
as a function of time at different shear rates and the curves received by Czarny [55] on the
experimental way. Later in his work, Kuhn developed the energetic model of the lubricating
greases thixotropy [56,57], and together with Balan suggested the experimental ways of
estimating the rheological density of energy with the use of the rotational cone-and-plate
rheometer [58]. In [59], he defined the tribological properties of the lithium and calcium greases
based on the mineral oil by means of the energetic parameters, and also presented the relations
between the viscoelastic properties of the lubricating grease, the friction in the frictional contact
and the elastic strain energy accumulation and the shear stress at the shearing of the grease.
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Kuhn's research proved that in the quantification of the tribological processes, the energy loss
resulting from the structural changes which take place in the frictional contact region must be
taken into account.
5. The rheological properties of the boundary layer in the lubricating

greases
Lubricating greases are, on the one hand, required the best possible slide and anti-
corrosion properties, and on the other hand, the lowest possible and independent of
conditions flow resistance at the supplying of the friction nodes. The problem of the flow
resistance of the lubricating greases is currently particularly important in the context of
lubrication systems. It results primarily from the fact of a higher and higher automation
of the systems. The flow resistance have negative influence on the proper functioning of
the central lubrication systems. An important factor reducing the resistance in the
lubrication systems is the appearance in the region of the lubricating grease contact with
the conduit wall, of the so called the boundary layer (or the wall effect) which has different
rheological properties than the rest of the grease's volume. The phenomenon of the
boundary layer formation while the suspension flows through the axisymmetric conduits
is frequently referred to as Segré-Silberberg's effect or the sigma effect. For the first time, the
phenomenon was thoroughly described in 1962 [60]. The influence of the boundary layer
formation on the fall of the suspension flow resistance is particularly visible in the small
diameter axisymmetric conduits where the suspension flow is laminar. It leads to the
decrease in the pressure gradient along the conduit. Simultaneously with the increase in
the conduit diameter, the boundary layer influence considerably decreases [61].
The first mentions of the boundary layer in the lubricating greases appeared in 1960. Bramhal
and Hutton [62] carried out the research on the influence of the wall types on the boundary
layer formation. The research was conducted with the use of a plunger viscometer. While doing
the research, they recorded a slip in the grease, which occurred in the area of the walls. Bramhal
and Hutton observed inconsiderable influence of the wall's material and the wall surface
topography on the grease slip. They explained the observed effect as a consequence of
repulsion of the soap particles suspended in the base oil from the walls.
An attempt of explaining the phenomenon of the boundary layer formation in the lubricating
greases within the area of the lubricating grease contact with the lubrication system conduit
wall and the working surface of the sliding pair was made by Czarny. In [52,63] he proves that
the boundary layer formation in the lubricating greases depends mainly on the surface material
which the lubricating grease reacts with. He observed the changes of the shear stress in the
commercial greases in the area of the wall made, among others, of methyl polymethacrylate,
polytetrafluoroethylene, polyamide, brass, bronze, duralumin and cast iron. The phenomenon
of the boundary layer formation was particularly visible at the low shear rates. According to
Czarny, the boundary layer formation is an outcome of the thickener's particles adsorption on
the surface of the material. Thus, during the flow of the grease, a toroidal space depleted of
the thickener is created. The number of the adsorbed thickener particles depends on the kind
of grease and on the collaborating materials, and is inversely proportional to the thickener
percentage.
Czarny and Moes [28] proposed a dependence describing the change of the shear stress in the
lubricating grease as a function of the distance from the wall:
ìï -(
z+d ü
)ï
t = t 0 í1 - e s ý , (16)
ïî ïþ
where: τ0 – yield stress, z – normal wall coordinate, d – surface layer thickness, s – thickness
of the boundary layer with the exponentially decreasing yield stress, down to its minimum
value on the wall τ = τw (Figure 8).
Figure 8. Stress distribution τ in the grease boundary layer as a function of the distance to wall z , according to Czarny
and Moes [28].
According to Czarny, the model can be used for practical purposes at specific design solutions
of lubrication systems. Parameter s and d values, needed for the determination of the stress
distribution, which depend on the kind of grease, temperature of the tribological pair, the kind
of the pair's wall material and its surface topography can be experimentally defined.
Czarny and Moes, during their research on the lithium soap thickened grease – Alvania EP2,
found that the value of the yield stress in the grease mass τ0 and at the wall τw rise along with
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the increase of the grease consistency level. Simultaneously, the increase determines the
reduction in the thickness of boundary layer s and surface layer d . The observed boundary
layer thickness s and surface layer d equaled, in the case of Alvania EP2, respectively 3.0-9.5
and 0.6-1.5 µm. According to Czarny, the boundary layer formation in the lubricating greases
is catalyzed by different thickener particles size as well as the lubricating grease temperature.
Along with the temperature increase, the thickness of the absorbed layer d increases. Czarny
explains the increase by an easier adsorption of the active soap particles on the material surface
at a higher temperature. The thickest, 25 µm boundary layer of Alvania EP2 was observed at
temperature of 373 K. It might be interesting to know that, for instance at temperature of 273
K, the boundary layer was approximately 2 µm thick.
Vinogradov et al. [64,65] investigated the shear stress decrease in the lubricating grease at the
wall. The research was carried out on the lithium and calcium soap as well as ceresine
thickened greases. All the researched lubricating greases formed the boundary layer. The
experiments were conducted with the use of the rotational cone-and-plate rheometer and of
the capillary rheometer. They found that the thickness of the boundary layer in the grease is
determined by the stress which is present there. Based on the Herschel-Bulkley model, they
defined dependences which enable the determination of the grease flow parameters in the gap
and in the axisymmetric conduit, including the wall effect.
The research of the lubricating grease flow in the conduits was conducted also by Swartz and
Hardy [66]. They recorded a decrease in resistance of the lubricating grease flow through the
steel axisymmetric conduits. According to their hypothesis, it was caused by bleeding of the
base oil on the conduit wall and by repulsing the thickener particles from the wall. The
hypothesis, however, was not experimentally verified.
Biernacki in [67-69] investigated the problem of influence of the wall material and of the grease
temperature on the boundary layer formation. He studied the phenomenon of the boundary
layer formation in the commercial greases, in the area of the walls made of plastics (polyamide,
polyvinyl chloride, methyl polymethacrylate, polytetrafluoroethylene) as well as the walls
made of metal (steel, copper, mazak, duralumin, aluminium) of different surface topography.
The research was carried out mainly with the use of the rotational coaxial cylinder rheometer.
In the lithium and calcium greases he recorded lower shear stress values at the walls of the
cylinders made of metal than at those made of plastics. The differences in the shear stress values
were particularly visible in the low shear rates range and at the low temperature. With the
increase of temperature and the shear stress, the differences in the values of the shear stress in
the greases depending on the wall material disappear. In the polymer and aluminium greases
Biernacki did not observed considerable differences in the shear stress values recorded at the
surface of the walls made of different materials.
Biernacki also investigated the problem of the boundary layer thickness in the complex lithium
and bentonite greases in the area of two copper and polypropylene plates which approach
parallel to each other. The experiment showed that the lithium grease at the copper plate forms
a 65 µm thick boundary layer. The depleted part of the lithium thickener was formed 27 µm
from the plate surface. Biernacki did not observe the boundary layer formation in the lithium
grease at the polypropylene plate. In the bentonite grease, the boundary layer was not formed
in any of the cases.
Delgado et al. in [70-72] did research on the influence of air, roughness of the steel conduit wall
surface, as well as the conduit diameter on the pressure drop at the horizontal flow of the
grease. They observed that the roughness of the conduit wall influences the formation of the
boundary layer in the lubricating grease. The reduction of the surface roughness considerably
reduced the pressure gradient. The differences grew with the conduit diameter reduction or
with the grease flow rise. Delgado et al. also found out that the air present in the lubricating
grease causes the reduction of the wall slip. According to their hypothesis, it is caused by the
fact that the air in the lubricating grease generates considerable differences in the moistening
of the internal walls of the conduit. The research was carried out mainly on the complex soap
lubricants.
6. Conclusions
A conclusion of the presented research is that the flow of the plastic greases in the lubrication
systems depends not only on the design of the systems but also on the kind of grease. Greases
are non-Newtonian fluids of a highly complex structure, and therefore the to carry out the
evaluation process of their behaviour in particular conditions is multi-stage and very difficult.
The flow resistance of the grease in particular elements of the lubrication system depend,
among others, on the structural viscosity of the grease. All greases get thinned, to a larger or
smaller extent, in the shearing process. At the distribution of the grease to the friction nodes
in a particular period of time, the flow resistance gets reduced as a result of the grease
thickener's microstructure degradation. The decrease in the grease flow resistance is strictly
correlated with the decrease of the shear stress in the grease. In the first seconds of supplying
a new portion of the grease into the main conduit of the lubrication system, the pump must in
the first place overcome the flow resistance generated by the grease, which is connected with
the occurrence of the yield stress in the grease. The value of the stress, as well as the charac‐
teristics of the shear thinning for a particular grease, among other factors, depend on the flow
rate generated by the lubrication pump, but also on the physical and chemical activity of the
environment. An important determinant on the generating the flow resistance in the lubrica‐
tion systems are the physical-chemical phenomena connected with the interaction of the grease
thickener particles suspended in the base oil. One of them is a phenomenon of the grease
thixotropy, consisting in its gel→sol→gel transition, namely the reduction in the grease
structural viscosity at its flow and a partial thickener microstructure reconstruction in the
phase of the grease relaxation, between the consecutive cycles of its distribution to the friction
nodes. The phenomenon is crucial in the case of the greases which stay in the conduits and
dividers of the lubrication system. It can be dangerous for the complex systems, working
cyclically (for instance, the central lubrication systems of big mining machines). A short-term,
uncontrolled increase in the flow resistance in such systems may lead to the excessive energy
consumption by the pump, and in the extreme cases, to damage of the charging unit, and
consequently, to the system failure.
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Critical for the question of the flow resistance is also the material used for the making of the
lubrication conduits as well as their surface topography. Some materials (copper, steel and cast
iron in particular) show the increased adsorption of the particles of the thickener on their
surface. It results in the generation of certain thickener depleted zones, in a shape of a ring,
presenting a lower structural viscosity. The flow resistance at the start of the pump dosing the
grease depending on the material of which the lubrication conduit is made, can be reduced
even by half. In the case when the roughness of the internal surface finish of the conduit is
higher or equal to the thickness of the thickener depleted layer, then the grease flow resistance
is considerably higher than the one which would be observed at the smooth surface finish.
While designing the lubrication systems, it is critical to pay attention to whether the roughness
of the lubrication conduit surface are as low as possible. It is important to mention here that
the pressure drops connected with the resistance, in the majority of the lubrication system
elements are local in their character, whereas in the lubrication conduits, there are constant
pressure drops. In the case of the particularly long conduits, the flow resistance for the entire
lubrication system is predominant there. Other elements which can increase the lubricant flow
resistance as well as the pressure in the system are various types of gaps in dividers. Also in
this case, their shape, section area and the material of which they are made are important.
Similarly complex is a problem of determining the resistance generated by the very friction
nodes and defining the pressure necessary to deliver the required grease portion to the bearing.
The most important design characteristics of the delivered grease flow resistance reduction
bearings are primarily their shape, dimensions of the bearings' working side surfaces, the
distribution and way the lubrication gaps are cut, as well as the circumferential backlash.
Nomenclature
m – index exponent
α1 – the not entangled particles shear stress, Pa
α2 – the entangled particles shear stress, Pa
β1– shear intensity for the not entangled particles, s-1
β2 – shear intensity for the entangled particles, s-1
γC – critical strain, %
γ̇ – shear rate, s-1

η – apparent viscosity (dynamic viscosity), Pas
η0 – viscosity at zero shear rate, Pas
η∞ – viscosity at infinite shear rate, Pas
η ′ – viscous component, Pas

η ″ – elastic component, Pas
| η ∗ | – complex viscosity, Pas

θ – thixotropy coefficient
λ – time-constant, s
μ – friction coefficient
τ – shear stress, Pa
τ0 – yield stress, Pa
χ1 – share of the not entangled particles
χ2 – share of the entangled particles
a – rheological parameter
d – surface layer thickness, µm
de – average diameter of the microcontact, mm
erh – sum of the rheological energy densities in the region of all microcontacts, J/mm3
er h e – rheological density of energy in the microcontact region, J/mm3
G ′ – storagemodulus, Pa
G ″ – lossmodulus, Pa
G0 – plateau modulus, Pa
N
| G ∗ | – complex modulus, Pa
h o * – average lubrication film thickness, mm
irh – friction intensity
k – Boltzmann constant, J/K

kb – parameter determining the time of the not entangled → entangled particles
kc – consistency factor of the thickener in the grease, Pas
kf – parameter determining the time of the entangled particles → not entangled particles
reaction m – index exponent
n – index exponent
pr – pressure, MPa
s – thickness of the boundary layer with the exponentially decreasing yield stress, µm
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T – temperature, K
w – elastic strain energy of the entangled particles
w ′ – elastic strain energy of the not entangled particles
z – normal wall coordinate
Author details
Maciej Paszkowski
Address all correspondence to: maciej.paszkowski@pwr.wroc.pl
Wroclaw University of Technology, Institute of Machines Design and Operation, Wroclaw,

Poland
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Section 2
Boundary Lubrication Applications

Chapter 4
Cryogenic Tribology in High-Speed Bearings and

Shaft Seals of Rocket Turbopumps
http://dx.doi.org/10.5772/55733
1. Introduction
In recent years, as a rule, improvement of the reliability of liquid propellant rockets becomes
an international technical problem for built-up of safe space transport systems. The high
performance, liquid propellant rocket engines require high-pressured turbopumps to deliver
extremely low temperature propellants of liquid oxygen (LO2, boiling point 90 K) and liquid
hydrogen (LH2, boiling point 20 K) to a combustion chamber in engine [1]. In LO2/LH2
turbopumps, cryogenic high-speed bearings and rotating-shaft seals are very important parts
to sustain high reliability of the high-rotating-shaft systems. The turbopump bearings are
directly equipped in cryogenic propellants in pump side [2]. The shaft seal systems are also
set up between the cryogenic pumps and the hot turbines to restrain the leakage of cryogenic
propellants and hot turbine gas [3].
These bearing and shaft seals have to operate under poor lubricating conditions due to
extremely small viscosity at cryogenic temperatures. Furthermore, the turbopump bearings
and shaft seals have to overcome a severe high-speed operation that has several critical speeds
demonstrating self-induced severe vibration of the rotating shaft. In order to develop turbo‐
pump bearings and shaft seals, many inexperienced technical and tribological problems must
be solved for extremely low temperature and high speed of operational conditions. Such
cryogenic tribological technology has been playing a key role in cryogenic turbopumps to
achieve high reliability.
This chapter presents a topical review of cryogenic tribological studies (for about 30 years in
Japan) on the research and development of the cryogenic high-speed bearings and shaft seals
of rocket turbopumps [4, 5]. The high-speed bearings and shaft seals were continually studied
for the LE-5 engine used in the Japanese H-I rocket (developed in 1986) and the LE-7 engine
used in the H-II rocket (developed in 1994). The bearings and shaft seals used in LO2/LH2
turbopumps of the LE-5 and LE-7 had a rotational speed level of 50,000 rpm and had been
studied and developed from the mid-1970 to the mid-1990. Specially, the all-steel bearings
(made of AISI 440C) of the LH2 turbopump of the LE-7 demonstrated high performance with
high reliability at high-speed level at 2 million DN (40 mm x 50,000 rpm). The shaft seal systems
in the LE-5/LE-7 turbopumps that used a mechanical seal, a floating ring seal (annular seal)
and a segmented seal are also reviewed.
Furthermore, for future space transport systems to reduce launch cost and to increase effi‐
ciency, advanced rocket engines which are characterized by high durability (long life) and high
performance (light weight) are required in recent years. Advanced bearing and shaft seal that
have high durability, i.e., a long life of 7.5 hours for the turbopump bearings used in reusable
space shuttle main engine (the SSME). Its required life is 15 times longer than that (30 minutes)
of the turbopump bearings used in the LE-7. At the first time, the SSME turbopump bearings
experienced a serious wear problem in LO2 due to poor self-lubrication of the retainer [6]. In
order to extend bearing life, the hybrid ceramic bearing with Si3N4 balls was used to reduce
serious wear in the conventional all-steel bearing. A new type of the retainer having PTFE/
bronze-powder insert was also developed to obtain sufficient self-lubrication of the hybrid
ceramic bearing. Consequently, the improvement of the SSME turbopump bearings needed a
long time of about 20 years [7].
Today, ultra-high speed level above 100,000 rpm is required to make a small and light
turbopump for advanced second-stage engine. These advanced research and development are
actively underway. In Japan, a new type of hybrid ceramic bearing having Si3N4 balls with a
single guided retainer demonstrated excellent performance at an ultra-high speed of 120,000
rpm (3 million DN) in LH2 and recorded the world’s top speed (in 2001) [8]. The result of this
bearing was applied to the LH2 turbopump (rotational speed, 90,000 rpm) of the RL60
demonstrator engine (in 2003). The RL60 demonstrator engine was developed in the USA with
international collaboration (USA, Japan, Russia and Sweden) and the LH2 turbopump was
developed by a Japanese company [9]. In Europe, for the VINCI engine under development,
high-DN hybrid ceramic bearing was tested in LH 2 at a speed of 70,000 rpm (2.8 million DN)
and continuous studies on a high-DN bearing was conducted at DN up to 3.3 million (120,000
rpm) in LH2 (in 2005) [10]. Furthermore, in Russia, for the developed RD0146 engine, its
rotational speed of the main LH2 turbopump was 123,000 rpm (3.08 million DN), but detail of
its bearing was unknown (in 2003) [11].
This chapter also reviews advanced bearings and shaft seals which were studied from the
mid-1990 to the mid-2000 after the development of turbopump bearings and shaft seals of
the LE-7 [4,5]. It is typical that a long-life bearing with single-guided retainer demonstrat‐
ed a long operation for 12 hours under 50,000 rpm. A hybrid ceramic bearing having single-
guided retainer and Si3N4 balls was able to demonstrate ultra-high-speed performance at
speeds up to 120,000 rpm and show excellent performance under 3 million DN. An annular
seal made of an Ag plated steel ring also presented two-phase seal performance at speeds
up to 120,000 rpm.
These historical reviews are intended to help the technical succession to next young generation
who challenges research and development of the future space transportation system. These
Cryogenic Tribology in High–Speed Bearings and Shaft Seals of Rocket Turbopumps 111
http://dx.doi.org/10.5772/55733
reviews are based on previous studies carried out by Japan Aerospace Exploration Agency
(JAXA) at Kakuda Space Center. All materials used in this chapter have been published by
papers.
Figure 1. Typical tribo-components and solid lubricants used in turbopumps
2. Bearings and shaft seals of turbopumps
2.1. Turbopumps and tribo–components
The LO2/LH2 turbopumps as well as the tribo-components, such as high-speed bearings and
rotating shaft-seals, were studied and developed to use in the LE-5 and LE-7. In reference to
the structure of the LH2 turbopump of the LE-7, the tribo-components and solid lubricants
used in the LE-5 and LE-7 turbopumps are typically indicated in Fig. 1 [4]. In addition, main
design parameters of the turbopumps and DN values of bearings for the LE-5 and LE-7 are
listed in Table 1 [5]. Here, the DN value that represents high-speed level of bearing is defined
as the product of the inner-race bore diameter D (in mm) and the pump rotational speed N (in
rpm). The rotor speed is typically restricted by the DN limits of the bearing.
Engine (thrust) LE-5 (10 tons) LE-7 (86 tons)

Rocket Second stage of H-1 First stage of H-2
Engine cycle Gas-generator cycle Staged-combustion cycle
Turbopump LO2 LH2 LO2 LH2
Pump pressure [MPa] 5.2 5.5 17.4 (25.8)* 27.0
Pump flow rate [kg/s] 20 3.6 212 (46)* 36
Shaft rotational speed [rpm] 16,500 50,000 18,000 42,000
Bearing DN [mm x rpm] 49.5 x 104 125 x 104 81 x 104 168 x 104
Turbine pressure [MPa] 0.48 2.4 19.1 20.6
Turbine temperature [K] 690 840 810 830
Turbine gas flow rate [kg/s] 0.39 0.42 14.9 33.6
Shaft power [kW] 130 490 4,700 19,700
Weight [kg] 23 25 160 200
For pre-burner in bracket; ( )*
Table 1. Design parameters of turbopumps and DN values of bearings for LE-5 and LE-7
a. LE-5 turbopumps
For the upper stage of the H-I rocket, the LE-5 had a gas-generator cycle with 10-ton thrust
and its chamber pressure of 3.4 MPa was relatively low. Its engine cycle is not able to achieve
a high engine performance due to an open cycle. For the LH2 turbopump of the LE-5, the pump
discharge pressure was relatively low at 5.5 MPa and the discharge flow rate was 51 liters/s.
The turbine pressure was 2.4 MPa. The paired bearings of 25-mm bore operated at a speed of
50,000 rpm (1.25 million DN) and sustained the shaft power of 490 kW [12].
For the LO2 turbopumps, the discharge pressure was 5.2 MPa and the discharge flow rate was
18 liters/s. The turbine pressure was 0.48 MPa. The paired bearings of 30-mm bore operated
at a speed of 16,500 rpm and sustained the shaft power of 130 kW. Basic design and technology
of the cryogenic tribo-components used in the small turbopumps was experimentally estab‐
lished under the development of the LE-5.
b. LE-7 turbopumps
For next technical challenge in the first stage engine of the H-II rocket, the LE-7 had a staged-
combustion cycle (similar to that of the SSME) with 100-ton thrust and a high chamber pressure
of 13 MPa. Its engine cycle can obtain high performance due to a closed engine cycle. For the
high-pressure, large LH2 turbopump of the LE-7, the pump discharge pressure was increased
to 27 MPa, and the discharge LH2 flow rate was 510 liters/s. The turbine pressure was relatively
high at 20.6 MPa. The paired bearings of 35-mm bore were at the inducer side, and the paired
bearings of 40-mm bore were at the turbine side. These bearings operated at a speed of 42,000
rpm (1.68 million DN) and sustained the shaft power of 19,700 kW [13,14].
For the LO2 turbopumps, the discharge pressure was 18 MPa for the main pump and 26 MPa
for the preburner pump, respectively. The total discharge LO2 flow rate was 240 liters/s. The
http://dx.doi.org/10.5772/55733
turbine pressure was 19.1 MPa. The paired bearings of 32-mm bore were located at the inducer
side and the paired bearings of 45-mm bore were at the turbine side. These bearings operated
at a speed of 18,000 rpm and sustained the shaft power of 4,700 kW [14,15].
c. Tribo-components in turbopumps
As shown in Fig. 1, it is important to prohibit severe friction and wear in cryogenic
environment that various solid lubricants are applied to the frictional parts in static and
dynamic tribo-components. Since the turbopums are operated under large power condi‐
tions connecting with high fluid and mechanical vibration, it must pay attention that many
components in contact are sure to generate relative motion and resulted in severe adhe‐
sive conditions. It needs proper lubrication to avoid severe frictional adhesion of assem‐
bled parts used in cryogenic environment.
The rotor of turbopump is directly supported by two sets of self-lubricated ball bearings in
cryogenic pump fluid. The shaft seal of turbopump is installed between the cryogenic pump
and the hot gas turbine. The shaft seal system must seal the cryogenic propellants and the
combustion gases (steam with rich hydrogen gas) safely and securely. High-speed compo‐
nents, such as bearings, shaft seals, Labyrinth seals, wear rings and balance pistons, used the
proper solid lubricants to protect them from severe friction and wear in the reduction (LH2)
or oxidation (LO2) environment of the cryogenic propellants. It is noted that these high-speed
tribo-components are important life-controlling parts in engines [4].
2.2. Self–lubricating bearings
2.2.1. Self–lubrication of retainer
The turbopump bearings are all-steel (AISI 440C) bearings that are self-lubricated by the PTFE
transfer film as a lubricant from the reinforced PTFE (polytetra fluoroethylene) retainer. AISI
440C is martensitic stainless steel (with 16-18%Cr) and is one of the most widely used bearing
materials in space systems because such high-Cr steel has a high corrosion resistance due to a
superficial surface layer of Cr2O3. The resin PTFE retainer is reinforced with glass fiber, carbon
fiber and laminated glass cloth to reduce wear as well as thermal contraction of the retainer.
Although PTFE material has poor mechanical strength at room temperature, it has the best
lubricant for use at cryogenic temperature because its mechanical tensile stress drastically
increases and reaches to 80 MPa in LO2 and 130 MPa in LH2, respectively. In order to reduce
wear of the PTFE composite retainer with poor thermal conductivity, sufficient cooling of the
retainer is need to eliminate heat generation detrimental to successful bearing operation at
high speeds [16].
Since LH2 and LO2 are particularly poor as lubricants because of their low viscosity under
conditions of reduction or oxidation, hydrodynamic fluid lubrication is less effective. It is noted
that the cryogenic pump fluids works to remove severe frictional heat and to prevent the
temperature rise in the bearing. At low temperatures, the PTFE transfer film as a lubricant is
kept to be hard and to sustain the bearing load, so that softening and rupturing of the transfer
film due to a rise in temperature have to be eliminated. Under poor cooling conditions, it
appears that the blackened transfer film due to thermal decomposition of PTFE should occur
at a high temperature above about 500 K, and the degraded transfer film was not able to sustain
the bearing load. Therefore, sufficient cooling by cryogenic fluids, as well as reduction of
frictional heat generation, is very important to produce a durable lubricant film transferred
from the retainer even in cryogenic fluid [14].
2.2.2. High–speed and load conditions of bearing
For the turbopump bearings, angular-contact bearings are usually used in pairs in duplex
mounts (back to back). For example, Table 2 shows main design parameters and internal load
conditions for the bearings used in the LH2 turbopumps of the LE-5 and LE-7 [17,18]. In this
table, the SVmax value (=Smax x Vmax/2) that represents the maximum product of stress times
spinning velocity in the contact ellipse zone at the inner race are shown. Here, Smax is the
maximum contact stress and Vmax is the maximum spinning velocity. The SVmax value is an
important factor related to lubrication and wear at the inner race with ball spinning [13,19].
High SVmax value leads to high frictional heating and to wear of the PTFE transfer film due
to spin wear. Under poor cooling condition and large tilted misalignment, the turbopump
bearings have an initial contact angel of 15-25 deg. with a large radial clearance to prevent a
loss of operating clearance from bearing seizer. As mention later, high-speed bearing has the
outer-race ball control that produces high ball spinning at the inner race. In order to reduce
the stress level within the spinning contact zone, race curvatures were controlled to be 0.54-0.56
for inner race and 0.52 for the outer race, respectively. The inner race has a counter-bore type
to gain sufficient cooling within the bearing.
As the centrifugal force developed on the balls increases at high speeds, the operational contact
angle at the inner and the outer races are changed to be different each other. The operational
contact angle at the inner race increases rather than the initial contact angle and decreases to
near zero at the outer race. This divergence of contact angles tends to increase ball spinning in
addition to rolling at the inner race. Its spin velocity due to ball spinning becomes high and
results in an occurrence of frictional heat generation. To contrast, rolling contact at the outer
race generates differential slip due to curvature of contact ellipse [20].
Under the outer-race control connected with ball spinning at the inner race, heat generation
due to ball spin is significantly higher than that of differentia slip, so that sufficient cooling is
necessary at the inner race side. Furthermore, sliding velocity of the rolling balls in contact
with the outer guide land and the ball pocket is high and resulted in a generation of frictional
heating of the retainer. The bearings were effectively cooled by the pump cryogenic fluids
circulating in the turbopumps. For example, Fig. 2 shows sliding frictional conditions of the
inner and outer raceways for the 25-mm-bore bearing that is at a speed of 50,000 rpm under a
thrust load of 980 N [16]. This bearing was used in the LH2 turbopump bearing for the LE-5.
In this figure, the distribution of the contact stress, the spinning velocity and the SV value with
spin at the inner race are shown. Pattern of spin wear generated by ball spinning becomes
similar to the distribution of the SV value. To contrast, for the outer race, the differential slip
velocity and the SV value with differential slip are light so that wear due to differential slip is
http://dx.doi.org/10.5772/55733
Parameters LE-5 LE-7
Bearing
Dimension [mm] 25 x 52 x 15 40 x 70 x 16
Pitch diameter [mm] 38.5 57
Ball diameter [mm] 7.938 9.525
Number of balls 11 13
Initial contact angle [deg.] 20 25
Initial radial clearance [μm] 57 137
Operating condition
Rotational speed [rpm] 50,000 46,000
Thrust pre-load [N] 784 1,176
Bearing DN [mm x rpm] 125 x 104 184 x 104
Internal load condition
Normal load at inner / outer races [N] 157 / 343 176 / 637
Maximum contact stress at inner / outer races (Smax) [GPa] 1.58 / 1.49 1.54 / 1.63
Maximum SV at inner race (SVmax) [N/mm2 x m/s] 2.4 x 103 3.1 x 103
Table 2. Design parameters and internal load conditions for LH2 turbopump bearings of LE-5 and LE-7
small. Furthermore, for the retainer, the sliding velocity is 50 m/s at the ball pocket and 45 m/
s at the outer guide land at a speed of 50,000 rpm, respectively.
For system design of the turbopump high-speed rotor, the thrust load applied on the rotor
due to unbalanced fluid pressures is balanced automatically by a balance piston mecha‐
nism during operation [17]. As a result, the turbopump bearings can operate only with a
6 Book Title
spring thrust load to remove internal clearance and control radial stiffness. However, the
1shaftunbalanced
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as well as the
pressures fluid action
is balanced aroundbythe
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operation
2radial load
[17]. As atoresult,
the thrust load on
the turbopump the bearing.
bearings Foronly
can operate example, the LH
with a spring 2 turbopump
thrust load to removebearings
internal
3of the LE-7 had
clearance to operate
and control radial at a speed
stiffness. of 42,000
However, rpmvibration
the shaft that was beyond
as well as thethe
fluidthird
actioncritical
around
4speedtheofimpeller
32,000 rpm and must support the high shaft-power under high shaft-vibration.
should add high dynamic radial load to the thrust load on the bearing. For example, the
5 LH2 turbopump bearings of the LE-7 had to operate at a speed of 42,000 rpm that was beyond the
Therefore, the bearings must have high combined radial and thrust load capacity at all
6 third critical speed of 32,000 rpm and must support the high shaft-power under high shaft-vibration.
7extremes of the
Therefore, thetutbopump
bearings mustoperating conditions
have high combined [14].
radial and thrust load capacity at all extremes of the
8 tutbopump operating conditions [14].
9
Vmax 2.8 m/s
SVmax 176
N/mm2 x m/s
Smax
Smax
Spin sliding at 1,480 N/mm2
Differential slip 1,470 N/mm2
inner raceway sliding
SVmax 4,140
Vmax 0.12 m/s
N/mm2 x m/s
10
11 Figure 2. Sliding frictional conditions at inner and outer raceways for LH2 bearing (25-mm bore,
2. Sliding
12Figure50,000 frictional
rpm, 980 N)conditions at inner and outer raceways for LH2 bearing (25-mm bore, 50,000 rpm, 980 N)
13
14 2.3 Shaft seal systems
15 The required functions for shaft seal systems vary for different engine cycles. Similar to the SSME,
16 the LE-7 has a two-stage combustion cycle. It requires a high pressure seal since the pressure in the
17 pump and turbine is extremely high. To contrast, the pressure of the pump and turbine in the LE-5
18 with a gas generation cycle is comparatively low. Design parameters (the seal diameter, rubbing
19 speed and seal pressure) for the seal elements used in the LE-5 and LE-7 turbopumps are listed in
20 Table 3 [21]. The seal elements are the LO2 seal, LH2 seal, gas helium (GHe) purge seal and turbine
21 gas seal. These shaft seals prevent or minimize the leakage of LO2 and LH2 for pump side and hot
2.3. Shaft seal systems
The required functions for shaft seal systems vary for different engine cycles. Similar to the
SSME, the LE-7 has a two-stage combustion cycle. It requires a high pressure seal since the
pressure in the pump and turbine is extremely high. To contrast, the pressure of the pump and
turbine in the LE-5 with a gas generation cycle is comparatively low. Design parameters (the
seal diameter, rubbing speed and seal pressure) for the seal elements used in the LE-5 and LE-7
turbopumps are listed in Table 3 [21]. The seal elements are the LO2 seal, LH2 seal, gas helium
(GHe) purge seal and turbine gas seal. These shaft seals prevent or minimize the leakage of
LO2 and LH2 for pump side and hot turbine gas (steam with rich hydrogen gas) for turbine
side. In order to make a short length of the shaft, the shaft seals have to be compactly installed
between the cryogenic pump and hot turbine.
Seal diameter [mm]—Rubbing velocity [m/s]

Parameters
(Rotating speed [rpm])— Seal pressure [MPa]— Seal type
Engine LE-5 LE-7
55—58 (18,000)—4.9—(b)
LO2 seal 46.6—40 (16,500)—0.98—(a)
50—120 (42,000)—7.1—(c)
LH2 seal 43.2—113 (50,000)—1.4—(a)
69—173 (42,000)—0.6—(d)
GHe purge seal 40—35 (16,500)—0.3—(b)
100—105 (18,000)—0.6—(b)
Turbine gas seal 70—61 (16,500)—0.3—(b)
55—58 (18,000)—16.7—(c)
(a) Mechanical seal, (b) Segmented seal, (c) Floating ring seal, (d) Lift-off seal
Table 3. Design parameters for seal elements used in LE-5 and LE-7 turbopumps
For the LO2 turbopumps, when the leakage of LO2 and hot turbine gas are mixed, an explosion
will occur. In order to separate the leakage of LO2 and hot turbine gas in safety, the system is
complicated and requires three types of seal elements (the LO2 seal, GHe purge seal and turbine
gas seal). The GHe purge seal installed between the LO2 seal and turbine gas seal supplies GHe
as a barrier gas. To contrast, for the LH2 turbopumps, the LH2 leakage can be discharged to the
turbine side so that the seal system is relatively simple. However, the rubbing speed of the seal
face becomes considerably high and the contacting seal face is opposite severe tribological
condition.
For the low-pressure turbopumps of the LE-5, the LO2 and LH2 seals used face-contact
mechanical seals to gain small leakage. The GHe purge seal and turbine gas seal used contact-
type segmented seal. For the high-pressure turbopumps of the LE-7, the LO2 seal, LH2 seal and
turbine gas seal used non-contact type, floating-ring seal (annular seal) due to high seal
pressure. For example, the shaft seal system of the high- pressure LO2 turbopump of the LE-7
is shown in Fig. 3 [22]. The shaft seal system was set up between the cryogenic pumps and the
hot turbine and prevented the mixing of the leakage of LO2 and hot turbine gas. The LO2 seal
was composed of a floating-ring seal. The turbine gas seal used two floating-ring seals to seal
the low temperature GH2 that made a barrier to the turbine hot gas. So that the turbine gas seal
http://dx.doi.org/10.5772/55733
was kept at a lower temperature against the hot turbine section and the reliability of the shaft-
seal system was further increased. Between the LO2 seal and the turbine gas seal, the segmented
circumferential seal (GHe purge seal), that had shrouded Rayleigh step hydrodynamic lift-
pads to increase opening force, was paired and purged with GHe to prevent mixing of the
leakage of LO2 and GH2.
The LH2 seal system of the high pressured LH2 turbopump was assembled with the floating-
ring seal and lift-off seal. The lift-off seal is similar to a face-contact mechanical seal and is in
contact with the mating ring (rotating seal-ring) and its leakage is small when the seal pressure
is low. As the rotational speed of the turbopump increases and the seal pressure becomes high,
the seal faces are automatically disengaged from contacting and changed to be non-contact
seal [21].
Figure 3. Shaft seal system for high-pressure LO2 turbopump of LE-7
3. Cryogenic tribological problems [4, 16, 20, 23]
LH2 is a particularly poor lubricant due to its extremely low viscosity (approximately equal to
that of room-temperature air) and chemical reducing effect to remove native oxide film and
to make fresh frictional surface, resulting in a severe lubricating condition at the frictional
interfaces. Furthermore, at extremely low temperatures in LH2, the specific heats and thermal
conductivities of tribo-materials drop off rapidly rather than those at the liquid nitrogen (LN2,
boiling point 77 K) temperature. At a high temperature in LN2, the specific heats and thermal
conductivities are less changed and same as those at a room temperature. In addition with
vaporization of LH2, it is easy to produce local hot spots at frictional interfaces, so that frictional
condition resulted in severe adhesive (welding) wear in LH2.
LO2 has high oxidization power and forms oxide film at frictional surfaces, so that oxide film
produces lower friction compared with that in LH2; however, in boiling of LO2, oxide wear
should increase due to high oxidization power. Active cooling is important to prohibit boiling
of LO2 at frictional interfaces. Furthermore, violent frictional heating in LO2 can lead to the
ignition of tribo-elements due to burn-out phenomenon occurring in nucleate boiling, that is
defined by engineering heat transfer. Under burn-out phenomenon in boiling, an extreme rise
in surface temperature was experienced because a marked reduction occurred in heat transfer.
For example, in boiling of LN2, the sliding surface of Ag-10%Cu alloy (melting point 1,155 K)
against Ti alloy (Ti-5Al-2.5Sn) melted due to burn-out wear during friction test [24]. The surface
coating of TiN or TiO2 had a high resistance to adhesive welding to the Ti alloy disk was able
to protect from burn-out wear. The results were applied to the balance-piston system in the
LH2 turbopump of the LE-7.
Figure 4. Friction and wear of PTFE pin against 440C disk in cryogenic GO2 as a function of pin temperature
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Figure 5. Friction and wear of PTFE pin against oxidized 440C disk in cryogenic GO2 as a function of pin temperature
It is noted that the tribo-characteristics at cryogenic temperatures tend to change complexly.

For example, Fig. 4 shows the change of friction and wear of a PTFE pin against a 440C steel
disk in cryogenic gaseous oxygen (GO2) as a function of pin temperature [23,25]. This figure
denotes the glass transition temperature of PTFE, about 170 K, 230 K and 260 K, those are
defined by relaxation of its amorphous layer in the PTFE band structure. When the frictional
environment changed from the liquid phase to the gas phase at boiling, the friction coefficient
increased drastically and wear began. To the glass transition temperature of 170 K (amorphous
layer begins to relax), the friction coefficient remains at a low constant value, but the specific
wear drastically decreased at 170 K. In an inert gaseous nitrogen (GN2), there was not such
drastically decrease in the specific wear at 170 K. After that, friction and wear begin to increase
gradually up to 230 K. The increase of friction and wear above 170 K surely depends on the
fact that the strength property of PTFE begins to decrease rapidly above 170 K.
However, when the surface of 440C steel was oxidized, the characteristic curve of friction and
wear depended on cryogenic temperatures was changed drastically. Figure 5 shows the change
of friction and wear of a PTFE pin in case of using an oxidized 440C steel disk [23,25]. At the
pin temperatures above boiling point of LO2 (90 K), the friction and wear of PTFE pin showed
relatively high values as compared with that showed in Fig. 4. As the pin temperature increased
from 90 K to near 170 K, the friction and wear of PTFE drastically decreased to low values. The
oxidized 440C steel disk was obtained by heating in air at about 623 K for 3 hours. The surface
of the oxidized 440C showed an increase of FeO/Fe2O3 film in comparison with Cr2O3 film. It
is noted that the oxidization of 440C steel should result in an increase of friction and wear of
PTFE. It seems that PTFE transfer film was less formed due to poor adhesion of PTFE against
FeO/Fe2O3, and frictional condition became to be severe. Thus, it is very interesting that the
friction and wear properties of PTFE changed characteristically at its glass transition temper‐
ature, depending on the oxidization of 440C steel.
For other friction tests, wear of PTFE in cryogenic GO2 was increased as surface roughness of
440C disk was increased; however, in cryogenic GN2, surface roughness had less effect on wear
increase of PTFE. Furthermore, friction and wear of PTFE against Si3N4 disk was determined
in cryogenic GO2 and GN2. In both cryogenic environments, friction coefficient was higher
than that of 440C disk. It was noted that wear of PTFE in GO2 was drastically high compared
with that in GN2. It was assumed that poor formation of PTFE transfer film on the SI3N4 disk
resulted in an increase of friction and wear in GO2. This result indicated that the hybrid ceramic
bearing with Si3N4 ball showed poor self-lubrication in LO2.
It is interesting to use ceramic material as tribo-materials in cryogenic environments. Friction

and wear behavior of typical fine ceramics against 440C disk were evaluated in LO2 and LN2.
Figure 6 and 7 show wear and friction of five kinds of the ceramic balls in comparison with
those in LO2 and LN2 [23], respectively. In all the cases of friction tests, the sliding contact
surface of ceramic pin was covered by the transfer film of wear debris of 440C steel. The metallic
transfer film prevented direct contact between metal and ceramic. As a result, the metal-to-
metal contact should control the friction and wear behavior of the sliding pair, and the order
of friction seemed to be less affected in the wear resistance of ceramic pins.
In LO2, Al2O3 indicated the lowest wear rate and was followed by SiC, Si3N4, Sialon and
ZrO2 in order of the wear resistance. For Al2O3 pin, the metallic oxide film of 440C seemed to
be strongly adhered onto the ceramic pin and resulted in an increase of protection of the pin
wear; however, wear of the 440C disk was prolonged. For SiC, Si3N4 and Sialon, sliding friction
in oxidized environment made the glassy formation of SiO2 film due to tribo-chemical reaction.
The hardness of SiO2 is much less than that of ceramic substrate and resulted in an increase in
the wear of ceramic pins. It was noted that the wear rate of ZrO2 was considerably high as
similar to that of self-mated 440C steels. Since ZrO2 has the lowest hardness compared with
other ceramics, the hard oxide film of 440C should increase wear of ZrO2 pin.
To the contrary, in LN2, Zr2O3 indicated the lowest wear rate and was followed by Si3N4, Sialon,
Al2O3 and SiC in order of the wear resistance. The high wear of Al2O3 and SiC pins was seemed
to be induced by lack of protective film of 440C steel due to weak adhesion to ceramic pin. It
is found that the order of wear resistance of ceramics against 440C steel in LO2 was opposed
to that in LN2 [23].
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At cryogenic temperatures, it is noted that sufficient cooling and the restriction of frictional
heat generation are essential to prohibit severe tribological conditions. In order to solve these
cryogenic tribological problems, it is important that (1) understanding the complex character‐
istics of tribology at low temperatures, (2) selection of the proper solid-lubricants against the
oxidation or reduction power, and (3) active cooling to remove severe frictional heat at local
hot spots [4].
Figure 6. Wear of five kinds of the ceramic balls against 440C disk in LO2 and LN2
Figure 7. Friction of five kinds of the ceramic balls against 440C disk in LO2 and LN2
4. High–speed bearings
4.1. Improvement of self–lubrication of retainer [16, 17, 18, 26, 27]
In the beginning of the development of the turbopump bearing for the LE-5, the bearing had
used the composite PTFE retainer reinforced with glass fiber or carbon fiber. The bearing tested
in LH2 by using a bearing tester showed that the glass fiber-reinforced PTFE retainer (24 wt.%
glass fiber and additive) could demonstrate stable bearing-torque performance as compared
with that of the carbon fiber-reinforced retainer (15 wt.% carbon fiber). From inspection of the
ball-pocket surface of the carbon fiber-reinforced retainer, it was found that pile-up of the wear
debris of carbon fiber might reduce supply of PTFE transfer film to ball surface. As a result,
the LH2 turbopump bearing selected the glass fiber-reinforced PTFE retainer; however, the
real turbopump test showed severe wear of the retainer when the turbopump was operated
under poor cooling conditions. This fact indicated low wear resistance of the glass fiber-
reinforced PTFE retainer under severe operation of turbopump [16,17].
For the rocket-turbopump bearings, a laminated glass cloth with PTFE binder (laminated glass
cloth of 45 wt.% and PTFE of 55 wt.%) was currently used because of its great strength to protect
against dangerous retainer rupture [4,17]. This retainer showed poor self-lubrication resulting
from abrasion by glass cloth layers exposed on the ball-pocket surface. During the develop‐
ment of the LH2 turbopumps for the LE-5, the bearing showed unstable high-temperature rise
and poor lubrication was observed, resulting in severe wear of the balls. In case of the reusable
turbopumps used in the SSME, the bearings similarly experienced a serious wear problem [6].
In order to improve the self-lubricating performance of the retainer, special surface treatment
of the retainer was developed [12,18]. The abrasive retainer surface with the exposed glass
cloth was chemically etched with hydrofluoric acid (HF) to a depth of 0.10-0.15 mm. Following
this treatment, smooth surface for the retainer was obtained. The sliding friction and wear
between the ball and ball-pocket surface was reduced, resulting in a sufficient supply of PTFE
transfer film from the retainer to the rolling balls.
For the HF etched retainer tested in LH2, detailed examination of the transfer film on the sound
ball surface with hardly any wear was conducted by electron probe microanalysis (EPMA)
[12]. The result indicated that F of PTFE of the retainer strongly depended on the Ca concen‐
tration on the map and resulted in the tribo-chemical formation of CaF2 transfer film. The
reacted oxide material (49 wt.% of glass fiber) consisted mainly of an oxide of Ca (CaO)
remained on the HF etched retainer surface. Therefore, it seems that the formation of CaF2
transfer film was conducted by tribo-chemical reaction between F of PTFE and CaO remained
on the retainer surface in chemical reduction environment in LH2.
In order to determine the effect of tribo-chemical formation of CaF2 in transfer film, additional
friction tests were conducted. Figure 8 shows the wear of PTFE composite pins with 15 wt.%
of various fillers against the 440C disk in cryogenic oxygen gas (GO2, 123 K) under a high
sliding speed (10 m/s) [15]. The PTFE composites with CaO and MgO fillers showed excellent
wear resistance (progression of the pin-wear was stopped) due to the formation of good
transfer film even in both cryogenic GO2 and GN2 (123 K). It seems that alkali-earth-metals
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Figure 8. Wear of PTFE composite pins with various fillers against 440C disk in cryogenic GO2 (123 K) under high-slid‐
ing speed (10 m/s)
such as Ca and Mg were able to react easily with F by severe dry sliding friction and resulted
in the formation of CaF2 and MgF2 within the transfer film [4]. The tribo-chemical formation
of CaF2 and MgF2 might enhance adhesion of transfer film. When CaF2 and MgF2 added as
fillers to PTFE, there was no tribo-chemical reaction, resulting in poor wear resistance.
Furthermore, oxidation of the Mo filler in GO2 seemed to be extremely effective except in GN2.
4.2. Development of elliptical ball–pockets of retainer [13, 14, 26]
During testing of the LH2 turbopump for the LE-7, the conventional bearings using a retainer
with circular pockets showed a significant temperature rise under high shaft vibration. Since
high shaft vibration increases the radial load applied to the bearings, ball excursion occurring
in the ball pockets of the retainer due to ball-speed-variation (BSV) becomes significantly large.
Figure 9 shows the ball excursion due to the BSV vs. the radial load for the 40-mm-bore bearing
at a speed of 42,000 rpm [13]. The ball excursion tends to increase with increasing of the radial
load. At a radial load of about 1.5 times thrust load, the ball excursion reaches a maximum
value. When the pocket clearance of the retainer is smaller than the maximum ball excursion,
severe contact occurs between the ball and the retainer pocket.
For the 40-mm-bore bearing, a retainer having elliptical pockets with a large pocket clearance
was developed. As shown in Fig. 10, this retainer with elliptical pockets is able to allow
maximum ball excursion due to BSV in the circumferential direction and to stabilize wobbling
of the retainer due to a narrow clearance in the axial direction [13]. The pocket clearance of 1.8
mm was twice as large as that of the conventional circular pocket. Consequently, the LE-7
Figure 9. Ball excursion due to BSV vs. radial load for LE-7 LH2 bearing at 42,000 rpm (40-mm-bore bearing)
Figure 10. Circular and elliptical pockets of retainer and ball pocket clearances for 40-mm-bore bearing
http://dx.doi.org/10.5772/55733
turbopump bearings with the elliptical-pocket retainer exhibited excellent performance by

reducing severe frictional heating and high wear of bearing components at a high-speed level
of 50,000 rpm (2 million DN). Basic study of the elliptical pocket of the retainer was conducted
in the development of the LE-5 turbopump bearing [12,17].
During the development of the LE-7A, the LH2 turbopump experienced severe operation
with high vibration of the rotating shaft. As a result, high vibration of the rotating heavy
turbine-disk increased radial load at the turbine-side bearings (40-mm bore) and broke the
retainer due to large BSV [26]. It was considered that the ball-retainer contact force due to
BSV bent the retainer and hoop stress occurred on the retainer inside, resulting in fracture
of the thin (weak) web section of the ball pocket. In order to gain high reliability of the
LH2 turbopump, the retainer using elliptical ball pocket was improved by increasing the
pocket clearance to 2.2 mm.
Figure 11. Maximum ball excursion vs. tilted misalignment under various thrust loads at 50,000 rpm (40-mm-bore
bearing)
Figure 12. Maximum ball excursion and tilted misalignment vs. thrust load at 50,000 rpm (40-mm-bore bearing)
Such BSV was also caused by inclination of the outer race to the shaft (tilted misalignment).
The effect of tilted misalignment in a level of 1.9-3.5 x 10-3 mm/mm on the tribo-characteristics
of 40-mm-bore ball bearing was determined. The bearing used a retainer having various
elliptical ball pockets to restrain the ball-retainer contact due to high BSV. The elliptical ball
pocket changed the pocket clearance (1.75mm, 1.95 mm and 2.15 mm). Figure 11 shows the
relationship of the tilted misalignment and the maximum ball excursion under various thrust
loads at a speed of 50,000 rpm [26]. It is understood that maximum ball excursion increased
with an enlargement of tilted misalignment.
Figure 12 shows the relationship of the maximum ball excursion and the tilted misalign‐
ment vs. the thrust load at a speed of 50,000 rpm [26]. The relationship of the maximum
ball excursion vs. the thrust load was calculated by assuming that the tilted misalign‐
ment linearly increased with an increase of the thrust load. As the thrust load increased,
the calculated maximum ball excursion tended to increase in a parabolic pattern. It was
found that, in case of the pocket clearance of 1.95 mm, ball-retainer contact due to ball
excursion possibly occurred within a limited range of thrust loads, resulting in high
increase of bearing torque and bearing temperature.
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Figure 13. Load capacity of transfer film under inner race ball-spinning in LH2
4.3. Performance of LH2 bearing [12, 13]
Performance of self-lubricating bearing coated with PTFE or MoS2 films was evaluated for the
LH2 turbopump bearing of the LE-5. The PTFE and MoS2 films were coated with rf-sputtering.
Bearing test was conducted for about 2 hours at a speed of 50,000 rpm in LH2. Frictional heating
was estimated from the temperature rise of cooling flow through the test bearing [12]. The
coated films are hoped to induce smooth running in the initial operation when the amount of
the PTFE transfer film is insufficient. The high self-lubricating performance and durability
were experimentally confirmed with the PTFE coated bearing indicating frictional heating of
170-250 W. For the MoS2 coated bearing, the frictional heating was 250-330 W and relatively
high. The retainer of the PTFE coated bearing showed less ball-pocket wear than that of the
MoS2 coated bearing.
For high-speed bearings, since the bearing was under the outer-race ball control at high speed,
the transfer film of the inner raceway was damaged due to the spinning of the ball. In order
to evaluate stable operating condition without bearing damage, the load capacity of the
transfer film under inner race ball-spinning in LH2 was determined as shown in Fig. 13[13].
This figure shows the critical load capacity, that is, maximum Herze stress (Smax) vs. maximum
spinning speed (Vmax). Under high thrust loads, an increasing of the bearing torque and
bearing temperature (at limit A) was determined by the bearing tester which could measure
the bearing torque in LH2. The film local rupture (at limit B) was also defined by the electrical
resistance monitoring between the inner race and outer race. Up to a Vmax of 5 m/s at 50,000
rpm, the transfer film was able to sustain a Smax up to 2 GPa. It was determined that the load
capacity of the transfer film depended more on Smax than on Vmax. So, in order to increase
durability of the bearing, it is important to limit the stress level to a Smax of 2 GPa to prevent
transfer-film rupture and sufficiently to cool the frictional heat due to high Vmax.
4.4. Durability of LO2 bearing [15]
It is noted that violent frictional heating in LO2 can lead to the ignition of tribo-elements due
to burn-out phenomenon. Burn out is overheat occurring in a transition from nucleate boiling
to film boiling at critical heat flux that is defined by engineering heat transfer. For the LO2
turbopump bearings (32-mm and 45-mm bore) of the LE-7, the durability and fatigue life were
evaluated by applying heavy radial loads at a speed of 20,000 rpm in LO2 or LN2. During
testing, the bearing-cartridge-acceleration (BCA), i.e., Gpk (peak value) and Grms (rot-mean-
square value), was monitored to detect bearing damage. Testing in LO2 for about 2.2 hours
under a system radial load of 5,880 N showed that excellent lubricating conditions without
abnormal BCA were obtained for all bearings.
Durability test in LN2 (to keep safety in the experience) under a heavy system radial load of
11,760 N was conducted at a speed of 20,000 rpm for about 5.1 hours [15]. The result detected
that the fatigue life of the bearing was about the same as the calculated B10 fatigue life. The
bearings were operated at steady conditions for 5.1 hours with 20 start-stops. For BCA on
bearings A/B, Gpk and Grms on the chart were abnormally separated from each other in a
pattern of abnormal BCA showing an increase of surface roughness due to an occurrence of
slight flaking. Then, at a total test time of 3.8 hours, the loaded and unloaded BCA abnormally
began to increase concomitantly. Examination of tested bearing B indicted that slight flaking
with very shallow depth (about 8.5 µm) was observed on the inner raceway.
4.5. Evaluation of turbopump bearings [14]
The durability of the bearings of the LO2/LH2 turbopumps used in the firing tests of the LE-7
was evaluated based of findings of wear inspection and X-ray photoelectron spectroscopic
(XPS) analysis of PTFE transfer film. Inspection of the turbopump bearings used in the engine
firing tests is essential for evaluation of their durability under engine operation.
a. Bearing wear
After the engine firing test, surface profiles of the raceways of the LH2 turbopump bearings
was evaluated [14]. The engine test was conducted for a total time of 31.4 minutes with 20
engine start-stops. The surface profiles included the thickness (1µm) of the initial film coatings
of sputtered PTFE film. It is obvious that the wear scars on the raceways of all bearings were
flat and spin wear was not observed despite conditions of higher ball spinning on the inner
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raceway. For the retainer with elliptical pockets, the wear depths in the pockets were smaller
than the depth (0.10-0.15 mm) of chemical etching of the glass cloth. The PTFE layer without
the abrasive glass cloth sufficiently remained at the bottom of the pocket wear scar.
To contrary, the all inner raceways of the LO2 turbopump bearings showed typical spin wear
with light oxidative wear [14]. These turbopump bearings tested for a total time of 34.6 minutes
with 23 engine start-stops. The surface profiles included the thickness of the initial film coatings
of sputtered PTFE film (1 µm) on Ion-plated Au film (0.4 µm). The wear depths of raceways
seemed to be relatively high; however, smooth surface roughness demonstrated mild wear
without severe adhesion due to metal-to-metal. For bearing D that was affected by turbine
whirling with radial overload, heavy spin wear with a wear depth of 7 µm was generated on
the inner raceway. Furthermore, slight flaking was observed on the inner and outer raceways.
This flaking was characterized by a very shallow depth and by fractures on the surface.
For the retainer with conventional circular pockets, the wear depths in the pockets were
relatively light compared with those of the LH2 bearing. The contact area in the retainer pocket
and on the ball surfaces was blackened by the thermally degraded transfer film. The degra‐
dation of the transfer film seemed to occur at a temperature above about 500 K. This was
confirmed by a heating test of the retainer. These facts indicated that the transfer film was
severely heated even in cryogenic fluid and the LO2 turbopump bearings were operated under
poor cooling conditions. Thus, to increase the durability of the bearings, it is apparent that
sufficient cooling is essential.
b. XPS analysis of transfer films
In order to evaluate the excellent lubricating conditions without severe wear, XPS depth
analysis of a transfer film on a ball used in the LH2 turbopump bearing of the LE-7 was
conducted. Inspected ball that showed excellent wear condition was from the turbine-side
bearing tested for 31.4 minutes in engine tests. The XPS depth analysis with an etching depth
of 30 nm (SiO2 rate) indicated that F(1s) and Fe(2p) spectra show the significant formation of
thick CaF2 and FeF2 film as shown in Fig. 14 [4]. It seemed that, due to the reduction power of
LH2, the reacted CaO (remained on the retainer surface chemically etched with HF) was tribo-
chemically changed to CaF2 with the F of PTFE retainer during bearing operation. In addition,
due to removing of native oxide film by the LH2 reducing power, a FeF2 film was formed by
a chemical reaction between the F of PTFE retainer and the Fe of 440C steel. It is noted that the
formation of FeF2 film at the stressed contact area resulted in demonstrating high resistance to
metal-to-metal adhesion and in leading to less wear [27].
Thus, the LH2 turbopump bearings used in the engine firing tests demonstrated excellent
performance due to the formation of thick CaF2 and FeF2 film. The tribo-chemical formation
of CaF2/FeF2 film possibly reduced wear at frictional interfaces within the bearings used in
LH2. The basic tribo-chemical reaction was determined as follows [4]:
( -CF2 - )n + CaO + Fe ® ( -CF2 -CO- )n + CaF2 + FeF2 (1)

Figure 14. XPS depth analysis of ball for LH2 turbopump bearing (turbine side)
On the contrary, for the LO2 turbopump bearings of the LE-7, the inspected ball was from the
turbine-side bearing that was tested for 34.6 minutes in engine tests and showed heavy spin
wear. Figure 15 shows the XPS depth analysis with an etching depth of 30 nm (SiO2 rate) for
the worn ball due to spin wear. It indicated that the oxidization power of LO2 prohibited the
tribo-chemical formation of CaF2 /FeF2 transfer film. This bearing was operated under poor
cooling conditions, so that the bearing wear was relatively increased and shallow flaking was
formed on the raceways. From the F spectrum, it was shown that very thin PTFE/CaF2 transfer
film was formed compared with the thick PTFE/CaF2 transfer film in the LH2 bearing. Fur‐
thermore, from the Fe spectrum, formation of Fe2O3 oxide film was typically shown. Fe2O3
oxide film was apt to form at elevated temperature, so that the oxidative mild wear in the
bearing was increased due to poor cooling conditions in LO2 [5]. As mention later (in 6.1.1),
for the bearing tested under sufficient cooling condition, the intense formation of Cr2O3 film
without Fe2O3 film was found beneath an extremely thin PTFE film, resulting in high resistance
to metal-to-metal adhesion and in a decrease of the bearing wear [28].
http://dx.doi.org/10.5772/55733
direction
Etching
Etching depth; 30 nm (SiO2 rate)
CaF2
Electron counts (cps)
Fe
Fe2O3
Binding energy (eV)
Figure 15. XPS depth analysis of ball for LO2 turbopump bearing (turbine side)
Figure 16. Face-contact mechanical seal for LH2 turbopump of LE-5

5. Turbopump shaft seals
5.1. Mechanical seal [29-34]
For the LE-5 turbopumps operating under the gas generator cycle, the contact-type
mechanical seal was able to use for the propellant seals because the pump and turbine
pressures were relatively low. Specially, for the LH2 turbopump, a high-speed mechani‐
cal seal was required to withstand high rubbing speed (113 m/s) at a speed of 50,000 rpm
in LH2. Figure 16 shows the face-contact mechanical seal with a seal diameter of 43.2 mm
developed for the LH2 turbopump of the LE-5 [29,30]. In order to reduce seal leakage of
LH2, it has a modified seal nose that could reduce the seal face distortion and control the
direction of its distortion (to contact at outside of the seal face) under low temperature and
high pressure. Furthermore, a modified vibration damper made of PTFE sheets is attach‐
ed around the seal nose to prevent fluttering during rapid start or stop of the turbopump.
When the closing force to contact seal faces is increased to make seal leakage smaller, wear
rate of the seal faces is increased due to the poor lubrication of LH2. If the closing force is set
to be smaller than the fluid opening force separating seal face each other, the leakage is
considered to be quite large because of the extremely low viscosity and density of LH2.
Therefore, to obtain the stable seal performance and the long wear life, it is important that the
proper balance between the closing force and the opening force is retained.
Critical value of the seal balance ratio that obtained stable seal performance and reduce wear
of the seal faces was experimentally and analytically evaluated [32,33]. In this study, the
experimental and analytical study on the friction power loss and seal performance was
conducted. It was indicated that the friction power loss fell to a small value after the seal faces
were sufficiently run-in. The seal balance ratio [B] that stabilized seal performance was in a
range of 0.77-0.82. The seal balance ratio [B] is determined by the following equation;
éë B ùû = B + Fsp / ( AsDP ) (2)
where, B is the fluid balance ratio, Fsp is the spring force of bellows, As is the seal area and △P
is the seal pressure. [B] is determined by the initial spring force of the bellows.
When the seal balance ratio was below 0.77, the leakage was apt to increase due to lack
of the closing force. In this case, the critical balance ratio [B]c that gains stable seal
performance showing small leakage was 0.77. To contrast, its balance ratio above 0.82
increased wear of the seal face by rise of the closing force. This high value of critical balance
ratio was due to large opening force that could be explained with leakage flow model,
assuming the phase change of leakage (from liquid phase to gas-liquid phase and gas
phase) due to viscous frictional heating at high rubbing speed. In this phase change model,
a state change of gas was assumed to be irreversibly adiabatic and a curve of gas expansion
expressed by the following equation;
http://dx.doi.org/10.5772/55733
Pv m = constant (3)
where, P is the pressure, v is the specific volume and m is the ausfluss exponent. As m decreases
with the temperature rise of gas due to viscous friction, the pressure of leakage flow increases
particularly in the gas region within gas-liquid phase, and it resulted in the increase of the
opening force. The analysis of phase change model of leakage was conducted using the flow
and energy equations of liquid and gas leakages.
Figure 17 shows the calculated and experimental results of the relationship between the seal
clearance and the opening force ratio [K] at a speed of 50,000 rpm in LH2. The opening force
ratio [K] is expressed by the following equation;
[K ] = Fo / ( AsDP ) (4)
where, Fo is the opening force. It was also shown that the opening force within seal clearance
increases linearly as the seal clearance decreases. After the seal faces were sufficiently run-in and
the seal clearance was maintained in an average of 0.6 µm, the opening force ratio [K] ap‐
proaches the critical balance ratio [B]c (= 0.77) that showed critical seal performance. As a result,
the difference of [K] and [B]c was decreased and it resulted in the reduction of the load on the
seal faces. The frictional loss power was decreased to a small value, resulting in a restrain of wear
rate of seal faces. If the seal clearance increases, the leakage becomes large; however, the load on
the seal faces is increased with the decrease of the opening force and the seal clearance would
become small enough to reduce leakage. Furthermore, the starting torque and static seal
performance were markedly affected by the change of the seal face distortion due to wear [31].
Durability of the mechanical seal was evaluated by the long-run test [29]. The long-run test
was conducted at a speed of 50,000 rpm with a seal pressure of 1.37 MPaG for 83 minutes. The
experimental results showed that the leakage gradually increased until total test time was 50
minutes. During its step, wear of the seal faces was running-in, then the leakage was stabilized.
It is noted that an extremely small LH2 leakage (8-19 cc/min) was kept during test. The seal
after the durability test indicated an excellent condition that maximum wear of carbon-ring
was 8 µm.
Temperature on the rubbing seal faces was estimated from the reduction rate of the hardness
of hard Cr plating on the rotating mating ring [34]. The estimated temperature of rubbing seal
face was possibly reached to be about 773 K at a rubbing speed of 113 m/s in LH2. In an initial
stage of running-in, extremely high temperature of the seal faces caused thermal cracks in wear
surface of the Cr plating, so that it is necessary to cool the contacting seal faces sufficiently.
When the cooling of the sealing unit is insufficient, the surface of the carbon seal ring showed
abnormal wear. Furthermore, the Cr plating showed better wear results than the tungsten
carbide (WC) coating, because the Cr plating easily forms thin transfer films of graphite
contained in the carbon. In the case of the WC coating, the transfer film of graphite was hardly
formed in LH2, resulting in an occurrence of severe seal wear.
Figure 17. Opening force ratio [K]vs. seal clearance at 50,000 rpm in LH2
5.2. Floating ring seal [22, 29, 35, 37]
A floating-ring seal is a type of no-contact annular seal without a rubbing seal surface. It has
a simple structure and is able to seal high-pressure fluids, restraining leakage through a small
clearance (gap) between the seal ring and the runner. Its gap is in an order of several dozens
of µm. The seal ring is free to move in the radial direction, and thus severe contact with the
rotating runner can be prevented. Leakage of floating-ring seal is much larger than that of face-
contact mechanical seal, but the floating-ring seal shows a high resistance to pressure and a
high reliability when used as high-pressure seal. A multi-seal system consisting of several seal
rings arranged in series is employed for the high-pressure turbopumps. The floating-ring seals
were developed and used in the LE-5 and LE-7.
Figure 18 shows the floating-ring seal with a seal diameter of 50 mm developed for the LO2
turbopump of the LE-7 [22,35]. The carbon seal ring is enclosed with a retainer of the same
material as the seal runner. Since the retainer contracts thermally nearly as much as the seal
runner at low temperature, the seal gap hardly changes. The seal gap was 50-60µm. When the
seal pressure increases, the floating ring is pressed against the secondary seal by the fluid force
and its movement in the radial direction is restrained. In order to smooth the radial movement
of the floating ring, on the secondary seal of the housing, the PTFE film was coated for the
LO2 seal and the MoS2 film was coated for the turbine gas seal (to seal the low temperature
GH2). For the GH2 leakage of the floating-ring seal used in the turbine gas seal, leakage rate
calculated by the quasi-one-dimensional compressible flow equation agreed quite well with
experimental value.
http://dx.doi.org/10.5772/55733
Figure 18. Floating ring seal for LO2 turbopump of LE-7
The leakage from the floating-ring seal for the LH2 and LO2 seal can be calculated from the
equation of the incompressible fluid flow in the rotating double cylinders when the leakage is
liquid phase flow and the mass flow flux (mass flow/seal area in the flow direction) is large
[29,35]. When the seal gap is narrow and the seal pressure is low, the mass flow flux of leakage
is reduced, and vaporization of leakage occurred by viscous frictional heating and pressure
drop changes liquid phase flow to gas-liquid phase flow (two-phase flow).
Comparison between the experimental and calculated leakage of LH2 was evaluated by the
mass flow flux of leakage for the floating-ring seal with one seal ring or two seal rings [29]. In
this study, the LH2 seal with a seal diameter of 32 mm and various seal gap of 30-86 µm was
tested at rotating speeds to 50,000 rpm. It is shown that the leakage of LH2 is less than the
calculated value from incompressible fluid flow equation because the leakage is changed to
be tow-phase flow. When the mass flow flux is large, most of leakage flows out in liquid phase.
This means that there is not sufficient time to vaporize the leakage to be tow-phase flow within
the seal gap.
A flow visualization study of floating-ring seal was conducted to identify the two-phase flow
area induced by viscous frictional heating and pressure drop [36]. In order to visualize the
two-phase flow in seal gap, the floating ring made of transparent hard plastic (polycarbonate)
was tested in a seal fluid of LN2. It was confirmed that the two-phase flow seemed to be
homogeneous mixture of liquid and vapor flow and the two-phase flow area increases with
increasing rotational speed and decreases leakage flow rate. When the two-phase flow area
was fully prolonged within the seal gap, the leakage rate contrary increased with instability
because the inlet flow resistance at the high-pressure side of the seal ring was reduced by two-
phase flow.
5.3. Segmented seal [22, 35, 37, 38]
Contact-type segmented seal were used in the GHe purge seals and the low pressured turbine
gas seals. The GHe purge seal used in the LO2 turbopump of the LE-7 is shown in Fig. 19 [22].
Segmented seal has a carbon seal ring cut into three segments. The segmented annular seal
ring is pressed on the seal runner with a coil spring and maintains high purge-pressure of GHe
as a barrier gas. Wear of the carbon seal ring is reduced by using the shrouded Rayleigh step
lift-pads to increase the opening force within the seal clearance. As the rubbing speed increases,
the opening force in the Rayleigh step increases, so that the rubbing speed is increased by
enlarging the seal diameter using a T-type runner.
Relationship between the purge pressure and the leakage rate of GHe purge seal was evaluated
at a steady speed of 20,000 rpm [22]. When the purge pressure is low, the seal face is kept to
be non-contact because the Rayleigh step increases the seal opening force. As the purge
pressure is set to be high, the seal face condition is changed from the non-contact state to the
contact state, it resulted that the dynamic leakage almost equals that of the resting state.
Furthermore, for the GHe purge seal combined with the LO2 floating-ring seal, the environ‐
mental temperature around the GHe purge seal was equal to that of LO2 leakage, so that the
carbon seal ring showed severe wear with an appearance of worn-out of the Rayleigh step.
Figure 19. GHe purge seal for LO2 turbopump of LE-7

http://dx.doi.org/10.5772/55733
Running Title 25
Withoutt
MoS2 coatiing
With MoS2
coating
Figure 20. Comparison of wear of MoS2 coated and uncoated seal surfaces
Change of the friction and wear of the carbon pin as a function of the pin temperature was
determined in the cryogenic GHe environment [23]. Friction test was conducted against the
Cr-plated steel disk at a sliding speed of 12 m/s and load of 9.8 N. When the pin temperature
is below the solidification temperature of CO2 (216 K), it is noted that lubricating property of
the carbon pin suddenly disappeared and friction and wear became intensive. When absorbed
CO2 gas was changed to be solid phase, lubricity of carbon was lost. This phenomenon
resembles that when phase of moisture is transfer to solid phase (ice) below 273 K, lubricity
decreases; be well known. From this fact, it seemed that severe wear of the GHe purge seal
was generated because the environmental temperature around the seal was lower than 216 K.
Spray MoS2 coating on the carbon seal face was drastically able to prohibit progression of wear
of the carbon seal ring at low temperature, as shown in Fig. 20.
After a total operating time of 29 minutes for the engine firing test, the GHe purge seal used
in the LE-7 indicated that the seal surfaces coated by MoS2 were found to be in excellent
condition and wear depth of the carbon seal ring was about 7 µm. It assumes that high opening
force produced by the Rayleigh step was kept by prohibit of wear of the Rayleigh step and the
GHe purge seal was operated under conditions of nearly no load on the seal surfaces due to
balance between the opening and closing forces.
6. Advanced bearings and shaft seals
Future space transport systems require reusable launch vehicles to reduce launch cost and to
increase efficiency. The durability of reusable turbopump bearings must be greater than that
of currently available (expendable) turbopumps. For the improved high-pressure LO2

turbopump of the SSME that reduced serious wear of the all-steel bearing, the hybrid ceramic
bearing with Si3N4 balls was developed and accomplished the required life of 7.5 hours. In this
case, to improve self-lubrication of the abrasive retainer made of glass cloth-reinforced PTFE,
a new type of the retainer that had PTFE/bronze-powder insert fitted on the ball pocket was
developed [7].
It is noted that, at high speeds, the hybrid ceramic bearing that consists of hard, light weight
ceramic balls as well as steel rings shows a lower centrifugal force on the ceramic ball. The
centrifugal force of the Si3N4 ball makes about 60 % lighter than that of the 440C steel ball. This
leads to a reduction of bearing load and a smaller contact area with a lower spinning speed,
resulting in a low level of heat generation due to ball spin. Additionally, good tribological
combinations of the ceramic balls against the steel rings result in a decrease in bearing wear
and in instances of seizure, even under insufficient lubricating conditions. Thus, the hybrid
ceramic bearing enables higher speed operation rather than the all-steel bearing.
On the other hand, advanced rocket engines that are characterized by high performance (light
weight) and high durability (long life) are required today. Ultra-high speed turbopump having
a rotational speed level of 100,000 rpm needs to make engine smaller and lighter. Hybrid
ceramic bearing is suitable to ultra-high speed turbopump because of lower centrifugal force.
In recent years, these advanced research and development on the hybrid ceramic bearing are
actively underway.
6.1. Single–guided bearing [27, 28, 39]
In order to increase the durability of self-lubricated bearing, it is apparent that sufficient

cooling and restriction of the frictional heat generation in the bearing are essential. Its notifi‐
cation is experimentally identified by a series of studies on the turbopump bearing. In order
to improve internal coolant flow through the bearing and to reduce bearing frictional torque,
a new type of bearing having a single-guided retainer was developed. Figure 21 shows the 25-
mm-bore bearing having a single-guided retainer with elliptical ball pockets [39]. The single-
guided retainer is guided only by one side of the outer-ring bore (land) to reduce land friction
and to increase the cooling ability within the bearing. However, reduce of retainer guiding is
apt to generate unstable wobbling at high speed, so that the elliptical ball pockets with narrow
axial clearance is needed to reduce wobbling of the retainer. For the elliptical ball pocket of the
single-guided retainer, its circumferential clearance of 1.3 mm was twice as large as that of the
conventional circular pocket to reduce ball-to-pocket interaction under high BSV. Further‐
more, the axial clearance of 0.1 mm was narrow to stabilize wobbling of the single-guided
retainer at high speeds.
Self-lubricating performance, bearing wear and transfer film of two-types of the single-guided
bearing, i.e., a hybrid ceramic bearing with Si3N4 and all-steel bearing, was evaluated under
high thrust loads at speeds up to 50,000 rpm in LH2, LO2 and LN2 [27,39]. Furthermore, to
evaluate the durability of the single-guided bearing for long-life bearing, the all steel bearing
was tested for total operation times up to 11.7 hours at a speed of 50,000 rpm with high thrust
http://dx.doi.org/10.5772/55733
loads in LO2 [28]. These bearings used the glass cloth-reinforced PTFE retainer which was
chemically treated with HF to improve self-lubrication.
Figure 21. Advanced bearing having single-guided retainer with elliptical ball pocket
Figure 22. Bearing torque of single-guided bearings and double guided bearing to 50,000 rpm in LH2
6.1.1. Self–lubricating performance and transfer film [27,39]
a. In LH2
Figure 22 shows the bearing torque of the single-guided bearings (hybrid ceramic bearing and
all-steel bearing) and the conventional double-guided bearing at speeds to 50,000 rpm in
LH2 [39]. It was observed that the bearing torque of the single-guided bearing effectively
decreased to about one-half of that of the double-guided bearing. Its result identified that
bearing torque induced by high-speed sliding of the outer land guide of the retainer almost
accounted for an overall bearing torque generated at high speeds. In addition, the hybrid
ceramic bearing showed lower bearing torque than the all-steel bearing at high speeds.
Critical load capacity of the single-guided bearing without a significant rise of the bearing torque
and bearing temperature was evaluated. For the single-guided hybrid ceramic bearing tested in
LH2, the critical thrust load was 1,960 N (Smax of inner race, 2.7 GPa) at 50,000 rpm and was two
times higher than that of the double-guided all-steel bearing. Furthermore, even when bear‐
ing torque increased with a rise of bearing temperature, the hybrid ceramic bearing was able to
sustain a thrust load of 2,840 N (Smax, 3.2 GPa) at 50,000 rpm without seizure in LH2. High critical
load capacity of the single-guided hybrid ceramic bearing was demonstrated [39].
Figure 23. XPS depth analysis of Si3N4 ball of hybrid ceramic bearing tested in LH2
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Figure 23 shows the XPS depth analysis of a Si3N4 ball taken from the hybrid ceramic bearing
tested in LH2 [27]. Its etching depth was 120 nm (SiO2 rate). It was found that a considerably
thick transfer film consisting of CaF2/FeF2 was formed on the ceramic balls. CaF2 and FeF2
seemed to be tribo-chemically formed by the reducing power of LH2. The considerably thick
transfer film of CaF2 and FeF2 led to exhibit high load capacity. For the all-steel bearing tested
in LH2, a thick CaF2 film was formed beneath an extremely thin PTFE overlay, but its thickness
of CaF2 transfer film was thinner than that of the hybrid ceramic bearing.
b. In LO2
In LO2, the hybrid ceramic bearing exhibited poor self-lubricating performance even at a low
speed of 10,000 rpm. To the contrary, the all-steel bearing indicated excellent load capacity
accompanied by a stable bearing and enabled to sustain a thrust load of 2,650 N (Smax, 2.7
GPa) at a speed of 50,000 rpm without seizure in LO2 [39].
For the hybrid ceramic bearing, an extremely thin, weakly adhesive PTFE film was formed on
ceramic balls and resulted in a poor load capacity of the bearing. For the all-steel bearing, the
intense formation of a Cr2O3 film was beneath an extremely thin PTFE film. It is noted that the
tribo-chemical formation of Cr2O3 film due to high oxidation power of LO2 could exhibit high
resistance to metal-to-metal adhesion leading to seizure [27].
c. In LN2
The hybrid ceramic bearing exhibited better load capacity than that of the all-steel bearing in
LN2. The hybrid ceramic bearing enabled to sustain a thrust load of 2,700 N (Smax, 3.1 GPa) at
a speed of 50,000 rpm without seizure. To the contrary, the all-steel bearing showed unstable
change of bearing torque and seized at a relatively light-thrust load of 1,470 N (Smax, 2.2 GPa)
at a speed of 50,000 rpm [39].
For the hybrid ceramic bearing, the thick transfer film consisting of FeF2/iron oxide formed on
the ceramic balls. To the contrary, the seized all-steel bearing was lubricated by only thin PTFE
transfer film, without the tribo-chemical formation of CaF2/FeF2/Cr2O3 films because of its inert
environment of LN2. This fact was determined by that the all-steel bearing once tested in
LH2 or LO2, whose bearing formed the CaF2/FeF2/Cr2O3 films, showed stable change of the
bearing torque without seizure even under high thrust loads above 1,470 N in LN2 [27].
6.1.2. Long–life bearing [28]

The single-guided all steel bearing was tested for a total operation time to 11.7 hours at a speed
of 50,000 rpm with high thrust loads to 2,400 N in LO2. During long-run test, one-hour
operation at a speed of 50,000 rpm was repeated nine times. The test bearing was effectively
cooled by the jet-cooling with using nozzles. During the long-run test, the bearing exhibited
stable variation of the bearing torque in a range of 93-95 N-mm [28]. The bearing exhibited
excellent self-lubrication performance that there was no abnormal change of the bearing torque
and bearing temperature.
From the examination of the bearing tested for the long-run test in LO2, it was observed
that sound surface conditions with hardly any wear were determined. The XPS depth
Figure 24. XPS depth analysis of SUS440C ball tested for long run in LO2 and new ball
analysis of a ball taken from the tested bearing is shown in Fig. 24 [28]. Its etching depth
was 30 nm (SiO2 rate). It is noted that the intense formation of a Cr2O3 film was detected
and its thickness was thicker than that of the native Cr2O3 film on the new ball. Under
sufficient cooling conditions in LO2, the thick Cr2O3 film formed by tribo-chemical reaction
could provide an extremely high resistance to metal-to-metal adhesion beneath an
extremely thin CaF2 film. To the contrary, under poor cooling conditions in LO2, the intense
formation of oxide film (Fe2O3) was mainly produced and led to large mild wear, as
discussed in the LO2 turbopump bearing. Furthermore, the formation of Fe2O3 might reduce
adhesion of PTFE transfer film, resulting in less lubricant within the bearing. The results
indicated that thick formation of a Cr2O3 film due to tribo-chemical reaction in LO2 is
important to reduce the bearing wear. Its effect needs sufficient cooling with jet within the
bearing components to eliminate the formation of Fe2O3 [28].
6.2. Fluorine–passivated bearing [28]
It is experimentally found that the FeF2 film formed by a tribo-chemical reaction between the
F of PTFE and Fe of 440C steel was facilitated by the high reduction power of LH2 and enhanced
to reduce the bearing wear in LH2. This may suggest that the FeF2 film has a good solid-
lubricant performance to improve the tribological performance of the bearing. Effect of the
coated FeF 2 film on the self-lubrication and durability of the all-steel bearing was evaluated.
An FeF2 film was chemically formed by means of a passivating surface treatment of fluorida‐
http://dx.doi.org/10.5772/55733
tion in hot pure F2 gas. The fluorine-passivated bearings coated with FeF2 film was tested by
long run for 11.7 hours at a speed of 50,000 rpm under high thrust loads in LH2, LO2 and LN2.
The fluorine-passivated bearings showed excellent self-lubrication in both LH2 and LN2 [28].
In a reduce environment of LH2, even under poor cooling conditions controlled by reducing
of the coolant flow, the fluorine-passivated bearing exhibited superior durability for a total
test time to 4.4 hours, as compared with signs of seizure for the untreated bearing. The XPS
analysis of the transfer film indicated that the fluorine-passivated bearing was tribo-chemically
lubricated by a thick CaF2 film overlaid on a thick FeF2/Cr2O3 films.
In an inert environment of LN2, the fluorine-passivated bearing showed excellent self-

lubrication and wear conditions for the long-run test up to 11.7 hours at a speed of 50,000 rpm.
Stable change of the bearing torque (75-80 N-mm) was shown for the passivated bearing during
the long-run test in LN2 [28]. The bearing test was repeated seven times at a speed of 50,000
rpm and a thrust load of 2,600 N in LN2. From the examination of the fluorine-passivated
bearing tested in LN2, sound surface conditions with hardly any wear were determined. It was
found that a thick CaF2 film was tribo-chemically formed on thick FeF2/Cr2O3 films of the
bearing. On the other hand, the untreated bearing was seized at a low thrust load of 1,470 N
due to less tribo-chemical reaction in LN2, as mentioned before. In such inert environment in
LN2, there was less formation of CaF2/FeF2/Cr2O3 films, so that poor self-lubrication and load
capacity of the bearing were shown.
To the contrary, in an oxide environment of LO2, the fluorine-passivated bearing indicated a

higher bearing torque with greater unstable change than that of the untreated bearing [28].
The bearing tests were repeated seven times of the bearing test at a speed of 50,000 rpm and a
thrust load of 2,450 N in LO2. Its total test time was 11.7 hours. During long-run test, high
bearing torque continued to vary erratically with the variation in a range of 75-120 N-mm. The
fluorine-passivated bearing tested in LO2 showed somewhat high wear. To the contrary, the
untreated bearing demonstrated excellent self-lubrication with hardly any wear during the
long-run test as mentioned before. It was clearly showed that the FeF2 film in LO2 made a
typical reduction in self-lubrication.
Inspection of the fluorine-passivated bearing tested in LO2 indicated that the initial coated film
of FeF2 was worm away. Its result also indicated that oxide power of LO2 restricted the tribo-
chemical formation of FeF2 film. Such reduction in self-lubrication possibly resulted from that
the coated FeF2 film restricted the tribo-chemical formation of Cr2O3 film in LO2, resulting in
an increase of metal-to-metal adhesion. These results indicated that excellent lubrication
depended on the tribo-chemical formation of CaF2/FeF2 films in LH2 or Cr2O3 film in LO2,
respectively. In order to obtain high self-lubrication and durability of the bearing, it is noted
that tribo-chemical reaction is necessary at the frictional interfaces within the bearing [4].
6.3. Ultra–high–speed hybrid ceramic bearing [8,40]
Based on previous bearing tests at high speeds up to 50,000 rpm, the hybrid ceramic bearing
(25-mm bore) was tested at ultra-high-speeds up to 120,000 rpm, and results were compared
with the all-steel bearing in LH2. At a ultra-high speed of 120,000 rpm, the inner-race growth
of 34µm due to centrifugal force results in a reduction of the radial clearance within the bearing.
Table 4 summarizes comparison of the bearing load and speed conditions for the hybrid
ceramic bearing and all-steel bearing at a speed of 120,000 rpm with a thrust load of 980 N [8].
At 120,000 rpm, the initial radial clearance of 77 µm was decreased to 43µm. For the hybrid
ceramic bearing, the maximum contact stress Smax at the inner race is apt to increase rather
than that of the all-steel bearing due to a high elastic modulus. However, the maximum
spinning velocity Vmax is reduced and resulted in a lower SVmax value that leads to a reduction
of the bearing temperature and spin wear. The maximum contact stress at the outer race
becomes higher due to centrifugal force. For sliding conditions of the retainer, the sliding
velocity at the outer land and ball pocket reaches to a high level of 110 m/s and the frictional
heat generation of the retainer is to be severe. For the cooling system to remove the bearing
heat generation at 120,000 rpm, effective jet cooling with nozzles needs to obtain sufficient
coolant flow within the bearing. The nozzles were directed to cool the single outer land-guiding
side of the retainer where high frictional heat is generated.
Parameters Hybrid ceramic bearing All-steel bearing

Bearing
Rotational speed [rpm] 120,000
Thrust load [N] 980
Initial contact angle [deg.] 20
Initial radial clearance [μm] 77
Operational radial clearance [μm] 43
Maximum contact stress at inner/outer races (Smax)
2.31 / 2.14 2.00 / 2.35
[GPa]
Maximum spinning velocity at inner race
5.8 7.5
(Vmax) [m/s]
Centrifugal force on ball [N] 454 1,120
Retainer
Sliding velocity at outer land [m/s] 108
Sliding velocity at ball pocket [m/s] 116
Table 4. Bearing load and speed conditions for hybrid ceramic and all-steel bearings at 120,000 rpm with 980 N (25-
mm bore)
Figure 25 shows the change of the bearing temperature at a steady speed of 120,000 rpm with
a thrust load of 2,160 N [8]. The hybrid ceramic bearing showed excellent performance with a
stable condition of the bearing temperature, compared to the seized all-steel bearing showing
an irregular change of high bearing temperature. When the thrust load was increased to 3,140
N, the hybrid bearing showed slight damage with a spiky rise of the bearing temperature. It
was found that the critical load capacity Smax without seizure at a speed of 120,000 rpm was
reached to 3.0 GPa (at a thrust load of 2,160 N) for the hybrid ceramic bearing and 2.0 GPa (980
N) for the all-steel bearing, respectively.
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Figure 25. Change of bearing temperature of hybrid ceramic and all-steel bearings at 120,000 rpm with 2,160 N
The power loss around the bearing was estimated based on the heat absorbed by the cooling
flow [8]. Figure 26 shows the power loss of the hybrid ceramic and all-steel bearings as a
function of rotational speed up to 120,000 rpm in LH2 under different cooling conditions at a
thrust load of 980 N. It was found that the power loss of the bearing significantly increased
above 80,000 rpm with increasing cooling flow rate. At 120,000 rpm, the power loss of the
bearing that contained the viscous power loss of 2.2 kW at the shaft side was estimated. The
power loss was 6.0 kW for the hybrid ceramic bearing and 6.4 kW for the all-steel bearing,
respectively. There was not typical difference of the power loss of the bearing because viscous
power loss within the bearing almost accounted for an overall power loss generated at ultra-
high speeds. It seems that the power loss around the bearing was mainly induced by viscous
drag and churning of the cooling flow passing through the bearing.
The components of the hybrid ceramic bearing were in excellent condition with regard to wear
at a speed of 120,000 rpm with a thrust load of 3,140 N in LH2 [40]. On the contrary, the seized
all-steel bearing exhibited severe adhesive wear. It was found that the ceramic balls formed
superficial micro-cracks on the contact track. Superficial micro-cracks visually extended in a
mesh-like pattern on the Si3N4 ball tested. It was shown that network of hair crack was
propagated along wide-ditch crack. A marked feature of these superficial micro-cracks was
that they were very shallow to about 3 µm at maximum and did not extend deeply into the
ball. From detailed observation with a scanning electron microscope (SEM), such wide-ditch
cracks seemed to be formed by removal of fragments fractured due to contact stress repeated
by the rolling balls as shown in Fig. 27. Thus, when the Si3N4 balls had lower mechanical
strength and fracture toughness, it was clear that wide-ditch cracks were apt to be formed.
Figure 26. Power loss of hybrid ceramic and all-steel bearings as a function of rotational speed up to 120,000 rpm in
LH2
An advanced study was conducted to select a tough Si3N4 ball capable of restraining crack
propagation as well as to evaluate the efficient bearing cooling with nozzles. A Si3N4 ball
having higher thermal-shock resistance, as well as higher fracture toughness, was found to
reduce the propagation of superficial micro-cracks, resulting in a decrease of ball wear.
Furthermore, it was observed that the cooling ability of the LH2 jet-flow aimed at the retainer
was superior to that aimed at the inner raceway, further reducing the propagation of thermal
micro-cracks on the Si3N4 balls. This result also indicated that micro-cracks on the balls were
possibly generated at the trace contacting the outer raceway due to a higher centrifugal force
under insufficient cooling conditions. Furthermore, under the same cooling rate, the four
nozzles achieved a higher cooling ability than the two nozzles with increasing jet speed above
208 m/s. The jet-speed of nozzles reached to the twice of the sliding speed of 108 m/s at the
retainer outer-land [40].
In order to prevent the propagation of superficial thermal micro-cracks on the balls, the outer
race contact stress was reduced by decreasing the outer race curvature to a limited value of
0.51. Furthermore, sufficient cooling at the outer raceway was gained by a proper clearance of
the outer land of the retainer. Decreasing the maximum outer-race stress to 2.0 GPa (thrust
load, 1,960 N) in conjunction with sufficient cooling through a narrow outer land clearance
could prevent the propagation of superficial micro-cracks even under insufficient cooling
conditions [40].
http://dx.doi.org/10.5772/55733
(a) Hair crack 0.01mm (b) Wide-ditch crack

Removing of fragments Wide-ditch crack
Hair crack
Figure 27. Process model of wide-ditch crack formation on Si3N4 ball
6.4. Ultra–high–speed two–phase seal [8]
The floating-ring seal due to noncontact-type is suitable for high-pressure turbopumps;

however, conventional seals using carbon seal-rings were weak under high speed and high
pressure conditions. Since metal seal-rings have higher mechanical strength and durability,
advanced floating-ring seal (with one-seal and two-seal rings) that used Ag-plated metal seal-
rings with a seal diameter of 30 mm [8]. This metal seal was studied at ultra-high speeds up
to 120,000 rpm in LH2. Calculated runner growth due to centrifugal force at 120,000 rpm was
29µm, so that the initial seal clearance (gap) was decreased as the rotational speed increased.
The test seal had an Ag-plated seal ring made of Inconel 718 that was the same material used
for the runner. The runner was coated with a Cr2O3 plasma spray, and this coating exhibited
excellent friction and wear without adhesion to Ag in LN2. In order to obtain smooth radial
movement of the seal ring, the static seal surface of the housing was coated with a sprayed
MoS2 film.
Figure 28 shows the seal performance of the one-ring seal vs. the two-ring seal up to a speed
of 100,000 rpm in LH2 [8]. These seals had a straight bore with a seal gap of 110-120 µm. Figure
29 also shows the phase change models of leakage flow within the seal gap [4]. Seal perform‐
ance depended on the two-phase flow (gas/liquid phase) of leakage, because the vaporization
of leakage was generated by the viscous friction heat and by the seal pressure drop. At lower
speeds, the leakage of the one-ring seal was relatively greater than that of the two-ring seal;
however, with increasing speed, the leakage of the one-ring seal was drastically decreased and
approached the same level of the two-ring seal due to enlargement of the two-phase flow.
For the two-ring seal, the two-phase flow was fully enlarged within the secondary seal ring
that was at the downstream of the primary seal ring. Seal leakage was reduced within limits;
however, the hydrodynamic force of the liquid phase flow that sustained the seal ring was lost
and resulted in seal-ring seizure at a relatively lower speed of 98,700 rpm. Also, shaft vibration
for the two-ring seal was likely produced by wobbling of the seal ring under severe rubbing
conditions and abruptly increased at speeds of more than 92,000 rpm before resulting in seal-
ring seizure at a speed of 98,700 rpm. Furthermore, in the two-ring seal with a seal gap of 70-80
µm, the primary seal-ring seized a speed of 108,600 rpm, because the hydrostatic force
decreased due to a low differential pressure.
Figure 28. Seal performance of one-ring seal vs. two-ring seal up to 100,000 rpm
http://dx.doi.org/10.5772/55733
Figure 29. Phase change models of leakage flow within seal gap at ultra-high speed
In contrast, the one-ring seal successfully functioned with no abnormal signs of seizure during
tests, because the liquid-phase flow remained within a seal clearance even though the two-
phase flow increased. As a result, the hydrodynamic force in the liquid-phase flow as well as
the hydrostatic force due to high differential pressure possibly helped to prevent seal-ring
seizure. At a steady speed of 120,000 rpm, the one-ring seal exhibited a stable leakage in a range
of 0.21-0.24 liters/s that is similar to leakage in the two-ring seal as shown in Fig. 28. Thus, the
one-ring seal was superior to the two-ring seal, preventing seal-ring seizure due to an increase
of two-phase flow within the sealing clearance.
7. Concluding remarks
For built-up of safe space transport system to achieve high reliability, cryogenic high-speed
bearing and shaft seal used in the rocket turbopumps are reviewed historically. These tribo-
components have specific lubrication, materials and design requirements in pumping cryo‐
genic liquid propellants in rocket engines. Nowadays, as earth scale issues of energy
conservation and environment preservation, a breakaway from the conventional fossil-fuel
society becomes a big problem. Clean hydrogen energy is attractive due to its energy efficiency
and its smaller impact on the environment, and it is expected to be a key technology in the 21st
century. It is proposed that, to build hydrogen infrastructure for LH2 storage and distribution,
development of an industrial tribo-system with long durability and high reliability is essential
and advances by supporting of cryogenic tribology studied for LH2 rocket system.
Acknowledgements
This paper is based on previous cryogenic tribology studies carried out by Japan Aerospace
Exploration Agency (JAXA) at Kakuda Space Center. These studies were also supported by
IHI Corporation for turbopumps, by NTN corporation for bearings and by Eagle Industry Co.,
LTD. for shaft seals, respectively. The author is indebted to researchers engaged for their
valuable support, to organizations for their enthusiastic cooperation. At last, the author has to
thank late Prof. Miyakawa, Y. of Hhosei University, as a pioneer in space tribology in Japan,
for his guidance to cryogenic tribology with profound appreciation.
Author details
Department of Mechanical Engineering, University of Tokyo, Tokyo, Japan
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Chapter 5
Titanium and Titanium Alloys as Biomaterials
Virginia Sáenz de Viteri and Elena Fuentes
http://dx.doi.org/10.5772/55860
1. Introduction
Bone and its several associated elements – cartilage, connective tissue, vascular elements and
nervous components – act as a functional organ. They provide support and protection for soft
tissues and act together with skeletal muscles to make body movements possible. Bones are
relatively rigid structures and their shapes are closely related to their functions. Bone metab‐
olism is mainly controlled by the endocrine, immune and neurovascular systems, and its
metabolism and response to internal and external stimulations are still under assessment [1].
Long bones of the skeletal system are prone to injury, and internal or external fixation is a part
of their treatment. Joint replacement is another major intervention where the bone is expected
to host biomaterials. Response of the bone to biomaterial intervenes with the regeneration
process. Materials implanted into the bone will, nevertheless, cause local and systemic
biological responses even if they are known to be inert. Host responses with joint replacement
and fixation materials will initiate an adaptive and reactive process [2].
The field of biomaterials is on a continuous increase due to the high demand of an aging
population as well as the increasing average weight of people. Biomaterials are artificial or
natural materials that are used to restore or replace the loss or failure of a biological structure
to recover its form and function in order to improve the quality and longevity of human life.
Biomaterials are used in different parts of the human body as artificial valves in the heart,
stents in blood vessels, replacement implants in shoulders, knees, hips, elbows, ears and dental
structures [3] [4] [5]. They are also employed as cardiac simulators and for urinary and
digestive tract reconstructions. Among all of them, the highest number of implants is for spinal,
hip and knee replacements. It is estimated that by the end of 2030, the number of total hip
replacements will rise by 174% (572,000 procedures) and total knee arthroplasties are projected
to grow by 673% from the present rate (3.48 million procedures) [6]. This is due to the fact that
human joints suffer from degenerative diseases such as osteoarthritis (inflammation in the
bone joints), osteoporosis (weakening of the bones) and trauma leading to pain or loss in
function. The degenerative diseases lead to degradation of the mechanical properties of the
bone due to excessive loading or absence of normal biological self-healing process. Artificial
biomaterials are the solutions to these problems and the surgical implantation of these artificial
biomaterials of suitable shapes help restore the function of the otherwise functionally com‐
promised structures. However, not only the replacement surgeries have increased, simulta‐
neously the revision surgery of hip and knee implants have also increased. These revision
surgeries which cause pain for the patient are very expensive and also their success rate is
rather small. The target of present researches is developing implants that can serve for much
longer period or until lifetime without failure or revision surgery [7]. Thus, development of
appropriate material with high longevity, superior corrosion resistance in body environment,
excellent combination of high strength and low Young´s modulus, high fatigue and wear
resistance, high ductibility, excellent biocompatibility and be without citotoxicity is highly
essential [8] [9].
In general, metallic biomaterials are used for load bearing applications and must have
sufficient fatigue strength to endure the rigors of daily activity. Ceramic biomaterials are
generally used for their hardness and wear resistance for applications such as articulating
surfaces in joints and in teeth as well as bone bonding surfaces in implants. Polymeric materials
are usually used for their flexibility and stability, but have also been used for low friction
articulating surfaces. Titanium is becoming one of the most promising engineering materials
and the interest in the application of titanium alloys to mechanical and tribological components
is growing rapidly in the biomedical field [10], due to their excellent properties.
This chapter is focused on the use of titanium and its alloys as biomaterials from a tribological
point of view. The main limitation of these materials is their poor tribological behavior
characterized by high friction coefficient and severe adhesive wear. A number of different
surface modification techniques have been recently applied to titanium alloys in order to
improve their tribological performance as well as osseointegration. This chapter includes the
most recent developments carried out in the field of surface treatments on titanium with very
promising results.
2. Biomaterial properties
The main property required of a biomaterial is that it does not illicit an adverse reaction when
placed into services, that means to be a biocompatible material. As well, good mechanical
properties, osseointegration, high corrosion resistance and excellent wear resistance are
required.
2.1. Biocompatibility
The materials used as implants are expected to be highly non toxic and should not cause any
inflammatory or allergic reactions in the human body. The success of the biomaterials is mainly
dependent on the reaction of the human body to the implant, and this measures the biocom‐
Titanium and Titanium Alloys as Biomaterials 157
http://dx.doi.org/10.5772/55860
patibility of a material [11]. The two main factors that influence the biocompatibility of a
material are the host response induced by the material and the materials degradation in the
body environment (Figure 1). According to the tissue reaction phenomena, the biocompati‐
bility of orthopedic implant materials was classified into three categories by Heimke [12], such
as “biotolerant”, showing distant osteogenesis (bone formation with indirect contact to the
material); “bioinert”, showing contact osteogenesis (bone formation with direct contact to the
material), and “bioactive”, showing bonding osteogenesis (bone formation with chemical or
biological bonding to the material).
Figure 1. Biological effects of a biomaterial
When implants are exposed to human tissues and fluids, several reactions take place between
the host and the implant material and these reactions dictate the acceptability of these materials
by our system. The issues with regard to biocompatibility are (1) thrombosis, which involves
blood coagulation and adhesion of blood platelets to biomaterial surface, and (2) the fibrous
tissue encapsulation of biomaterials that are implanted in soft tissues.
2.2. Mechanical properties
The most important mechanical properties that help to decide the type of material are hardness,
tensile strength, Young´s modulus and elongation. An implant fracture due to a mechanical
failure is related to a biomechanical incompatibility. For this reason, it is expected that the
material employed to replace the bone has similar mechanical properties to that of bone. The
bone Young´s modulus varies in a range of 4 to 30 GPa depending on the type of the bone and
the direction of measurement [13] [14].
2.3. Osseointegration
The inability of an implant surface to integrate with the adjacent bone and other tissues due
to micromotions, results in implant loosening [15]. Osseointegration (capacity for joining with
bone and other tissue) is another important aspect of the use of metallic alloys in bone
applications (Figure 2). A good integration of implant with the bone is essential to ensure the
safety and efficacy of the implant over its useful life. It has been shown in previous studies [16],
that enhancement of the bone response to implant surfaces can be achieved by increasing the
roughness or by other surface treatments [17]. Although the precise molecular mechanisms
are not well understood, it is clear that the chemical and physical properties of the surface play
a major role in the implant – surface interactions through modulation of cell behavior, growth
factor production and osteogenic gene expression [18] [19] [20].
Figure 2. Schematic drawing of the principles of osseointegration [21]
Furthermore, it is known that even if initial implant stability is achieved, the bone may retreat
from or be isolated from the implant because of different reasons or situations listed below:
http://dx.doi.org/10.5772/55860
1. Reaction of the implant with a foreign body as debris from implant component degrada‐
tion or wear, or to toxic emissions from the implant [22]
2. Damage or lesion to the bone through mechanical trauma surgery
3. Imposition of abnormal or unphysiological conditions on the bone, such as fluid pressures

or motion against implant components
4. Alteration to the mechanical signals encouraging bone densification; strain reductions or

stress-shielding of replaced or adjacent bone.
2.4. High corrosion resistance
All metallic implants electrochemically corrode to some extent. This is disadvantageous for
two main reasons: (1) the process of degradation reduces the structural integrity and (2)
degradation products may react unfavorably with the host. Metallic implant degradation
results from both electrochemical dissolution and wear, but most frequently occurs through
a synergistic combination of the two [23] [24]. Electrochemical corrosion process includes
both generalized dissolution uniformly affecting the entire surface and localized areas of
a component.
Metal implant corrosion is controlled by (1) the extent of the thermodynamic driving forces
which cause corrosion (oxidation/reduction reactions) and (2) physical barriers which limit the
kinetics of corrosion. In practice these two parameters that mediate the corrosion of orthopedic
biomaterials can be broken down into a number of variables: geometric variables (e.g., taper
geometry in modular component hip prostheses), metallurgical variables (e.g., surface micro-
structure, oxide structure and composition), mechanical variables (e.g., stress and/or relative
motion) and solution variables (e.g., pH, solution proteins and enzymes) [25].
The corrosion resistance of a surgically implanted alloy is an essential characteristic since the
metal alloys are in contact with a very aggressive media such as the body fluid due to the
presence of chloride ions and proteins. In the corrosion process, the metallic components of
the alloy are oxidized to their ionic forms and dissolved oxygen is reduced to hydroxide ions.
The corrosion characteristics of an alloy are greatly influenced by the passive film formed on
the surface of the alloy and the presence of the alloying elements.
2.5. Wear resistance
Wear always occurs in the articulation of artificial joints as a result of the mixed lubrication
regime. The movement of an artificial hip joint produces billions of microscopic particles that
are rubbed off cutting motions. These particles are trapped inside the tissues of the joint capsule
and may lead to unwanted foreign body reactions. Histocytes and giant cells phagocytose and
“digest” the released particles and form granulomas or granuloma-like tissues. At the
boundary layer between the implant and bone, these interfere with the transformation process
of the bone leading to osteolysis. Hence, the materials used to make the femoral head and cup
play a significant role in the device performance. Since the advent of endoprosthetics, attempts
have been made to reduce wear by using a variety of different combinations of materials and
surface treatments.
Nowadays, the materials used for biomedical applications are mainly metallic materials such
as 316L stainless steel, cobalt chromium alloys (CoCrMo), titanium-based alloys (Ti-6Al-4V)
and miscellaneous others (including tantalum, gold, dental amalgams and other “specialty”
metals). Titanium alloys are fast emerging as the first choice for majority of applications due
to the combination of their outstanding characteristics such as high strength, low density, high
immunity to corrosion, complete inertness to body environment, enhanced compatibility, low
Young´s modulus and high capacity to join with bone or other tissues. Their lower Young´s
modulus, superior biocompatibility and better corrosion resistance in comparison with
conventional stainless steels and cobalt-based alloys, make them an ideal choice for bio-
applications [26]. Because of the mentioned desirable properties, titanium and titanium alloys
are widely used as hard tissue replacements in artificial bones, joints and dental implants.
3. Titanium and titanium alloys
The elemental metal titanium was first discovered in England by William Gregor in 1790, but
in 1795 Klaproth gave it the name of titanium. Combination of low density, high strength to
weight ratio, good biocompatibility and improved corrosion resistance with good plasticity
and mechanical properties determines the application of titanium and its alloys in such
industries as aviation, automotive, power and shipbuilding industries or architecture as well
as medicine and sports equipment.
Increased use of titanium and its alloys as biomaterials comes from their superior biocompat‐
ibility and excellent corrosion resistance because of the thin surface oxide layer, and good
mechanical properties, as a certain elastic modulus and low density that make that these metals
present a mechanical behaviour close to those of bones. Light, strong and totally biocompatible,
titanium is one of the few materials that naturally match the requirements for implantation in
the human body. Among all titanium and its alloys, the mainly used materials in biomedical
field are the commercially pure titanium (cp Ti, grade 2) and Ti-6Al-4V (grade 5) alloy. They
are widely used as hard tissue replacements in artificial bones, joints and dental implants. As
a hard tissue replacement, the low elastic modulus of titanium and its alloys is generally
viewed as a biomechanical advantage because the smaller elastic modulus can result in smaller
stress shielding.
Other property that makes titanium and its alloys the most promising biomaterials for implants
is that titanium-based materials in general rely on the formation of an extremely thin, adherent,
protective titanium oxide film. The presence of this oxide film that forms spontaneously in the
passivation or repassivation process is a major criterion for the excellent biocompatibility and
corrosion resistance of titanium and its alloys.
Concerning the medical applications of these materials, the use of cp (commercially pure)
Titanium is more limited to the dental implants because of its limited mechanical properties.
http://dx.doi.org/10.5772/55860
In cases where good mechanical characteristics are required as in hip implants, knee implants,
bone screws, and plates, Ti-6Al-4V alloy is being used [27] [28]. One of the most common
applications of titanium alloys is artificial hip joints that consist of an articulating bearing
(femoral head and cup) and stem [24], where metallic cup and hip stem components are made
of titanium. As well, they are also often used in knee joint replacements, which consist of a
femoral and tibial component made of titanium and a polyethylene articulating surface.
Figure 3. Schematic diagram of artificial hip joint (left) and knee implant [29] (right)
3.1. Wear problems in titanium and titanium alloys
The fundamental drawback of titanium and its alloys which limits wider use of these materials
include their poor fretting fatigue resistance and poor tribological properties [30] [31], because
of its low hardness [32]. Their poor tribological behavior is characterized by high coefficient
of friction, severe adhesive wear with a strong tendency to seizing and low abrasion resistance
[33]. Titanium tends to undergo severe wear when it is rubbed between itself or between other
materials. Titanium has tendency for moving or sliding parts to gall and eventually seize. This
causes a more intensive wear as a result of creation of adhesion couplings and mechanical
instability of passive layer of oxides, particularly in presence of third bodies (Figure 4). Owing
to this effect, in cases of total joint replacements made of titanium head and polymer cup, the
10%-20% of joints needs to be replaced within 15-20 years and the aseptic loosening accounts
for approximately 80% of the revisions [34]. The reason for the failure of the implants is due
to the high friction coefficient of these materials that can lead to the release of wear debris from
the implant into the bloodstream that results in an inflammation of the surrounding tissue and
gives rise to the bone resorption (osteolysis) [35] [36], which ultimately leads to loosening of
the implant and hence the implant has to be replaced by a new one.
Contact
Direction load force
of sliding
Wear
debris
Transfer film
Depends on environment Tribo-modified
(chemistry, humidity,
temperature, etc.)
wear track and
Substrate possible subsurface
damage
Figure 4. Schematic representation of a sliding tribological coating with the presence of third bodies [37]
3.2. Corrosion behaviour of titanium and titanium alloys
All metals and alloys are subjected to corrosion when in contact with body fluid as the body
environment is very aggressive owing to the presence of chloride ions and proteins. A variety
of chemical reactions occur on the surface of a surgically implanted alloy. The metallic
components of the alloy are oxidized to their ionic forms and dissolved oxygen is reduced to
hydroxide ions.
Most metals and alloys that resist well against corrosion are in the passive state. Metals in the
passive state (passive metals) have a thin oxide layer (TiO2 in case of titanium) on their surface,
the passive film, which separates the metal from its environment [38]. Typically, the thickness
of passive films formed on these metals is about 3-10 nm [39] and they consist of metal oxides
(ceramic films). The natural oxide is amorphous and stoichiometrically defective. It is known
that the protective and stable oxides on titanium surfaces (TiO2) are able to provide favorable
osseointegration. The stability of the oxide depends strongly on the composition structure and
thickness of the film [40].
Because of the presence of an oxide film, the dissolution rate of a passive metal at a given
potential is much lower than that of an active metal. It depends mostly on the properties of
the passive film and its solubility in the environment. These films which form spontaneously
on the surface of the metal prevent further transport of metallic ions and/or electrons across
the film. To be effective barriers, the films must be compact and fully cover the metal surface;
they must have an atomic structure that limits the migration of ions and/or electrons across
the metal oxide–solution interface; and they must be able to remain on the surface of these
alloys even with mechanical stressing or abrasion, expected with orthopedic devices [25].
http://dx.doi.org/10.5772/55860
The relatively poor tribological properties and possible corrosion problems have led to the
development of surface treatments to effectively increase near-surface strength, improving the
hardness and abrasive wear resistance thereby reducing the coefficient of friction as well as
avoiding or reducing the transference of ions from the surface or bulk material to the sur‐
rounding tissue.
3.3. Osseointegration of titanium and titanium alloys
When an implant is surgically placed within bone there are numerous biological, physical,
chemical, thermal and other factors functioning that determine whether or not osseointegra‐
tion will occur.
Titanium and its alloys have been widely used for dental and orthopedic implants under load-
bearing conditions because of their good biocompatibility coupled with high strength and
fracture toughness. Despite reports of direct bonding to bone, they do not form a chemical
bond with bone tissue. For the last decade, various coatings have been attempted to provide
titanium and its alloys with bond-bonding ability, which spontaneously bond to living bone.
Hydroxyapatite plasma spray coatings are widely used in cementless hip replacement surgery,
but the hydroxyapatite coating, although exhibiting a very good biocompatibility, presents
some disadvantages including delamination of the coating layer from the substrate, difficulties
in controlling the composition of the coating layer and degradation of the coating layer itself,
which can release debris becoming a source of third body wear [41].
A strong and durable bone to implant connection can be achieved by the formation of a stable
bone tissue at the bone-implant interface by proper implant surface treatments, as can be
electrochemical deposition, dipping and physical vapor deposition techniques [42].
3.4. Surface treatments of titanium and titanium alloys
Surface engineering can play a significant role in extending the performance of orthopedic
devices made of titanium several times beyond its natural capability.
The main objectives of surface treatments mainly consist of the improvement of the tribological
behaviour, corrosion resistance and osseointegration of the implant. There are coatings for
enhanced wear and corrosion resistance by improving the surface hardness of the material
that can be applied by different surface modifications techniques such as surface oxidation,
physical deposition methods like ion implantation and plasma spray coatings, as well as
thermo-chemical surface treatments such as nitriding, carburizing and boriding [43] [44].
Great efforts have been devoted to thickening and stabilizing surface oxides on titanium to
achieve desired biological responses. The biological response to titanium depends on the
surface chemical composition, and the ability of titanium oxides to absorb molecules and
incorporate elements. Surface topography plays a fundamental role in regulating cell behavior,
e.g. the shape, orientation and adhesion of cells.
One possible alternative to solve tribological problems and which is going to explain more
detail consists of protecting the alloy surface by means of biocompatible Diamond-Like Carbon
(DLC) coatings. “Diamond-Like Carbon” is a generic term referring to amorphous carbon

films, deposited by either Physical Vapor Deposition (PVD) or Plasma-Enhanced Chemical
Vapor Deposition (PECVD). DLC coatings basically consist of a mixture of diamond (sp3) and
graphite (sp2). The relative amounts of these two phases will determine much of the coating
properties. They are thus metastable and mostly amorphous, “crystalline” clusters being too
small or too defective to reach graphite or diamond structures. Both the mechanical and the
tribological properties of DLC coatings have been studied for about 30 years, and several
different types of DLC coatings can currently be found. DLC films are attractive biomedical
materials due to their relatively high hardness, low friction coefficient, owing to the solid
lubricant because of its graphite and amorphous carbon contents [31], good chemical stability
and excellent bio and hemocompatibility [45] [44] [46] [47]. Cells are seen to grow well on these
films coated on titanium and other materials without any cytotoxicity and inflammation.
Oxidation remains the most popular technique for the surface modification of Ti alloys; these
oxide layers on titanium are commonly produced by either heat treatment [48] [49] [50] or
electrolytic anodizing [51]. Thermal oxidation results in the formation of a 15-30 µm thick
titanium dioxide layer of the rutile phase. However, due to their long-term high temperature
action, thermal diffusion processes can also lead to the formation of a diffusion sub-layer
consisting of an oxygen solid solution in α-Ti, and development of phase segregation and
coalescence which may cause substrate embrittlement and worsened mechanical and/or
corrosion performance.
Conventional anodic oxidation, which is carried out in various solutions providing passivation
of the titanium surface, generates thin films of amorphous hydrated oxide or crystalline TiO2
in the anatase form [52]. These films exhibit poor corrosion resistance in some reducing acids
and halide solutions, while rutile generally possesses much better protective properties.
However, recent developments in high voltage anodizing allow the production of crystalline
rutile/anatase films at near to ambient temperature [53]. By anodic oxidation, elements such
as Ca and P can be imported into the surface oxide on titanium and the micro-topography can
be varied through regulating electrolyte and electrochemical conditions. The presence of Ca-
ions has been reported to be advantageous to cell growth, and in vivo data show implant
surfaces containing both Ca and P enhance bone apposition on the implant surface.
Furthermore, there are alternative methods to improve the biocompatibility such as biocom‐
patible chemicals [54] and materials such as ceramics for coating. In some studies, titanium
surfaces were modified using phosphoric acid in an “in vitro” study to improve the biocom‐
patibility of dental implants. Results indicated that pretreatment of the implant with phos‐
phoric acid caused no citotoxicity to the osteoblasts [55]. Micro arc oxidation method in
phosphoric acid on titanium implants provided chemical bonding sites for calcium ions during
mineralization [56].
Moreover, there have been developed coatings for high osseointegration. Hydroxyapatite
(HA) coating is a proven method to improve the implants´ mechanical bonding [57] [58],
biocompatibility and improve the osseointegration. The higher the degree of osseointegration,
the higher is the mechanical stability and the probability of implant loosening becomes smaller.
The process of osseointegration depends upon the surface properties such as surface chemis‐
http://dx.doi.org/10.5772/55860
try, surface topography, surface roughness and mainly the surface energy. TiO2, calcium
phosphate, titania/hydroxiapatite composite and silica coating by the sol-gel method can be
applied on the surface of the titanium and titanium alloys. Plasma Electrolytic Oxidation (PEO)
or Micro-Arc Oxidation (MAO) technique is used for the synthesize TiO2 layer. This technique
is based on the modification of the growing anodic film by arc micro-discharges, which are
initiated at potentials above the breakdown voltage of the growing oxide film and move
rapidly across the anode surface. This technology provides a solution by transforming the
surface into a dense layer of ceramic which not only prevents galling but also provides excellent
dielectric insulation for contact metals, helping to protect them against aggressive galvanic
corrosion. PEO process transforms the surface of titanium alloys into a complex ceramic matrix
by passing a pulsed, bi-polar electrical current in a specific wave formation through a bath of
low concentration aqueous solution. A plasma discharge is formed on the surface of the
substrate, transforming it into a thin, protective layer of titanium oxide, without subjecting the
substrate itself to damaging thermal exposure.
Among all the above mentioned surface treatments, Diamond-Like Carbon coating and Plasma
Electrolytic Oxidation are the most promising ones applied on titanium surfaces. These two
treatments are explained in more detail in the following sections.
3.4.1. Diamond-like carbon coatings

In some biomedical applications continuously sliding contact is required, subjecting the
implant to aggressive situations. To achieve and maintain higher efficiency and durability
under such increasingly more severe sliding conditions, protective and/or solid coatings are
becoming prevalent.
These coatings can generally be divided in two broad categories [59] : “soft coatings”, which
are usually good for solid lubrication and exhibit low friction coefficients, and “hard coatings”,
which are usually good for protection against wear, and exhibit low wear rates and hence
longer durability (Figure 5).
It would thus seem to be difficult to associate low friction and high wear resistance with all
types of coating in most tribological contacts. Some trade-offs can be found in combining both
hard and soft materials in composite or multilayer coatings, which require complex procedures
and further optimization of the deposition process. Nevertheless, a diverse family of carbon-
based materials seems to “naturally” combine the desired set of tribological properties,
providing not only low friction but also high wear resistance. These materials are widely
known as the diamond and Diamond-Like Carbon (DLC) coatings. They are usually harder
than most metals and/or alloys, thus affording very high wear resistance and, at the same time,
impressive friction coefficients generally in the range of 0.05-0.2 [60] [61] [62]. In some cases,
friction values lower than 0.01 have been reported [63] [64], offering a sliding regime often
referred to as “superlubricity”. These exceptional tribological abilities explain the increasing
success of Diamond-Like Carbon coatings over the years, both in industrial applications and
in the laboratory. The exceptional tribological behavior of Diamond-Like Carbon films appears
to be due to a unique combination of surface chemical, physical, and mechanical interactions
at their sliding interfaces [65].
Figure 5. Classification of coatings with respect to hardness and coefficient of friction, highlighting the special case of
carbon-based coatings
Since their initial discovery in the early 1950s, Diamond-Like Carbon coatings have attracted
the most attention in recent years, mainly because they are cheap and easy to produce and
offer exceptional properties for demanding engineering and medical applications. They can
be used in invasive and implantable medical devices. These films are currently being evaluated
for their durability and performance characteristics in certain biomedical implants including
hip and knee joints and coronary stents.
Diamond-Like Carbon is the only coating that can provide both high hardness and low friction
under dry sliding conditions. These films are metastable forms of carbon combining both sp2
and sp3 hybridizations, including hydrogen when a hydrocarbon precursor is used during
deposition. The tribological behavior of Diamond-Like Carbon films requires a solid back‐
ground on the chemical and structural nature of these films, which, in turn, depends on the
deposition process and/or parameters. The chemical composition, such as the hydrogen and/
or nitrogen content or the presence of other alloying elements, controls the mechanical and
tribological properties of a sliding pair consisting of DLC on one or both sliding surfaces [66].
For example, DLC samples containing different concentrations of titanium (Figure 6) have also
been examined “in vitro” to obtain a biocompatible surface that is hard, preventing abrasion
and scratching [67].
It is well known that Diamond-Like Carbon films usually present smooth surfaces, except
maybe in the case of films formed by unfiltered cathodic vacuum arc deposition (Figure 7).
Roughness of the films on industrial surfaces will then be mainly controlled by the substrate
roughness and can therefore be minimized.
http://dx.doi.org/10.5772/55860
Figure 6. Scheme of titanium doped DLC coating. In this case, the first titanium layer was deposited in order to im‐
prove adhesion of DLC coating to the substrate and relax stress of the coating
Figure 7. SEM (Scanning electron microscopy) micrograph of Ti-DLC coating deposited by physical vapour deposition
technique using cathodic arc evaporation method
A frequently observed feature in tribological testing of Diamond-Like Carbon films is the

formation of transfer layer. The formation of carbonous transfer layer on the sliding surface
was observed to reduce the friction coefficient [68].
DLC coatings are usually applied by means of Cathodic Arc Evaporation Physical Vapor
Deposition technology. An arc can be defined as a discharge of electricity between two
electrodes. The arc evaporation process begins with the striking of a high current, low voltage
arc on the surface of a cathode that gives rise to a small (usually a few microns wide) highly
energetic emitting area known as a cathode spot. The localised temperature at the cathode spot
is extremely high (around 15000 °C), which results in a high velocity (10 km/s) jet of vaporised
cathode material, leaving a crater behind on the cathode surface.
The plasma jet intensity is greatest normal to the surface of the cathode and contains a high
level of ionization (30%-100%) multiply charged ions, neutral particles, clusters and macro-
particles (droplets). The metal is evaporated by the arc in a single step, and ionized and
accelerated within an electric field. Theoretically the arc is a self-sustaining discharge capable
of sustaining large currents through electron emission from the cathode surface and the re-
bombardment of the surface by positive ions under high vacuum conditions.
If a reactive gas is introduced during the evaporation process dissociation, ionization and
excitation can occur during interaction with the ion flux and a compound film will be depos‐
ited. Without the influence of an applied magnetic field the cathode spot moves around
randomly evaporating microscopic asperities and creating craters. However if the cathode spot
stays at one of these evaporative points for too long it can eject a large amount of macro-
particles or droplets as seen above. These droplets are detrimental to the performance of the
coating as they are poorly adhered and can extend through the coating.
A recent tribological study carried out about the effect of deposition of Diamond-Like Carbon
coatings on a substrate of Ti-6Al-4V for knee implants has confirmed that these types of coating
improve the tribological response of substrate decreasing the coefficient of friction (µ) (Table
1) and reducing the wear of the surface (Figure 8) [69]. For this study fretting tests were
performed using alumina balls as counter body, bovine serum as lubricant and a continuous
temperature of 37 ºC, trying to simulate real environment.
Sample µ ± SD (standard deviation) Disc Wear Scar, Maximum Depth (µm)
Ti-6Al-4V 0.86 ± 0.08 10 ± 3
Ti-DLC 0.24 ± 0.01 Polishing Effect
Table 1. Friction coefficients values and ball and disc wear scars measurements
(a) (b)
Figure 8. SEM micrographs of the fretting tests wear scars. Ti-6Al-4V (left), Ti-DLC (right)
http://dx.doi.org/10.5772/55860
3.4.2. Plasma electrolytic oxidation treatment
In biomedical application titanium is the most employed alloy due to its biocompatibility as
an implant material, attributed to surface oxides spontaneously formed in air and/or physio‐
logical fluids [70]. Cellular behaviors, e.g. adhesion, morphologic change, functional alteration,
proliferation and differentiation are greatly affected by surface properties, including compo‐
sition, roughness, hydrophilicity, texture and morphology of the oxide on titanium [71] [72].
The natural oxide is thin (about 3–10nm in thickness [39] ) amorphous and stoichiometrically
defective. It is known that the protective and stable oxides on titanium surfaces are able to
provide favorable osseointegration [73] [74]. The stability of the oxide depends strongly on the
composition structure and thickness of the film [75].
On titanium and its alloys a thin oxide layer is formed naturally on the surface of titanium
metal in exposure to air at room temperature [76] [77] [78]. Titania (TiO2) exists in three
polymorphic forms: rutile, anatase and brookite. Rutile, stable form of titania at ambient
condition, possesses unique properties [79]. The metastable anatase and brookite phases
convert to rutile upon heating. However, contact loads damage this thin native oxide film
and cause galvanic and crevice corrosion as well as corrosion embrittlement. Moreover,
the low wear resistance and high friction coefficient without applied protective coatings
on the surface gravely limit its extensive applications. The most accepted technique for the
surface modification of Ti alloys is oxidation. Anodizing produces anatase phase of titania
that shows poor corrosion resistance in comparison with rutile phase. Recent develop‐
ments in high voltage anodizing cause a crystalline rutile/anatase film at near to room
temperature.
Attempts to improve surface properties of titanium and its alloys over the last few decades
have led to development of Plasma Electrolytic Oxidation (PEO) technique by Kurze et al.
[80] [81], which is a process to synthesize the ceramic-like oxide films at high voltages.
This technique is based on the modification of the growing anodic film by spark/arc micro-
discharges in aqueous solutions (Figure 9), which are initiated at potentials above the
breakdown voltage of the growing oxide film and move rapidly across the anode surface
[53]. Since they rapidly develop and extinguish (within 10-4-10-5 s), the discharges heat the
metal substrate to less than 100-150 ºC. At the same time the local temperature and pressure
inside the discharge channel can reach 10-3-10-4 K and 10-2-10-3 MPa, respectively, which is
high enough to give rise to plasma thermo-chemical interactions between the substrate and
the electrolyte. These interactions result in the formation of melt-quenched high-tempera‐
ture oxides and complex compounds on the surface, composed of oxides of both the
substrate material and electrolyte-borne modifying elements. The result is a porous oxide
coating.
The PEO coating shows a significantly higher thickness (18 µm ± 4 µm) than PVD coatings and
also a different morphology. The external part of the layer is porous (with pore diameter
ranging from 3 to 8 µm) (Figure 10). The coating becomes increasingly compact on going
towards the interface with the substrate. This kind of morphology leads to a relatively high
surface roughness.
Figure 9. Photography of the arc micro-discharges in PEO process
(a) (b)
Figure 10. SEM micrographs of porosity of the external layer in PEO treatment. a) overview and b) detail
This method is characterized by the titanium surface, at near-to-ambient bulk temperature,

into the high temperature titanium oxide (rutile) modified by other oxide constituents.
Economic efficiency, ecological friendliness, corrosion resistance, high hardness, good wear
resistance, and excellent bonding strength with the substrate are the other characteristics of
this treatment [82] [83] [84].
The main conversion products formed by the PEO treatment are titanium oxides: rutile and
anatase, typical anodic oxidation products of titanium. The structure and composition of
anodic oxide films are known to be strongly dependent on film formation temperature and
potential [85] [86]. In the case of PEO coatings, both the electrolyte composition and the current
http://dx.doi.org/10.5772/55860
density regime have an influence on the phase composition and morphology of the anodic
oxide layer [87]. A higher spark voltage causes a higher level of discharge energy, which
provides a larger pore [88].
The influence of electrolyte characteristics on the phase composition of PEO films on titanium
has previously been studied [89] [90]. It has been shown that surface layers composed of rutile,
anatase, rutile/anatase, as well as oxides of electrolyte elements (e.g. Al2O3, MgO, WO3), their
hydroxides and complex oxides (e.g. Al2TiO5, AlPO4, CaWO4, BaTiO3, MnTiO3, etc.) can be
produced.
Surfaces containing Ca and/or P induce osteoinduction of new bones and become bioactive.
Ca and P ions can be incorporated into the layer, controlling the electrolyte employed during
the electro oxidation process, and they further transform it into hydroxyapatite by a hydro‐
thermal treatment [41].
One technique that could show the effect of the electrolyte in the chemical composition of the
coating could be the EDS (Energy Dispersive Spectroscopy) technique. In the following graphs
a comparative study can be observed. The results of different samples, uncoated cp Ti, a coating
obtained with a commercial electrolyte and a coating prepared in an aqueous electrolyte
containing calcium phosphate and β-glycerophosphate, are showed in the following spec‐
trums. The Ca- and P-containing titania coatings produced by PEO improve the bioactivity of
the titanium-constructed orthopedic implant [91]. In Figure 11, in spectrum b) and c) can be
observed the difference in the calcium quantity presented into the coating.
The biological response to titanium depends on the surface chemical composition and the
ability of titanium oxides to absorb molecules and incorporate elements [92]. Surface topog‐
raphy plays a fundamental role in regulating cell behaviour, e.g. the shape, orientation and
adhesion of cells [93] [94]. As a surface begins to contact with biological tissues, water
molecules first reach the surface. Hence, surface wettability, initially, may play a major role in
adsorption of proteins onto the surface, as well as cell adhesion. Cell adhesion is generally
better on hydrophilic surfaces. It is known that changes in the physicochemical properties,
which influence the hydrophilicity of Ti dioxide, will modulate the protein adsorption and
further cell attachment [39]. By anodic oxidation, elements such as Ca and P can be imported
into the surface oxide on titanium and the micro-topography can be varied through regulating
electrolyte and electrochemical conditions. The presence of Ca-ions has been reported to be
advantageous to cell growth, and “in vivo” data show implant surfaces containing both Ca
and P enhance bone apposition on the implant surface.
Some experiments carried out to study the tribological behaviour of the PEO-treated Ti-6Al-4V
by means of dry sliding tests against PS (plasma sprayed) Al2O3–TiO2 and compared with that
of thin PVD coatings showed that the best tribological behavior, both in terms of low coefficient
of friction and high wear resistance (i.e. low wear damage) was displayed by the PEO treated
samples. The highest wear resistance was displayed by the PEO-treated samples, with
negligible wear loss even under the highest applied load of 35 N. This good tribological
behavior should be mainly related to the superior thickness of this coating that can better
support the applied load.
(a)
(b)
(c)
Figure 11. a) analysis

Figure 11. a) Microchemical Microchemical analysis
of cp Ti, of cp Ti, b) microchemical
b) microchemical analysis
analysis of coating of coating
prepared prepared
with with commercial
commercial electro‐ electrolyte, c) m
of coating
lyte, c) microchemical prepared
analysis with prepared
of coating calcium phosphate and phosphate
with calcium β-glycerophosphate electrolyte.
and β-glycerophosphate electrolyte.
The biological response to titanium depends on the surface chemical composition and the ability of titanium
The PEO treatment leads to a very good tribological behavior, significantly reducing both wear
molecules and incorporate elements [92] . Surface topography plays a fundamental role in regulating cell behav
and friction oforientation
the Ti-6Al-4V alloy, ofeven
and adhesion cells under
[93] [94]high
. As aapplied loads to
surface begins (up to 35with
contact N).biological
This goodtissues, water molec
tribological behaviour should
surface. Hence, be mainly
surface related
wettability, to themay
initially, superior
play athickness
major roleofinthis coating,ofwhich
adsorption proteins onto the surf
adhesion. Cell adhesion is generally better on hydrophilic surfaces. It is known that changes in the physicoc
which influence the hydrophilicity of Ti dioxide, will modulate the protein adsorption and further cell attachm
oxidation, elements such as Ca and P can be imported into the surface oxide on titanium and the micro-topogr
through regulating electrolyte and electrochemical conditions. The presence of Ca-ions has been reported to b
cell growth, and “in vivo” data show implant surfaces containing both Ca and P enhance bone apposition on the
Some experiments carried out to study the tribological behaviour of the PEO-treated Ti-6Al-4V by means o
against PS (plasma sprayed) Al2O3–TiO2 and compared with that of thin PVD coatings showed that the best tri
both in terms of low coefficient of friction and high wear resistance (i.e. low wear damage) was displayed b
http://dx.doi.org/10.5772/55860
can better support the applied load. The main wear mechanism is micro-polishing and the
coating thickness dictates its tribological life [95].
Last studies carried out have concluded that the PEO surface treatments enhance the biological
response “in vitro”, promoting early osteoblast adhesion, and the osseointegrative properties
“in vivo”, accelerating the primary osteogenic response, as they confirmed by the more
extensive bone-implant contact reached after 2 weeks of study [94].
4. Conclusions
Titanium and its alloys are considered to be among the most promising engineering materials
across a range of application sectors. Due to a unique combination of high strength-to-weight
ratio, melting temperature and corrosion resistance, interest in the application of titanium
alloys to mechanical and tribological components is growing rapidly in a wide range of
industries, especially in biomedical field, also due to their excellent biocompatibility and good
osseointegration. In such application, components made from Ti-alloys are often in tribological
contact with different materials (metals, polymers or ceramics) and media, under stationary
or dynamic loading and at various temperatures. These contact loads can cause damage of the
thin native oxide film which passivates the titanium surface; and the metal can undergo
intensive interactions with the counterface material and/or the surrounding environment.
These interactions can generate various adverse effects on titanium components, such as high
friction or even seizure (galvanic and crevice corrosion) as well as corrosion embrittlement,
which lead to the premature failure of the implanted systems. The development of new
specialized surface modification techniques for titanium and its alloys is therefore an increas‐
ingly critical requirement in order to control or prevent these effects and improve osseointe‐
gration, hence extending the lifetime of the implant.
Physical Vapour Deposition (PVD) technique allows develop Diamond-Like Carbon coatings
that can be doped with different elements as titanium, tantalum, silver… which are biocom‐
patible and increase the corrosion and wear resistance of the substrate, diminishing friction
coefficient.
Plasma Electrolytic Oxidation (PEO) technique provides a possibility for the variation of
composition and structure of the surface oxide film and attracts special interest for the
corrosion protection and the optimization of friction and wear of titanium alloys as well as
enhance the osseointegration.
Acknowledgements
The authors acknowledge financial support from the Spanish Ministry of Science and Inno‐
vation obtained in the project: CSD2008-00023 FUNCOAT (in the frame of the CONSOLIDER
INGENIO-2010 program) and from the Basque Government.
Author details
Virginia Sáenz de Viteri* and Elena Fuentes

*Address all correspondence to: virginia.saenzdeviteri@tekniker.es
IK-Tekniker, Eibar, Spain
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Section 3
Testing and Modeling

Chapter 6
New Scuffing Test Methods

for the Determination of the
Scuffing Resistance of Coated Gears
Remigiusz Michalczewski, Marek Kalbarczyk,

Michal Michalak, Witold Piekoszewski,
Marian Szczerek, Waldemar Tuszynski and
Jan Wulczynski
http://dx.doi.org/10.5772/54569
1. Introduction
1.1. Scuffing of gear teeth
In modern machines the problems of the prevention of scuffing of the gear teeth is still very
important. One of the reasons is that for many years the technique development is related to
increasing the loading of the friction surfaces accompanied by decreasing their size [1]. In the
case of gears, the risk of scuffing occurrence rises because of potential design and assembly
mistakes, unexpected overloads, as well as extremely different speeds of the rotation of gears,
because both very high speeds and very low speeds may cause scuffing [2]. The occurrence of
one of the mentioned factors may lead to very serious gear failures.
Apart from the above mentioned factors, the problems of using proper lubricating oils, with
high extreme-pressure (EP) properties cannot be neglected.
In gears, the surface destroyed by scuffing appears at the addendum and dedendum of the
tooth. This results from the sliding speed of the meshing teeth that reaches the highest values
at these places of the gear tooth.
Failures of the gear teeth flanks due to scuffing are shown in Figure 1.
(a) (b)
Figure 1. Photographs of failures of the gear teeth flanks due to scuffing: a) “non-symmetric” scuffing observed in
gear service, resulting from the incorrect distribution of load along the tooth [3], b) scuffing on the flank of the test
gear due to poor extreme-pressure (EP) properties of the tested gear oil during the gear scuffing experiments per‐
formed by the authors
Another example of scuffing of gears concerns the rudder speed brake power drive unit of a
space shuttle, observed during its inspection after grounding [4]. Figure 2 a) shows the pinion
and ring gear of the power drive unit of the space shuttle. Figure 2 b) presents the pinion tooth
with wear at the tip and scuffing on dedendum. It was postulated that early shutdown of one
of three hydraulic motors driving the gearbox could cause scuffing - in a differential gearbox,
early shutdown of one motor could cause the overloading with potential for scuffing.
(a) (b)
Figure 2. Photographs of the components of the rudder speed brake power drive unit of a space shuttle: a) pinion
and ring gear of the power drive unit, b) damaged pinion tooth [4]
From the above example, it is absolutely apparent that the prevention of scuffing is still an
important challenge, even in the high-tech sector.
1.2. Scuffing — How is it brought about?
To better understand scuffing, Figure 3 presents the interpretative models of the phenomena
in different phases of this process, caused by the continuously increasing load. The models
New Scuffing Test Methods for the Determination of the Scuffing Resistance of Coated Gears 187
http://dx.doi.org/10.5772/54569
concern the contact between two balls of the four-ball tribosystem (the rotating upper ball with
one of the three stationary lower balls) during the testing of the automotive gear oils of API
GL-4 and GL-5 performance levels. Such oils contain chemically active extreme-pressure (EP)
lubricating additives to prevent scuffing. API GL-4 oils are used to lubricate synchronised
manual transmissions of European cars and contain up to 4% of EP additives. API GL-5 oils
containing up to 6.5% of EP additives are employed to lubricate automotive gears especially
susceptible to scuffing, i.e. hypoid gears, in axles operating under various combinations of
high-speed/shock-load and low-speed/high-torque conditions.
It should be emphasised here that a four-ball tribosystem is very often used for tribological
testing of the performance of automotive gear oils.
The lower graph in Figure 3 presents the friction torque curve (Mt) obtained at continuously
increasing load (P). The brackets over the graph indicate particular phases of the scuffing
process. In these phases, the friction coefficient values (µ) were determined, and they are given
in the red rectangles in the graph area. The thick red line below the graph denotes the time
from the beginning of the run until the occurrence of the scuffing initiation reflected by a sharp
rise in the friction torque.
The interpretative models of phenomena related to scuffing are presented over the graph in
Figure 3. Because the models concern the contact zone between two balls of the four-ball
tribosystem where the upper ball rotates and the lower ball is stationary, the direction of the
movement was indicated in the upper part of the models by an arrow. If there is no arrow, the
given model illustrates no movement of the balls, i.e. at the beginning of the run (before the
motor of the tribotester starts).
For the phase “scuffing initiation,” the upper model in Figure 3 illustrates the surface that did
not exhibit very rough topography typical of scuffing (shown in the surface topography
image), while the lower one concerns the surface already destroyed by scuffing.
In the models, three characteristic zones in the wear scar surface layer were identified: a
chemically modified zone through the action of the lubricating additives and the steel surface,
a zone of plastic deformation, and a zone of elastic deformation. All of these zones are described
in the legend above the models in Figure 3.
1.2.1. Phase: “Beginning of run”
After immersing the test balls in the tested gear oil and applying the initial load close to
0, a phenomenon known as physical adsorption or physisorption appears. In this phase,
adsorbed molecules constitute the boundary layer on the friction surface, which protects
the surface asperities against direct contact. The model with the heading “Beginning of
run” in Figure 3 illustrates this, reflecting the situation before the start of the relative
movement of the test balls.
Lubricating oil Chemically modified zone

........... Zone of plastic deformation
and chemical modification
Boundary layer Plastically deformed zone Elastically deformed zone
Desorbed molecules Core materials
Upper ball - rotating

Beginning of run e
ct zon
(microscale) nta Lower balls (3) - stationary
Co
Scuffing initiation
microscale
Mixed friction . . .
(microscale) . . .. ... . . . .. .. .
.. ...... ... ... ..... .. .... ...........
.. .... . .. . . . .. . . . . . . .
.............. .. ...................... ......... ....
.
. . . .. . . . . ..... . .. . .... ..... ..
.
. . . .. . .
. . . .. .. . . .. . . .. .... . . .. .
. ...... .. .. ... ... ..... ... .. .. .. ...........
. ....... .. ..... .. .. . .. . .. .. .... ..
. ..... ... ............ .. ...... ....... .
.. .. . . .. .... . .. .. .. .
. . .. ... . .. . .
Mixed friction Scuffing

(microscale) propagation
Scuffing
10 10000
9 GL-4/GL-5 9000
8 8000
 = 0.11
Friction torque, M t in Nm
7 7000
Applied load, P in N
6 6000
5
P 5000
4  = 0.10 4000
3 3000
2 Mt 2000
 = 0.15
1  = 0.12 1000
0 0
0 2 4 6 8 10 12 14 16 18
T ime in s
Figure 3. Models of scuffing in different phases for the automotive gear oils of the API GL-4 and GL-5 performance levels
Figure 3. Models of scuffing in different phases for the automotive gear oils of the API GL-4 and GL-5 performance
levels
1.2.2. Phase: “Mixed friction”
In publications, the terms “mixed friction” and “mixed lubrication” are often used equivalently and concern the same phenomena.
For the purpose of this chapter, one can assume that occurrences during the regime of the mixed lubrication result in the mixed
friction with its specific friction coefficient.
http://dx.doi.org/10.5772/54569
1.2.2. Phase: “Mixed friction”
In publications, the terms “mixed friction” and “mixed lubrication” are often used equivalently
and concern the same phenomena. For the purpose of this chapter, one can assume that
occurrences during the regime of the mixed lubrication result in the mixed friction with its
specific friction coefficient.
The phase “Mixed friction” concerns the first stage of the run from the moment of the start of
the relative movement between the test balls to the scuffing initiation reflected by a sharp rise
in the friction torque. Its duration is denoted by the thick red line below the graph with the
friction torque (Mt) and applied load (P) - Figure 3.
In this phase the mixed friction occurs. This can be stated on the basis of the fundamental
criterion that is the friction coefficient value. The friction coefficients typical of particular types
of friction were adopted from the work [5], where the four-ball tribosystem was also employed.
From that work, it implies that the mixed friction occurs in the four-ball tribosystem when the
friction coefficient is in the range between 0.07 and 0.1. Thus, the authors determined the
friction coefficient at the 2nd second of the four-ball experiment, being 0.1, denote the mixed
friction.
It is worth noting here that the idea of the occurrence of the mixed friction regime (instead of
EHL, i.e. elastohydrodynamic lubrication) at the very start of the relative movement between
the test balls (load is close to 0) is also supported in the mentioned work [5]. From that work
it is apparent that “pure” EHL occurs in the four-ball tribosystem only under conditions of a
low load and high speed.
At mixed friction, the micro-EHL films mainly carry the load and the mating surfaces are
protected from direct contact by the boundary layer. But at some micro-zones, due to the failure
of the micro-EHL film surface, asperities locally collide, which is illustrated in the model with
the heading “Mixed friction” in Figure 3.
Due to collisions of surface asperities, the temperature in the micro-contact rises. At a higher
temperature, physically adsorbed molecules may be attracted to the surface with greater
forces, and chemical adsorption or chemisorption appears. The decomposition of the active
compounds in the lubricating additives catalyses the transformation of some chemically
adsorbed molecules into chemical compounds at higher temperatures.
The collision of the surface asperities and the local high pressure of the oil induced by the
approaching asperities bring about elastic (reversible) and plastic (irreversible) deformations
of the contacting surface. Due to the thermal (temperature rise) and mechanical activation
(plastic deformation causing surface defects), the conditions exist for the initiation of the
diffusion of “active” atoms from the lubricating compounds (e.g. sulphur atoms) into the
surface layer.
The described phenomena lead to the formation of inorganic chemical compounds of iron with
sulphur, phosphorus, and oxygen, coming from EP lubricating additives in the tested gear oil.
Such additives (based on organic S-P compounds) form e.g. iron sulphide FeS [6]. FeS
compounds, apart from hampering the creation of adhesive bonds with their shear strength
being 1/5th that of steel and their hardness being 1/4th that of steel, facilitate shearing of the
chemically modified surface asperities, and the shear plane is transferred to the thin FeS layer,
which protects the surface from tearing out the material from deeper layers, reducing the wear
intensity.
For the tested oil, containing EP lubricating additives, the surface asperities are covered by the
protective layer of the above mentioned chemical compounds. This is illustrated in the
respective model in Figure 3. Due to this, for the gear oils with EP lubricating additives, the
scuffing initiation is delayed to appear at much higher loads than in the case of oils without
lubricating additives (e.g. API GL-1 ones, not presented here).
1.2.3. Scuffing phase: “Scuffing initiation”
In this phase, scuffing initiates - the friction torque (Mt) sharply increases and measured friction
coefficient values exceed the maximum value assumed for the mixed friction, i.e. 0.1 [5].
The scuffing initiation occurs at a load called the scuffing load, which is characteristic for each
tested lubricating oil. At this load, the lubricating film collapses, the number of colliding
surface asperities drastically increases, and the destruction changes its occurrence from the
micro- to macro-scale and scuffing appears. Initially only part of the friction surface undergoes
scuffing. It can be observed in the surface topography image of the border between the surface
that did not exhibit very rough topography typical of scuffing (left side) and the surface
destroyed by scuffing (right side) - Figure 3.
The described phenomena leading to scuffing are illustrated in the models with the heading
“Scuffing initiation” in Figure 3. The upper model concerns the surface that did not exhibit
very rough topography typical of scuffing, where still the mixed friction exists, while the lower
one refers to the surface already destroyed by scuffing.
The upper model shows that the micro-scale phenomena in the zone intact by scuffing are
similar to those described in the phase “Mixed friction” apart from the thickness of elastic and
plastic deformations which increased due to rising load. Probably, in view of plastic defor‐
mation that causes surface defects, the reactive diffusion of “active” atoms from the EP
lubricating additives (e.g. sulphur atoms) into the surface layer takes place and iron sulphides
form, which is confirmed by other researchers, e.g. in the work [7]. The diffusively modified
micro-zones inside the highest asperities are plastically deformed and are indicated in the
respective model as orange spots - Figure 3.
By observing phenomena in the part of the friction surface that undergoes scuffing, one can
indicate that the situation changes radically. The lower model illustrates that, in the first phase
of scuffing, the lubricating film no longer exists, nor is there any boundary layer. This leads to
a rapid intensification of the material destruction. Much plastic deformation appears, turning
into the transfer, flowing and mingling of the material of the rubbing test balls. For the tested
oils with EP lubricating additives, much of the surface layer starts to be chemically modified.
This will be decisive for the scuffing propagation character.
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1.2.4. Scuffing phase: “Scuffing propagation”
This phase refers to the scuffing process, after its initiation. It is reflected by a sharp increase
in the friction torque (Mt), accompanied by a high intensity of the lower test balls wear - Figure
4 a, b). This situation is illustrated in the models with the heading “Scuffing propagation” in
Figure 3.
(a) (b) (c)
Figure 4. Development of the wear of the lower test balls due to scuffing: a) at scuffing initiation, b) at 12th seconds of
the run (scuffing propagation), c) at the end of the run; images obtained at the same magnification
For the tested gear oils, after the scuffing initiation due to rapid chemical reactions of their EP
additives with the surface, a rise in the friction torque is mitigated to quickly stabilise at
relatively low value - Figure 3. It is accompanied by continuously evolving wear of the lower
test balls that is not intensive - Figure 4 b, c). A drop in the pressure in the contact zone due to
wear, brings about the possibility of oil introduction into the contact zone and the regeneration
of the boundary layer on much of the friction surface. Such an action is indicated by the friction
coefficient within the range 0.11 to 0.15, typical of boundary friction. On the basis of the work
[5], which also concerns four-ball experiments, it was assumed that the boundary friction
occurs in the four-ball tribosystem when the friction coefficient is in the range between 0.09
and 0.15. The determined values of the friction coefficient being in the middle and upper limit
typical of boundary friction denote that some part of the friction surface must have undergone
scuffing; It can be assumed from [5] that “full scuffing” occurs when the friction coefficient
exceeds 0.3. The specific state of the surface layer in this phase is called the “Secondary
Boundary Layer” (SBL) in the work [8]. The round model in the micro-scale concerning the
scuffing propagation (Figure 3) illustrates the places of oil appearance in the contact zone. Let
us call them “the micro-pockets.” One can presume that inside the oil micro-pockets the
following phenomena take place: the intensive adsorption and desorption of the base oil and
lubricating additives molecules on/from the steel surface, chemical reactions of the lubricating
additives with the surface, and - in view of plastic deformation that causes surface defects -
the diffusion of “active” atoms from the lubricating compounds (e.g. sulphur atoms) into the
surface layer. In view of the transfer and mingling of the material of the rubbing test balls, the
chemically modified zones appear across the entire zone of plastic deformations - orange spots.
For the API GL-4 and GL-5 gear oils, the effective chemical modification of the surface mitigates
the increase of the wear scar diameter - Figure 4 b, c) - in the phase of the SBL formation,
accompanied by a mitigated rise in the friction torque and a decreasing friction coefficient
(Figure 3).
1.3. Gear tests of scuffing
Nowadays, two manners of the improvement of the resistance to scuffing of gears are in use
in the world. One is focused on the improvement of extreme-pressure (EP) properties of gear
oils. The other one is related to the improvement of the properties of gear materials, e.g. by the
deposition of thin hard coatings onto the tooth flank surface.
The verification of the quality of gear oils and new techniques of surface engineering of the
tooth surface of gears requires that gear testing should be used. The most known is a unique
complex of gear test methods developed in the Gear Research Center (FZG) at the Technical
University of Munich. Approximately, 500 FZG gear test rigs are used around the world [9].
The most often used and popular gear tests for lubricating oils are performed using the FZG
A/8.3/90 scuffing test method. Unfortunately, this method makes it impossible to differentiate
between gear oils having very good extreme-pressure (EP) properties, from the point of view
of the resistance to gear scuffing [10]. This is why various scientific centres have developed
their own test methods [10-13].
Recognising the problem of the low resolution of A/8.3/90 scuffing test, the FZG has developed
two new scuffing methods denoted as A10/16.6R/90 and S-A10/16.6R/90 (S - shock). The new
test methods are described in detail in the literature, e.g. [14-19]. They are carried out under
much severer conditions compared to the A/8.3/90 test. This is a result of the reduced face
width of the small gear (pinion), doubling rotational speed, and reversing the direction of
rotation. Additionally, according to the S-A10/16.6R/90 method, the test is started at once with
a load at which the failure is expected, hence the name “scuffing shock test.” Shock loading
prevents the test gears from running-in and in turn increases their susceptibility to scuffing,
which further increases the method resolution.
Nowadays, one of the research directions in numerous scientific centres in the world is an
improvement in the scuffing resistance of toothed gears, achievable by the deposition of thin,
hard, low-friction coatings onto the gear teeth, e.g. the a-C:H:W or MoS2/Ti coatings [20-22].
For the last several years, intensive research work has also been performed on this subject in
the Tribology Department of ITeE-PIB. Until now, the FZG A/8.3/90 gear scuffing test method
has been used most often in various scientific centres, which, like in the case of testing gear
oils, exhibits a resolution that is too low to differentiate between the coated gears from the
point of view of their resistance to scuffing [23-25] - Figure 5. It should be explained here that
a-C:H:W and a-C:H coatings are DLC (diamond-like carbon) coatings, and the a-C:H:W coating
has an outermost DLC layer doped with W (tungsten).
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13
12
11
10
9
FLS
8
7
6
5
4
a-C:H:W - a-C:H:W MoS2/Ti - MoS2/Ti a-C:H - a-C:H
Figure 5. Failure load stages (FLS) obtained for the tested coatings (both gears coated) - FZG A/8.3/90 test method;
data compiled from [23-25]
It is apparent from Figure 5 that the failure load stages (FLS), indicating the gear resistance to
scuffing exceed the maximum number 12, so that the it is impossible to differentiate between
the coated gears using the FZG A/8.3/90 test method.
To solve this problem, in the Tribology Department of ITeE-PIB, research was undertaken to
apply the new FZG scuffing tests for coated gears to differentiate between their resistance to
scuffing. Because the FZG test methods are dedicated exclusively to lubricating oils, their
application for testing coated gears required introducing significant modifications - unique
test methods have been developed, being the subject of this chapter. They are called the “Gear
Scuffing EP Test for Coatings” and “Gear Scuffing Shock Test for Coatings.”
2. New test methods
2.1. Idea of the methods
The main difference between the test methods designed by the authors and the gear scuffing
tests A10/16.6R/90 and S-A10/16.6R/90, developed by FZG, is a rise in the initial oil temperature
to 120 °C, adoption of a failure criterion related to wear of the wheel (big gear), and resigning
from the criterion of invalidation of the test results when wear of the wheel exceeds 20 mg.
The tests are performed on a pair of lubricated test gears with a coating (it can be applied on
one or both the gears) at a constant rotational speed, and at the initial temperature of the
lubricating oil identical for all the runs - until a failure load stage (FLS) is determined, i.e., such
a load at which at least one of the failure criteria is met. In the Gear Scuffing EP Test for
Coatings, based on the FZG S-A10/16.6R/90 test, the load is increased stepwise, from the lowest
to the highest value. According to the Gear Scuffing Shock Test for Coatings, based on the FZG
S-A10/16.6R/90 test the load is not increased in stages from the lowest value, but the expected
failure load is applied to an unused gear flank (hence, the name “shock test”). In the shock test,
each change of the load requires an unused gear flank; therefore, before subsequent runs, the
test gears should be disassembled and reversed or replaced with new ones.
Although the authors have introduced some significant changes to the FZG gear scuffing tests,
the core procedures of performing the tests are the same as in the FZG tests, and they can be
found in the relevant publications, e.g. in [14].
To better explain the differences between the “old” FZG gear scuffing test A/8.3/90 and the
new test methods designed by the authors, the test conditions according to each method and
the failure criteria are specified in Table 1.
After starting the run, the oil in the test chamber is heated by the heaters and friction. The oil
temperature is allowed to rise freely. No cooling system is used in the tests.
Like in the FZG gear scuffing tests, if the failures are observed only within 1 mm from the tooth
addendum, they are only scratches, or the failures are so small that the original criss-cross-
grinding pattern (Figure 6) is still intact, they should be neglected when calculating the total
area of the failures.
Figure 6. Original criss-cross-grinding pattern on the test gear teeth - stylus profilometry image
The failure load stage (FLS) is the main measure of the resistance of the test gears to scuffing.
According to the Gear Scuffing EP Test for Coatings, the FLS is such a load at which the main
failure criterion specified in Table 1 has been met. According to the Gear Scuffing Shock Test
for Coatings, the FLS is such a load at which at least one of the failure criteria has been met
and, when at the load stage lower by 1, neither of the failure criteria has been met.
When there is significant decohesion of the coating due to poor adhesion to the surface, the
run should be invalidated.
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Gear scuffing test Gear Scuffing EP Test for Gear Scuffing Shock Test for
FZG A/8.3/90 Coatings Coatings
based on FZG A10/16.6R/90 based on FZG S-A10/16.6R/90
Purpose of test Testing lubricating Testing coatings deposited on Testing coatings deposited on
oils gears gears
Test gear type FZG A-type FZG A10-type FZG A10-type

(pinion and wheel (pinion width 10 mm, wheel (pinion width 10 mm, wheel width
width 20 mm) width 20 mm) 20 mm)
Test materials 20MnCr5 20MnCr5, but at least one gear 20MnCr5, but at least one gear
coated coated
Motor rotational speed 1500 rpm 3000 rpm 3000 rpm
Circumferential speed 8.3 m/s 16.6 m/s 16.6 m/s
Direction of motor rotation “Normal” “Reversed” (R) “Reversed” (R)
Run duration 15 min. 7 min. 30 s 7 min. 30 s
Maximum load stage 12 10 12
Maximum loading torque 535 N·m 373 N·m 535 N·m
Maximum Hertzian pressure1.8 GPa 2.2 GPa 2.6 GPa
Loading type Stepwise, from load Stepwise, from load stage 1 Shock
stage 1 (i.e. starting with a load at which
the failure is expected)
Initial lubricating oil 90 ºC 120 ºC 120 ºC

temperature
Temperature stabilisation No No No
during the run by cooling
Type of lubrication Dip lubrication Dip lubrication Dip lubrication
Main failure criterion for Ap ≥ area of one Ap > area of one Ap > area of one
FLS determination pinion tooth (≈200 pinion tooth (≈100 mm2) pinion tooth (≈100 mm2), or Ww >
mm2)a 200 mgb
Additional criteria of failure None Failures on the pinion teeth Failures on the pinion teeth
assessment
Criterion of invalidation of None Significant decohesion of the Significant decohesion of the

the run coating coating
a
Ap - total area of failures on the pinion
b
Ww - wear (mass loss) of the wheel
Table 1. Comparison of the FZG gear scuffing test and the methods designed by the authors
After run completion at a given load stage, the failures on the pinion teeth should be noted
using the symbols from Table 2. These data are used for additional failure assessment,
complementarily to FLS.
Mode of wear Symbol Appearance
Polishing W
Scratches R
Scoring B
Scuffing Z
Table 2. Modes of wear of the test pinion (small gear)
Polishing can be identified when the “mirror-like” surface on the tooth flank is observed with
the disappearing criss-cross-grinding pattern shown in Figure 6.
Scratches appear as shorter or longer fine lines in the sliding direction of the tooth flanks.
Scoring marks run in the same direction as scratches. On the basis of CEC L-07-95 standard
[26], it can be adopted that they occur singly or in zones as light, medium or deep grooves
continuing towards the tip of the tooth and having a rougher appearance than the criss-cross-
grinding pattern (Figure 6).
Scuffing marks occur as single, fine marks or strips, or areas covering a part or all of the flank
width. According to CEC L-07-95 standard, they appear as dull areas with the roughness much
greater than the original criss-cross-grinding pattern shown in Figure 6. In this case, the
grinding pattern is no longer visible.
The difference between scuffing and scoring is that scuffing originates from the adhesive bond
creation between the mating surfaces, which are then sheared, and scoring results from
mechanical abrasion of the surface by the very hard wear particles under conditions of a very
high load. Like scuffing, scoring is one of the most dangerous modes of gear wear.
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When both test gears are uncoated, a respective standardised test method A10/16.6R/90 or
S-A10/16.6R/90, developed by FZG should be used. However, to compare the results with
the new test methods, it is necessary to start a run at the initial oil temperature of 120 °C
rather than 90 °C.
2.2. Test gears
A photograph of the FZG A10 scuffing test gears employed in the tests according to the
developed methods is shown in Figure 7.
Figure 7. Photograph of the FZG A10 scuffing test gears
The A10 test gears are made of 20MnCr5 steel. They are carburized, case hardened, tempered
and Maag criss-cross ground. The surface hardness is HRC = 60 + 2 and the case hardness depth
(CHD) is 0.6 to 0.9 mm (Eht). The effective face width of the pinion is 10 mm, and the wheel is
20 mm. The number of pinion teeth is 16, and wheel 24. The gears are identical to the ones used
to perform tests according to the FZG A10/16.6R/90 and S-A10/16.6R/90 methods.
2.3. Test equipment
For the complex testing of gears, a back-to-back gear test rig, denoted as T-12U, was designed
in the Tribology Department of ITeE-PIB in Radom. Its photograph is presented in Figure 8
and kinematic schemes are presented in Figure 9.
The T-12U test rig is equipped with a control-measuring system, which consists of measuring
transducers (thermocouple, speed transducer) and the controller (Figure 8).
Figure 8. Photograph of the T-12U gear test rig
(a) (b)
(c)
Figure 9. Kinematic schemes of the T-12U gear test rig: a) front view, b) top view, c) loading equipment; 1 - thermo‐
couple, 2 - test wheel, 3 - test pinion, 4 - vent, 5 - test chamber, 6 - shafts torsion angle indicator, 7 - load clutch, 8 -
front shaft, 9 - slave chamber, 10 - drive clutch, 11 - electric motor, 12 - loading lever, 13 - weight hanger, 14 - weights,
15 - heaters, 16 - frame, 17 - concrete base
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During runs, the following quantities are measured: rotational speed, lubricating oil temper‐
ature, motor current load, time, and the number of motor revolutions. The measured values
are displayed on the controller.
The test rig is mounted on the concrete base equipped with vibration-dumping feet.
The T-12U gear test rig is a back-to-back rig (Figure 9) where the test gears (2) and (3), located
in the test chamber (5), are connected by two shafts to the slave gears, located in the chamber
(9). The front shaft (8) has two parts. Between them there is the load clutch (7). To apply the
loading torque between the meshing gears, before the run, one part of the shaft (the left part
of the front shaft (8) is fixed to the base with the lock-pin via the clutch and its support. A
round-shaped loading lever (12) is placed on the right part of the clutch (7), and then the weight
hanger (13) is suspended and the appropriate number weights (14) put on it. They give a static
loading torque by twisting the shafts, which is measured indirectly using the torsion angle
indicator (6). When the load has been applied, the two halves of the clutch (7) are firmly fixed
against each other with the bolts. Then, the lock-pin is removed to close the safety cover. During
the run, this loading torque “circulates” between the gears. In the back-to-back solution the
motor (11) must overcome only the friction between gears, rolling bearings, and some minor
components of friction (friction against seals, internal friction in the oil). Thus, the whole design
is very simple and compact.
An AC squirrel-cage motor (11) of the nominal rotational speed of 3000 rpm is used to drive
the rig. It is controlled by the frequency converter, which enables to change the rotational speed
within a wide range.
In the gear scuffing tests the test gears are dip lubricated. In the test chamber where the test
gears are located, there are heaters (15) to heat up the lubricating oil. The thermocouple (1),
with the measuring point inserted in the lubricating oil, is to measure the oil temperature. A
PID regulator is used to protect against overheating of the lubricating oil.
The motor (11) of the machine is automatically stopped when the preset time elapses. The
required time is set on the controller panel. Additionally, the operator can read out the number
of motor revolutions to confirm the correct duration of the run. The number of motor revolu‐
tions is displayed on the controller panel (Figure 8) connected to the speed transducer.
In the T-12U machine, the friction torque can be measured indirectly by measurement of the
motor current load, which can be assumed to be proportional to the friction torque.
The test rig has a special support on the side cover of the test chamber (5) for mounting
vibration transducers (accelerometers) to enable the operator to monitor the level of vibrations
along different axes. However, now there is no possibility to automatically stop the motor
when the vibration level is very high. This feature (together with other features like direct
measurement of the friction torque) will be included in a new test rig, denoted as T-12UF, being
developed at present.
Additional equipment includes a mass comparator for a very precise determination of the mass
loss (wear) of the wheel.
2.4. Test materials
The gears coated with the low-friction a-C:H:W coating (trade name: WC/C) of DLC type and
composite low-friction MoS2/Ti coating (trade name: MoST) were tested. All material combi‐
nations were tested: coating-coating (both gears coated), coating-steel, steel-coating, and steel-
steel for reference (both gears without the coating). In all cases, mineral, automotive gear oil
of API GL-5 performance level and of SAE 80W-90-viscosity grade was used for lubrication.
2.5. Statistical analysis
To check statistical differences between the results obtained (FLS values), the uncertainty of
measurement was assessed for the both developed test methods. This was done according to
the procedures specified in the document EA-4/16 G:2003, which are binding in the accredited
laboratories meeting the requirements of ISO/IEC 17025:2005.
Once the uncertainty of measurement has been calculated, the test result “y” and the uncer‐
tainty of measurement “U” should be reported as ”y ± U.”
As a normal practice, the uncertainty of measurement is given in relation to the average value
of the measurement. For example, in the case of the gear scuffing shock tests, the respective
formula derived by the authors is expressed as follows:
U = 0.45 + 0.06 * FLS (1)
where:
U - uncertainty of measurement,
FLS - failure load stage.
According to ILAC-G8:03/2009, if the uncertainty intervals expressed by U do not overlap each

other, one can say that the compared results are statistically different.
3. Results and discussion
3.1. Gear Scuffing EP Test for Coatings
3.1.1. Material combinations with the a-C:H:W coating
Failure load stages (FLS) obtained for the tested material combinations with the a-C:H:W
coating are presented in Figure 10. The coated gear is dark grey coloured, and the uncoated
one is light grey.
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11
10
9
8
FLS
7
6
5
4
Combination of tested materials
Figure 10. Failure load stages (FLS) obtained using the Gear Scuffing EP Test for Coatings for the tested material com‐
binations with the a-C:H:W coating
Figure 10 shows that the Gear Scuffing EP Test for Coatings is unable to differentiate between
the tested material combinations from the point of view of the main criterion - FLS. All the FLS
values exceed the maximum load stage, i.e. 10th. Thus, the additional criteria of failure
assessment, related to the wear of the pinion after runs at particular load stages, were taken
into account - Table 3. The table presents the symbolic modes of the wear of the test pinion at
particular load stages for the tested material combinations with the a-C:H:W coating, and the
mode of wear that appeared most often on the pinion teeth was considered. Below are the
symbols of the wear modes, the total area of failures on the pinion (Ap) are given. The used
symbols of wear were presented earlier in Table 2.
Load stage
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap ≈ 0
Load stage
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap ≈ 0
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap ≈ 0
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap ≈ 0
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap ≈ 0
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap ≈ 0
10
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap ≈ 0
Table 3. Modes of the wear of the test pinion at particular load stages for the tested material combinations with the
a-C:H:W coating, together with the total area of failures on the pinion (Ap); Gear Scuffing EP Test for Coatings
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As can be observed in Table 3 for the tested material combinations, the three modes of wear
that appear most often on the pinion teeth are scratches, polishing, and scoring. The uncoated
pinion undergoes the process of polishing through the rubbing by the hard a-C:H:W coating
deposited on the meshing wheel. Similar action was observed on the uncoated wheel meshing
the coated pinion (results not shown here). The role of such polishing is to be explained in
further experiments planned by the authors.
To sum up this part of the experiment, the Gear Scuffing EP Test for Coatings gives minor
differences between the tested material combinations with the a-C:H:W coating, observed only
when the pinion is uncoated and the wheel is coated. From the point of view of the practical
applications of the a-C:H:W coating in gears, the situation when the both gears are coated
seems to be better than in the case of one of the gears uncoated, because it is exposed to the
abrasive action of the meshing coated gear, which results in polishing and scoring.
3.1.2. Material combinations with the MoS2/Ti coating
Failure load stages (FLS) obtained for the tested material combinations with the MoS2/Ti
one is light grey.
11
10
9
8
FLS
7
6
5
4
Figure 11. Failure load stages (FLS) obtained using the Gear Scuffing EP Test for Coatings for the tested material com‐
binations with the MoS2/Ti coating
Figure 11 shows that the Gear Scuffing EP Test for Coatings is unable to differentiate
between the tested material combinations from the point of view of the main criterion - FLS.
As in the case of testing the a-C:H:W coating, all the FLS values exceed the maximum load
stage, i.e. 10th. Thus, the additional criteria of failure assessment, related to the wear of the
pinion after runs at particular load stages, were taken into account - Table 4. The table
presents the symbolic modes of the wear of the test pinion at particular load stages for the
tested material combinations with the MoS2/Ti coating, which is the mode of wear that
appeared most often on the pinion teeth was considered. Below are the symbols of the wear
modes, and the total area of failures on the pinion (Ap) are given. The used symbols of wear
were presented earlier in Table 2.
Load stage
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap ≈ 0
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap ≈ 0
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap = 5 mm2
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap = 10 mm2
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap = 10 mm2
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Load stage
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap = 10 mm2
10
Ap ≈ 0 Ap ≈ 0 Ap ≈ 0 Ap = 10 mm2
MoS2/Ti coating, together with the total area of failures on the pinion (Ap); Gear Scuffing EP Test for Coatings
As can be observed in Table 4 for the tested material combinations, the two modes of wear that
appear most often on the pinion teeth are scratches and scoring. In the material combination
of the uncoated pinion meshing the coated wheel, the pinion bears the mark of scoring caused
by the rubbing by the hard coating deposited on the meshing wheel.
Thus, the Gear Scuffing EP Test for Coatings gives minor differences between the tested
material combinations with the MoS2/Ti coating, observed only when the pinion is uncoated
and the wheel is coated. From the point of view of the practical applications of the MoS2/Ti
coating in gears, the situation when the both gears are coated seems to be better than in the
case of one of the gears uncoated as it is exposed to the abrasive action of the meshing coated
gear, which results in scoring. However, when one of the gears needs to remain uncoated,
using the a-C:H:W coating is more preferable than MoS2/Ti, because a-C:H:W causes less wear
of the uncoated gear.
3.2. Gear scuffing shock test for coatings
3.2.1. Material combinations with the a-C:H:W coating
Failure load stages (FLS) obtained for the tested material combinations with the a-C:H:W
one is light grey. The assessed uncertainties of measurement for each result obtained are also
shown in the Figure.
Figure 12 shows that the Gear Scuffing Shock Test for Coatings makes it possible to differentiate
between the tested material combinations. The best resistance to scuffing (highest FLS) is
observed when both gears are coated.
14
13
12
11
10
FLS
9
8
7
6
5
4
Figure 12. Failure load stages (FLS) obtained using the Gear Scuffing Shock Test for Coatings for the tested material
combinations with the a-C:H:W coating
Under “shock” conditions, when the pinion is uncoated and the wheel is coated with the a-
C:H:W coating, the resistance to scuffing is slightly higher than in the case when the pinion is
coated and the wheel is uncoated. Hypothetically, there is a transfer of graphite (solid
lubricant) from the a-C:H:W coated gear to the teeth of the uncoated one, which is more
effective for the wheel coated than in the opposite situation, because the area of the coated
steel surface of the wheel (larger gear with 24 teeth) is greater than in the case the coating is
deposited on the pinion (small gear having only 16 teeth). However, one must have in mind
that the difference in the scuffing resistance of the two material combinations is not statistically
significant, because the measurement uncertainties overlap each other.
In comparison to the case of the both gears uncoated, when the a-C:H:W coating is deposited
on one or two gears, much higher resistance to scuffing is observed. This is a result of a high
surface energy for metals (here for steel) promoting adhesive bonding in the steel-steel contact,
and smaller affinity in the different materials than when both of them are identical (i.e. steel-
steel), which protects the surface from adhesive bonding. Yet another phenomenon can be
attributed to it. When one of the mating materials (coating) is much harder than the other one
(steel), or when two very hard materials are in contact (coating-coating) there is a reduction in
the tendency to adhesive bonding, hence scuffing.
The additional criteria of failure assessment, related to the wear of the pinion after runs at
particular load stages, were also taken into account - Table 5. The table presents the symbolic
modes of the wear of the test pinion at particular load stages for the tested material combina‐
tions with the a-C:H:W coating, which is the mode of wear that appeared most often on the
http://dx.doi.org/10.5772/54569
pinion teeth was taken into account. The photographs of the most often appearing mode of
wear of the pinion at the highest load stage are shown also shown in the table. Red-shadowed
cells in the table denote the failure load stage (FLS). Below are given the symbols of the wear
modes, the total area of failures on the pinion (Ap), and wear of wheel (Ww). The used symbols
of wear were presented earlier in Table 2.
As can be observed in Table 5 for the tested material combinations, the three modes of wear
that appear most often on the pinion teeth are scratches, scuffing, and scoring. When one or
both gears are a-C:H:W-coated, only scratches and scoring predominate on the pinion teeth.
What was observed also during the Gear Scuffing EP Test for Coatings, and what seems to by
typical of “the action” of the a-C:H:W coating, the uncoated gear undergoes the process of
polishing or scoring through the rubbing by the hard coating deposited on the meshing gear.
The polishing on the wheel teeth flanks can be seen in Figure 13.
Figure 13. Photograph of the tooth flank of the uncoated wheel, polished by the a-C:H:W-coated pinion; Gear Scuff‐
ing Shock Test for Coatings
Load stage
Ap = 26 mm2
Ww = 1 mg
Load stage
Ap = 703 mm2
Ww - not measured
9
10
Ap ≈ 0
Ww = 180 mg
11
Ap = 5 mm2 Ap ≈ 0
Ww = 76 mg Ww = 2 mg
Ap ≈ 0
Ww = 338 mg
12
Ap = 6 mm2 Ap = 318 mm2

Ww = 145 mg Ww = 3 mg
a-C:H:W coating, together with the total area of failures on the pinion (Ap), and wear of wheel (Ww), obtained in the
Gear Scuffing Shock Test for Coatings; red-shadowed cells - the failure load stage (FLS)
http://dx.doi.org/10.5772/54569
Scuffing is observed only when both gears are uncoated - Table 5. This is one of the most
dangerous modes of gear wear. As mentioned earlier, scuffing marks occur as single, fine
marks or strips, or areas covering a part or all of the flank width. They appear as dull areas
with the roughness much greater than the original criss-cross-grinding pattern shown in
Figure 6. In this case, the grinding pattern is no longer visible.
To sum up this part of the experiment, the Gear Scuffing Shock Test for Coatings gives a much
better resolution than the Gear Scuffing EP Test. However, one needs to have in mind that the
cost of the former is about four-times higher than in the case of the latter, because the “shock
tests” require more test gears to be used. From the point of view of the practical applications
of the a-C:H:W coating in gears, the situation when the both gears are coated seems to be better
than in the case of one of the gears uncoated, because it is exposed to the abrasive action of the
meshing coated gear, which results in polishing or scoring. This positively verifies the
observations taken during performing the Gear Scuffing EP Test for Coatings.
3.2.2. Material combinations with the MoS2/Ti coating

Failure load stages (FLS) obtained for the tested material combinations with the MoS2/Ti
coating are presented in Figure 14.
14
13
12
11
10
FLS
9
8
7
6
5
4
Figure 14. Failure load stages (FLS) obtained using the Gear Scuffing Shock Test for Coatings for the tested material
combinations with the MoS2/Ti coating
Figure 14 shows that the best resistance to scuffing (highest FLS) is observed when both gears
are coated with the MoS2/Ti coating, or when the uncoated pinion meshes the coated wheel.
As in the case of the a-C:H:W coating, when only the wheel is MoS2/Ti-coated, under “shock”
conditions the resistance to scuffing is higher than in the situation when only the pinion coated.
Hypothetically, there is a transfer of MoS2 (solid lubricant) from the teeth of the coated gear to
the uncoated one. The transfer is more effective in the case of the MoS2/Ti-coated wheel
meshing the uncoated pinion than in the opposite situation, because the area of the coated steel
surface of the larger gear (wheel) is greater than in the case when the coating is deposited on
the small gear (pinion).
In comparison to the case when both gears are uncoated, a much higher resistance to scuffing
is observed when the MoS2/Ti coating is deposited on one or two gears. The respective
mechanisms of this behaviour were described earlier.
Table 6 presents the symbolic modes of wear of the test pinion at particular load stages for the
tested material combinations with the MoS2/Ti coating. As in the case of the a-C:H:W coating,
the mode of wear that appeared most often on the pinion teeth was taken into account. The
photographs of the most often appearing mode of wear of the pinion at the highest load stage
are also shown in the table. Red-shadowed cells in the table denote the failure load stage (FLS).
Below are given the symbols of the wear modes, the total area of failures on the pinion (Ap)
and wear of wheel (Ww). The symbols of wear were presented earlier in Table 2.
As can be observed in Table 6 for the tested material combinations, the two modes of wear that
appear most often on the pinion teeth are scuffing and scoring. When one or both gears are
coated, only scoring predominates on the pinion teeth.
When the pinion is coated and the wheel is uncoated, and when both the gears are coated, identical
results were obtained for the two investigated coatings - FLS values are respectively 11 and
higher than 12 (Figures 12 and 14). Therefore, the main criterion of assessment of the resist‐
ance to scuffing (FLS) makes it impossible to differentiate between these two situations. Under
these circumstances, the analysis of additional criteria of failure assessment, related to the modes
of wear at particular load stages, like in the previous cases can give additional, valuable
information. In the case of the material combinations with the a-C:H:W coating, the predominat‐
ing mode of wear of the pinion were only scratches. For the material combinations with the
MoS2/Ti coating, the pinion wear was much more sever, and scoring instead of scratches could
be met most often. Thus, the a-C:H:W coating provides better protection against severe wear
than MoS2/Ti, especially when it is deposited on the both gears. This positively verifies the
observations taken during performing the Gear Scuffing EP Test for Coatings.
Load stage
Ap = 26 mm2
Ww = 1 mg
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Load stage
Ap = 703 mm2
Ww - not measured
9
10
Ap = 32 mm2
Ww = 11 mg
11
Ap ≈ 0 Ap ≈ 0
Ap = 109 mm2
Ww = 25 mg
12
Ap ≈ 0 Ap ≈ 0
Table 6. Modes of wear of the test pinion at particular load stages for the tested material combinations with the
MoS2/Ti coating, together with the total area of failures on the pinion (Ap), and wear of wheel (Ww), obtained in the
Gear Scuffing Shock Test for Coatings; red-shadowed cells - the failure load stage (FLS)
4. Summary and conclusions
The authors have developed unique test methods, being the subjects of this chapter. They are
called the “Gear Scuffing EP Test for Coatings” and “Gear Scuffing Shock Test for Coatings.”
The analysis of the values of the failure load stage (FLS), reflecting the resistance to scuffing,
shows that the developed Gear Scuffing EP Test for Coatings has too little resolution to
differentiate between the tested material combinations - coating-coating (both gears coated),
coating-steel, steel-coating, and also steel-steel (both gears without a coating). Additional
criteria of failure assessment need to be employed to reveal minor differences between the
tested material combinations observed only when the pinion is uncoated and the wheel is
coated.
In comparison, Gear Scuffing Shock Test for Coatings makes it generally possible to differen‐
tiate between the tested material combinations from the point of view of the main criterion of
assessment of the gear resistance to scuffing, i.e. FLS. Thus, this test method has a sufficient
resolution. However, as in the case of the Gear Scuffing EP Test for Coatings, apart from the
analysis of only FLS values, analysis of the additional criteria of failure assessment related to
predominating modes of wear at particular load stages is recommended and may give
additional, valuable information. For the two coatings tested (a-C:H:W and MoS2/Ti), the best
resistance to scuffing/scoring (FLS > 12) is observed when both gears are coated; however, the
a-C:H:W coating gives a slightly better protection against severe wear than MoS2/Ti - only
scratches instead of scoring are observed for a-C:H:W.
Although the Gear Scuffing Shock Test for Coatings gives a much better resolution than the
Gear Scuffing EP Test, one needs to have in mind that the cost of the former is about four-times
higher than in the case of the latter, because the “shock tests” require more test gears to be
used.
In the both tests, when one or both gears are coated, three modes of wear occur most often on
the pinion teeth - polishing, scratches, or scoring. Scuffing is observed only when the two gears
are uncoated.
The following conclusions can be drawn:

• The developed Gear Scuffing Shock Test for Coatings has been successfully verified by the
testing of thin, hard coatings deposited on the gears; therefore, it can be implemented in the
laboratories of the R&D centres devoted to surface engineering and the engineering of
advanced materials intended for modern toothed gears, having in mind that this test is
rather expensive.
• If the coating is intended for application on gears, from the point of view of the high‐
est achievable resistance to scuffing/scoring, it is recommended that both meshing gears
are a-C:H:W-coated.
• Although the T-12U gear test rig has been effectively employed in the performed research,
it is suggested that its research capacities should be extended by the measurement and data
http://dx.doi.org/10.5772/54569
acquisition of the friction torque, which will make it possible to investigate, as postulated
by gear transmissions manufacturers, the possibility of the reduction of friction between the
meshing teeth by the application of a low-friction coating. At present, a new version of the
T-12U test rig, denoted as T-12UF, is being developed within the framework of the Strategic
Programme executed at ITeE-PIB in Radom, and the planned deadline of this work is in
2013.
• Both the differentiation between the tested objects (lubricating oils, material combinations)
and the predictability of gear failures in real applications (transmissions) are important
when assessing gear tests. This is why the authors plan to verify the results obtained by
application of coated gears in transmissions (speed reducers) of different devices manufac‐
tured by one of the Polish producers. What is more, at present another test rig - a back-to-
back bevel gear test rig, denoted as T-30 - is being developed in the Tribology Department
of ITeE-PIB in Radom with the deadline in 2012. The reason is that until now widely used
test devices and methods have allowed researchers to perform runs on only spur gears
having the tooth geometry significantly different than the geometry of bevel gears. The new
tribotester will allow researchers to better predict the failures of bevel gears.
Acknowledgements
Scientific work was financed:

• From the means of the Minister of Science and Higher Education, executed within the
Strategic Programme “Innovative Systems of Technical Support for Sustainable Develop‐
ment of the Country’s Economy” within Innovative Economy Operational Programme.
• By the National Centre for Research and Development (NCBiR) within the scope of the R&D
project No. N R03 0019 06.
The authors wish to express their thanks also to Dr. Maksim Antonov from Tallinn University
(Estonia) for his support with the gear scuffing tests and helpful discussions, within the
framework of Marie Curie RTN (6th EU FP); Contract No MRTN-CT-2006-035589.
Author details
Remigiusz Michalczewski*, Marek Kalbarczyk, Michal Michalak, Witold Piekoszewski,

Marian Szczerek, Waldemar Tuszynski and Jan Wulczynski
*Address all correspondence to: remigiusz.michalczewski@itee.radom.pl
Institute for Sustainable Technologies - National Research Institute (ITeE-PIB),Tribology De‐

partment, Radom, Poland
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Materials for Production of Gear Wheels. ZEM 1975; 1 39-58 (in Polish).
[2] Tomaszewski J., Drewniak J., editors. Scuffing of Gears. Gliwice: CMG KOMAG; 2007
(in Polish).
[3] ARTEC Machine Systems. Failure by scuffing due to poor distribution of load. http://
www.artec-machine.com/images/failure_due_to_poor_distribution_of_load_1.pdf
(accessed 22 September 2012).
[4] Kratz S.H., Wedeven L.D., Black W.F., Carlisle D.J., Wedeven G.G. Simulation of Space
Shuttle Gear Performance. In: proceedings of the III World Tribology Congress, 2005,
Washington, USA.
[5] Kuo W.F., Chiou Y.C., Lee R.T. A Study on Lubrication Mechanism and Wear Scar in
Sliding Circular Contacts. Wear 1996;201 217-226.
[6] Ku P.M., editor. Interdisciplinary Approach to Friction and Wear. Washington D.C.:
Southwest Research Institute; 1968.
[7] Makowska M., Matuszewska A., Gradkowski M. Migration of Active Elements from a
Lubricant to the Material of the Friction Pair. Tribologia 2011;4 163-176 (in Polish).
[8] Wachal A. Analysis of Boundary Layer Estimating Criteria in Lubricating Oils Inves‐
tigations. ZEM 1983;3 325-332.
[9] Höhn B.-R., Oster P., Schedl U. Pitting Load Capacity Test on The FZG Gear Test Rig
with Load-Spectra and One-Stage Investigations. Tribotest journal 1999;5-4 417-430.
[10] Szczerek M., Tuszynski W. A Method for Testing Lubricants under Conditions of
Scuffing. Part I. Presentation of the Method. Tribotest journal 2002;8-4 273-284.
[11] Piekoszewski W., Szczerek M., Tuszynski W. The Action of Lubricants under Extreme
Pressure Conditions in a Modified Four-Ball Tester. Wear 2001;249 188-193.
[12] Tuszynski W., Michalczewski R., Piekoszewski W., Szczerek M. Effect of Ageing
Automotive Gear Oils on Scuffing and Pitting. Tribology International 2008;41 875-888.
[13] Bisht R.P.S., Singhal S. A Laboratory Technique for the Evaluation of Automotive Gear
Oils of API GL-4 Level. Tribotest journal 1999;6-1 69-77.
[14] Method to Assess the Scuffing Load Capacity of Lubricants with High EP Performance
Using an FZG Gear Test Rig. FVA Information Sheet No. 243 Status June 2000.
[15] Höhn B.-R., Michaelis K., Eberspächer C., Schlenk L. A Scuffing Load Capacity Test
with the FZG Gear Test Rig for Gear Lubricants with High EP Performance. Tribotest
journal 1999;5-4 383-390.
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[16] Michaelis K., Höhn B.-R., Graswald C. Scuffing Tests for API GL-1 to GL-5 Gear
Lubricants. In: proceedings of the 13th International Colloquium Tribology, 2002,
Ostfildern, Germany.
[17] Michaelis K., Höhn B.-R., Oster P. Influence of Lubricant on Gear Failures - Test
Methods and Application to Gearboxes in Practice. Tribotest journal 2004;11-1 43-56.
[18] Höhn B.-R., Oster P., Tobie T., Michaelis K. Test Methods for Gear Lubricants. Goriva
i maziva 2008;47-2 141-152.
[19] Tuszynski W. Performance Classification of Automotive Gear Oils Using the Gear
Scuffing Shock Test. Tribologia 2009;2 259-274 (in Polish).
[20] Kalin M., Vižintin J. The Tribological Performance of DLC-Coated Gears Lubricated
with Biodegradable Oil in Various Pinion/Gear Material Combinations. Wear 2005;259
1270-1280.
[21] Martins R.C., Moura Paulo S., Seabra J.O. MoS2/Ti Low-Friction Coating for Gears.
Tribology International 2006;39 1686-1697.
[22] Martins R., Amaro R., Seabra J. Influence of Low Friction Coatings on The Scuffing
Load Capacity and Efficiency of Gears. Tribology International 2008;41 234-243.
[23] Szczerek M., Michalczewski R., Piekoszewski W. The Problems of Application of PVD/
CVD Thin Hard Coatings for Heavy-Loaded Machine Components. In: proceedings of
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[24] Michalczewski R., Piekoszewski W., Szczerek M., Tuszynski W. The Lubricant-Coating
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[25] Michalczewski R., Piekoszewski W., Szczerek M., Tuszynski W. Scuffing Resistance of
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[26] CEC L-07-95: Load Carrying Capacity Test for Transmission Lubricants (FZG Test Rig).
Chapter 7
Introduction of the Ratio of the Hardness to

the Reduced Elastic Modulus for Abrasion
Giuseppe Pintaude
http://dx.doi.org/10.5772/55470
1. Introduction
Modeling the wear rate is a complex process. The several possibilities of chemical, physical
and mechanical changes at the interface are the most probable reasons for this [1]. In this
manner, it is reasonable to consider the wear rate as a stochastic process [2, 3], and indeed this
approach was taken into account by Archard [4], when he formulated his well-known model.
Since then, the majority of available models are based on his proposition, independent on the
characteristics of mechanical system. Considering a sharp contact, both Torrance [5] and Yi-
Ling & Zi-Shan [6] for sliding and rolling abrasion, respectively, modified Archard’s equation
based on elastic effects, and the ratio of the hardness (H) to the Young’s modulus (E) was the
main parameter of the models. In a tribological system with dissimilar materials, for example
a ceramic abrading a metal, one material can experience the yielding and the other the brittle
failure. This difference in the mechanical behaviors can be decisive for the final performance
to wear.
The use of Young’s modulus to model the wear resistance was applied for coatings [7]; it
appeared in other modifications of Archard’s equation [8], and even in empirical relationships
between the wear rate and the mechanical properties [9]. Eventually, in all cited cases, the
elastic modulus was not the reduced one (Er), as will be treated here.
A selection of parameters involving hardness and elastic moduli can be summarized (Table
1) [9-11]. All of them have physical meanings that possess some interest for abrasion resistance
of materials. The last parameter presented in Table 1, H3/E2, is proportional to the load that
defines the transition between elastic to plastic contact in a ball-on-plane system, applying the
analytical solutions provided by Hertz in Contact Mechanics [12], where the reduced modulus
is already taken into account.
Parameter Physical meaning (taking into account a rigid-plastic material)
H/E Deformation relative to yielding [9]
(H/E)2 Transition on mechanical contact – elastic to plastic [9]
H2/2E Modulus of resilience [9]
H/Er 2 Resistance to the plastic indentation [10]
H /E
3 2
Resistance to the plastic indentation [11]
Table 1. Parameters based on the hardness and elastic moduli, used as indicators of abrasion resistance and their
physical meanings
Using some of the abovementioned solutions, a case study will be presented. For two tribo‐
logical pairs with known wear coefficients, the ratio of hardness to reduced modulus works
well than the single property of the worn material (E). The expectation regarding the H/Er ratio
is confirmed also by other aspects used to characterize abrasion, especially the cutting
efficiency.
2. Modelling abrasion with E/H ratio
In 1980 Torrance [5] published a model for abrasive wear rate based on the elastic recovery
after scratching, supposing that the abrasive particle has a conical geometry. This choice is
suitable, because there is an analytical model to describe the changes at the recovered surface
[13]. Some years later, another paper [6] adopted the same physical basis but here the appli‐
cation occurred to systems where the abrasive particles roll, instead of slide. The key similar‐
ities and differences of both manuscripts will be discussed below.
First of all, it is important to see the main definition presented in [13], because it was the basis
for the referred models. This reference presents an equation that relates the reduced modulus
with the amount of elastic recovery, he (indicated in Figure 1), considering a conical indenter:
H ´p ´ a
he = h - hP = (1)
Er
In Equation 1 the term Er is the reduced modulus, defined as:
2
1 1 - vi 1 -n 2
= + (2)
Er Ei E
where,
Er is the reduced modulus;
Introduction of the Ratio of the Hardness to the Reduced Elastic Modulus for Abrasion 219
http://dx.doi.org/10.5772/55470
Ei is the Young’s modulus of conical indenter;

νi is the Poisson’s ratio of conical indenter;
E is the Young’s modulus of tested material, and;
ν is the Poisson’s ratio of tested material.
Figure 1. Elastic recovery during an indentation process. Symbology - a: indentation radius, he: elastic recovery; hP: fi‐
nal depth; h: the maximum depth; hC: contact depth and hS: deflected depth. Adapted from ISO 14577-1 [14]
A modern definition for the term E/(1-ν2) can be found in ISO/FDIS 14577-1 standard [14],
and it is called as ‘indentation modulus’, using the symbol EIT. Exactly this term was used
by references [5] and [6]. In this way, the mechanical properties of abrasive particle were
discarded in both cases. It is notable that this aspect has not been ruled out by Stilwell and
Tabor [13] in 1961.
A great difference between the Torrance’s paper [5] and the Yi-Ling and Zi-Shan one [6] is with
respect to the volume of wear. In the former, it was taken as directly proportional to h2, and
for the latter, related to hP2, following the symbology of Figure 1. The latter can be considered
as more appropriate because it takes into account the elastic effects at a worn surface, so that
the final formulation provided by [6] will be presented. Thus, an equation for wear rate, Q
(m3/m), can be written as:
W
Q=C K (3)
H P
where,
W is the applied load;
H is the hardness of worn material;
C is a constant and;
KP will be called here as partial wear coefficient, based on elastic effects during indentation,
defined as (1 + k × H / E )2, being k another constant.
In order to differentiate the use of elastic modulus to the reduced one, another symbology will
be considered for the latter case, where KP’ is introduced:
K P ' = (1 + k ´ H / Er )
2
(4)
where,
k is a constant.
To define the constant C, Yi-Ling and Zi-Shan [6] made use of nine constants to fit the
experimental results. The constant k of term KP varies with many variables of tribosystem. On
the other hand, although Torrance [5] has not make use of constants to fit experimental results
obtained by others [15-17], he chose a material as reference (a steel of 401 HV hardness), and
all cases were then compared with this material (Equation 5). In this way, he only needed to
calculate the constant k (=10), finding a very interesting result, as can be seen in Figure 2.
bi * =
(
H 1 + 10 H ref / Eref ) (5)
H ref (1 + 10 H / E )
Figure 2. Relative wear resistance (βi) as a function of relative partial wear coefficient (βi*), as defined in [5]. Experi‐
mental points derived from [15-17]
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Figure 2 shows a linear relationship between the relative wear resistance βi and the relative
partial wear coefficient, defined in [4] as βi* (Equation 5). The experimental points used to build
this curve included pure metals and heat-treated steels. These groups of materials do not
present the same behavior when they are abraded by hard particles (Figure 3).
In other words, a pure metal with similar hardness of heat-treated steel presents a higher
abrasion resistance. This implies that steels present a different slope on a wear resistance curve
when it is put as a function of hardness. Using the ratio of the hardness to the Young’s modulus,
Torrance [5] put in the same curve these referred groups of materials, which present, a priori,
different behaviors. This kind of result was also described in reference [19], but based on a
different approach. This research made use of the abrasion factor (fab) definition (Equation 6
and Figure 4 [20]) to describe the wear resistance. It is a parameter related with the cutting
efficiency, i.e., when this factor is equal to unity only the micro-cutting would be the wear
mechanism, while for values correspondent to zero no removal of material would be detected.
The experimental results obtained in [19] are shown in Figure 5.
Figure 3. Schematic representation of the wear resistance (Q’ = 1/Q) produced by hard particles as a function of hard‐
ness, considering pure metals and heat-treated steels. Adapted from reference [18]
A 2 - A1
f ab = (6)
A2
where,
A1 is the cross section area relative to pileup produced by a single scratch and;
A2 is the cross section area relative to the groove produced by a single scratch.
Figure 4. Abrasion factor definition (areas A1 and A2 defined in Equation 6). Real profile adapted from reference [20]
Figure 5. Abrasive wear resistance (Q’) produced by flint particles as a function of wear debris hardness-to-fab ratio.
Adapted from reference [19], which defines Q’ as a non dimensional parameter
Again, in Figure 5 both pure metals and steels are put in the same curve, showing that the
hardness alone, in some cases, is not a complete descriptor of the wear resistance. The similarity
between the results presented in Figure 2 and Figure 5 opens a possibility to the abrasion factor
to be described as a function of the hardness-to-elastic modulus ratio.
Although in reference [19] the elastic effects have not been incorporated to the model, there
are results in the literature relating the pileup formation (Figure 6, [21]) with the mechanical
properties [22]. In this case, it is possible to consider that the pileup formation (hc/h) works for
http://dx.doi.org/10.5772/55470
static (hardness test) and kinetic cases (scratch test), being the higher the pileup, the smaller
the cutting efficiency.
Figure 6. Physical parameters extracted from a residual profile of a spherical indentation. Notation: ac is the indenta‐
tion radius at the contact, and s is the height associated to the indentation morphology. Pileup is associated to the
hc/h ratio. Adapted from reference [21]
In reference [22] an equation that correlates the pileup formation with the H/E ratio, based on
results obtained in scratch tests conducted with a Berkovich indenter (Figure 7) can be found:
hC
h
= 0.41498 ln E H - 0.14224 (7)
Important evidence was detected in [23] that the application of Equation (7) was dependent
on the level of applied load.
Figure 7. Relation between the pileup (hc/h) and the ln(E/H), obtained after scratch tests with Berkovich indenter.
Adapted from reference [22]
3. Case study
Two tribological pairs were studied, also considered in a previous investigation [24]. Their
wear rates are known: glass abrading a quenched and tempered (Q&T) 52100 steel [25], and
alumina wearing a hard metal [26]. The mechanical properties, determined from instrumented
indentation testing, used to calculate the partial wear coefficients, KP and KP’ (Equations 3 and
4), are presented in Table 2. To calculate the reduced modulus (Equation 2), Poisson’s ratios
were extracted from [27].
As seen in the previous item, due to the similarity of Figures 2 and 5, the partial wear coefficient
can be well related to the abrasion factor (cutting efficiency), fab. An indirect way to know the
fab factor is found in reference [28], which defined it as the ratio between the wear coefficient
K (Archard’s definition) and the ploughing fraction of friction coefficient (µp). The cutting
efficiency values, following this definition, are 0.106 for glass abrading bearing steel and 0.079
for alumina wearing hard metal, a difference of 34%. As the constant KP’ can vary along a broad
range (Figure 8), we select a value so as to the difference is also 34%, and for this purpose it is
8.25.
Material H, GPa E, GPa Er , GPa H/E H/Er

Soda-lime glass 4.07 69 0.080 0.103
53.24
Q&T steel 5.5 180* 0.023 0.076
Alumina 19.6 376.1 0.052 0.088
222.43
Hard metal (grade K) 11 480 0.023 0.049
Table 2. Mechanical properties of selected tribological pairs. *Obs.: Q&T steel is a wire-drawing, which implies in a
reduction of elastic modulus due to the work-hardening effect
An example of variation in KP’ value with k factor is presented in Figure 8, for the tribological
pairs considered in Table 2. Another pair was added (calcite-fluorite) in this figure, in order
to help the discussion with their differences.
Figure 8. Variation of KP’ wear coefficient with factor k for three cases
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The resulting values of partial wear coefficients, using 8.25 as k factor, are presented in
Table 3.
Pair KP (equation 3) KP’ (equation 4)
Glass - Q&T steel 1.41 2.66
Alumina – Hard metal 1.41 1.98
Table 3. Partial wear coefficient values for selected tribological pairs
Table 3 shows that the KP values were similar for the studied pairs, while the KP’ did not follow
this trend. The wear coefficients of tribological pairs (K values) determined using sliding
abrasion tests were 0.014 and 0.008, for glass against steel [25] and alumina against hard metal
[26], respectively. Visibly this difference in wear rates is only reflected by the KP’ values, which
is a direct result of the ratio of hardness to the reduced modulus.
Another observation for the KP values is that the similarity presented in Table 3 is not affected
by the variation of the k factor. On the contrary, KP’ is strongly dependent on this factor, as
can be seen in Figure 8.
One can ask about the good agreement with experimental data found in [5] and [6] when they
used only the Young’s modulus in wear model. The key point for that is the superiority of
abrasive hardness in relation to the worn surface. All experimental results in these cases were
performed using abrasives much harder than the tested materials, such that the mechanical
properties of them can be considered as unaltered along the tests. An investigation [29] showed
significant changes in glass particles when they abraded steel surfaces, even for non heat-
treated ones. The same thing was demonstrated in [30] for different abrasives wearing WC-Co
thermal sprayed coatings. When the abrasive particle is relatively soft to the abraded material,
their mechanical properties play a key role during the wear process, and an extensive discus‐
sion on it can be found in [31].
In addition, in reference [24] these tribological pairs were separated using the difference in the
plasticity index, δH, defined in [32] (Equation 8), being the smallest difference related to the
calcite-fluorite, and the largest for glass-steel pair within the materials analyzed in [24]. This
aspect seems to be important again when one observes Figure 8. When the difference is
insignificant, as in the case of calcite-fluorite, the variation of KP’ with k factor is minor, and
on the other hand, for the case of the glass-steel pair, for a notable difference in the plasticity
index, a great variation of KP’ with the k factor occurs.
δH = 1 − 14.3(1 − ν − 2ν 2) H E (8)
A brief discussion of the k factor is instructive. Following [6], this factor is especially associated
to the particle geometry. As stated, a hypothetical KP’ of calcite-fluorite pair would be less
affected by the variation on k factor. Therefore, one can imagine a small fragment of mineral
used in Mohs scale [33] and, considering the previous assertive, conclude that its geometry
would not be important. Probably, this is not the case. The k factor should be understood in a
broad manner, i.e., all variables of a system can alter its value. Thus, slight changes in tribo‐
logical variables could bring higher alterations in the wear coefficient for the pair glass-steel
than for the other described cases. At this moment, no experimental result is available to
corroborate this hypothesis, but it is an interesting field to be explored further.
Finally, a discussion concerning the Equation (7) and the values presented in Table 2 is
valuable. If the values of H/E ratio for steel and alumina were applied in Equation (7), the
results would be similar. A similar height of pileup for these materials obviously is not a
reasonable result, taking into account the experimental values obtained for wear and friction
coefficients for them. Nevertheless, applying the reduced modulus in the place of E in that
equation, one can find fewer tendencies to form pileup after abrasion of steel by glass, which
means a higher cutting efficiency in this case, meeting with the values described before.
Consequently, it is more a case of successful application of reduced modulus to predict changes
at the mechanical contact.
4. Conclusions and final remarks
The viability of the use the hardness-to-reduced modulus ratio to model the wear coefficient
for abraded materials was demonstrated. Previous models were developed taking into account
only the Young’s modulus of worn surface, discarding the properties of abrasive material.
These cases work only for pairs where the abrasive particle is harder than the abraded material
and it was demonstrated that they fail when the abrasive hardness is relatively low.
In addition, other questions were discussed and they open some possibilities to carry out future
research. First, the model of wear coefficient treated here involves higher requirements,
because a constant is needed. This constant seems to affect more the wear coefficient of some
pairs than the others, and the reason for that is not clear. Finally, an extensive work could be
made exploring the relation between cutting efficiency (abrasion factor) and H/Er ratio,
computing a large variation of the applied load and the abrasive (indenter) properties.
Probably, an investigation based on these aspects should supply answers to the improvement
of a wear model containing the H/Er ratio.
Nomenclature
A1 and A2 Cross section areas used in the definition of abrasion factor
a Indentation radius
ac Indentation radius at the contact
C Constant
http://dx.doi.org/10.5772/55470
E Young’s modulus
Ei Young’s modulus of indenter
Er Reduced modulus
Eref Young’s modulus of a reference material
fab Abrasion factor or cutting efficiency
H Vickers hardness of the worn material
H d Vickers hardness of wear debris
H ref Vickers hardness of a reference material
h Maximum depth at applied load
hC Contact depth
he Elastic recovery
hP Final depth
hS Deflected depth
K Wear coefficient
KP Partial wear coefficient, defined as (1 + k × H / E )2
KP’ Partial wear coefficient calculated with Er instead of E
k Constant
Q Wear rate
Q’ Wear resistance (= 1/Q)
s Height associated to the indentation morphology
W Applied load
βi Relative wear resistance
βi* Relative partial wear coefficient
δH Plasticity parameter
µp Ploughing fraction of friction coefficient, taken as 0.2
ν Poisson’s ratio of the worn material
νi Poisson’s ratio of the indenter

Acknowledgements
Financial support for this study was provided by CNPq under project no. 306727/2011-0.
Author details
Giuseppe Pintaude*
Address all correspondence to: giuseppepintaude@gmail.com
Mechanical Academic Department, Federal University of Technology – Paraná, Curitiba,

Brazil
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[25] Pintaude G., Bernardes F.G., Santos M.M., Sinatora A., Albertin E. Mild and Severe
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[33] Broz M.E., Cook R.F., Whitney D.L. Microhardness, Toughness, and Modulus of
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Chapter 8
Artificial Slip Surface: Potential Application in Lubricated

MEMS
M. Tauviqirrahman, R. Ismail, J. Jamari and

D.J. Schipper
http://dx.doi.org/10.5772/55745
1. Introduction
1.1. Background
For the last years, there has been a tremendous effort towards the development of Micro-
Electro-Mechanical System (MEMS) for a wide variety of applications in aerospace, automo‐
tive, biomedical, computer, agricultural industries, electronic instrumentation, industrial
process control, biotechnology, office equipment, and telecommunications. MEMS devices
integrate chemical, physical, and even biological processes in micro-scale technology
packages.
Stiction (a subtraction of ‘static friction’) in micro-system technology has been a problem ever
since the advent of surface micromachining in the eighties of the last century. As the overall
size of the machine is reduced, the capillary and surface tension force of liquid become large,
which induce stiction rendering the devices to fail or malfunction. In particular, stiction forces
created between moving parts that come into contact with one another, either intentionally or
accidentally, during operation are a common problem with micro-mechanical devices.
Stiction-type failures occur when the interfacial attraction forces exceed restoring forces.
Consequently, the surfaces of these parts either temporarily or permanently adhere to each
other, causing device malfunction or failure.
Several approaches to address the stiction between two opposing surfaces have been presented
in the various literatures [1-4]. The basic approaches to prevent stiction include increasing
surface roughness (topography) and/or lowering solid surface energy by coating with low
surface energy materials. This includes self-assembled molecular (SAM) coatings, hermetic
packaging and the use of reactive materials in the package [5].
Other attractive technique to tackle the stiction problem is by inserting a lubricant into the
region around the interacting devices to reduce the chance of stiction-type failures. As is well-
known, many MEMS devices include moving (sliding/rolling) surfaces and thus it is necessary
to apply a lubricant between the contacting surfaces to reduce friction and wear. However, a
significant barrier to the development of MEMS lubrication is the problem of achieving
effective tribological performance of their moving parts. This is because the lubricant behavior
is different at micro-scale compared to macro-scale. At the macroscopic level, it is well accepted
that the boundary condition for a viscous fluid at a solid wall is no-slip, i.e. the fluid velocity
matches the velocity of the solid boundary. While the no-slip boundary condition has been
proven experimentally to be accurate for a number of macroscopic flows, it remains an
assumption that is not based on physicals principles. At micro-scale level, certain phenomena
must be taken into account when analyzing liquid flows such as a slip condition at solid wall
boundaries.
As a consequence of the MEMS technology revolutionary application to many areas, it is

possible for scientists to observe the boundary slip on micro/nano-meter scale. A variety of
techniques are now available that are capable of probing lubricant flow on micro-scales and
are therefore suitable for the investigation of boundary conditions. There are three techniques
so far for detecting the boundary slip: nano-particle image velocimetry (NPIV) [6], atomic force
microscope (AFM) [7-9] and surface force apparatus (SFA) [10]. The NPIV technique is a direct
observation method with a measurement precision depending on the size of the nano-particles
but with poor moderate accuracy. The AFM and SFA are indirect observation techniques based
on the assumption that boundary slip takes place precisely on the interface of liquid and solid.
These methods need a high accuracy boundary slip model to infer the slip velocity. Boundary
slip has been observed not only for a hydrophobic surface [6, 7, 10] but also for a hydrophilic
surface [8, 9]. Therefore, the slip evidence has been generally accepted and for certain cases
the no-slip boundary condition is not valid.
There is a large body of literature dealing with the analysis of lubricant slip flow based on the
analytical and numerical solution of molecular dynamic simulations [11, 12], Lattice-Boltz‐
man [13, 14], and the Reynolds equation [15-23]. The accurate description of slip at the wall is
very difficult and still remains a subject of intensive research. The so-called Navier slip model
and the critical shear stress model are usually used to describe a boundary slip. In fact, nearly
two hundred years ago Navier [24] proposed a general boundary condition that incorporates
the possibility of fluid slip at a solid boundary. Navier's proposed boundary condition as‐
sumes that the velocity, u, at a solid surface is proportional to the shear stress at the surface. It
reads: u = b (du/dz) where b is the slip length and du/dz is the shear rate. The slip length b, which
is defined as the distance beyond the solid/liquid interface at which the liquid velocity extrapo‐
lates to the velocity of the solid, is used to quantify a boundary slip. If b = 0 then the generally
assumed no-slip boundary condition is obtained. If b = finite, fluid slip occurs at the wall, but its
effect depends upon the length scale of the flow. The Navier-slip boundary condition is the most
widely used boundary condition with the methods based on the solution of continuum equations.
In micro-scales such as MEMS, the boundary condition will play a very important role in
determining the lubricant flow behavior. Control of the boundary condition will allow a degree
Artificial Slip Surface: Potential Application in Lubricated MEMS 233
http://dx.doi.org/10.5772/55745
of control over the hydrodynamic pressure in confined systems and be important in lubricated-
MEMS. To prevent a stiction, in a controlled way, one is able to enhance, a hydrophobic/
hydrophilic behavior of surfaces. If one surface is hydrophobic (slip) and the other is hydro‐
philic (no-slip) the sliding velocity or displacement between the surfaces is accommodated by
shear at the hydrophobic surface (the lubricant is kept in the contact by the hydrophilic
surface). In this way wear of the surfaces is prevented and the surfaces are able to move because
stiction is prevented.
The slip situation, however, can be controlled to obtain a positive effect by surface technology.
Coating and texturing technologies can be used to engineer large slip. In practice, a large slip
can be made using super-hydrophobic surfaces. Such surfaces can be manufactured by grafting
or by deposition of hydrophobic compounds on the initial surface at a certain zone. Super-
hydrophobic surfaces were originally inspired by the unique water-repellent properties of the
lotus leaf. It is the combination of a very large contact angle and a low contact-angle hysteresis
that defines a surface as super-hydrophobic. Implementing the slip property (hydrophobicity)
on a surface in a wide range of application for the mechanical components is of great challenge
by numerous authors recently. In published works [15-23], both experimentally and numerical‐
ly, slip surface is able to reduce friction force at the contacting surfaces and finally reduce energy
consumption, increase component's life-time and reduce economic and environmental costs.
1.2. Problem statement
In classical liquid lubrication it is assumed that surfaces are fully wetted and no-slip occurs
between the fluid and the solid boundary. In MEMS, this wetting is actually an unwanted process
because it can encourage the occurrence of stiction and as a result micro-parts can not be moved
[25]. It is expected that slip can reduce the friction and improve the load support. However, with
respect to the engineered slip pattern, the choice of slip zone on a certain surface must be taken
carefully in relation to such tribological performances. In other words, an inappropriate slip
zone pattern on a certain surface or the election of inappropriate surface containing a slip situation
may lead to the deterioration of the lubrication performance. How to control the boundary slip
in the application of a lubricated-MEMS is one of the challenging tasks in the future. This chapter
will explore the provision of a new lubrication model based on the continuum approach for
moving parts in MEMS in order to improve the tribological performance of lubricated con‐
tacts. In MEMS, by lubrication, low friction force and high load support are the goals which want
to be achieved. The artificial slip surface will be introduced as one of the solutions to improve
the lubrication performance of MEMS so as MEMS with a longer life-time can be obtained. The
term "artificial slip surface" is used to address a non-homogeneous engineered slip/no-slip
pattern, i.e. a surface consisting of a slip zone and a no-slip zone.
2. Research methods
Full film lubrication of lubricated contact is often described by the Reynolds theory [26].
According to the classical Reynolds theory, no-slip boundary is assumed and the convergent
geometrical wedge is one of the most important conditions to generate hydrodynamic

pressure. Therefore, the lubrication model for lubricated MEMS will be an extension of the
classical lubrication theory. This means that modeling the lubricant through very narrow gap,
normally modeled by assuming no-slip at the boundaries will be modified by introducing a
boundary slip.
2.1. Modified reynolds equation
The classical Reynolds equation that is valid under no-slip condition can be generalized for
taking into account slip conditions. It is then possible, for any film height distributions, to
calculate the pressure distribution and the shear rate profile. The model of lubrication
presented here is based on the fact that slip of the lubricant will exist at the interface of a
lubricated sliding contact. Thus, a boundary slip is employed both on the moving and
stationary surface, see Figure 1. The proposed lubrication model with slip leads to a modified
Reynolds equation as presented in Eq. (1).
¶ çæ h 3 h + 4 hm ( t +  b ) + 12 m  t b ¶p ö÷ uw ¶ æ h + 2 hm t ö
2 2 2
= ç ÷
¶x ç 12 m
è ( )
h h + m ( t +  b ) ¶x ÷ 2 ¶x çè h + m ( t +  b ) ÷ø
ø (1)
2
t m ¶h h ¶p ¶h h t m + 2 t b m
-uw +
h + m ( t +  b ) ¶x 2 m ¶x ¶x h + m ( t +  b )
The physical meanings of the symbols in Eq. (1) are as follows: h the lubrication film thickness
(gap) at location, p the lubrication film pressure, μ the lubricant viscosity, α the slip coefficient
(subscripts t and b denote the top (stationary) and bottom (moving) surface, respectively) and
uw the velocity of the moving surface. It can be seen in that if the slip coefficient α is set to zero
(no-slip condition), Eq. (1) reduces to the classical Reynolds equation. It should be noted that
the product of multiplication of the slip coefficient by the viscosity, αμ , is usually called as ‘slip
length’ b.
Eq. (1) is derived by following the usual approach to deduce the Reynolds equation from the
Navier-Stokes system by assuming classical assumptions except that boundary slip is applied
both on the stationary surface and moving surface as depicted in Figure 1.
Eq. (1) can be derived by considering the equilibrium of an element of fluid.
¶ 2u 1 ¶p
= (2)
¶z 2 m ¶x
where z lies along the direction across the thickness of the film, and u is the velocity field. To
obtain the velocity profile, Eq. (2) can be integrated twice.
5
Artificial Slip Surface: Potential Application in Lubricated MEMS
http://dx.doi.org/10.5772/55745
1
2
3 Lx
4 Sxt
5
6
7
8
9
z hi lubricant h(x)
10
ho
11
12 x
13
14
Sxb uw
15
16
Figure 1. Schematic of a lubricated sliding contact with artificial slip surface applied both on the stationary and the mov‐
ing surface. The boundary slip zones (Sxt and Sxb ) are located at the leading edge of the contact. (Note: uw is the sliding ve‐
locity, Lx is contact length, hi and ho are inlet and outlet film thickness, respectively, h(x) is variable film thickness).
1 ¶p 2
u= z + C1z + C2 (3)
2 m ¶x
C1 and C2 in this case are either constants or functions of x and can be solved by applying a
boundary condition for u. The bottom and the top surfaces have the slip condition based on
slip length model.
¶u ü
at z = 0, u = uw +  b m ï
¶z z = 0 ï
ý (4)
¶u ï
at z = h , u = -t m
¶z z = h ï
þ
This gives
1 ¶p 2 æ uw h ¶p h + 2 t m ö h + t m
u= z -ç + ÷ z + uw (5)
è h + m ( t +  b ) 2 m ¶x h + m ( t +  b ) ø h + m ( t +  b )
2 m ¶x ç ÷
h ¶p  b m ( h + 2 t m )
- (6)
2 m ¶x h + m ( t +  b )
This velocity is used to compute the flow rate, q by integrating across the fluid film thickness,
h. When q is differentiated to fulfill the continuity of flow, assuming μ is constant; this gives a
modified Reynolds equation as stated in Eq. (1).
When full film lubrication is assumed, the entire load w is carried by the lubricant film and the
calculation is simply an integration of the lubricant film pressure distribution over contact
area, i.e.
Lx
w = ò p( x)dx (7)
0
The friction force f generated by the lubrication system is due to the fluid viscous shear. It is
calculated by integrating the shear stress over the surface area. These shear stresses are given
by
æ ¶u ö
t ( x, z ) = ç m ÷ (8)
è ¶z ø z = h
The simulation results will be presented in dimensionless form, i.e. P = ph o2 / μL x uw for the
dimensionless pressure, W = wh o2 / (uw μ L x2) for the dimensionless load support (where w is
the load per unit width), F = f h o / μuw L x for dimensionless friction force (where f is the friction
force per unit width), and m = F / W for dimensionless friction coefficient. In the present study,
the dimensionless slip length A is determined by normalizing the slip length b with the outlet
film thickess ho. For slip analysis in the following computations, the dimensionless slip length
A varies from 3 to 300, which are reasonable values of the slip length based on the results
published in literature [17, 18, 20].
2.2. Solution method
The modified Reynolds equation, Eq. (1) is discretized over the flow using the finite volume
method, and is solved using the tridiagonal matrix algorithm (TDMA), [27]. By employing the
discretization scheme, the computed domain is divided into a number of control volumes
using a grid with uniform mesh size. The grid independency is validated by various numbers
of mesh sizes. An assumption is made that the boundary pressures are zero at both sides of
the contact.
A numerical simulation is conducted to investigate the possible application so as a boundary

slip can be beneficial to achieve a high load support and low friction force. In order to maximize
the performance of lubrication, the boundary conditions (slip zones, Sxt and Sxb, see Figure 1)
of the model are optimized through a parametric analysis. The object of optimization is to
maximize the hydrodynamic load support. The load support satisfies two main functional
purposes: (a) carry the applied external load, and (b) to minimize the contact between the
opposing solids, and thus wear. The optimization analysis attempts to satisfy both functional
requirements with a single design parameter, the slip zone.
http://dx.doi.org/10.5772/55745
The parametric analysis is performed using a developed computer code to investigate the effect
of various slip parameters on the lubrication performances (load support, friction force, and
friction coefficient). A parametric study is conducted with the variation of slip parameters (slip
zone and slip length) over a large range of values considering different performance param‐
eters. The design variables and the objective function are referred to as the optimization
variables. The design variables are independent quantities which are varied in order to achieve
the optimum design. The objective function is the dependent variable that is maximized, i.e.
the load support. In the present study, the design variables are slip zones as indicated in Figure
1. The algorithm used in the present study is depicted on Figure 2.
Figure 2. Flow chart for numerical method.

Figure 2. Flow chart for numerical method.
3. Key results
The behavior of traditional (no-slip) hydrodynamic lubrication between the opposing surfaces can be estimated
of the Reynolds equation. The derivation of the classical Reynolds equation is based on the assumption of
lubricant and the surfaces. In the classical Reynolds lubrication, the mechanism to generate a pressure is du
wedge effect. An artificial slip surface presented here is designed to be able to carry the external load during lu
wedge effect is not present. This situation is very beneficial in designing lubricated-MEMS which exhibits paral
In this chapter, there are two main investigations. At first, the study is conducted in order to validate the d
3. Key results
The behavior of traditional (no-slip) hydrodynamic lubrication between the opposing surfaces
can be estimated by a classical form of the Reynolds equation. The derivation of the classical
Reynolds equation is based on the assumption of no-slip between the lubricant and the
surfaces. In the classical Reynolds lubrication, the mechanism to generate a pressure is due to
the convergent wedge effect. An artificial slip surface presented here is designed to be able to
carry the external load during lubrication even if the wedge effect is not present. This situation
is very beneficial in designing lubricated-MEMS which exhibits parallel gaps.
In this chapter, there are two main investigations. At first, the study is conducted in order to
validate the developed numerical scheme. It assures that the numerical method used can be
employed for solving other hydrodynamic characteristics. The no-slip case of lubricated
contact is of main interest due to the availability of the analytical solution. Secondly, the study
will be extended to explore the effect of the slip zone of the artificial slip surface on pressure,
load support, friction force, and friction coefficient. The comparison between the modified
sliding contact containing an artificial slip surface and the traditional one is conducted in order
to describe the benefit of the use of an artificial slip pattern quantitatively.
3.1. No-slip condition
The modified Reynolds equation (Eq. (1)) is the governing equation for the fluid lubrication
system containing a boundary slip. If the slip coefficient, α , is set to zero, Eq. (1) reduces to the
classical Reynolds equation. In this section, in order to validate the developed computer code
containing a numerical scheme using finite volume method combined with tridiagonal matrix
algorithm (TDMA), the classical Reynolds equation (no-slip condition) is solved numerically
for calculating the pressure distribution, and finally the friction in a lubricated sliding contact
as depicted in Figure 1 and Table 1, respectively. These results are compared with the analytical
solution based on the work of Cameron [28] as follows:
x æ x ö
K ç 1 - ÷÷
6uw m Lx Lx çè Lx ø
p= (9)
ho2 æ ö
2
( 2 + K ) çç 1 + K - K Lx ÷÷
è x ø
for the pressure distribution where K = (hi /ho) – 1, and
Lx muw æ 4 ln(1 + K ) 6 ö
f = ç - ÷ (10)
ho è K (2 + K ) ø
for the friction force per unit width.

x  x 
K  1  
6uw  Lx Lx  Lx 
p (8)
ho2  
2
 2  K   1  K  K Lx 
 x 
http://dx.doi.org/10.5772/55745
for the pressure distribution where K = (hi /ho) – 1, and
L  u  4 ln(1
In Figure 3 the numerical results 6 
 K ) obtained
f  x w   (9) with TDMA as well as analytical results for the
ho  K (2  K ) 
dimensionless pressure distribution along the bottom wall of the contact are shown alongside
those obtained forfrom the Reynolds approximation. The wedge ratio h* of 2.2 was considered
the friction force per unit width.
based on the fact that a maximum load support for a no-slip contact occurs when h* = 2.2 [28].
In the present study the3 wedge
In Figure ratioresults
the numerical h* is obtained
definedwith
as the
TDMA inlet filmasthickness
as well overforthe
analytical result theoutlet film pressure distribut
dimensionless
the bottom wall of the contact are shown alongside those obtained from the Reynolds approximation. The wedge ratio h* o
thickness, hi/h0, considered
and sometimes quoted as slope incline ratio in other literature. It is observed
based on the fact that a maximum load support for a no-slip contact occurs when h* = 2.2 [28]. In the present
from Figure 3 that theratio
wedge maximum
is definederror isfilm
as inlet within 0.01%
thickness between
over the outletthe
filmpressure
thickness, hobtained from
i/h0, sometimes the as slope incline r
quoted
analytical solution andfrom
observed the Figure
numerical result.
3 that the maximum error is within 0.01% between the pressure obtained from the analytical solutio
numerical result.
0.35
Numerical solution Analytical solution [24]
Dimensionless pressure, P
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0.00 0.20 0.40 0.60 0.80 1.00
Dimensionless x coordinate, X
Figure 3. Normalized pressure distribution along the bottom wall of the linear wedge with no-slip boundary condi‐
Figure 3. Normalized pressure distribution along the bottom wall of the linear wedge with no-slip boundary condition for an optimal w
tion for an optimal wedge ratio h* of 2.2.
h* = 2.2.
The comparison Thebetween

comparisonthe dimensionless
between friction
the dimensionless friction force
force F F obtained
obtained with
with the the numerical
numerical prediction and the analytical so
prediction and the analytical
presented in Tablesolution
1. Like theare presented
result in Table
of the pressure 1. Like the
distribution, thepredicted
result of the pressure
dimensionless friction force shows v
agreement with the analytical solution. In general, the numerical solution of the classical Reynolds equation is matched
distribution, thethepredicted dimensionless friction force shows very good agreement with the
analytical solution. It assures that the numerical method used is valid and thus can be extended for analys
analytical solution. In general,
hydrodynamic the numerical solution of the classical Reynolds equation is
characteristics.
matched well with the analytical solution. It assures that the numerical method used is valid
and thus can be extended for analysing other hydrodynamic characteristics.Dimensionless friction, F
Analytical solution [28] 0.77
Numerical prediction [present study] 0.77
Table 1. Dimensionless
The comparison between the analytical solution performed by Cameron [28]friction force, F simulation code.
and the numerical
Analytical solution [28] 0.77

3.2. Artificial slip surface
Numerical prediction [present study] 0.77
In MEMS, liquid lubrication has generally been omitted due to high hydrodynamic friction force that occurs in f
Compared with a solid coating, stiction prevention using liquid lubrication is less practical. However, recent stud
Table 1. The comparison between the analytical solution performed by Cameron [28] and the numerical simulation
demonstrated that it is possible for Newtonian liquids to slip along very smooth solid walls [20] and this result may ma
code.
3.2. Artificial slip surface
In MEMS, liquid lubrication has generally been omitted due to high hydrodynamic friction
force that occurs in fluid film. Compared with a solid coating, stiction prevention using liquid
lubrication is less practical. However, recent studies have demonstrated that it is possible for
Newtonian liquids to slip along very smooth solid walls [20] and this result may make liquid
lubricants for MEMS devices feasible. The main advantage of a liquid lubricant over a solid
lubricant is that they generally produce no-contact shear stresses. Unfortunately, a stiction-
type failure due to a large shear and capillary forces occurs. In [15, 16], a lubrication model of
low load contacts was proposed to reduce such stiction or friction. The idea behind that work
was how to use a lubricant that does not wet one of the solid surfaces. It was found that a half-
wetted bearing generates a significant friction reduction compared to a traditional bearing.
In order to reduce stiction, two principal methods are available, chemical and physical
modification of the surfaces. To generate wall slip, in the chemical approach, the chemical
composition of the surface is altered. In the physical approach, the surfaces are roughened to
decrease the effective contact area [29].
In practice, the slip zone of the artificial slip surface can be prepared from (super)hydrophobic
surface which uses chemical properties as well as micro- and nano-structures in order to
achieve a high level of friction force reduction. The main characteristic of (super)hydrophobic
surfaces is the slip length. Extensive studies have confirmed that the chemical treatment of the
surfaces generates a slip length in the order of 1 µm [30], while longer slip length up to 100
µm can be obtained through a combination of a hydrophobic surface with textured structure
[20, 31, 32]. In the present study, it will be shown by the computational analysis that a longer
slip length applied on the slip zone of the artificial slip surface leads to a greater friction force
reduction in combination with an improved load support.
3.2.1. Beneficial surface of slip

Recently, the use of an engineered slip surface has become popular with respect to lubrication,
since this type of surface enhancement would give a better tribological performance. The great
challenge for an engineered slip surface from the perspective of a numerical simulation is
choosing the optimal slip zone geometry with respect to the lubrication performance. Two
engineered slip surface modes were used currently: homogeneous slip surface (i.e. slip applied
over the whole surface) and artificial slip surface (i.e. surface consisting of slip zone and no-
slip zone). It can be noted that term “artificial slip surface” was sometimes also called as
heterogeneous slip/no-slip surface [17, 18] and mixed slip surface [19]. The first study to mention
using a homogeneous slip was dedicated by Spikes [15, 16] who numerically studied the effect
of slip profiles on friction. The author pointed out that by introducing the half-wetted bearing
having a homogeneous slip boundary on one of the surfaces, a reduced friction can be ob‐
tained. Subsequently, an experimental study was published in [20] confirming the finding of
[15, 16]. However, in addition to the friction reduction, it was shown that a homogeneous slip
surface usually has a negative effect, i.e. the decrease in the load support. If the lubricated contact
exhibits a perfect slip property, it was found that the fluid load support was only half of that
without slip [115, 19, 21, 23]. Clearly, this is unwanted effect with respect to the lubrication.
Therefore, to date, an artificial slip surface has become of great interest by some researchers
[17-19, 21, 23] with the focus of how to balance the slip effect on the load support and friction.
The big question with respect to the tribological performance of lubricated-MEMS emerges in
accordance with at which wall boundary slip must be applied, at the stationary surface, moving
http://dx.doi.org/10.5772/55745
surface, or both of them. Besides that, the types of slip zone pattern become also great issue.
Therefore, a series of simulations were conducted with such boundaries to find the best possibility
of slip boundary application in terms of load support. Investigations were made for four kinds
of slip boundaries to find the best boundary slip in terms of tribological performance, i.e. (1) slip
applied on both the stationary and moving surfaces is referred as 'condition 1', (2) slip applied
on the stationary surface is referred as 'condition 2', (3) slip applied on the moving surface is
referred as 'condition 3', and (4) no-slip condition applied on the both of surfaces is referred as
'condition 4'. Here, a homogeneous slip surface is employed for all slip conditions.
Figure 4 presents the effect of the wedge ratio h* on the dimensionless load support W. It is
shown that the contact with homogeneous slip condition of 1, 2, and 3 have a negative effect,
i.e. a reduced load support. The highest achievement of a load support W is obtained when
the slip is applied on the stationary surface (condition 2). However, the value of the predicted
load support is much lower than the conventional lubricated contact for all values of wedge
ratio. It is only half of what the conventional Reynolds theory predicts for an optimal wedge
ratio of a traditional slider contact. Fortunately, the direct trend of homogeneous slip to
decrease the load support W is counterbalanced by the fact that such surface also reduces
friction significantly. This is indicated in Figure 5 which shows the comparison between the
dimensionless friction F for condition 2 and the condition 4 for the range of wedge ratio, h*.
The reduced friction as an advantageous effect in the lubrication can be explained by the fact
that the boundary slip tends to reduce the wall shear rate at a prescribed film thickness, and
then the wall shear stress and friction. Therefore, in the following design for the maximal
lubrication performance, the lubricant has a no-slip boundary condition at the moving solid
surface but can slip along the stationary surface. In the next section, the geometry of the
boundary slip zone making an artificial slip surface will be investigated in order to achieve a
higher load support as well as a low friction force.
condition 1 condition 2
Dimensionless load support, W
0.18
condition 3 condition 4
0.15
0.12
0.09
0.06
0.03
0.00
1 1.3 1.6 1.9 2.2 2.5 2.8
Wedge ratio, h*
Figure 4. Dimensionless load support versus wedge ratio for several homogeneous boundary slip conditions. (Note: slip on stationary
Figure 4. Dimensionless load support versus wedge ratio for several homogeneous boundary slip conditions. (Note:
surfaces (condition 1); slip on stationary surface (condition 2); slip on moving surface (condition 3); traditional no-slip (condition 4)).
slip on stationary andcases,
moving surfaces (condition 1); slip on stationary surface (condition 2); slip on moving surface
the dimensionless slip length A of 20 is assumed.
(condition 3); traditional no-slip (condition 4)). For the slip cases, the dimensionless slip length A of 20 is assumed.
1.2
ionless friction force, F
1.0 condition 2
condition 4
0.8
0.6
0.4
0.00
1 1.3 1.6 1.9 2.2 2.5 2.8
Wedge ratio, h*
Figure 4. Dimensionless load support versus wedge ratio for several homogeneous boundary slip conditions. (Note: slip on stationary and
surfaces (condition 1); slip on stationary surface (condition 2); slip on moving surface (condition 3); traditional no-slip (condition 4)). For
cases, the dimensionless slip length A of 20 is assumed.
1.2
Dimensionless friction force, F

1.0 condition 2
condition 4
0.8
0.6
0.4
0.2
0.0
1 1.3 1.6 1.9 2.2 2.5 2.8
Wedge ratio, h*
Figure 5. Dimensionless friction force versus wedge ratio at boundary condition in which slip applied on the stationary surface (cond
Figure 5. Dimensionless friction force versus wedge ratio at boundary condition in which slip applied on the station‐
compared to the no-slip condition (condition 4).
ary surface (condition 2) compared to the no-slip condition (condition 4).
3.2.2. The optimum slip zone of the artificial slip surface

3.2.2. The optimum slip zone of the artificial slip surface
This section is intended to investigate the optimum slip zone of the artificial slip surface for several values of wedge ratios
This section isrespect
intended to investigate
to the load support. the optimum slip zone of the artificial slip surface for
several valuesInofthewedge ratios h* with respect to the load support.
following computations, as discussed in the previous section, for a high load support, it is considered that the artific
surface will take place on the stationary surface, whereas no-slip condition occurs on the moving surface. The parameter
In the followingwhichcomputations, as discussed
SxD = Sx/Lx) is introduced in order in the previous
to completely definesection, for a high
the dimensionless loadAsupport,
slip zone. parametric analysis is condu
it is considered that the
varying artificial slip
the dimensionless slipsurface
zone SxDwill
fromtake place
zero (i.e. on the
no-slip stationary
boundary) surface,
to one (i.e. whereas
homogeneous boundary slip). The ef
no-slip condition occurs
slip zone on the
geometry on themoving surface.
load support The inparameter
is presented SxDbe(in
Figure 6. It can which
shown SxDload
that the =S x x is
/L
support) has a maximum valu
SxD = 0.65 and h* = 1 (i.e. parallel sliding surfaces). It should be noted that no hydrodynamic pressure can be built up in
introduced insliding
ordersurfaces
to completely define the dimensionless slip zone. A parametric analysis
for traditional no-slip contact. From Figure 6, it is also shown that with the increase in wedge ratio h*, a cle
is conducted by varying
of the maximum theload
dimensionless
support toward to slip zone
outlet can Sbe from zero
xDobserved in this(i.e. no-slip
work. boundary)
In addition, the maximumto load support de
one (i.e. homogeneous boundary
with the increase slip).
in h*. A first The effect
conclusion offorslip
is that the zone geometry
best artificial on the
slip surface withload support
respect is support performa
to the load
slip zone must be employed on the leading edge of the parallel sliding contact.
presented in Figure 6. It can be shown that the load support has a maximum value when SxD
= 0.65 and h* = 1 (i.e. parallel sliding surfaces). It should be noted that no hydrodynamic
pressure can be built up in parallel sliding surfaces for traditional no-slip contact. From Figure
6, it is also shown that with the increase in wedge ratio h*, a clear shift of the maximum load
support toward to outlet can be observed in this work. In addition, the maximum load support
decreases with the increase in h*. A first conclusion is that for the best artificial slip surface
with respect to the load support performance, the slip zone must be employed on the leading
edge of the parallel sliding contact.
Figure 7 shows the normalized representation of lubrication film pressure distributions as a

function of wedge ratio which are predicted by the modified Reynolds equation (Eq. (1)). For
slip configuration, the optimal slip zone SxD of 0.65, is employed. It can be shown that compared
with the no-slip boundary condition, the artificial slip surface yields a positive fluid pressure.
However, the performance improvement obtained through artificial slip surface is rather mild
for the high wedge ratio. Obviously, the lower the base geometry wedge ratio (thus leads to
the parallel sliding contact), the larger improvement that boundary slip can induce. In other
words, using the artificial slip surface considered here, the maximum pressure occurs not at a
http://dx.doi.org/10.5772/55745
0.4

h* = 1 h* = 1.4
h* = 2.2 h* = 3
0.3
0.2
0.1
0.0
0.0 0.2 0.4 0.6 0.8 1.0
Dimensionless slip zone, SxD
Figure 6. Effect of the dimensionless slip zone of the artificial slip surface SxD on the dimensionless load support W for several wedge ratios h*.
Figure 6. Effect of the dimensionless slip zone of the artificial slip surface SxD on the dimensionless load support W for
several wedge Figure
ratios h*.
7 shows the normalized representation of lubrication film pressure distributions as a function of wedge ratio which
predicted by the modified Reynolds equation (Eq. (1)). For slip configuration, the optimal slip zone SxD of 0.65, is employed. I
convergent be wedge
shownas predicted
that by the
compared with classical
the no-slip Reynolds
boundary assumption
condition, the artificial (h*
slipopt = 2.2yields
surface [28]),a positive
but at afluid pressure. How
parallel surface. The predicted maximum pressure for a parallel gap is over three times as large
the performance improvement obtained through artificial slip surface is rather mild for the high wedge ratio. Obviously, the lo
the base geometry wedge ratio (thus leads to the parallel sliding contact), the larger improvement that boundary slip can induc
as the maximum pressure
other words, using obtained
the artificial from a no-slip
slip surface contact
considered here, when the wedge
the maximum pressureratio h*not
occurs = 2.2. From wedge as pred
at a convergent
this perspective,
by the the well-chosen
classical artificial(h*slip
Reynolds assumption surface
opt = 2.2 pattern
[28]), but can surface.
at a parallel be considered as amaximum
The predicted potential pressure for a parallel
application iswhich is possible for lubricated-MEMS based devices with respect to the load
over three times as large as the maximum pressure obtained from a no-slip contact when the wedge ratio h* = 2.2. From
perspective, the well-chosen artificial slip surface pattern can be considered as a potential application which is possible
support. In lubricated-MEMS
this way, liquid lubricants
based devices withon the tomodified
respect opposing
the load support. In this surfaces
way, liquid(i.e. artificial
lubricants on theslip
modified opposing sur
surface) can(i.e.
prevent
artificialthe
sliplubrication to break
surface) can prevent down during
the lubrication to breakdevice operation
down during to the point
device operation to the where
point where they no longer
they no longer give
proper proper lubrication.
lubrication.
Figure 8 shows the 0.7dimensionless surface friction force F at the bottom surface. It can be seen
that the friction of the artificial
h* = 1slip surface becomes smaller than that of a traditional no-slip
0.6
lubricated contact especiallyh*when
= 1.2 S is larger than about 0.6. This agrees with the numerical
Dimensionless presure, P
xD
h* = 2.2
analysis of Wu et 0.5
al. [19] eventhough the slip model and numerical method used are different.
h* = 2.2 (no-slip)
One can remark that when there is no wedge effect (i.e. h* = 1) and SxD = 0.65, the artificial slip
0.4 h* = 3.2
surface gives the minimum dimensionless friction force of 0.65, while the no-slip lubricated
contact gives its dimensionless
0.3 minimum friction of 0.77 at h*optimal = 2.2, see Table 1. It means
that the optimized artificial slip surface of lubricated-MEMS can produce a lower friction force
0.2
than a no-slip contact.
0.1
3.2.3. Effect of dimensionless slip length on lubrication performance
0
The hydrophobicity of 0 a solid surface,
0.2 as discussed
0.4 in the0.6previous section,
0.8 is usually
1 expressed
in terms of a slip length, which quantifies the extent xtocoordinate,
Dimensionless which theXfluid elements near the surface
are affected by the surface energy and the surface geometry. The surface energy is an intrinsic
property of zone
a material that can be controlled by chemical treatment, such as etching approach
Figure 7. Lubrication film pressure distributions for several values of wedge ratio. The slip profiles are calculated for optimized dimensionles
SxD = 0.65 and dimensionless slip length A = 20.
and/or coat-on/cast approach. The surface roughness of a hydrophobic solid material can be
Figure 8 shows the dimensionless surface friction force F at the bottom surface. It can be seen that the friction of the artificial
surface becomes smaller than that of a traditional no-slip lubricated contact especially when SxD is larger than about 0.6. This ag
with the numerical analysis of Wu et al. [19] eventhough the slip model and numerical method used are different. One can rem
that when there is no wedge effect (i.e. h* = 1) and SxD = 0.65, the artificial slip surface gives the minimum dimensionless fri
force of 0.65, while the no-slip lubricated contact gives its dimensionless minimum friction of 0.77 at h*optimal = 2.2, see Table
means that the optimized artificial slip surface of lubricated-MEMS can produce a lower friction force than a no-slip contact.
other words, using the artificial slip surface considered here, the maximum pressure occurs not at a convergent wedge as pred
by the classical Reynolds assumption (h*opt = 2.2 [28]), but at a parallel surface. The predicted maximum pressure for a paralle
is over three times as large as the maximum pressure obtained from a no-slip contact when the wedge ratio h* = 2.2. From
perspective, the well-chosen artificial slip surface pattern can be considered as a potential application which is possibl
244 Tribology - Fundamentals
lubricated-MEMSand Advancements
based devices with respect to the load support. In this way, liquid lubricants on the modified opposing sur
(i.e. artificial slip surface) can prevent the lubrication to break down during device operation to the point where they no longer
proper lubrication.
0.7
h* = 1
0.6 h* = 1.2
Dimensionless presure, P
h* = 2.2
0.5
h* = 2.2 (no-slip)
0.4 h* = 3.2
0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1
Dimensionless x coordinate, X
Figure 7.film
Figure 7. Lubrication Lubrication
pressurefilm pressure distributions
distributions for values
for several several values of wedge
of wedge ratio.
ratio. TheThe slip
slip profilesare
profiles are calculated
calculated forfor
optimized dimensionles
zone SxD = 0.65 and dimensionless slip length A = 20.
optimized dimensionless slip zone SxD = 0.65 and dimensionless slip length A = 20.
Figure 8 shows the dimensionless surface friction force F at the bottom surface. It can be seen that the friction of the artificia
surface becomes smaller than that of a traditional no-slip lubricated contact especially when SxD is larger than about 0.6. This a
with the1.2
numerical analysis of Wu et al. [19] eventhough the slip model and numerical method used are different. One can re
that when there is no wedge effect (i.e. h* = 1) and SxD = 0.65, the artificial slip surface gives the minimum dimensionless fri
1 while the no-slip lubricated contact gives its dimensionless minimum friction of 0.77 at h*optimal = 2.2, see Table
force of 0.65,
means that the optimized artificial slip surface of lubricated-MEMS can produce a lower friction force than a no-slip contact.
0.8
0.6
0.4 h* = 1
h* = 1.4
0.2 h* = 2.2
h* = 3
0
0 0.2 0.4 0.6 0.8 1
Figure 8. Effect of the dimensionless slip zone of the artificial slip surface SxD on the dimensionless friction force F at bottom surface for
Figure 8. Effect of the dimensionless slip zone of the artificial slip surface SxD on the dimensionless friction force F at bot‐
values of wedge ratio h*. The slip profiles are evaluated for dimensionless slip length A = 20.
tom surface for several values of wedge ratio h*. The slip profiles are evaluated for dimensionless slip length A = 20.
tuned in order3.2.3. Effect of dimensionless

to increment its hydrophobicity slipand
length on alubrication
obtain performance
super-hydrophobic solid surface
[33, 34]. In this section, from the numerical point of view, the effect of slip length
The hydrophobicity of a solid surface, as discussed in the previous section, is usually expressedonin the
terms of a slip length,
lubrication behavior
quantifies is
thestudied. The the
extent to which dimensionless slipthe
fluid elements near length
surfaceis varied
are affectedfrom
by the3surface
to 300.energy and the surface geometr
surface energy is an intrinsic property of a material that can be controlled by chemical treatment, such as etching approach
Figure 9 shows the effect
coat-on/cast of slip zone
approach. of theroughness
The surface artificial ofslip a surface for several
hydrophobic dimensionless
solid material can be tuned slip
in order to increme
hydrophobicity and obtain a super-hydrophobic solid surface [33, 34]. In this section, from the numerical point of view, the ef
length valuesslip
onlength
the dimensionless load support. As indicated in Figure 9, the increase in
on the lubrication behavior is studied. The dimensionless slip length is varied from 3 to 300.
the
slip length leads to an increase in the predicted load support. Generally, the larger the slip
length at theFigure
optimized slip
9 shows the zone
effect ofzone
of slip theofartificial
the artificialslip zone, for
slip surface theseveral
higher the loadslipsupport.
dimensionless length values on the dimensi
load support. As indicated in Figure 9, the increase in the slip length leads to an increase in the predicted load support. Gen
the larger the slip length at the optimized slip zone of the artificial slip zone, the higher the load support. However,
dimensionless slip length is larger than 30, the dimensionless load support is not affected significantly with the increase
dimensionless slip length. So, the increase of the load support is not infinitely large. It can be deduced that there is no flui
support for a lubricated-MEMS when it contains no-slip condition (A = 0). It indicates that the absence of the wedge effect
pressure generation at parallel lubricated sliding contact has been counterbalanced by the influence of the ariticial slip s
application. Again, this condition is very advantageous in engineering a lubricated-MEMS which demonstrates parallel gaps.
0.4
3.2.3. Effect of dimensionless slip length on lubrication performance
The hydrophobicity of a solid surface, as discussed in the previous section, is usually expressed in terms of a slip length
quantifies the extent to which the fluidArtificial
elementsSlip Surface:
near Potential
the surface Application
are affected by thein surface
Lubricated MEMS
energy 245
and the surface geome
http://dx.doi.org/10.5772/55745
surface energy is an intrinsic property of a material that can be controlled by chemical treatment, such as etching approach
coat-on/cast approach. The surface roughness of a hydrophobic solid material can be tuned in order to increm
hydrophobicity and obtain a super-hydrophobic solid surface [33, 34]. In this section, from the numerical point of view, the
However, when
slipdimensionless slip length
length on the lubrication behaviorisislarger
studied.than 30, the dimensionless
The dimensionless loadfrom
slip length is varied support
3 to 300.is
not affected significantly with the increase in the dimensionless slip length. So, the increase of
the load support is not infinitely large. It can be deduced that there is no fluid load support
Figure 9 shows the effect of slip zone of the artificial slip surface for several dimensionless slip length values on the dimen
load support. As indicated in Figure 9, the increase in the slip length leads to an increase in the predicted load support. Ge
for a lubricated-MEMS when
the larger the it contains
slip length at the no-slip
optimizedcondition
slip zone of(Athe= artificial
0). It indicates
slip zone,that the absence
the higher the load support. Howeve
of the wedge effect on theslip
dimensionless pressure
length is generation
larger than 30,atthe
parallel lubricated
dimensionless sliding
load support contact
is not affectedhas been with the increas
significantly
counterbalanced by the influence of the ariticial slip surface application. Again, this condition
dimensionless slip length. So, the increase of the load support is not infinitely large. It can be deduced that there is no flu
support for a lubricated-MEMS when it contains no-slip condition (A = 0). It indicates that the absence of the wedge effec
is very advantageous in engineering
pressure generation a lubricated-MEMS
at parallel lubricated sliding contactwhich
has beendemonstrates
counterbalanced parallel gaps. of the ariticial slip
by the influence
application. Again, this condition is very advantageous in engineering a lubricated-MEMS which demonstrates parallel gap
0.4
0.3
0.2
A=3
A = 30
0.1 A = 300
A = 0 (no-slip)
0.0
0 0.2 0.4 0.6 0.8 1
Figure 9. Effect of the dimensionless slip zone of the artificial slip surface SxD on the dimensionless load support W for
several values of dimensionless slip length A. All profiles are calculated for parallel sliding surfaces (h* = 1).
In Figure 10 the effect of slip zone of the artificial slip surface for several dimensionless slip
length values on the dimensionless friction force is presented. As is well-known, the ability to
control and manipulate friction force during sliding is extremely important key to prolong a
life-time of lubricated-MEMS. Better understanding of the friction force phenomena at micro-
scales is needed to provide designers and engineers the required tools and capabilities to
control friction force and predict failure of lubrication in MEMS.
As can be seen in Figure 10 that the artificial slip surface leads to a reduction of the friction
force for all dimensionless slip length. The friction force decreases with increasing the slip zone
Sx. It can be seen that when the slip zone covers over the whole surface, i.e. homogeneous slip
surface, the friction forces has a minimum value, especially for a high slip length. If the
reduction in friction force is of only particular interest, the homogeneous slip surface (SxD = 1)
is very beneficial. But if the performance is also related to the load support, homogeneous slip
is not recommended because when SxD = 1, the predicted load support is very small for all
wedge ratios, see Fig. 6. With respect to the influence of the dimensionless slip length, opposite
to the hydrodynamic load support, the dimensionless friction force becomes smaller for higher
dimensionless slip length. Therefore, the optimized artificial slip surface is a very promising
lubrication in MEMS.
As can be seen in Figure 10 that the artificial slip surface leads to a reduction of the friction force for all dimensionless slip l
The friction force decreases with increasing the slip zone Sx. It can be seen that when the slip zone covers over the whole su
i.e. homogeneous slip surface, the friction forces has a minimum value, especially for a high slip length. If the reduction in fr
force is of only particular interest, the homogeneous slip surface (SxD = 1) is very beneficial. But if the performance is also rela
the load support, homogeneous slip is not recommended because when SxD = 1, the predicted load support is very small
wedge ratios, see Fig. 6. With respect to the influence of the dimensionless slip length, opposite to the hydrodynamic load su
way to increase the hydrodynamic
the dimensionless friction forceperformance
becomes smallerand the stability
for higher of the
dimensionless sliplubricated MEMS
length. Therefore, the optimized artificia
system because it gives
surface an advanced
is a very promising way load to support inhydrodynamic
increase the combinationperformance
with a reduced
and the friction force.
stability of the lubricated MEMS s
because it gives an advanced load support in combination with a reduced friction force.
1.2
1.0
0.8
0.6
0.4 A=3
A = 30
0.2 A = 300
A = 0 (no-slip)
0.0
0.0 0.2 0.4 0.6 0.8 1.0
Figure 10. Effect of the dimensionless slip zone of the artificial slip surface SxD on the dimensionless friction force F for several val
Figure 10. Effectdimensionless slip length A.
of the dimensionless Allzone
slip profiles
of are
thecalculated
artificial for
slipparallel
surface sliding surfaces
SxD on (h* = 1).
the dimensionless friction force F for
several values of dimensionless slip length A. All profiles are calculated for parallel sliding surfaces (h* = 1).
The combined effect of slip zone parameter on load support and friction force can be better analyzed using the dimensi
friction coefficient. In the present study the dimensionless friction coefficient m is defined as the ratio of the dimensionless fr
The combined effect of slip zone parameter on load support and friction force can be better
coefficient F to the dimensionless load support W. Figure 11 shows the variation of the dimensionless friction coefficient m
analyzed using the of
function dimensionless
the dimensionlessfriction
slip zonecoefficient.
SxD for variousIn the
slip present
lengths study that
A. It appears the when
dimensionless
the dimensionless slip zone is sm
friction coefficient
than 0.2,mtheisfriction
defined as theincreases
coefficient ratio ofsignificantly.
the dimensionless After SxD = friction coefficient
0.2, increasing F towill
the slip zone thebe less significant
reduction of the friction coefficient. It can also be deduced from Figure 11 that dimensionless friction coefficient m will de
dimensionless load support W. Figure 11 shows the variation of the dimensionless friction
with the increase of the dimensionless slip length A, especially for small SxD. It implies that the minimum dimensionless fr
coefficient mcoefficient
as a function
is accord ofwiththe dimensionless
the the slip zone
highest dimensionless SxD for
load support various
(when slip lengths A. It
SxD = 0.65).
appears that when the dimensionless slip zone is smaller than 0.2, the friction coefficient
increases significantly. After SxD = 0.2, increasing the slip zone will be less significant to the
reduction of the friction coefficient. It can also be deduced from Figure 11 that dimensionless
friction coefficient m will decrease with the increase of the dimensionless slip length A,
especially for small SxD. It implies that the minimum dimensionless friction coefficient is accord
with the the highest dimensionless load support (when SxD = 0.65).
Numerical results show that the hydrodynamics of a lubrication film confined between a
moving no-slip surface and a stationary with an artificial slip surface differ significantly from
that of a film confined between two no-slip surfaces. It is found that a homogeneous slip
boundary on one surface produces a lower hydrodynamic pressure in a lubricated sliding
contact at various conditions (slope incline, and slip length), resulting in a reduced load
support which reduces the positive effect of slip on friction. However, if the surface is designed
with an optimal artificial slip pattern (the slip zone is applied on 0.65 of contact length), even
http://dx.doi.org/10.5772/55745
160
Dimensionless friction coefficient, m

140
A =3
120
A = 30
100 A = 300
80
60
40
20
0
0 0.2 0.4 0.6 0.8 1
Figure 11. Effect of the dimensionless slip zone of the artificial slip surface SxD on the dimensionless friction coefficient m for several values of
Figure 11. Effect dimensionless
of the dimensionless slip zone of the artificial slip surface S surfaces
slip length A. All profiles are calculated for parallel sliding xD
on the dimensionless friction coefficient
(h* = 1).
m for several values of dimensionless slip length A. All profiles are calculated for parallel sliding surfaces (h* = 1).
when there is no wedge effect, the load support has a maximum value. In addition, the friction
Numerical results show that the hydrodynamics of a lubrication film confined between a moving no-slip surface and a stationary
force can decrease
with ansignificantly. Therefore,
artificial slip surface it is very
differ significantly frombeneficial
that of a filmtoconfined
makebetween
one oftwo
theno-slip
contacting
surfaces. It is found that a
homogeneous slip boundary on one surface produces a lower hydrodynamic pressure in a lubricated sliding contact at various
surfaces in lubricated-MEMS
conditions (slope incline,with anlength),
and slip artificial slip
resulting in a surface
reduced loadforsupport
achieving idealthelubrication
which reduces positive effect of slip on friction.
However, if the surface is designed with an artificial slip pattern (the slip zone is applied on 0.65 of contact length), even when
performance, there
i.e. reduced
is no wedge friction coefficient
effect, the load support hasand increased
a maximum value. load support.
In addition, the friction force can decrease significantly. Therefore,
it is very beneficial to make one of the contacting surfaces in lubricated-MEMS with an artificial slip surface for achieving ideal
lubrication performance, i.e. reduced friction coefficient and increased load support.
References
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Coatings For MEMS: Characteristics and Recent Developments. Sensors and Actua‐
tors A: Physical 2000;82(1–3): 219–223.
[3] Tagawa M, Ikemura M, Nakayama Y, Ohmae N. Effect of Water Adsorption on Mi‐

crotribological Properties of Hydrogenated Diamond-Like Carbon Films. Tribology
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[4] Smallwood SA, Eapen KC, Patton ST, Zabinski JS. Performance Results of MEMS
Coated with a Conformal DLC. Wear 2006;260: 1179–1189.
[5] van Spengen WM, Puers R, De wolf I. On The Physics of Stiction and Its Impact on
The Reliability of Microstructures. Journal of Adhesion Science and Technology
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[6] Pit R, Hervet H, Leger L. Direct Experimental Evidence of Slip in Hexadecane: Solid
Interfaces. Physical Review Letters 2000;85: 980–983.
[7] Craig VSJ, Neto C, Williams DRM. Shear-Dependent Boundary Slip in an Aqueous
Newtonian Liquid. Physical Review Letters 2001;87(054504).
[8] Bonaccurso E, Kappl M, Butt HJ. Hydrodynamic Force Measurements: Boundary

Slip of Hydrophilic Surfaces and Electrokinetic Effects. Physical Review Letters
2002;88(076103).
[9] Bonaccurso E, Butt HJ, Craig VSJ. Surface Roughness and Hydrodynamic Boundary
Slip of A Newtonian Fluid in A Completely Wetting System. Physical Review Letters
2003;90(144501).
[10] Zhu YX, Granick S. Rate-Dependent Slip of Newtonian Liquid at Smooth Surfaces.
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[11] Priezjev NV, Darhuber AA, Troian SM. Slip Behaviour in Liquid Films on Surfaces of
Patterned Wettability: Comparison Between Continuum and Molecular Dynamics
Simulations. Physical Review E 2005;71(041608).
[12] Cottin-Bizonne C, Barentin C, Charlaix E, Bocquet L, Barrat JL. Dynamics of Simple

Liquids at Heterogeneous Surfaces: Molecular Dynamics Simulations and Hydrody‐
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[21] Tauviqirrahman M, Ismail R, Jamari, Schipper DJ. Effect of Boundary Slip on The
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Chapter 9
Friction and Wear of a Grease Lubricated Contact —

An Energetic Approach
Erik Kuhn
http://dx.doi.org/10.5772/55837
1. Introduction
Lubricating greases are colloid disperse systems with visco-elastical properties. These special
lubricants have a wide range of application. More than 90% of the ball bearings are grease
lubricated but also gears and journal bearings are application examples for greases.
The composition of greases consists of a base oil and a thickener (of course some additives can
be found in commercial lubricants). The thickener forms a network which leads to a complex
rheological and tribological behaviour.
Tribological contacts lubricated by greases are often working under mixed friction conditions.
The situation inside the grease film determines the content of fluid friction. The situation inside
the tribological gap influences the content of solid friction.
A special phenomenon is the structural degradation due to the effects of friction. It leads to a
dependence on time of the grease behaviour.
Aims of this chapter are the description of the liquid friction process inside the grease film and
of the procedure of structural degradation. Both phenomena have a strong influence on the
friction and wear behaviour of the whole tribo-system.
2. General definitions and terminology
The presented work is based on a conception of friction and wear that investigates the process
from an energy point of view. Some ideas differ from well-known definitions so that they need
to be introduced here for better understanding.
A tribological contact describes the geometrical situation of rubbing bodies with interactions in
the sense of the tribological process.
Friction is (only) an energy expenditure.
Wear is a production of irreversibility due to affected friction energy. It covers all elements of
a tribo-system [1].
This chapter distinguishes between wear volume and volume of the removed material.
Wear volume is presented by the material area where irreversible friction effects lead to an excess
of a critical energetic level. (in contrast to the removed material volume (loss of material)).
Mixed friction describes an energy expenditure in several states of friction that exists simulta‐
neously inside the same tribo-system (see also [2]). A direct contact of the solid bodies is not
necessary for mixed friction of a lubricated couple (mix of solid and liquid friction).
Lubricating greases are colloid disperse systems with visco-elastical properties.
The grease structure is characterised by the geometry and the distribution of the thickener, the
interactions between the thickener and the tribo-system and the ability of storing energy.
3. Energy balance for a grease lubricated contact
Grease lubricated contacts are often working in mixed friction. That means liquid friction
(grease film) and solid friction (asperity deformation) have to be considered. An idea of the
situation inside the lubricated contact is presented in the next figures.
Figure 1. Grease lubricated contact with two rough surfaces
The surface profile is modelled with a spherical shape of the asperities and the gap configu‐
ration can be illustrated with Fig.2.
The situation of a single contact in consideration of the simple idea of lubricant layers inside
the grease film is presented in Fig.3.
Friction and Wear of a Grease Lubricated Contact — An Energetic Approach 253
http://dx.doi.org/10.5772/55837
Figure 2. Modelled mixed friction contact of a grease lubricated gap
Figure 3. Single contact and modelled contact situation inside the grease film
The grease topography comes from IR-microscopy and presents the density distribution. In
Fig.3 the contact of two density areas inside the greases film is highlighted.
Investigations of the surface profile and of the density distribution of the grease lead to a
discrete contact model. Random variables are asperity height ξ1,2, radius of the modelled
asperity shape ρ1,2 and the observed density δ1,2. All random parameters can be described with
the Gaussian distribution.
For the contact probability F illustrated in Fig.3 (left) can be obtained [3]
z z -x 2 ug 1 ug 2 r g2 r g2
F( z , u, r ) = ò ò f (x1 ) f (x 2 )dx1dx 2 × ò f ( r1 )dr1 × ò f ( r2 ) × ò f (d 1 ) dd 1 × ò f (d 2 ) dd 2 (1)
0 0 uk 1 uk 2 r k1 rk2
An energy balance is created by investigation of a single grease lubricated contact. The

expended energy is formed as a sum of different contents
W friction = å Wi =1..n (2)

i
The assumption of mixed friction leads to the consideration of two main contents of the friction
energy.
Wmixed - friction = Wsolid + W fluid (3)
A proposal is made with
Wsolid = eelast / plast × Velast / plast × nelast / plast (4)
Wliquid = erheo1,2,3 × Vrheo1,2,3 × nrheo1,2,3 + esolidif × nsolidif × Vsolidif + etensile × Vtensile × ntensile + ewave × Vwave × nwave (5)
In Eq.(4) and (5) the notation energy density for the selected mechanism multiplied by stressed
volume and by the number of contacts with the same mechanism is used. For a single contact
n=1 holds.The solid friction from Eq.(4) considers the deformation (elastically/plastically) of
the stressed asperities. Information about this is given in [4].
The summands in Eq.(5) describe the shearing process in different gap situations (index rheo),
solidification effects in the center of the observed gap (index solidif), tensile stress in the outlet
of the contact (index tensile) and the formation of a friction wave (index wave).
Figure 4. Different stress situations for the grease inside the contact geometry (erheo1,2,3)
http://dx.doi.org/10.5772/55837
4. Liquid friction inside the grease film
4.1. Stress situation inside the gap geometry
As mentioned before a micro single contact of a grease lubricated couple is observed and the
stress situation is analysed. The idea of the process model developed here is illustrated in Fig.5.
Figure 5. Grease lubricated gap between two asperities (micro single contact). Shear stress is the most important
stress mechanism of the grease. Normal force (+) leads to solidification effects. Normal force (-) leads to tensile stress.
In addition the possibility of a friction wave inside the grease film is observed. The idea is
clarified in the Fig.6.
Figure 6. Schematic representation of a friction wave caused by the contact of volume elements of the grease film
with different properties
4.2. Empirical proposals to quantify the friction energy
The experimental work is focused on the quantification of the energy expenditure during the
shear process of a lubricant. This requires an experimental procedure that simulates the liquid
friction inside the grease film.
A proposal is made by the use of a rheometer [5], [6]. Shearing a grease sample in a rotating
or oscillating test can be interpreted as a fluid friction experiment. All reaction measured by
the rheometer is caused by the grease behaviour. The plate and cone in a rheometer configu‐
ration does not lead to the state of mixed friction. Although the test conditions are fare from
real contact situation rheometer tests are helpful for fundamental investigations of fluid
friction.
A picture of a cone-plate configuration is shown in Fig.7.
Figure 7. Evolution of the observed shear stress (left) during a rheometer experiment with a cone-plate system (right)
in rotational modus
The energy per volume that is necessary to shear the grease during the experiment can be
obtained from a shear test (Fig.7). The experimental conditions are constant shear rate and
constant test temperature. To compare different grease samples the test time for each experi‐
ment has to be held constant.
An empirical proposal [7] is made with
t
erheo = g&const × ò t (V )dV (6)
0
with erheo the energy density for the shear process [J/m3], t the test time [s], γ̇ the shear rate [1/
s] and ς the current time [s].
A more interesting experimental procedure is an oscillating rheometer test [Fig.8]. The grease
behaviour can be observed in a wide range of the oscillating amplitude. For the investigation
http://dx.doi.org/10.5772/55837
of fluid friction inside the grease film experiments within the linear visco-elastical range can
be analysed.
To quantify the friction behaviour the following proposal [3] can be used
G¢ × g elast 2
erheo - elast = (7)
cos d
G ′ is the storage modulus [Pa], γ is the deformation [-] and δ is the phase different angle. Eq.
(7) describes the energy per volume J/m3 to deform the sample elastically and is related to
the thickener.
Figure 8. Typical evolution of the storage modulus and the loss modulus during an amplitude sweep (oscillating
measurement)
4.3. Results from experimental work
The energy expenditure expressed by the rheological energy density erheo−elast presents the
liquid friction behaviour of the investigated grease samples. Equation (7) observes only the
shear mechanism inside the tribological gap. To compare the greases the same deformation
(oscillating amplitude) has to be used. Some greases with the same thickener type (Li-soap)
and the same base oil (mineral oil) were observed by a variation of soap content and test
temperature.
Figure 9. Energy densities from the linear visco-elastical range = 20 ° C for different soap contents
An increase of the soap content leads to an increase of the liquid friction. Experiments with a
temperature ϑ = 50 ° C and the same grease samples deliver the results in Fig.10.
Figure 10. Energy densities for a test temperature = 50 ° C (same conditions as Fig.9)
Compared with the test temperature of ϑ = 20 ° C lower values of the energy densities are
obtained. This behaviour is in accordance with the experience that fluid friction is decreasing
with an increasing temperature. A more or less linear correlation of energy density and soap
content can be observed.
http://dx.doi.org/10.5772/55837
Figure 11. Critical energy level vs. soap content
Figure 12. Energy densities for the crossing point vs. soap content
5. Irreversible effects due to friction
5.1. Idea of the structural degradation of lubricating greases
A typical curve obtained from rheometer experiments for constant shear rate and temperature
(rotational mode) shows a strong dependence on time. The drop of shear stress versus stress
time is an indirect expression of the structural degradation and well known from many papers
[8],[9],[10].
To illustrate the friction effects AFM-investigations made by [11] are presented below (Fig.
13). The change of thickener structure caused by the liquid friction is evident. The geometry
and distribution of the thickener is completely different to the initial situation and it can be
assumed that the new grease structure shows a different tribological behaviour.
Volume elements inside the grease film are modelled to observe the tribological process.
Because of the thickener distribution these volume elements have different properties as
elasticity, density, level of accumulated energy, level of critical energy etc.. The consequence
of the property distribution is a different tribological behaviour of the observed volume
elements forming a lubricant layer. The contact situation of two assumed grease layer com‐
posed of different volume elements is presented in Fig. 14.
Figure 13. Left- fresh grease sample, right- grease stressed in a rheometer [11]
Liquid friction between two modelled grease layer. Different volume elements have different
rheological and tribological properties.
An energy stress is applied to the control volume if liquid friction take place (Fig.15). Due to
this energy stress an energy accumulation process, a dissipation process and a transition
process (overstep of a critical energy level) starts.
http://dx.doi.org/10.5772/55837
Figure 14. Liquid friction between two modelled grease layer. Different volume elements have different rheological
and tribological properties.
Figure 15. Modelled volume element inside the grease film. Left – unstressed, right – stressed by liquid friction
The degradation of the grease structure begins with a transition process within a volume
element. Overstepping a critical energy density initiates an irreversible change of the structure.
A contact model is developed to describe the energetic situation of critical exceedance.
To quantify the number of exceedance of critical energy level a stationary Gaussian process is
used. Information about the conditions and definitions can obtained in [1] and [12].
L
1
e ®0 e × L ò
E éë N 0 (u) ùû = lim × E[ A( x , e ) × h¢( x)]dx (8)
0
u2
1 m2 2 m0 (9)
E éë N 0 (u) ùû = × ×e
2p m0
Figure 16. New model to describe the energetic situation fort he transition process inside the grease film [1]
Initial situation is described with Eq. (8) and the expectation of the number of overstepping
N 0 can be determined with Eq. (9). This proposal uses spectral moments m2; m0.
An example [1] was quantified by using density distribution from IR-microscopy to determine
the parameter m2; m0. A mean value of the critical energy level was assumed.
Figure 17. Influence of the critical energy level of the number of oversteps [1]
http://dx.doi.org/10.5772/55837
5.2. Thermodynamic investiagtions
5.2.1. General aspects

Friction process within a tribo-system is an irreversible process. It means that input of friction
energy leads to irreversible effects. This approach interpreted friction and wear process as an
cause-effect-chain.
Different authors tried to find relations between the system behaviour expressed by mass loss
(wear) and entropy flow/production [15]-[19]. Abdel-Aal [18] expressed the conjecture that
relation between frictional heat generation and heat dissipation is related to wear transition.
This author pointed out [19] that there exists a one to one relationship between entropy
generation and mass loss. Doelling et al. [17] give the argumentation that there exists a strong
correlation between components wear and entropy flow.
Ling et al. [13] give an experimental description of a correlation between wear and entropy
flow in lubricated sliding systems.
„Sliding wear is an irreversible degradation of surfaces induced by friction. On a microscopic
scale irreversible physical interactions between the sliding surfaces – including plastic
deformation of asperities, fracture, delamination, abrasive plowing, and corrosive wear,
among others – creates friction resistance forces, dissipates power, and generates irreversible
entropy. Since the physical interactions responsible for friction and wear monotonically
produce entropy, entropy becomes a time base for wear” [13].
“The entropy production, in fact, enable one to bridge the atomic scale phenomena with the
macro scale response” [14] in [13]. “In addition friction and wear, from the vantage point of
thermodynamics irreversible transform mechanical energy into other forms through dissipa‐
tive processes. Therefore, entropy production is believed to be a propitious measure for a
systematic study of wear and friction” [15].
All these investigations pointed out that the application of irreversible thermodynamics is a
promising tool to analyse the tribological processes.
5.2.2. Entropy and structural degradation

The aim of this chapter is a description of relation between energetic situation of the tribo-
system and the degradation of grease structure. Tribo-sytems as solid surface 1, solid
surface 2 and lubricant are investigated but also subsystems as lubricant layer 1 against
lubricant layer 2.
Source of irreversible processes are thermodynamic forces X i (i = 1, 2...) (gradient of tempera‐
ture, gradient of concentration...). These forces Xi evoke corresponding flows I i (i = 1, 2, ...) (heat
flow, diffusion flow...) The generalisation of classical thermodynamic to describe irreversible
effects leads to an investigation of local equilibrium. That means there exist macroscopic small
system areas that are provided in equilibrium while the whole system is out of equilibrium.
Two principles of thermodynamic are used: the linear dependence of flows and thermody‐
namic forces, and the Onsager-reciprocity [20].
For the entropy generation can be written

dS
= ∑ Ii ⋅ X i
dt i
The variation of entropy is influenced by two terms
dS = dSout + dSin (10)
Heat transfer across the boundary of the modelled system (subsystem) delivers the entropy
dSout . Entropy related to mechanisms taking place inside the system is described with dSin
(entropy production). The intention is to relate the entropy production inside the system with
different irreversible effects caused by the friction process within the grease layer. It can be
written
dS
r× + divs = Q (11)
dt
with σ - entropy flow density (σ = ℑ / T ; ℑ =heat flow density) and Θ - local entropy increase
per unit time (Θ = − (ℑ, gradT ) / T 2) [20]
Written in differential form and related to time
dS dSin dQ1- 2 dm dm
= - + se × e - sa × a (12)
dt dt dt dt dt
d me dma
with se ⋅ - entropy transported into the system with mass transport; sa ⋅ - entropy
dt dt
transported out of the system by mass loss. Sin describes the entropy production inside the
system and ( ± )SQ1−2 leads to a change of system entropy by heat transfer across the system
boundaries.
Eq. (12) describes the entropy balance for an open thermodynamic system (with exchange of
mass). As Abdel-Aal [18] pointed out only the entropy source strength, namely entropy created
in the system, should be used as a basis for systematic description of the irreversible process
(degradation of materials).
The process of structural degradation can be described as a process of energy accumulation,
energy dissipation and transition of critical energy levels. Each of these mechanisms delivers
a contribution to an entropy balance and will change the production term in Eq.(10) and (12).
Entropy production (for the observed volume element) is determined by fluid friction and its
effects. The process of solid friction (for a mixed friction contact) delivers only a heat portion
into the modelled system. The tribo-subsystem can be illustrated with Fig.18.
http://dx.doi.org/10.5772/55837
The transport processes modeled from the investigated tribo-system are presented in Fig. 19,
20 and 21.
As a consequence of the modelled mechanisms for the entropy production can be written as
Figure 18. Tribo-subsystem (grease layer against grease layer) inside the general tribo-system
Figure 19. Observed contact situation (section of a complete tribological system). Solid rubbing body and some mod‐
elled grease layers. Heat transport: Q1 - heat amount from solid friction transported into the solid material and into
the grease layer; Q2 - heat amount from liquid friction flows into layer 1 and 2; Q3 - same as Q2; QCOND presents the
heat flow by conduction from layer to layer; V - velocities of the observed layers
Figure 20. Imagine of transport of thickener structure in and out of the observed volume element (mass transport)
Figure 21. Modelled entropy transport processes inside the observed system (entropy flow) [22]
As a consequence of the modelled mechanisms for the entropy production can be
Written with
dSin dSacc dSdiss dStrans

= + + (13)
dt dt dt dt
It means the process of energy accumulation the process of energy dissipation and the
transition of an critical energy level produce entropy. Any chemical potential is disregarded
in this investigation. We may rewrite Eq.(12)
dS æ dSacc dSdiss dStrans ö dQ1- 2 dm dm

=ç + + ÷- + se × e - sa × a (14)
dt è dt dt dt ø dt dt dt
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An assumption is made that heat flow gets a (−) that means for a balance that heat leaves the
observed volume element.
It can be proposed
edef × V R × Vacc
Sacc = (15)
Tacc
with edef the energy density used for deformation process, ςR describes the part of friction
energy which is accumulated, V acc the accumulation volume and T acc the temperature of
accumulation process.
2
G '× g critic
Strans = (16)
cos d
from oscillating rheometer measurements (see Eq.(7)). The temperature situation is assumed
as T solid > T layer 1 > T layer 2. Furthermore it is assumed that different temperature appears for
different mechanism. It means
T acc ≠ T diss ≠ T trans .
In general it is conceivable that part of heat generated by solid friction (asperity
deformation) enters the first modelled grease layer. Part of this thermal load will be conducted
into the next lubricant layer. Liquid friction between the modelled layers leads to a transport
of heat into the layers.
An interesting description of the entropy production term for different processes at sliding
interfaces comes from [21].
To link the energetic situation with the structural degradation the entropy production term
has to be simplified. The friction energy W f is observed with the temperature T f . It can be
obtained
Tf
*
e Rrheo = T f × ( r a × sa ) -
Va
(Se - SQ1-2 ) (17)
An interpretation delivers (ρa ⋅ sa) as an entropy density leaving the system with the mass
exchange. It means an increasing energetic release by entropy flow out of the system with the
*
degraded structure leads to an increasing capacity to withstand stresses expressed by eRheo .
To use some experimental results some assumption were made. The specific entropy can be
determined by
æ T ö
s = c × ln çç str ÷÷ (18)
è Tunstr ø
with index str for the stressed layer and unstr for the unstressed layer. Test temperature in the
rheometer was used for T unstr . An increasing temperature with an increasing soap content
during the friction process was assumed because all measurements show a direct correlation
between soap content and fluid friction (see Fig. 10). To link the specific entropy leaving the
*
system with the degradation process the parameter eRheo for the crossing point (rheometer tests)
is used.
*
Fig. 22 presents the tendency of eRheo vs. s .
*
Figure 22. Correlation between eRheo (the crossing point) and specific entropy
Fig. 22 presents the assumed correlation between energetic stress and energetic release.
Finally some conclusions were made
dS &
> Sprod + S&Q1- 2 + m
& × se (19)
dt
http://dx.doi.org/10.5772/55837
• A significant energetic release by the transport of degraded structure out of the system can
be observed.
dS &
= Sprod + S&Q1- 2 + m
& × se (20)
dt
• No significant energetic release by the transport of degraded structure out of the system can
be observed.
dS
< Ṡ prod + Ṡ Q1−2 + ṁ ⋅ se
dt
• An additional entropy source happens (for example the mentioned friction wave).
6. Conclusions
Some new definitions of general tribological subjects are made. A proposal for an energy
balance of a grease lubricated contact is given and empirical proposals for quantification are
presented. With the help of rheometer tests the fluid friction was investigated and results are
illustrated. The degradation process of the grease structure is described with energetic
parameters. An open thermodynamic system is created and described. The influence of the
energy flow on the degradation process is presented too.
Author details
Erik Kuhn
Address all correspondence to: erik.kuhn@haw-hamburg.de
Department of Mechanical Engineering and Production, Hamburg University of Applied

Sciences, Germany
References
[1] Kuhn,E.: Tribology of lubricating greases. An energetical approach of the tribological

process (in German). expert verlag, 2009
[2] Fleischer,G.: Criterions of mixed friction (in German). Tribologie und Schmierung‐
stechnik, Berlin Technik Verlag 1985
[3] Kuhn,E.: Investigation of the Structural Degradation of Lubricating Greases due to

Tribological Stress. Intern. Colloquium Tribology Esslingen, 2012.
[4] Fleischer,G.: Scientific findingy by Tross from a contemprorary point of view. (in
German) 3rd Arnold Tross Colloquium, Hamburg 2007
[5] Kuhn,E.: Inherent tribo-system response to optimise the process conditions. 8th Ar‐
nold Tross Colloquium, Hamburg 2012
[6] Kuhn,E.: Tribological stress and structural behaviour of lubricating greases. ECO‐
TRIB 7.-9.6.2011 Vienna
[7] Kuhn,E.: Energetics of the time dependent flow behaviour of greases. Applied Rheol‐
ogy June 1997, p.118-122
[8] Czarny,R.: Lubricating greases. WNT Publisher, Warsaw, 2004 (in Polish)
[9] Delgado,M.A.: Manufacture and flow process of lubricating greases. PhD thesis.Uni‐
versity of Huelva, Spain, 2005
[10] Åström, H.: Grease in elastohydrodynamic lubrication. PhD thesis, Lulea University,
1993
[11] Franco, J.M. ; Delgado,M.A. and Valencia,C.: Combined oxidative-shear resistance of

castor oil-based lubricating greases. 3rd Arnold Tross Colloquium. Hamburg 2007. Proc.
pp.18-59
[12] Dierich,P.: Modelling the influence of roughnes on the wear prediction. Habil-thesis.
(in German), Zittai 1986
[13] Ling,F.F.; Bryant,M.D. ang Doelling,K.L.: On irreversible thermodynamics for wear

prediction. Wear 253(2002)1165-1172
[14] Buldum,A.; Ciraci,S.: Atomic-scale study of dry sliding friction. Phys. Rev. B55(4)
(1997) 2606-2611.
[15] Aghdam,A.B., Khonsari,M.M.: On the relation between wear and entropy in dry slid‐
ing contact. Wear 270(2011) 781-790
[16] Doelling, K.L.; Ling, L.L.; Bryant, M.D. and Heilman, B.P.: An experimental study of
the correlation between wear and entropy flow in machinery components. Journal of
Applies Physics . 88(2000)5
[17] Abdel-Aal, H.A.: On the interdependence between kinetics of friction- released ther‐
mal energy and the transition in wear mechanisms during sliding of metallic pairs.
Wear 253, (2002), pp. 11-12
[18] Abdel-Aal, H.A.: Wear and irreversible entropy generation in dry sliding.Annals Du‐
narea de Jos of Galati, Fascicle,VIII,pp.34-44
[19] Basarov, I.P.: Thermodynamic. D.V.W., Berlin 1964 (in German)

http://dx.doi.org/10.5772/55837
[20] Bryant, M.D.: Entropy and dissipative processes of friction and wear. SERBIATRIB
09, 11th Intern. Conf. on Tribology 13.5.-15.5.2009, pp.3-8.
[21] Kuhn,E.: Experimental investigations of the structural degradation of lubricating

greases. GfT-conference Göttingen 2012
Section 4
Sustainability of Tribosystems
Chapter 10
Innovative “Green” Tribological Solutions for Clean

Small Engines
Xana Fernández-Pérez, Amaya Igartua,

Roman Nevshupa, Patricio Zabala, Borja Zabala,
Rolf Luther, Flavia Gili and Claudio Genovesio
http://dx.doi.org/10.5772/55836
1. Introduction
Since its invention in the last quarter of the nineteenth century and during all the twentieth
century, two-stroke engines penetrated in many industrial, automotive and handheld appli‐
cations where engines with high specific power, simple design, light overall weight and low
cost are required. Presently, two-stroke engines are commonly used in motorcycles, scooters,
chainsaw, agricultural machinery, railways grinding machines, outboard applications, etc.
Usually, the moving parts of a two-stroke motor are lubricated either by using mixture of oil
with fuel or by pumping oil from a separate tank. Both designs use total-loss lubrication
method, with the oil being burnt in the combustion chamber. Therefore, the lubricating oil
must meet specific requirements: it must have an optimal balance of light and heavy oil
components to lubricate at high temperature, it must produce no deposits (carbon sooty and
other) on moving parts, and it should be ash-less. In addition, the oil should provide good
protection of moving parts at high speed under deceleration of engine with the throttle closed,
when the engine usually suffers from oil-starvation.
Also, two-stroke engine produce more contaminants than four-stroke engines, due to oil
burning in the combustion chamber. Therefore, it is very important to reduce these contami‐
nations to meet ecological requirements.
Most challenging issue of the European technological strategy resides in complete substitu‐
tion of fossil-based fuels and lubricating oils with renewable eco-friendly and high perform‐
ance materials. Esters and polyglycols were identified as alternative base oils because of their
high biodegradability, low toxicity; low ash formation and absence of polymer compo‐
nents, in [1]. Synthetic esters are characterized by their polar structure, high wear resist‐
ance, good viscosity-temperature behaviour, miscibility with non-fossil fuels. Esther-base oils
can be blended with various components like antifoam agents, oxidation inhibitors, pour-
point depressants, antirust agents, detergents, anti-wear agents, friction reducers, viscosity
index improvers, etc., to create environmental friendly prototype engine oils and to meet the
changing environmental requirements in low sulphur fuels and other alternative fuels and
their application to engine oils.
Low metal additives content and clean-burnt characteristics result in less engine fouling with
much reduced ring stick and lower levels of dirt built-up on ring grooves, skirts and under
crowns. Owing to the presence of polar ester groups in the molecule which have higher
adhesion to metal surface, esters have much better lubricity than hydrocarbons. The perform‐
ance of the ester-based lubricating oils can be further improved by selecting a proper base oil
and additive package.
Another important problem is related with performance of fuel injector system when bio fuels
are used. Diesel injection nozzles consist of a body (usually in Ni-Cr steel) and needle valve
(High speed steel, HSS), fitted together with very strict tolerances. The design of the nozzle,
i.e., the number of orifices, their diameters, positions and drilling angles depend on specific
engine application. The current trend is to use multi-hole nozzles with very small holes with
diameter of only 0.10 - 0.14 mm in order to improve the fuel atomization and flow pattern.
Heat treatments are applied to the body and the needle to obtain the necessary hardness both
on the surface and in the core of the parts and to face the following problems:
• fatigue failures at high stress areas due to repeated pulses of very high injection pressures;
• thermal shocks.
Adequate finishing of the orifice surfaces is very important also to optimize the erosion
resistance.
The usage of new diesel blends characterized by different physical and chemical properties as
compared with the traditional fuels could lead to modifications both in the choice of materials,
geometry and positioning of orifices or their surface finishing to ensure the correct spray
pattern. This work describes the results of our recent studies aimed at solving the problems
related to the introduction of new eco-friendly oils and lubricants.
2. New prototype engine oils
2.1. Oil characterization
Three different synthetic ester base oils have been selected to formulate three prototype engine
oils with the same additive composition. These oils are different mixtures of fully saturated
polyglicol-ester and mono-ester types and designated as SEMO 4, SEMO 5 and SEMO 10. Same
additive package has then been added to the three bases. After comparative characterization
Innovative “Green” Tribological Solutions for Clean Small Engines 277
http://dx.doi.org/10.5772/55836
of these prototype oils and selection of the oil with the best tribological performance (SEMO
10), a new improved formulation was developed based on the selected lubricating oil,
designated SEMO 36. In addition, conventional mineral oil for two-stroke engines was used
as reference oil. The additive package composition of the reference oil is different but it is ash-
free as well as the other SEMO oils.
Oil viscosity was characterized according to ASTM D-445-06 standard procedure in [3], and
viscosity index was determined using ASTM D-2270-04 in [4].
Deposit forming tendency of the oils was characterized by the Coker test at 250 °C during 12
h. Some physical and rheological properties of the lubricating oils are shown in Table 1. Among
the prototype lubricating oils, SEMO 10 has the lowest viscosity both at 40 and 100 °C, the
highest flash point and the lowest deposit forming tendency.
Unleaded petrol (E228) and bioethanol E85 (mixture of 85% of ethanol with 15% of gasoline)
were selected to test miscibility of the lubricating oils with standard and alternative fuels. For
this purpose two different lubricant/fuel ratios were used. Regarding to the miscibility method
A (90% lubricant in fuel), SEMO 10 as well as SEMO 5 demonstrated good miscibility both
with unleaded petrol and E85. Compared to this, the results for the 2% mixtures according
(method B) differed. All tested lubricants proved to be perfectly miscible with EN228 fuel,
whereas only SEMO 36 demonstrated to be fully miscible with E85. According to both
miscibility methods the reference oil was only miscible with EN228. SEMO 36, when compared
to its original prototype SEMO 10, has a much higher viscosity. Flash point for this lubricant
is lower than for SEMO 10 but still higher than 200 °C.
Ref. Oil SEMO 4 SEMO 5 SEMO 10 SEMO 36
Density, g/ml 0.877 0.915 0.917 0.935 0.999
Viscosity @ 40ºC,mm2/s 59.5 84.9 94 45.8 113.3
Viscosity @ 100ºC, mm2/s 8.6 12.5 13.2 8.0 18.3
Viscosity index 117 144 140 147 181
Flash point, ºC 120 204 190 260 218
Pour Point, ºC -21 -39 -33 -39 not tested
Deposit forming * 9 4 3 9 not tested
Miscibility Method A (90% EN228 Good Good Good Good not tested
lubricant in fuel)
E85 Poor Poor Good Good Good
Miscibility Method B (2% EN228 Good Good Good Good Good

lubricant in fuel)
E85 Poor Poor Poor Poor Good
*Rating on base 10
Table 1. Properties of the engine oils

Wettability of the surface of the cylinder liner by lubricating oil is important for corrosion- and
wear-protection of the piston rings and cylinder liner at the start-up when the temperature of
the components is low. In this work, the wetting characteristic of the tested oils was determined
using the Sessile Drop method. The resulting contact angles of the drops of various oils on the
honed surface of the cylinder liner are shown in Table 2. Same method could not be used to
determine wettability of the piston ring because of the small width of the ring. Therefore, the
following procedure for qualitative comparison of the wettability of the piston ring by different
oils in [12] was applied: 1 µl of oil was placed on the circular flat surface of the phosphate cast
iron piston ring and then, after 30 s, the extension of the oil drop along this surface was
measured.
Oil Contact angle on honed cast iron, (º) Spread distance of the oil on the
piston ring, (mm)
SEMO 4 46.1±3.1 5.33±0.04
SEMO 5 43.4±0.2 5.39±0.05
SEMO 10 33.1±1.1 7.01±0.12
SEMO 36 50.8±0.5 3.78±0.17
Table 2. Contact angle and oil spread distance
The contact angle for SEMO 36 oil on the honed cast iron was the highest among all the tested
lubricating oils. The contact angles of SEMO 5 and SEMO 4 were very similar one to each other
and only slightly lower than for SEMO 36. SEMO 10 had the lowest contact angle and the
largest drop spread for all tested oils. The behaviour of the drop spread of the tested lubricating
oils over the piston ring surface is similar to that of the contact angle, bearing in mind that
large contact angle values correspond to small spread distances.
Biodegradability and toxicity of the lubricating oils were examined according to the recom‐
mendations of the Organization for Economic Co-operation and Development (OECD) in [5].
Biodegradability of lubricating oils was tested using OECD 301F Manometric Respirometry
Method consisting of the measurement of oxygen uptake by a stirred solution of the test
substance in a mineral medium, inoculated with micro-organisms in [6]. Toxicity of the
lubricating oils was studied using “Alga, Growth Inhibition Test” OECD 201 in [7] and ”Daph‐
nia Magna” 24 h Acute Immobilisation Test OECD 202 in [8]. In the “Alga, Growth Inhibition
Test”, selected green algae were exposed to various concentrations of the test oils over several
generations under defined conditions. Results of biodegradability test are shown in Table 3.
As expected, all synthetic ester base oils successfully passed the biodegradability test, while
the reference mineral oil was not biodegradable according to the standard procedure OECD
301 Biodegradation of SEMO 5 and SEMO 10 exceeded 70%. In toxicity tests both with Alga
and Daphnia Magna, the oils were classified as not harmful for aquatic organisms according
to the standard procedures OECD 201 and 202 (see Table 4).
http://dx.doi.org/10.5772/55836
Time (days) SEMO 4 SEMO 5 SEMO 10 REF
7 29.4 41.3 25.2 27.6
14 36.2 68.4 53.5 38.7
21 52.0 79.6 69.6 33.4
28 61.1 81.2 75.7 51.2
Ultimate > 60% > 60% > 60% < 60%
Table 3. Biodegradability of oils (% of biodegraded oil) in [12].
Oil EC50/EL50 Classification EC50/EL50 Classification

with Alga, mg/l OECD 201 with Daphnia Magna, mg/l OECD 202
SEMO 4 >100 not harmful * >1000 not harmful *
SEMO 36 - - >1000 not harmful *
*With respect to aquatic organisms.
EC50/EL50 is that concentration of test substance which results in a 50% reduction in either growth or growth rate
relative to the control.
Table 4. Results of the toxicity tests in [12].
2.2. Tribological evaluation according to DIN 51834-2
Tribological evaluation of lubricating oils was done using ball-on-disk configuration with
reciprocating motion according to the standard procedure DIN 51834-2 in [9]. Ball and disk
were made of 100Cr6 steel. The ball, 10 mm in diameter, performed reciprocating motion with
a stroke of 1 mm and a friction frequency 50 Hz. Normal load was 50 N during short run-in
period 45 s and 300 N during the test 60 min. The ball and the disk were immersed in the
lubricating oil, which temperature during the test was constant and 50 °C. Friction force was
measured as function of time. Friction coefficient was calculated as the ratio of the tangential
force to the normal force.
After test completion, diameter of the wear scar on the ball was measured using optical
microscope, and, from this data, volume wear of the ball was calculated for each lubricating
oils tested.
Evolution of the friction coefficient in friction evaluation tests is shown in Figure 1. Oils with
low additive content: SEMO 4, SEMO 5 and SEMO 10 showed an interval of frictional insta‐
bility after the run-in period. In the instability period, which lasted from 400 up to 800 s, there
are some sharp peaks indicating damage of surface and seizure, probably due to micro-
welding. The reference lubricating oil had a less pronounced instability period without sharp
peaks, while SEMO 36 did not present any instability. Final values of friction coefficient after
60 min and the diameters of the wear scar on the ball are shown in Table 5.
Figure 1. Evolution of friction coefficient in time during tribological evaluation tests of the following oils: a) SEMO 4,
b) SEMO 5, c) reference oil, d) SEMO 10, e) SEMO 36. Inset in graph e) shows the initial part of the plot together with
the curve of the normal load in [12].
Oil Final µfr Diameter of wear scar, µm Estimation of worn volume,

mm3
SEMO 4 0.119 ± 3.40*10-5 884 6.01*10-3
SEMO 5 0.111 ± 4.34*10 -5

885 6.02*10-3
REF 0.122 ± 2.73*10-5 517 6.99*10-4
SEMO 10 0.125 ± 3.81*10-5 929 7.32*10-3
SEMO 36 0.123 ± 1.54*10-5 459 4.36*10-4
Table 5. Friction coefficient and wear of the ball in tribological evaluation test of oils (DIN 51834-2) in [12].
The volume of worn material of the ball was estimated geometrically on the basis of the
diameter of the wear scar using the following equation (1):
http://dx.doi.org/10.5772/55836
V=
π
3
( R 3 - ( R 2 + a 2) R 2 - a 2) (1)
where R =5 mm is the radius of the ball and a is the radius of the circular wear scar.
Wear specific energy, Ew, that is, the ratio of the dissipated energy, E, during friction per unit
mass of worn material Δm, is an important characteristic which shows the ability of a material
to resist wearing. This is a complex parameter taking into account both friction, which
characterizes energy supply to the material in the friction zone, and wear intensity. This
parameter is considered a very useful tool to compare standard tribological evaluation and
simulated tests in [10]. Wear specific energy was determined using the following equation
in [12]:
tf
vm F N ∫t μ fr (t )dt
Ew =
E
=
i (2)
∆m ∆m
Where vm is mean sliding velocity obtained with a reciprocating frequency of 50 Hz and 1 mm

stroke, FN is the normal load, μfr is the friction coefficient, ti and tf are respectively the initial
and final time points of friction test time interval.
In this study, only ball wear was determined as specified by DIN 51834-2. So, the absolute
value of wear specific energy could not be determined; since wear of the disk was not meas‐
ured. However, by using the ball mass loss in the denominator of eq. (2), the upper bound
estimation of the wear specific energy can be determined. This upper bound can be used for
qualitative comparison of anti-wear properties of the lubricating oils under constant friction
conditions. These values, determined using eq. (2), are shown in Figure 2. SEMO 36 and the
reference oil have much higher values of the wear specific energy, than other oils. Therefore,
these lubricating oils improve contacting surfaces wear protection since much larger energy
should be dissipated to produce the same wear as compared to SEMO 4, SEMO 5 and SEMO
10 lubricants.
Figure 2. Friction coefficient and wear specific energy in [12].

2.3. Piston ring/cylinder liner simulation
Tribological simulation was performed using cast iron phosphated piston ring and cast iron
cylinder liner using reciprocating motion configuration. The samples for the tests were cut
from real engine parts (Minsel M165 two-stroke engine manufactured by Abamotor Energía)
keeping original curved surfaces and surface finishing. The conformal contact between the
piston ring and the cylinder counterpart was reproduced by placing a piston ring on a suitable
frame, A, and fixing it by means of a clamp, B (Figure 3). Wear of the components was
determined by weighting and geometry measurements.
A - frame for fixing the piston ring segment, B – fixing clamp, C – base with oil bath for fixing cylinder liner sample.
Figure 3. Experimental set-up for piston ring/cylinder liner simulation.
The piston ring segments performed a reciprocating motion with a stroke of 1 mm and a friction
frequency 40 Hz. Normal load was 50 N during short run-in period 45 s and 300 N during the
test 90 min. During the test, the piston ring segment and the cylinder liner sample were
immersed in the oil, which temperature was constant at 200 °C.
The mass change of the piston ring segments and cylinder liner sample was determined from
weighting the components before and after friction tests. Since the mass change can be due to
two competitive processes: (i) wear out and (ii) deposit formation from the oil at elevated
temperature, estimation of wear out by weighting can give erroneous results. Indeed, after the
tests the surface colour became yellowish and remained after dissolvent cleaning indicating
some sparingly soluble deposits formed on the surface due to some chemical reaction.
Therefore, in addition to the determination of the mass change, worn volume was calculated
from surface geometry. Surface morphology of the friction zone was studied using white light
confocal microscopy at three different zones along the wear track on the cylinder liner sample.
The acquired 3D surface images were 0.5 mm wide in the direction of friction and each image
contained 138 cross-section profiles of the wear track yielding totally 414 profiles for each
sample. Firstly, the cross-section profiles were averaged for each sample and then among
different samples tested using the same lubricating oil. Worn volume of the samples of cylinder
liner was calculated as a product of a mean cross-section area of the groove and the total length
of the groove. The cross-section area was determined by numerical integration of the cross-
section profiles and then worn mass was calculated from the worn volume using the density
of cast iron.
http://dx.doi.org/10.5772/55836
Surface chemical composition of the friction zone of cylinder liner samples was characterized
using Energy Dispersion X-Ray Spectroscopy (EDS).
Evolution of friction coefficient in time during friction between piston ring segment and a piece
of the cylinder liner is shown in Figure 4. It is possible to highlight the increment of the
coefficient of friction μfr for lubricants SEMO 4 and SEMO 5 overtaking the constant value
reached by the lubricant of reference. In fact, for SEMO 4 and SEMO 5, friction coefficient
gradually rose during the experiment (90 min) and did not stabilize. The growth behaviour
was almost linear in time.
Initial friction coefficient was about 0.2 and the final one about 0.33 in both cases. SEMO 10
and SEMO 36 showed different behaviour. The initial values were 0.2 and 0.14 for SEMO 10
and SEMO 36, correspondingly.
Figure 4. Evolution of friction coefficient in time during piston ring/cylinder liner simulation test. a) SEMO 4, b) SEMO
5, c) reference oil, d) SEMO 10, e) SEMO 36. Inset in the graph e) shows the initial part of the plot together with the
curve of the normal load in [12].
At the beginning, after a run-in period, friction coefficient increased and reached maximum.
For SEMO 36 the maximum was reached usually between 100 and 200 s from the beginning
of the test, while for SEMO 10 the period of increase was longer and the maximum was reached
after 700 to 1700 s from the beginning of the test. After reaching the maximum, friction
coefficient decreased slowly and stabilized at 0.14 and 0.11 for SEMO 10 and SEMO 36,
correspondingly. The friction coefficient of lubricant SEMO 10 showed a slow decline until
reaching a constant value lower than the reference one. Friction coefficient for the improved
lubricant SEMO 36 levelled out rapidly at a very low value and showed less scatter, probably
due to some sort of surface deposition on the contact surfaces.
The averaged cross-section profiles of each liner sample tested are reported in Figure 5.
Different scales of magnitude are used for better visualization of the mean contact surface
profile. It is possible to notice very good performance of the lubricant SEMO 10 and its
improvement in the lubricant SEMO 36. Samples tested using SEMO 4 and SEMO 5 had deep
grooves with the maximum depth 22 to 25µm. The samples tested using the reference oil and
SEMO 10 had less deep grooves with a maximum depth of 4 to 5µm. Surface of the samples
tested using SEMO 36 oil had some thin scratches in the direction of friction while grooves had
not been formed.
Figure 5. Average cross-section profile of the friction zone of cylinder liner samples tested using different lubricants in
[12].
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Figure 6 shows images of the friction zone of the piston ring segments after friction simulation
tests with different lubricating oils. Wear and damage of the surface as function of the oil used
was similar to that in the cylinder liner. In tests with SEMO 4 and SEMO 5, the material in the
friction zone was heavily damaged. The wear can be classified to be of the adhesive type with
intensive plastic deformation and edging. When the reference oil and SEMO 10 oil were used
in the tests, the damage of the material was less pronounced than for SEMO 4 and SEMO 5,
but the wear in all cases was of the adhesive type. Only small damage was observed on the
piston ring segments when using SEMO 36. In this case, only summits of the circular grooves
of the piston ring presented some wear and deformation. From the point of view of hydrody‐
namic lubrication these results may seem to be surprising, since, with the same additive
composition, higher wear rate occurs for thinner oil (SEMO 10 in our case) than more viscous
oils (SEMO 4 and SEMO 5). Therefore, these results lead to the following conclusions: 1) the
lubrication regime should be of a boundary type and 2) surface protection against wear for
SEMO 10 and SEMO 36 oils seems to be resulting from the formation of surface layer as a result
of adsorption of oil components or tribochemical reactions between the oil components and
the base material.
Figure 6. Optical images of the friction zone of the piston ring segments after friction simulation tests using different
lubricants. The scale of each image is the same and shown by a scale bar in [12].
Results of the mass change measurements of the components are shown in Table 6. Worn mass
calculated from the worn volume is plotted vs. measured mass change in Figure 7 (dots). The
experimental data are fitted by linear function with two adjusted parameters: slope and
intersect (dashed line in Figure 7). The solid line is a linear fit with a fixed slope 1 and adjusted
intersect. Coefficients of determination for these linear regressions are 0.983 and 0.949,
correspondingly, indicating statistically significant linear relationship between the mass
change and worn mass determined from the geometry of the groove. Therefore, the deposit
formation has not much influence on the mass change and the last can be used as a measure
of the components wear out in these tests. The upper bound of the wear specific energy was
determined in accordance with eq. (2), using the cylinder liner mass change in the denominator
of eq. (2).
Oil Final µfr Mass change, mg Worn volume (cylinder.) mm3
cylinder segment
SEMO 4 0.34 -3.95 -1.41 -1.12*10-2
SEMO 5 0.32 -3.68 -3.22 -9.8*10-3
REF 0.20 -1.1 -0.64 -1.74*10-3
SEMO 10 0.14 -0.94 -1.25 -2.3*10-3
SEMO 36 0.11 -0.09 1.23 0
Table 6. Results of friction simulation tests in [12].
Figure 7. Mass wear determined from the geometry of the groove vs. mass change of the cylinder liner samples. The
dashed line is a linear regression of experimental data with two adjusted parameters: slope and intercept. The solid
line is a linear regression with a fixed slope 1 in [12].
Final friction coefficient and wear specific energy are shown in Figure 8. SEMO 36 oil showed
the best antifriction and wear resistance characteristics among all tested lubricants. Friction
coefficient was almost a half of that for the reference oil, while specific wear energy was 7.8
times higher than for the reference oil. In comparison with the ball-on-disk tests, wear specific
energy for SEMO 36 lubricant was much lower in the tribological simulation test; however, oil
temperature in these two tests was different. When the ball-on-disk evaluation tests were
performed at the same temperature as in the simulation test (200 °C), the value of wear specific
http://dx.doi.org/10.5772/55836
energy was similar to that in the simulation test: 0.14 GJ/g in the ball-on-disk at 200 °C vs. 0.18
GJ/g in the piston ring/cylinder liner simulation test. Although these values are only upper
bound estimations of the real values, they are close to one another. According to the structural-
energetic approach in [10], this means that the dominating wear mechanism in both cases is
the same. Then, a significant decrease in the wear specific energy from 3.97 to 0.14 GJ/g with
temperature increase from 50 to 200 °C implies changing in dominating wear mechanism at
higher temperature. It can be stated that, under the applied experimental conditions, the
chemical compositions of the base oil and the additives had greater influence on the tribological
performance of the lubricants than their rheological properties.
Figure 8. Friction coefficient and wear specific energy in friction simulation tests in [12].
2.4. Surface characterization
Surface chemical composition of the friction zone of cylinder liner samples was characterized
using Energy Dispersive X-Ray Spectroscopy (EDS). Table 7 shows surface chemical compo‐
sition for three different surfaces:
• friction zone of the cylinder tested using SEMO 36 lubricant,
• untouched surface of the same cylinder, and
• reference cylinder not immersed neither heated in lubricating oil.
Fe O C Si Mn
Friction zone 61.5±1.9 11.5±0.7 23.5±3.2 2.83±0.68 0.615±0.085
Untouched zone 84.0±3.6 7.36±0.46 3.41±3.31 4.19±0.07 1.11±0.17
Reference sample 92.5±0.3 2.95±0.46 0.1 3.59±0.52 0.935±0.255
Table 7. Surface chemical composition (at.%) of the cylinder liner samples tested with SEMO 36 lubricating oil
Silicon and manganese were alloying elements of the base material and did not show important
variations in their concentration, whereas the most important variation was in the carbon and
oxygen content. There was no significant difference for other elements since the oils had no
metal-containing additives. Figure 9 shows surface concentration of four elements relative to
iron. After the test, during which a cylinder was immersed in the SEMO 36 oil and heated at
200 °C, carbon and oxygen concentrations on untouched surfaces were slightly higher than on
the reference sample, e.g., the sample not immersed into the oil. However, carbon and oxygen
concentrations drastically increased on the surface of the friction zone, on which carbon was
each forth atom. Also, in contrast to the untouched surface and the reference surface, on the
surface of the friction zone, carbon concentration was higher, than the oxygen one. One can
infer from these data that friction induced tribochemical reactions between oil components
and base material to form surface layer enriched with carbon and oxygen. This surface layer
or sliding lacquer may protect mating surfaces from adhesion and/or damage yielding lower
friction and wear in [10].
Figure 9. Surface concentration of elements relative to iron in [12].
2.5. Experimental evaluation in real two-stroke engines (Minsel M165)
After previous simulation tribological test the performance of the oils was evaluated in real
two-stroke engines (Minsel M165) with a swept volume of 158 cm³, a stroke of 54 mm,
compression ratio 7,1:1, power (ISO 1585) 3.53/4.8 kW/HP, maximum torque 120 Nm and 4500
rpm rotation speed. Scuffing tests were performed using various lubricating oil – petrol
mixtures in order to evaluate the lubricating performance of the lubricants under extreme load
conditions. The test conditions applied are shown in Table 8, and the tested oil-fuel composi‐
tions are shown in Table 9.
Figure 10 shows the photographs of the engine components after scuffing tests, in which the
reference mineral oil was used in a mixture with pure petrol and bioethanol. Increase in the
bioethanol content in the fuel led to decrease in carbon soot deposition on the engine cylinder
and piston. Also, when bioethanol was used, the surface was less damaged under extreme
working conditions.
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Test step Speed, rpm Time, min Power
% HP
1 2000 5 0 0
2 4000 20 50 2.4
3 4000 20 75 3.2
4 2000 5 0 0
5 4500 90 100 full load
6 2000 5 0 0
Table 8. Experimental conditions for scuffing tests of real two-stroke engines
Fuel Reference oil New developed oils

SEMO 10 SEMO 36
Petrol 2% 2% 2%
E10 2% - -
E20 2% - -
E85 2% - 2%
Table 9. Oil – petrol combinations tested in a real two-stroke engine scuffing test
Figure 10. Macro images of two-stroke engine components after scuffing test using a mixture of mineral oil with pet‐
rol (a,d), bioethanol E10 (b,e) and bioethanol E20 (c,f) in [12].
Figure 11. Macro images of two-stroke engine components after scuffing test using mixture of SEMO 10 lubricating
oil with petrol: a) piston, b) cylinder, c) exhaust side, d) intake in [12].
Figures 11 show the photographs of the engine components after scuffing tests using a SEMO
10 – petrol mixture. Some seizure between compression piston ring and cylinder was observed
when using a mixture of SEMO 10 with petrol. Several vertical abrasion marks were formed
in the exhaust zone of the cylinder, where the temperature was higher. However, the piston
and cylinder were quite clean with only some carbon soot deposits in the exhaust zone. The
state of the cylinder head was quite healthy and clean in the intake zone, the carbon residues
were considered normal.
Figure 12 shows the pictures of the engine components after scuffing test using SEMO 36
lubricating oil with petrol and bioethanol fuels. When using a mixture of SEMO 36 with
bioethanol E85 or petrol, no scuffing or seizure was observed. Only light scratches were found
on the cylinder surface, which were more pronounced when using petrol. In this case, carbon
soot deposits formed intensively on the top part of the piston. The piston and cylinder were
very clean, when using bioethanol.
In addition, gaseous emissions from the engine were analyzed for various fuel-oil mixtures
with different proportions of bioethanol to petrol: 20%, 30% and 85%. The gas emissions
were measured using the Directive CE 2002/88, Portable, SH3 modality as reference limits.
The differences in power and consumption were negligible when using bioethanol E10 and
E20. When compared with the petrol, the NOx emissions showed an increasing trend and
the emissions of CO and CH diminished in tests with bioethanol and reference oil. When
using E85, the reference mineral oil was not miscible, but the new developed oil SEMO 36
was totally miscible. When using bioethanol E85, a considerable reduction in engine power
was observed yielding value 13% to 22% less than in the tests with petrol. At the same time
fuel consumption increased slightly between 7% and 20%, and gaseous emissions were
considerably reduced (see Table 10). When using SEMO 36 the reduction in NOx emission
was the most significant as compared with other gases and was probably due to the lower
temperature generated.
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Figure 12. Macro images of two-stroke engine components after scuffing test using mixture of SEMO 36 lubricating
oil with bioethanol E85 (a, b, c) and petrol (d, e, f): a), b), d), e) piston, c), f) cylinder in [12].
Oil Type and % Power Consumption NOx CHx CO

(kW) (g/kWh) (g/kWh) (g/kWh) (g/kWh)
SH3 Limit Normative 5.36 161 603
Petrol/Ref. Oil 2% 5.46 397 1.469 139.8 333.2
E10 + 2% Ref. oil 5.44 385 1.573 124.1 314.8
E20 + 2% Ref. oil 5.5 382 2.29 128 251.5
E85 + 2% Ref. oil 4.8 427 2.29 109.8 43.11

(not miscible)
E85 + 2% SEMO 36 4.3 478 0.689 119.5 32.93

(miscible)
Table 10. Emission of gases from two-stroke engine tested with different lubricating oil– petrol combinations in [12].
2.6. Life cycle
The lifecycle analysis for a 2-stroke engine fed by petrol and E85 was carried out using the
model M 165 Minsel engine running in a tiller during 1000 h, which characteristics are shown
in Table 11.
Model of machine Tiller 3002
Machine weight 90-110 kg
Engine model M165 Minsel 2-stroke
Engine weight 12.8 kg
Engine life 1000 h
Scuffing test results OK
Engine power 3 kW
Emissions Directive 97/68/CE and later 2002/88/CE and 2004/26/CE
Table 11. Characteristics of the engine used in life-cycle analysis
Two fuel + oil pairs named as “Cleanengine systems” were compared with the Conventional
system for the same engine working in the same application. In the alternative Cleanengine
system I the engine was fed by a mixture of bioethanol E20 and mineral oil. In the alternative
Cleanengine system II, the engine was fed by bioethanol and newly developed advanced and
biodegradable lubricating oil SEMO 36. The fuel and oil consumption for the conventional and
two alternative systems is shown in Table 12.
Conventional Cleanengine Cleanengine

system (I) system (II)
Fuel consumption Petrol BioE20 BioE85

per functional unit 900 kg 1123 kg 1405 kg
Oil consumption Mineral oil Mineral oil SEMO 36

per functional unit 36 kg 23 kg 29 kg
Table 12. Parameters of the conventional and alternative systems used in the life-cycle analysis
The Eco-indicator 99 Methodology was used for the Impact Assessment method. The compo‐
nents of the environmental impact are shown in Figure 13 a), while the total environmental
impact is shown in Figure 13 b). Almost all components of the environmental impact as well
as the total environmental impact were higher for fossil fuel. However, the climate change was
more affected by the renewable system.
The global environmental impact evaluated by Lifecycle Assessment tools for the Cleanengine
system I and II using bioethanol was lower than for the reference system using petrol. The
comparison between two alternative systems Cleanengine I and Cleanengine II showed that
the last one had slightly higher environmental impact due to higher fuel and lubricant
consumption that can be related to the lower calorific value of the ethanol compared to the
petrol. While the reduction of the environmental impact is attributed to the reduction in
emissions, the use of a biodegradable nontoxic lubricant will further reduce the environmental
impact of the Cleanengine II system.
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Figure 13. Results of the life-cycle and environmental impact analysis for the conventional and two alternative sys‐
tems: a) components of the environment impact, b) total environmental impact in [12].
3. Nozzles for future engines
Compared to conventional liquid hydrocarbon fuels, bio-fuels exhibit considerable differences

in their physical properties which significantly influence on the injector flow as well as on primary
and secondary spray break-up processes. As a consequence, spray mixture formation of bio-
fuels is considered to be largely different compared to conventional fuels under engine operat‐
ing conditions with severe consequences on the combustion and emission characteristics. Hence,
injection and combustion system optimization as well as optimization of the injector configura‐
tion (number of nozzle holes, diameter, spray targeting, etc.) for bio-fuels requires a detailed
knowledge of how the fuel properties influence the injector flow and spray atomization
characteristics. Optimization of the nozzles materials and design is an important task which will
open new markets and enlarge the number of potential customers for eco-friendly applications.
3.1. Tribological evaluation
Different metal-doped DLC coatings were developed by Physical Vapour Deposition method
(PVD). Friction and wear tests were carried out using SRV tribometer with “cylinder-on-disc”
configuration in lubricated conditions. The coatings were deposited on steel cylinders and
disks. The cylinder, 15 mm in diameter, performed reciprocating motion with a stroke of 2 mm

and a friction frequency 50 Hz. Normal load was 50 N during short run-in period 30 s and 200
N during the test 60 min. The cylinder and the disk were immersed in fluids, which temper‐
ature during the test was constant and 25 °C.
Both Cr- and Ti DLC coatings had good friction and wear behaviour and they could be a good
alternative to improve tribological properties of the actual uncoated nozzles.
Figure 14. Average cross-section profile of the friction zone of discs samples (uncoated reference, Cr and Ti DLC) test‐
ed using different fuels, AGIP and B50. Different scales of magnitude are used for better visualization of the mean
contact surface profile.
Surface morphology of the friction zone was studied using white light confocal microscopy.
The averaged cross-section profiles for each sample tested are shown in Figure 14. It is possible
to notice very good performance of the coatings, them had deeper grooves with a maximum
depth of 5.45 µm. Cr DLC tested against AGIP fuel had better performance than Ti DLC. Two
different scales of magnitude, Z, are used for better visualization of the mean contact surface
profile. From 5 to -5µm for coated discs (Cr DLC and Ti DLC lubricated with AGIP ref and
B50) and from 16 to -16µm for uncoated ref samples.
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3.2. Corrosion characterization
Corrosion resistance of different materials and coatings used for nozzles fabrication (Cr and
Ti DLC) was characterized using electrochemical impedance spectroscopy and potentiody‐
namic polarization techniques in order to determine the kinetics parameters and the corrosion
mechanisms of these materials in NaCl 0.5M or K2SO4 0.2M in [12].
Base nozzles material, uncoated steel X82WMo, was also characterized under corrosion
conditions and compared with DLC coated samples of the same material. The electrolyte used
in these tests was K2SO4 0.2M. Cr DLC coating offered excellent corrosion protection. The
coating did not exhibit any pores or defects, protecting effectively the substrate during
immersion.
Open-circuit potential (OCP) was measured during 2200 s in order to analyze the samples
tendency with the exposure time. After that, an electrochemical impedance spectroscopy was
performed in a frequencies range from 10 k to 10 mHz. Once impedance measurements
finished, a potentiodynamic potential swept was applied from OCP-0.2 V to OCP+0.6 V at a
scan rate of 0.5 mV/s.
Coated nozzles had more positive potential than the reference ones. For all surfaces, OCP was
stable after first 2200 s of immersion. The difference between three nozzles regarding impe‐
dance results was very notable. Cr and Ti DLC coated samples had a semicircle Nyquist
diagrams implying that the electrolyte did not reach the substrate during the immersion in the
dissolution. The coating acted as an effective protective barrier. Uncoated nozzle had lower
corrosion resistance. Two time constants could be clearly distinguished from two maxima in
the Nyquist plots.
5000
Ref. Uncoated
4000 Cr DLC
Ti DLC
Zre (Ohm)
3000
2000
1000
Zim (Ohm)
0
0 500 1000 1500 2000 2500 3000
Figure 15. Nyquist diagrams. Impedance data of coated and uncoated nozzle in K2SO4.
Table 13 shows the parameters obtained from equivalent circuit simulation of the experimental
data and Figure 16 shows the equivalent circuits used in the simulation process.
Samples OCP R1 CPE1 R2 CPE2 ΖΟ

(Nozzle appl.) (V) (kΩ/cm2) (μF/cm2) (kΩ/cm2) (μF/cm2) (μΩ−1·σ 1/2; σ 1/2)
Yo=58.45 Yo=140.7
Nozzle Uncoated -0.556 0.035 1.10
n=0.82 n=0.94
Yo=0.75
Nozzle Cr DLC -0.022 12780 - - -
n=0.94
Yo=0.34 Yo=0.02
Nozzle Ti-DLC -0.354 10.38 - -
n=0.639 B=3.23
Table 13. Equivalent circuit parameters of coated and uncoated nozzles
Figure 16. Equivalent circuits used for the experimental data simulation. Circuit A) for Nozzle Cr DLC; circuit B) for un‐
coated nozzle and circuit C) for Ti DLC coating.
Polarization curves for the coated nozzle are shown in Figure 17.
0
-0,8 -0,3 0,2 0,7
-2 E(V vsAG/AgCl)
-4
log I(A)
-6
Ref
-8
Cr DLC
-10 Ti DLC
-12
Figure 17. Polarization curves on coated and uncoated nozzles immersed in K2SO4
Cr DLC coating had passive behaviour and low corrosion current of the order of 10-9A for
potentials near to OCP. Coating Ti DLC also had passive behaviour in a wide zone of the anodic
http://dx.doi.org/10.5772/55836
branch. Cr DLC and Ti DLC notably improved substrate corrosion behaviour reducing its
corrosion current by several orders of magnitude (see table 14).
Samples Ecorr (V) Icorr (μA/cm2)
Nozzle Ref. Uncoated -0.533 18.5

Nozzle Cr DLC -0.039 0.003
Nozzle Ti DLC -0.331 0.18
Table 14. Corrosion current of coated and uncoated nozzles calculated using Tafel approach
3.3. Experimental evaluation in real four-stroke engines (Minsel M430)
The injectors were tested in the Minsel M-430 engine manufactured by Abamotor Energía, SL.
The parameters of the engine and test conditions are shown in Table 15.
Bore 85 mm
Stroke 75 mm
Displacement 426 c.c.
Compresion ratio 19,3: 1
Power NB 8,4 / 8,7 Cv
Rpm 3000
Torque 23Nm / 2000 RPM
Dry weight 45 Kg
Table 15. Characteristics of the engine used in engine tests to evaluate the different alternative nozzles (Cr DLC and Ti
DLC).
During the test the engine worked for 50 hours at full load (3000 rpm). Biodiesel B30 was used
as a fuel, which was a mixture of FAME (100% Biodiesel) with diesel B at a rate of 30%.
Figure 18. The engine on test bench and the tested nozzles installed on the engine
3.4. Nozzle characterization after test in the engine
Scanning electron microscope (SEM) and energy dispersion X-Ray spectroscopy (EDS) were
used for characterization of the nozzles geometry after the engine tests. Cr DLC coating had
better behaviour than Ti DLC.
The microanalysis showed that for the all coatings the deposited layer on the needle persisted
after the test, with the exception of the tip where the Ti DLC layer has been detached
Additionally, the spray holes geometries of the nozzle body were analysed after endurance
test with two different fluids: reference standard fuel and 30% biodiesel.
Figure 19 shows the scanning electron microscope images (EDS) of the nozzle body tip before
the engine test (real part and its corresponding silicon model for orifices internal characteristics
analysis), whereas Figures 20 and 21 show the nozzles after the tests with standard diesel fuel
and B30 fuel, correspondingly. Though large quantities of carbonaceous deposits could be
observed on free surfaces for both fuels, no deposits were found on internal surface of spray
holes.
Figure 19. Nozzle body tip and silicon model with labelled holes
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Figure 20. Images of the nozzle after endurance test with standard diesel fuel
Figure 21. Images of the nozzle after endurance test with B30 fuel
Finally, nozzle deposits were analyzed by Thermal Gravimetric Analysis (TGA), which
showed no big difference in deposits composition for the nozzles operated with standard diesel
and B30 blend.
4. Conclusions
Fully formulated prototype lubricants based on synthetic esters had low toxicity for aqueous
organisms (algae and Daphnia Magna) and high biodegradability evaluated by the Mano‐
metric Respirometry Method.
Among three developed prototype lubricating oils, SEMO 10 had the best tribological per‐
formance which was comparable with that of the reference mineral oil. Further improvement
of the tribological properties of this lubricating oil was achieved by additive re-formulation.
The developed lubricant, SEMO 36, exceeded the reference mineral oil in tribological per‐
formance.
http://dx.doi.org/10.5772/55836
Our findings indicated that, in addition to the rheological properties of the lubricating oil,
deposit build-up was an important factor controlling the tribological performance of the oil
both in simulation experiments and real two-stroke engines. Two kinds of deposits: carbon
soot and transparent sliding lacquer were observed on the engine components after tests.
Build-up of a transparent sliding lacquer was especially important in the case of SEMO 36 oil
and it was related with considerable reduction both in wear rate and friction coefficient. For
SEMO 36, surface chemical analysis of the friction zone showed important changes in surface
chemical composition, which was especially marked by increase in carbon and oxygen content.
It is evident that formation of the sliding deposits stemmed from tribochemical reactions
between the oil components and base material (cast iron and steel). The chemical state of carbon
and oxygen atoms on the surface of friction zone should be further investigated for better
understanding of these mechanisms.
Tests in real two-stroke engines were performed using mixtures of the developed lubricant
with petrol or bioethanol. In both cases, no seizure between piston ring and cylinder liner was
observed. When using bioethanol, the engine components were clean without important
carbon soot deposits.
Engine power slightly decreased and fuel consumption slightly increased - on a volumetric
basis when bioethanol E85 was blended with the newly developed lubricating oil SEMO 36.
However, these results might be related with lower calorific value of ethanol as compared with
petrol. Besides, the new lubricating oil improved scuffing resistance in combination with
miscible lubricants and significantly reduced the environmental impact. In addition to low
toxicity and high biodegradability, emissions of CO, NOx and hydrocarbons from engines
lubricated with the newly developed lubricants were lower than with traditional mineral oil
and much below the limits established for portable applications.
Concluding, a new generation of lubricating oils for two-stroke engines have been developed
combining low friction, good protection against wear and scuffing, no ash residue, low carbon
soot or other deposit formation. These lubricating oils are compatible with bioethanol E85.
Application of Cr DLC coating on injection nozzles significantly increased the corrosion

resistance and improved behaviour in engine test.
Though Ti-DLC coating also improved substrate corrosion resistance, its performance in
engine test was worse than for Cr DLC coating.
Deposit chemical composition and the nozzle performance did not significantly vary in
endurance tests when standard diesel was substituted by B30 blend.
Acknowledgements
The authors acknowledge financial support of the European Commission, the project Clea‐
nEngine “Advanced technologies for highly efficient Clean Engines working with alternative
fuels and lubes” under contract TST5-CT2006-031241, and the Spanish Minister of Science and
Innovation, for co-financing the project under contracts ENE 2008-00652-E/ALT “Tecnologías
Avanzadas para motores limpios altamente eficientes, trabajando con combustibles y lubri‐
cantes renovables”, RYC-2009-0412 and BIA2011-25653. Also, the authors acknowledge
support received from other partners who participated in the projects: ARIZONA Chemical,
OBR, GUASCOR Power, BAM, AVL and INSTITUTO MOTORI.
We appreciate the useful help of Olatz Areitioaurtena and Raquel Bayón on performing
Biodegradability, toxicity and corrosion characterizations and tests.
Author details
Xana Fernández-Pérez1, Amaya Igartua1, Roman Nevshupa2, Patricio Zabala3, Borja Zabala3,
Rolf Luther4, Flavia Gili5 and Claudio Genovesio6
1 Fundación Tekniker, Avda, Otaola, Eibar, Spain
2 Instituto de Ciencias de la Construcción Eduardo Torroja (IETcc), c/ Serrano Galvache, Ma‐

drid, Spain
3 Abamotor Energía, SL, B. Astola, Abadiano, Spain
4 Fuchs Europe GmbH, Mannheim D, Germany
5 CRF StradaTorino Orbassano, Italy
6 FIRAD S.p.A, Fabbrica Italiana Ricambi Apparati Diesel, Bagnolo, ItaIy
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PVD multilayer coatings for gears application. Industrial Lubrication and Tribology. V.
63/1. P. 17–26.
[16] Alajbegovic, A; Meister, G; Greif, D; Basara, B; (2001) Three Phase Cavitating Flows in
High Pressure Swirl Injectors. 4th Int. Conf. on Multiphase Flow – ICMF'01, May 27 –
June 1, 2001, New Orleans, Louisiana, U.S.A.
[17] Von Berg, E; Alajbegovic, A; Tatschl R; Krüger, C; Michels, U; (2001) Multiphase Mod‐
eling of Diesel Sprays with the Eulerian/Eulerian Approach (DaimlerChrysler AG),
ILASS-Europe 2001, Sept. 2-6, 2001, Zürich, Switzerland
[18] Von Berg, E; Alajbegovic, A; Greif, D; Poredos, A; Tatschl, R; Winklhofer, E (2002);

Break-up Model for Diesel Jets based on Locally Resolved Flow Field in the Injection Hole,
ILASS-Europe 2002, Sept. 9-11, 2002, Zaragoza, Spain
Chapter 11
A Sensor System for Online Oil Condition Monitoring of

Operating Components
Manfred R. Mauntz, Jürgen Gegner,

Ulrich Kuipers and Stefan Klingau
http://dx.doi.org/10.5772/55737
1. Introduction
A web-based oil diagnosis system for continuous online lubricant condition monitoring is
presented. The new approach utilizes sensor detection of chemical aging of engineering oils
and their additives or first traces of wear debris by precision measurement of the electrical
properties. The basic concept and physical background are introduced in detail.
The application potential of the sensor system is discussed on the example of the early
identification of critical operating conditions for premature white etching cracks failures of
rolling bearings in industrial gearboxes. Causative vibration loading is revealed prior to any
component damage. Large roller bearings in wind energy gearboxes unusually often fail
prematurely, i.e. clearly before the nominal L10 life. The failure is characterized by axial raceway
cracks, from which branching and spreading crack systems, partly decorated by white etching
microstructure, develop into the depth by corrosion fatigue. High localized friction coeffi‐
cients, resulting from the specific vibration caused mixed friction operating conditions, initiate
tensile stress induced cleavage-like brittle spontaneous surface cracking. The basic idea of the
novel failure detection condition monitoring system is the early identification of chemical
aging of the lubricant and its additives under the influence of vibration loading.
The sensor effectively controls the proper operation conditions of, e.g., bearings and gears in
gearboxes. The online diagnostics system measures components of the specific complex
impedance of oils. For instance, metal abrasion due to wear debris, broken oil molecules,
forming acids or oil soaps, result in an increase of the electrical conductivity, which directly
correlates with the degree of contamination of the oil. For additivated lubricants, the stage of
degradation of the additives can also be derived from changes in the dielectric constant. The
determination of the reduction in the oil quality by contaminations and the quasi continuous
evaluation of wear and chemical aging follow the holistic approach of a real-time monitoring
of an alteration in the condition of the oil-machine system. The measuring signals can be
transmitted online to a web-based monitoring system via LAN, WLAN or serial interfaces of
the sensor. Control of the relevant damage mechanisms, e.g. tribiological wear or oil aging,
during proper operation below certain tolerance limits then allows preventive, condition-
oriented maintenance to be carried out, if necessary, long before regular overhauling. Outage
durations are reduced and the life of components and machines is increased.
2. Basic sensor concept and physical principles
2.1. Basic sensor concept

The basic sensor concept of the novel engineering oil monitoring system is based on the
measurement of complex oil impedance components X, particularly the specific electrical
conductivity κ and the relative permittivity εr. Due to their temperature dependence, the oil
temperature T is also recorded [1-3]. Two or more electrodes, between which the oil flows,
serve as a basic sensor. Resistance and capacity are measured independently of each other.
Zero-mean periodic quantities are used to prevent polarization effects. Figure 1 shows the
sensor in its triple plate design.
Figure 1. Sensor in triple plate design.
Oils are electrical non-conductors. The electrical residual conductivity of pure oils lies in the
range below 1 pS/m. For comparison, the electrical conductivity of the electrical non-conductor
distilled water is larger by six orders of magnitude.
Broken oil molecules, acids, abrasive (metallic) wear, ions, oil soaps, etc., cause an increase of
the oil conductivity κ. It rises with increasing ion concentration and mobility. The electrical
conductivity of almost all impurities is high compared to the extremely low corresponding
property of original pure oils.
The basic sensor represents an electrode arrangement, in which the measured oil is used as
electrical conductor and as dielectric material for conductivity and relative permittivity
A Sensor System for Online Oil Condition Monitoring of Operating Components 307
http://dx.doi.org/10.5772/55737
Figure 2. Temperature dependence of the electrical conductivity of sample oil.
measurement, respectively. Oil is an electrical non-conductor. High resistance of the basic

sensor and resulting low measurement currents provide best interference sensitivity to
interspersed electromagnetic fields. Due to the very small currents, moreover, sufficient
interference suppression is achieved. To prevent polarization effects, zero-mean alternating
current voltages are measured as test signals. However, no capacitive current components may
be measured simultaneously during a conductivity measurement because the capacitive
current is much higher than its ohmic components. Thus, rather high requirements are set on
analog sensor electronic systems, which are met with the reported measurement procedure.
The conductivities of the insulating construction elements and insulation of electrical feed‐
through are about the same size as for the pure oils to be analyzed. The developed basic sensors
and precise sensor electronic system ensure that the conductivity of feedthroughs and
substrates may not be included into the test results. The active basic sensor unit consists of two
or several basic sensor plates which are fixed to metal pins of a glass/metal feedthrough in a
constant distant from each other. The plates of the basic sensor are arranged in the middle of
the measuring chamber, allowing for an adequate incident flow of the flowing medium. A
special alignment of the sensor housing parts is thus not necessary in this design. The extension
characteristics of the sensor housing materials and the glass/metal feedthrough pins are exactly
adjusted to the material characteristics of the used feedthrough glass. The compression
strength is above 10 MPa
2.2. Temperature compensation
The ion mobility and thus the electrical conductivity κ depend upon the internal friction of the
oil and therefore also on its temperature. The oil conductivity increases with temperature.
Figure 2 shows the dependence of the conductivity κ on the temperature change ΔT.
Already for about 3 °C alteration in temperature, the conductivity changes by about 25%. The
electrical conductivity κ is a temperature function that depends on oil impurities rather than
on the oil itself. The type of pollution and its temperature dependence cannot be assumed to
be known. To improve the comparability of measurements, a self-learning adaptive temper‐

ature compensation algorithm is implemented. An integral alteration of the oil quality can then
be assessed by the temperature compensated conductivity value, whereas the type of con‐
tamination is not determinable. The relative permittivity is measured with the same basic
sensor arrangement as used for the electrical conductivity.
The electrical conductivity and relative permittivity are to be measured with respect to a
reference temperature TR as close as possible to the operating temperature of the oil. These
parameters can be evaluated by means of temperature-dependent approximating polyno‐
mials, as demonstrated below exemplarily for the electrical conductivity:
κR = κR,0 + (aΔT C + bΔT C2 + cΔT C3) × κM (1)
Here, κR and κR,0 denote the approximate and previously calculated (old) electrical conductivity
of the oil at the reference temperature TR, respectively. TC stands for the current temperature
of the oil and κM is the electrical conductivity measured without temperature compensation.
Moreover, a, b, und c are the coefficients of the approximating polynomial to be adaptively
determined. The temperature difference is defined as follows:
ΔT = T R - T C (2)
The oil temperature TC is measured for this temperature compensation. The use of a polyno‐
mial of the third order in Eq. (1) ensures good approximation while keeping the computational
effort for the applied microcomputer reasonably low. Figure 3 shows the measured values of
the electrical conductivity κ after temperature compensation.
Figure 3. Measured conductivity values after temperature compensation.

http://dx.doi.org/10.5772/55737
2.3. Calculation and linear approximation of relative permittivity and conductivity
In a series of experiments on the non-additivated lubricating oil FVA03, fresh demineralized

water was added to a volume of 3.01%. The oil conductivity data measured as a function of
the water content are found to follow a linear relationship in good approximation. The
theoretical course of the relative permittivity is calculated for dilute solutions according to
different mixing rules by truncating a Taylor series expansion of the model equations after the
linear term. The model of Lichtenecker is evaluated in Figure 4. Lichtenecker developed the
formula of Eq. (3) for calculating the dielectric constant of a homogeneous mixture εr [4]:
f
εr = εr,add × ε1- f
r,oil (3)
The permittivity of the addition and the oil, respectively, is denoted εr,add and εr,oil. With the
volume fraction f of the addition, 1−f becomes the volume fraction of the oil.
Figure 4. Electrical permittivity εr measured as a function of the water content and model fit according to Eq. (3).
3. Premature failures of rolling bearings and correlation with oil aging
Bearings in industrial, e.g. wind turbine, gearboxes unusually often suffer from a significantly
shorter life than calculated by white etching cracks [5, 6]. Figure 5 shows the light-optical
micrograph of a typical metallographic microsection [5]. The overrolling direction from left to
right indicates surface initiation and top-down propagation of the extended crack system.
These early failures are characterized by mostly axial raceway cracks, revealing vertical semi
to fully circular cleavage-like lenticular brittle spontaneous incipient cracks in preparatively
opened original fracture faces [5, 6]. Occasionally, pock-like spallings are associated with the
Figure 5. Radial microsection of a branching and spreading white etching crack system.
surface cracks, as shown exemplarily in Figure 6 [6]. The developing deep crack systems are
open to the raceway, from which oil penetrates and promotes further corrosion fatigue crack
growth as well as local secondary microstructural changes in the form of crack path decorating
white etching constituents. It is evident from fractography and X-ray diffraction (XRD) residual
stress analyses that the cleavage-like incipient cracks are caused by frictional tangential tensile
stresses [5, 6], which occur in subregions of the contact area in specific, vibrationally induced
mixed friction operating conditions [5–8].
Figure 6. Inner ring raceway with typical axial cracks and few associated pock-like spallings.
http://dx.doi.org/10.5772/55737
XRD based material response analyses of run rolling bearings, suffering from white etching
cracks on still largely undamaged raceways, reveal the causative vibration loading [5]. It is
further reported that lubricant aging occurs under the influence of vibrations [7, 8]. An example
of an infrared spectrum of used oil from rig test run of a roller bearing is provided in Figure
7 [7]. The verified O‒H and C=O oxidation bands indicate operational acidification of the oil,
also reflected in the dissolution of MnS inclusion lines on the raceway (cf. Figure 8), as a result
of polycondensation reactions towards resinification and beginning lacquer formation. It is
this aging of the lubricating oil and its additives, which can be detected at an early stage by
the new sensor so that a gearbox operating at critical conditions is identified.
Figure 7. Oxidation peaks in the infrared spectrum of a used non-additivated aliphatic lubricating oil run under vibra‐
tion loading in a rolling bearing rig test (λ is the wavelength).
The mentioned crack initiation by tribochemical reactions is also found on lateral surfaces of
rollers. In Figure 8 [5], a scanning electron microscope (SEM) image, taken in the secondary
electron imaging mode, is shown on the left. Residues of manganese and sulphur, detected in
the crack-like defect by energy dispersive X-ray spectroscopy (Figure 8, on the right), indicate
the causative tribo chemical dissolution of nonmetallic MnS inclusions [5, 7, 8].
4. Trial of the oil sensor system on a bearing and gear test rig
On a bearing and gear test rig, the new sensor based oil quality monitoring system is applied.
Various load cycles are run and speeds and torques are measured. The results of the trial are
described, evaluated and discussed in the following sections.
4.1. Loss of power and trial run characteristics

The speed-related power P(n) of the test rig is given as follows:
Figure 8. SEM image of a crack on a bearing roller with elemental mapping of Mn and S.
P = M ⋅ ω with ω = 2π ⋅ n (4)
Here, M denotes the torque, ω and n respectively stand for the angular velocity and rotational
speed. The implemented power loss ∆P is derived from the transmission ratio NÜ:
∆ P = ω 1 ⋅ (M 1 - N Ü ⋅ M 2) (5)
M1 and M2 indicate the torque of the drive and the load, respectively. In the first trial on the
test rig, the rolling bearing is intentionally damaged. The time-dependent power loss in the
gear, as derived from the measuring signal characteristics, is represented in Figure 9.
Figure 9. Calculated power loss ΔP.

http://dx.doi.org/10.5772/55737
After switching to a higher load, the power loss increases abruptly before the bearings run in.
Towards the end of the trial, the bearings reveal indication of advanced deterioration. A wide
lubrication gap and vibrations when overrolling spalling results in higher oscillation ampli‐
tudes, which leads to the automatic shutdown of the test rig eventually. The measuring results
obtained with the oil sensor system are presented in the following.
4.2. Conductivity of the lubricating oil
Figure 10 shows the test readings of the conductivity measurement of the lubricating oil. The
current bearing wear and the deteriorating oil condition in the conducted trial are reflected in
the change of the electrical conductivity plotted vs. running time in the diagram.
Figure 10. Measurement of the electrical conductivity κ vs. running time t.
New oil from the storage container exhibits a conductivity κ of 2312 pS/m. After filling into
the trial gear and before the start-up of the test rig, a conductivity of 2791 pS/m is measured.
This increase can be attributed to existing residual impurities in the gear. During the trial run,
the conductivity κ of the gear oil increases to 16868 pS/m. Besides changes in temperature,
conductivity increase is caused, e.g., by wear debris and removed material from spalling,
impurities, broken oil molecules or forming oil soap. As described above, the temperature
dependence of the electrical conductivity of the used gear oil is compensated and the oil
conductivity measured in the gear trial is converted into the relevant conductivity value at 40
°C. Figure 11 shows the development of the temperature compensated oil conductivity with
running time during the gear trial.
In the case of an initially low load, the electrical conductivity increases linearly with running
time. It is to be assumed that the low bearing wear in this area also increases proportional to
the time.
During the necessary intermediate shutdown (interruption) and run-up of the drive machine
to 330 Nm, the conductivity is virtually constant. After switching over to the higher load, the
Figure 11. Time curve of the temperature compensated oil conductivity derived from Figure 10.
oil conductivity increases strongly. Here, the bearing run-in (shakedown) is shown as reduc‐
tion in the conductivity increase. More than about 30 minutes prior to the final forced shut‐
down of the trial run by an oscillation sensor, the conductivity remains almost constant
followed by a temporary rise directly before disconnection. After switching off the test gear,
the oil conductivity decreases strongly. This clearly emphasizes the influence of the additives.
During the loading stages, more impurities per time unit are produced than bound to additives.
After shutting down the test rig, no further oil contamination occurs while the effect of
additives still continues.
The variations in electrical conductivity are depicted in Figure 12. In this diagram, the curve
follows averages respectively calculated over 3 minutes.
Figure 12. Alteration of the electrical conductivity, expressed as ∆κ40/∆t, vs. running time t.
http://dx.doi.org/10.5772/55737
When starting up at 2000 revolutions per minute and a torque of 150 Nm, a relatively constant
change in conductivity from 0.6 to 0.8 pS/(m×3 min), equivalent to 3.3 to 4.4 fS/(m×s), occurs.
In the case of higher load (330 Nm, 3000 min–1), the change in conductivity rises up to 3.8 pS/
(m×3 min), i.e. 21.1 fS/(m×s). After the intermediate load increase, the effect on the change of
the oil conductivity appears stronger. This may be attributed to the time-dependent formation
of impurities and changes in bearing stressing as can be expected during the development of
spalling. Figure 13 shows the inner ring of the failed planet bearing with massive damage of
the raceway at the end of the trial.
Figure 13. Heavily spalled inner ring raceway of the tested cylindrical roller bearing.
The connection between the change in conductivity κ and the loss of power ∆P in the gear is
also evaluated. Figure 14 represents this progress graphically. Both the increasing change in
oil conductivity and the gear power loss correlate with the bearing wear.
Figure 14. Alteration of the electrical conductivity as function of power loss of the gearbox.
In the diagram of Figure 14, a trend line is drawn as polynomial of the third order. The higher
the increases in conductivity and loss of power in the gear, the stronger the bearing wear
occurs. Exceptional changes to the system, e.g. switching of the load conditions, are not taken
into account.
4.3. Relative permittivity of the lubricating oil
In addition to the electrical conductivity, the relative permittivity εr of the oil is measured. In
the case of oils not enriched with additives, the water content can be determined that way.
There are good prospects that the dwindling efficacy of the additives can be detected by means
of the dielectric constant measurement. Figure 15 shows the time development of the relative
permittivity during the trial run. Due to the dependence on temperature, this development is
also depicted in the diagram.
Figure 15. Time curves of the relative permittivity εr and the temperature T as a function of the running time t.
The change of the relative permittivity could be caused by a combination of the effects of a
chemical reaction of additives, water evaporation from the oil and the temperature dependence
of the cell constants as well as the relative permittivity itself. During the trial run, the temper‐
ature increases from 42 to 52.9 °C. The temperature dependence justifies the developed
adaptive, self-learning temperature compensation technique. Figure 16 shows the temperature
compensated time development of the relative permittivity during the gear trial.
5. Approach for condition monitoring of additivated lubricating oils
A direct connection between the electrical conductivity and the degree of contamination of oils
is found. An increase of the electrical conductivity of the oil in operation can thus be interpreted
as increasing wear or contamination of the lubricant. The aging of the oil is also evident in the
degradation of additives. The used additives reveal high conductivity compared with the oil.
The consumption of the additives is reflected in a reduction of the electrical conductivity and
permittivity of the oil. The gradient, i.e. the time derivative, of the conductivity or the dielectric
constant progression respectively represents a measure of the additive degradation and
consumption. The full additive degradation is indicated by the slope of zero (bathtub curve).
http://dx.doi.org/10.5772/55737
Figure 16. Time curve of the temperature compensated relative permittivity εr.
Then the measurement signal increases further with increasing pollution, water entry, etc.
Figure 17 schematically shows the temperature compensated time curve of the permittivity of
additivated oil continuously contaminated by the addition of wear debris, water or oil acids
from chemical aging. Once the additives are consumed, the vanishing shielding effect results
in a characteristic re-increase.
Figure 17. Temperature compensated permittivity.
The most commercially available particle counters only detect particles as small as 4 µm. In a
very early stage of wear of bearings, gears, hydraulic cylinders, etc., however, particularly
smaller particles are produced. A preventive maintenance lowing, rather than rigid inspection
intervals, therefore requires recognition of even the smallest particles. These particles are far
more common in the oils of functioning machines than larger ones. Oil aging can be involved
in the failure, for instance, of rolling bearings [7].
6. Web-based decentralized lubricant quality monitoring system
The integration into a suitable communication structure and the realization of an online
monitoring system offers an interesting practice-oriented utilization of the oil sensor system.
This is briefly discussed below.
Preferred areas of application of the sensor system are energy production and automated
technical plants that are operated locally, like e.g. wind turbines, generators, hydraulic systems
or gearboxes. Plant employers are interested in continuous automated in vivo examination of
the oil quality rather than interrupting the operation for regular sampling. Online oil status
monitoring significantly improves the economic and ecological efficiency by increasing
operating safety, reducing down times or adjusting oil change intervals to actual requirements.
Once the oil condition monitoring sensors are installed on the plants, the measuring data can
be displayed and evaluated elsewhere. A flexible decentralized monitoring system also enables
the analysis of measuring signals and monitoring of the plants by external providers. A user-
orientated service ensuring the quantitative evaluation of changes in the oil-machine system,
including the recommendation of resulting preventive maintenance measures, relieves plant
operators, increases reliability and saves costs.
In a web-based decentralized online oil condition monitoring system, the sensor signals are
preferably transferred through the Internet to a database server and recorded on an HTML
page as user interface [8]. Figure 18 shows the displayed measured data.
Figure 18. Displayed measured data.
Following authentication, a simple web browser permits access via the wired or wireless LAN.
In case of alarm signals, an immediate automated generation of warning messages, for instance
by e-mail or SMS, is possible from any computer with Internet connection. Figure 19 shows
the new sensor system with communication unit [9].
http://dx.doi.org/10.5772/55737
Figure 19. WearSens® sensor system with communication unit.
7. Conclusions
The online diagnostics system measures components of the specific complex impedance of
oils. For instance, metal abrasion due to bearing wear at the tribological contact, broken oil
molecules, acids or oil soap cause an increase in electrical conductivity that directly correlates
with the degree of pollution of the oil. The dielectrical properties of the oils are especially
determined by the water content, which, in the case of products that are not enriched with
additives, becomes accessible by an additional accurate measurement of the relative permit‐
tivity. In the case of oils enriched with additives, statements on the degradation of additives
can also be deduced from recorded changes in the relative permittivity.
Indication of damage and wear is measured as an integral factor of, e.g., the degree of pollution,
oil aging and acidification, water content and the decomposition state of additives or abrasion
of the bearings. It provides informative data on lubricant aging and material loading as well
as the wear of the bearings and gears for the online operative monitoring of components of
machines. Additional loading, for instance, by vibration induced mixed friction in rolling-
sliding contact (rolling bearings, gears, cams, etc.) causes specific faster oil aging, e.g., in the
course of premature component failures. Verified in roller bearing vibration rig tests, the oil
suffers from significant acidification by polycondensation reactions and incipient resinifica‐
tion, as proven by infrared spectroscopy of used lubricant. The application potential of the
sensor is discussed on the example of the prevention of early rolling bearing failures in
industrial gearboxes, of which vibrational contact loading is the root cause.
For an efficient machine utilization and targeted damage prevention, the new electrical online
oil condition monitoring system offers the prospect to carry out timely preventative mainte‐
nance on demand rather than in rigid inspection intervals. The determination of impurities or
reduction in the quality of the lubricants and the quasi continuous evaluation of the bearing
and gear wear and oil aging meet the holistic approach of a real-time monitoring of a change
in the condition of the oil-machine system.
The measuring signals can be transmitted to a web-based condition monitoring system via
LAN, WLAN or serial interfaces of the sensor system. The monitoring of the tribological wear
mechanisms during proper operation below the tolerance limits of the components then allows
preventive, condition-oriented maintenance to be carried out, if necessary, long before regular

overhauling, thus reducing outages caused by wear while simultaneously increasing the
overall lifetime of the oil-machine system.
On a bearing and gear rig test, various load cycles are run and the functionality of the intro‐
duced electric online condition monitoring sensor system is tested successfully. The evaluation
of the experiment is presented.
Author details
Manfred R. Mauntz1*, Jürgen Gegner2, Ulrich Kuipers3 and Stefan Klingau1
*Address all correspondence to: mrm@cmc-instruments.de
1 cmc Instruments GmbH, Eschborn, Germany
2 University of Siegen, Siegen, Germany
3 South Westphalia University of Applied Sciences, Hagen, Germany
References
[1] Gegner, J., Kuipers, U., Mauntz, M. Ölsensorsystem zur Echtzeit-Zustandsüberwa‐

chung von technischen Anlagen und Maschinen, Technisches Messen 77; 2010. pp.
283-292.
[2] Kuipers, U., Mauntz, M. Ölsensorsystem – Sensorsystem zur Messung von Kompo‐
nenten der komplexen Impedanz elektrisch gering leitender und nichtleitender Flu‐
ide, dessen Realisierung und Anwendung, German Patent Application N° 10 2008
047 366.9, Applicant: cmc Instruments GmbH, German Patent Office, Munich, Filing
date: 15.09.2008, in German.
[3] Kuipers, U., Mauntz, M. Verfahren, Schaltungsanordnung, Sensor zur Messung

physikalischer Größen in Fluiden sowie deren Verwendung, European Patent Appli‐
cation N° EP 09000244, European Patent Office, Munich; 09.01.2009, in German.
[4] Lichtenecker, K., Rother, K. Die Herleitung der logarithmischen Mischungsgesetzes

aus allgemeinen Prinzipien der stationären Strömung, Physikalische Zeitschrift, 1931,
32, pp. 255-260.
[5] Gegner, J. Tribological Aspects of Rolling Bearing Failures, In: C.-H. Kuo (ed.), Tri‐
bology – Lubricants and Lubrication, Rijeka: InTech; 2011. Chap. 2, pp. 33-94.
http://dx.doi.org/10.5772/55737
[6] Nierlich, W., Gegner, J. Einführung der Normalspannungshypothese für Mischrei‐

bung im Wälz-Gleitkontakt, Düsseldorf: VDI Reports 2147, VDI Wissensforum; 2011.
pp. 277-290, in German.
[7] Gegner, J., Nierlich, W. Operational Residual Stress Formation in Vibration-Loaded

Rolling Contact, Advances in X-ray Analysis, Vol. 52; 2008, pp. 722-731.
[8] Nierlich, W., Gegner, J. Material Response Bearing Testing under Vibration Loading,
In: J. M. Beswick (ed.), Advances in Rolling Contact Fatigue Strength Testing and Re‐
lated Substitute Technologies, STP 1548, ASTM International, West Conshohocken,
Pennsylvania, USA, 2012.
[9] Gegner, J., Kuipers U., Mauntz, M. New Electric Online Oil Condition Monitoring
Sensor – an Innovation in Early Failure Detection of Industrial Gears, 4th Internation‐
al Multi-Conference on Engineering and Technological Innovation, 19.-22-07.2011,
Orlando, Florida, USA 2011, Proceedings Volume I, International Institute of Infor‐
matics and Systemics, Winter Garten, Florida, USA, 2011, pp. 238-242.
[10] Gegner, J., Kuipers U., Mauntz, M. High-precision online sensor condition monitor‐
ing of industrial oils in service for the early detection of contamination and chemical
aging, Sensor+Test Conferences 07.-09.06.2011, Nürnberg, AMA Service GmbH,
Wunstorf, 2011, pp. 702-709.

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Section 1 Lubrication and Properties of Lubricants 1

Chapter 1 Fundamentals of Lubricants and Lubrication 3

Chapter 2 Lubrication and Lubricants 55

Chapter 3 Some Aspects of Grease Flow in Lubrication Systems and

Section 2 Boundary Lubrication Applications 107

Chapter 4 Cryogenic Tribology in High-Speed Bearings and Shaft Seals of

Chapter 5 Titanium and Titanium Alloys as Biomaterials 155

Section 3 Testing and Modeling 183

Chapter 6 New Scuffing Test Methods for the Determination of the

Chapter 7 Introduction of the Ratio of the Hardness to the Reduced

Chapter 8 Artificial Slip Surface: Potential Application in

Chapter 9 Friction and Wear of a Grease Lubricated Contact — An

Section 4 Sustainability of Tribosystems 273

Chapter 10 Innovative “Green” Tribological Solutions for Clean

Chapter 11 A Sensor System for Online Oil Condition Monitoring of

Lubrication and Properties of Lubricants

Fundamentals of Lubricants and Lubrication

Additional information is available at the end of the chapter

• to keep moving parts apart from each other,

• to take heat out of the contact by their through pass,

• to keep surfaces clean,

• to transport functional additives toward the surface and

• to transfer power in the application (hydraulic, automatic transmission, breaks). [6, 8]

Lubricants are regulated internationally and locally, e. g. by ASTM (American Standard of

2.1. Single bonds: Tetrahedral binding

Figure 1. Tetrahedral binding of carbon

Carbon may bind to another one by corner to corner. (Figure 2)

Figure 2. Corner to corner binding state

Figure 3. Branched structures by carbon to carbon binding

Figure 4. Cyclic Structures by carbon-carbon binding

Ground State - low in energy Rotated State - Higher energy

Figure 5. Energy rise in rotated structures

Figure 6. Excitation by pushing molecules to one another by shear stress

2.2. Double bonds

Figure 7. Double bonding

Figure 8. E and Z structures in double bond

2.3. Triple bonds

Figure 9. Triple bond present in a hydrocarbon

3. Base oils in lubrication: General comments about specie and groups

Within a general scheme, base oils are identified as Groups.

Group I+: Oils that are in a VI range of 103-108.

Group II+: Oils in the VI range of 113-119.

Group III+: Oils providing a VI at least of 140.

Group V: All other oils, e.g. esters, polyglycoles, phosphate esters.

4. Saturated natural hydrocarbons

Methane Ethane Propane Butane

Figure 10. Methane, Ethane, Propane, Butane

Figure 11. Pentane, Hexane, Heptane

Figure 12. Methylbutane (Isopentane), 2,2-Dimethylpropane (Neopentane), Cyclohexane

Figure 13. C11-C13 Iso paraffines

Figure 14. Representatives of saturated hydrocarbons as typical lubricants

4.1. Cyclic hydrocarbons (Naphtenes)

Figure 15. Principal Structure of Napthenic Hydrocarbons

4.2. Aromatic hydrocarbons (Alkyl aromats)

Figure 16. Alkyl Aromats and Naphtalenes