Surface Engineering

• Definition: Modification of near-surface Examples of Surface

structure, chemistry or property of a
substrate in order to achieve superior Engineering Processes
performance and/or durability. It is an
enabling technology and can impact a wide
range of industrial sectors.
- Combining chemistry, physics, and
mechanical engineering with
metallurgy and materials science, it
contributes to virtually all
engineering disciplines.
- It can be done on a given surface
by metallurgical, mechanical,
physical, and chemical means, or
by producing a thick layer or a thin Coated
coating.
- Both metallic and non-metallic Textured
surfaces can be engineered to
provide improved property or
performance.
Examples of Plasma
Engineered Surfaces Spray
Multilayer Coating
Coatings
Nitrided

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 What are the benefits and where are they used?
• Specific properties rely on surfaces Cutting
- Wear, friction, corrosion, fatigue, reflectivity, emissivity,
color, thermal/electrical conductivity, bio-compatibility, etc.
• Benefits
- Extend product life (durability)
- Improve resistance to wear, oxidation and corrosion
(performance)
- Satisfy the consumer's need for better and lower cost Forming
components
- Reduce maintenance (reliability and cost)
Decoration
- Reduce emissions and environmental waste
- Improve the appearance; visually attractivity
- Improve electrical conductivity
- Improve solderability Bio-medical

- Metallize plastic component surfaces

- Provide shielding for electromagnetic and radio frequency
radiation.
• By improving durability, it reduces waste of natural
resources and energy.
• Surface engineered automotive parts and components
can extend warranties and reduce emissions. For Automotive
example: A hardened engine valve will last a minimum of
five years without replacement. 7
Offic e of Science
U.S. Department
of Energy
 Scales of Surface Engineering
• Surface engineering technologies span:
Duplex
- Five orders of magnitude in Coatings
thickness Superlattice
Coatings
- It can vary from several mm for
weld overlays to a few atomic
layers or nanometers for
physical vapor deposition (PVD)
and chemical vapor deposition
(CVD) coatings or ion
implantation. Atomic-layer
deposition is also possible.
- Three orders of magnitude in ~1 mm thick
hardness
- Example of coating hardness Multilayer
range from 250-300 Hv for soft Coatings
metal or spray coatings, 3500 Thermal Spray
Hv for Titanium Nitride PVD Coating
coatings and up to 10,000 Hv for
diamond coatings
Superhard
- Almost infinite possibilities in the CVD-Diamond
range of compositions and/or Films
microstructure
- Nano-composite, nano-layered,
amorphous, crystalline, quasi- 8
crystalline, etc.
Pioneering
Science and
 Evolution and Significance of Surface Engineering

- It is an enabling technology
- It can combine various surface
treatments with thin film and
coating deposition.
- It can substantially improve wear
and corrosion resistance of
structural components.
- It increases component lifetime
and resistance to aggressive
environments.
- It can produce functional coatings
that modify biocompatibility and
optical and electrical properties of
critical components

Single component (1980s)

Evolution of Multicomponent, Multilayer (1990s)

Coating
(2000 and beyond)
Architectures Nanostructured,
Superlattice, Gradient
9
Pioneering
Science and Adaptative (smart)
 Classification of Surface Engineering Processes
Plasma
Plasma
• The traditional, well established Spray
Nitriding
processes:
- Painting
- Electroplating
- Galvanizing
- Thermal and plasma spraying
- Nitriding. Carburizing, Boriding
• The more technologically advanced Plasma-source
coating technologies: Ion Implantation

- Physical and chemical vapor

deposition
- Ion implantation
- Ion-assisted deposition
- Ion-beam mixing
- Laser treatment CVD
• Nowadays, a multitude of options are
available to select and specify a
treatment or a combination of Ion-beam PVD
treatments to engineer the surfaces deposition
of components or structures.

10
Offic
U.S.
 Classification of Various Coating Methods

SURFACE COATING METHODS

Molten or semi-
Gaseous State Solution State
molten State

CVD PVD IBAD Chemical Electrochemical Sol gel Laser Thermal

solution deposition spraying
deposition

Plasma variants Chemical Electroless Chemical Plasma variants

reduction deposition conversion

K.Holmberg, A. Matthews, “Coatings Tribology”,

Ed.D.Dowson, Tribology Series, 28, Elsevier, 1994.
Major Emphasis of
This Course

11
Physical Vapor Deposition (PVD)
Chemical Vapor Deposition (CVD)

• Are special methods by which a

protective hard or soft film can
be produced
- Preferably on the outer
surfaces of a machine
element
- Desired results: superior
performance, protection,
durability. Various engine parts treated by PVD
Gear systems

Multilayer CVD coatings

 CVD and PVD: Enabling Surface Technologies
Processes
• CVD/PVD can effectively modify near-
surface structure and/or chemistry of
mechanical parts or components and
hence improve their performance and
increase their durability/reliability.
• As enabling technologies, they can
impact a wide range of industrial
sectors.
• Both metallic and non-metallic
surfaces can be engineered by CVD
and PVD.

Diamond

Products
Multi-layer

Nano-composite or
Applications
-structured

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Pioneering Office of Science
Science and U.S. Department
Technology of Energy
 MODERN PRACTICES IN PVD AND CVD ARC-PVD

PACVD

One Process
One System
Many Coating Solutions

TINALOX™
TiAlN TiCN
CCplusC DLC

TIN
MoS2
B4C
c
c
Make Your
Choice
MultiLayer CBN
CrN
WC-C Courtesy of CemeCon, GMBH
ALOX™
TiB2 14
Large-scale Systems

In-line PVD

Sputtering

Arc-PVD
CVD 15
 Physical Vapor Deposition (PVD)
Thermal Evaporation

• PVD: A type of vacuum

deposition process where a
material is vaporized in a
vacuum chamber, transported
atom by atom across the
chamber to the substrate, and
condensed into a film at the
substrate's surface.
Ion Beam Sputtering

Film Magnetron Sputtering

<W>=4.88nm
16
It provides
Pioneering
the kind of super-critical, non-equilibrium chemical/physical states needed for the
Office of Science
U.S. Department
synthesis of new coatings with unusual properties, such as super-hardness or -low friction
Science and
Technology of Energy
Classification of PVD

Physical Vapor Deposition (PVD)

Evaporative PVD Sputtering PVD

Resistive Diode

Inductive Magnetron

Electron Ion Beam

Beam Gun
Triode
Arc

Laser

K.Holmberg, A. Matthews, “Coatings Tribology”, Ed.D.Dowson, Tribology Series, 28, Elsevier, 1994.

12
Examples of Plasma-based PVD Processes

Ion plating Activated reactive evaporation Cathodic arc deposition

Bias sputter deposition Ion-beam assisted Dual ion-beam sputtering

deposition

13
Evaporative PVD Processes

• EB Evaporation PVD
• Thermal Evaporation PVD
• Laser Evaporation or
Ablation

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 Sputter Deposition
Basics:
• A voltage is applied across a rarified gas.
• Breakdown of the gas forms a glow
discharge plasma.
• Positive ions from the plasma strike the
negative electrode.
• Energy from the ions is transferred to
target atoms.
• A few of these may escape from the
target surface (they are sputtered).
• The sputtered atoms condense on the
substrate forming a film.

Magnetron: a device in which a magnet system

on the back of the cathode deflects the
electrons, thus lengthening the ionization path.
The accelerated ions transfer their momentum
to particles of the coating material, which
are then deposited on the substrate.
20

Magnetron
Pioneering
Science and
Office of Science

Technology
Various Sputtering Methods
Schematic representation

• Cold Cathode DC Diode

sputtering
• DC triode Sputtering
• AC Sputtering
• Rf Sputtering
• DC Magnetron Sputtering
- Unbalanced Magnetron
- Balanced Magnetron
- Pulsed DC Magnetron
- Ion and Plasma Beam
Sputtering

Ion-beam sputtering 21
Sputtering Mechanism

•Bombardment of solid (target) by high

energy chemically inert ions (e.g. Ar+)
That are extracted from plasma.

•Such bombardment causes ejection

of atoms from the target which are then
re-deposited on the surface of the
substrate purposely located in the
vicinity of the target.

17
Diode vs Magnetron Sputtering
Diode

•Comments:
•Simple, relative ease in
fabrication and thickness
uniformity over large area
•Realtively high deposition
pressure and relatively
high substrate temperature

Magnetron Comments:
•High deposition rates, low
deposition pressure, low
substrate temperature, can be
scaled up, so commonly used
for industrial production
•More complex than planar
diode systems
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 Ion Beam Sputtering
Dual-ion-beam sputtering

A physical vapor deposition process in which

the coating material (target) is removed from
the surface of the coating source (cathode) by
a flux of high energy ions and deposited upon It can also be used to sputter-off or
the surface of substrates. clean substrate surface
19
ARC PVD
• Main Characteristics
- High Vaporization Rate
- High Ionization Rate
- High Throughputs
- High Deposition Rate
Micro/macro-droplets
- Strong film/substrate May cause problems
bonding

20
PVD, CVD Systems
Nitride coatings (TiN, CrN, ZrN)
Carbide and Carbonitride coatings
(TiC, TiCN)
Multicomponent Coatings
(TiAlN)
DLC and Diamond Coatings etc.
Thickness: 1 to 100 microns
Operating Temperature : RT to 500-600º C

Arc PVD

Sputtering PVD

rf CVD
26
 FILTERED ARC

•The filtered cathodic arc may be used to produce a range coatings

• It reduce/eliminate microdroplets associated with conventional arc evaporation
•High deposition rates are available for most materials and compounds
•It does not promote/cause poisoning of the cathodes in reactive deposition
•It provides very ionization
•It is cheaper than electron beam methods
•It is suitable for most metals including high temperature materials (Ta,W,C)
•It cannot be used for evaporating semi-/ or di-electric materials
27
•It cannot be used for evaporating low heat conductivity materials Office of Science
Pioneering
Ion Beam Assisted Deposition

It is a vacuum-deposition process
that combines physical vapor deposition
(PVD) with ion-beam bombardment .

A vapor of coating atoms is generated

with an electron-beam evaporator and
deposited on a substrate. Ions, typically
gaseous, are simultaneously extracted
from a plasma and accelerated into the
growing PVD film at energies of several
hundred to several thousand
electronvolts (eV).

• Good for high-value added applications or science

• Difficulty in scaling-up
28
 Chemical Vapor Deposition (CVD)
Plasma Enhanced CVD
• CVD is a process in which
the gaseous species are
transported to the reaction
chamber, activated
thermally or by a plasma in
the vicinity of the
substrate, and made to
react to form a solid
deposit on the substrate
surface (R. F. Bunshah) As in DLC Coatings
• CVD is a relatively mature
technique Hot-filament CVD
Conventional CVD • Used in electronic,
optoelectronic, tooling
industry, ceramic fiber
production etc,

•It is possible to deposit

films of uniform thickness
and low porosity even on
substrates of complicated
shape in CVD. 29
Classification of CVD
Chemical Vapour Deposition (CVD)

Chemical Vapor Infiltration

Metal - Organic Metal – Organic

Vapor Phase Epitaxy

Hot Filament
Laser Assisted

Electron Assisted

Low Pressure Plasma- Assisted

DC Pulse AC rf Microwave
Atomic Layer Epitaxy
Normal Pressure Plasma Plasma Plasma Plasma Plasma

K.Holmberg, A. Matthews, “Coatings Tribology”, Ed.D.Dowson, Tribology Series, 28, Elsevier, 1994.
30
 The Gas-Phase Chemistry of CVD Processes

• Thermal-Decomposition Reactions:
- Hydrocarbon Decomposition CH4(g) → C(s)+2H2(g)
- Halide Decomposition WF6(g) → W(s)+3F6(g)
- Carbonyl Decomposition Ni(CO)4(g) → Ni(s)+4CO(g)
- Hydride Decomposition SiH4(g) → Si(s)+2H2(g)
• Hydrogen Reduction: CVD TiN and TiC Coated Tool Inserts
SiCl4(g)+2H2(g) → Si(s)+4HCl(g)
• Co-reduction:
TiCl4(g)+2BCl3(g)+5H2(g) → TiB2(s)+10HCl(g)
• Reactions Leading to Carbide and
Nitride Formation:
TiCl4(g)+CH4(g)→ TiC(s)+4HCl(g)
3SiCl4(g)+4NH3(g) → Si3N4(s)+12HCl(g)
CVD is able to produce single or multilayer coatings with composite or nanostructured
architectures. It is not a line of sight process, hence allows the coating of complex shaped
engineering components. Major drawbacks: Safety issue (hazardous, flammable gases), 31
high-temperature requirement.
 Example of Plasma Assisted CVD
Plasma-enhanced CVD

Used in
Deposition
Of DLC

Chemical/Physical Events
That Control Nucleation
Hot-filament CVD and Growth 32
 Future Directions in PVD and CVD Processes
1980s 1900s 2000s
Single component

Multicomponent, Multilayer
Smart
Processes Nanostructured,
Superlattice, Gradient
(hybrids, etc.)
Textured, Adaptive (smart)

Novel Coating Architectures for the 21st Century

Nano-composite Sculptured Coatings
coatings

Superlattice and/or multi-layer coatings 33

 Key References
• ASM Handbook: Surface Engineering, by Faith Reidenback, ASM-International,
Metals Park, OH, 1994
• Surface Engineering: Fundamentals of Coatings by P. K. Datta and J. S. Gray,
Royal Society of Chemistry, 1993
• Chemical Vapor Deposition (Surface Engineering Series, V. 2)
by J.-H. Park and T. S. Sudarshan, ASM-International, Metals Park OH, 2001.
• Chemical vapour deposition of coatings by K.L. Choy, Progress in Materials
Science, 48 (2003) 57–170.
• Advanced Surface Coatings: A Handbook of Surface Engineering, by D. S.
Rickerby, A. Mathews, Blackie Academic and Professional Publ. 1991.
• Handbook of Hard Coatings, by R. F. Bunshah, William Andrew
Publishing/Noyes, 2001.
• Handbook of Physical Vapor Deposition (PVD) Processing by
D. M. Mattox, William Andrew Publishing/Noyes, 1998.
• Handbook of Thin-Film Deposition Processes and Techniques - Principles,
Methods, Equipment and Applications, by K. Seshan, William Andrew
Publishing/Noyes, 2002.

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