Chapter 6: Corrosion and Degradation of Materials

Corrosion: formation of nanometalic oxidative film (metals)

Degradation: polymers
Ceramics: Resistant to corrosion or degradation
Metals corrosion
Electrochemical considration
M Mn+ + ne
Al Al3+ +3e-

Fe Fe2+ +2e-

The site at which oxidation takes place is called the anode; oxidation is sometimes
called an anodic reaction. The electrons generated from each metal atom that is
oxidized must be transferred to and become a part of another chemical species is
reduction reaction. 1
 2H+ + 2e- H2

 Reduction reaction in an acid solution containing dissolved oxygen

 Reduction reaction in a neutral or basic solution containing dissolved

oxygen

 Reduction of a multivalent metal ion to a lower valence state

 Reduction of a metal ion to its electrically neutral atom

 The location at which reduction occurs is called the cathode.
 It is possible for two or more of the preceding reduction reactions to occur
simultaneously.

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 An overall electrochemical reaction must consist of at least one oxidation
and one reduction reaction and will be their sum; often the individual
oxidation and reduction reactions are termed half-reactions.

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Electrode Potentials

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Influence of Concentration and Temperature on Cell Potential

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 Corrosion penetration rate—as a function of specimen
weight loss, density, area, and time of exposure

Expression relating corrosion rate and current density

 The rate r, in units of mol/m s, is determined using the expression.
2.

Polarization
 The displacement of each electrode potential from its equilibrium value is termed
polarization, and the magnitude of this displacement is the overvoltage, normally
represented by the symbol ƞ.
Activation Polarization
 All electrochemical reactions consist of a sequence of steps that occur in
series at the interface between the metal electrode and the electrolyte
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solution. Activation polarization
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  At equilibrium, equality of rates of oxidation and reduction, and
their relationship to the exchange current density

 At rate r oxidation. Equilibrium exists when

Concentration Polarization
 Concentration polarization exists when the reaction rate is limited by
diffusion in the solution.

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 The mathematical expression relating concentration polarization
overvoltage ƞc and current density i is

 Where R and T are the gas constant and absolute temperature, respectively, n and F
have the same meanings as before, and iL is the limiting diffusion current density.

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Corrosion Rates from Polarization Data

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 Under particular environmental conditions, some normally active metals and
alloys, lose their chemical reactivity and become extremely inert. This
phenomenon, termed passivity, is displayed by chromium, iron, nickel, titanium,
and many of their alloys.
 It is believed that this passive behavior results from the formation of a highly
adherent and very thin oxide film on the metal surface, which serves as a
protective barrier to further corrosion.
 Stainless steels are highly resistant to corrosion in a rather wide variety of
atmospheres as a result of passivation.
ENVIRONMENTAL EFFECTS

 The variables in the corrosion environment, which include fluid velocity,

temperature, and composition, can have a decided influence on the corrosion
properties of the materials that are in contact with it.

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 FORMS OF CORROSION

 Uniform Attack
 Galvanic Corrosion
 Galvanic corrosion occurs when two metals or alloys having different
compositions are electrically coupled while exposed to an electrolyte.
 The less noble or more reactive metal in the particular environment experiences
corrosion; the more inert metal, the cathode, is protected from corrosion.

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 Crevice Corrosion

 Electrochemical corrosion may also occur as a consequence of concentration

differences of ions or dissolved gases in the electrolyte solution and between two
regions of the same metal piece.

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 Pitting
 Pitting is another form of very localized corrosion attack in which small pits
or holes form.

Intergranular corrosion

 As the name suggests, intergranular corrosion occurs preferentially along grain

boundaries for some alloys and in specific environments. The net result is that a
macroscopic specimen disintegrates along its grain boundaries. This type of corrosion
is especially prevalent in some stainless steels. When heated to temperatures
between 500 oC and 800 oC (950 F and 1450 F) for sufficiently long time periods, these
alloys become sensitized to intergranular attack.
 It is believed that this heat treatment permits the formation of small precipitate
particles of chromium carbide (Cr23C6) by reaction between the chromium and carbon
in the stainless steel.

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  Intergranular corrosion is an especially severe problem in the welding of stainless
steels, when it is often termed weld decay.

Selective Leaching
 Selective leaching is found in solid solution alloys and occurs when one element or
constituent is preferentially removed as a consequence of corrosion processes. The
most common example is the dezincification of brass, in which zinc is selectively
leached from a copper–zinc brass alloy.

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 Stainless steels may be protected from intergranular corrosion by the following
measures: (1) subjecting the sensitized material to a high-temperature heat
treatment in which all the chromium carbide particles are redissolved, (2)
lowering the carbon content below 0.03 wt% C so that carbide formation is
minimal, and (3) alloying the stainless steel with another metal such as niobium or
titanium, which has a greater tendency to form carbides than does chromium so
that the Cr remains in solid solution.

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 Erosion–Corrosion

 Erosion–corrosion arises from the combined action of chemical attack and mechanical
abrasion or wear as a consequence of fluid motion.
 Virtually all metal alloys, to one degree or another, are susceptible to erosion–
corrosion.

 Erosion–corrosion is commonly found in piping, especially at bends, elbows, and

abrupt changes in pipe diameter—positions where the fluid changes direction or flow
suddenly becomes turbulent.
 Propellers, turbine blades, valves, and pumps are also susceptible to this form of
corrosion.

 One of the best ways to reduce erosion–corrosion is to change the design to

eliminate fluid turbulence and impingement effects.
 Other materials may also be used that inherently resist erosion. Furthermore,
removal of particulates and bubbles from the solution lessens its ability to erode.

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 Stress Corrosion
 Stress corrosion, sometimes termed stress corrosion cracking, results from the
combined action of an applied tensile stress and a corrosive environment; both
influences are necessary.

 In fact, some materials that are virtually inert in a particular corrosive medium
become susceptible to this form of corrosion when a stress is applied. Small cracks
form and then propagate in a direction perpendicular to the stress.
Hydrogen Embrittlement

 Various metal alloys, specifically some steels, experience a significant reduction in

ductility and tensile strength when atomic hydrogen (H) penetrates into the material.
CORROSION ENVIRONMENTS

 Corrosion environments include the atmosphere, aqueous solutions, soils, acids, bases,
inorganic solvents, molten salts, liquid metals, and, last but not least, the human body.
On a tonnage basis, atmospheric corrosion accounts for the greatest losses.

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 CORROSION PREVENTION

 Inhibitors are substances that, when added in relatively low concentrations to the
environment, decrease its corrosiveness.
 One of the most effective means of corrosion prevention is cathodic protection; it
can be used for all eight different forms of corrosion as discussed earlier and may, in
some situations, completely stop corrosion.

 The oxidized metal is often called a sacrificial anode, and magnesium and zinc are
commonly used because they lie at the anodic end of the galvanic series. This form of
galvanic protection for structures buried in the ground

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  Rate of oxidation (i.e., the rate of film thickness increase) and the tendency of the
film to protect the metal from further oxidation are related to the relative volumes
of the oxide and metal. The ratio of these volumes, termed the Pilling–Bedworth
ratio, may be determined from the following expression

 where AO is the molecular (or formula) weight of the oxide, AM is the atomic weight of
the metal, and ƍO and ƍM are the oxide and metal densities, respectively. For metals
having P–B ratios less than unity, the oxide film tends to be porous and unprotective.

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 Kinetics

 Oxidation film growth curves for linear, parabolic, and logarithmic rate laws.

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 Corrosion of Ceramic Materials

 Ceramic materials are much better suited to withstand most of these environments for
reasonable time periods than are metals.

Degradation of Polymers

 Polymeric materials also experience deterioration by means of environmental

interactions. However, an undesirable interaction is specified as degradation rather
than corrosion because the processes are basically dissimilar. Whereas most metallic
corrosion reactions are electrochemical, polymeric degradation is physiochemical; that
is, it involves physical as well as chemical phenomena.

 Covalent bond rupture as a result of heat energy, chemical reactions, and radiation is
also possible, typically with an attendant reduction in mechanical integrity. Because
of the chemical complexity of polymers, their degradation mechanisms are not well
understood.

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 SWELLING AND DISSOLUTION

 When polymers are exposed to liquids, the main forms of degradation are swelling
and dissolution. With swelling, the liquid or solute diffuses into and is absorbed
within the polymer; the small solute molecules fit into and occupy positions among
the polymer molecules.
 Thus the macromolecules are forced apart such that the specimen expands or swells.
Furthermore, this increase in chain separation results in a reduction of the secondary
intermolecular bonding forces; as a consequence, the material becomes softer and
more ductile.

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 In general, polymers are much more resistant to attack by acidic and alkaline
solutions than are metals. For example, hydrofluoric acid (HF) corrodes many metals
as well as etch and dissolve glass, so it is stored in plastic bottles

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 BOND RUPTURE

 Bond rupture may result from exposure to radiation or heat and from chemical
reaction.
Radiation Effects
 Certain types of radiation [electron beams, x-rays, beta- and gama-rays, and ultraviolet
(UV) radiation] possess sufficient energy to penetrate a polymer specimen and interact
with the constituent atoms or their electrons. One such reaction is ionization, in which
the radiation removes an orbital electron from a specific atom, converting that atom into
a positively charged ion.
Chemical Reaction Effects

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 Thermal Effects
 Higher bonding energies result in more thermally stable materials. For example, the
magnitude of the C—F bond is greater than that of the C—H bond, which in turn is
greater than that of the C—Cl bond. The fluorocarbons,having C—F bonds, are among
the most thermally resistant polymeric materials and may be used at relatively high
temperatures.
 When poly(vinyl chloride) is heated to 200 0C for even a few minutes it discolors and
gives off large amounts of HCl, which accelerates continued decomposition. Stabilizers
such as ZnO can react with the HCl, providing increased thermal stability for poly(vinyl
chloride).

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 WEATHERING

 Many polymeric materials serve in applications that require exposure to outdoor

conditions.
 Any resultant degradation is termed weathering, which may be a combination of several
different processes.
 Under these conditions, deterioration is primarily a result of oxidation, which is initiated
by ultraviolet radiation from the sun.
 Some polymers, such as nylon and cellulose, are also susceptible to water absorption,
which produces a reduction in their hardness and stiffness. Resistance to weathering
among the various polymers is quite diverse.
 The fluorocarbons are virtually inert under these conditions; some materials, however,
including poly(vinyl chloride) and polystyrene, are susceptible to weathering.

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