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Chapter 17
Introduction
Electrochemical considerations
Corrosion rates
Prediction of corrosion rates
Passivity
Environmental effects
Forms of corrosion
Corrosion environments
Corrosion prevention
Oxidation
Swelling and dissolution
Bond rupture
Weathering
By way of contrast, a classic automobile of the same vintage as the one above that is
rusting away in a field in Bodie, California. Its body is made of a plain-carbon steel
that at one time was painted. This paint offered limited protection for the steel, which
is susceptible to corrosion in normal atmospheric environments.
Learning Objectives
Introduction
Deteriorative mechanisms
- Metals
In metals, there is actual material loss either by dissolution (corrosion) or by the
formation of nonmetallic scale or film (oxidation).
- Ceramics
Ceramic materials are relatively resistant to deterioration, which usually occurs at
elevated temperatures or in rather extreme environments; the process is frequently
called corrosion.
- Polymers
Polymers may dissolve when exposed to a liquid solvent, or they may absorb the
solvent and swell; also, electromagnetic radiation (UV) and heat may cause
alterations in their molecular structure. The processes are called degradation.
Introduction
Corrosion of metals
- Corrosion is defined as the destructive and unintentional attack of a metal.
- Corrosion is a chemical reaction in which there is transfer of electrons from one
chemical species to another.
- Corrosion is electrochemical and ordinarily at the surface.
Importance of corrosion
Approximately 5% of an industrialized nations income is spent on corrosion
prevention and the maintenance or replacement of products lost or contaminated as
a result of corrosion reactions.
Advantage of corrosion
- Etching procedures make use of the selective chemical reactivity of grain
boundaries or various microstructural constituents.
- The current developed in dry-cell batteries is a result of corrosion processes.
7
Electrochemical Considerations
Oxidation reaction
- Metal atoms characteristically lose or give up electrons in what is called an
oxidation reaction.
M Mn+ + nen: valence (number of valence electrons)
(17.1)
(17.2a)
Al Al3+ + 3e-
(17.2b)
Electrochemical Considerations
Reduction reaction
- The electrons generated from each metal atom that is oxidized must be transferred
to and become a part of another chemical species in what is termed a reduction
reaction.
- In acid solutions, which have a high concentration of hydrogen ions
2H+ + 2e- H2
- For an acid solution having dissolved oxygen
(17.3)
(17.5)
(17.6)
(17.7)
Electrochemical Considerations
10
Electrochemical Considerations
(17.8) oxidation
(17.9) reduction
Electrochemical Considerations
(17.11)
(17.12)
12
Electrochemical Considerations
Electrode potentials
- If the iron and copper electrodes are connected electrically, reduction will occur for
copper at the expense of the oxidation of iron.
- Cu2+ ions will deposit (electrodeposit) as metallic copper on the copper electrode,
while iron dissolves (corrodes) on the other side of the cell and goes into solution
as Fe2+ ions.
(17.14a)
(17.14b)
Electrochemical Considerations
- Galvanic couple
Two metals electrically connected in a liquid electrolyte wherein one metal becomes
an anode and corrodes, while the other acts as a cathode.
- An electric potential or voltage will exist between the two cell halves, and its
magnitude can be determined if a voltmeter is connected in the external circuit.
- Various electrode pairs have different voltages; the
magnitude of such a voltage may be thought of as
representing the driving force for the electrochemical
oxidation-reduction reaction.
Cu2+ + Fe Cu + Fe2+ (0.780V)
Fe2+ + Zn Fe + Zn2+ (0.323V)
(17.15)
- Standard half-cell: a half-cell of a metal electrode
immersed in a 1M solution of ions and at 25C.
Fig. 17.3 An electrochemical cell consisting of iron and
zinc electrodes, each of which is immersed in a 1M
solution of its ion. The iron electrodeposits while the zinc
14
corrodes.
Electrochemical Considerations
V20
(17.16b)
Electrochemical Considerations
Increasingly inert
(cathodic)
Increasingly active
(anodic)
(oxidation)
Au3+ + 3e- Au
O2 + 4H+ + 4e- 2H2O
Pt2+ + 2e- Pt
Ag+ + e- Ag
Fe3+ + e- Fe2+
O2 + 2H2O + 4e- 4(OH-)
Cu2+ + 2e- Cu
2H+ + 2e- H2
Pb2+ + 2e- Pb
Sn2+ + 2e- Sn
Ni2+ + 2e- Ni
Co2+ + 2e- Co
Cd2+ + 2e- Cd
Fe2+ + 2e- Fe
Cr3+ + 3e- Cr
Zn2+ + 2e- Zn
Al3+ + 3e- Al
Mg2+ + 2e- Mg
Na+ + e- Na
K+ + e- K
Standard electrode
potential, V0 (V)
+1.420
+1.229
~+1.200
+0.800
+0.771
+0.401
+0.340
0.000
-0.126
-0.136
-0.250
-0.277
-0.403
-0.440
-0.744
-0.763
-1.662
-2.363
-2.714
-2.924
16
Electrochemical Considerations
M 1n ne M 1
V10
M 1 M 1n ne
V10
M 2n ne M 2
V20
M 1 M 2n M 1n M 2
V 0 V20 V10
(17.18)
RT
V V2 V1
ln M 1n
nF
n
RT
M
0
0
1
RT
V V2 V1
ln
(17.19)
n
V2 V20
ln M 2n
nF
M
2
nF
R: gas constant, 8.31 J/molK
n: number of electrons participating in either of the half-cell reactions,
F: Faraday constant (96500 C/mol)
17
n
n
[ M 1 ] & [ M 2 ] : molar ion concentrations
V1 V10
Electrochemical Considerations
- At 25C
RT
M 1n
V V V
ln
nF
M 2n
0
2
0
1
J
298 K
8.31
n
M
0
0
mol K
ln 1n
V V2 V1
C
M2
n 96500
mol
0.02566 M 1n J
0
0
ln
V V2 V1
n
n
M2 C
V V V
0
2
0
1
M
0.0592
n log M
n
1
n
2
(17.20)
to give V in volts.
For reaction spontaneously, V must be positive.
18
(b) Compute the cell potential at 25C if the Cd2+ and Ni2+ concentrations are 0.5 and
10-3 M, respectively. Is the spontaneous reaction direction still the same as for the
standard cell?
(a) From Table 17.1
V0 = +0.403
V0 = -0.250
Cd2+ + 2e- Cd
V0 = -0.403
Ni2+ + 2e- Ni
Ni2+ + 2e- Ni
Therefore
V0 = -0.250
Cd Cd2+ + 2e-
V0 = +0.403
Ni2+ + Cd Ni + Cd2+
2
0.0592
[ M Cd
]
0
0
V VCd VNi
log
[ M Ni2 ]
n
Ni2+
2e-
Ni
V0
= -0.250
Ni2+ + Cd Ni + Cd2+ V
V = 0.403 - 0.250 = 0.153 (V)
0.0592 103
0.403 0.250
log
2
0.5
0.073 (V)
19
The same as for the standard cell.
Example Problem
0.0592
log Cion
n
0.0592
V
0
.
763
log
0
.
10
Anode reaction:
0.793(V )
A
2
V V0
0.0592
log 0.05 0.288(V )
2
Example Problem
One end of an iron wire is immersed in an electrolyte of 0.02 M Fe2+ ions and the other
in an electrolyte of 0.005 M Fe2+ ions. The two electrodes are separated by a porous
wall. (a) Which end of the wire will corrode? (b) What will be the potential difference
between the two ends of the wire when it is just immersed in the electrolytes?
(Fe2+ + 2e- Fe
V0 = -0.440V)
(a) The end of the wire that will corrode will be the one immersed in the more dilute
electrolyte, which is the 0.005 M one. Thus, the wire end in the 0.005 M solution
will be the anode.
(b)
Electrochemical Considerations
Increasingly inert
(cathodic)
Increasingly active
(anodic)
Platinum
Gold
Graphite
Titanium
Silver
316 Stainless steel (passive)
304 Stainless steel (passive)
Inconel (80Ni-13Cr-7Fe) (passive)
Nickel (passive)
Monel (70Ni-30Cu)
Copper-nickel alloys
Bronzes (Cu-Sn alloys)
Copper
Brasses (Cu-Zn alloys)
Inconel (active)
Nickel (active)
Tin
Lead
316 Stainless steel (active)
304 Stainless steel (active)
Cast iron
Iron and steel
Aluminum alloys
Cadmium
Commercially pure aluminum
Zinc
Magnesium and magnesium alloys
Galvanic series
- This represents the relative reactivities
of a number of metals and commercial
alloys in seawater.
- The alloys near the top are cathodic
and unreactive, whereas those at the
bottom are most anodic.
- Most metals and alloys are more stable
in an ionic state than as metals. In
thermodynamic term, there is a net
decrease in free energy in going from
metallic to oxidized states.
- Essentially all metals occur in nature
as compounds. Two notable exceptions
are the noble metals gold and platinum.
22
Corrosion Rates
Corrosion rate
- The rate of material removal as a consequence of the chemical action.
- Real corroding systems are not at equilibrium; there will be a net flow electrons
from anode to cathode, which means that the half-cell potential parameters
(Table 17.1) cannot be applied.
- Half-cell potentials: (1) the magnitude of a driving force, (2) determine
spontaneous reaction directions, (3) provide no information as to corrosion rates.
- Corrosion penetration rate (CPR)
The thickness loss of material per unit of time.
KW
CPR
At
(17.23)
23
Corrosion Rates
(17.24)
24
Corrosion Rates
It
w
nF M
ItM
w
nF
iAtM
w
nF
i: current density (A/cm2), A: area (cm2).
25
Activation polarization
- Activation polarization refers to the condition wherein the reaction rate is
controlled by the one step in the series that occurs at the slowest rate.
- The term activation is applied to this type of polarization because an activation
energy barrier is associated with this slowest, rate-limiting step.
1. Adsorption of H+ ions from the solution
The slowest of the steps determines
onto the zinc surface.
the rate of the overall reaction.
2. Electron transfer from the zinc to form a
hydrogen atom.
H+ + e- H
3. Combining of two hydrogen atoms to
form a molecule of hydrogen.
2H H2
4. The coalescence of many hydrogen
molecules to form a bubble.
Fig. 17.6 Schematic representation of possible
steps in the hydrogen reduction reaction, the
27 rate
of which is controlled by activation polarization.
- For activation polarization, the relationship between overvoltage and current density
is
a log
i
i0
(17.25)
rate: rred
i0
nF
(17.26)
i
i0
(17.25)
29
Concentration polarization
- Concentration polarization exists when the reaction rate is limited by diffusion in
the solution.
- When the reaction is low and/or the concentration of H+ is high, there is always an
adequate supply of hydrogen ions available in the solution at the region near the
electrode interface (Fig. 17.8a).
- At high rates and/or low H+ concentrations, a depletion zone may be formed in the
vicinity of the interface, inasmuch as the H+ ions are not replenished at a rate
sufficient to keep up with the reaction (Fig. 17.8b). Thus, diffusion of H+ to the
interface is rate controlling, and the system is concentration polarized.
- It generally occurs only for reduction reactions because for oxidation, there is
virtually an unlimited supply of metal atoms at the corroding electrode interface.
- It may be noted that overvoltage is independent of current density until i
approach iL (the limiting diffusion current density); at this point, C decreases
abruptly in magnitude.
2.3RT
i
C
log1
(17.27)
30
nF
i
L
i
VH V( H / H ) H log
2
i0
H
i
VZn V( Zn / Zn2 ) Zn log
i0
Zn
VH VZn
i
nF
34
- In the second case, both concentration and activation polarization control the
reduction reaction, whereas only activation polarization is important for oxidation.
Fig. 17.11 shows both polarization curves; corrosion potential and corrosion current
density correspond to the point at which the oxidation and reduction lines intersect.
Example Problem
wnF
It
M t
IM
nF
Cu Cu 2 2e n 2
8.5g 2 96500 A s / mol
t
1722 s 28.7 min
15 A 63.5g / mol
36
Example Problem
A mild steel cylindrical tank 1 m high and 50 cm in diameter contains aerated water to
the 60 cm level and shows a loss in weight due to corrosion of 304 g after 6 weeks.
Calculate (a) the corrosion current and (b) the current density involved in the corrosion
of the tank. Assume uniform corrosion on the tanks inner surface and that the steel
corrodes in the same manner as pure iron. (MFe: 55.85 g/mol, F: 96500 As/mol.)
50
40
ItM
wnF
I
(a) w
nF
tM
2
60
Fe Fe 2e n 2
0.289 A
2.53 10 5 A / cm 2
2
11380cm
37
Example Problem
The wall of a steel tank containing aerated water is corroding at a rate of 54.7 mdd.
How long will it take for the wall thickness to decrease by 0.50 mm? (Fe: 7.87 g/cm3)
5
.
47
10
(10cm) 2 day
cm 2 day
5.47 10 4 g / cm 2 day
6.95 10 5 cm / day
depth of corrosion per day =
3
7.87 g / cm
0.50 10 1 cm
t
719days
5
6.95 10 cm / day
38
Example Problem
Zn Zn 2 2e n 2
w
ItM i area tM
nF
nF
39
For Hydrogen
V(H+/H2) = 0 V
i0 = 10-10 A/cm2
= -0.08
log
H
/ H2 )
i0
H
i
For zinc oxidation VZn V( Zn / Zn2 ) Zn log
i0
Zn
At equilibrium VH VZn
40
iC
iC
V
Zn log
V( H / H ) H log
2
i0 ( Zn / Zn 2 )
i0
H
Zn
V( H / H ) H log iC H log i0H V( Zn / Zn 2 ) Zn log iC Zn log i0Zn
2
1
log iC
Zn H
1
10
7
log iC
0
.
763
)
0
.
08
)
log
10
0
.
09
log
10
3.924
0.09 ( 0.08)
iC 103.924 1.19 104 (A/cm2)
iC 1.19 104
r
(b)
i
VC V( H / H ) H log C
2
i0
H
1.19 104
0.486 (V)
VC 0 ( 0.08) log
10
10
41
Passivity
Passivity
- Some normally active metals and alloys, under particular environmental conditions,
lose their chemical reactivity and become extremely inert. This phenomenon is
termed passivity.
- Passivity is displayed by Cr, Fe, Ni, Ti, and many of their alloys.
- 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. If damaged, the protective film normally reforms very rapidly.
- Electrochemical potential vs current density
1. At low potential values, within the active region the behavior is like a normal
metal.
2. With increasing potential, the current density suddenly decrease to a very low
value that remains independent of potential; this is termed the passive region.
3. At even higher values, the current density again increases with potential in the
transpassive region.
42
Passivity
Fig. 17.12 Schematic polarization curve for a metal that displays an active-passive
43
transition.
Passivity
Fig. 17.13 Demonstration of how an activepassive metal can exhibit both active and
passive corrosion behavior.
44
Environmental Effects
Fluid velocity
In most instances, increasing fluid velocity enhances the rate of corrosion due to
erosive effects.
Temperature
For the great majority of corrosion situations, the rates rise with increasing
temperature.
Composition
- In many situations, increasing the concentration of the corrosive species produces
a more rapid rate of corrosion.
- For materials capable of passivation, raising the corrosive content may result in
an active-to-passive transition, with a considerable reduction in corrosion.
Cold work
A cold-worked metal is more susceptible to corrosion than the same material in an
annealed state.
45
Forms of Corrosion
46
Forms of Corrosion
47
Forms of Corrosion
Galvanic corrosion
- It 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 will experience
corrosion; the more inert metal, the cathode, will be protected from corrosion.
- Example: steel screws corrode when in contact
with brass in a marine environment.
- When two alloys are coupled in seawater, the
one lower in the galvanic series (Table 17.2) will
experience corrosion.
- The rate of galvanic attack depends on the
relative anode-to-cathode surface areas that are
exposed to the electrolyte, and is related directly
to the cathode-anode area ratio. The reason is
that corrosion rate depends on current density.
Fig. 17.14 Galvanic corrosion of a magnesium shell
that was cast around a steel core.
48
Forms of Corrosion
Anodic-cathodic behavior of steel with zinc and tin outside layers exposed to the
atmosphere. (a) Zinc is anodic to steel and corrodes (V0 for Zn and Fe are -0.763 V
and -0.440 V, respectively. (b) Steel is anodic to tin and corrodes (the tin layer was
perforated before the corrosion began) (V0 for Sn is -0.136 V).
49
Cu
Forms of Corrosion
Steel
Steel
Cu
Effect of area relationships between cathode and anode for copper-steel couples
immersed in seawater. (a) Small cathode (copper rivets) and large anode (steel
plates) cause only slight damage to steel. (b) Small anode (steel rivets) and large
cathode (copper plates) cause severe corrosion of steel rivets.
50
Forms of Corrosion
51
Forms of Corrosion
Crevice corrosion
- Electrochemical corrosion may 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. For such a concentration cell, corrosion occurs in
the locale that has the lower concentration. Corrosion preferentially occurring at
these positions is called crevice corrosion.
- The crevice must be wide enough for the solution to penetrate, yet narrow enough
for stagnancy; usually the width is tenths of meters.
Fig. 17.15 On this plate, which was immersed in seawater, crevice corrosion52has
occurred at the regions that were covered by washers.
Forms of Corrosion
- After oxygen has been depleted within the crevice, oxidation of the metal occurs at
the crevice (Fig. 17.16). Electrons from this electrochemical reaction are conducted
through the metal to adjacent external regions, where they are consumed by reduction.
O2 2 H 2O 4e 4OH
53
Forms of Corrosion
- In many aqueous environments, the solution of H+ and Cl- ions, which are
especially corrosive.
Prevention of crevice corrosion
- Using welded instead of riveted or bolted joints.
- Using nonabsorbing gaskets when possible.
- Removing accumulated deposits frequently.
- Designing containment vessels to avoid stagnant areas and ensure complete
drainage.
54
Forms of Corrosion
Pitting
- A form of very localized corrosion attack in which small pits or holes form.
- The pits or holes ordinarily penetrate from the top of a horizontal surface
downward in a nearly vertical direction.
Mechanism for pitting (next page)
It is probably the same as for crevice corrosion in that oxidation occurs within the pit
itself, with complementary reduction at the surface. It is supposed that gravity causes
the pits to grow downward, the solution at the pit tip
becoming more concentrated and dense as pit growth
progresses.
Improvement of pitting-resistance
- Specimens polished surfaces display a greater resistance to
pitting corrosion.
- For stainless steel, alloying with about 2% molybdenum Fig. 17.17 The pitting of a
304 stainless steel plate
by
enhances their resistance significantly.
55
an acid-chloride solution.
Forms of Corrosion
M Cl H 2O MOH H Cl
In this way a high acid concentration builds up at the bottom of the pit, which makes
56
the anodic reaction rate increase, and the whole process becomes autocatalytic.
Forms of Corrosion
Intergranular corrosion
- It occurs preferentially along grain boundaries for some alloys and in specific
environments. A macroscopic specimen disintegrates along its grain boundaries.
- When some stainless steel are heated to temperatures between 500 and 800C for
sufficiently long time periods, they become sensitized to intergranular attack.
Mechanism of intergranular corrosion
This heat treatment permits the formation of small precipitate particles of chromium
carbide (Cr23C6). These particles form along the grain boundaries. Both the
chromium and the carbon atom must diffuse to the grain boundaries to form the
precipitates, which leaves a chromium-depleted zone adjacent to the grain boundary.
This grain boundary is now highly susceptible to
corrosion.
Fig. 17.18 Schematic illustration of chromium
carbide particles that have precipitated
along grain boundaries in stainless steel,
and
57
the attendant zones of chromium depletion.
Forms of Corrosion
Weld decay
Intergranular corrosion is an especially severe problem in the welding of stainless
steels, when it is often termed weld decay (Fig. 17.19).
Protection from intergranular corrosion
- Subjecting the sensitized material to a
high-temperature heat treatment in which
all the chromium carbide particles are
redissolved.
- Lowering the carbon content below 0.03
wt% so that carbide formation is minimal.
- 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 Cr remains
in solid solution.
Forms of Corrosion
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.
- Example: dezincification of brass.
- The mechanical properties of the alloy are significantly impaired, because only a
porous mass of copper remains in the region that has been dezincified.
59
Forms of Corrosion
Erosion-corrosion
- Erosion-corrosion arises from the combined action of chemical attack and
mechanical abrasion or wear as a consequence of fluid motion.
- It is especially harmful to alloys that passivate by forming a protective surface film;
the abrasive action may erode away the film, leaving exposed a bare metal surface.
- 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.
- Increasing fluid velocity normally enhances the rate of
corrosion.
- A solution is more erosive when bubbles and suspended
particulate solids are present.
60
Forms of Corrosion
61
Forms of Corrosion
Forms of Corrosion
- The stress that produces stress corrosion cracking need not be externally applied; it
may be a residual one that results from rapid temperature changes and uneven
contraction, or for a two-phase alloys in which each phase has a different
coefficient of expansion.
Prevention from stress corrosion
- Reducing the stress.
- Annealing
63
Types of Corrosion
64
Forms of Corrosion
65
Corrosion Environments
Corrosive environments
- Atmosphere: oxygen dissolved moisture
- Aqueous solutions: freshwater (oxygen), seawater (sodium chloride)
- Soils
- Acids
- Bases
- Inorganic solvents
- Molten salts
- Liquid metals
- Human body
Materials
- For freshwater use
Cast iron, aluminum, copper, brass, some stainless steels.
- For seawater use
Titanium, brass, some bronzes, copper-nickel alloys, nickel-chromium-
66
molybdenum alloys.
Corrosion Prevention
Corrosion prevention
- Material selection: the most common and easiest way.
- Environmental alteration: lowering the fluid temperature and/or velocity, many
times increasing or decreasing concentration of some species, adding inhibitors in
relatively low concentration to the environment.
- Design: easy washing and shutdown, provision for the exclusion of air.
- Coatings
The coating must be nonreactive in the corrosive environment and resistant to
mechanical damage that exposes the bare metal to the corrosive environment.
- Cathodic protection
Inhibitor
- Substances that, when added in relatively low concentration to the environment,
decrease its corossiveness.
- Inhibitors are normally used in closed systems such as automobile radiators and
steam boilers.
67
Corrosion Prevention
Cathodic protection
- Cathodic protection can be used for all 8 different forms of corrosion as discussed
earlier and may, in some situations, completely stop corrosion.
- Cathodic protection involves supplying, from an external source, electrons to the
metal to be protected, making it a cathode; the reaction is thus forced in the
reduction direction.
- Galvanic protection
The metal to be protected is electrically connected to another metal that is more
reactive in the particular environment. The oxidized metal is often called a
sacrificial anode, and magnesium and zinc are commonly used as such because
they lie at the anodic end of the galvanic
series (Fig. 17.22a).
68
Corrosion Prevention
- Impressed current
The source of electrons is an impressed current from an external dc power source
(Fig. 17.22b) for an underground tank. The negative terminal of the power source is
connected to the structure to be protected. The other terminal is joined to an inert
anode (often graphite), which is buried in the soil; high-conductivity backfill
material provides good electrical contact between the anode and surrounding soil.
A current path exists between the cathode and anode through the intervening soil,
completing the electrical circuit.
Corrosion Prevention
70
Oxidation
Oxidation
Oxidation of metal alloys is possible in gaseous atmospheres, normally air, wherein
an oxide layer or scale forms on the surface of the metal. This phenomenon is
frequently termed scaling, tarnishing, or dry corrosion.
Mechanisms
- Oxidation half-reaction occurs at the
metal-scale interface
M M 2 2e
(17.29)
(17.31)
(17.28)
Oxidation
72
Oxidation
A0 M
P-B ratio =
AM 0
(17.32)
AO: molecular weight of the oxide, AM: atomic weight of the metal,
73
Oxidation
1.16
1.28
1.40
1.52
1.59
1.60
1.68
1.77
1.79
1.99
1.99
2.27
Nonprotective
K
Li
Na
Cd
Ag
Ti
Ta
Sb
Nb
U
Mo
W
0.45
0.57
0.57
1.21
1.59
1.95
2.33
2.35
2.61
3.05
3.40
3.40
74
Oxidation
W 2 K1t K 2
(17.34)
K1 & K2: time-independent constants at a given temperature.
- In the oxidation of metals for which the scale is porous or flakes off, the oxidation
rate expression is linear:
W K 3t
(17.35)
K3: constant.
- For very thin oxide layers (< 100 nm) that form at relatively low temperatures, the
dependence of weight gain on time is logarithmic:
W 2 K 4 logK5t K 6
(17.36)
Oxidation
Fig. 17.25 Oxidation film growth curves for linear, parabolic, and
logarithmic rate laws.
76
Ceramic materials
- Ceramic materials, being compounds between metallic and nonmetallic elements,
may be thought of as having already been corroded.
- Ceramic materials are frequently utilized because of their resistance to corrosion.
- Ceramic materials are much better suited to withstand most of severe environments
for reasonable time periods than are metals.
Corrosion of ceramic materials
- Ceramic materials are exceedingly immune to corrosion by almost all
environments, especially at room temperature.
- Corrosion of ceramic materials generally involves simple chemical dissolution, in
contrast to the electrochemical processes found in metals.
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Degradation of Polymers
Degradation of polymers
- Polymeric degradation is physiochemical; it involves physical as well as chemical
phenomena.
- Polymers may deteriorate by swelling and dissolution.
- Covalent bond rupture.
- Chemical reactions.
- Radiation.
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Swelling
- 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 specimen expands.
- 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.
- The liquid solute lowers the glass transition temperature of polymers.
- Swelling may be considered to be a partial dissolution process in which there is
only limited solubility of the polymer in the solvent.
Dissolution
- Dissolution, which occurs when the polymer is completely soluble, may be thought
of as just a continuation of swelling.
- The greater the similarity of chemical structure between the solvent and polymer,
the greater is the likelihood of swelling and/or dissolution.
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Table 17.4 Resistance to degradation by various environments for selected plastic materials.
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Bond Rupture
Scission
- Scission is the severence or rupture of molecular chain bonds. This causes a
separation of chain segments at the point of scission and a reduction in the
molecular weight.
- Bond rupture may result from exposure to radiation or to heat, and from chemical
reaction.
Radiation effects
- One reaction is ionization, in which the radiation removes an orbital electron from
a specific atom, converting that atom into a positively charged ion. As a
consequence, one of the covalent bonds associated with the specific atom is broken,
and there is a rearrangement of atoms or groups of atoms at that point.
- This bond breaking leads to either scission or crosslinking at the ionization site,
depending on the chemical structure of the polymer and also on the dose of
radiation.
- Stabilizers may be added to protect polymers from ultraviolet damage.
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Bond Rupture
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Weathering
Weathering
- Many polymeric materials serve in applications that require exposure to outdoor
conditions. Any resultant degradation is termed weathering.
- The deterioration is primarily a result of oxidation, which is initiated by ultraviolet
radiation from the sun.
- The fluorocarbons are virtually inert under these conditions.
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