CHAPTER 17:

CORROSION AND DEGRADATION

ISSUES TO ADDRESS...
Why does corrosion occur?
What metals are most likely to corrode?
How do temperature and environment affect
corrosion rate?
How do we suppress corrosion?

Chapter 17-1

 WhatisCorrosion?
It is degradation of properties of material in
service.

Deteriorative mechanism depends on type

ofmaterial
Metals
Materialslossbydissolution(corrosion)
By the formation of nonmetallic scale or film
(oxidation)

Ceramics
Known for better corrosion resistance properties
evenatelevatedtemperatures

Chapter 17-

 Polymers
Degradation is more relevant term in case of
polymers
Polymers may dissolve when exposed to a liquid
solvent,or
Theymayabsorbthesolventandswellalso,
Electromagneticradiation(primarilyultraviolet)and
Heat may cause alterations in their molecular
structure.

Chapter 17-

THE COST OF CORROSION

Corrosion:
--the destructive electrochemical attack of a material.
--Al Capone's
ship, Sapona,
off the coast
of Bimini.
Photos courtesy L.M. Maestas, Sandia
National Labs. Used with permission.

Cost:
--4 to 5% of the Gross National Product (GNP)*
--this amounts to just over $400 billion/yr**
* H.H. Uhlig and W.R. Revie, Corrosion and Corrosion Control: An
Introduction to Corrosion Science and Engineering, 3rd ed., John Wiley
and Sons, Inc., 1985.
**Economic Report of the President (1998).

Chapter 17-2

Can corrosion be used

advantageously?
Drycells
Carbattery
Etching

Chapter 17-

Corrosion of Metals
Corrosion is defined as the destructive and
unintentionalattackofametal
It is electrochemical in nature and begins at the
surface
As a rule of thumb, corrosion rate increases with
increase in temperature of corrosive medium,
increase in velocity of corrosive fluid flow,
increase in dissolved oxygen in the corrosive
medium, increase in dissolved hydrogen in
corrosivemediumetc.

Chapter 17-

Electrochemical Considerations
Oxidation
Achemicalreactioninwhichthereistransferof
electrons from one chemical species to another
andmetalatomslossorgiveupelectron.
Examplesinwhichmetalsoxidizeare
Fe Fe 2 2e

Al

Al

3
e
Thesiteatwhichoxidationtakesplaceiscalled

the anode; oxidation is sometimes called an

anodicreaction.

Chapter 17-

 The electrons generated from each metal atom

that is oxidized must be transferred to an
become a part of another chemical species in
whatistermedareductionreaction.
Forexample,somemetalsundergocorrosioninacid
solutions, while have concentration of hydrogen
(H+)ions,theH+ionsarereducedasfollows:

2 H 2e H 2
andhydrogengas(H2)isevolved.

Chapter 17-

 Reduction
Other reduction reactions are possible,
dependingonthenatureofthesolutiontowhich
themetalisexposed.Foranacidsolutionhaving
dissolvedoxygen,reductionaccordingto
O 2 4 H 4e 2 H 2 O
willprobablyoccur.

Thelocationatwhichreductionoccursiscalled
thecathode.

Chapter 17-

CORROSION OF ZINC IN ACID

Two reactions are necessary:
-- oxidation reaction: Zn Zn2 2e
-- reduction reaction: 2H 2e H2(gas)
H+
oxidation reaction
Zn
Zn2+
H+

Zinc

flow of e2ein the metal

H+
H+

Acid
solution

H+
H+

H2(gas)
H+
reduction reaction

Adapted from Fig. 17.1, Callister

6e. (Fig. 17.1 is from M.G.
Fontana, Corrosion Engineering,
3rd ed., McGraw-Hill Book
Company, 1986.)

Other reduction reactions:

-- in an acid solution

O2 4H 4e 2H2O

-- in a neutral or base solution

O2 2H2O 4e 4(OH)
Chapter 17-3

Electrode Potentials
Cu 2 Fe Cu Fe 2

HalfCellReactions
Fe Fe 2 2e

Cu 2 2e Cu
A potential of 0.780 V
results for a copper iron
galvanic cell when the
temperatureis25C(77F)
Fig: An electrochemical cell consisting of iron and copper
electrodes, each of which is immersed in a 1M solution of its
ion.Ironcorrodeswhilecopperelectrodeposits.

Chapter 17-

 ConceptofGalvanicCouple
When a current passes through the external
circuit, electrons generated from the oxidation
ofironflowtothecoppercellinorderthatCu2+
be reduced. In addition there will be some net
ion motion from each cell to the other across
themembrane.Thisiscalledagalvaniccouple
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
betweenthetwocellhalves,anditsmagnitude
canbedeterminedifavoltmeterisconnectedin
theexternalcircuit.

Chapter 17-

Fe 2 Zn Fe Zn 2

Thepotentialassociatedwith
thiscellreactionis0.323V.

Fig: An electrochemical cell consisting of iron and zinc

electrodes, each of which is immersed in a 1M solution of its
ion.Theironelectrodepositswhilethezinccorrodes.

Chapter 17-

The Standard EMF Series

These measured cell voltages represent only
difference in electrical potential and thus it is
convenient to establish a reference point, or
reference cell, to which other cell halves may be
compared.
Reference cell, arbitrarily chosen is the standard
hydrogenelectrode.
It consists of an inert platinum electrode in a 1M
solutionofH+ions,saturatedwithhydrogengasthatis
bubbledthroughthesolutionatapressureof1atm.and
a temperature of 25C (77F). The platinum itself does
nottakepartintheelectrochemicalreaction;itactsonly
asasurfaceonwhichhydrogenatomsmaybeoxidized
orhydrogenionsmaybereduced.

Chapter 17-

STANDARD HYDROGEN (EMF) TEST

Two outcomes:
e-

H2(gas) 2e

Platinum

metal, M

ne-

e-

Mn+ H+
ions
H+
25C

1M Mn+ soln 1M H+ soln

--Metal is the anode (-)

o
Vmetal
0 (relative to Pt)

e-

nemetal, M

e-

--Metal sample mass

Mn+
ions

H+ 2eH+

Platinum

--Metal sample mass

25C

1M Mn+soln 1M H+ soln

--Metal is the cathode (+)

o
Vmetal
0 (relative to Pt)

Standard Electrode Potential

Chapter 17-4

 The electromotive force (emf) series is

generatedbycouplingtothestandardhydrogen
electrode,standardhalfcellsforvariousmetals
and ranking them according to measured
voltage represents the corrosion tendencies for
the several metals; those at the top (i.e. gold
and platinum) are noble or chemically inert.
Moving down the table, the metals become
increasingly more active, that is susceptible to
oxidation. Sodium and potassium have the
highestreactivities.

Chapter 17-

 The voltages in table are for the halfreactions as

reductionreactions,withtheelectronsonthe
lefthandsideofthechemicalequation;
For oxidation, the direction of the reaction is
reversedandthesingofthevoltagechanged.

Chapter 17-

m
o
r
e
a
n
o
d
i
c
m
o
r
e
c
a
t
h
o
d
i
c

STANDARD EMF SERIES

EMF series
metal
Au
Cu
Pb
Sn
Ni
Co
Cd
Fe
Cr
Zn
Al
Mg
Na
K

o
Vmetal

Metal with smaller

o

Vmetal corrodes.

+1.420 V
Ex: Cd-Ni cell
+0.340
+
- 0.126
- 0.136
- 0.250
o
- 0.277 V =
- 0.403 0.153V
Cd
Ni
25C
- 0.440
- 0.744
- 0.763
1.0 M
1.0 M
- 1.662
Cd 2+ solutionNi 2+solution
- 2.262
- 2.714
Data based on Table
- 2.924 17.1, Callister 6e.

Chapter 17-5

EFFECT OF SOLUTION CONCENTRATION

Ex: Cd-Ni cell with
Ex: Cd-Ni cell with
standard 1M solutions
non-standard solutions
RT X
o
o
o
o
VNi
VCd
0.153
VNi VCd VNi VCd
ln
nF Y
-

Cd

25C

Ni

1.0 M
1.0 M
Cd2+ solution Ni2+solution

n = #eper unit
oxid/red
Cd
Ni
T
reaction
(=2 here)
F=
XM
YM
Faraday's
Cd2+ solution Ni2+solution constant
Reduce VNi - VCd by =96,500
C/mol.

--increasing X
--decreasing Y

Chapter 17-7

m
o
r
e
a
n
o
d
i
c
m
o
r
e
c
a
t
h
o
d
i
c

GALVANIC SERIES

(
a
c
t
i
v
e
)

(
i
n
e
r
t
)

Ranks the reactivity of metals/alloys in seawater

Platinum
Gold
Graphite
Titanium
Silver
316 Stainless Steel
Nickel (passive)
Copper
Nickel (active)
Tin
Lead
316 Stainless Steel
Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium

Based on Table 17.2,

Callister 6e. (Source of
Table 17.2 is M.G. Fontana,
Corrosion Engineering, 3rd
ed., McGraw-Hill Book
Company, 1986.)

Chapter 17-8

Corrosion Rates
The halfcell potentials are thermodynamic
parametersthatrelatetosystemsatequilibrium.
From an engineering perspective, we are
interestedinpredictingtheratesatwhichsystems
corrode; this requires the utilization of other
parameters,asdiscussedonthenextslide.

Chapter 17-

 Thecorrosionrate,ortherateofmaterialremoval
as a consequence of the chemical action, is an
important corrosion parameter. This may be
expressed as the corrosion penetration rate
(CPR),orthethicknesslossofmaterialperunitof
time.Theformulaforthiscalculationis

KW
CPR
At

Chapter 17-

whereWistheweightlossafterexposuretimet;
and A represent the density and exposed
specimenarea,respectively,and
K is a constant, its magnitude depending on the
systemofunitsused.
The CPR is conveniently expressed in terms of
eithermilsperyear(mpy)ormillimetersperyear
(mm/yr).
In the first case, K = 534 to give CPR in mpy
(where I mil = 0.001 in.), and W,, A, and t are
specified in units of milligrams, grams per cubic
centimeter,squareinches,andhours,respectively.

Chapter 17-

 Inthesecondcase,K=87.6formm/yr,andunits
for the other parameters are the same as for mils
per year, except that A is given in square
centimeters.
Formostapplicationsacorrosionpenetrationrate
less than about 20 mpy (0.50 mm/yr) is
acceptable.

Chapter 17-

 Also, there is an electric current associated with

electrochemical corrosion reactions, we can also
expresscorrosionrateintermsofthiscurrent,or,
more specifically, current density i.e., the
currentperunitsurfaceareaofmaterialcorroding
which is designated i. The rate r, in units of
mol/m2s,isdeterminedusingtheexpression

i
r
nF

where, n is the number of electrons associated

with the ionization of each metal atom, and F is
Faradaysconstantandequalsto96,500C/mol.

Chapter 17-

PASSIVITY
Some normally active metals and alloys, under
particular environmental conditions, lose their
chemical reactivity and become extremely inert.
This phenomenon, termed passivity, is displayed
bychromium,iron,nickel,titanium,andmanyof
theiralloys.
Itisfeltthatthispassivebehaviorresultsfromthe
formationofahighlyadherentandverythinoxide
film on the metal surface, which serves as a
protectivebarriertofurthercorrosion.

Chapter 17-

 Stainless steels are highly resistant to

corrosion in a rather wide variety of
atmospheresasaresultofpassivation.They
containatleast11%chromium,which,asa
solidsolution alloying element in iron,
minimizes the formation of rust instead, a
protective surface film forms in oxidizing
atmospheres.
(Stainless
steels
are
susceptible to corrosion in some
environments, and therefore are not always
"stainless.")

Chapter 17-

 Aluminum is highly corrosion resistant in

many environments because it also
passivates. If damaged, the protective film
normallydeformsveryrapidly.However,a
change in the character of the environment
(e.g., alteration in the concentration of the
active corrosive species) may cause a
passivated material to revert to an active
state. Subsequent damage to a preexisting
passive film could result in a substantial
increase in corrosion rate, by as much as
100,000times.

Chapter 17-

Environmental Effects
Thevariablesinthecorrosionenvironment,which
include fluid velocity, temperature, and
composition,canhaveadecidedinfluenceonthe
corrosion properties of the materials that are in
contactwithit.Inmostinstances,increasingfluid
velocity enhances the rate of corrosion due to
erosiveeffects.
The rates of most chemical reactions rise with
increasing temperature; this also holds for the
great majority of corrosion situation& Increasing
theconcentrationofthecorrosivespecies(e.g.,H+
ionsinacids)inmanysituationsproducesamore
rapidrateofcorrosion.

Chapter 17-

 However for materials capable of passivation,

raising the corrosive content may result in an
activetopassive transition, with a considerable
reductionincorrosion.
Cold working or plastically deforming ductile
metalsisusedtoincreasetheirstrength;however,
a coldworked metal is more susceptible to
corrosion than the same material in an annealed
state.Forexample,deformationprocessesareused
to shape the head and point of a nail;
consequently, these positions are anodic with
respecttotheshankregion.Thus,differentialcold
working on a structure should be a consideration
when a corrosive environment may be
encounteredduringservice.

Chapter 17-

Type 316 Stainless Steel

Type316stainlesssteelhasexcellentmechanical
propertiesandalsohasexcellentcorrosion
resistance.Itiswidelyusedforutensils,scissors
andmetallicimplantsbecauseofitsexcellent
corrosionresistance.
188stainlesssteelmeans18%Crand8%Ni.
Chromiumisthemostimportantalloyingelement
forimpartingcorrosionresistancetoironand
steel.

Chapter 17-

Stainless steel ..
Stainlesssteelisnotaspecificalloybuta
genericterm.Crmustbemorethan12%for
havingcorrosionresistance.Niprovides
shineandCr.Providescorrosionresistance.
188ismostpopularstainlesssteel.

Chapter 17-

FORMS OF CORROSION
Stress corrosion

Stress & corrosion

Uniform Attack work together
Erosion-corrosion
Oxidation & reduction at crack tips.
Break down of passivating
occur uniformly over
layer by erosion (pipe
surface.
elbows).

Selective Leaching

Preferred corrosion of
one element/constituent
(e.g., Zn from brass (Cu-Zn)).

Intergranular

Forms
of
corrosion

Pitting

Downward propagation
of small pits & holes.

Fig. 17.8, Callister 6e.

(Fig. 17.8 from M.G.
Fontana, Corrosion
Engineering, 3rd ed.,
McGraw-Hill Book
Company, 1986.)

Corrosion along
grain boundaries,
Galvanic
often where special Dissimilar metals are Crevice Between two
pieces of the same metal.
phases exist.
physically joined. The
Rivet holes
g.b.
more anodic one
prec.
corrodes.(see Table
17.2) Zn & Mg
attacked
Fig. 17.6, Callister 6e. (Fig. 17.6 is
very
anodic.
zones
courtesy LaQue Center for Corrosion
Fig. 17.9, Callister 6e.

Technology, Inc.)

Chapter 17-9

UNIFORM ATTACK
Uniform attack is a form of electrochemical
corrosion that occurs with equivalent intensity
over the entire exposed surface and often leaves
behindascaleordeposit.Inamicroscopicsense,
the oxidation and reduction reactions occur
randomly over the surface. Some familiar
examplesincludegeneralrustingofsteelandiron
and thetarnishing ofsilverware. This isprobably
themostcommonformofcorrosion.Itisalsothe
leastobjectionablebecauseitcanbepredictedand
designedforwithrelativeease.

Chapter 17-

GALVANIC CORROSION
Galvanic corrosion occurs when two
metals or alloys having different
compositionsareelectricallycoupledwhile
exposedtoanelectrolyte.
Thelessnobleormorereactivemetalinthe
particular environment will experience
corrosion;themoreinertmetal,thecathode,
willbeprotectedfromcorrosion.

Chapter 17-

Galvanic Corrosion ..
So,ifaCuplatecarryingasteelscrewis
submergedinseawater,whichmetalwould
tendtocorrodefaster?CuorSteel?
Whyistin(Sn)coatingprovidedto
iron/steelcontainerscontainingfoodstuff?
Simpleexperimentationtoseetheabove
phenomenon.

Chapter 17-

Rusting .
Whydoesnorustingtakeplaceondry
exposediron?
Drillingrigs.
Electroplating,chemicalcoatingssuchas
thatproducedbyreactionofsteelwith
dilutesolutionofphosphoricacid
(phosphatizing),paints,ceramiccoatings,
galvanizingetc.areallusedtoavoidrusting/
corrosion.

Chapter 17-

Al and its alloys ..

Aluminumanditsalloyshavesuperior
resistancetocorrosionandaretherefore
usedformanyapplicationssuchasaircraft
skin,architecturaluses,storagetanks,
pipelines,boats,shiphulls,pipelines,cans,
cookingutensils,processingequipments,
packagingetc.Sometime,formationof
Al2O3(Alumina)onthesurfacealso
providesbettercorrosionresistance.

Chapter 17-

Fig:Galvaniccorrosion.

Steel screws corrode

when in contact with
brass in a marine
environment;orifcopper
and steel tubing are
joined in a domestic
water heater, the steel
will corrode in the
vicinity of the junction.
Depending on the nature
of the solution, one or
more of the reduction
reactions will occur at
thesurfaceofthecathode
material.
Chapter 17-

 The galvanic series indicates the relative

reactivities, in sea water, of a number of metals
and alloys. When two alloys are coupled in
seawater, the one lower in the series will
experiencecorrosion.
Some of the alloys in the table are grouped in
brackets.Generallythebasemetalisthesame.for
thesebracketedalloys,andthereislittledangerof
corrosion if alloys within a single bracket are
coupled. It is also worth noting from this series
that some alloys are listed twice (e.g., nickel and
the stainless steels), in both active and passive
states.

Chapter 17-

 Therateofgalvanicattackdependsontherelative
anodetocathodesurfaceareasthatareexposedto
the electrolyte, and the rate is related directly to
the cathodeanode area ratio; that is, for a given
cathode area, a smaller anode will corrode more
rapidly than a larger one. The reason for this is
that corrosion rate depends on current density
(Equation 24), the current per unit area of
corroding surface, and not simply the current.
Thus,ahighcurrent densityresultsfortheanode
when its area is small relative to that of the
cathode.

Chapter 17-

 A number of measures may be taken to

significantly reduce the effects of galvanic
corrosion.Theseincludethefollowing:
If coupling of dissimilar metals is necessary, choose
twothatareclosetogetherinthegalvanicseries.
Avoid an unfavorable anodetocathode surface area
ratio;useananodeareaaslargeaspossible.
Electricallyinsulatedissimilarmetalsfromeachother.
Electrically connect a third, anodic metal to the other
two; this is a form of cathodic protection, discussed
presently.

Chapter 17-

CREVICE CORROSION
Electrochemical corrosion may also occur as a
consequence of concentration differences of ions or
dissolved gases in the electrolyte solution, and between
tworegionsofthesamemetalpiece.
For such a concentration cell, corrosion occurs in the
localethathasthelowerconcentration.
A good example of this type of corrosion occurs in
crevicesandrecessesorunderdepositsofdirtorcorrosion
productswherethesolutionbecomesstagnantandthereis
localizeddepletionofdissolvedoxygen.
Corrosion preferentially occurring at these positions is
called crevice corrosion. The crevice must be wide
enoughforthesolutiontopenetrate,yetnarrowenoughfor
stagnancy; usually the width is several thousandths of an
inch.

Chapter 17-

Chapter 17-

 The proposed mechanism forcrevicecorrosionis

illustrated in Figure on previous slide. After
oxygen has been depleted within the crevice,
oxidation of the metal occurs at this position.
Electrons from this electrochemical reaction are
conducted through the metal to adjacent external
regions, where they are consumed by reduction
reaction. In many aqueous environments, the
solution within the crevice has been found to
develop high concentrations of H+ and Cl ions,
which are especially corrosive. Many alloys that
passivate are susceptible to crevice corrosion
becauseprotectivefilmsareoftendestroyedbythe
H+andClions.

Chapter 17-

 Crevice corrosion occurs in bolted and

riveted joints as was illustrated in the
previous figure. It may be prevented by
using welded instead of riveted or bolted
joints, using nonabsorbing gaskets where
ever possible, removing accumulated
deposits frequently and by designing in
such a way that containment vessels has
proper provision for thorough cleaning and
one has to avoid stagnant areas to ensure
completedrainage

Chapter 17-

Pitting
Pitting is another form of very localized
corrosionattackinwhichsmallpitsorholes
form. They ordinarily penetrate from the
top of a horizontal surface downward in a
nearly vertical direction. It is an extremely
insidious type of corrosion, often going
undetectedandwithverylittlematerialloss
until failure occurs. An example of pitting
corrosionisshowninfigureonnextslide.

Chapter 17-

Chapter 17-

 Themechanismforpittingisprobablythesameas
for crevice corrosion in that oxidation occurs
withinthepititself,withcomplementaryreduction
at the surface. It is supposed that gravity causes
thepitstogrowdownward,thesolutionatthepit
tip becoming more concentrated and dense as pit
growth progresses. A pit may be initiated by a
localized surface defect such as a scratch or a
slightvariationincomposition.
Infact,ithasbeenobservedthatspecimenshaving
polished surfaces display a greater resistance to
pittingcorrosion.
Stainless steels are somewhat susceptible to this
form of corrosion; however, alloying with about
2% molybdenum enhances their resistance
significantly.

Chapter 17-

INTERGRANULAR CORROSION
Intergranular corrosion occurs preferentially
along grain boundaries for some alloys and in
specific environments. The net result is that a
macroscopicspecimendisintegratesalongitsgrain
boundaries.
This type of corrosion is especially prevalent in
some stainless steels. When heated to
temperatures between 500 and 8000 C (950 and
14500F)for sufficientlylongtime periods,these
alloysbecomesensitizedtointergranularattack.
Intergranular corrosion is an especially severe
problemintheweldingofstainlesssteels,whenit
is often termed weld decay. Figure shows this
typeofintergranularcorrosion.

Chapter 17-

Chapter 17-

 Stainless steels may be protected from

intergranularcorrosionbythefollowingmeasures:
(1) subjecting the sensitized material to a high
temperature heat treatment in which all the
chromiumcarbideparticlesareredissolved,
(2)loweringthecarboncontentbelow0.03wt%C
sothatcarbideformationisminimal,and
(3) alloying the stainless steel with another metal
such as niobium or titanium, which has a greater
tendencytoformcarbidesthandoeschromiumso
thattheCrremainsinsolidsolution.

Chapter 17-

SELECTIVE LEACHING
Selectiveleachingisfoundinsolidsolutionalloys
and occurs when one element or constituent is
preferentiallyremoved as a consequence of
corrosionprocesses.
The most common example is the dezincification
ofbrass,inwhichzincisselectivelyleachedfrom
acopperzincbrassalloy.

Chapter 17-

 The mechanical properties of the alloy are

significantlyimpaired,sinceonlyaporousmassof
copper remains in the region that has been
dezincified.Inaddition,thematerialchangesfrom
yellowtoaredorcoppercolor.
Selectiveleachingmayalsooccurwithotheralloy
systems, in which aluminum, iron, cobalt,
chromium, and other elements are vulnerable, to
preferentialremoval.

Chapter 17-

EROSION-CORROSION
Erosioncorrosion arises from the combined
actionofchemicalattackandmechanicalabrasion
orwearasaconsequenceoffluidmotion.
Virtuallyallmetalalloys,toonedegreeoranother,
aresusceptibletoerosioncorrosion.
It is especially harmful to alloys that passivateby
forming a protective surface film; the abrasive
actionmayerodeawaythefilm,leavingexposeda
baremetalsurface.
If the coating is not capable of continuously and
rapidlyreformingasaprotectivebarrier,corrosion
maybesevere.
Relatively soft metalssuchascopperand leadare
alsosensitivetothisformofattack.

Chapter 17-

 The nature of the fluid can have a dramatic

influence on the corrosion behavior. Increasing
fluid velocity normally enhances the rate of
corrosion. Also, a solution is more erosive when
bubbles and suspended particulate solids are
present.
Erosioncorrosion is commonly found in piping,
especiallyatbends,elbows,andabruptchangesin
pipe diameterpositions where the fluid changes
direction or flow suddenly becomes turbulent.
Propellers,turbineblades,valves,and.pumpsare
also susceptible to this form of corrosion. Figure
onnextslideillustratestheimpingementfailureof
anelbowfitting.

Chapter 17-

Chapter 17-

 One of the best ways to reduce erosion

corrosion is to change the design to
eliminatefluidturbulenceandimpingement
effects.Othermaterialsmayalsobeutilized
that inherently resist erosion. Furthermore,
removal of particulates and bubbles from
thesolutionwilllessenitsabilitytoerode.

Chapter 17-

STRESS CORROSION
Stress corrosion, sometimes termed stress
corrosion cracking, results from the combined
actionofanappliedtensilestressandacorrosive
environment;bothinfluencesarenecessary.
Infact,somematerialsthatarevirtuallyinertina
particular corrosive medium become susceptible
tothisformofcorrosionwhenastressisapplied.
Small cracks form and then propagate in a
direction perpendicular to the stress, with the
resultthatfailuremayeventuallyoccur.

Chapter 17-

Stress corrosion
Stresscorrosionleadstothephenomenonof
delayedfractureinwhichastresstoosmall
tobreakthespecimenimmediately,
fracturesitafteraperiodofservice.
Thisisatimedependentphenomenon
requiringpresenceofaparticular
environmentandalsoatensilestress,may
beasaresidualstress.

Chapter 17-

Stress corrosion .
Timerequiredforfailuredecreasesasthe
stressincreasesorastheconcentrationof
corrosivemediumincreases.
Exampleofstresscorrosionfailure:
HartshillRectangleforKyphosispatients.

Chapter 17-

 Failure behavior is characteristic of that for a

brittle material, even though the metal alloy is
intrinsicallyductile.Furthermore,cracksmayform
at relatively low stress levels, significantly below
thetensilestrength.
Most alloys are susceptible to stress corrosion in
specific environments, especially at moderate
stresslevels.
For example, most stainless steels stress corrode in
solutions containing chloride ions, whereas brasses are
especiallyvulnerablewhenexposedtoammonia.
Figure on next slide is a photomicrograph in which an
example of intergranular stress corrosion cracking in
brassisshown.

Chapter 17-

Chapter 17-

 The stress that produces stress corrosion cracking

neednotbeexternallyapplied;itmaybearesidual
onethatresultsfromrapidtemperaturechangesand
uneven contraction, or for twophase alloys in
which each phase has a different coefficient of
expansion. Also, gaseous and solid corrosion
products thatareentrappedinternallycangiverise
tointernalstresses.
Probably the best measure to take in reducing or
totally eliminating stress corrosion is to lower the
magnitudeofthestress.Thismaybeaccomplished
by reducing the external load or increasing the
crosssectional area perpendicular to the applied
stress. Furthermore, an appropriate heat treatment
may be used to anneal out any residual thermal
stresses.

Chapter 17-

Stress corrosion cracking .

Stresscorrosioncrackingtakesplaceboth
incrystallineandnoncrystallinematerials.
Also,inmetals,thecrackpropagationpath
maybeintergranularortransgranular.
Ifaglasspieceisstressedintensionand
watervaporsarepresent,SCCdoestake
place.

Chapter 17-

HYDROGEN EMBRITTLEMENT
Various metal alloys, specifically some steels,
experienceasignificantreductioninductilityand
tensile strength when atomic hydrogen (H)
penetrates into the material. This phenomenon is
referred to as hydrogen embrittlement; The
terms hydrogeninduced cracking and hydrogen
stresscrackingaresometimesalsoused.
Hydrogenembrittlementisatypeoffailureandis
consideredasaformofcorrosion.

Chapter 17-

Hydrogen embrittlement
Absorption of hydrogen into high strength
steel reduces the bond strength. Such
hydrogen can be removed by heating for a
suitabletimeatabout200C.
Crackformationatthesurfaceisfollowed
bycrackpenetrationintothematerialtillit
reachesacriticalsizeforstaticfailureofthe
remainingsection.

Chapter 17-

 In response to applied or residual tensile stresses,

brittle fracture occurs catastrophically as cracks
grow and rapidly propagate. Hydrogen in its
atomicform(Hasopposedtothemolecularform,
H2) diffuses interstitially through the crystal
lattice, and concentrations as low as several parts
per million can lead to cracking. Furthermore,
hydrogeninduced cracks are most often
transgranular, although intergranular fracture is
observed for some alloy systems. A number of
mechanisms have been proposed to explain
hydrogen embrittlement; most of them are based
on the interference of dislocation motion by the
dissolvedhydrogen.

Chapter 17-

 Hydrogen embrittlement is similar to stress

corrosion; in that a normally ductile metal
experiences brittle fracture when exposed to both
a tensile stress and a corrosive atmosphere.
However, these two phenomena may be
distinguished on the basis of their interactions
with applied electric currents. Whereas cathodic
protection reduces or causes a cessation of stress
corrosion, it may, on the other hand, lead to the
initiation or enhancement of hydrogen
embrittlement.
Forhydrogenembrittlementtooccur,somesource
ofhydrogenmustbepresent,and,inaddition,the,
possibilityfortheformationofitsatomicspecies.

Chapter 17-

 Situations wherein these conditions are met

include the following: pickling of steels in
sulfuric acid; electroplating; and the presence of
hydrogenbearing atmospheres (including water
vapor) at elevated temperatures such as during
weldingandheattreatments.
Also, the presence of what are termed "Poisons"
such as sulfur (i.e., H2S) and arsenic compounds
accelerates hydrogen embrittlement; these
substances retard the formation of molecular
hydrogenAndtherebyincreasetheresidencetime
of atomic hydrogen on the metal surface.
Hydrogen sulfide, probably the most aggressive
poison, is found in petroleum fluids, natural gas,
oilwellbrines,andgeothermalfluids.

Chapter 17-

 Highstrength steels are susceptible to hydrogen

embrittlement, and increasing strength tends to
enhance the material's susceptibility. Martensitic
steels are especially vulnerable to this type of
failure;bainitic,ferritic,andspheroiditicsteelsare
more resilient. Furthermore, FCC alloys
(austenitic stainless steels, and alloys of copper,
aluminum, and nickel) are relatively resistant to
hydrogen embrittlement, mainly because of their
inherently high ductilities. However, strain
hardening these alloys will enhance their
susceptibilitytoembrittlement.

Chapter 17-

 Some of the techniques commonly used to

reduce the likelihood of hydrogen
embrittlement include reducing the tensile
strength of the alloy via a heat treatment,
removal of the source of hydrogen,
"baking" the alloy at an elevated
temperature to drive out any dissolved
hydrogen, and substitution of a more
embrittlementresistantalloy.

Chapter 17-

Corrosion Environments
Corrosiveenvironmentsinclude
The atmosphere: On a tonnage basis, atmospheric
corrosionaccountsforthegreatestlosses.
Aqueoussolutions,soils,acids,bases,
Inorganicsolvents,moltensalts,
Liquidmetals,andthehumanbody.
Moisture containing dissolved oxygen is the primary
corrosive agent, but other substances, including sulfur
compounds and sodium chloride, may also contribute.
This is especially true of marine atmospheres, which
arehighlycorrosivebecauseofthepresenceofsodium
chloride. Dilute sulfuric acid solutions (acid rain) in
industrial environments can also cause corrosion
problems.

Chapter 17-

 Water environments can also have a variety of

compositionsandcorrosioncharacteristics.
Freshwaternormallycontainsdissolvedoxygen,aswell
asothermineralsseveralofwhichaccountforhardness.
Seawater contains approximately 3.5% salt
(predominantly sodium chloride), as well as some
mineralsandorganicmatter.Seawaterisgenerallymore
corrosive than freshwater, frequently producing pitting
andcrevicecorrosion.
Cast iron, steel, aluminum, copper, brass, and some
stainlesssteelsaregenerallysuitableforfreshwateruse.
whereas titanium, brass, some bronzes, coppernickel
alloys, and nickelchromiummolybdenum alloys are
highlycorrosionresistantinseawater.

Chapter 17-

 Soils have a wide range of compositions

and
susceptibilities
to
corrosion.
Compositional variables include moisture,
oxygen,saltcontent,alkalinity,andacidity,
aswellasthepresenceofvariousformsof
bacteria. Cast iron and plain carbon steels,
both with and without protective surface
coatings, are found most economical for
undergroundstructures.

Chapter 17-

CONTROLLING CORROSION
Metal oxide
Metal (e.g., Al,
stainless steel)

Self-protecting metals!

--Metal ions combine with O

to form a thin, adhering oxide layer that slows corrosion.

Reduce T (slows kinetics of oxidation and reduction)

Add inhibitors
--Slow oxidation/reduction reactions by removing reactants
(e.g., remove O2 gas by reacting it w/an inhibitor).
--Slow oxidation reaction by attaching species to
the surface (e.g., paint it!).

Cathodic (or sacrificial) protection

--Attach a more anodic material to the one to be protected.

Adapted
from Fig.
17.14,
Callister
6e.

e.g., zinc-coated nail

Zn2+

zinc

2e- 2esteel

zinc

e.g., Mg Anode

steel
pipe

e-

from Fig. 17.13(a),

Cu wire Adapted
Callister 6e. (Fig. 17.13(a) is
M.G. Fontana, Corrosion
Mg Mg2+ from
Engineering, 3rd ed.,
anode
McGraw-Hill Book Co., 1986.)
Earth
Chapter 17-10

Corrosion control (summary) .

MaterialSelection:
1. Metallic
2. NonmetallicPolymers(weak)
Ceramics(brittle)
Polymersandceramicscanbeused:
Asliners
Asgaskets
Ascoating

Chapter 17-

Corrosion control (summary) .

Coatings:
Metallic
Organic
Inorganic
Zncoating
Electroplating
Tincoating

Chapter 17-

Corrosion control (summary) .

Clad(coreandcladwithrollingoperation)
Cladisalwaysacorrosionresistant
material,suchas
Steelcladwithstainlesssteel
AluminumcladwithhighstrengthAlalloy

Chapter 17-

Corrosion control (summary) .

Design:
Avoidexcessivestresses
Avoiddissimilarmetalcontact
Avoidcrevices
Excludeair
Overdesign

Chapter 17-

Corrosion control (summary) .

EnvironmentalControl:
Temperature
Velocity
Oxygen
Concentration
Cleaning
Inhibitors

Chapter 17-

CORROSION OF CERAMIC MATERIALS

They are exceedingly immune to corrosion by
almost all environments, especially at room
temperature. Corrosion of ceramic materials
generallyinvolvessimplechemicaldissolution,in
contrasttotheelectrochemicalprocessesfoundin
metals.
Ceramicmaterials.arefrequentlyutilizedbecause
oftheirresistancetocorrosion.Glassisoftenused
tocontainliquidsforthisreason.

Chapter 17-

 Refractoryceramicsmustnotonlywithstandhigh
temperatures and provide thermal insulation but,
in many instances, must also resist high
temperature attack by molten metals, salts, slags,
andglasses.
Some of the new technology schemes for
convertingenergyfromoneformtoanotherthatis
more useful require relatively high temperatures,
corrosive atmospheres, and pressures above the
ambient.
Ceramic materials are much better suited to
withstand most of these environments for
reasonabletimeperiodsthanaremetals.

Chapter 17-

DEGIRADATION OF POLYMERS
Polymeric materials also experience deterioration
by means of environmental interactions. As
degradation rather than corrosion because the
processesarebasicallydissimilarfrommetals.
Most metallic corrosion reactions are
electrochemical, but by contrast, polymeric
degradationisphysiochemical;thatis,itinvolves
physical as well as chemical phenomena. Further
more, a wide variety of reactions and adverse
consequences are possible for polymer
degradation.

Chapter 17-

 Polymers may deteriorate by swelling and

dissolution. Covalent bond rupture, as a
result of heat energy, chemical reactions,
and radiation is also possible, ordinarily
with an attendant reduction in mechanical
integrity.
Examplesofpolymerdegradation:
Polyethylene,ifexposedtohightemperaturesin
an. oxygen atmosphere, suffers, an impairment
of its mechanical properties by becoming
brittle. Also, the utility of polyvinyl chloride
may be limited because this material may
become colored when exposed to high
temperatures, although such environments do
notaffectitsmechanicalcharacteristics.

Chapter 17-

SWELLING AND DISSOLUTION

When polymers are exposed to liquids, the main
formsofdegradationareswellinganddissolution.
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
specimenexpandsorswells.
Furthermore, this increase in chain separation
results in a reduction of the secondary
intermolecularbondingforces;

Chapter 17-

 Asaconsequence,thematerialbecomessofterand
more ductile. The liquid solute also lowers the
glass. transition temperature and, if depressed
belowtheambienttemperature,willcauseaonce
strongmaterialtobecomerubberyandweak.
Swelling may be considered to be a partial
dissolution process in which there is only limited
solubilityofthepolymerinthesolvent.
Swellingandresultingcrackinginpolystyrene.
CrazingandresultingcrackinginPMMA.

Chapter 17-

 Dissolution, which occurs when the polymer, is

completely soluble, may be thought of as just a
continuation of swelling. As a rule of thumb, the
greater the similarity of chemical structure between
thesolventandpolymer,thegreateristhelikelihood
of swelling and/or dissolution. For example, many
hydrocarbon rubbers readily absorb hydrocarbon
liquidssuchasgasoline.
Sometime deterioration of polymers is desirable.
Such polymers are called biodegradable polymers.
Biodegradable polymers are attacked by the
microorganisms in the soil and decompose the
polymers into compound that enrich the soil
environment.Theprocessiscalledbiodegradation.

Chapter 17-

Biodegradable Polymers ..
Biodegradableplasticsareusedasplastic
containersforreforestationprojects.Asthe
rootsgolonger,plasticcontainerdegrades
givingtherootsfullfreedomtogrow.
Anothertypeofdegradablepolymersare
calledablativepolymers.Theyarealso
knownassacrificialpolymersandareused
ascoatingonthenoseconeofaspacecraft
forprotectingthespacecraftduringthere
entryintoearthsatmosphere.

Chapter 17-

Ablative materials
Whenablativematerialsaresubjectedto
hightemperatures,theydecompose.
Absorptionofheatofvaporizationduring
theevolutionofgaseousdecomposition
productsdissipatesthefrictionalheatand
actstocooltheremainingmaterial.In
addition,aninsulatinglayerofcarbonized
residueformsontheheatedsurface.

Chapter 17-

 Swellinganddissolutiontraitsalsoareaffectedby
temperature as well as characteristics of the
molecular structure. In general, increasing
molecular weight, increasing degree of
crosslinking and crystallinity, and decreasing
temperature result in a reduction of these
deteriorativeprocesses.
Polymers are much more resistant to attack by
acidic and alkaline solutions than are metals.
Materials that exhibit outstanding resistance to
attack by both solution types include polytetra
fluoroethylene (and other fluorocarbons) and
polyetheretherketone.

Chapter 17-

BOND RUPTURE
Polymers. may also experience degradation by a
processtermedscissiontheseverenceorrupture
ofmolecularchainbonds.Thiscausesaseparation
of chain segments at the point of scission and a
reductioninthemolecularweight.
Some of the physical and chemical properties of
polymers may be adversely affected by this form
ofdegradation.
Bond rupture may result from exposure to
radiationortoheat,andfromchemicalreaction.

Chapter 17-

Bond rupture .
Scission(breakage)ofpolymericchainsis
ofgreatimportance,Deteriorationis
observedbyobservingthechangesin
mechanicalpropertiesduringexposuretoa
specificdeteriorativeenvironment.
Onetypeofdegradationinvolvesproduction
ofmonomer.PMMAbehavesinsucha
fashion.

Chapter 17-

Bond rupture .
ThereactioninPMMAscasestartsatone
oftheendsofpolymericchainandis
repeateduntiltheentirepolymericchainis
consumed.
Incaseofpolyethylene(PE),behaviouris
quitedifferent.Scissionofchainsoccurs
randomlyalongthelengthofthepolymeric
chain.Thisresultsinshorteningofaverage
chainlengthandcorrespondingchangesin
mechanicalpropertiesofthepolymer.

Chapter 17-

Degradation of polymers .
Precautions:Sometimesthefumes
producedbyburningofpolymersisnot
agreeableandinrarecases,maybe
dangerous.Forexample,ifweburnPVC,
gasessuchasphosgene(COCl2)andfurans
areevolvedandtheyarehighlypoisonous.
Theyarebioaccumulativeandcanbevery
dangerousindeed,eveninsmalldosage.

Chapter 17-

Degradation of polymers .
Roomtemperaturedeteriorationcantake
placeinpresenceofozone,oxygenorhigh
energyradiationsuchasUVlight.UVlight
isparticularlyharmfultoproductsmadeout
ofPVCsuchasplasticchairs.
Certainpolymers(speciallyelastomers)
containdoublybondedcarbonandsuch
polymersaresusceptibletoattackbyO3.

Chapter 17-

Degradation of polymers .
Toimpedetherateofdeteriorationdueto
O3andO2,antiozonants(primarydiamines)
andantioxidants(aminesandphenols)can
beincorporated.

Chapter 17-

RADIATION EFFECTS
Certaintypesofradiation(electronbeams,xrays,
and rays, and ultraviolet radiation) possess
sufficientenergytopenetrateapolymerspecimen
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
positivelychargedion.
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
atomsatthatpoint.

Chapter 17-

 This bond breaking leads to either scission or

crosslinking at the ionization site, depending on
thechemicalstructureofthepolymerandalsoon
thedoseofradiation.Stabilizersmaybeaddedto
protectpolymersfromultravioletdamage.
Crosslinking may be induced by irradiation to
improvethemechanicalbehavioranddegradation
characteristics. For example, radiation is used
commercially to crosslink poly ethylene to
enhance its resistance to softening and flow at
elevatedtemperatures;indeed,thisprocessmaybe
carried out on products that have already been
fabricated.

Chapter 17-

CHEMICAL REACTION EFFECTS

Oxygen,ozone,andothersubstancescancauseor
accelerate chain scission as a result of chemical
reaction. This effect is especially prevalent in
vulcanized rubbers that have doubly bonded
carbon atoms along the backbone molecular
chains, and that are exposed to ozone (03), an
atmospheric pollutant. One such scission reaction
mayberepresentedby

Chapter 17-

 The chain is severed at the point of the double

bond;
RandR'representgroupsofatomsbondedtothe
chainthatareunaffectedduringthereaction.
Ordinarily,iftherubberisinanunstressedstate,a
filmwillformonthesurface,protectingthebulk
materialfromanyfurtherreaction.

Chapter 17-

THERMAL EFFECTS
Thermal degradation corresponds to the scission
ofmolecularchainsatelevatedtemperatures;
As a consequence, some polymers undergo
chemical reactions in which gaseous species are
produced.
Thesereactionsareevidencedbyaweightlossof
material;apolymer'sthermalstabilityisameasure
ofitsresiliencetothisdecomposition.
Thermal stability is related primarily to the
magnitude of the bonding energies between the
variousatomicconstituentsofthepolymer:higher
bonding energies result in more thermally stable
materials.

Chapter 17-

 For example, the magnitude of the C F bond is

greaterthanthatoftheCHbond,whichinturn
isgreaterthanthatoftheCClbond.
Thefluorocarbons,havingCFbonds,areamong
the most thermally resistant polymeric materials
and may be utilized at relatively high
temperatures.

Chapter 17-

Weathering
Many polymeric materials serve in applications
that require exposure to outdoor conditions. Any
resultant degradation from outdoor conditions is
termed weathering, which may, in fact, be a
combinationofseveraldifferentprocesses.
Undertheseconditionsdeteriorationisprimarilya
resultofoxidation,whichisinitiatedbyultraviolet
radiationfromthesun.
Some polymers such as nylon and cellulose are
susceptibletowaterabsorption,whichproducesa
reductionintheirhardnessandstiffness.

Chapter 17-

 Resistance to weathering among the various

polymersisquitediverse.
The fluorocarbons are virtually inert under these
conditions; but some materials, including
polyvinyl chloride and polystyrene, are
susceptibletoweathering.

Chapter 17-

Thank you

Chapter 17-