Forms of Corrosion

Classification

Appearance of corroded metal

Visual inspection, little magnification
Examination before cleaning
 Uniform Corrosion
Environment has access to entire exposed
surface
Metal uniform composition and
metallurgy
Some degree of non-uniformity OK
in the definition
Uniform attack over surface
thinning penetration failure
ia
Penetration rate, m / year 3.27 ; i A / cm2 ; D g / cm3
nD
e.g. Atmospheric corrosion, steel in acids
Greatest destruction of metal in tonnage
Predictable and hence acceptable for design.
Prevention:
Coatings, inhibitors, cathodic protection
 Origin of Localized corrosion
Material
Segregation
Inclusions
Different phases
Grain boundaries
Environment
Oxygen concentration
Chloride ion concentration
pH
Flow rate
Mechanical
Static stress
Fluctuating stress
 Galvanic Corrosion
Attack at the junction of two dissimilar alloys
One of the two is corroded preferentially

Corrosion attack is greatest here!

Resistance in the electrolyte limits
the attack to area close to the
junction
Higher resistance through longer
electrolyte path

Cathode may be damaged by H

Junction of copper and galvanized steel domestic water pipes.
http://activerain.com/blogsview/2616661/survival-of-the-fittest-galvanic-corrosion
 Thermodynamics
Standard oxidation-reduction (redox)
when a standard half cell of Copper is
potentials/emf series, 25C
coupled to NHE, the voltmeter reads
Redox Electrode 0.337V
reaction/Half potential i.e. ECu/Cu2+= 0.337 V
cell vs. NHE, in noble
volts
Using concept of half cell potential, we
Au3++3e=Au +1.498 can calculate cell potential for any
Fe3++3e=Fe2+ +0.771 couple!

Cu2++2e=Cu +0.337
However, real systems are mostly not
2H++2e=H2 0 STANDARD!
Ni2++2e=Ni -0.250
Fe2++2e=Fe -0.440 Galvanic series--- in salt water at 25
active C, Alloys too!
Zn2++2e=Zn -0.763
Mg2++2e=Mg -2.363
 Galvanic

Connected dissimilar metals (may be attractive from

economic point of view to designers) p.d. driving
force for e flow
Active metal corrodes faster anode
Nobler metal corrodes slowly cathode
Eg. Dry cell=>carbon/ammo. chloride/Zn or Mg
Emf & galvanic series help exception do occur!
Corrosion products may change galvanic potential over
time rate
Polarization of reduction rxn usually dominates
Accelerated galvanic corrosion if nobler metal is not readily
polarized, cathodically.
 Area Effect
Galvanic Coupling

Exchange
current!
io,H 2 io,H 2 io,H 2
+ 2(Zn,1cm ) 2(Pt,1cm ) 2(Pt,10cm )

EH /H+
2

Ecorr
-

io,Zn,1cm2 iC
iB
EM/M+
iA

log I (current)
 Galvanic
Environmental effects:
Steel/Zn in domestic water , Zn corrodes
At T>80 C, steel anodic since corrosion products on
Zn nobler!
GC is greater near seashore, condensate is conducting
GC does not occur in dry environments
Distance effect:
GC is greatest near the junction
If solution is highly conducting over larger distance
If pure water => sharp groove.
 Galvanic

Area effect:
Unfavorable : small anode : large cathode
Which is better, a steel bolt in a brass
structure, or a brass bolt in a steel structure?
The steel will be the anode, so a small steel
bolt in a large brass structure will suffer severe
galvanic corrosion. A brass bolt will be
protected by the steel structure
 Brass bolt in a steel structure Steel bolt in a brass structure

Small brass cathode will cause Small steel anode will suffer
small increase in corrosion of large increase in corrosion due
steel structure. Bolt will be to coupling with brass
protected from corrosion by structure.
coupling to steel
Case study (Fontana):
MS tank entirely coated with baked phenolic paint
Bottom coating damaged due to mech. Reasons corrosion!
New tanks 18-8 SS clad bottoms welded to MS side with only side painted.
All paint coatings are permeable unfavorable area effect fast failures by
GC
Solution: paint the bottom, too!

Rule: if only one of the metals is to be coated, coat the

noble metal!
 Prevention
Materials selection- close in the galvanic series
Avoid unfavorable area effect
Insulate
Add inhibitors to aggressiveness
Design (thicker) anodic parts & for easy replacements
Install 3rd metal anodic to both.

Galvanic corrosion can be useful!

Dry cells & batteries
Cathodic protection
Cleaning Silver : Al pan water + baking soda
Silver sulphide is reduced back to Ag. 3Ag2S + 2Al 6Ag + Al2S3
 Crevice Corrosion
Small volumes of stagnant solution in occluded interstices, beneath
deposits and seals, lap joints or in crevices, under nuts and rivet heads.
=> Intense corrosion!
Deposits of sand, dust, scale and corrosion products, too.

Common in metals and alloys which owe their resistance to the stability of a
passive film, since these films are unstable in the presence of high concentrations
of Cl and H+ ions.

Corrosion site:
wide enough to permit liquid entry
Narrow enough to maintain a stagnant zone.
 Mechanism

later stage
Initial stage

Source: Fontana
Oxidation : M M e
Re duction : O2 2 H 2O 4e 4OH
rate of oxidation rate of reduction, both inside and outside
Inside :
the O2 depletes reduction stops inside ! but M M continues

Excess + ve charge (M+)

Migration of Cl in to the crevice to balance
Hydrolysis
M Cl H 2O MOH H Cl

Both Cl and H+ accelerate corrosion by destroying the film

Within crevice : pH = 2-3
[Cl] in crevice = 3 - 10 times the bulk [Cl]
 Features
Occurs in many media (Cl most intense)
Long incubation period 6-12 months
Active passive metals are especially susceptible
eg. SS bolt falling in SS tank
 Prevention
Use welds rather than bolted or riveted joints
design installations to enable complete draining (no
corners or stagnant zones)
hydrofuge any interstices that cannot be eliminated
grease all seals and seal planes, use only solid, non-
porous seals, etc.
Close the crevices by caulking, welding, soldering
Remove suspended solids
Inspect and remove the deposits frequently
 Pitting
Features
Extremely localized attack=> holes
Pit: a cavity or hole with dia << depth
% weight loss- small
Difficult to detect
Difficult to measure or compare
Take months/years to show up
Grow in the direction of gravity
Extended initiation period = f(metal, environment)
Autocatalytic
Pits tend to undercut the surface- detection difficult
 Increasing [FeCl3], T

18-8 SS

No corrosion Pitting Uniform corrosion

Intermediate
stage
 Pitting morphology

http://www.argentumsolutions.com
/wiki/en/Pitting_Corrosion

http://www.ukplumbersforums.co.uk
 Mechanism
Growth: Similar to crevice corrosion
Autocatalytic- self propagating
O2 O2

Passive Cl- Cl-

OH- OH-

e M+ M+
e
Passive-active cell Active
E~ 0.5V

Corrosion Pit

Because of the possibility of passive active cell formation, deep pitting is much more
common with passive metals than with non-passive metals.
 Pitting
Inside the pit
Excess +ve charge
Migration of Cl
Hydrolysis: M+Cl + H2O => MOH + H+Cl
No O2 reduction inside the pit
Action of Cl
Chloride ions break down passivity or prevent its formation in iron,
chromium, nickel, cobalt, and the stainless steels.
Oxide film theory: Cl penetrates the oxide film through pores or defects
easier than do other ions, such as SO42. Alternatively, Cl may colloidally
disperse the oxide film and increase its permeability.
Adsorption theory: Cl adsorbs on the metal surface preferentially.
Adsorbed Cl favours hydration of metal ions and increases the ease with
which metal ions enter into solution. i.e. adsorbed chloride ions increase
the exchange current (decrease overvoltage) for anodic dissolution.
Breakdown of passivity by Cl occurs locally- preferred surface sites:
small variations in the passive - film structure and thickness
 Pit initiation
Unclear
Momentarily rate of dissolution increases at a point
Surface scratch, emerging dislocation, defect (sulphide
inclusions)
Random variation in solution composition
New pits:
Unstable
May become inactive
(dense solutions) can be swept away by stray convection
currents
Gravity effect:
dense concentrated solution inside the pit
Therefore, stable growth in the direction of gravity
 Pitting- Tubular corrosion products
Tube growth mechanism
Interface Fe(OH)2 +
dissolved O2 => Fe(OH)3
Precipitation of Fe(OH)3
in neutral bulk solution
A pit (anode) is usually
surrounded by large
passive area (cathode)
where reduction occurs
Pits are well spaced
 Pitting Evaluation

Relationship between pit depth and the

number of pits

Pit depth as a function

of exposed area

It is the deepest pit that causes failure!

 Pitting: Cyclic Polarization Test

An important variant of potentiodynamic

polarization is the cyclic polarization test.
used to evaluate pitting susceptibility
The potential is swept in a single cycle (or slightly less
than one cycle)
Examine - size of the hysteresis
The existence of the hysteresis is usually indicative of
pitting
the size of the loop is often related to the amount of
pitting
 Epit = Ebd = pitting
transpassive
potential or breakdown
Epit potential- pits inititate
Erp = repassivation
Erp potential
Passive
range
Presence of loop=> alloy
E is susceptible to pitting
corrosion
Active Large size loop- more
range
pitting

log i
 Corrosion potential > Epit
can be established by
dissolved oxidizer

Pits initiate above Epit

Existing pits can grow between Epit and Erp Or Eprot
Below Erp, pits neither initiate nor grow..metal is passive
 Pitting- Prevention
Same methods as applied to crevice corrosion
decreasing aggressiveness [Cl, acidity, T] of
environ., elimination of stagnant areas, surface
cleaning, design for complete drainage
Proper material selection for given environ.
316 SS (18Cr-8Ni-2Mo) better than 304
Test in specific environ. before use
Ordinary steel more resistant than SS!
Use adequate inhibitor concentration- careful!
 Filiform Corrosion
A type of crevice corrosion
Underfilm corrosion- occurs under the films
Red/brown corrosion filaments
Ex. Steel, Al, Mg, surfaces covered by Sn, Ag, Au,
phosphate enamel, laquer coatings
Only affects surface appearance
Food packaging/canning industry
Network of corrosion product trails
Active head- where corrosion occurs
Red/brown corrosion product trail- inactive
 Initiation
At edges, scratches, defects- moisture penetration
Propagates as narrow 0.05 to 3 mm wide
filaments under the coating
Substrate metal penetration is minimal
Filaments do not cross inactive tails of other
filaments
Tail of the earlier one supplies oxygen to the head
 Environmental factors
Relative humidity
0-65 no corrosion
65-80 thin filaments
80-90 wide
95 blisters + scattered filiform
100 % blisters
Coatings with low water permeability good
Filaments follow grinding and polishing marks
Mechanism- unclear
Active head
Trailing inactive tail
 Osmotic action: supplies H2O to the head ; since [Fe2+ ]
//Osmosis: movement of solvent molecules through a semi-permeable
membrane into a region of higher solute conc, in a direction that tends to
equalize the solute conc on either sides of the membrane

Corrosionclinic.com

Deaerated head and aerated tail

Corrosion restricted to the head- since H2O and hydrolysis
generate acidic environ
Self propagating
 Filiform.

Prevention
Low humidity storages
Coat with brittle films
Cracks at the head => admits O2
So differential O2 concentration is removed
Not very beneficial- handling brittle coated
material is difficult.
Develop films of low permeability.
 IGC (Intergranular Corrosion)
Grain boundaries: more reactive than the grain
Usually this has negligible effect on corrosion
However, in certain environments,
GB become very reactive
Localized attack
Disintegration of material/loss of strength
3 material causes
Impurity segregation- ex. Fe in Al
A.E. (alloying element) enrichment- ex. Zn in brass
A.E. depletion- Cr in SS
 Sensitization in SS
SS- at least 12% Cr for protective film
Ex. 18-8 SS (304 grade) 0.06-0.08 %C
Sensitization
500-800 C, few minutes-hours
Cr23C6 formation at GB, if C >0.02%
Cr depletion in the neighboring region
Unfavorable area ratio
 Sensitization
Accelerated attack in the Cr depleted zone along the GB

Cr23C6

Cr depleted zone- anodic

Unfavorable area
ratio!
 Weld Decay
18-8 SS
In severe environments, decay
occurs
Weld decay zone is little away from
the weld
Upon welding, the metal is heated
to sensitization temperature
With gas welding- decay zone- wider Deposited
weld
Arc welding- decay zone- narrower Area of weld decay
-Metal heated to
sensitization T
 Sensitization control
Heat treatment-
Solutionising 1065-1125 C => Cr gets dissolved
water quench => Cr remains in solution, does not get time to
recombine with C
Problem for large vessels
Add carbide formers (stabilizers)
Nb, Ta, Ti => 347, 321 grades
Greater affinity for C than Cr has
Add sufficient quantity to consume C
Use C < 0.03 % => 304L variety- extra low carbon steels
Methods to minimise C
During steel making- low C ferro-chrome, O2 blow, Vacuum
Avoid C-pickup
Dont clean with greasy/oily rags before welding
SS casting- organic binders, baked oil sand => surface enrichment
Ex. 0.16C on surface, and 0.03 at the core.
 Stress Corrosion Cracking (SCC)
SCC is a term used to describe service failures in
engineering materials that occur by slow environmentally
induced crack propagation. The observed crack propagation
is the result of combined & synergistic interaction of
mechanical & corrosion reactions.
Necessary:
Tensile stress
Susceptible material
Potent cracking environment

http://www.met-tech.com/
Environment Tensile stress

SCC

Metallurgy
(susceptible
material) intergranular SCC of an Inconel heat exchanger tube
with the crack following the grain boundaries
 Misconception- SCC is a result of stress
concentration at corrosion generated surface
flaws, K Y c
Although stress concentration does occur, in an
environment, KSCC < Kc
Neither factor acting independently or alternately
would result in the same result.
 Stresses
Usually < Y.S.
Tensile
Applied
Residual
Usually static loading (where cyclic loading-
CF)
SCC is described in metallic alloy failures
Pure metals, ceramics, polymers, too.
 Environments
An environment that causes SCC in an alloy may
not cause SCC in another alloy
A benign environment may change into an
aggressive environment with a change in T,
degree of aeration, and/or concentration of ionic
species
Usually aqueous
Bulk solution
Layer of moisture
Presence of specific chemical species
 Alloy-Environment Combinations
Alloy Environment
Carbon steel Hot nitrate, hydroxide,
carbonate/bicarbonate solutions
High strength steel Aqueous electrolytes esp. containing H2S
Austenitic Stainless steel Hot concentrated Cl solutions, Cl
contaminated steam
Al & Ti alloys Aqueous Cl , Br , I solutions
-brass Ammoniacal solutions

In general, SCC is observed in alloy-environ combinations that

result in formation of a film
Role of film is unclear!
Great concern- corrosion resistant alloys exposed to aggressive
environs.
 SCC- crack initiation processes
At surface discontinuities
Pre-existing (or corrosion induced) surface
features
e.g. grooves, laps, burrs from fabrication
processes like grinding, welding/joining
inclusions
 SCC- crack initiation processes
At corrosion pits
Pits form from
Prior cleaning operations, e.g. pickling
During exposure to service environs
Can form
At inclusions exposed to surface
By a breakdown in the protective films
Pitting to cracking transition depends on
Electrochemistry at the base of the pit
Pit geometry
Stress and stain rate at the base of the pit
No detailed relationship exists, the crack initiation is
difficult to measure.
 w = lateral corrosion
l = penetration
l
10
Generally, if w , pit acts as a
crack initiation site
Pit walls must show some passivating w
tendency for aspect ratio to exceed 1. l
If ratio = 1 , uniform corrosion !
Although local stress and strain rate are
important, some pits do not initiate
cracks
Therefore, electrochemistry of pit is
more imp.
 Crack initiation by IGC or slip dissolution

H2 M+ H2

M+

Anodic phase at the GB Cathodic phase at the GB

 G GB energy S1 S2
S1 ,S2- surface energy

IGC attack continues until

G S cos S cos
1 2 G1 G2
(Robertson & Bakish)

G
 Slip Dissolution: from local corrosion at emerging slip
plane in passivating environ (J.C. Scully) Healing may
occur at such
rate that only
a tip is left
Slip Slip step bare
plane surface

Too slow healing- general

corrosion
Too quick- no attack at all

Alloy surface After plastic deformation repassivation except

& production of wide slip step Small passive area
 Thermodynamics of SCC
Knowledge of thermodyn conditions to know if
cracking is feasible
Anodically assisted SCC
Conditions
Dissolution/oxidation of metal must be thermodynamically
possible
A protective film that must be thermodynamically stable
There are crack advance processes where the crack
advance is controlled by anodic dissolution but
Total crack length > that can be accounted for by total charge
transfer! (Faradays law)
da
However, crack growth rate 0 , if anodic current
dt
density is zero
 Thermodyn. requirement for simultaneous film
formation and oxidation
For crack to propagate
corrosion current from the wall
1
corrosion current from the tip

A M+W M+T

Belief: Activity of the crack tip relative to the

wall is a consequence of greater dynamic
strain at the tip than along the walls
 Critical Potentials for SCC
Zone 2
Potential, E

Zone 1

log i
Potentiodynamic polarization curve and electrode potential zones
at which the SCC occurs.
Zone 1 & 2: transgranular SCC is likely
Zone 1: simultaneous conditions for film formation on the crack walls
and corrosion at the tip
Zone 2: In addition, SCC potential > pitting potential, hence initiation
by pitting
IGSCC: wider range of zones
chemical inhomogenities at GB produce a different chemical response
relative to bulk material.
 SCC-Prevention
design with the right materials
reduce stresses
remove critical environmental species such as
hydroxides, chlorides, and oxygen
avoid stagnant areas and crevices in heat
exchangers where chloride and hydroxide
might become concentrated. Low alloy steels
are less susceptible than high alloy steels, but
they are subject to SCC in water containing Cl
ions.
 Corrosion Fatigue

Fatigue: crack propagation due to a cyclic

stress
Corrosion: makes both crack initiation and
propagation easier
Corrosion Fatigue
reduction of fatigue resistance due to presence of
a corrosive environ.
Catastrophic failures in aerospace, marine,
nuclear structures
 Corrosion Fatigue - S-N Curve
Stress Amplitude
Fatigue Limit in
many alloys

Air

Corrosion

log (cycles to failure, Nf)

In CF, fatigue limit is absent i.e. failure stress decreases continuously

with no. of cycles! No SAFE stress range!
Endurance limit- stress range below which a material will endure
specified number of cycles
 Ref: N.P. Inglis & G.F. Lake in Corrosion by Evans

Material Fatigue Limit Corrosion Fatigue

(air), MPa limit, MPa
(Tested in water)
Mild steel 117 14
Mild steel Ni plated 77 <21
Nitralloy Steel 227 35
Nitralloy steel, nitrided 255 172
18/8/1 Cr/Ni/W steel, 122 76
annealed
Same air cooled from 122 45
650C
 Environmental factors
Fatigue failure cracks
usually transgranular
Sometimes follow the G.B., too, over short distance
CF is prevalent in pit producing environs.- initiation
At high cyclic stresses, CF fracture is controlled by
mechanics; electrochemical effect is small since t is
short.
CF is prominent at low frequency
Greater contact t between the surface & the corrosive
At very low frequency surface is always passive
Very high frequency not enough t for environ. rxns
There is a maximum as a f(frequency)
 Features of Fatigue Failure
Stage I- Crack initiation usually at surface
Initiation time 25-50 % of Nf. c is very small.
Stage II crack growth/propagation in pulses
Crack progress burst blunting of tip progress.
50-75% of Nf.
Beach marks- wave for each burst- each burst may
represent no. of cycles after blunting.
Stage III C.S. too small to withstand app. => final
tensile shear failure

Corrosive environ. influences Stage I & II

 A propeller blade broken by corrosion fatigue.
Evidence is the classic beach marks of the fatigue
crack propagation, and the staining of corrosion
Ref: http://piattaformaisaers.altervista.org/teoria

Smooth bright surface Corrosion

with beach marks! products

fuselage of Aloha Airlines Flight 243

1988, a Boeing 737
metal fatigue exacerbated by crevice corrosion

Rough brittle fracture, app >UTS

Fatigue Corrosion Fatigue
 Effect on stage I
Processes

http://www.ndt-ed.org

Normal fatigue occurs by crack initiation from localized pd -

PSBs
Corrosive environ. s stage I time by alternate initiation
mechanisms
Local galvanic couples between phases
Dissolution of metal after mechanical disruption of passive films
by PSBs
Metal dissolution due to active sites in PSBs
Dissolution of GB regions- sensitized SS Completely changed
Pitting corrosion initiation mechanisms

Usually lower the frequency, more effective the corrosive in

ing stage I time.
Effect on stage II Processes

Test pre-craked samples to isolate the effect on

propagation => da/dN vs K.
Corrosive environ. results in faster crack
propagation rates
Acceleration of the normal crack growth
General corrosion of the crack tip in addition to
propagation from stress.
When crack opens up, corrosive oxidizes the surface
Precludes tip welding possibility => maintains longer crack
than in non-oxidizing environs.
Corrosion products build up = wedging effect
 Prevention
Reduce stress on the component
By design change- avoid stress conc/vibrations
Stress relieving heat treatments
Shot peening
High TS material- not good
Ordinary fatigue
Delays crack initiation but propagation is fast
Corrosion fatigue
Crack initiation is easy- from corrosion, propagation is fast, too.
Corrosion Inhibitors/Cathodic protection
Coatings-
Ni, Cr, Cu electrodeposited- such that no tensile stesses are
introduced, No H charging into the metal
Eg. Addition of Na Naphthalene trisulphonate to Ni plating bath
decreases tension to zero or ve.
Cr plated steels contain H & tension in the coating
Heat to T>440C => compressive stresses OR Shot peen after plating
Nitride coatings - in volume => compression, like chemical peening
 Relationship of SCC and CF
As m s, & amplitude s => CF
approaches SCC
high mean stress
with low amplitude

high mean stress

+
0 mean stress
-
 Selective Leaching
Removal of one element from an alloy
Dezincification
Yellow brass (70 Cu-30 Zn)
Assumes red colour
2 types
Layer type (Uniform) www.sailnet.com
In high brasses (high Zn)
In acidic environ.
Plug type (localized)
In low brasses
In neutral, alkaline environs.

http://www.corrosionlab.com/dezincification.brass-heat-exchanger.htm
 Zn addition to Cu its corrosion resistance
Dezincified portion
Porous
Weak
Permeable
Overall dimensions do not change
Mechanisms
2 theories
Zn dissolves leaving vacant sites
Cant explain high rate of dezincification since diffusion will be slow
3 step mechanism
Brass dissolves
Zn2+ stays in solution
Cu plates back on (porous deposit permits easy contact solution/brass
 Prevention
O2 removal ( aggressiveness)
Cathodic protection
Both solutions not economical
Use red brass ~15% Zn or cupronickels
Add inhibiting A.E. eg. As, Sb, P ---redeposited as a film
Other examples (also called dealloying)
Graphitic corrosion - GCI
Al in Al bronze in acids
Si in Si bronze
High surface area of dealloyed materials =>catalysts,
sensors Erlebacher J. et al, Nature 410, 450-453 (2001)
The final structure usually has spongy nature, consisting
of interconnected pores or tunnels in a skeleton of the
pure, or almost pure inert metal
Pore and filament size is 5-50nm and surface area as high
as 20m2/g compare vs. Natural zeolites 100 m2/g
 Graphitic corrosion
Grey Cast Iron
Selective leaching of Fe- leaves behind graphite
Graphite cathodic to Fe Galvanic cell
Porous mass left graphite + rust + voids
Strength , metallic properties
Slow process- uniform corrosion
Failures of underground pipelines handling
hazardous materials
Remedy: Use SG or malleable iron
Since graphite is discontinuousnot held together
 Cavitation Damage

Formation and collapse of vapour bubbles near

metal surface
Hydraulic turbines, ship propellers, pump impellers
Cyclic fluctuations in pressure
Low P => cavity formation repetition
High pressure => cavity implosion
Collapsing bubbles produce shock waves with
pressure ~ 103 atm (1000MPa) => plastic deformation-
evidence of slip lines,
generate fatigue conditions
Nucleation is easy at rough surfaces
 http://www.cdcorrosion.com/mode
_corrosion/corrosion_erosion.htm

Propeller cavitation,
materials.open.ac.uk

xaharts.org
 Hemispherical bubble collapse at the surface creates
high speed jets of liquid into the surface with velocity
of 100s of m/s => shock waves
Appearance- similar to pitting but pits are closely
spaced & surface is rougher
Film is not necessary
Prevention:
Same techniques as are used for erosion corrosion
Design- for lower pressure differences in flow streams
Smooth finish
Better material
Coatings- rubber/plastic. spalling
Cathodic protection => H2 evolution cushions the shock
waves
 Fretting Corrosion
Occurs at contact areas between materials under load
subjected to vibrations and slip, in the air.
Appearance: pits/grooves surrounded by corrosion
products
Failures: seizing, galling (Galling usually refers to the adhesive wear and transfer of material between
metallic surfaces in relative converging contact during sheet metal forming and other industrial operations), loss of

tolerences, loosening of mating parts => fatigue failure

Engine components, automotive parts, bolted parts,
bolted tie plates on rails, press fitted ball bearings race on
shaft.
Conditions conducive for fretting
An interface under load
Vibration/repeated relative motion (<1 mm amplitude)
Enough load and motion to cause slip/deformation
 Mechanisms
Wear oxidation mechanism
Cold welding- rupturing at contact points
fragments=> oxidized with heating
Loss of metal, accumulation of oxide residue
Oxidation-wear mechanism
Metals are mostly protected by oxide layers
Rupture of layers at the asperities
Oxide debris
Exposed metal reoxidizes due to frictional heat in air
 Fretting corrosion
Remedy
Lubricate with low viscosity oils and greases
This decreases friction and oxygen contact
Increase the hardness of mating materials- shot
peening/cold working
Roughening of the surface => increases friction so slip

Increase load to slip
Use gaskets to absorb vibrations and air access.
Increase relative motion
Fretting corrosion does not occur on surfaces in continuous
motion eg bearings.
 Hydrogen Damage
Hydrogen damage includes:
Hydrogen embrittlement (loss of ductility)
Hydrogen cracking (hydrogen stress cracking)
Hydrogen blistering
Hydrogen - induced cracking (H.I.C.)
Sulfide stress cracking
Examples
a stressed high - strength carbon steel or a martensitic stainless
steel immerse in dilute sulfuric or hydrochloric acid
may crack in a few minutes Hydro
appearance of S.C.C gen
if the alloy is cathodically polarized, cracking happens in shorter time
Cracking: 12% Cr martensitic steel screws (cathode) in contact with
an Al roof (anode) in a moist atmosphere
steel springs during pickling in sulfuric acid or after electroplating
catalyst poisons in acids: sulfur or As compounds favor entrance of
H into the metal lattice, When H2S (poison) failures are described
as sulfide stress cracking (S.S.C.).
Stressed high - strength steels (C-steels or 9% Ni steels) fail within days/weeks after
exposure to oil well brines or to natural gas containing H2S
 H atoms enter the metal interstitially either through a corrosion
reaction or by cathodic polarization
Steels with interstitial H lose ductility (hydrogen embrittlement)
usually crack only if app or R is sufficiently high => hydrogen
cracking
Steels are less susceptible to hydrogen cracking above RT
iron better catalyzes: Hads + H+ + e H2
Unlike catalyst poisons (previous slide), hydrogen escapes as molecular H2
and less adsorbed H
C-steels heat - treated
to form martensite - susceptible to hydrogen cracking
Pearlitic less suscepticle
spheroidized carbide structure - less susceptible than pearlite, bainite, or
martensite
Austenitic steels are immune under most exposure conditions
 Mechanism of Hydrogen Damage
development of internal pressure:
interstitial atomic H is released as molecular hydrogen at
voids or other favored sites
Evidence : formation of blisters containing hydrogen when
ductile metals are cathodically polarized or exposed to
certain corrosive
Under similar conditions, a less ductile metal cracks
Characteristic of hydrogen cracking: a specific delay time for
appearance of cracks after stress is applied
Specimen initially charged cathodically, baked at 150 C
for varying t to reduce hydrogen content
Delayed fracture times and min for cracking of 0.4% C
steel as a function of H content.
A critical minimum stress exists, below
which delayed cracking does not take place
in any time
decreases with dissolved H content
 Delay in fracture because
time required for hydrogen to diffuse to
specific areas near a crack nucleus until the
concentration reaches a damaging level
arrays of imperfection sites produced by plastic
deformation of metal just ahead of the crack
crack propagates discontinuously because
plastic deformation occurs first
hydrogen diffuses
Crack propagates
Plastic deformation again
 Pipeline failures by H.I.C. (from
blisters)
In steels, nonmetallic inclusions eg. MnS provide
internal flaws where hydrogen blisters often nucleate
three steps:
1. Formation of H atoms at the steel surface and adsorption
on the surface
2. Diffusion of H atoms into the steel substrate
3. Accumulation of hydrogen atoms at hydrogen traps, such
as voids around inclusions in the steel matrix, leading to
increased internal pressure, crack initiation and
propagation, and linkage of separate cracks
Internal cracks are nucleated where stress intensity is
highest, such as at elongated inclusions oriented
parallel to the rolling direction
can occur in the absence of any app or R
Hydrogen - induced cracking
(H.I.C.)
 Hydrogen Damage- prevention
Factors that reduce hydrogen absorption in the corrosion
process
alloying with a small % of Pt or Pd catalyzes formation of molecular
hydrogen at surface
any processing of steel that minimizes sharp internal surfaces at
the inclusion interface, eg. Avoid low rolling T
reducing the sulfur content in the steel and by controlling the
shape of sulfides eg. by adding calcium- cleaner steel!
Eliminate cathodic protection, stray currents, galvanic couples
pH > 8 is beneficial in sulphide HIC
experience of the oil industry: U.T.S. is inversely related to
HIC resistance
in H2S environments, steels of hardness > Rc 22 should be avoided (do
annealing)
based on KIC for steels exposed to aqueous H2S solutions, Rc 22
corresponds to a critical surface flaw depth of about 0.5 mm
Removal of sulphides to below 50 ppm
Inhibitors
HIC is reversible: baking between 100 -650C restores
ductility