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METB113/1Corrosion and Protection Methods
METB113ENGINEERING MATERIALS
CORROSION AND PROTECTION METHODS
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METB113/2Corrosion and Protection Methods
Types and Its Mechanisms
Protection & Control MethodsStructure Analysis
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METB113/3Corrosion and Protection Methods
Corrosion: -- the destructive and unintentional electrochemical
attack of a materials.Rate of corrosiondepends upon temperature and concentration of
reactants and products.
Metals have free electrons that setup electrochemical cellswithin
their structure.
Metals have tendency to go back to low energystate by corroding.
Ceramics and polymers suffer corrosion by direct chemical attack.
-- Ex: Al Capone's
ship, Sapona,
off the coast
of Bimini.
Cost:-- 4 to 5% of the Gross National Product (GNP)*-- in the U.S. this amounts to just over $400 billion/yr**
Photos courtesy L.M. Maestas, SandiaNational Labs. Used with permission.
Introduction
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METB113/4Corrosion and Protection Methods
OxidationReduction Reactions
A metal (EgZn) placed in HCl undergoes corrosion.
Zn + 2HCl ZnCl2+ H2or
Zn + 2H+ Zn2+ + H2also
Zn Zn 2+ + 2e- (oxidation half cell reaction)
2H+ + 2e- H2 (Reduction half cell reaction)
Oxidation reaction: Metals form ions at local anode. Reduction reaction: Metal is reduced in local charge at
local cathode.
Oxidation and reduction takes place at same rate.
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METB113/5Corrosion and Protection Methods
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Two reactions are necessary:-- oxidation half-cell reaction:-- reductionhalf-cell reaction:
Zn Zn2 2e
2H
2e H2(gas)
Other reductionreactions in solutions with dissolved oxygen:
-- acidic solution -- neutral or basic solution
O2 4H 4e 2H2O O2 2H2O 4e 4(OH)
ELECTROCHEMICAL CORROSION
Zinc
Oxidation reactionZn Zn2+
2e-Acidsolution
reduction reaction
H+H+
H2(gas)
H+
H+
H+
H+
H+
flow of e-in the metal
Ex: consider the corrosion of zinc in an acid solution
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METB113/6Corrosion and Protection Methods
Standard electrode Half-Cell Potential of Metals
Oxidation/Reduction half cell potentials are compared withstandard hydrogen electrode
half cell potential.
Voltage of metal (Ex: Zn) is
directly measured against
hydrogen half cell electrode.
Anodic to hydrogen More tendency to corrode
Examples:-Fe (-0.44), Na (-2.74)
Cathodic to hydrogen Less tendency to corrode
Examples:-Au (1.498), Cu (0.33)
Figure 12.
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METB113/7Corrosion and Protection Methods
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Standard Hydrogen Electrode
Oxidation/Reduction half cell potentials are compared withstandard hydrogen electrodehalf cell potential.
Two outcome:
0o
metalV (relative to Pt)
Standard Electrode Potential
Adapted from Fig. 16.2,
Callister & Rethwisch 3e.
-- Electrodeposition
-- Metal is the cathode (+)
Mn+
ions
ne-
e- e-
25
C
1M Mn+soln1M H+ soln
Platinum
metal,M H
+
H+
2e-
0o
metalV (relative to Pt)
-- Corrosion
-- Metal is the anode (-)
Platinum
metal,M
Mn+
ions
ne- H2(gas)
25
C
1M Mn+soln1M H+ soln
2e
-
e-e-
H+
H+
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METB113/8Corrosion and Protection Methods
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Standard EMF Series
metalo
Metal with smaller
V corrodes.
EMFseries
AuCuPbSn
NiCoCdFeCr
ZnAlMgNaK
+1.420 V+0.340- 0.126- 0.136
- 0.250- 0.277- 0.403- 0.440- 0.744
- 0.763- 1.662- 2.363- 2.714- 2.924
metalVmetal
o
Data based on Table 17.1,Callister 7e.
moreanodic
more
cathodic
V =0.153V
o
Adapted from Fig. 16.2,Callister & Rethwisch 3e.
-
1.0 M
Ni2+ solution
1.0 M
Cd2 + solution
+
25
C NiCd
Ex: Cd-Ni cell
V < V Cd corrodesCdo
Nio
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METB113/9Corrosion and Protection Methods
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Effect of Solution Concentration and Temperature
Ex: Cd-Ni cell withstandard 1 M solutions
VNio
VCdo 0.153 V
-
Ni
1.0 M
Ni2+ solution
1.0M
Cd2 + solution
+
Cd 25
C
Ex: Cd-Ni cell with
non-standard solutions
Y
Xln
nF
RTVVVV
o
Cd
o
NiCdNi
n= #e-per unitoxid/redreaction(= 2 here)F=Faraday'sconstant= 96,500C/mol.
Reduce VNi- VCdby-- increasingX-- decreasing Y-- increasing T
- +
Ni
YM
Ni2+ solution
XM
Cd2 + solution
Cd T
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METB113/10Corrosion and Protection Methods
Microscopic galvanic cell can exist in metals or alloys due to
difference in structure, composition and stress concentration.
When single electrodeis immersed in an air-free electrolyte,
microscopiccathodes and anodes are formed on the surface due
to difference in structure and composition.
Oxidation reaction occurs at local anodeand reduction reaction
at local cathode.
If iron is immersed in
oxygenated water,
2Fe + 2H2O + O2 2Fe2++ 4OH- 2Fe(OH)2
Microscopic Galvanic Cell Corrosion of Single Electrode
Fe Fe2++ 2e-
O2+ 2H2O + 4e- 4OH-
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METB113/11Corrosion and Protection Methods
Grain-grain-boundary Electrochemicalcells
Grain boundaries are more anodicand hence get corroded
by electrochemical attack.
Grain boundaries are at higher energy.
Impurities migrateto grain boundaries.
Solute segregation might cause grain boundaries to
become more cathodic.
Cartridge Brass
Grain
BoundaryGrain boundary
(anode)
Grain boundary
(cathode)
anode
Figure 12.913-11
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METB113/12Corrosion and Protection Methods
Multiple Phase Electrochemical Cells In multiple alloys, one phase is more anodicthan another.
Corrosion rates are higherin multiphase alloys.
Example:In pearlite gray cast iron, graphite flake is
cathodic than surrounding pearlite matrix.
Anodic pearlite corrodes
Steel, in martensiticcondition
(single phase) after quenching
from austenitic condition, has
better corrosion resistance. Impurities in metals leads toprecipitationof intermetallic
phases and hence forms anodic and cathodic regions
leading to corrosion.Figure 12.10
After Metals handbook, vol. 7, 8thed., American Society for Metals, 1972, p.83.13-12
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METB113/13Corrosion and Protection Methods
Rate of Uniform Corrosion Faradays equation:
W = weight of metal (g), corroded or electroplated in an
aqueous solution in time t, seconds.
I = Current flow A, i = current density A/cm2
M = atomic mass of metal g/mol
n = number of atoms/electron produced or consumedF = Faradays Constant, A = area, cm2
Corrosion rateis expressed as weight loss per unit areaper
unit time or loss in depth per unit time.
nF
iAtM
nF
ItMW
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METB113/15Corrosion and Protection Methods
Activation and Concentration Polarization
Activation polarization:Electrochemical reactions that are controlled by
the slowest stepin the reaction sequence.
There is a critical activation energyto surmount energy barrier associated
with slowest step.
Figure 12.15After M. G. Fontana and N. D. Greene, Corrosion Engineering, 2nded., McGraw-Hill, 1978, p.15.13-15
Polarization controls the corrosion rate.
1. Adsorption of H+from solutiononto zinc surface.
2. Electron transfer from zinc tohydrogen atom.
3. Reduction of hydrogen.4. Combining two atom hydrogen
together.
5. Coalescence of many hydrogenmolecules to form bubbles.
The slowest of these steps controlthe overall reaction.
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METB113/16Corrosion and Protection Methods
Concentration polarization:
exists when the reaction rate is limited by the diffusion of ions in the
solution. Example:Reduction rate of H+ions at surface is controlled by diffusion
of H+ions onto metal surface.
Activation and Concentration Polarization
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METB113/17Corrosion and Protection Methods
Passivation
Passivation is loss of chemical reactivityin
presence of an environmental condition.
Formation of surface layerof reaction products that
inhibit further reaction. Oxide film theory: Passive film is always a
diffusion barrier of reaction products.
Adsorption theory: Passive metals are covered
by chemisorbed films of oxygen.
Examples:-Stainless steel, nickel alloys,
titanium and aluminum alloys.
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METB113/19Corrosion and Protection Methods
Uniform and Galvanic Types of Corrosion
Uniform or general attack corrosion:Reaction
proceeds uniformly on the entire surface.
Controlled by protective coatings, inhibitors and
cathodic protection.
Galvanic or two metal corrosion:
Electrochemical reaction leads to corrosion of on
metal.
Zinc coatings on steel protects steel as zinc is anodictosteel and corrodes.
Large cathode area to small anode area should be
avoided.
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METB113/20C i d P t ti M th d
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METB113/20Corrosion and Protection Methods
Pitting Corrosion
Pitting:Localized corrosive attacks that
produces holes or pits in a metal.
Results in sudden unexpected failure as pits go
undetected(covered by corrosion products). Pitting requires an initiation
periodand grows in
direction of gravity. Pits initiate at structural
and compositional
heterogeneities. Pitting of stainless steel
Figure 12.20
Courtesy of LaQue Center for Corrosion Technology, Inc.13-20
METB113/21C i d P t ti M th d
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METB113/21Corrosion and Protection Methods
Growth of Pit
Growth of pit involves dissolution of metalin pitmaintaining high acidity at the bottom.
Anodic reactionat the
bottom and cathodic
reactionat the metal
surface.
At bottom, metal chloride + water Metal
hydroxide + free acid.
Some metals (stainless steel) have better resistance
than others (titanium).
Figure 12.21
After M. G. Fontana and N. D. Greene, Corrosion Engineering, 2nded., McGraw-Hill, 197813-21
METB113/22C i d P t ti M th d
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METB113/22Corrosion and Protection Methods
Figure 12.21
After M. G. Fontana and N. D. Greene, Corrosion Engineering, 2nded., McGraw-Hill, 197813-21
Crevice Corrosion
Localized electrochemical corrosion in crevicesand undershielded surfaces where stagnant solutions can exist.
Occurs under valve gaskets, rivets and bolts in alloy systemslike steel, titanium and copper alloys.
Anode:M M++ e-
Cathode:O2+ 2H2O + 4e- 4OH-
As the solution is
stagnant, oxygen is used up
and not replaced.
Chloride ions migrate tocrevice to balance positive charge and form metal hydroxideand free acidthat causes corrosion. Figure 12
nd
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METB113/24C i d P t ti M th d
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METB113/24Corrosion and Protection Methods
Stress Corrosion Stress corrosion cracking (SCC):Cracking caused by
combined effect of tensile stressand corrosive environment. Stress might be residual and applied.
Only certain combination
of alloy and environment
causes SCC. Crack initiates at pit or
other discontinuity.
Crack propagatesperpendicular
to stress Crack growth stops if either stress or corrosive environment
is removed.
Figure 12.27
After R. W. Staehle.13-24
METB113/25C i d P t ti M th d
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METB113/25Corrosion and Protection Methods
Erosion Corrosion and Cavitation Damage
Erosion corrosion: Acceleration in rate of corrosion due torelative motionbetween corrosive fluid and surface.
Pits, grooves, valleys appear on surface in directionof
flow.
Corrosion is due to abrasive actionand removal ofprotective film.
Cavitation damage:Caused by collapseof air bubbles or
vapor filled cavities in a liquid near metal surface.
Rapidly collapsing air bubbles produce very high pressure(60,000 PSI) and damage the surface.
Occurs at metal surface when high velocity flow and
pressure are present.
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METB113/28Corrosion and Protection Methods
Mechanisms of Oxidation
Oxidation partial reaction: M M 2++ 2e-
Reduction partial reaction: O2+ 2e- O2-
Oxidation starts by lateral expansionof discrete oxide nuclei.
Metal diffusesas electrons or cations across oxide films.
Sometimes O2-ions diffuse to oxide metal interface and
electrons diffuse to oxide gas interface.
Figure 12.30
After L.L. Shreir (ed.) Corrosion, vol.1, 2nded., Newnes-Butterwirth, 1976, p. 1:242.13-28
METB113/29Corrosion and Protection Methods
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METB113/29Corrosion and Protection Methods
Oxidation Rates Oxidation rate is expressed
as weight gainedper unit area. Linearoxidation behavior
W = KLt
If ion diffusionis controlling the step (EgFe, Cu)
W2 = Kpt+C Kp= Parabolic rateconstant, C = constant
Some metals follow logarithmic ratelawW = KeLog(Ct + A) C, A = constants, Ke= logarithmic
rate constant
Examples:-Al, Cu, Fe (at slightly elevated temperature)
W=weight gained
per unit area
KL = linear rate
constant.T = time
Figure 12.31
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METB113/30Corrosion and Protection Methods
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METB113/30Corrosion and Protection Methods
Corrosion ControlMaterial Selection
Metallic Metals:
Use proper metal for particular environment.
For reducing conditions, use nickel and copper alloys.
For oxidizing conditions, use chromium based alloys.
Nonmetallic Metals:
Limit use of polymersin presence of strong inorganic
acids.
Ceramics have better corrosion resistance but arebrittle.
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METB113/31Corrosion and Protection Methods
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METB113/31Corrosion and Protection Methods
Coatings
Metallic Coatings:Used to protect metal by
separatingfrom corrosive environment and
serving asanode.
Coating applied through electroplatingor rollbonding.
might have several layers.
Inorganic coatings:Coating with steel and glass.
Steel is coated with porcelain and lined with glass.
Organic coatings:Organic polymers (paints and
varnishes) are used for coatings.
Serve as barrier but should be applied carefully.
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Corrosion and Protection Methods
Design
General design rules:Provide allowancefor corrosion in thickness.
Weldrather than rivet to avoid crevice corrosion.
Avoid dissimilar metalsthat can cause galvanic
corrosion.
Avoid excessive stress and stress concentration.
Avoid sharp bendsin pipes to prevent erosioncorrosion.
Design tanks and containers for early draining.design so that parts can be easily replaced.
Design heating systems so that hot spotsdo notoccur.
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METB113/33Corrosion and Protection Methods
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Corrosion and Protection Methods
Alteration Environment
Lower the temperature Reduces reaction
rate.
Decrease velocityof fluids Reduces
erosion corrosion.
Removing oxygen from liquids reducescorrosion.
Reducing ion concentration decreases
corrosion rate. Adding inhibitors inhibitors are retarding
catalystsand hence reduce corrosion.
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METB113/34Corrosion and Protection Methods
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Corrosion and Protection Methods
Cathodic Protection
Electrons are suppliedto the metal structure tobe protected.
Example:Fe in acid
Fe Fe2+
+ 2e-
2H++ 2e- H2Corrosion of Fe will be
prevented if electrons
are supplied to steel
structure.
Electrons can be supplied by external DCsupply
or galvanic couplingwith more anodic metal.
Figure 12.33
After M. G. Fontana and N. D. Greene, Corrosion Engineering, 2nded., McGraw-Hill, 1978, p.207.13-34
METB113/35Corrosion and Protection Methods
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Corrosion and Protection Methods
Anodic Protection
Externally impressed anodic currents form
protective passive filmson metal and alloy
surfaces.
Anodic currents are applied bypotentiostat toprotect metals that passivate.
Current makes them more passive and decreases
the corrosion rate.
Figure
12 34
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