CHAPTER 16

Corrosion and Degradation of Materials

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).

ELECTROCHEMICAL REACTIONS

Half-cell Reaction (Oxidation) Loss of Electron (s) M = Mn+ + neCharge neutrality is maintained by reduction reaction Half-cell Reaction (Reduction) Gain of Electrons Examples Acid Solution: Acid Solution with dissolved O2 Neutral or Basic Solution with O2 2H+ + 2e- = H2 O2 + 4H+ + 4e- = 2H2O O2 + 2H2O + 4e- = 4(OH-) Mn+ + e- = M(n-1)+ or Mn+ + ne- = M

CORROSION OF ZINC IN ACID Two reactions are necessary: -- oxidation reaction: Zn Zn 2 + + 2e -- reduction reaction: 2H+ + 2e H2 (gas )
H+ oxidation reaction Zn Zn2+ H+

Zinc

flow of e2ein the metal

H+ H+

H+ H+

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

H2(gas) H+ reduction reaction

STANDARD HYDROGEN (EMF) TEST Two outcomes:

--Metal sample mass
enemetal, M

--Metal sample mass

eeH+ 2eH+

eH2(gas) Mn+ H+ ions H+ 25C 2ePlatinum

nemetal, M

Mn+ ions

1M Mn+ soln 1M H+ soln

1M Mn+ soln 1M H+ soln

25C

--Metal is the anode (-)

o Vmetal < 0 (relative to Pt)

--Metal is the cathode (+)

o Vmetal > 0 (relative to Pt)

Standard Electrode Potential

Platinum

STANDARD EMF SERIES

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

+1.420 V Ex: Cd-Ni cell +0.340 + - 0.126 - 0.136 - 0.250 o V = - 0.277 0.153V - 0.403 Cd Ni 25C - 0.440 - 0.744 - 0.763 1.0 M 1.0 M - 1.662 Cd2+ solution Ni2+ solution - 2.262 - 2.714 Data based on Table - 2.924 17.1, Callister 6e.

o Vmetal

Metal with smaller

Vmetal corrodes.
o

more anodic

more cathodic

CONDITIONS FOR SPONTANEOUS REACTION

Generalized Reaction M1 = M1n+ + neM2n+ + ne- = M2 -V1o +V2o Oxidation Reduction

For the overall reaction: Overall cell Potential :

M1 + M2n+ = M1n+ + M2 Vo = (V2o V1o ) > 0 : Spontaneous

T and Concentration dependence V = (V2o V1o) (RT/nF) ln ((M1n+)/(M2n+)) = (V2o V1o) (0.0592/n) log (M1n+)/(M2n+))

ANORTHER EXAMPLE OF CORROSION

Cathode Cu + H+ reduction 2H+ + 2e H2 (gas ) H+ Zn2+ Anode

Zn

2eH+ H+ Acid H+

oxidation H+ H+

O2 + 4H+ + 4e 2H2 O

EFFECT OF SOLUTION CONCENTRATION Ex: Cd-Ni cell with standard 1M solutions

o o VNi VCd = 0.153

Ex: Cd-Ni cell with non-standard solutions

o VNi VCd = VNi

o VCd

RT X 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 =96,500 Reduce VNi - VCd by C/mol.

-- increasing X -- decreasing Y

GALVANIC SERIES Ranks the reactivity of metals/alloys in seawater more cathodic (inert)
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.)

more anodic (active)

CORROSION RATES

Corrosion Penetration rate (CPR) KW CPR = At W (mg) = Wt. loss at time t (h) ; = density (g/cc) ; K = constant and A (Sq inch) specimen area K = 534 ; CPR in mpy (1 mil = 0.001 in.)

i r= nF i = Current density i.e current for unit surface area of the material corroding

Corrosion rate

pp. 572-581 , W. D. PREDICTION OF CORROSION RATES Callister, 5th edition

Polarization

-- Displacement of each equilibrium potential from its equilibrium value

Overvoltage () -- Magnitude of displacement involved in polarization

= 0.621V (0.763V ) = +0.142V

Potential of Zn electrode Equilibrium Potential

Electrochemical cell consisting of standard Zn and H2 electrode

ACTIVATION POLARIZATION

Activation Polarization -- Refers to a condition where the reaction rate is governed by the step with slowest rate -- Activation Energy Barrier in slowest step SEQUENCE OF STEPS

Schematic representation of possible steps in the hydrogen reduction reaction (Rate controlled by activation Polarization)

ACTIVATION POLARIZATION

Eq. 1
Equilibrium is dynamic

2H+ + 2e- = H2 H2 = 2H+ + 2e-

rred roxi

ACTIVATION POLARIZATION -- At Equilibrium rred = roxi

Depends on electrochemical systems

Plot of activation polarization overvoltage Vs logarithm of Current Density

CONCENTRATION POLARIZATION

Reaction Rate -- Reaction rate by diffusion in the solution -- The diffusion of H+ to the Interface is rate controlling

For H2 reduction, Schematic representation of H+ distribution in the vicinity of Cathode (a) Low reaction Rate (b) High reaction Rate

Overvoltage Vs Logarithm of Current Density

Concentration Polarization

Overvoltage -- Decrease of Overvoltage as i

iL

Activation-Concentration Polarization

Overvoltage -- Sum of activation and Concentration contribution

REACTION RATE LIMITED BY ACTIVATION POLARIZATION

Exchange current density; H2 Half cell

Potential of uncoupled H2 Half cell

Ox Rate = Red. Rate at Vc and ic Potential of uncoupled Zn Half cell

Exchange current density, Zn Half cell

ELECTRODE KINETIC BEHAVIOUR OF Zn IN ACID SOLUTION

REACTION RATE LIMITED BY ACTIVATION and CONCENTRATIONPOLARIZATION

Ox Rate = Red. Rate at Vc and ic

ELECTRODE KINETIC BEHAVIOUR OF METAL, M

PASSIVITY

i, Increases

i, Decreases, and remains Constant

Linear

SCHEMATIC POLARIZATION CURVE FOR A METAL THAT DISPLAYS ACTIVE-PASSIVE TRANSITION

PASSIVITY

Solution 1

Solution 2

ACTIVE-PASSIVE METAL EXHIBITING ACTIVE AND PASSIVE CORROSION

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)).

Pitting

Intergranular
Corrosion along grain boundaries, often where special phases exist.
g.b. prec. attacked zones
Fig. 17.9, Callister 6e.

Forms of corrosion

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.)

Galvanic

Crevice Between two Dissimilar metals are pieces of the same metal. physically joined. The Rivet holes more anodic one corrodes.(see Table 17.2) Zn & Mg Fig. 17.6, Callister 6e. (Fig. 17.6 is very anodic. courtesy LaQue Center for Corrosion
Technology, Inc.)

CONTROLLING CORROSION Self-protecting metals!

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

--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,

e.g., zinc-coated nail Zn2+

e.g., Mg Anode

zinc 2e- 2esteel

zinc

Callister 6e.

steel pipe

e-

Cu wire Mg Mg2+ anode Earth

Adapted from Fig. 17.13(a), Callister 6e. (Fig. 17.13(a) is from M.G. Fontana, Corrosion Engineering, 3rd ed., McGrawHill Book Co., 1986.)

SUMMARY Corrosion occurs due to:

--the natural tendency of metals to give up electrons. --electrons are given up by an oxidation reaction. --these electrons then are part of a reduction reaction.

Metals with a more negative Standard Electrode Potential are more likely to corrode relative to other metals. The Galvanic Series ranks the reactivity of metals in seawater. Increasing T speeds up oxidation/reduction reactions. Corrosion may be controlled by:
-- using metals which form a protective oxide layer -- reducing T -- adding inhibitors -- painting --using cathodic protection.