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Chapter 18: Corrosion

Issues to address... Why does corrosion occur? What metals are most likely to corrode? How do T and environment affect corrosion rate? How do we suppress corrosion?

Corrosion is often the life-limiting degradation process in engineering alloys.


Al Capones Sapona, wrecked off Bimini.

We are unable to adequately prevent and predict corrosion because a quantitative understanding of the entire damage process does not exist.

This lack of understanding costs 4 - 5% of the GNP annually. On this basis, 1997 corrosion costs totaled just over $400 billion.

Uhlig & Revie (1985) Economic Report of the President (1998).

When it comes to corrosion, OSU is there.

Photos/info courtesy of R. Buchheit, OSU Anderson 205- 18-1 Anderson 205- 18-2

Corrosion of Zn in an Acid Solution


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

Standard Hydrogen (emf) Test


Two outcomes:
Metal sample mass eneeH2(gas) Mn+ H+ ions H+
1M Mn+ soln 1M H+ soln

Metal sample mass eeH+ 2eH+

H+ oxidation reaction Zn Zn2+ H+

2eBased on Fig. 18.4, Callister

neMn+ ions

Zinc flow of e2ein the metal

H+ H+

H+

Acid solution
Based on Fig. 18.1, Callister

H+ H2(gas) H+ reduction reaction

25C

1M Mn+ soln 1M H+ soln

25C

Other reduction reactions... -in an acid: -in a neutral or base: O2 + 2H2O + 4e 4(OH) O2 + 4H+ + 4e 2H2O
Anderson 205- 18-3

metal is the anode (-) o Vmetal < 0 (relative to Pt)

metal is the cathode (+) o Vmetal > 0 (relative to Pt)

Standard Electrode Potential

Anderson 205- 18-4

Standard emf Series


Metal Standard Electrode o Metal with smaller Potential, Vmetal o Vmetal corrodes Au +1.420 V Cu +0.340 Ex: Cd-Ni cell Pb -0.126 + Sn -0.136 Ni -0.250 Co -0.277 Cd -0.403 Fe -0.440 Cr -0.744 Cd 25C Ni Zn -0.763 Al -1.662 1.0 M 1.0 M Mg -2.363 Cd2+ solution Ni2+ solution Na -2.714 K -2.924
Based on Table 18.1, Callister Anderson 205- 18-5

Corrosion in a Grapefruit!
Cathode Cu

Anode

H+ reduction 2H+ + 2e H2 (gas) O2 + 4H+ + 4e 2H2O H+ H+

H+ 2e-

Zn2+

Zn

oxidation H+

Acid H+

H+

Anderson 205- 18-6

Effect of Solution Concentration


Ex: Cd-Ni cell with standard 1M solutions
o o VNi - VCd= 0.153V

The Galvanic Series


Ranks the reactivity of metals/alloys in seawater
Platinum Gold Graphite Titanium Silver 316 Stainless Steel (passive) Nickel (passive) Table 18.2, Copper Callister Nickel (active) (Partial list) Tin Lead 316 Stainless Steel (active) Iron/Steel Aluminum Alloys Cadmium Zinc Magnesium Anderson 205- 18-8

Ex: Cd-Ni cell with non- standard solutions


o o RT X VNi - VCd = VNi - VCd ln nF Y +
n: #e- per unit oxidation/ reduction reaction (= 2 here) F: Faradays constant (96,500C/mol)

Cd

25C

Ni

Cd

Ni

1.0 M 1.0 M Cd2+ solution Ni2+ solution

XM YM Cd2+ solution Ni2+ solution

Can reduce VNi - VCd by:


- increasing X - decreasing Y

Anderson 205- 18-7

Based on Table 18.2, Callister

Uniform Attack
oxidation & reduction reactions occur uniformly over the surface.

Stress-corrosion Erosion-corrosion
Stress and corrosion combine at crack tips. Breakdown of passivating layer by erosion (pipe elbows).

Self-protecting metals!

Selective leaching
Preferred corrosion of one element/constituent [e.g., zinc from brass (Cu-Zn)].

Pitting Forms of corrosion


Downward propagation of small pits/holes.
Fig. 18.17, Callister

Metal oxide Metal (e.g., Al, -Metal ions combine with O ions to form a stainless steel) thin, adhering oxide layer that slows corrosion.

Controlling Corrosion

Reduce T (slows kinetics of oxidation and reduction). Add Inhibitors


-slow oxid./reduction reactions by removing reactants (e.g., remove O2 gas by reacting it with an inhibitor) -slow oxid. reaction by attaching species to oxid. surface. (e.g., paint)

Intergranular
Corrosion along grain boundaries, often where 2nd phases exist.

Galvanic
Dissimilar metals are Crevice physically joined and Occurs between two the more anodic one pieces of the same metal. corrodes. Rivet holes (See Table 18.2 Galvanic series: zinc, magnesium are very anodic) Fig. 18.15,
Callister Anderson 205- 18-9

Cathodic (or sacrificial) protection


-attach a more anodic material to the one to be protected. e.g., zinc-coated nail Zn2+
Fig. 18.23 Callister

e.g., Mg Anode

zinc

Fig. 18.18, Callister

2e- 2esteel

zinc

steel pipe

e-

Cu wire Fig. 18.22(a) Mg Mg2+ Callister anode Earth


Anderson 205- 18-10