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 Capone’s 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+ sol’n 1M H+ sol’n

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

25°C

1M Mn+ sol’n 1M H+ sol’n

25°C

• 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 25°C 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: Faraday’s constant (96,500C/mol)

-

+

Cd

25°C

Ni

Cd

T

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

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