2010 KPTrumble

MSE 230

HW11 Solutions (04/16)

Spring 2010

1. As presented in lecture, the overall anode and cathode reactions are as follows:
Fe Fe 3+ + 3e - (anode) 3 3 0 2 + H 2 0 + 3e - 3OH - (cathode) 4 2 3 3 3+ Fe + 0 2 + H 2 0 Fe + 3 OH 4 2 Fe(OH)3
The iron actually dissolves as Fe and then is oxidized further by a second step of the same cathode reaction.
2+

The two-step reaction can be written as:

Fe Fe 2+ + 2e - (anode) 1 0 2 + H 2 0 + 2e - 2OH - (cathode) 2 Fe 2+ Fe 3+ + 1e - (anode)

Step 1

1 1 0 2 + H 2 0 + 1e - OH - (cathode) Step 2 4 2 3 3 3+ Fe + 0 2 + H 2 0 Fe + 3 OH 4 2 Fe(OH)3

2. (a) Iron and chromium are similar or the same in all four factors that determine solid solubility. Callister does not have an Fe-Cr phase diagram, but it shows that the solid solubility of Cr in Fe increases from about 5 wt.% Cr at room temperature to complete solubility above ~820C. Iron Chromium 1. Atomic size: 0.124 nm 0.125 nm 2. Crystal structure bcc bcc 3. Electronegativity 1.8 1.6 4. Valences (bold: most common)* +2, +3 +2, +3, +6 *Other sources (e.g., Sargent and Welch periodic table) indicate the most common valence of Fe is +3. (b) Chromium is actually more anodic than iron, -0.744 V (Cr ) versus -0.440 V (Fe ) or -0.036 V (Fe ) standard reduction potentials which at first might seem surprising since adding chromium to iron makes the alloy more corrosion resistance. (c) The chromium effect is mainly to increase scale (reaction product) adhesion so the alloy passivates. (d) Nickel is more cathodic (inert) than iron, so adding Ni reduces the overall tendency for oxidation (corrosion).
3+ 2+ 3+

2010 KPTrumble

3. (a) Food Cans Zinc prevents corrosion of Fe even if the coating is breached (say if the can is badly dented), but goes into solution if sufficiently acidic, contaminating the food. This may only be a problem if the can is open and oxygen absorbed from the air provides a cathode reaction. Tin protects from corrosion only if not scratched to expose Fe. It is less anodic than Zn and exhibits less dissolution into most foodstuffs, but is also much more expensive than Zn. (b) Outdoor Fencing No problem with contamination as in food cans. Zinc is best, for it is anodic with respect to Fe. Tin protects as long as the integrity of its film is preservedunlikely in this application. Also, tin is much more expensive. 4. (a) PTFE, Nylon 6,6, PEEK, PET are listed as "S" = Satisfactory in non-polar solvents (Epoxy is also rated S, but is not a thermoplastics) (b) Of the four thermoplastics having satisfactory non-polar solvent resistance, only PTFE has adequate toughness at -20C, as indicated by the glass transition temperature: PTFE Nylon 6,6 PEEK PET Tg (C) -97 57 143 69

5. The silicone does not have a double bond in its structure, unlike most of the other elastomers, which is the main point of attack in the reactions that lead to weathering. Also the Si O Si O Si O backbone of the silicone rubber molecule is more oxidation resistant (its already an oxide, so to speak) than the C C C C C C backbone of isobutylene and especially the C C = C C C C = C C backbone of the other elastomers.