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HW #10 Solutions Problem #1) Cell potentials can be determined qualitatively from Fig 17.2.

The quantitative estimates given here have been obtained from other information outside the textbook. If you answers differ slightly because of this, that is acceptable. Volume ratios are from given data.
Case Corrosive System Iron Tin Brass Austenitic Stainless Silica Glass Low C Steel Cu Mg Zn Monel Plastic Stainless Steel Cast Iron 2024 Al Electrode Identification Anode Cathode Cathode 0.5 Anode Cathode Anode Cathode 0.2 Anode Anode Anode Cathode 0.1 0.20 None 3.00 None 1.4 0.67 Yes, Zn protected 3.00 None Cell Potential (Volts) 0.45 Volume Ratio (V[cath]/V[an]) 0.33 Cathodic Protection? Yes, Tin protected

II

III

IV

Relative Rates: Rate[III] > Rate[II] > Rate[I] > Rate[IV] > Rate[V] NOTE: Rate determinations should be based primarily on cell voltages, with volume ratio used as a secondary criterion in cases where cell potentials are close. In all cases here, volume ratios reinforce, rather than work against, predictions from estimated cell voltage.

QUESTION #2: For the material systems given in design options (i) and (iii) in Problem #1, consider the four assembly configurations shown on the following page, and determine: a) The likely site where corrosion will first appear. b) The relative rate of corrosion in the four assembly options. c) Two strategies for eliminating or reducing the corrosion identified in part (i).

Problem #2: Assembly Options


A B C A B C

i)

iii)

ii)

C B

iv)

A C B

SOLUTION: Cell potential estimates were made as in the previous problem. Design Option I: Mild Steel (A) -Yellow Brass (B) Tin (C) Configuration (i): Two Possible Cells a) Brass [cathode] + Tin [anode]: Cell Potential 0.25 V b) Brass [cathode] + Steel [anode]: Cell Potential 0.45 V Brass/Steel faster. Corrosion on steel side of steel-brass interface. Tin cathodically protected by steel. Configuration (ii): Two Possible Cells c) Brass [cathode] + Tin [anode]: Cell Potential 0.25 V d) Tin [cathode] + Steel [anode]: Cell Potential 0.20 V Brass/Tin likely to be faster. Corrosion on tin side of tin-brass interface. No cathodic protection: Most cathodic material not in contact with both other two anodic metals. Lower potential, so lower rate than (i). Configuration (iii): Cells same as configuration (i), thus same corrosion potential characteristics, but lower ratio of cathode/anode volume [1/2 vs 1/1]. Thus, lower rate than (i).

Configuration (iv): Cells same as configuration (ii), thus same corrosion potential characteristics, but higher ratio of cathode/anode volume [2/1 vs. 1/1]. Thus, higher rate than (ii).

Summary of Expected Relative Rates: Rate[i] > Rate[iii] Rate[iv] > Rate[i]

Design Option III: Cu (A) -Zn (B) Mg (C) Configuration (i): Two Possible Cells e) Cu [cathode] + Zn [anode]: Cell Potential 0.9 V f) Zn [cathode] + Mg [anode]: Cell Potential 0.5 V Cu/Zn faster. Corrosion on Zn side of Cu-Zn interface. No cathodic protection. Configuration (ii): Two Possible Cells g) Copper [cathode] + Mg [anode]: Cell Potential 1.4 V h) Zinc [cathode] + Mg [anode]: Cell Potential 0.5 V Copper/magnesium much faster. Corrosion on Mg side of Cu-Mg interface. No cathodic protection: Most cathodic material not in contact with both other two anodic metals. Higher cell potential, thus faster than (i). Configuration (iii): Cells same as configuration (i), thus same corrosion potential characteristics, but higher ratio of cathode/anode volume [2/1 vs. 1/1]. Thus, higher rate than (i). Configuration (iv): Cells same as configuration (ii), thus same corrosion potential characteristics, but higher ratio of cathode/anode volume [2/1 vs 1/1]. Thus, higher rate than (ii). Summary of Expected Relative Rates: Rate[iv] > Rate[ii] > Rate[iii] > Rate[i] There are many options for providing corrosion prevention. Some possibilities: i) Paint cathode j) Reassemble for cathodic protection (not an option for Mg anode) k) Add-on for cathodic protection (not an option for Mg anode) l) Utilize impressed current

Problem #3) a) An anodic coating such as Tin on galvanized steel would only function for a limited time, until the entire layer was corroded. At that point, the underlying metal would begin to corrode. However, these coatings would continue to protect the coated metal if the layer was damaged. b) Noble coatings such as chromium act entirely by preventing direct exposure of the coated metal to the environment. Not only do they fail when the coating is damaged, they make the situation worse by creating a galvanic cell that will corrode small areas of exposed material (which will be relatively anodic compared to the coating itself). c) Surface oxide layers will only function if they are coherent (creating a complete insulating coating on the metal surface. This only occurs for a few metals with oxides of similar volume to the metal underneath. Damaging the layer would allow for the metal to oxidize, and the small exposed area would tend to corrode at a faster rate than the entire larger part without a coating. d) Polymer coatings like paint will be subject to damage from solvents and UV light. They will fail to protect the metal if damaged, and the small exposed area would tend to corrode at a faster rate than the entire larger part without a coating. Problem #4) Many possible differences might be cited between degradation of ceramics and polymers compared with metals. Some reasonable choices listed in the text include: a) Ceramics: (1) Since ceramics are essentially the products of metal oxidation, they are virtually immune to the forms of attack that corrode metals. (2) Ceramic corrosion usually involves acidic or basic environments, and different ceramics are stable versus these two different pH ranges. (3) Ceramic degradation often involves simple dissolving in a solution, which will not usually occur for most structural metals. (4) Ceramics are electrically insulating, which means that the electrochemical processes involved in metals are extremely difficult to maintain (electrons cant move). b) Polymers: (1) Most polymers are also insulators, and thus cant maintain electrochemical reactions, (2) Polymers are highly susceptible to attack by solvents of similar chemical makeup, (3) Polymers are damaged by UV light, (4) Polymer degradation often involves breaking of the long chain molecules (scission), (5) Polymers are often subject to swelling and dissolving. Problem #5) Using the Nernst equation (Eqn 16.19), we find
n+ RT [ M 1 ] "V = (V #V ) # ln nF [ M 2n+ ] 0 2 0 1

= (#0.403 # (#0.763)) #

(8.314)(373) [0.1] ln (2)(96, 500) [5.0]

= (0.360) + (0.063) = 0.423 V

Problem #6) The Pilling-Bedworth equation (16.33) gives the following ratio of oxide volume to metal volume:

PB =

Ao " M (150.71)(7.30) = = 0.67 aAM " o 2(118.71)(6.95)

This ratio (less than one) indicates a coating too small in volume to provide a coherent barrier layer.