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234 The Science and Engineering of Materials Instructor’s Solution Manual

The electrode potential from the Nernst equation is:

E = −0.14 + (0.0592/2)log(0.0842) = −0.172 V
Note that the logarithm is to the base 10 in this equation.

22–4 A half-cell produced by dissolving copper in water produces an electrode potential

of +0.32 V. Calculate the amount of copper that must have been added to 1000 ml of
water to produce this potential.

Corrosion and Wear

Solution: From the Nernst equation, with Eo = 0.34 and the molecular weight of
copper of 63.54 g/mol, we can find the number of grams “x” added to
1000 ml of the solution. For Cu2+, n = 2.
0.32 = 0.34 + (0.0592/2)log(x / 63.54)
log (x / 63.54) = (−0.02)(2) / 0.0592 = −0.67568
x / 63.54 = 0.211 or x = 13.4 g Cu per 1000 ml H2O

22–5 An electrode potential in a platinum half-cell is 1.10 V. Determine the concentration

of Pt4+ ions in the electrolyte.
Solution: From the Nernst equation, with Eo = 1.20 and the molecular weight of
platinum of 195.09 g/mol, we can find the amount “x” of Pt added per
1000 ml of solution. For Pt, n = 4.
22–1 A gray cast iron pipe is used in the natural gas distribution system for a city. The
1.10 = 1.20 + (0.0592/4)log(x / 195.09)
pipe fails and leaks, even though no corrosion noticeable to the naked eye has
occurred. Offer an explanation for why the pipe failed. log (x / 195.09) = −6.7568
Solution: Because no corrosion is noticeable, the corrosion byproduct apparently x / 195.09 = 0.000000175
is still in place on the pipe, hiding the corroded area. The circumstances
x = 0.00003415 g Pt per 1000 ml H2O
suggest graphitic corrosion, an example of a selective chemical attack.
The graphite flakes in the gray iron are not attacked by the corrosive
22–6 A current density of 0.05 A/cm2 is applied to a 150-cm2 cathode. What period of
soil, while the iron matrix is removed or converted to an iron oxide or
time is required to plate out a 1-mm-thick coating of silver onto the cathode?
hydroxide trapped between the graphite flakes. Although the pipe
appears to be sound, the attacked area is weak, porous, and spongy. The Solution: The current in the cell is I = iA = (0.05 A/cm2)(150 cm2) = 7.5 A
natural gas can leak through the area of graphitic corrosion and eventu-
The weight of silver that must be deposited to produce a 1 mm = 0.1 cm
ally cause gas accumulations leading to an explosion.
thick layer is:
22–2 A brass plumbing fitting produced from a Cu-30% Zn alloy operates in the hot w = (150 cm2)(0.1 cm)(10.49 g/cm3) = 157.35 g
water system of a large office building. After some period of use, cracking and leak-
From the Faraday equation, with n = 1 for silver:
ing occur. On visual examination no metal appears to have been corroded. Offer an
explanation for why the fitting failed. 157.35 g = (7.5 A)(t)(107.868 g/mol) / (1)(96,500 C)
Solution: The high zinc brasses are susceptible to dezincification, particularly t = 18,769 s = 5.21 h
when the temperature is increased, as in the hot water supply of the
building. One of the characteristics of dezincification is that copper is 22–7 We wish to produce 100 g of platinum per hour on a 1000 cm2 cathode by electro-
redeposited in the regions that are attacked, obscuring the damage. plating. What plating current density is required? Determine the current required.
However the redeposited copper is spongy, brittle, and weak, permit-
Solution: In the Faraday equation, n = 4 for platinum, which has an atomic
ting the fitting to fail and leak. Therefore dezincification appears to be
weight of 195.09 g/mol. The weight of platinum that must be
a logical explanation.
deposited per second is 100 g / 3600 s/h = 0.02778 g/s.
22–3 Suppose 10 g of Sn2+ are dissolved in 1000 ml of water to produce an electrolyte. 0.02778 g/s = (i)(1000 cm2)(195.09 g/mol) / (4)(96,500 C)
Calculate the electrode potential of the tin half-cell.
i = 0.055 A/cm2
Solution: The concentration of the electrolyte is:
The current must then be:
C = 10 g / 118.69 g/mol = 0.0842 M
I = iA = (0.055 A/cm2)(1000 cm2) = 55 A

233
 CHAPTER 22 Corrosion and Wear 235 236 The Science and Engineering of Materials Instructor’s Solution Manual

22–8 A 1-m-square steel plate is coated on both sides with a 0.005-cm-thick layer of zinc. The current is (2.54 × 10−6 A/cm2)(1000 cm2) = 2.54 × 10−3
A current density of 0.02 A/cm2 is applied to the plate in an aqueous solution. A = 2.54 mA
Assuming that the zinc corrodes uniformly, determine the length of time required
before the steel is exposed. 22–11 A corrosion cell is composed of a 300 cm2 copper sheet and a 20 cm2 iron sheet,
Solution: The surface area includes both sides of the plate: with a current density of 0.6 A/cm2 applied to the copper. Which material is the
anode? What is the rate of loss of metal from the anode per hour?
A = (2 sides)(100 cm)(100 cm) = 20,000 cm2
Solution: In the Cu-Fe cell, the iron is the anode.
The weight of zinc that must be removed by corrosion is:
I = iCuACu = iFeAFe
w = (20,000 cm2)(0.005 cm)(7.133 g/cm3) = 713.3 g
(0.6 A/cm2)(300 cm2) = iFe(20 cm2)
From Faraday’s equation, where n = 2 for zinc:
iFe = 9 A/cm2
(0.02 A/cm2)(20,000 cm2)(t)(65.38 g/cm3)
713.3 g = The weight loss of iron per hour (3600 s) is:
(2)(96,500 C)
w = (9 A/cm2)(20 cm2)(3600 s)(55.847 g/mol) / (2)(96,500 C)
t = 5264 s = 1.462 h
= 187.5 g of iron lost per hour
22–9 A 2-in.-inside-diameter, 12-ft-long copper distribution pipe in a plumbing system is
accidentally connected to the power system of a manufacturing plant, causing a cur- 22–12 A corrosion cell is composed of a 20 cm2 copper sheet and a 400 cm2 iron sheet,
rent of 0.05 A to flow through the pipe. If the wall thickness of the pipe is 0.125 in., with a current density of 0.7 A/cm2 applied to the copper. Which material is the
estimate the time required before the pipe begins to leak, assuming a uniform rate of anode? What is the rate of loss of metal from the anode per hour?
corrosion. Solution: In the Cu-Fe cell, the iron is the anode.
Solution: If the pipe corroded uniformly, essentially all of the pipe would have I = iCuACu = iFeAFe
to be consumed before leaking. The volume of material in the pipe,
which has an inside diameter of 2 in. and an outside diameter of 2.25 (0.7 A/cm2)(20 cm2) = iFe(400 cm2)
in., is: iFe = 0.035 A/cm2
V = (π/4)[(2.25 in.)2 − (2 in.)2](12 ft)(12 in./ft) = 120.17 in.3 The weight loss of iron per hour (3600 s) is:
The density of copper is 8.96 g/cm3 = 0.323 lb/in.3. The weight of mate- w = (0.035 A/cm2)(400 cm2)(3600 s)(55.847 g/mol) / (2)(96,500 C)
rial to be corroded is:
= 14.58 g of iron lost per hour
w = Vr = (120.17 in.3)(0.323 lb/in.3) = 38.81 lb = 17,621 g
Note that the rate of iron lost per hour when the anode area is large is
From Faraday’s law, with n = 2 for copper: much smaller than the rate of iron loss when the anode area is small
17,621 g = (0.05 A)(t)(63.54 g/mol) / (2)(96,500 C) (Problem 22–11).
t = 1.07 × 109 s = 34 years 22–13 Alclad is a laminar composite composed of two sheets of commercially pure alu-
minum (alloy 1100) sandwiched around a core of 2024 aluminum alloy. Discuss the
22–10 A steel surface 10 cm × 100 cm is coated with a 0.002-cm thick layer of corrosion resistance of the composite. Suppose that a portion of one of the 1100 lay-
chromium. After one year of exposure to an electrolytic cell, the chromium layer is ers was machined off, exposing a small patch of the 2024 alloy. How would this
completely removed. Calculate the current density required to accomplish this affect the corrosion resistance? Explain. Would there be a difference in behavior if
removal. the core material were 3003 aluminum? Explain.
Solution: The volume and weight of chromium that must be removed are: Solution: The Alclad composed of 2024 and 1100 alloys should have good cor-
V = (10 cm)(100 cm)(0.002 cm) = 2 cm3 rosion resistance under most circumstances. The 1100 alloy has good
corrosion resistance, since it is nearly pure aluminum, when it com-
w = (2 cm3)(7.19 g/cm3) = 14.38 g pletely covers the underlying 2024 alloy. Furthermore, if the 1100
There are 31.536 × 106 s per year. The surface area of the chromium is layer is disturbed by machining, scratching, or other means, the 1100
(10 cm)(100 cm) = 1000 cm2. From Faraday’s law, with n = 3 for alloy serves as the anode and protects the 2024 alloy. The surface area
chromium: of the 1100 alloy is large, and even corrosion of the 1100 alloy will be
slow.
(i)(1000 cm2)(31.536 × 106 s)(51.996 g/mol)
14.38 g = When the 3003 alloy is coated with 1100 alloy, a disturbance of the
(3)(96,500 C)
surface is more critical. The 3003 alloy will serve as the anode; since
i = 2.54 × 10−6 A/cm2 the surface area of the 3003 anode is likely to be small compared to the
surface area of the 1100 alloy, corrosion may occur rapidly.
 CHAPTER 22 Corrosion and Wear 237 238 The Science and Engineering of Materials Instructor’s Solution Manual

22–14 The leaf springs for an automobile are formed from a high-carbon steel. For best The steel should be a low carbon steel to assure that carbides do not pre-
corrosion resistance, should the springs be formed by hot working or cold working? cipitate even when the cooling rates are slow. If problems persist, a
Explain. Would corrosion still occur even if you use the most desirable forming quench anneal heat treatment might be used to redissolve the carbides.
process? Explain.
22–17 A steel nut is securely tightened onto a bolt in an industrial environment. After sev-
Solution: If we form the springs cold, residual stresses are likely to be intro-
eral months, the nut is found to contain numerous cracks, even though no externally
duced into the product, leading to a stress cell and corrosion of the
applied load acts on the nut. Explain why cracking might have occurred.
spring. Forming the springs hot will reduce the level of any residual
stresses introduced into the spring and minimize the stress cell. Solution: When the nut is tightly secured onto the bolt, residual stresses are
likely to be introduced into the assembly. The presence of numerous
However, the steel will contain ferrite and pearlite (forming a composi-
cracks suggests that stress corrosion cracking may have occurred as a
tion cell), not to mention grain boundaries, inclusions, and other poten-
result of these stresses.
tial sites for corrosion cells. Corrosion is still likely to occur even if the
springs were produced by hot working.
22–18 The shaft for a propellor on a ship is carefully designed so that the applied stresses
are well below the endurance limit for the material. Yet after several months, the
22–15 Several types of metallic coatings are used to protect steel, including zinc, lead, tin,
shaft cracks and fails. Offer an explanation for why failure might have occurred
cadmium, aluminum, and nickel. In which of these cases will the coating provide
under these conditions.
protection even when the coating is locally disrupted? Explain.
Solution: The propellor is under a cyclical load during operation, but it is also in
Solution: Aluminum, zinc, and cadmium are anodic compared to iron; conse-
a marine environment which may provide a relatively aggressive elec-
quently these three elements should provide protection (serving as
trolyte. Failure, it is noted, requires some time to occur. Corrosion-
sacrificial anodes) to the iron even if the coating is disrupted.
fatigue sounds like a strong possibility in this case. Even though the
Nickel, tin, and lead are cathodic compared to iron; when these coatings stress is nominally below the endurance limit for the shaft, corrosion
are disrupted, small anodic regions of iron are exposed and corrosion encouraged by the stress will lead to loss of material or development
may occur rapidly. of pits in the shaft. This will increase the stress acting on the shaft and
further encourage corrosion. The result is the eventual formation of
22–16 An austenitic stainless steel corrodes in all of the heat-affected zone (HAZ) fatigue cracks, encouraged by corrosion, which cause the shaft to fail.
surrounding the fusion zone of a weld. Explain why corrosion occurs and discuss
the type of welding process or procedure that might have been used. What might 22–19 An aircraft wing composed of carbon fiber-reinforced epoxy is connected to a tita-
you do to prevent corrosion in this region? nium forging on the fuselage. Will the anode for a corrosion cell be the carbon fiber,
the titanium, or the epoxy? Which will most likely be the cathode? Explain.
Solution: Since the entire heat affected zone has corroded, the entire heat
affected region must have been sensitized during the welding process. Solution: Titanium is expected to serve as the anode and corrode, while carbon
Sensitization means that chromium carbides have precipitated at the is expected to be the cathode. Titanium is more anodic than carbon, or
austenite grain boundaries during joining, reducing the chromium graphite. Both are electrical conductors, they are in physical contact
content in the austenite near the carbides. The low chromium content with one another at the junction between the wing and the fuselage,
austenite serves as the anode and corrosion occurs. and both can be exposed to the environment.
Based on our observation of the corrosion, we can speculate that the The epoxy should not participate in the electrochemical cell; epoxy is
austenitic stainless steel is not a low carbon steel (that is, the steel con- an electrical insulator.
tains more than 0.03%C). The welding process was such that the heat
affected zone experienced long exposure times and slow rates of cool- 22–20 The inside surface of a cast iron pipe is covered with tar, which provides a protec-
ing. Nearest the fusion zone, the steel was all austenite at the peak tem- tive coating. Acetone in a chemical laboratory is drained through the pipe on a
peratures developed during welding; however the slow rate of cooling regular basis. Explain why, after several weeks, the pipe begins to corrode.
provided ample time for carbide precipitation as the region cooled
Solution: During use, the acetone serves as a solvent for the tar; the protective
between 870 and 425oC. A bit further from the fusion zone, the steel was
tar coating is eventually dissolved and the cast iron pipe is then
exposed to the 870 to 425oC temperature range for a long time, permit-
exposed to any corrosive material that is drained through the pipe.
ting carbides to precipitate and sensitize the steel.
The long times and slow cooling rates may have been a result of the 22–21 A cold-worked copper tube is soldered, using a lead-tin alloy, into a steel connec-
welding process—a low rate of heat input process, or inefficient process, tor. What types of electrochemical cells might develop due to this connection?
will introduce the heat slowly, which in turn heats up the surrounding Which of the materials would you expect to serve as the anode and suffer the most
base metal which then acts as a poor heat sink. Preheating the steel prior extensive damage due to corrosion? Explain.
to welding would also result in the same problems.
Solution: Several cells may develop. Composition cells include those between
The stainless steel should be welded as rapidly as possible, using a high the solder and the steel, with the steel serving as the anode and the
rate of heat input process, with no preheat of the steel prior to welding. solder as the cathode. The steel then corrodes.
 CHAPTER 22 Corrosion and Wear 239 240 The Science and Engineering of Materials Instructor’s Solution Manual

A composition cell may also develop between the copper and the solder. In this case, 22–25 Two sheets of a 1040 steel are joined together with an aluminum rivet (Figure
the solder will act as the anode. 22–20). Discuss the possible corrosion cells that might be created as a result of this
joining process. Recommend a joining process that might minimize some of these
Microcomposition cells may also develop. The steel contains ferrite and cementite; the
cells.
ferrite will act as the anode. In addition, the lead-tin solder is a two-phase alloy con-
taining nearly pure tin (b) and a solid solution of tin in lead (a). Lead is most likely to Solution: Composition cells: Aluminum may act as the anode in comparison to
serve as the anode with respect to tin. the steel, thus causing corrosion of the aluminum. In addition, ferrite
may serve as the anode to cementite within the steel.
A concentration cell is also possible, particularly in the crevice between the copper
tube and the steel. The material adjacent to the crevice will act as the anode. Stress cells: The aluminum rivet is deformed when the joint is produced,
causing the most highly cold worked portion of the rivet to act as the
Finally, the copper tube is cold worked; the cold working may cause a stress cell to
anode. In addition, grain boundaries in both the steel and the aluminum
develop. This may be accentuated by the soldering process; during soldering, the cop-
may act as anodes for a stress cell.
per tube at the soldered joint will heat, perhaps to a high enough temperature to allow
stress relieving to occur. This again helps to provide the stress cell between the cold Concentration cells: Crevice corrosion may occur between the two steel
worked and stress relieved portions of the tube. sheets and also between the aluminum rivet and the steel sheets.
A fusion welding process, in which a filler material having a composi-
22–22 Pure tin is used to provide a solder connection for copper in many electrical uses.
tion similar to that of the 1040 steel, might be the best way to minimize
Which metal will most likely act as the anode?
most of these cells.
Solution: From the galvanic series, we find that tin is anodic to copper; there-
fore the tin anode is expected to corrode while the copper cathode is 22–26 Figure 22–21 shows a cross-section through an epoxy-encapsulated integrated cir-
protected. cuit, including a small microgap between the copper lead frame and the epoxy poly-
mer. Suppose chloride ions from the manufacturing process penetrate the package.
22–23 Sheets of annealed nickel, cold-worked nickel, and recrystallized nickel are placed What types of corrosion cells might develop? What portions of the integrated circuit
into an electrolyte. Which would be most likely to corrode? Which would be least are most likely to corrode?
likely to corrode? Explain.
Solution: Composition cells can develop between gold and aluminum (with the
Solution: The cold worked nickel sheet is expected to have the poorest corrosion aluminum serving as the anode and corroding); gold and copper (with
resistance due to the residual stresses introduced during the cold work- the copper serving as the anode and corroding); and aluminum and sili-
ing process. con (with aluminum serving as the anode and corroding).
The annealed nickel sheet should be most resistant to corrosion; the
22–27 A current density of 0.1 A/cm2 is applied to the iron in an iron-zinc corrosion cell.
grain size is expected to be particularly large and no residual stresses are
Calculate the weight loss of zinc per hour (a) if the zinc has a surface area of 10 cm2
expected; consequently a stress cell is unlikely. In addition, the annealed
and the iron has a surface area of 100 cm2 and (b) if the zinc has a surface area of
sheet is expected to have the most uniform composition, that is, the least
100 cm2 and the iron has a surface area of 10 cm2.
segregation, so a composition cell is also unlikely.
Solution: (a) I = iFeAFe = (0.1 A/cm2)(100 cm2) = 10 A
The recrystallized nickel sheet should have intermediate corrosion resist-
ance; the residual stresses should have been eliminated as a result of the wZn = (10 A)(3600 s)(65.38 g/mol) / (2)(96,500 C)
heat treatment but the grain size may be smaller than in the annealed
= 12.2 g of Zn lost per hour
sheet.
(b) I = iFeAFe = (0.1 A/cm2)(10 cm2) = 1 A
22–24 A pipeline carrying liquid fertilizer crosses a small creek. A large tree washes down
wZn = (1 A)(3600 s)(65.38 g/mol) / (2)(96,500 C)
the creek and is wedged against the steel pipe. After some time, a hole is produced
in the pipe at the point where the tree touches the pipe, with the diameter of the hole = 1.22 g of Zn lost per hour
larger on the outside of the pipe than on the inside of the pipe. The pipe then leaks
The loss of zinc is accelerated when the zinc anode area is small.
fertilizer into the creek. Offer an explanation for why the pipe corroded.
Solution: One possibility for the corrosion is a concentration cell caused by 22–28 Determine the Pilling-Bedworth ratio for the following metals and predict the
microbial corrosion. The point of contact between the tree and the pipe behavior of the oxide that forms on the surface. Is the oxide protective, does it flake
produces a low oxygen environment and also a location at which vari- off the metal, or is it permeable? (see Appendix A for the metal density)
ous microbes may grow. As the microbes grow on the pipe, a low oxy-
Solution: The Pilling-Bedworth relation is
gen environment is further encouraged. A galvanic cell is produced,
with the pipe beneath the fallen tree (and thus the microbes) serving P-W = MWoxide pmetal / n MWmetal poxide
as the anode and the remainder of the pipe acting as the cathode.
From metal density data listed in Appendix A, the calculated P-W ratios
Localized corrosion will then continue until a hole is corroded through
are shown in the table below.
the wall of the pipe.
 CHAPTER 22 Corrosion and Wear 241 242 The Science and Engineering of Materials Instructor’s Solution Manual

Oxide density Metal density To completely oxidize the copper, assuming that the rate of oxidation is
(g/cm3) (g/cm3) n P-W ratio the same from both sides of the sheet, we need to determine the time
required to oxidize 0.75 cm / 2 sides = 0.375 cm:
Mg-MgO 3.6 1.738 1 0.80
y = 0.375 cm = (7.56 × 10 6 cm 2 / h )( t ) or t = 18,601 h
Na-Na2O 2.27 0.967 2 0.57
Ti-TiO2 5.1 4.507 1 1.47 22–31 At 800oC, iron oxidizes at a rate of 0.014 g/cm2 per hour; at 1000oC, iron oxidizes
Fe-Fe2O3 5.3 7.87 2 2.12 at a rate of 0.0656 g/cm2 per hour. Assuming a parabolic oxidation rate, determine
Ce-Ce2O3 6.86 6.6893 2 1.14 the maximum temperature at which iron can be held if the oxidation rate is to be
less than 0.005 g/cm2 per hour.
Nb-Nb2O3 4.47 8.57 2 2.74
W-WO3 7.3 19.254 1 3.33 Solution: The rate is given by an Arrhenius equation, rate = Aexp(−Q/RT). We
can find the constants A and Q from the data provided.
The oxides that form in magnesium and sodium are expected to be non-
adherent, or tend to flake off, since the oxide volume is substantially 0.014 g/cm2.h = Aexp(−Q/(1.987 cal/mol.K)(800 + 273K)
larger that the metal volume. A P-W ratio of less than 1 indicates this 0.0656 g/cm2.h = Aexp(−Q/(1.987 cal/mol.K)(1000 + 273K)
condition.
Taking logarithms of both sides:
The oxides that form on iron, niobium, and tungsten are expected to be
adherent but permeable. A P-W ratio of more than 2 indicates that the −4.2687 = ln A − 0.0004690Q
oxide volume is much less than that of the metal volume. −2.7242 = ln A − 0.0003953Q
The oxides that form on titanium and cesium are expected to be protec- 1.5445 = 0.0000737 Q or Q = 20,957 cal/mol
tive; a P-W ratio of 1 to 2 indicates this condition.
−4.2687 = ln A − (0.000469)(20,957)
22–29 Oxidation of most ceramics is not considered to be a problem. Explain. ln A = 5.56
Solution: Most ceramics are already oxides—thus materials such as MgO and A = 260
Al2O3 are expected to be inert in an oxidizing atmosphere. Non-oxide
ceramics, however, may sometimes be subjected to oxidation To keep the oxidation rate below 0.005 g/cm2.h, the maximum tempera-
problems. ture is:
rate = 260 exp( −20,957/RT) = 0.005
22–30 A sheet of copper is exposed to oxygen at 1000oC. After 100 h, 0.246 g of copper
are lost per cm2 of surface area; after 250 h, 0.388 g/cm2 are lost, and after 500 h, ln (0.005/260) = −20,957 / (1.987)(T)
0.550 g/cm2 are lost. Determine whether oxidation is parabolic, linear, or logarith- ln (0.00001923) = −10.859 = −10,547/T
mic, then determine the time required for a 0.75 cm sheet of copper to be com-
pletely oxidized. The sheet of copper is oxidized from both sides. T = 971 K = 698oC

Solution: Let’s assume that the rate is parabolic: We can determine the constant
“k” in the oxidation equation y = kt for each time, first converting
the rate in g/cm2 to thickness y in cm:
y1 = V/A = (0.246 g / 8.93 g/cm3) / 1 cm2 = 0.0275 cm
y2 = V/A = (0.388 g / 8.93 g/cm3) / 1 cm2 = 0.0434 cm
y3 = V/A = (0.549 g / 8.93 g/cm3) / 1 cm2 = 0.0615 cm
If oxidation is parabolic, the value for k should be the same for each
time:
0.0275 cm = k (100 h) or k = 7.56 × 106 cm2/h

0.0434 cm = k (250 h) or k = 7.53 × 106 cm2/h

0.0615 cm = k (500 h) or k = 7.56 × 106 cm2/h

Therefore the rate of oxidation must be parabolic.