Askeland Science and Engineering 7e ISM Chapter 10

Chapter 10: Solid Solutions and Phase Equilibrium
10-10 How much of a temperature change is required to bring liquid magnesium from solid-
liquid equilibrium to vapor-liquid equilibrium at 1 atmosphere? (See Figure 10-2.)
Solution:
Reading the graph in Figure 10-2, we read about 433 °C difference between the two
lines at 1 atm. If the Y axis were scaled, we could find out the temperature difference at
any pressure.
10-11 The unary phase diagram for SiO2 is shown in Figure 10–18. Locate the triple point
where solid, liquid, and vapor coexist and give the temperature and the type of solid
present. What do the other “triple” points indicate?
Solution: (a) The solid-liquid-vapor triple point occurs at 1713°C; the solid
phase present at this point is β-cristobalite.
(b) The other triple points describe the equilibrium between two
solids and a vapor phase.
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10-13 Natural diamond is formed approximately 120 to 200 km below the earth’s surface
under high pressure and high temperature conditions. Assuming that the average
density of the earth is 5500 kg/m3, use this information and the unary phase diagram for
C (Figure 10–19) to calculate the range of the earth’s geothermal gradient (rate of
increase of temperature with depth). Estimate the pressure below the earth’s surface as
ρgh where ρ is density, g is gravity, and h is depth. Note that 10 kbar = 109 Pa.
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Solution: The pressure P in the given depth range needs to be determined.
This can be estimated by
P = ρgh,
where ρ is the density, g is the acceleration due to gravity, and h is
the depth. At 120 km,
P120 = 5500 kg/m3 × 9.81 m/s2×120 × 103m = 6.47 × 109 Pa = 65 kbar.
At 200 km,
P200 = 5500 kg/m3 × 9.81 m/s2 × 200 × 103m = 1.08 × 1010 Pa = 108 kbar.
The temperature range for which diamond is stable at 65 kbar and
108 kbar of pressure can be determined according to the unary
phase diagram for carbon (Figure 10–20). At 108 kbar (200 km), the
temperature range is approximately 4100°C to 4200°C and at 65
kbar (120 km), the temperature range is 4150°C to 4400°C.
The range of the geothermal gradient is
At 200 km : (4100/200) to (4200/200), which is 20.5 to 21°C/km.
At 120 km : (4150/120) to (4400/120), which is 34.6 to 36.7°C/km.
Thus the range is from 20.5°C / km to 36.7°C / km.

It should be noted that tectonic and volcanic activity can
significantly affect local temperature and pressure and also cause
movement of material to different depths. Most natural diamond
that is mined is brought closer to the surface by deep volcanic
eruptions.
10-22 A 15 kg block of copper is being alloyed with zinc and brought to the solubility limit at
200°C. How much zinc is required? (See Figure 10-4)
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Solution:
Reading the graph, we see that the solubility limit at 200 °C is about 35 wt% Zn. Thus,

= 0.35
+ 15 kg Cu
= 8.1 kg Zn
10-23 A 115 kg total of copper and zinc (4 parts Zn to 6 parts Cu) is mixed at 400°C. How much
of the zinc is in excess of solubility? (See Figure 10-4.)
Solution:
First we separate the 115 kg mathematically into 46 kg Zn and 69 kg Cu. In this case we
know that there is more zinc than the copper can absorb at this temperature. Figure 10-
4 shows that the solubility limit at 400°C is about 38%. We set up a relation of the
amount of zinc and copper in solution:

= 0.38
69 kg Cu +
= 42.3 kg Cu
Taking the difference between this amount in solution and the amount supplied, we find
the excess is
46 kg Cu − 42.3 kg Cu = 3.7 kg Cu
10-26 What is the difference between limited and unlimited solid solubility?
Solution:
Unlimited solid solubility is when two phases are mixed together producing one single
phase in both liquid and solid form. The liquid would have the same composition,
properties and structure everywhere and if cooled would produce a single uniform
structure with no existent interface. Limited solid solubility is when two phases are
mixed together producing a two-phase solid upon solidification (similar to having too
much salt in water) due to the saturation of one alloy into the other. Solubility increases
with temperature.
10-27 Copper and nickel have unlimited solid solubility in each other whereas lead and iron
are completely insoluble. Using the Hume-Rothery rules, justify these conditions. Show
your work.
Solution:
Based on Hume-Rothery’s Rules, we would predict that Cu-Ni are 100% soluble while Fe-
Pb are not soluble:
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Element Structure %Δr Valence Unlimited
solubility
Cu FCC 2.82% +2 Yes
Ni FCC 2.82% +1 Yes
Pb FCC 41.1% +4 No
Fe BCC/FCC 41.1% +2, +3 No
10-28 Which of the following elements would be expected to have unlimited solid solubility in
gold? (a) Ag; (b) Al; and (c) Fe.
Solution:
Of the elements, silver is the only element to potentially have unlimited solubility with
gold since all values are predominately the same. Aluminum is structurally close, but the
electronic state is very different from gold. Iron electronic state and crystal structures
differ from gold making it insoluble in gold.
Element Structure %Δr Electronegativity Valence Unlimited
solubility
Au FCC 0 2.4 +1 Yes
Ag FCC 0 1.9 +1 Yes
Al FCC 0.69% 1.5 +3 No
Fe BCC/FCC 13.80% 1.8 +2, +3 No
10-29 Based on Hume-Rothery’s conditions, which of the following systems would be expected
to display unlimited solid solubility? Explain.
(a) Au–Ag (b) Al–Cu (c) Al–Au (d) U–W
(e) Mo–Ta (f) Nb–W (g) Mg–Zn (h) Mg–Cd
Solution: (a) rAu = 1.442 v = +1 FCC

rAg = 1.445 v = + 1 FCC
Δr = 0.2 % Yes
(b) rA1 = 1.432 v = +3 FCC
rCu = 1.278 v = +1 FCC
Δr = 10.7 % No
(c) rAl = 1.432 v = +3 FCC
rAu = 1.442 v = +1 FCC
Δr = 0.7 % No
(d) rU = 1.38 v = +4 Ortho
rW = 1.371 v = +4 FCC
Δr = 0.7 % No
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(e) rMo = 1.363 v = +4 BCC
rTa = 1.43 v = +5 BCC
Δr = 4.7 % No
(f) rNb = 1.426 v = +4 BCC
rW = 1.371 v = +4 BCC
Δr = 3.6 % Yes
(g) rMg = 1.604 v = +2 HCP
rZn = 1.332 v = +2 HCP
Δr = 17 % No
(h) rMg = 1.604 v = +2 HCP
rCd = 1.490 v = +2 HCP
Δr = 7.1 % Yes
The Au–Ag, Mo–Ta, and Mg–Cd systems have the required radius
ratio, the same crystal structures, and the same valences. Each of
these might be expected to display complete solid solubility. (The Au–
Ag and Mo–Ta do have isomorphous phase diagrams. In addition, the
Mg–Cd alloys all solidify like isomorphous alloys; however, a number
of solid-state phase transformations complicate the diagram.)
10-30 Identify which of the following oxides when added to BaTiO3 are likely to exhibit 100%
solid solubility: (a) SrTiO3; (b) CaTiO3; (c) ZnTiO3; and (d) BaZrO3. All of these oxides have
a perovskite crystal structure.
Solution: The Hume-Rothery rules must be checked for the various
combinations.
Crystal Structure: All of these oxides have the perovskite crystal
structure.
Values for the valence and atomic radii of the elements are given in
Appendix B and shown in the table below.
Atom Valence Atomic Radius (Å)
Ba +2 2.176
Sr +2 2.151
Ca +2 1.976
Zn +2 1.332
Ti +4 1.475
Zr +4 1.616
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Note that all of the oxides have a formula ABO3 where A = atom with
valence +2 and B = atom with valence +4. Thus we need to compare
the atoms of the same valence for their size factor.
Valence:
All oxides pass the criterion for valence of ions.
Size:
The combinations of Ba:Sr and Ba:Ca meet the 15% rule while the
combination of Ba:Zn does not. The combination of Ti:Zr meets the
15% rule.
Electronegativity:
All systems meet the electronegativity criterion.
Based on the information above, SrTiO3, CaTiO3 and BaZrO3 are likely
to exhibit 100% solid solubility while ZnTiO3 may not.
10-31 Suppose 1 at% of the following elements is added to copper (forming a separate alloy
with each element) without exceeding the solubility limit. Which one would be expected
to give the higher strength alloy? Are any of the alloying elements expected to have
unlimited solid solubility in copper?
(a) Au
(b) Mn
(c) Sr
(d) Si
(e) Co
Solution: For copper: rCu = 1.278 Å
(a) Au: r = 1.442 rAu − rCu May be unlimited
∆r = = +12.8% solubility
rCu
(b) Mn: r = 1.12 ∆r = –12.4 % Different structure

(c) Sr: r = 2.151 ∆r = +68.3 % Highest Strength
(d) Si r = 1.176 ∆r = –8.0 % Different structure
(e) Co: r = 1.253 ∆r = –2.0 % Different structure
The Cu–Sr alloy would be expected to be strongest (largest size
difference). The Cu–Au alloy satisfies Hume-Rothery’s conditions and
might be expected to display complete solid solubility — in fact, it
freezes like an isomorphous series of alloys, but a number of solid-
state transformations occur at lower temperatures.
10-32 Suppose 1 at% of the following elements is added to aluminum (forming a separate alloy
to give the higher strength alloy? Why? (a) Mn; (b) Mg; (c) Cu; and (d) Zn.
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Solution: For aluminum: r = 1.432 Å (FCC structure with valence of 3)
(a) Mn: r = 1.12 ∆r = –21.8%
(b) Mg: r = 1.604 ∆r = 12.0%
(c) Cu: r = 1.278 ∆r = –10.8%
(d) Zn: r = 1.332 ∆r = 7.0%
Mn is expected to give the higher strength alloy since the Mn atoms are
most different in size from the Al atoms.
10-33 Suppose 1 at% of the following elements is added to aluminum (forming a separate alloy
to give the smallest reduction in electrical conductivity? Are any of the alloy elements
expected to have unlimited solid solubility in aluminum?
(a) Li
(b) Ba
(c) Be
(d) Cd
(e) Ga
Solution: For aluminum: r = 1.432 Å (FCC structure with valence of 3)
(e) Li: r = 1.519 ∆r = 6.1% BCC valence = 1
(f) Ba: r = 2.176 ∆r = –52.0% BCC valence = 2
(g) Be: r = 1.143 ∆r = –20.2% HCP valence = 2
(h) Cd: r = 1.49 ∆r = 4.1% HCP valence = 2
(i) Ga: r = 1.218 ∆r = 14.9% Orthohombic valence = 3
The cadmium would be expected to give the smallest reduction in electrical
conductivity, since the Cd atoms are most similar in size to the aluminum
atoms. None are expected to have unlimited solid solubility, due either to
difference in valence, atomic radius, or crystal structure.
10-34 Which of the following oxides is expected to have the largest solid solubility in Al2O3?
(a) Y2O3
(b) Cr2O3
(c) Fe2O3
Solution: The ionic radius of Al3+ = 0.51 Å
(a) rY3+ = 0.89 0.63 − 0.51
∆r = × 100 = 74.5%
0.51
(b) rCr3+ = 0.63 Δr = 23.5%
(c) rFe3+ = 0.64 Δr = 25.5%
We would expect Cr2O3 to have a high solubility in Al2O3; in fact, they
are completely soluble in one another.
10-38 What is a binary phase diagram and what information can be learned from it? In terms
of thermodynamics, what is meant by the term “equilibrium phase diagram”?
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Solution:
A binary phase diagram shows the different equilibrium phase that may exist between
two elements when mixed or alloyed together. The diagram may be used as a guide in
the processing of an alloy consisting predominately of the two elements. These are
called equilibrium diagrams because they pertain to very slow processes that allow the
ultimate phases to be established. In terms of thermodynamics, we consider these
phases to be stable with the lowest energy.
10-39 What is the significance of the liquidus curve? Solidus curve?

Solution:
The liquidus curve indicates the highest temperature the solid phase may exist in an
alloy system. The solidus curve indicates the lowest temperature the liquid phase may
exist in an alloy system.
10-40 What is an alloy? In general, what is the difference in the melting behavior of an alloy
from that of a pure component?
Solution:
An alloy is a material composed of two or more elements. While a pure component has
a definite melting point, an alloy generally has a temperature range where the solid and
liquid phases co-exist before complete melting is attained.
10-41 Determine the degrees of freedom under the following conditions:

(a) Tl–20 wt% Pb at 325°C and 400°C;
(b) Tl–40 wt% Pb at 325°C and 400°C;
(c) Tl–90 wt% Pb at 325°C and 400°C.
Refer to the phase diagram in Figure 10–8(d).
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Solution: The Gibbs Phase Rule is
C + 1 = F + P,
where C is the number of components, F is the number of degrees of freedom, and P
is the number of phases present for an equilibrium phase diagram at constant
pressure.
For Tl–20 wt% Pb at 325°C,
P = 2 (solid solution and liquid) and C = 2 (Pb and Tl), hence
F = C–P + 1 = 1
There is one degree of freedom.
P = 1 (liquid) and C = 2 (Pb and Tl), hence
F = C–P + 1 = 2–1 + 1 = 2
There are two degrees of freedom.
P = 1 (solid solution) and C = 2 (Pb and Tl), hence
F = C–P + 1 = 2–1 + 1 = 2
F = C–P + 1 = 2–1 + 1 = 2
P = 2 (solid solution and liquid) and C = 2 (Pb and Tl), hence
F = C–P + 1 = 1
There is one degree of freedom.
F = C–P + 1 = 2–1 + 1 = 2
10-42 Locate the following points in the Bi-Sb phase diagram and indicate the phases present
and their relative amounts (a) 60 at% Bi at 250°C; (b) 30 at% Bi at 500°C; and (c) 50 at%
Bi at 600°C. (See Figure 10-20.)
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Solution: (a) 60 at% Bi = 40 at% Sb at 250˚C
S: 40 at% Sb 100% S
(b) 30 at% Bi = 70 at% Sb
There are two phases present: S and L.
S: 86 at% Sb
L: 55 at% Sb
70 − 55
at% S = ×100% = 48%
86 − 55
86 − 70
at% L = ×100% = 52%
86 − 55
(c) 50 at% Bi = 50 at% Sb
L: 50 at% Sb 100% L
10-43 Determine the composition range in which the Tl–Pb alloy at 350°C is (a) fully liquid; (b)
fully solid; and (c) partly liquid and partly solid. Refer to Figure 10–8(d) for the Tl–Pb
phase diagram. Further, determine the amount of liquid and solid solution for Tl–25
wt% Pb and Tl–75 wt% Pb at 350°C and also the wt% Pb in the liquid and solid solution
for both of the alloy compositions.
235
Solution: At 350°C, the Tl–Pb system exists as various phases as follows:
Fully liquid: From 0 wt% to 22 wt% Pb and from 82 wt% to 100 wt% Pb
Fully solid or solid solution: From 30 wt% to 68 wt% Pb
Partly liquid and partly solid: From 22 wt% to 30 wt% Pb and 68 wt% to 82 wt% Pb.
Using the lever rule, the amount of liquid and solid solution can be determined.
For a Tl-25 wt% Pb alloy at 350°C,
% Liquid = [(30–25)/(30–22)]] × 100 = 62.5%
% Solid solution = [(25–22)/(30–22)] × 100 = 37.5%
For a Tl-75 wt% Pb alloy at 350°C,
% Liquid = [(75–68)/(82–68)]] × 100 = 50%
% Solid solution = [(82–75)/(82–68)] × 100 = 50%
The wt% Pb in the solid solution and liquid are determined by the point where the
tie line intersects the solidus and liquidus, respectively.
For a Tl-25 wt% Pb alloy at 350°C, there is
22 wt% Pb in the liquid and 30 wt% Pb in the solid solution.
For a Tl-75 wt% Pb alloy at 350°C, there is
82 wt% Pb in the liquid and 68 wt% Pb in the solid solution.
10-44 Determine the liquidus temperature, solidus temperature, and freezing range for the
following NiO–MgO ceramic compositions. [See Figure 10–8(b).]
(a) NiO–30 mol% MgO (b) NiO–45 mol% MgO
(c) NiO–60 mol% MgO (d) NiO–85 mol% MgO
Solution: (a) TL = 2330°C Ts = 2150°C FR = 180°C

(b) TL = 2460°C Ts = 2250°C FR = 210°C
(c) TL = 2570°C Ts = 2380°C FR = 190°C
(d) TL = 2720°C Ts = 2610°C FR = 110°C
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10-45 Determine the liquidus temperature, solidus temperature and freezing range for the
following Al2O3 – Cr2O3 ceramic compositions: (a) Al2O3 – 30wt% Cr2O3, (b) Al2O3 –
50wt% Cr2O3 and (c) Al2O3 – 75wt% Cr2O3. (See Figure 10-9.)
Solution:
a) TL = 2125°C TS = 2075°C Freezing range = 50°C
b) TL = 2175°C TS = 2100°C Freezing range = 75°C
c) TL = 2225°C TS = 2260°C Freezing range = 65°C
10-46 Determine the phases present, the compositions of each phase, and the amount of each
phase in wt% for the following Al2O3 – Cr2O3 ceramic at 2150°C: (a) Al2O3 – 30wt% Cr2O3,
(b) Al2O3 – 50wt% Cr2O3 and (c) Al2O3 – 75wt% Cr2O3. (See Figure 10-9.)
Solution:
10-47 For an Ag-60 wt% Pd alloy determine the (a) liquidus temperature; (b) solidus
temperature; and (c) freezing range. (See Figure 10-21.)
237
Solution:
(a) The liquidus temperature is 1270°C (b) The solidus temperature is 1230°C (c) The
freezing range is 40°C
10-48 Locate the following points in the Ag-Pd phase diagram and indicate the phases present
and their relative amounts (a) 50 wt% Pd at 1300°C; (b) 80 wt% Pd at 1425°C; and (c) 90
wt% Ag at 1100°C. (See Figure 10-21.)
Solution:
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10-49 Determine the liquidus temperature, solidus temperature, and freezing range for the
following MgO–FeO ceramic compositions. (See Figure 10–22.)
(a) MgO–25 wt% FeO
(b) MgO–45 wt% FeO
(c) MgO–65 wt% FeO
(d) MgO–80 wt% FeO
Solution: (a) TL = 2600°C Ts = 2330°C FR = 370°C

(b) TL = 2340°C Ts = 1900°C FR = 440°C
(c) TL = 2000°C Ts = 1610°C FR = 390°C
(d) TL = 1750°C Ts = 1480°C FR = 270°C
phase in mol% for the following NiO–MgO ceramics at 2400°C. [See Figure 10–8(b).]
(a) NiO–30 mol% MgO
(b) NiO–45 mol% MgO
(c) NiO–60 mol% MgO
(d) NiO–85 mol% MgO
Solution: (a) L: NiO–30 mol % MgO 100% L
(b) L: 38% MgO 62 − 45
%L= ×100% = 70.8%
62 − 38
S: 62% MgO 45 − 38
%S= × 100% = 29.2%
62 − 38
(c) L: 38% MgO 62 − 60
%L= × 100% = 8.3%
62 − 38
S: 62 % MgO 60 − 38
%S= × 100% = 91.7%
62 − 38
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(d) S: 85% MgO 100% S
phase in wt% for the following MgO–FeO ceramics at 2000°C.
(a) MgO–25 wt% FeO
(b) MgO–45 wt% FeO
(c) MgO–60 wt% FeO
(d) MgO–80 wt% FeO
(See Figure 10–21.)
Solution: (a) S: 25 % FeO 100% S

(b) S: 39% FeO 65 − 45
%S= ×100% = 76.9%
65 − 39
L: 65% FeO 45 − 39
%L = × 100% = 23.1%
65 − 39
(c) S: 39% FeO 65 − 60
%S= ×100% = 19.2%
65 − 39
L: 65% FeO 60 − 39
%L= × 100% = 80.8%
65 − 39
(d) S: 80% MgO 100% L
10-52 Consider a ceramic composed of 30 mol% MgO and 70 mol% FeO. Calculate the
composition of the ceramic in wt%.
Solution: MWMgO = 24.312 + 16 = 40.312 g/mol
MWFeO = 55.847 + 16 = 71.847 g/mol
(30)(40.312)
wt% MgO = × 100% = 19.4%
(30)(40.312) + (70)(71.847)
(70)(71.847)
wt% FeO = × 100% = 80.6%
(30)(40.312) + (70)(71.847)
10-53 A NiO–20 mol% MgO ceramic is heated to 2200°C. Determine (a) the composition of the
solid and liquid phases in both mol% and wt%; (b) the amount of each phase in both
mol% and wt%; and (c) assuming that the density of the solid is 6.32 g/cm3 and that of
the liquid is 7.14 g/cm3, determine the amount of each phase in vol% [See Figure 10–
8(b).]
Solution: MWMgO = 24.312 + 16 = 40.312 g/mol
MWNiO = 58.71 + 16 =74.71 g/mol
(a) L: 15 mol% MgO
(15)(40.312)
wt % MgO = × 100% = 8.69%
(15)(40.312) + (85)(74.71)
S: 38 mol % MgO
(38)(40.312)
wt% MgO = × 100% = 24.85%
(38)(40.312) + (62)(74.71)
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38 − 20
(b) mol% L = × 100% = 78.26% mol% S = 21.74%
38 − 15
The original composition, in wt% MgO, is
(20)(40.312)
× 100% = 11.9%
(20)(40.312) + (80)(74.71)
24.85 − 11.9
wt% L = × 100% = 80.1% wt% S = 19.9%
24.85 − 8.69
80.1/ 7.14
(c) vol% L = × 100% = 78.1%
(80.1 / 7.14) + (19.9 / 6.32)
vol% S = 21.9%
10-54 A Nb–60 wt% W alloy is heated to 2800°C. Determine (a) the composition of the solid
and liquid phases in both wt% and at%; (b) the amount of each phase in both wt% and
at%; and (c) assuming that the density of the solid is 16.05 g/cm3 and that of the liquid is
13.91 g/cm3, determine the amount of each phase in vol%. (See Figure 10–23.)
Solution: (d) L: 49 wt % W
49/183.85
at% W = × 100% = 32.7%
(49/183.85) + (51/92.91)
α: 70 wt % W
(70/183.85)
at% W = × 100% = 54.1
(70/183.85) + (30/92.91)
70 − 60
(e) wt% L = × 100% = 47.6% wt% α = 52.4%
70 − 49
The original composition, in wt% W is
60/183.85
× 100% = 43.1%
(60/183.85) + (40/92.91)
54.1 − 43.1
at% L = ×100% = 51.4% wt% α = 48.6%
54.1 − 32.7
47.6/13.91
(f) vol % L = × 100% = 51.2%
(47.6/13.91) + (52.4/16.05)
vol% α = 48.8%
10-55 How many grams of nickel must be added to 500 grams of copper to produce an alloy
that has a liquidus temperature of 1350°C? What is the ratio of the number of nickel
atoms to copper atoms in this alloy? [See Figure 10–8(a).]
Solution: We need 60 wt% Ni to obtain the correct liquidus temperature.
x
% Ni = 60 = × 100% or x = 750g Ni
x + 500g
Ni atoms (750g)(N A )/(58.71g/mol)
= = 1.62
Cu atoms (500g)(N A )/(63.54g/mol)
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10-56 How many grams of nickel must be added to 500 grams of copper to produce an alloy
that contains 50 wt% α at 1300°C? [See Figure 10–8(a).]
Solution: At 1300°C, the composition of the two phases in equilibrium are L: 46 wt % Ni and α:
58 wt% Ni
The alloy required to give 50% α is then
x − 46
× 100 = 50% α or x = 52 wt % Ni
58 − 46
The number of grams of Ni must be
x
× 100% = 52 or x = 541.7 g Ni
x + 500
10-57 How many grams of MgO must be added to 1 kg of NiO to produce a ceramic that has a
solidus temperature of 2200°C? [See Figure 10–8(b).]
Solution: MWMgO = 40.312 g/mol MWNiO = 74.71g/mol
38 mol% MgO is needed to obtain the correct solidus temperature.
(38)(40.312)
wt% MgO = × 100% = 24.85%
(38)(40.312) + (62)(74.71)
The number of grams required is
x
× 100% = 24.85% or x = 331 g of MgO
x + 100
10-58 How many grams of MgO must be added to 1 kg of NiO to produce a ceramic that
contains 25 mol% solid at 2400°C? [See Figure 10–8(b).]
Solution: L:38 mol% MgO MWMgO = 40.312g/mol
S: 62 mol% MgO MWNiO = 74.71g/mol
x − 38
× 100% = 25%S or x = 44 mol% MgO
62 − 38
(44)(40.312)
wt% MgO = × 100% = 29.77%
(44)(40.312) + (56)(74.71)
The number of grams of MgO is then
x
× 100% = 29.77% or x = 424g MgO
x + 1000
10-59 We would like to produce a solid MgO–FeO ceramic that contains equal mol
percentages of MgO and FeO at 1200°C. Determine the wt% FeO in the ceramic. (See
Figure 10–22.)
Solution: Only solid is present at 1200°C. MWMgO = 40.312g/mol
MWFeO = 71.847g/mol
(50)(71.847)
50 mol% FeO: = 64.1 wt % FeO
(50)(40.312) + (50)(71.847)
10-60 We would like to produce a MgO–FeO ceramic that is 30 wt% solid at 2000°C.
Determine the composition of the ceramic in wt%. (See Figure 10–22.)
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Solution: L: 65 wt% FeO S: 38 wt% FeO
65 − x
30 wt % = ×100% or x = 56.9 wt % FeO
65 − 38
10-61 A Nb–W alloy held at 2800°C is partly liquid and partly solid. (a) If possible, determine
the composition of each phase in the alloy, and (b) if possible, determine the amount of
each phase in the alloy. (See Figure 10–23.)
Solution: (a) L:49 wt% W α:70 wt% W
(b) Not possible unless we know the original composition of the alloy.
10-62 A Nb–W alloy contains 55% α at 2600°C. Determine (a) the composition of each phase,
and (b) the composition of the alloy. (See Figure 10–23.)
Solution: L:22 wt% W α: 42 wt% W

x − 22
0.55 = or x = 33wt% W
42 − 22
10-63 Suppose a 1200 lb bath of a Nb–40 wt% W alloy is held at 2800°C. How many pounds of
tungsten can be added to the bath before any solid forms? How many pounds of
tungsten must be added to cause the entire bath to be solid? (See Figure 10–23.)
Solution: Solid starts to form at 2800°C when 49 wt% W is in the alloy. In 1200
lb of the original Nb–40% W alloy, there are (0.4)(1200) = 480 lb W
and 720 lb Nb. The total amount of tungsten that must be in the final
alloy is
x
0.49 = or x = 692 lb W total
x + 720
or 692–480 = 212 additional pounds of W must be added
To be completely solid at 2800°C, the alloy must contain 70 wt% W.
The total amount of tungsten required in the final alloy is
x
0.70 = or x = 1680 lb W total
x + 720
or 1680–480 = 1200 additional pounds of W must be added
10-64 A fiber-reinforced composite material is produced, in which tungsten fibers are

embedded in a Nb matrix. The composite is composed of 70 vol% tungsten. (a) Calculate
the wt% of tungsten fibers in the composite, and (b) suppose the composite is heated to
2600°C and held for several years. What happens to the fibers? Explain. (See Figure 10–
23.)
243
Solution: (70cm3 )(19.254 g / cm3 )
(a) wt = = 83.98 wt % W
(70)(19.254) + (30)(8.57)
(b) The fibers will dissolve. Since the W and Nb are completely
soluble in one another and the temperature is high enough for
rapid diffusion, a single solid solution will eventually be produced.
10-65 Suppose a crucible made from pure nickel is used to contain 500 g of liquid copper at
1150°C. Describe what happens to the system as it is held at this temperature for
several hours. Explain. [See Figure 10–8(a).]
Solution: Cu dissolves Ni until the Cu contains enough Ni that it solidifies
completely. When 10% Ni is dissolved, freezing begins.
x
0.10 = or x = 55.5 g Ni
x + 500
When 18% Ni dissolved, the bath is completely solid.
x
0.18 = or x = 109.8 g Ni
x + 500
10-68 A Bi-60 at% Sb alloy is cooled under equilibrium conditions from the liquid state.
Determine (a) the temperature at which the first solid nucleus forms and its
composition; (b) the compositions and relative amounts of the phases at 450°C; and (c)
the temperature at which the last liquid is present and its composition. (See Figure 10-
20.)
Solution:
(a) 510˚C, 88% at% Sb
(b) There are two phases present: S and L.

S: 80 at% Sb
L: 42 at% Sb
60 − 42
at% S = ×100% = 47%
80 − 42
80 − 60
at% L = ×100% = 53%
80 − 42
(c) 360˚C, 20 at% Sb
10-69 Equal moles of MgO and FeO are combined and melted. Determine (a) the liquidus
temperature, the solidus temperature, and the freezing range of the ceramic, and (b)
determine the phase(s) present, their composition(s), and their amount(s) at 1800°C.
244
Solution: MWMgO = 40.312 g/mol MWFeO = 71.847 g/mol
(1mol FeO)(71.847 g/mol)
wt % FeO = = 64.1%
(1 mol FeO)(71.847) + (1 mol MgO)(40.312)
(a) TLiq = 2000°C Ts = 1620°C FR = 380°C
(b) L: 75% FeO S: 50% FeO
64.1 − 50
%L= × 100% = 56.4% % S = 43.6%
75 − 50
10-70 Suppose 75 cm3 of Nb and 45 cm3 of W are combined and melted. Determine (a) the
liquidus temperature, the solidus temperature, and the freezing range of the alloy, and
(b) determine the phase(s) present, their composition(s), and their amount(s) at 2800°C.
Solution: (45cm3 )(19.254 g/cm3 )
wt % W = ×100 = 57.4wt %
(45)(19.254) + (75)(8.57)
(a) TLiq = 2900°C Tss = 2690°C FR = 210°C
(b) L: 49% W 70 − 57.4
%L = = 60%
70 − 49
α: 70% W % α = 40%
10-71 A NiO–60 mol% MgO ceramic is allowed to solidify. Determine (a) the composition of
the first solid to form, and (b) the composition of the last liquid to solidify under
equilibrium conditions. [See Figure 10-8(b).]
Solution: 1st α: 80% MgO Last L:35% MgO
10-72 A Nb–35% W alloy is allowed to solidify. Determine (a) the composition of the first solid
to form, and (b) the composition of the last liquid to solidify under equilibrium
conditions. (See Figure 10–23.)
Solution:
(a) 57 wt% W at 2675˚C
(b) 15 wt% W at 2560˚C
10-73 For equilibrium conditions and a MgO–65 wt% FeO ceramic, determine (a) the liquidus
temperature; (b) the solidus temperature; (c) the freezing range; (d) the composition of
the first solid to form during solidification; (e) the composition of the last liquid to
solidify; (f) the phase(s) present, the composition of the phase(s), and the amount of the
phase(s) at 1800°C; and (g) the phase(s) present, the composition of the phase(s), and
the amount of the phase(s) at 1600°C. (See Figure 10–22.)
Solution: (a) Liquidus = 2000°C
(b) Solidus = 1605°C
(c) Freezing range = 2000–1605 = 395°C
(d) First Solid: 40% FeO
(e) Last liquid: 88% FeO
245
(f) L: 75% FeO 65 − 51
%L= × 100% = 58%
75 − 51
α: 51% FeO % α = 42%
(g) α: 65% FeO 100% α
10-74 Figure 10–24 shows the cooling curve for a NiO–MgO ceramic. Determine (a) the
liquidus temperature; (b) the solidus temperature; (c) the freezing range; (d) the
pouring temperature; (e) the superheat; (f) the local solidification time; (g) the total
solidification time; and (h) the composition of the ceramic.

(d) Pouring temperature = 2775°C
(e) Superheat = 275–2690 = 85°C
(f) Local Solidification time = 27–5 = 22 min
(g) Total solidification time = 27 min
(h) 80% MgO
10-75 For equilibrium conditions and a Nb–80 wt% W alloy, determine (a) the liquidus
temperature; (b) the solidus temperature; (c) the freezing range; (d) the composition of
the first solid to form during solidification; (e) the composition of the last liquid to
solidify; (f) the phase(s) present, the composition of the phase(s), and the amount of the
phase(s) at 3000°C; and (g) the phase(s) present, the composition of the phase(s), and
the amount of the phase(s) at 2800°C. (see Figure 10–23.)
(d) First solid: 90% W
(e) Last liquid: 64% W
246
(f) L: 70% W 85 − 80
%L = × 100% = 33.3%
85 − 70
α: 85% W % α = 66.7%
(g) α: 80% W 100% α
10-76 Figure 10–25 shows the cooling curve for a Nb–W alloy. Determine (a) the liquidus
temperature; (b) the solidus temperature; (c) the freezing range; (d) the pouring
temperature; (e) the superheat; (f) the local solidification time; (g) the total
solidification time; and (h) the composition of the alloy.
Solution: Liquidus = 2900°C
Solidus = 2710°C
Freezing range = 2900–2710 = 190°C
Pouring temperature = 2990°C
Superheat = 2990–2900 = 90°C
Local Solidification time = 340–40 = 300 s
Total solidification time = 340 s
Nb–60 wt% W
10-77 Cooling curves are shown in Figure 10–25 for several Mo–V alloys. Based on these
curves, construct the Mo–V phase diagram.
Solution: TLiquidus TSolidus
0% V 2630°C
20% V 2500°C 2320°C
40% V 2360°C 2160°C
60% V 2220°C 2070°C
80% V 2100°C 1970°C
100% V 1930°C
10-79 For the nonequilibrium conditions shown for the MgO–65 wt% FeO ceramic, determine
(a) the liquidus temperature; (b) the nonequilibrium solidus temperature; (c) the
freezing range; (d) the composition of the first solid to form during solidification; (e) the
composition of the last liquid to solidify; (f) the phase(s) present, the composition of the
phase(s), and the amount of the phase(s) at 1800°C; and (g) the phase(s) present, the
247
composition of the phase(s), and the amount of the phase(s) at 1600°C. (See Figure 10–
22.)

(d) First solid: 40% FeO
(e) Last liquid: 92% FeO
(f) L: 75% FeO 65 − 46
%L= ×100% = 65.5%
75 − 46
S:46% FeO % S = 34.5%
(g) L: 88% FeO 65 − 55
%L= ×100% = 30.3%
88 − 55
S: 55%FeO % S = 69.7%
10-80 For the nonequilibrium conditions shown for the Nb–80 wt% W alloy, determine (a) the
liquidus temperature, (b) the nonequilibrium solidus temperature, (c) the freezing
range, (d) the composition of the first solid to form during solidification, (e) the
composition of the last liquid to solidify, (f) the phase(s) present, the composition of the
phase(s), and the amount of the phase(s) at 3000°C, and (g) the phase(s) present, the
composition of the phase(s), and the amount of the phase(s) at 2800°C. (See Figure 10–
23.)
(d) First solid: 90% W
(e) Last liquid: 40% W
(f) L:70% W 88 − 80
%L= × 100% = 44.4%
88 − 70
α:88% W % α = 55.6%
(g) L:50% W 83 − 80
%L= × 100% = 9.1%
83 − 50
α: 83% W % α = 90.9%
10-84 A copper–nickel alloy that solidifies with a secondary dendrite arm spacing (SDAS) of
0.001 cm requires 15 hours of homogenization heat treatment at 1100°C. What is the
homogenization time required for the same alloy with a SDAS of 0.01 cm and 0.0001
cm? If the diffusion coefficient of Ni in Cu at 1100°C is 3 × 10–10 cm2/s, calculate the
constant c in the homogenization time equation. What assumption is made in this
calculation?
248
Solution: The relationship between homogenization time and the SDAS is given
by Equation 10-6:
t = c (SDAS)2/Ds.
For SDAS = 0.001 cm, t = 15 hr = 15 × 3600 = 54,000 s,
c = (54,000 × 3 × 10–10)/(0.001)2
c = 16.2 s.
For the same alloy, for an SDAS of 0.01 cm, the homogenization time is
given by
t = 16.2(0.01)2/(3 × 10–10)
t = 5,400,00 s
t = 1500 hrs (or 62.5 days).
For an SDAS of 0.0001 cm, the homogenization time is given by
t = 16.2 (0.0001)2/(3 × 10–10)
t = 540 s (or 9 minutes).
One of the assumptions made in this calculation is that the diffusion
coefficient does not change as the composition of the copper-nickel
matrix changes during homogenization.
249
250

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Chapter 10: Solid Solutions and Phase Equilibrium

Thus the range is from 20.5°C / km to 36.7°C / km.

Cu FCC 2.82% +2 Yes

Ni FCC 2.82% +1 Yes

Fe BCC/FCC 41.1% +2, +3 No

Au FCC 0 2.4 +1 Yes

Ag FCC 0 1.9 +1 Yes

Al FCC 0.69% 1.5 +3 No

Fe BCC/FCC 13.80% 1.8 +2, +3 No

Solution: (a) rAu = 1.442 v = +1 FCC

(b) Mn: r = 1.12 ∆r = –12.4 % Different structure

10-39 What is the significance of the liquidus curve? Solidus curve?

10-41 Determine the degrees of freedom under the following conditions:

Solution: (a) TL = 2330°C Ts = 2150°C FR = 180°C

Solution: (a) TL = 2600°C Ts = 2330°C FR = 370°C

Solution: (a) S: 25 % FeO 100% S

Solution: L:22 wt% W α: 42 wt% W

10-64 A fiber-reinforced composite material is produced, in which tungsten fibers are

(b) There are two phases present: S and L.

(c) 360˚C, 20 at% Sb

Solution: (a) Liquidus = 2690°C

Solution: (a) Liquidus = 2000°C

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