CHAPTER 10

PHASE DIAGRAMS

PROBLEM SOLUTIONS

Solubility Limit

10.1 Consider the sugar–water phase diagram of Figure 10.1.

(a) How much sugar will
will dissolve in 1000 g of w
water
ater at 60°C?
(b) If the saturated liquid solution in part (a) is cooled to 20°C, some of the sugar will precipitate
precipitate out as a
solid. What will be the composition
composition of the saturated
saturated liquid solution (in
(in wt% sugar) at 20°C?
(c) How much of the solid sugar will come out of solution upon cooling to 20°C?

Solution

(a) We are asked to determ

determine in 1000 g of water at 60°C. From the
ine how much sugar will dissolve in
solubility limit curve, at 60 °C the maximum concentration
concentration of sugar in the syrup is about 70 wt%. It is now possible
to calculate the mass of sugar using Equation 5.6 as

msugar
Csugar (wt%) = × 100
msugar + mwater

msugar
70 wt% = × 100
msugar + 1000 g

Solving for msugar yields msugar = 2330 g

(b) Again using this same plot, at 20°C the solubility limit (or the concentration of the saturated solution)
is about 64 wt% sugar.
(c) The mass of sugar in this saturated solution aatt 20°C ( m′ sugar ) may also be calculated using Equation

5.6 as follows:

m′ sugar
64 wt% = × 100
m′ sugar + 1000 g

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which yields a value for m′ sugar of 1778 g. Subtracting the latter
latter from the for
former
mer of these sugar concentra
concentrations
tions
yields the amount of sugar that precipitated out of the solution upon cooling m′′ sugar ; that is

m′′ sugar = m sugar − m′ sugar = 2330 g − 1778 g = 552 g

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 Microstructure

10.2 Cite three variables that determine the microstructure of an alloy.

Solution

Three variables that determine the microstructure of an alloy are (1) the alloying elements present, (2) the
concentrations of these alloying elements, and (3) the heat treatment of the alloy.

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 One-Component (or Unary) Phase Diagrams

10.3 Consider a specimen of ice that is at –15°C and 10 atm pressure. Using Figure 10.2, the pres
pressure–
sure–
temperature phase diagram for H 2O, determine the pressure to which the specimen must be raised or lowered to
cause it (a) to melt, and (b) to sublime.

Solution

The figure below shows the pressure-temperature phase diagram for H 2O, Figure 10.2; a vertical line has

been constructed at –15°C, and the location on this line at 10 atm pressure (point B
B)) is also noted.

(a) Melting occurs, (by changing pressure)

pressure) as, moving vertical
vertically
ly (upward) along this li
line,
ne, we cross the
Solid-Liquid phase boundary. This occurs at approximately 1,000 atm; thus, the pressure of the specimen m
must
ust be
raised from 10 to 1,000 atm.
(b) In order to determine the pressure at which sublimation occurs at this temperature,
temperature, we move vertically
downward along this line from 10 atm until we cross the Solid-Vapor
Solid-Vapor phase boundary. This intersection occurs at
approximately 0.003 atm.

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 Binary Isomorphous Systems

10.4 Given here are the solidus and liquidus temperatures for
for the copper–gold system. Construct the
phase diagram for this system
system and label each region.

Composition Solidus Liquidus

(wt% Au) Temperature (°C) Temperature (°C)

0 1085 1085
20 1019 1042
40 972 996
60 934 946
80 911 911
90 928 942
95 974 984
100 1064 1064

Solution

The copper-gold phase diagram is constructed below.

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 Interpretation of Phase Diagrams
(Binary Isomorphous Systems)
(Binary Eutectic Systems)
(Equilibrium Diagrams Having Intermediate Phases or Compounds)

10.5 Cite the phases that are present and the phase compositions for the following alloys:
(a) 25 wt% PPb–75
b–75 wt% Mg at 425°C
(b) 55 wt% Z
Zn–45
n–45 wt% Cu
Cu at 600°C
(c) 7.6 lbm Cu and 144.4 lbm Zn at 600°C
(d) 4.2 mol Cu and 1.1 mol Ag at 900°C

Solution

(a) For an alloy composed of 25 wt% Pb-75 wt% Mg and at 425°C, from Figure 10.20, only the
wt% α phase is
present; its composition iiss 25 wt% Pb-75 wt
wt%
% Mg.

(b) For an alloy composed

composed of 55 wt% Zn-45
Zn-45 wt% Cu and at 600°C, from Figure 10.19, β and γ phases are
present, and

Cβ = 51 wt% Zn-49 wt% Cu

Cγ = 58 wt% Zn-42 wt% Cu

composed of 7.6 lbm Cu and 144.4 lbm Zn and at 600°C, we must first determine the Cu
(c) For an alloy composed

and Zn concentrations (using Equation 5.6), as

7.6 lbm
CCu = × 100 = 5.0 wt%
7.6 lbm + 144.4 lb m

144.4 lbm
CZn = × 100 = 95.0 wt%
7.6 lb m + 144.4 lbm

From Figure 10.19, only the L phase is present; its composition is 95.0 wt% Z
Zn-5.0
n-5.0 wt% Cu.

composed of 4.2 mol Cu and 1.1 mol Ag and at 900°C, it is necessary to determine the Cu
(d) For an alloy composed
and Ag concentrations in weight percent. However, we must first compute
compute the masses of Cu and Ag (in grams)
grams)
using a rearranged form of Equation 5.7:

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 ′ u = nmCu ACu = (4.2 m
mC mool)(63.55 g/
g /mol) = 266.9 g

′ g = nmAg AAg = (1.1 mol)(107.87 g/mol) = 11118.7 g

mA

Now, using Equation 5.6, concentrations of Cu and Ag are determined as follows:

26
266.
6.9
9g
CCu = × 100 = 69.2 wt%
266.9 g + 118.7 g

118.
118.7
7g
CAg = × 100 = 30.8 wt%
266.9 g + 118.7 g

From Figure 10.7, α and liquid phases are present; and

Cα = 8 wt% Ag-92 w% Cu
CL = 45 wt% Ag-55 wt% Cu

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 10.6 Is it possible to have a copper–silver alloy that, at equilibrium, consists of an α phase of composition
4 wt% Ag–96 wt% Cu, and also a β phase of composition 95 wt%
wt% Ag–5 wt% Cu? If so, what will
will be the
approximate temperature of the alloy? If this is not possible, explain why.

Solution

It is possible to have a Cu-Ag alloy, which at equilibrium consists of an α phase of composition 4 wt% Ag-
96 wt% Cu and a β phase of composition 95 wt% Ag-5 wt% Cu. From Figure 10.7 a horizontal ttie
ie can be
constructed across the α + β region at 690 °C which intersects the α−(α + β) phase boundary at 4 wt% Ag, and also
the (α + β)–β phase boundary at 95 wt% Ag.

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 10.7 A 40 wt% Ni–60
Ni–60 wt% Cu alloy
alloy is slowly cooled from 1400°C (2550°F) to 1150°C (2190°F).
(a) At what temperature
temperature does the first solid phase form?
(b) What is the composit
composition
ion of this solid phase?
(c) At what temperature
temperature does the liquid soli
solidify?
dify?
(d) What is the composit
composition
ion of this last remaining
remaining liquid phase?

Solution

Shown below is the Cu-Ni phase diagram (Figure 10.3a) and a vertical line constructed at a composition of
40 wt% Ni-60 wt% Cu.

(a) Upon cooling a 40 wt% Ni-60

Ni-60 wt% Cu alloy form
form 1400°C, the first solid phase forms at the
temperature at which this vertical line intersects the L–(α + L
L)) phase boundary--i.e., at about 1280 °C.
(b) The composition of this solid
solid phase corresponds to the intersection
intersection with the L–(α + L
L)) phase boundary,
of a tie line constructed across the α + L phase region at 1320°C--i.e., Cα = 53 wt% Ni-47 wt% Cu.

(c) Complete solidification

solidification of the alloy occurs at the int
intersection
ersection of this same
same vertical line at 40 wt% Ni
with the (α + L
L)–
)–α phase boundary--i.e., at about 1230 °C.

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 (d) The composition of the last li
liquid
quid phase remaining prior to complete
complete solidification
solidification corresponds to the
intersection with the L–(α + L
L)) boundary, of the tie line constructed across the α + L phase region at 1270°C--i.e.,
CL is about 29 wt% Ni-71 wt% Cu.

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 10.8 Determine the relative amounts (in terms of mass fractions) of the phases for the alloys and
temperatures given in Problem 10.5.

Solution

(a) For an alloy composed of 25 wt% Pb-75 wt% Mg and at 425°C, only the α phase is present; therefore
Pb-75
W = 1.0.
α

(b) For an alloy composed of 55 wt% Zn-45 wt% Cu and at 600 °C, compositions of the β and γ phases are

Cβ = 51 wt% Zn-49 wt% Cu

Cγ = 58 wt% Zn-42 wt% Cu

And, since the composition of the alloy, C0 = 55 wt% Zn-45 wt% Cu, then, using the appropriate lever rule

expressions and taking compositions in weight percent zinc

C − C
Wβ = γ 0 = 58 − 55 = 0.43
Cγ − Cβ 58 − 51

C0 − Cβ 55 − 51
Wγ = = = 0.57
Cγ − Cβ 58 − 51

(c) For an alloy composed of 7.6 lbm Cu and 144.4 lbm Zn (95.0 wt% Zn-5.0 wt% Cu) and at 600 °C, only
the liquid phase
phase is present; therefore, WL = 1.0

(d) For an alloy composed of 4.2 mol Cu and 1.1 mol Ag (30.8 wt% Ag-69.2 wt% Cu) and at 900 °C,

compositions of the α and liquid phases are

Cα = 8 wt% Ag-92 w% Cu
CL = 45 wt% Ag-55 wt% Cu

And, since the composition of the alloy, C0 = 30.8 wt% Ag-69.2 wt% Cu, then, using the appropriate lever rule

expressions and taking compositions in weight percent silver

CL − C0 45 − 30.8
Wα = = = 0.38
CL − Cα 45 − 8

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 C0 − Cα 30.8 − 8
WL = = = 0.62
CL − Cα 45 − 8

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 10.9 A magnesium–lead alloy of mass 9.5 kg consists of a solid α phase that has a composition just
slightly below the
the solubility limi
limitt at 300°C.
(a) What mass of lead is in the alloy?
(b) If the alloy is heated to 400°C, dissolved in the α phase without exceeding
400°C, how much more lead may be dissolved
the solubility limit of this phase?

Solution

(a) This portion of the problem asks that we calculate, for a Pb-Mg alloy,
alloy, the mass of lead in 9.5 kg of tthe
he
solid α phase at 300°C just below the solubility limit. solubility limit for the α phase at 300°C
limit. From the Figure, the solubility
corresponds to the position (composition) of the α-α + Mg2Pb phase boundary at this temperature, which is about

17 wt% Pb. Therefore, the mass of Pb in the alloy is just (0.17)(9.5

(0.17)(9.5 kg) = 1.615 kg
(b) At 400°C, the solubility limit of the α phase increases to to approximately 32 wt% Pb. In order to
determine the additional amount of Pb that may be added (m
( mPb ), we utilize a modified form of Equation 5.6 as
'

1.
1.61
615
5 kg + mPb’
CPb = 32 wt% = × 100
9.5 kg + mPb’

Solving for mPb' yields mPb' = 2.096 kg.

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 within the α + liquid-phase region. If the
10.10 A 40 wt% Pb–60 wt% Mg alloy is heated to a temperature within
mass fraction of each phase is 0.5, then estimate:
(a) The temperature of the alloy
(b) The compositions of the two phases

Solution

(a) We are given that mass fractions of α and liquid phases are both 0.5 for a 40 wt% Pb-60 wt% Mg
that the mass
alloy and are asked to estimate the temperature
temperature of the alloy. Using the appropriate phase diagram,
diagram, Figure 10.20, by
trial and error with a ruler, a tie line within the α + L phase region that is divided in half for an alloy of this
composition exists at about 540°C.
(b) We are now asked to deter
determine
mine the com
compositions
positions of the
the two phases. This is accomplished
accomplished by noting
the intersections of this tie line with
with both the solidus and liquidus lines. From these interse
intersections,
ctions, Cα = 26 wt% Pb,
and CL = 54 wt% Pb.

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 10.11 For alloys of two hypothetical metals A and B, there exist an α, A-rich phase and a β, B-rich phase.
From the mass fractions of both phases for two different alloys (given below), which are at the same temperature,
determine the composition of the phase boundary (or solubility limit) for (a) α and (b) β phases at this temperature.

Alloy Fraction α Fraction β

Composition Phase Phase

60 wt% A–40 wt% B 0.56 0.44

30 wt% A–70 wt% B 0.12 0.88

Solution

The problem is to solve for compositions at the phase boundaries for both α and β phases (i.e., Cα and Cβ).
We may set up two independent lever rule expressions, one for each composition, in terms of Cα and Cβ as follows:

Cβ − C01 Cβ − 60
Wα1 = 0.56 = =
Cβ − Cα Cβ − Cα

Cβ − C02 Cβ − 30
Wα 2 = 0.12 = =
Cβ − Cα Cβ − Cα

In these expressions, compositions

compositions are given in w
wt%
t% of A. Solving for Cα and Cβ from these equations, yield

Cα = 90 (or 90 wt% A-10 wt% B)

Cβ = 21.8 (or 21.8 wt% A-78.2 wt% B)

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 10.12 Is it possible to have a copper–silver alloy of composition 20 wt% Ag–80 wt% Cu that, at
equilibrium, consists of α and liquid phases having mass fractions Wα = 0.80 and WL = 0.20? If so, what will be the
the
approximate temperature of the alloy? If such an alloy is not possible, explain why.

Solution

Yes, it is possible to have a Cu-Ag alloy of composition 20 wt% Ag-80 wt% Cu which consists of mass
fractions Wα = 0.80 and WL = 0.20. Using the appropriate phase diagram,
diagram, Figure 10.7, by trial and error with a

ruler, the tie-line segments within the α + L phase region are proportioned such that

CL − C0
Wα = 0.8 =
CL − Cα

for C0 = 20 wt% Ag. This occurs at about 800°C.

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 10.13 For 5.7 kg of a magnesium–lead alloy of composition 50 wt% Pb–50 wt% Mg, is it possible, at
equilibrium, to have α and Mg2Pb phases with respective masses of 5.13 and 0.57 kg? If so, what will be the
approximate temperature of the alloy? If such an alloy is not possible, then explain why.

Solution

It is not possible to have a 50 wt% Pb-50 wt% Mg alloy that has masses of 5.13 kg and 0.57 kg for the α
and Mg2Pb phases, respectively. In order to demonstrate this, it is first necessary to determine the mass fracti
fraction
on of

each phase as:

mα 5.13 kg
Wα = = = 0.90
mα + mMg 2 Pb 5.13 kg + 0.57 kg

WMg 2 Pb = 1.0
.00
0 − 0.
0.90
90 = 0.
0.10
10

Now, if we apply the lever rule expression for Wα

CMg 2 Pb − C0
Wα =
CMg 2 Pb − Cα

Since the Mg2Pb phase exists only at 81 wt% Pb, and C0 = 50 wt% Pb

81 − 50
Wα = 0.
0.90
90 =
81 − Cα

Solving for Cα from this expression yields Cα = 46.6 wt% Pb. From Figure
Figure 10.20, the maximum concentration of
Pb in the α phase in the α + Mg2Pb phase field is about
about 42 wt% Pb. Therefore, this alloy
alloy is not possible.
possible.

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 10.14 Determine the relative amounts (in terms of volume fractions) of the phases for the alloys and
temperatures given in Problems 10.5a and b. Given here are the approximate densities
densities of the various metals at the
the
alloy temperatures:

Temperature Density
Metal (°C) (g/cm3)

Cu 600 8.68
Mg 425 1.68
Pb 425 10.96
Zn 600 6.67

Solution
This problem asks that we determine the phase volume fractions for the alloys and temperatures in

Problems 10.5a and b. This is accomplished by using the technique illus

illustrated
trated in Example Problem
Problem 10.3, and also
the results of Problems 10.5 and 10.8.

(a) This is a Pb-Mg alloy at 425°C, wherein only the α phase is present. Therefore, Vα = 1.0.

(b) This is a Zn-Cu alloy at 600°C, wherein

Cβ = 51 wt% Zn-49 wt% Cu

Cγ = 58 wt% Zn-42 wt% Cu
Wβ = 0.43

Wγ = 0.57
ρZn = 6.67 g/cm3
ρCu = 8.68 g/cm3

Using these data it is first necessary to compute the densities of the β and γ phases using Equation 5.13a. Thus

100
ρβ =
CZn (β) CCu (β)
+
ρZn ρC u

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 100 3
= = 7.52 g/cm
51 49
+
cm3
6.67 g / cm 8.68 g / cm3

100
ρ =
γ CZn (γ ) CCu ( γ )
+
ρZn ρCu

100
= = 7.39 g/cm3
58 42
3
+ 3
6.67 g / cm
cm 8.68 g / cm

Now we may determine

determine the Vβ and Vγ values using Equation 10.6. Thus,

Wβ
ρβ
Vβ = Wβ Wγ
+
ρβ ργ

0.43
7.52 g /cm3
7.5
= = 0.43
0.43 0.57
+
7.52 g / cm3 cm3
7.39 g / cm

Wγ
ργ
Vγ = Wβ Wγ
+
ρβ ργ

0.57
7.39 g /cm3
7.3
= = 0.57
0.43 0.57
3
+ 3
7.52 g / cm 7.39 g / cm
cm

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 Mechanical Properties of Isomorphous Alloys

10.15 It is desirable to produce a copper–nickel alloy that has a minimum noncold-worked

noncold-worked tensile strength
of 380 MPa (55,000 psi) and a ductility of at least 45%EL. Is such an alloy possible? If so, what must be its
composition? If this is not possible, then explain w
why.
hy.

Solution

From Figure 10.6a, a tensile strength greater than 380 MPa is possible for compositions between about 32
and 90 wt% Ni. On the other hand, according to Figure 10
10.6b,
.6b, ductilities greater than 45%E
45%EL
L exist for
compositions less than about 13 wt% and greater than about 94 wt%
wt% Ni. Therefore, such an alloy is not possible
inasmuch, that in order to meet the stipulated criteria:

For a TS > 380 MPa 32 wt% < CNi < 90 wt%

For %EL > 45% CNi < 13 wt% or CNi > 94 wt%

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 Development of Microstructure in Eutectic Alloys

10.16 Briefly explain why, upon solidification, an alloy of eutectic composition forms a microstructure
consisting of alternating layers of the two solid phases.

Solution

Upon solidification, an alloy of eutectic composition forms a microstructure consisting

consisting of alternating layers
of the two solid phases because during the solidification atomic diffusion must occur, and with this layered
configuration the diffusion path length for the atoms is a minimum.

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 10.17 Is it possible to have a magnesium–lead alloy in which the mass fractions of primary α and total α
are 0.60 and 0.85, respectively,
respectively, at 460°C? Why or why not?

Solution

In order to make this determination, we need to set up the appropriate lever rule expression for each of
these quantities. From Figure 10.20 and at 460°C, C = 41 wt% Pb, CMg Pb = 81 wt% Pb, and C = 67 wt%
α 2 eutectic
Pb.
For primary α

Ceutectic − C0 67− C0
Wα' = = = 0.60
Ceutectic − Cα 67 − 41

Solving for C0 gives C0 = 51.4 wt% Pb.

Now the analogous expression for total α

CMg 2 Pb − C0 81 − C0
Wα = C − Cα = 81 − 41 = 0.85
M g 2 Pb

which yields a value of 47 wt% Pb for C0. Therefore, since these two C0 values are different, this alloy is not

possible..
possible

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 10.18 For a lead–tin alloy of composition 78.0 wt% Sn–22 wt% Pb and at 180°C do the following:
(a) Determine the mass fraction of α phase.
(b) Determine the mass fraction of β phase.
(c) Determine the mass fraction of primary β microconstituent.
mass
(d) Determine the mass fracti
fraction
on of eutectic microconstituent.

(e) Determine the m

mass
ass fraction of eutectic β.
eutectic

Solution

(a & b) This portion of the problem mass fractions of α and

problem asks that we determine the mass β phases for an
78 wt% Sn-22 wt% Pb alloy (at 180°C). In order to do this, it is necessary to
to employ the lever rule using a tie line
line
that extends entirely across the α + β phase field.
Figure and at 180°C, Cα = 18.3 wt% Sn, Cβ = 97.8 wt% Sn,
From Figure
and Ceutectic = 61.9 wt% Sn. Therefore, the two lever-rule expre
expressions
ssions are as follows:

Cβ − C0 97.8 − 78
(a) Wα = = = 0.249
Cβ − Cα 97.8 − 18.3

C0 − Cα 78 − 18.3
(b) Wβ = = = 0.751
Cβ − Cα 97.8 − 18.3

mass fractions of primary β and eutectic microconstituents for

(c & d) Now it is necessary to determine the mass
this same alloy. This requires that we utilize
utilize the lever rule and a tie line that extends from the m
maximum
aximum solubilit
solubility
y
of Pb in the β phase at 180°C (i.e., 97.8 wt% Sn) to the eutectic composition
composition (61.9 wt% Sn). Thus

C0 − Ceutectic 78 − 61.9
(c) Wβ ' = = = 0.448
Cβ − Ceutectic 97.8 − 61.9

Cβ − C0 97.8 − 78
(d) We = = = 0.552
Cβ − Ceutectic 97.8 − 61.9

(e) And, finally, we are asked to ccompute

ompute the mass fraction of eutectic β, Weβ. This quantity
fraction quantity is si
simply
mply the

difference between the mass fractions of total β and primary β as

Weβ = Wβ – Wβ' = 0.751 – 0.448 = 0.303

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 10.19 Consider the hypothetical eutectic phase diagram for metals A and B, which is similar to that for the
lead–tin system. that: (1) α and β phases exist at the A and B extremities of the phase diagram, respectively;
system. Assume that:
composition is 36 wt% A–64 wt% B; and (3) the composition of the α phase at the eutectic
(2) the eutectic composition
temperature is 88 wt% A–12 wt% B. Determine the composition
composition of an alloy that will yield primary β and total β
primary
mass fractions of 0.376 and 0.761, respectively.

Solution

We are given a hypothetical eutectic phase diagram for which Ceutectic = 64 wt% B, Cα = 12 wt% B at the
eutectic temperature, and also that Wβ' = 0.376 and Wβ = 0.761; from this this we aare
re asked to
to determine
determine the
composition of the alloy.
alloy. Let us write lever rule expressions for Wβ' and Wβ

C0 − Cα C0 − 12
Wβ = = = 0.761
Cβ − Cα Cβ − 12

C0 − Ceutectic C0 − 64
Wβ' = = = 0.376
Cβ − Ceutectic Cβ − 64

Thus, we have two simultaneous equations with C0 and Cβ as unknowns. Solving them for C0 gives C0 = 76.1 wt% B.

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 10.20 For a 64 wt% Zn–36 wt% Cu alloy, make schematic sketches of the microstructure that would be
observed for conditions of very slow cooling at the following temperatures: 900°C, 820°C, 750°C, and 600°C.
Label all phases and indicate
indicate their approximate com
compositions.
positions.

Solution

The illustration below is the Cu-Zn

Cu-Zn phase diagram (Figure 10.19). A vertical line at a composition
composition of
64 wt% Zn-36 wt% Cu has been drawn, and, in addition, horizontal arrows at the four temperatures called for in the
statement (i.e., 900°C, 820°C, 750°C, and 600°C).
problem statement

On the basis of the locations of the four temperature-composition points, schematic sketches of the four respective
microstructures along with phase compositions are represented as follows:

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 10.21 For a 52 wt% Zn–48 wt% Cu alloy, make schematic sketches of the microstructure that would be
observed for conditions of very slow
slow cooling at the foll
following
owing temperatures: 950°C, 860°C, 800°C, and 600°C.
Label all phases and indicate
indicate their approximate com
compositions.
positions.

Solution

The illustration below is the Cu-Zn

Cu-Zn phase diagram (Figure 10.19). A vertical line at a composition
composition of
52 wt% Zn-48 wt% Cu has been drawn, and, in addition, horizontal arrows at the four temperatures called for in the
statement (i.e., 950°C, 860°C, 800°C, and 600°C).
problem statement

On the basis of the locations of the four temperature-composition points, schematic sketches of the four respective
microstructures along with phase compositions are represented as follows:

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 10.22 The room-temperature tensile strengths of pure copper and pure silver are 209 MPa and 125 MPa,
respectively.
(a) Make a schematic graph of the room-temperature
room-temperature tensile
tensile strength vers
versus
us composition ffor
or all
compositions between pure copper and pure silver.
silver. (Hint: You may want to consult Sections 10.10 and 10.11, as
well as Equation 10.24 in Problem 10.36.)

(b) On this same graph, schematically plot tens

tensile
ile strength versus composition at 600°C.
(c) Explain the shapes of these
these two curves, as well as any differenc
differences
es between them.

Solution

The (a) and (b) portions of the problem ask that we make schematic plots on the same graph for the tensile
strength versus composition for copper-silver alloys at both room temperature and 600 °C; such a graph is shown
below.

(c) Upon consultation of the Cu-Ag phase diagram (Figure 10.7) we note that, at room ttemperature,
emperature, silver
is virtually insoluble in copper (i.e., there is no α-phase region at the left extremity of the phase diagram);
diagram); the same
may be said the solubility of copper in silver and for the β phase. Thus, only the α and β phase will exist for all
compositions at room temperature;
temperature; in other words, there will be no solid-solution strengt
strengthening
hening effects at room
temperature. All other things being equal, the tensil
tensilee strength will depend (approximatel
(approximately)
y) on the tensile strengths
of each of the α and β phases as well as their phase fractions in a manner described by Equation 10.24 for the elastic
modulus (Problem 10.36). That is, for this problem

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 (TS )alloy ≅ (TS )αVα + (TS )βVβ

in which TS and V denote tensile strength and volume fraction, respectively, and the subscripts represent the
mass fractions of the α and
alloy/phases. Also, mass β phases change linearly with changing composition (according to
the lever rule). Furthermore, inasm
inasmuch
uch as the densities of both Cu and Ag are similar, weight and volume fractions

of the α and β phases will also be similar

similar (see E
Equation
quation 10.6). In summary, tthe
he previous discussion explains the
linear dependence of the room temperature tensile strength on composition as represented in the above plot given
that the TS of pure copper is greater than for pure silver (as stipulated in the problem statement).
At 600°C, the curve will be shifted to significantly lower tensile strengths inasmuch as tensile strength
diminishes with increasing
increasing temperature (Section
(Section 7.6, Figure 7.14). In addition, according to Figure 10.7, about 4
wt% of silver will dissolve in copper (i.e., in the α phase), and about 4 wt% of copper will dissolve in silver (i.e., in
the β phase). Therefore, solid-solution
solid-solution strengthening will occur
occur over these compositions ranges,
ranges, as noted in the
graph shown above. Furthermore, between 4% Ag and 96% Ag, the curve will be approximately
approximately linear for the same
reasons noted in the previous paragraph.

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 Equilibrium Diagrams Having Intermediate Phases or Compounds

10.23 Two intermetallic compounds, A3B and AB3, exist for elements A and B. If the compositions for A3B
and AB3 are 91.0 wt% A–9.0 wt% B and 53.0 wt% A–47.0 wt% B, respectively, and element A is zirconium, identify
element B.

Solution

Probably the easiest way to solve this problem is to first compute the ratio of the atomic weights of these
two elements using Equation 5.9a; then, since we know the atomic weight of zirconium (91.22 g/mol), it is possible
to determine the atomic weight of element B, from which an identification may be made.
First of all, consider the A3B intermetallic
intermetallic compound; inasmuch as it contains three ti
times
mes the number of A

atoms than and B atoms, its composition in atomic

atomic percent is 75 at% A-25 at% B. Equation 5.9a may be written in
the form:

CB AA
′ = 25 at% =
CB × 100
CA AB + CB AA

where AA and AB are the atomic weights for elements A and B, and CA and CB are their compositions in weight
percent. For this A3B compound, and making the appropriate substitutions in the above equation leads to

(9.0 wt % B)( AA )
25 at % B = × 100
(91.0 wt % A )( AB ) + (9.0 wt % B
B))( AA )

Now, solving this expression

expression yields,

A = 0.297 A
B A

Since zirconium is element A and it has an atomic weight of 91.22 g/mol, the atomic weight of element B is just

AB = (0.297)(91.22 g/mol) = 27.09 g/mol

Upon consultation of the period table of the elements (Figure 2.6) we note the element that has an atomic weight
closest to this value is aluminum
aluminum (26.98 g/mol). Therefore, elem
element
ent B is aluminum, and the ttwo
wo intermetallic
intermetallic
compounds are Zr3Al and ZrAl3.

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 Congruent Phase Transformations
Binary Eutectic Systems
Equilibrium Diagrams Having Intermediate Phases or Compounds
Eutectoid and Peritectic Reactions

10.24 Figure 10.40 is the tin–gold phase diagram, for which only single-phase regions are labeled.
Specify temperature–composition points at which all eutectics, eutectoids, peritectics, and congruent phase
transformations occur. Also, for each, w
write
rite the reaction upon cooling.
cooling.

Solution

Below is shown the tin-gold phase diagram (Figure 10.40).

eutectics on this phase diagram. One exists at 10 wt% Au-90 wt% Sn and 217°C. The
There are two eutectics
reaction upon cooling is

L → α+β

The other eutectic exists at 80 wt% Au-20 wt% Sn and 280°C. This reaction
reaction upon cooling is

L → δ+ζ

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 There are three peritectics. wt% Au-70 wt% Sn and 252°C. Its reaction
peritectics. One exists at 30 wt% reaction upon cool
cooling
ing is
as follows:

L+γ → β

The second peritectic exists at 45 wt% Au-55 wt% Sn and 309 °C. This reaction
reaction upon cooli
cooling
ng is

L+δ → γ

The third peritectic exists at 92 wt% Au-8 wt% Sn and 490 °C. This reaction
reaction upon cooli
cooling
ng is

L+η → ζ

There is one congruent melting point at 62.5 wt% Au-37.5 wt% Sn and 418°C. Its reaction upon cooling is

L → δ

No eutectoids are present.

present.

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 10.25 Construct the hypothetical phase diagram for metals A and B between room temperature 20°C and
700°C given the following information:
● The melting temperature of metal A is 480°C.
● The maximum solubility of B in A is 4 wt% B, which occurs at 420°C.
● The solubility of B in A at room temperature is 0 wt% B.

● One eutectic occurs at 420°C and 18 wt% B–82 wt% A.

● A second eutectic occurs at 475°C and 42 wt% B–58 wt% A.
● The intermetallic compound AB exists at a composition of 30 wt% B–70 wt% A, and melts
congruently at 525°C.
● The melting temperature of metal B is 600°C.
● The maximum solubility of A in B is 13 wt% A, which occurs at 475°C.
● The solubility of A in B at room temperature is 3 wt% A.

Solution

Below is shown the phase diagram for these two A and B metals.

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 Ceramic Phase Diagrams

10.26 From Figure 10.24, the phase diagram for the MgO–Al2O3 system, it may be noted that the spinel
solid solution exists over a range of compositions, which means that it is nonstoichiometric at compositions other
than 50 mol% MgO–50 mol% Al 2O3.

(a) The maximum nonstoichiometry on the Al 2O3-rich side of the spinel phase field exists at about 2000°C
corresponding to approximately 82 mol% (92 wt%) Al2O3. Determine the type of vacancy defect that is produced
and the percentage of vacancies that exist at this composition.
(b) The maximum nonstoichiometry on the MgO-rich side of the spinel phase field exists at about 2000°C
corresponding to approximately 39 mol% (62 wt%) Al2O3. Determine the type of vacancy defect that is produced
and the percentage of vacancies that exist at this composition.

Solution

(a) For this portion of the problem, we are to determine tthe

he type of vacancy defect that is produced on the
Al2O3-rich side of the spinel phase field (Figure 10.24) and the percentage of these vacancies at the maximum
3+
nonstoichiometry (82 mol% Al2O3). On the alumina-rich side of this
this phase field, there is an excess of Al ions,
3+ 2+
which means that some of the Al ions substitute for Mg charge neutrality, Mg2+
ions. In order to maintain charge
3+
vacancies are formed, and for every Mg 2+ vacancy formed, two Al ions substitute for three Mg2+ ions.
Now, we will calculate the percentage of Mg2+ vacancies that exist at 82 mol% Al2O3. Let us ar
arbitrarily
bitrarily
choose as our basis 50 MgO-Al2O3 units of the stoichiometric material, which consists of 50 Mg 2+ ions and 100

Al3+ ions. Furthermore, llet

et us designate the number of Mg2+ vacancies as xx,, which means that 2x Al 3+ ions have
been added and 3x Mg2+ ions have been removed (two of which are filled with Al 3+ ions). Using our 50 MgO-
Al2O3 unit basis, the number of moles of Al 2O3 in the nonstoichiometric material is (100 + 2xx)/2;
)/2; similarly the
number of moles of MgO is (50 – 3xx).
). Thus, the expression for the
the mol% of Al2O3 is just

⎡⎢ 100 + 2 x ⎤⎥
2
mol% Al2 O3 = ⎢ 100 + 2 x ⎥ × 100
⎢ + (50 − 3x) ⎥
⎢⎣ 2 ⎥⎦

If we solve for x when the mol% of Al2O3 = 82, then x = 12.1. Thus, adding 2x or (2)(12.1) = 24.2 Al3+ ions to the

original material consisting of 100 Al 3+ and 50 Mg2+ ions will produce 12.1 Mg2+ vacancies. Therefore, the
percentage of vacancies is just

12.1
% vacancies = × 100 = 8.1%
100 + 50

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 (b) Now, we are asked to make the same determinations
determinations for the MgO-rich side of the spinel phase field,
thiss case, Mg2+ ions are substituting for Al 3+ ions. Since the Mg2+ ion has a lower charge
for 39 mol% Al2O3. In thi

than the Al3+ ion, in order to maintain charge neutrality, negative charges must be eliminated, which may be
accomplished by introducing O2– vacancies. For every 2 Mg2+ ions that substitute for 2 Al 3+ ions, one O2– vacancy
is formed.
2–
Now, we will calculate the percentage of O vacancies that exist at 39 mol% Al 2O3. Let us arbitrarily
choose as our basis 50 MgO-Al 2O3 units of the stoichiometric material which consists of 50 Mg2+ ions 100 Al3+

et us designate the number of O2– vacancies as yy,, which means that 2y Mg2+ ions have been
ions. Furthermore, llet
added and 2y Al3+ ions have been removed. Using our 50 MgO-Al2O3 unit basis, the number of moles of Al2O3 in

the nonstoichiometric material is (100 – 2 yy)/2;

)/2; similarly the
the number of moles of MgO is (50 + 2yy).
). Thus, the
expression for the mol% of Al 2O3 is just

⎡ 100 − 2y ⎤
⎢ 2 ⎥
mol% Al2 O3 = ⎢ 100 − 2y
⎥ × 100
⎢ + (50 + 2 y) ⎥
⎣⎢ 2 ⎦⎥

7.91 O2– vacancies are produced in the

If we solve for y when the mol% of Al2O3 = 39, then y = 7.91. Thus, 7.91

original material that had 200 O2– ions. Therefore, the percent
percentage
age of vacancies is just

7.91
% vacancies = × 100 = 3.96%
200

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 The Gibbs Phase Rule

10.27 In Figure 10.41 is shown the pressure–temperature phase diagram for H2O. Apply the
the Gibbs phase
rule at points A, B, and C; that is, specify the number of degrees of freedom at each of the points—that is, the
number of externally controllable variables that need be specified to completely define the system.

Solution

We are asked to specify the value of F for Gibbs phase rule at points A, B, and C on the pressure-
temperature diagram for H2O, Figure 10.42, which is shown below.

Gibbs phase rule in general form is

P+F=C+N

For this system, the number of components, C, is 1, whereas N, the number of noncompositional variables, is 2--viz.
temperature and pressure.
pressure. Thus, the phase rule now becomes

P+F=1+2=3
Or
F=3–P

where P is the number of phases present at equilibrium.

At point A, only a single (liquid) phase is present (i.e., P = 1), or

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 F=3–P=3–1=2

which means that both temperature and pressure are necessary to define the system.
At point B which is on the phase boundary between liquid and vapor phases, two phases are in equilibrium
(P = 2); hence

F=3–P=3–2=1

Or that we need to specify the value of either temperature or pressure, which determines the value of the other
(pressure or temperature).
And, finally, at point C, three phases are present—viz. ice I, vapor, and liquid—and the number of degrees
of freedom is zero since

F=3–P=3–3=0

Thus, point C is an invariant point (in this case a triple point), and we have no choice in the selection of externally
controllable variables in order to define the system.

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 The Iron-Iron Carbide (Fe-Fe3C) Phase Diagram

Development of Microstructure in Iron-Carbon Alloys

10.28 What is the carbon concentration of an iron–carbon alloy for which the fraction of total ferrite
0.95?

Solution

This problem asks that we compute the carbon concentration of an iron-carbon alloy for which the fraction
of total ferrite is 0.95. Application of the lever rule (of the form of Equati
Equation
on 10.12) yields

CFe3C − C0′ 6.7 − C0′

WFe3C = 0.95 = =
CFe3C − Cα 6.70 − 0.022

and solving for C0′

C0′ = 0.356 wt% C

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 10.29 Consider 1.1 kg of austenite containing 0.20 wt% C, cooled to below 727°C.
(a) How many kilograms of total ferrite form?
form?
(b) How many ki
kilograms
lograms of ceme
cementite
ntite form?
(c) How many kilograms of pearlite phase form?
(d) How many kilograms of proeutectoid phase form?

Solution

This problem asks us to consider various aspects of 1.1 kg of austenite containing 1.2 wt% C that is cooled
to below the eutectoid.
(a & b) For this portion of the problem, we are asked to determine how much tota
totall ferrite and cementite
form. Application of the appr
appropriate
opriate lever rule expression
expression yields

CFe3C − C0 6.70 − 1.2

(a) Wα = = = 0.824
CFe3C − Cα 6.70 − 0.022

which, when multiplied by the total mass of the alloy, gives (0.824)(1.1 kg) = 0.906 kg of total ferrite.
Similarly, for total cementite,

C0 − Cα 1.2 − 0.022
(b) WFe3C = = = 0.176
CFe3C − Cα 6.70 − 0.022

And the mass of total cementite that forms is (0.176)(1.1 kg) = 0.194 kg.
(c & d) Now we are asked to calculate how m
much
uch pearlite and the proeutectoid phase (cem
(cementite)
entite) form.
Applying Equation 10.22, in which C1′ = 1.2 wt% C

(c) W p = 6.70 − C1′ = 6.70 − 1.2 = 0.926

6.70 − 0.76 6.70 − 0.76

which corresponds to a mass of (0.926)(1.1 kg) = 1.02 kg. Likewise, from

from Equation 10.21

C1′ − 0.76 1.2 − 0.76

(d) WFe3C' = = = 0.074
5.94 5.94

which is equivalent to (0.074)(1.1 kg) = 0.0815 kg of the total 1.1 k

kgg mass.

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 10.30 Compute the mass fractions of proeutectoid ferrite and pearlite that form in an iron–carbon alloy
containing 0.23 wt% C.

Solution

The mass fractions of proeutectoid ferrite and pearlite that form in a 0.23 wt% C iron-carbon alloy are

considered in this problem. From Equation 10.20

C0′ − 0.022 0.23 − 0.022

Wp = = = 0.281
0.74 0.74

And, from Equation 10.21 (for proeutectoid ferrite)

0.76 − C0′ 0.76 − 0.23

Wα' = = = 0.716
0.74 0.74

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 10.31 The mass fractions of total ferrite and total cementite in an iron–carbon alloy are 0.866 and 0.134,
respectively. Is this a hypoeutectoid or hypereutectoid alloy? Why?

Solution
In this problem we are given values of Wα and WFe C for an iron-carbon alloy (0.866 and 0.134,
3

respectively), and then are asked to specify whether the alloy is hypoeutectoid
hypoeutectoid or hypereutectoid. Employment of
the lever rule for total α leads to

CFe3C − C0 6.70 − C0
Wα = 0.866 = =
CFe3C − Cα 6.70 − 0.022

Now, solving for C0, the alloy composition, leads to C0 = 0.92 wt% C. Therefore, the alloy
alloy is hypereutectoid since
C is greater than 0.76 wt% C.
0

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 10.32 Consider 2.9 kg of a 99.5 wt% Fe–0.5 wt% C alloy that is cooled to a temperature just below the
eutectoid.
(a) How many kilograms of proeutectoid ferrite
ferrite form?
(b) How many kilograms of eutectoid ferrite
ferrite form?
(c) How many kilograms of cementite form?

Solution

In the problem, we are asked to consider 2.9 kg of a 99.5 wt% Fe-0.5 wt% C alloy that is cooled to a
temperature below the eutectoid.
(a) Equation 10.21 must be used in computing the amount of proeutectoid ferrite
ferrite that form
forms.
s. Thus,

0.76 − C0′ 0.76 − 0.50

Wα' = = = 0.351
0.74 0.74

Or, (0.351)(2.9 kg) = 1.02 kg of proeutectoid ferrite forms.

(b) In order to determine the amount of eutectoid ferrite, it first beco

becomes
mes necessary to compute the amo
amount
unt
of total ferrite using the lever rule applied entirely across the α + Fe3C phase field, as

CFe3C − C0′ 6.70 − 0.50

Wα = = = 0.928
CFe3C − Cα 6.70 − 0.022

which corresponds to (0.928)(2.9 kg) = 2.692 kg. Now, the amount of eutectoid ferrit
ferritee is just the difference
between total and proeutectoid
proeutectoid ferrites, or

2.692 kg – 1.02 kg = 1.67 kg

(c) With regard to the amount of cementite that forms, again aapplication
pplication of the lever rule across the
entirety of the α + Fe3C phase field, leads to

C0′ − Cα 0.5 − 0.022

WFe3C = = = 0.072
CFe3C − Cα 6.70 − 0.022

which amounts to (0.072)(2.9 kg) = 0.208 kg cementite in the alloy.

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 10.33 Is it possible to have an iron–carbon alloy for which the mass fractions of total cementite and
proeutectoid ferrite are 0.057 and 0.484, respectively?
respectively?

Solution

This problem asks if it is possible to have an iron-carbon alloy for which WFe3C = 0.057 and Wα' = 0.484. In

order to make this determination, it is necessary to set up lever rule expressions for these two mass fractions in
terms of the alloy composition,
composition, then to solve for the alloy composit
composition
ion of each; if both alloy composition valu
values
es are
equal, then such an alloy is possible. The lever-rule expression for the mass fraction of total cementite is

C0 − Cα C0 − 0.022
WFe3C = = = 0.057
CFe3C − Cα 6.70 − 0.022

Solving for this C0 yields C0 = 0.40 wt%

wt% C. Now for Wα' we utilize Equation 10.21 as

0.76 − C0′
Wα' = = 0.484
0.74

This expression leads to C0′ = 0.40 wt%

wt% C. And, since C0 and C0′ are the same, this alloy is possible
possible..

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 10.34 Compute the mass fraction of eutectoid cementite in an iron–carbon alloy that contains 0.84 wt% C.

Solution

This problem asks that we compute the mass fraction of eutectoid cementite in an iron-carbon alloy that
contains 0.84 wt% C. In order to solve this problem it is necessary to compute mass fractions of total and

proeutectoid cementites, and then to subtract the latter from the former. To calculate the mass fraction of total
cementite, it is necessary to use the lever rule and a tie line that extends across the entire α + Fe3C phase field as

C0 − Cα 0.84 − 0.022
WFe3C = = = 0.122
CFe3C − Cα 6.70 − 0.022

Now, for the mass

mass fraction of proeutectoi
proeutectoid
d cementite we use Equation 10.21

C1′ − 0.76 0.84 − 0.76

WFe3C' = = = 0.013
5.94 5.94

And, finally, the mass fraction of eutectoid cementite WFe is just

3C"

WFe = WFe – WFe = 0.122 – 0.013 = 0.109

3C'' 3C 3C'

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 10.35 The mass fraction of eutectoid ferrite in an iron–carbon all
alloy
oy is 0.71. On the basis of this
information, is it possible
possible to determine the composition
composition of the alloy? If so, what is its
its composition? If this is not
possible, explain why.

Solution

Yes, it is possible
possible to determine the alloy composition;
composition; and, in fact, ther
theree are two possible answers.
answers. For the
first, the eutectoid ferrite exists in addition to proeutectoid ferrite (for a hypoeutectoid alloy). For this case the mass
fraction of eutectoid ferrite (W
(Wα'') is just the difference between total ferrite and proeutectoid ferrite mass fractions;

that is

Wα'' = Wα – Wα'

Now, it is possible to write expressions for Wα (of the form of Equation 10.12) and Wα' (Equation 10.21) in terms of
C0, the alloy com
composition.
position. Thus,

CFe3C − C0 0.76 − C0
Wα" = −
CFe C − Cα 0.74
3

6.70 − C0 0.76 − C0
= − = 0.71
6.70 − 0.022 0.74

And, solving for C0 yields C0 = 0.61 wt% C.

For the second possibility, we have a hypereutectoid alloy wherein all of the ferrite is eutectoid ferrite.
Thus, it is necessary to set up a lever rule expression wherein
wherein the mass fraction of total ferrit
ferritee is 0.71. Therefore,

CFe3C − C0 6.70 − C0
Wα = = = 0.71
CFe3C − Cα 6.70 − 0.022

And, solving for C0 yields C0 = 1.96 wt% C.

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 10.36 Often, the properties of multiphase alloys may be approximated by the relationship

E (alloy) = EαVα + EβVβ (10.24)

where E represents a specific property (modulus of elasticity, hardness, etc.), and V is the volume fraction. The

subscripts α and β denote the existing phases or microconstit

microconstituents.
uents. Employ this relat
relationship
ionship to determi
determine
ne the
approximate Brinell hardness of a 99.8 wt%
wt% Fe–0.2 wt% C alloy. Assume Brinell hardnesses of 80 and 280 for
ferrite and pearlite, respectively, and that volume fractions may
may be approximated by mass fractions.

Solution

This problem asks that we determine the approximate Brinell hardness of a 99.8 wt% Fe-0.2 wt% C alloy,
using a relationship similar
similar to Equation 10.24. First, we com
compute
pute the mass fract
fractions
ions of pearlite and proeutectoid
ferrite using Equations 10.20 and 10.21, as

C0′ − 0.022 0.20 − 0.022

Wp = = = 0.241
0.74 0.74

0.76 − C0′ 0.76 − 0.20

Wα' = = = 0.757
0.74 0.74

Now, we compute the Brinell hardness of the alloy using a modified

modified form of the Equation as

HBalloy = HBα’Wα’ + HBpWp

= (80)(0.757) + (280)(0.241) = 128

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 The Influence of Other Alloying Elements

10.37 A steel alloy is

is known to contain 93.65 w
wt%
t% Fe, 6.0 wt%
wt% Mn, and 0.35 wt% C.
(a) What is the approximate eutectoid temperature of this alloy?
(b) What is the proeutectoid phase when this alloy is cooled to a temperature just below the eutectoid?

(c) Compute the relative

relative amounts of the proeutectoid phase and pear
pearlite.
lite. Assume that there are no
alterations in the positions of other phase boundaries with the addition of Mn.

Solution

(a) From Figure 10.38, the eutectoi

eutectoid
d temperature for 6.0 wt% Mn is approximately 700°C.
approximately
(b) From Figure
Figure 10.39, the eutectoid
eutectoid composit
composition
ion is approximately 0.44 wt% C. Since the
the carbon
concentration in the alloy (0.35 wt%) is less than the eutectoid (0.44 wt% C), the proeutectoid phase is ferrite.
(c) Assume that the α–(α + Fe3C) phase boundary is at a negl
negligible
igible carbon concentr
concentration.
ation. Modifying

Equation 10.21 leads to

Wα' = 0.44 − C0′ = 0.44 − 0.35 = 0.20

0.44 − 0 0.44

Likewise, using a modified Equation 10.20

C0′− 0 0.35
Wp = = = 0.80
0.44 − 0 0.44

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