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Answers Sheet (II) - Merged
Answers Sheet (II) - Merged
Answers Sheet (II) - Merged
4.1 Describe and illustrate the solidification process of a pure metal in terms of the nucleation
and growth of crystals.
In general, the solidification of a pure metal involves: the formation of stable nuclei in
the liquid melt; the growth of these nuclei into stable nuclei in the liquid melt; and the
formation of a solidified structure containing grains formed from the crystals. These
three stages are illustrated below.
Crystals
Nuclei Grains
4.2 Define the homogeneous nucleation process for the solidification of a pure metal.
4.3 In the solidification of a pure metal, what are the two energies involved in the
transformation? Write the equation for the total free-energy change involved in the
transformation of liquid to produce a strain-free solid nucleus by homogeneous
nucleation. Also illustrate graphically the energy changes associated with formation of a
nucleus during solidification.
An embryo refers to a solidified cluster of atoms which is unstable and can thus
redissolve. A nucleus is a comparatively larger stable cluster which can grow into a
crystal. The dimension defining the boundary between an embryo and a nucleus is the
critical radius.
4.5 During solidification, how does the degree of undercooling affect the critical nucleus
size? Assume homogeneous nucleation.
In general, the greater the degree of undercooling of a liquid melt, the smaller the critical
radius of the nuclei formed.
4.6 Distinguish between homogeneous and heterogeneous nucleation for the solidification of
a pure metal.
In homogeneous nucleation of a liquid metal, the nuclei are formed from atoms of the
metal solidifying. In heterogeneous nucleation, impurity atoms or container surfaces act
as nucleating agents.
4.7 Calculate the size (radius) of the critically sized nucleus for pure platinum when
homogeneous nucleation takes place.
The critical radius of nucleus is calculated as,
−2γ Tm
r* =
∆H f ∆T
where γ = 240 × 10−7 J/cm 2 , ∆H f = −2160 J/cm3 , Tm = 2045 K
and the undercooling ∆T = 0.2Tm = 0.2(2045 K) = 409 K. Substituting,
4.8 Calculate the number of atoms in a critically sized nucleus for the homogeneous
nucleation of pure platinum.
Substituting,
4.9 Calculate the size (radius) of the critical nucleus for pure iron when nucleation takes
place homogeneously.
4.10 Calculate the number of atoms in a critically sized nucleus for the homogeneous
nucleation of pure iron.
4 4
Vol. of critical-sized nucleus = π r *3 = π (9.72 × 10−8 cm)3 = 3.85 ×10−21 cm3
3 3
Vol. of unit cell of Pt = a = (0.28664 × 10−9 m)3 = 2.355 ×10−29 m3 = 2.355 × 10−23 cm3
3
4.11 Describe the grain structure of a metal ingot that was produced by slow-cooling the metal
in a stationary open mold.
In general, equiaxed grains are formed adjacent to the cold mold wall where rapid
4.12 Distinguish between equiaxed and columnar grains in a solidified metal structure.
Equiaxed grain dimensions are approximately equal in all directions whereas columnar
grains are elongated in a particular direction.
4.13 How can the grain size of a cast ingot be refined? How is grain refining accomplished
industrially for aluminum alloy ingots?
The grain size of a cast ingot can be refined by: solidifying the metal at a rapid rate; and
adding grain refining agents (heterogeneous nucleating agents). Grain refining of
aluminum ingots is accomplished through chill casting and by adding grain refining
agents such as titanium and/or boron.
Single crystals can be produced by introducing a single crystal as a seed crystal. The
seed continuously rotates as it is slowly lowered and then withdrawn from the melt.
4.15 How are large silicon single crystals for the semiconductor industry produced?
Large single crystals of silicon are produced using a pure silicon seed crystal with a pure
silicon melt (Czochralski process).
A metal alloy is a mixture of two or more metals or of a metal (metals) and a non-metal
(nonmetals). A solid solution is a type of alloy which is solid and consists of two or more
elements atomically dispersed in a single phase structure.
4.17 Distinguish between a substitutional solid solution and an interstitial solid solution.
A substitutional solid solution is one in which the solute atoms of the elements replace
those of the solvent atoms in the crystal lattice. An interstitial solid solution is one in
which the solute atoms of the elements are positioned in the interstitial spaces between
the solvent atoms of the crystal lattice.
4.18 What are the conditions that are favorable for extensive solid solubility of one element in
another?
4.19 Using the data in the following table, predict the relative degree of solid solubility of the
following elements in aluminum:
(a) copper (c) magnesium (e) silicon
(b) manganese (d) zinc
Use the scale very high, 70–100%; high, 30–70%; moderate, 10–30%;low, 1–10%; and
very low, < 1%.
(a) low (b) very low (c) moderate (d) high (e) low
4.20 Using the data in the following table, predict the relative degree of atomic solid solubility
of the following elements in iron:
(a) nickel (c) molybdenum (e) manganese
(b) chromium (d) titanium
Use the scale very high, 70–100%; high, 30–70%; moderate, 10–30%;low, 1–10%; and
very low, < 1%.
(a) high (b) very high (c) moderate (d) low (e) moderate
4.22 Describe and illustrate the following types of point imperfections that can be present in
metal lattices: (a) vacancy, (b) divacancy, and (c) interstitialcy.
Vacancy
Interstitialcy
4.23 Describe and illustrate the following imperfections that can exist in crystal lattices:
(a) Frenkel imperfection and (b) Schottky imperfection.
4.24 Describe and illustrate the edge– and screw–type dislocations. What type of strain fields
surround both types of dislocations?
An edge dislocation is a line imperfection caused by an extra half plane of atoms between
two normal planes of atoms. Whereas a screw dislocation is a line imperfection created
by applying upward and downward shear stress to regions of a perfect crystal separated
by a common plane.
The strain fields associated with the edge and screw dislocations are shown below:
Grain boundaries are surface imperfections that separate grains of different orientations.
The grain boundary, a narrow region between two grains, is approximately two to five
atomic diameters in width and contains mismatched atoms from adjacent grains. Grain
boundaries are favorable sites for the nucleation and growth of precipitates because the
irregular atom arrangement at grain boundaries provides lower atomic packing and high
energy. Atoms are thus able to diffuse more rapidly to form precipitates.
4.26 Why are grain boundaries easily observed in the optical microscope?
Grain boundaries can be easily observed under an optical microscope because they etch
more rapidly than grains. Chemical etching thus produces tiny grooves along grain
boundaries which appear as dark lines under an optical microscope because they reflect
light less intensely.
4.27 How is the grain size of polycrystalline materials measured by the ASTM method?
In the ASTM method of measuring grain size of polycrystalline materials, the grain size
number, n, is defined by the equation N = 2n −1 , where N is the number of grains per
square inch, measured on a polished and etched surface at a magnification of 100x.
4.28 If there are 600 grains per square inch on a photomicrograph of a metal at 100x, what is
its ASTM grain-size number?
N = 600 = 2n −1
ln 600 = ( n − 1)(ln 2)
6.397 = (n − 1)(0.693)
n = 9.23 + 1 = 10.23
N = 1600 = 2n−1
ln1600 = (n − 1)(ln 2)
7.378 = (n − 1)(0.693)
n = 10.64 + 1 = 11.64
4.30 Determine, by counting, the ASTM grain-size number of the low–carbon sheet steel
shown in Fig. P4.30. This micrograph is at 100x.
N = 40 = 2n−1
ln 40 = (n − 1)(ln 2)
3.689 = (n − 1)(0.693)
n = 5.3 + 1 = 6.3
4.31 Determine the ASTM grain-size number of the type 430 stainless steel micrograph shown
in Fig. P4.31.This micrograph is at 200x.
2002
No. of grains at 100 × = (100)
100 2
= 400 grains/in 2
N = 400 = 2n −1
ln 400 = (n − 1)(ln 2)
5.99 = (n − 1)(0.693)
n = 8.64 + 1 = 9.64
4.32 What is a thermally activated process? What is the activation energy for such a process?
A thermally active process is one which requires a definite amount of thermal energy to
overcome an activation energy barrier and enter the reactive state.
4.33 Write an equation for the number of vacancies present in a metal at equilibrium at a
particular temperature and define each of the terms. Give the units for each term and use
electron volts for the activation energy.
4.34 (a) Calculate the equilibrium concentration of vacancies per cubic meter in pure copper
at 850ºC. Assume that the energy of formation of a vacancy in pure copper is 1.00 eV.
(b) What is the vacancy fraction at 800ºC?
nυ −1.00 eV −10.81
= exp -5 =e = 2.02×10-5 vacancies/atom
N (8.62 ×10 eV/K)(1073 K)
4.35 (a) Calculate the equilibrium concentration of vacancies per cubic meter in pure silver at
750ºC. Assume that the energy of formation of a vacancy in pure silver is 1.10 eV. (b)
What is the vacancy fraction at 700ºC?
nυ −1.10 eV −13.12
= exp -5 =e = 2.01×10-6 vacancies/atom
N (8.62 × 10 eV/K)(973 K)
4.36 Write the Arrhenius rate equation in the (a) exponential and (b) common logarithmic
forms.
4.37 Draw a typical Arrhenius plot of log10 of the reaction rate versus reciprocal absolute
temperature, and indicate the slope of the plot.
A typical Arrhenius plot of the logarithmic reaction rate is shown below for the SI
absolute Kelvin temperature scale. The relationship between the log10 of the reaction rate
and the inverse absolute temperature is linear with a slope of –Q/(2.303R).
.
Intercept = log10 (const.)
Q
log10 of reaction rate
Slope = −
2.303R
∆ (log10 rate)
=
∆ (1/T )
T, K
1
, K -1
T
4.39 Write the equation for Fick’s first law of diffusion, and define each of the terms in SI
units.
4.40 What factors affect the diffusion rate in solid metal crystals?
4.41 Write the equation for Fick’s second law of diffusion in solids and define each of the
terms.
Fick’s second law of diffusion in solids, written for the x-direction, is:
dC x d dC x
= D
dt dx dx
dC x
where = rate of change of the concentration of the diffusing species in the x-direction;
dt
dC x
= concentration gradient of the diffusing species in the x-direction;
dx
D = diffusion coefficient of the diffusing species.
4.42 Write the equation for the solution to Fick’s second law for the diffusion of a gas into the
surface of a solid metal crystal lattice.
4.43 Describe the gas-carburizing process for steel parts. Why is the carburization of steel
parts carried out?
In the gas carburizing process for steel parts, the parts are placed in a furnace in contact
with a gas rich in CO at about 927ºC. The carbon from the gas diffuses into the surface
of the steel part and increases the carbon content of the outer surface region of the part.
The higher carbon concentration at the surface makes the steel harder in this region. A
steel part can thus be produced with a hard outer layer and a tough low carbon steel inner
core. This duplex structure is important, for example, for many types of gears.
4.44 Consider the gas carburizing of a gear of 1018 steel (0.18 wt %) at 927ºC (1700ºF).
Calculate the time necessary to increase the carbon content to 0.35 wt % at 0.40 mm
below the surface of the gear. Assume the carbon content at the surface to be 1.15 wt %
and that the nominal carbon content of the steel gear before carburizing is 0.18 wt %. D
(C in λ iron) at 927ºC = 1.28 × 10 –11 m2/s.
The time required for this diffusion process is calculated using Fick’s second law,
Cs − C x x
= erf
Cs − Co 2 Dt
erf z z
Thus,
55.90
0.8209 0.95 z= = 0.959
0.8247 x t
0.8427 1.0 t = 3397.7 s = 56.6 min.
4.45 The surface of a steel gear made of 1022 steel (0.22 wt % C) is to be gas-carburized at
927ºC (1700ºF). Calculate the time necessary to increase the carbon content to 0.30 wt %
at 0.030 in. below the surface of the gear. Assume the carbon content of the surface to be
1.20 wt %. D (C in λ iron) at 927ºC = 1.28 × 10 –11 m2/s.
Given: Cs = 1.20% Co = 0.22% C x = 0.30%
ft -4 −11 2
x = 0.03 in.(0.3048 m/ft) = 7.62 ×10 m D927, C = 1.28 × 10 m / s
12 in.
erf z z
Thus,
2 2
106.49 106.49
0.9103 1.2 t= = = 7, 446.6 s = 124 min.
0.9184 x z 1.234
0.9340 1.3
1.15 − C x
= erf (0.89798)
0.95
0.7707 0.85
x 0.89798 Substituting,
0.7970 0.90 1.15 − C x
= 0.7959 C x = 0.394 wt %
0.95
erf z z Thus,
2 2
139.75 139.75
0.8209 0.95 t= =
z 0.978
0.8333 x
0.8427 1.0
t = 20, 400 s = 340 min. = 5.67 h
1.25 − C x
= erf (0.7823)
1.05
erf z z
Thus, 0.7312 = erf (0.7823)
0.7112 0.75
Substituting,
x 0.7823
0.7421 0.80 1.25 − C x
= 0.7312 C x = 0.48 wt %
1.05
Cs − C x 1.20 − 0.40 x
= = erf
C s −Co 1.20 − 0.18 2 (1.28 × 10-11 m 2 / s)(27,000 s)
4.51 If boron is diffused into a thick slice of silicon with no previous boron in it at a
temperature of 1100ºC for 5 h, what is the depth below the surface at which the
concentration is 1017 atoms/cm3 if the surface concentration is 1018 atoms/cm3?
D = 4 × 10 –13 cm2/s for boron diffusing in silicon at 1100ºC.
x
0.90 = erf −4
= erf z
1.697 × 10
Cs − C x 1018 − 1016 x
= = erf
C s −Co 1018 − 0 2 (2.0 × 10-12 cm 2 / s)(2.16 × 104 s)
x
0.99 = erf −4
= erf z
4.157 × 10
§ 91.287 ·
0.999 = erf ¨ ¸ = erf z
© t ¹
erf z z Thus,
2 2
ª 91.287 º ª 91.287 º
0.9981 2.2 t=« » =«
¬ z ¼ ¬ 2.35 »¼
0.9990 x
0.9993 2.4
t = 1508 s = 25.1 min.
4.54 If the diffusivity in Prob. 4.53 had been 1.5 × 10 –13 cm2/s, at what depth in micrometers
would the phosphorus concentration be 1 × 10 15 atoms/cm3?
Cs − C x
Since = 0.999, erf z is still 2.35. Thus, for the same diffusion period,
C s −Co
ª x º
z=« » = 2.35, x = 7.07 ×10−5 cm = 0.707 µm
«¬ 2 (1.5 ×10-13 cm 2 / s)(1509 s) »¼
4.55 Arsenic is diffused into a thick slice of silicon with no previous arsenic in it at 1100ºC. If
the surface concentration of the arsenic is 5 × 10 18 atoms/cm3, and its concentration at
1.2 µm below the silicon surface is 1.5 × 10 16 atoms/cm3, how long must the diffusion
time be? (D = 3.0 × 10 –14 cm2/s for As diffusing in Si at 1100ºC.)
§ 346.4 ·
0.9970 = erf ¨ ¸ = erf z
© t ¹
2 2
ª 346.4 º ª 346.4 º
t=« » =« = 26, 700 s = 7.42 h
¬ z ¼ ¬ 2.12 »¼
4.56 Calculate the diffusivity D in square meters per second for the diffusion of nickel in FCC
iron at 1100ºC. Use values of D 0 = 7.7 × 10 –5 m2/s; Q = 280 kJ/mol;
R = 8.314 J/ (mol· K).
° ª -280,000 J/mol º ½°
D = Do e −Q / RT = (7.7 × 10−5 m 2 / s) ®exp « »¾
¯° ¬ [8.314 J/(mol ⋅ K)] (1373 K) ¼ ¿°
= (7.7 ×10−5 m 2 /s)(e-24.53 )
= 1.71×10-15 m 2 /s
4.57 Calculate the diffusivity in m2/s of carbon in HCP titanium at 700ºC. Use
D 0 = 5.10 × 10 – 4 m2/s; Q = 182 kJ/mol; R = 8.314 J/ (mol· K).
° ª -182,000 J/mol º ½°
D = Do e −Q / RT = (5.10 × 10−4 m 2 /s) ®exp « »¾
°¯ ¬ [8.314 J/(mol ⋅ K) ] (973 K) ¼ °¿
= (5.10 ×10−4 m 2 /s)(e-22.49 )
= 8.64×10-14 m 2 /s
4.58 Calculate the diffusivity in m2/s for the diffusion of zinc in copper at 350ºC. Use D 0 =
3.4 × 10 –5 m2/s; Q = 191 kJ/mol.
4.59 The diffusivity of manganese atoms in the FCC iron lattice is 1.5 × 10 –14 m2/s at 1300ºC
and 1.5 × 10 –15 m2/s at 400ºC. Calculate the activation energy in kJ/mol for this case in
this temperature range. Data: R = 8.314 J/(mol·K).
The activation energy may be calculated using the Arrhenius type equation,
1.5 × 10−14 m 2 /s ª −Q § 1 1 ·º
−15 2
= exp « ¨ − ¸»
1.5 × 10 m /s ¬ 8.314 J/(mol ⋅ K) © 1573 K 673 K ¹ ¼
10 = exp ¬ª (1.0226 × 10−4 )Q ¼º
4.60 The diffusivity of copper atoms in the aluminum lattice is 7.5 × 10 –13 m2/s at 600ºC and
2.5 × 10 –15 m2/s at 400ºC. Calculate the activation energy for this case in this
temperature range. [R = 8.314 J/(mol·K).]
The activation energy associated with copper diffusing into aluminum for this
temperature range is,
D600, C ª −Q § 1 1 · º
= exp « ¨ − ¸»
D400, C ¬ R © T2 T1 ¹ ¼
4.61 The diffusivity of iron atoms in the BCC iron lattice is 4.5 × 10 –23 m2/s at 400ºC and
5.9 × 10 –16 m2/s at 800ºC. Calculate the activation energy in kJ/mol for this case in this
temperature range. [R = 8.314 J/(mol·K).]
The activation energy associated with iron diffusing into BCC iron for this temperature
range is,
D800 C −Q 1 1
= exp −
D400 C R T2 T1
5.9 × 10−16 m 2 /s −Q 1 1
= exp −
4.5 ×10−23 m 2 /s 8.314 J/(mol ⋅ K) 1073 K 673 K
13,111,111.1 = exp (6.662 × 10−5 )Q
ln(13,111,111.1) = (6.662 × 10−5 )Q
Q = 246, 007 J/mol = 246 kJ/mol
8.2 In the pure water pressure-temperature equilibrium phase diagram (Fig. 8.1) what phases
are in equilibrium for the following conditions:
(a) Along the freezing line
(b) Along the vaporization line
(c) At the triple point
(a) Along the freezing line, liquid and solid phases are in equilibrium.
(b) Along the vaporization line, liquid and vapor phases exist in equilibrium.
(c) At the triple point, all three phase – vapor, liquid and solid – coexist.
8.3 How many triple points are there in the pure iron pressure-temperature equilibrium phase
diagram of Fig. 8.2? What phases are in equilibrium at each of the triple points?
Three triple points can be identified having the following phases in equilibrium:
8.4 Write the equation for Gibbs phase rule and define each of the terms.
P + F = C +2
8.5 Refer to the pressure-temperature equilibrium phase diagram for pure water (Fig. 8.1) and
answer the following:
(a) How many degrees of freedom are there at the triple point?
(b) How many degrees of freedom are there along the freezing line?
The binary isomorphous alloy system is a two-component system in which the two
elements are completely soluble in each other in the liquid and solid states and form a
single type of crystal structure for all compositions.
8.7 What are the four Hum-Rothery rules for the solid solubility of one element in another?
The four Hum-Rothery rules for the solid solubility of one element in another are:
1. The crystal structure of each element of the solid solution must be the same.
2. The size of the atoms of each of the two elements must not differ by more
than fifteen percent.
3. The elements should not form compounds with each other; there should be no
appreciable difference in the electronegativities of the two elements.
4. The elements should have the same electron valence.
8.8 A number of elements along with their crystal structures and atomic radii are listed in the
following table. Which pairs might be expected to have complete solid solubility in each
other?
Pairs of these elements which may be expected to have complete solid solubility in each
other are:
8.9 Derive the lever rule for the amount in weight percent of each phase in two-phase regions
of a binary phase diagram. Use a phase diagram in which two elements are completely
soluble in each other.
Xl + Xs =1
Considering the weight balance of B in the alloy as a whole and the sum of B in the two
phases, we arrive at:
w0 = X l wl + X s ws
w0 = (1 − X s ) wl + X s ws
wo − wl
Wt fraction of solid phase = X s =
ws − wl
(a)
(i) The phases present are the liquid and solid (L + α).
(ii) The chemical composition of liquid is wl = 62 wt % Ni while that of the
solid is ws = 74 wt % Ni.
(iii) The weight percent of solid and liquid are:
74 − 70
Wt % of liquid phase = × 100% = 33.3%
74 − 62
70 − 62
Wt % of solid phase = ×100% = 66.67%
74 − 62
Solid α
phase
100% Liquid
Liquid
phase L
1350ºC 1500ºC
8.11 Describe how the liquidus and solidus of a binary isomorphous phase diagram can be
determined experimentally.
The liquidus and solidus of a binary isomorphous phase diagrams can be determined
experimentally by measuring cooling rate for several specific alloy compositions and
plotting the corresponding liquid-solid curves. The phase diagram can then be
constructed by plotting the liquidus and solidus temperatures versus composition of the
alloys.
A cored structure is produced in a 70% Cu-30% Ni alloy when the alloy is cooled
rapidly; without sufficient time for complete solid-state diffusion, concentration gradients
remain in the alloy structure.
8.13 How can the cored structure in a 70% Cu-30% Ni alloy be eliminated by heat treatment?
The cored structure can be eliminated in ingots and castings by heat treating at elevated
temperatures. This homogenization process accelerates the required solid-state diffusion
and thus produces a homogeneous structure in the alloy.
8.14 Explain what is meant by the term liquation. How can a liquated structure be produced in
an alloy? How can it be avoided?
8.15 Consider the binary eutectic copper-silver phase diagram in Fig. 8.31. Make phase
analyses of an 88 wt % Ag-12 wt % Cu alloy at the temperatures (a) 1000ºC, (b) 800ºC,
(c) 780o C + ∆T , (d) 780o C − ∆T. In the phase analysis, include:
(i) The phases present
(ii) The chemical compositions of the phases
(iii) The amounts of each phase
(iv) Sketch the microstructure by using 2 cm diameter circular fields.
(a) At 1000ºC:
(b) At 800ºC,
93 − 88
Wt % liquid phase = ×100% = 33.3%
93 − 78
88 − 78
Wt % beta phase = × 100% = 66.6%
93 − 78
(c) At 780o C + ∆T ,
91.2 − 88
Wt % liquid phase = × 100% = 16.6%
91.2 − 71.9
88 − 71.9
Wt % beta phase = × 100% = 83.4%
91.2 − 71.9
91.2 − 88
Wt % alpha phase = × 100% = 3.84%
91.2 − 7.9
88 − 7.9
Wt % beta phase = × 100% = 96.16%
91.2 − 7.9
8.16 If 500g of a 40 wt % Ag-60 wt % Cu alloy is slowly cooled from 1000ºC to just below
780ºC (see Fig. 8.31):
(a) How many grams of liquid and proeutectic alpha are present at 850ºC?
(b) How many grams of liquid and proeutectic alpha are present at 780o C + ∆T ?
(c) How many grams of alpha are present in the eutectic structure at 780o C − ∆T?
(d) How many grams of beta are present in the eutectic structure at 780o C − ∆T?
(a) At 850ºC,
40 − 7.9
Wt % liquid = × 100% = 72.8%
52 − 7.9
40 − 7.9
Wt % liquid = × 100% = 50.2%
71.9 − 7.9
71.9 − 40
Wt % proeutectic α = × 100% = 49.8%
71.9 − 7.9
Weight of liquid phase = 500 g × 0.502 = 251 g
Weight of proeutectic α = 500 g × 0.498 = 249 g
(c) In the eutectic structure at 780o C − ∆T, the number of grams of α present is,
91.2 − 40
Wt % total α = × 100% = 61.5%
91.2 − 7.9
Weight of total α = 500 g × 0.615 = 307.5 g
(d) In the eutectic structure at 780o C − ∆T, the number of grams of β present is,
40 − 7.9
Wt % total β = × 100% = 38.5%
91.2 − 7.9
Weight of β = 500 g × 0.385 = 192.5 g
Since the alloy contains 60 wt % proeutectic β, the wt % Sn must lie between 61.9 wt %
and 97.5 wt %:
x − 61.9
% proeutectic β = = 0.60
97.5 − 61.9
x = 0.6(35.6) + 61.9 = 83.3%
8.18 A Pb-Sn alloy (Fig. 8.11) contains 40 wt % β and 60 wt % α at 50ºC. What is the average
composition of Pb and Sn in this alloy?
100.0 − x
% α= = 0.60, x = 100 − 0.6(98.0) = 41.2%
100.0 − 2.0
8.19 An alloy of 30 wt % Pb and 70 wt % Sn is slowly cooled from 250ºC to 27ºC (see Fig.
8.11).
(a) Is this alloy hypoeutectic or hypereutectic?
(b) What is the composition of the first solid to form?
(c) What are the amounts and composition of each phase that is present at 183º C + ∆T ?
(d) What is the amount and composition of each phase that is present at 183º C − ∆T ?
(e) What are the amounts of each phase present at room temperature?
(a) This alloy is hypereutectoid; the composition lies to the right of the eutectic point.
(b) The first solid to form is solid solution β containing approximately 98 % Sn.
(c) At 183º C + ∆T , the compositions of the phases present are 61.9% Sn in liquid phase
and 19.2% Sn in beta phase. The amounts of the respective phases present are:
97.5 − 70
Wt % liquid = × 100% = 77.2%
97.5 − 61.9
70 − 61.9
Wt % beta = × 100% = 22.8%
97.5 − 61.9
(d) At 183º C − ∆T , the compositions of the phases present are 19.2 % Sn in α phase and
97.5 % Sn in β phase. The amounts of the respective phases present are:
97.5 − 70
Wt % total α = × 100% = 35.1%
97.5 − 19.2
70 − 19.2
Wt % total beta = × 100% = 64.8%
97.5 − 19.2
(e) As the alloy is cooled below the eutectic temperature, the tin content in the alpha
phase and the lead content in the beta phase are further reduced. However, at room
temperature (20ºC), equilibrium is not achieved because the diffusion rate is so slow.
Referring to Fig. 8.11, if the solvus line is extrapolated to 20ºC, the approximate
composition of alpha and beta are 2.0% and 100.0 %, respectively. Thus,
8.20 Consider the binary peritectic iridium-osmium phase diagram of Fig. 8.32. Make phase
analyses of a 70 wt % Ir-30 wt % Os at the temperatures (a) 2600ºC (b) 2665o C + ∆T ,
and (c) 2665o C − ∆T . In the phase analyses include:
(i.) The phases present
(ii.) The chemical compositions of the phases
(iii.) The amounts of each phase
(iv.) Sketch the microstructure by using 2 cm diameter circular fields.
(a) At 2600ºC,
(i) Phases Present: Liquid and alpha phases
(ii) Compositions of Phases: 16% Os in liquid phase; 38% Os in alpha phase
(iii) Amounts of phases:
Solid α
30 − 16
Wt % alpha = × 100% = 63.6% phase
38 − 16
38 − 30 Liquid
Wt % liquid = × 100% = 36.4% phase L
38 − 16
(a) At 2600ºC,
(i) Phases Present: Alpha and beta phases
(ii) Compositions of Phases: 43% Os in alpha phase; 61.5% Os in beta phase
(iii) Amounts of phases:
Solid α
61.5 − 60
Wt % alpha = × 100% = 8.1% phase
61.5 − 43
60 − 43 Beta
Wt % beta = × 100% = 91.9% phase
61.5 − 43
(b) At 2665o C + ∆T ,
(i) Phases Present: Liquid and beta phases
(ii) Compositions of Phases: 23% Os in alpha phase; 61.5% Os in beta phase
(iii) Amounts of phases:
Solid β
61.5 − 60
Wt % liquid phase = × 100% = 3.9% phase
61.5 − 23
60 − 23 Liquid
Wt % beta phase = × 100% = 96.1% phase
61.5 − 23
8.22 Describe the mechanism that produces the phenomenon of surrounding in a peritectic
alloy which is rapidly solidified through the peritectic reaction.
8.23 Can coring and surrounding occur in a peritectic-type alloy which is rapidly solidified?
Explain.
In a rapidly solidified peritectic alloy, coring can occur during the formation of the
primary alpha phase and subsequently, the cored alpha phase can be surrounded by the
beta phase during the peritectic reaction.
8.24 Consider an Fe-4.2 wt % Ni alloy (Fig. 8.16) that is slowly cooled from 1550 to 1450ºC.
What weight percent of the alloy solidifies by the peritectic reaction?
Referring to Fig. 8.16 on the following page, during the peritectic reaction, liquid and δ
phases react to form solid γ:
4.2 − 4.0
Wt % γ = × 100% = 66.7%
4.3 − 4.0
8.25 Consider an Fe-5.0 wt % Ni alloy (Fig. 8.16) that is slowly cooled from 1550 to 1450ºC.
What weight percent of the alloy solidifies by the peritectic reaction?
5.4 − 5.0
Wt % γ = × 100% = 36.4%
5.4 − 4.3
8.26 Determine the weight percent and composition in weight percent of each phase present in
an Fe-4.2 % Ni alloy (Fig. 8.16) at 1517 o C + ∆T .
Just above the eutectic temperature, the alloy composition is: 4.0 wt % Ni in the δ phase
and 5.4 wt % Ni in the liquid phase. The weight percentages of these phases are:
4.2 − 4.0
Wt % liquid = × 100% = 14.3%
5.4 − 4.0
5.4 − 4.2
Wt % δ = × 100% = 85.7%
5.4 − 4.0
4.3 − x
Wt % δ = = 0.40 x = 4.18%
4.3 − 4.0
8.28 What is a monotectic invariant reaction? How is the monotectic reaction in the copper-
lead system important industrially?
A monotectic invariant reaction is one in which a liquid phase reacts isothermally to form
a solid phase and a new liquid phase. The monotectic reaction is important industrially to
the copper-lead system because it can produce a nearly pure lead phase in copper-zinc
brasses which improves the machining properties of the alloys; the lead sufficiently
reduces the ductility of the alloys to cause machined chips to naturally break away from
the workpiece.
8.29 In the copper-lead (Cu-Pb) system (Fig. 8.23) for an alloy of Cu-10 wt % Pb, determine
the amounts and compositions of the phases present at (a) 1000ºC (b) 955o C + ∆T , (c)
955o C − ∆T , and (d) 200ºC.
(a) At 1000ºC,
Compositions of Phases: 100% Cu, 0% Pb in α phase;
81% Cu, 19% Pb in L1 phase
Amounts of Phases:
19 − 10 10 − 0
Wt % α = × 100% = 47.4% Wt % L1 = × 100% = 52.6%
19 − 0 19 − 0
(b) At 955o C + ∆T ,
Compositions of Phases: 100% Cu, 0% Pb in α phase;
64% Cu, 36% Pb in L1 phase
Amounts of Phases:
36 − 10 10 − 0
Wt % α = × 100% = 72.2% Wt % L1 = × 100% = 27.8%
36 − 0 36 − 0
(c) At 955o C − ∆T ,
Compositions of Phases: 100% Cu, 0% Pb in α phase;
13% Cu, 87% Pb in L2 phase
87 − 10 10 − 0
Wt % α = × 100% = 88.5% Wt % L2 = × 100% = 11.5%
87 − 0 87 − 0
(d) At 200ºC,
Compositions of Phases: 99.995% Cu, 0.005% Pb in α phase;
0.007% Cu, 99.993% Pb in β phase
Amounts of Phases:
99.99 − 10 10 − 0
Wt % α = × 100% = 90% Wt % β = ×100% = 10%
99.99 − 0 99.99 − 0
(a) At 955o C + ∆T ,
Amounts of Phases:
70 − 36 87 − 70
Wt % L2 = × 100% = 66.7% Wt % L1 = × 100% = 33.3%
87 − 36 87 − 36
(b) At 955o C − ∆T ,
Amounts of Phases:
87 − 70 70 − 0
Wt % α = × 100% = 19.5% Wt % L2 = × 100% = 80.5%
87 − 0 87 − 0
(c) At 200ºC,
99.99 − 70 70 − 0
Wt % α = × 100% = 30% Wt % β = × 100% = 70%
99.99 − 0 99.99 − 0
8.31 What is the average composition (weight percent) of a Cu-Pb alloy that contains 30 wt %
L1 and 70 wt % α at 955o C + ∆T ?
x−0
Wt % L1 = = 0.30 x = 10.8%
36 − 0
cooling
Eutectic Reaction: L → α +β
cooling
Eutectoid Reaction: α → β +γ
cooling
Peritectic Reaction: α + L → β
cooling
Peritectoid Reaction: α+β → γ
There are zero degrees of freedom at the invariant reaction points in binary phase
diagrams.
8.33 How are eutectic and eutectoid reactions similar? What is the significance of the –oid
suffix?
The eutectic and eutectoid reactions are similar in that they both involve the
decomposition of a single phase into two solid phases. The –oid suffix indicates that a
solid, rather than liquid, phase is decomposing.
8.34 Distinguish between (a) a terminal phase and (b) an intermediate phase.
A terminal solid solution phase occurs at the end of a phase diagram, bordering on pure
components. Whereas, an intermediate solid solution phase occurs within a composition
range inside the phase diagram and is separated from other phases in a binary diagram by
two-phase regions.
8.35 Distinguish between (a) an intermediate phase and (b) an intermediate compound.
Intermediate phases, which may occur in binary metal or ceramic phase diagrams,
represent a range of solid solution compositions. Conversely, an intermediate compound
has a fixed composition and definite stoichiometry at room temperature and is formed
between two metals or a metal and a nonmetal.
8.36 What is the difference between a congruently melting compound and an incongruently
melting one?
A congruently melting compound maintains its composition right up to its melting point.
Whereas an incongruently melting compound undergoes peritectic decomposition upon
heating; the solid compound decomposes into a liquid and another solid solution.
(a) The maximum solid solubility in weight percent of zinc in copper in the solid solution
α is 39%.
(b) The intermediate phases are β, γ, δ, and ∫.
(c) The three-phase invariant reactions are:
8.38 Consider the aluminum-nickel (Al-Ni) phase diagram of Fig. 8.33 on the following page.
For this phase diagram:
(a) Determine the coordinates of the composition and temperature of the invariant
reactions.
(b) Write the equations for the three-phase invariant reactions and name them.
(c) Label the two-phase regions in the phase diagram.
8.39 Consider the nickel-vanadium (Ni-V) phase diagram of Fig. 8.34. For this phase diagram
repeat questions (a), (b), and (c) of Prob. 8.38.
8.40 Consider the titanium-aluminum (Ti-Al) phase diagram of Fig. 8.35. For this phase
diagram, repeat questions (a), (b), and (c) of Prob. 8.38.
As indicated in the ternary diagram figure below, the composition of point y is 20% A,
30% B and 50% C.
30%
20%
50%