Chapter 4 Solidification, Crystalline Imperfections, and Diffusion in Solids

CHAPTER 4 SOLIDIFICATION, CRYSTALLINE IMPERFECTIONS, AND DIFFUSION IN SOLIDS
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.
Liquid
Nuclei
4.2
Grain Boundaries
Liquid
Crystals
Grains
Define the homogeneous nucleation process for the solidification of a pure metal.
In a homogeneous nucleation process, the liquid metal is sufficiently undercooled and
thus able to provide the atoms to form nuclei.
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.
GT = GV + Gs
3
= r 2 G + 4 r 2
4
= Volume free energy +
Surface free energy
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Retarding energy,
Gr*
Free Energy Change, G
The two energies involved in the

solidification of a pure metal are
surface free energy and volume free
energy. These energies contribute to
the total free energy, GT :
GT = GV + Gs
r*
Radius of particle, r
Driving energy, GV
4.3
Foundations of Materials Science and Engineering
54
4.4
In the solidification of a metal, what is the difference between an embryo and a nucleus?
What is the critical radius of a solidifying particle?
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,
r* =
2 Tm
H f T
where = 240 107 J/cm 2 , H f = 2160 J/cm3 , Tm = 2045 K

and the undercooling T = 0.2Tm = 0.2(2045 K) = 409 K. Substituting,
r* =
4.8
2(240 107 J/cm 2 )(2045 K)

= 1.11107 cm
3
(-2160 J/cm )(409 K)
Calculate the number of atoms in a critically sized nucleus for the homogeneous
nucleation of pure platinum.
The number of atoms in a critically sized nucleus is found as,
Volume of nucleus
Volume of nucleus
=
Volume per atom (Vol. of unit cell)(No. atoms per unit cell)
Using the critical radius result of Problem 4.7,
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55
4
4
Vol. of critical-sized nucleus = r *3 = (1.11 107 cm)3 = 5.73 1021 cm3
3
3
3
Vol. of unit cell of Pt = a = (0.32939 109 m)3 = 3.574 1029 m3 = 3.574 1023 cm3
Vol. per atom =
3.574 1023 cm3

= 8.935 1024 cm3 /atom
4 atoms/FCC unit cell
Substituting,
Volume of nucleus
5.73 10-21 cm3
=
= 641 atoms
Volume per atom 8.935 10-24 cm3 /atom
4.9
Calculate the size (radius) of the critical nucleus for pure iron when nucleation takes
place homogeneously.
For iron, = 204 107 J/cm 2 , H f = 2098 J/cm3 , Tm = 1808 K
The amount of undercooling is then T = 0.2Tm = 0.2(1808 K) = 361.6 K and
the critical radius becomes,
r* =
4.10
2 Tm
2(204 107 J/cm 2 )(1808 K)
=
= 9.7210-8 cm
3
H f T
( 2098 J/cm )(361.6 K)
Calculate the number of atoms in a critically sized nucleus for the homogeneous
nucleation of pure iron.
The relevant volumes, based on the solution of Problem 4.9, are:
4
4
Vol. of critical-sized nucleus = r *3 = (9.72 108 cm)3 = 3.85 1021 cm3
3
3
3
Vol. of unit cell of Pt = a = (0.28664 109 m)3 = 2.355 1029 m3 = 2.355 1023 cm3
2.355 1023 cm3
= 1.178 1023 cm3 /atom
Vol. per atom =
2 atoms/BCC unit cell
Thus, the number of atoms in a critically sized nucleus is:

Volume of nucleus
3.85 10-21 cm3
=
= 327 atoms
Volume per atom 1.178 10-23 cm3 /atom
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
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56
cooling occurs during solidification. Elongated columnar grains are formed in the metal
ingot interior, in the direction of thermal gradients, due to slow cooling of the metal in the
mold interior.
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.
4.14
What special techniques must used to produce single crystals?

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).
4.16
What is a metal alloy? What is a solid solution?

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?
Four conditions favor extensive solid solubility:
1. less than 15% difference between the atomic diameters of the elements forming
the solid solution;
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57
2. identical valence of the elements;

3. similar electronegativities;
4. common crystal structure of the elements.
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, 70100%; high, 3070%; moderate, 1030%;low, 110%; and
very low, < 1%.
Element
Aluminum
Copper
Manganese
Magnesium
Zinc
Silicon
(a) low
4.20
Atom Radius
(nm)
Crystal
Structure
Electronegativity
Valence
0.143
0.128
0.112
0.160
0.133
0.117
FCC
FCC
Cubic
HCP
HCP
Diamond Cubic
1.5
1.8
1.6
1.3
1.7
1.8
+3
+2
+2, +3, +6, +7
+2
+2
+4
(b) very low
(c) moderate
(d) high
(e) low
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, 70100%; high, 3070%; moderate, 1030%;low, 110%; and
very low, < 1%.
Element
Iron
Nickel
Chromium
Molybdenum
Titanium
Manganese
(a) high
Smith
Atom Radius
(nm)
Crystal
Structure
Electronegativity
Valence
0.124
0.125
0.125
0.136
0.147
0.112
BCC
FCC
BCC
BCC
HCP
Cubic
1.7
1.8
1.6
1.3
1.3
1.6
+2, +3
+2
+2, +3, +6
+3, +4, +6
+2, +3, +4
+2, +3, +6, +7
(b) very high
(c) moderate
(d) low
(e) moderate
58
4.21
Calculate the radius of the largest interstitial void in the BCC iron lattice. The atomic
radius of the iron atom in this lattice is 0.124 nm, and the largest interstitial voids occur at
the (, , 0); (, , 0); (, , 0); (, , 0), etc., type positions.
For BCC crystal structure,
a=
4 R 4(0.124 nm)
=
= 0.286 nm
3
3
Letting x = Fe atom radius + Interstitial void radius,
a
4
a
RFe
1 2 1 2 5 2
a + a = a
16
4
16
5
x=
a = 0.559a = (0.559)(0.286 nm) = 0.160 nm
16
Rvoid
x2 =
a
2
The interstitial void radius is thus,

Rvoid = x RFe = 0.160 nm 0.124 nm = 0.036 nm
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.
a) A vacancy, a point defect, is an atomic site which is missing an atom.
b) A divacancy is a defect in a crystal lattice where two atoms are missing from
adjoining atomic sites.
c) An interstitialcy is a point defect where an atom occupies an interstitial site between
surrounding atoms in normal sites.
Vacancy
Interstitialcy
4.23
Describe and illustrate the following imperfections that can exist in crystal lattices:
(a) Frenkel imperfection and (b) Schottky imperfection.
a) A Frenkel imperfection is a vacancy-interstitialcy pair which sometimes occurs in
ionic crystals.
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59
b) A Schottky imperfection is a cation-anion divacancy which sometimes occurs in

ionic crystals.
Frenkel Imperfection
4.24
Schottky Imperfection
Describe and illustrate the edge and screwtype 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.
Dislocation Line
Screw Dislocation
The strain fields associated with the edge and screw dislocations are shown below:
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60
4.25
Describe the structure of a grain boundary. Why are grain boundaries favorable sites for
the nucleation and growth of precipitates?
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
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61
4.29
If there are 400 grains per square inch on a photomicrograph of a ceramic material at
200x, what is its ASTM grain-size number?
N = 1600 = 2n1
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 lowcarbon sheet steel
shown in Fig. P4.30. This micrograph is at 100x.
Estimating 40 grains/in2 from the micrograph,
N = 40 = 2n1
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.
Estimating 100 grains/in2 from the micrograph,
2002
(100)
100 2
= 400 grains/in 2
No. of grains at 100 =
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.
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62
where
nv = NCe Ev / kT
nv = number of vacancies per cubic meter of metal
N = total number of atom sites per cubic meter of metal
Ev = activation energy to form a vacancy (eV)
T = absolute temperature (K)
k = Boltzmann's constant = 8.62 106 eV/K
C = constant
4.34
(a) Calculate the equilibrium concentration of vacancies per cubic meter in pure copper
at 850C. Assume that the energy of formation of a vacancy in pure copper is 1.00 eV.
(b) What is the vacancy fraction at 800C?
a) In general, the equilibrium number of vacancies is nv = NCe Ev / kT . For copper,
N o Cu
(6.02 1023 atoms/at. mass)(8.96 106 g/m3 )
=
= 8.49 1028 atoms/m3
N=
at. mass Cu
(63.54 g/at. mass)
Substituting and assuming Ev = 1.00 eV at 1123 K,

1.00 eV
n = (8.49 1028 atoms/m3 ) exp
-5
(8.62 10 eV/K)(1123 K)
= 2.77 10 24 vacancies/m 3
b) The vacancy fraction at 1073 K is,
10.81
n
1.00 eV
= exp
= 2.0210-5 vacancies/atom
=e
-5
N
(8.62 10 eV/K)(1073 K)
4.35
(a) Calculate the equilibrium concentration of vacancies per cubic meter in pure silver at
750C. Assume that the energy of formation of a vacancy in pure silver is 1.10 eV. (b)
What is the vacancy fraction at 700C?
a) The equilibrium number of vacancies is calculated as nv = NCe Ev / kT . Thus for
silver,
N o Cu
(6.02 1023 atoms/at. mass)(10.5 106 g/m3 )
N=
=
= 5.86 1028 atoms/m3
at. mass Cu
(107.870 g/at. mass)
Substituting and assuming Ev = 1.10 eV for vacancies formed at 1023 K,
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63

1.10 eV
n = (5.86 1028 atoms/m3 ) exp
-5
(8.62 10 eV/K)(1023 K)
= 2.24 1023 vacancies/m 3
b) The vacancy fraction at 973 K is,
13.12
n
1.10 eV
= exp
= 2.0110-6 vacancies/atom
=e
-5
N
(8.62
10
eV/K)(973
K)
4.36
Write the Arrhenius rate equation in the (a) exponential and (b) common logarithmic
forms.
a) Rate of reaction = CeQ / RT
b) log10 rate = log10 constant
4.37
Q
2.303RT
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.)
log10 of reaction rate
Q
2.303R
(log10 rate)
=
(1/T )
Slope =
T, K
1
, K -1
T
4.38
Describe the substitutional interstitial diffusion mechanisms in solid metals.
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64
During substitutional diffusion of atoms in a solid alloy crystal lattice, solute atoms move
into positions of solvent atoms in the matrix through a vacancy mechanism. In interstitial
diffusion, small solute atoms move between the interstices of the solvent lattice.
4.39
Write the equation for Ficks first law of diffusion, and define each of the terms in SI
units.
Ficks first law of diffusion is given by:
2
atoms m atoms 1

or in SI unit form, 2 =
3
m
m s s m
where J = flux or net flow of atoms;
D = proportionality constant called the diffusivity (atomic conductivity) or
diffusion coefficient;
dC
= concentration gradient.
dx
J = D
4.40
dC
dx
What factors affect the diffusion rate in solid metal crystals?

The diffusion rate in solid metal crystals is affected by five factors:
1.
2.
3.
4.
5.
4.41
Type of diffusion mechanism;

Temperature of diffusion;
Concentration of the diffusion species (concentration gradient);
Type of crystal structure;
Type of crystal imperfections present.
Write the equation for Ficks second law of diffusion in solids and define each of the
terms.
Ficks second law of diffusion in solids, written for the x-direction, is:
dC x d dC x
= D
dt
dx dx
where
4.42
dC x
= 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.
Write the equation for the solution to Ficks second law for the diffusion of a gas into the
surface of a solid metal crystal lattice.
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65
Ficks second law of diffusion, for the diffusion of a gas into the surface of a solid metal
crystal lattice is:
x
Cs C x
= erf
2 Dt
Cs Co
where Cs = surface concentration of element in gas diffusing into the surface;

Co = initial uniform concentration of element in solid;
C x = concentration of element at distance x from surface at time t ;
x = distance from surface;
D = diffusivity of diffusing solute element;
t = time.
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 927C. 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 927C (1700F).
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 iron) at 927C = 1.28 10 11 m2/s.
The time required for this diffusion process is calculated using Ficks second law,
x
Cs C x
= erf
2 Dt
Cs Co
where:
Cs = 1.15% Co = 0.18% C x = 0.35%

x = 0.40 mm = 4 10-4 m
Substituting
Smith
D927 C = 1.28 1011 m 2 / s
1.15 0.35
4 104 m
= erf
1.15 0.18
2 (1.28 10-11 m 2 / s) t
55.90
0.8247 = erf
= erf z
t
66
Interpolating from Table 4.5,
4.45
erf z
0.8209
0.8247
0.8427
0.95
x
1.0
0.8247 0.8209
x 0.95
=
0.8427 0.8209 1.0 0.95
x = 0.959
Thus,
55.90
= 0.959
t
t = 3397.7 s = 56.6 min.
z=
The surface of a steel gear made of 1022 steel (0.22 wt % C) is to be gas-carburized at

927C (1700F). 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 iron) at 927C = 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.
Cs C x 1.20 0.30
7.62 104 m
=
= erf
C s Co 1.20 0.22
2 (1.28 10-11 m 2 / s) t
106.49
0.9184 = erf
= erf z
t

erf z
0.9184 0.9103 x 1.2

=
0.9340 0.9103 1.3 1.2
Thus,
2
0.9103
0.9184
0.9340
4.46
1.2
x
1.3
x = 1.234
106.49
106.49
t=
=
z
1.234
= 7, 446.6 s = 124 min.
A gear made of 1020 steel (0.20 wt % C) is to be gas-carburized at 927C (1700F).

Calculate the carbon content at 0.90 mm below the surface of the gear after a 4.0-hour
carburizing time. Assume the carbon content at the surface of the gear is 1.00 wt %.
D (C in iron) at 927C = 1.28 10 11 m2/s.
Given: Cs = 1.00% Co = 0.20% C x = ? t = 4 h = 14,400 s
x = 0.09 mm = 9.0 10-4 m D927 C = 1.28 1011 m 2 / s
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67
Cs C x 1.00 C x
9.0 104 m
=
= erf
C s Co 1.00 0.20
2 (1.28 10-11 m 2 / s)(14,400 s)
1.25(1 C x ) = erf (1.0482)

erf z
1.0482 1.00
x 0.8427
=
1.10 1.00
0.8802 0.8427
x = 0.8608
Thus, 0.8608 = erf (1.0482)
0.8427
x
0.8802
4.47
1.00
1.0482
1.10
Substituting,
1.25(1 C x ) = 0.8608 C x = 0.311 wt %

Calculate the carbon content at 0.04 in. below the surface of the gear after a 7.0-hour
D (C in iron) at 927C = 1.28 10 11 m2/s.
Given: Cs = 1.15% Co = 0.20% C x = ? t = 7 h = 25,200 s
x = 0.040 in. = 1.02 10-3 m D927 C = 1.28 1011 m 2 / s
Cs C x 1.15 C x
1.02 103 m
=
= erf
C s Co 1.15 0.20
2 (1.28 10-11 m 2 / s)(25,200 s)
1.15 C x
= erf (0.89798)
0.95
Smith
erf z
0.7707
x
0.7970
0.85
0.89798
0.90
0.89798 0.85
x 0.7707
=
0.90 0.85
0.7970 0.7707
x = 0.7959
Thus, 0.7959 = erf (0.89798)

Substituting,
1.15 C x
= 0.7959 C x = 0.394 wt %
0.95
68
4.48
The surface of a steel gear made of 1018 steel (0.18 wt % C) is to be gas-carburized at

927C (1700F). Calculate the time necessary to increase the carbon content to 0.35 wt
% at 1.00 mm below the surface. Assume the carbon content of the surface of the gear is
1.20 wt %. D (C in iron) at 927C = 1.28 10 11 m2/s.
Given: Cs = 1.20% Co = 0.18% C x = 0.35%
x = 1.0 mm = 1.0 10-3 m D927 C = 1.28 1011 m 2 / s
Cs C x 1.20 0.35
1.00 103 m
=
= erf
C s Co 1.20 0.18
2 (1.28 10-11 m 2 / s) t
139.75
0.8333 = erf
= erf z
t

erf z
0.8333 0.8209
x 0.95
=
0.8427 0.8209 1.0 0.95
Thus,
2
0.8209
0.8333
0.8427
4.49
0.95
x
1.0
x = 0.978
139.75
139.75
=
t=
z
0.978
t = 20, 400 s = 340 min. = 5.67 h

Calculate the carbon content at 0.95 mm below the surface of the gear after an 8.0hour
D (C in iron) at 927C = 1.28 10 11 m2/s.
Given: Cs = 1.25% Co = 0.20% C x = ? t = 8 h = 28,800 s
x = 0.95 mm = 9.5 10-4 m D927 C = 1.28 1011 m 2 / s
Cs C x 1.25 C x
9.50 104 m
=
= erf
C s Co 1.25 0.20
2 (1.28 10-11 m 2 / s)(28,800 s)
1.25 C x
= erf (0.7823)
1.05
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69
4.50
erf z
0.7112
x
0.7421
0.75
0.7823
0.80
0.7823 0.75
x 0.7112
=
0.80 0.75
0.7421 0.7112
x = 0.7312
Thus, 0.7312 = erf (0.7823)

Substituting,
1.25 C x
= 0.7312 C x = 0.48 wt %
1.05
A gear made of 1018 steel (0.18 wt % C) is to be gas-carburized at 927C (1700F). If

the carburizing time is 7.5 h, at what depth in millimeters will the carbon content be 0.40
wt %? Assume the carbon content at the surface of the gear is 1.20 wt %. D (C in iron)
at 927C = 1.28 10 11 m2/s.
Given: Cs = 1.20% Co = 0.18% C x = 0.40%
t = 7.5 h = 27,000 s D927 C = 1.28 1011 m 2 / s
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)
0.7843 = erf (850.52 x) = erf z

4.51
erf z
0.7707
0.7843
0.7970
0.85
x1
0.90
0.7843 0.7707
x 0.85
= 1
0.7970 0.7707 0.90 0.85
x1 = 0.8759
Substituting,
z = 0.8759 = 850.52 x
x = 0.00103 m = 1.03 mm
If boron is diffused into a thick slice of silicon with no previous boron in it at a

temperature of 1100C 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 1100C.
Given: Cs = 1018 atoms/cm3 C x = 1017 atoms/cm3 Co = 0.0
t = 5.0 h = 1.8 104 s D1100 C = 4.0 1013 cm 2 / s
Smith
70
Cs C x 1018 1017
x
erf
=
=
C s Co
1018 0
2 (4.0 10-13 cm 2 / s)(1.80 104 s)
0.90 = erf
= erf z
4
1.697 10
erf z
0.9000 0.8802 x1 1.1

=
x1 = 1.166
0.9103 0.8802 1.2 1.1
z
Substituting,
4.52
x
0.8802
1.1
z = 1.166 =
0.9000
x
1.697 104
0.9103
1.2
x = 1.98 104 cm
If aluminum is diffused into a
thick slice of silicon with no previous aluminum in it at a temperature of 1100C for 6 h,
what is the depth below the surface at which the concentration is 1016 atoms/cm3 if the
surface concentration is 1018 atoms/cm3?
D = 2 10 12 cm2/s for aluminum diffusing in silicon at 1100C.

t = 6.0 h = 2.16 104 s D1100 C = 2.0 1012 cm 2 / s
Cs C x 1018 1016
x
erf
=
=
C s Co
1018 0
2 (2.0 10-12 cm 2 / s)(2.16 104 s)
0.99 = erf
= erf z
4
4.157 10
erf z
0.9900 0.9891 x1 1.8

=
0.9928 0.9891 1.9 1.8
x1 = 1.824
z
Substituting,
0.9891
0.9900
0.9928
Smith
1.8
x
1.9
x
4.157 104
x = 7.58 104 cm
z = 1.824 =
71
4.53
Phosphorus is diffused into a thick slice of silicon with no previous phosphorus in it at a

temperature of 1100C. If the surface concentration of the phosphorus is 1 10 18
atoms/cm3 and its concentration at 1 m is 1 10 15 atoms/cm3, how long must the
diffusion time be? D = 3.0 10 13 cm2/s for P diffusing in Si at 1100C.
x = 1.0 m = 1.0 10-4 cm D1100, C = 3.0 1013 cm 2 / s
Cs C x 1018 1015
104 cm
=
=
erf
C s Co
1018 0
2 (3.0 10-13 cm 2 / s) t
91.287
0.999 = erf
= erf z
t

erf z
0.9990 0.9981
x 2.2
=
0.9993 0.9981 2.4 2.2
Thus,
2
0.9981
0.9990
0.9993
4.54
2.2
x
2.4
91.287
91.287
=
t=
z
2.35
t = 1508 s = 25.1 min.
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?
Since
Cs C x
= 0.999, erf z is still 2.35. Thus, for the same diffusion period,
C s Co
x
= 2.35,
z=
2 (1.5 10-13 cm 2 / s)(1509 s)
4.55
x = 2.35
x = 7.07 105 cm = 0.707 m
Arsenic is diffused into a thick slice of silicon with no previous arsenic in it at 1100C. If
the surface concentration of the arsenic is 5 10 18 atoms/cm3, and its concentration at
1.2 m 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 1100C.)
Given: Cs = 5.0 1018 atoms/cm3 C x = 1.5 1016 atoms/cm3 Co = 0.0
x = 1.20 10-6 m = 1.20 10-4 cm
Smith
D1100, C = 3.0 1014 cm 2 / s
72
Cs C x 5.0 1018 1.5 1016

1.20 104 cm
=
=
erf
C s Co
5.0 1018 0
2 (3.0 10-14 cm 2 / s) t
346.4
0.9970 = erf
= erf z
t

0.9970 0.9953
x 2.0
=
0.9981 0.9953 2.2 2.0
2
x = 2.12 and,
346.4
346.4
t=
=
= 26, 700 s = 7.42 h
z
2.12
4.56
Calculate the diffusivity D in square meters per second for the diffusion of nickel in FCC
iron at 1100C. Use values of D 0 = 7.7 10 5 m2/s; Q = 280 kJ/mol;
R = 8.314 J/ (mol K).
The diffusivity of the nickel into FCC iron at 1373 K is:

-280,000 J/mol
D = Do e Q / RT = (7.7 105 m 2 / s) exp
[8.314 J/(mol K)] (1373 K)
= (7.7 105 m 2 /s)(e-24.53 )

= 1.7110-15 m 2 /s
4.57
Calculate the diffusivity in m2/s of carbon in HCP titanium at 700C. Use

D 0 = 5.10 10 4 m2/s; Q = 182 kJ/mol; R = 8.314 J/ (mol K).
The diffusivity of carbon into HCP titanium is:

-182,000 J/mol
D = Do e Q / RT = (5.10 104 m 2 /s) exp
[8.314 J/(mol K) ] (973 K)

= (5.10 104 m 2 /s)(e-22.49 )
= 8.6410-14 m 2 /s
4.58
Calculate the diffusivity in m2/s for the diffusion of zinc in copper at 350C. Use D 0 =
3.4 10 5 m2/s; Q = 191 kJ/mol.
The diffusivity of zinc into copper at 623 K is:
Smith
73

-191,000 J/mol
D = Do e Q / RT = (3.40 104 m 2 /s) exp
[8.314 J/(mol K) ] (623 K)
= (3.40 105 m 2 /s)(e-36.88 )

= 3.2910-21 m 2 /s
4.59
The diffusivity of manganese atoms in the FCC iron lattice is 1.5 10 14 m2/s at 1300C
and 1.5 10 15 m2/s at 400C. Calculate the activation energy in kJ/mol for this case in
this temperature range. Data: R = 8.314 J/(molK).
The activation energy may be calculated using the Arrhenius type equation,
D1300, C
D400, C
Q 1 1
exp(Q / RT2 )
= exp

R
exp(Q / RT1 )
T2 T1
where T1 = 400, C = 673 K and T2 = 1300, C = 1573 K. Substituting,
1.5 1014 m 2 /s
Q
1
1
= exp
2
15
1.5 10 m /s
8.314 J/(mol K) 1573 K 673 K
10 = exp (1.0226 104 )Q
ln(10) = (1.0226 10 4 )Q
Q = 22, 518 J/mol = 22.5 kJ/mol
4.60
The diffusivity of copper atoms in the aluminum lattice is 7.5 10 13 m2/s at 600C and
2.5 10 15 m2/s at 400C. Calculate the activation energy for this case in this
temperature range. [R = 8.314 J/(molK).]
The activation energy associated with copper diffusing into aluminum for this
temperature range is,
Q 1 1
D600, C
= exp

D400, C
R
T2 T1
where T1 = 400, C = 673 K and T2 = 600, C = 873 K. Substituting,
Smith
74

7.5 1013 m 2 /s
Q
1
1
= exp
15
2
2.5 10 m /s
8.314 J/(mol K) 873 K 673 K
300 = exp (4.094 105 )Q
ln(300) = (4.094 10 5 )Q
Q = 139, 320 J/mol = 139.3 kJ/mol
4.61
The diffusivity of iron atoms in the BCC iron lattice is 4.5 10 23 m2/s at 400C and
5.9 10 16 m2/s at 800C. Calculate the activation energy in kJ/mol for this case in this
temperature range. [R = 8.314 J/(molK).]
The activation energy associated with iron diffusing into BCC iron for this temperature
range is,
D800 C
D400 C
Q 1 1
= exp

R T2 T1
where T1 = 400 C = 673 K and T2 = 800 C = 1073 K. Substituting,
5.9 1016 m 2 /s
Q
1
1
=
exp
4.5 1023 m 2 /s
8.314 J/(mol K) 1073 K 673 K
13,111,111.1 = exp (6.662 105 )Q
ln(13,111,111.1) = (6.662 105 )Q
Q = 246, 007 J/mol = 246 kJ/mol
Smith
75
CHAPTER 8 PHASE DIAGRAMS
8.1
Define (a) a phase in a material and (b) a phase diagram.

(a) A phase in a material is a microscopic region that differs in structure and/or
composition from another region.
(b) A phase diagram is a graphical representation of the phases present within a
materials system for a range of temperatures, pressures and compositions.
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:
1. vapor, liquid and Fe
2. vapor, Fe, and Fe
3. vapor, Fe, Fe
8.4
Write the equation for Gibbs phase rule and define each of the terms.
The equation for the Gibbs phase rule is:
P + F = C +2
where P = the number of phases that coexist within a specific system
F = the degrees of freedom for the system
C = the number of components in the system
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?
Smith
Foundations of Materials Science and Engineering Solution Manual
168
(a) At the triple point, there are zero degrees of freedom.

(b) Along the freezing line of pure water, there is one degree of freedom.
8.6
What is a binary isomorphous alloy system?

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?
Crystal
Structure
Silver
Palladium
Copper
Gold
Nickel
Aluminum
Sodium
FCC
FCC
FCC
FCC
FCC
FCC
BCC
Atomic
radius (nm)
0.144
0.137
0.128
0.144
0.125
0.143
0.185
Crystal
Structure
Lead
Tungsten
Rhodium
Platinum
Tantalum
Potassium
Molybdenum
FCC
BCC
FCC
FCC
BCC
BCC
BCC
Atomic
radius (nm)
0.175
0.137
0.134
0.138
0.143
0.231
0.136
Pairs of these elements which may be expected to have complete solid solubility in each
other are:
SilverPalladium
SilverGold
Silver-Rhodium
CopperNickel
8.9
PalladiumPlatinum
PalladiumRhodium
PalladiumGold
RhodiumPlatinum
TantalumMolybdenum
TantalumTungsten
GoldPlatinum
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.
Smith
169
The lever-rule equations can be derived by first recognizing that the sum of the weight
fractions of the liquid and solid phases which must equal 1.
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
Combining these two equations gives
w0 = (1 X s ) wl + X s ws
Solving for the Xs gives the first lever-rule:
Wt fraction of solid phase = X s =
wo wl
ws wl
Similarly, the second lever-rule is found to be:

Wt fraction of liquid phase = X l =
8.10
ws w0
ws wl
Consider an alloy containing 70 wt % Ni and 30 wt % Cu (see Fig. 8.3).

(a) At 1350C make a phase analysis assuming equilibrium conditions. In the phase
analysis include the following:
(i.) What phases are present?
(ii.) What is the chemical composition of each phase?
(iii.) What amount of each phase is present?
(b) Make a similar phase analysis at 1500C.
(c) Sketch the microstructure of the alloy at each of these temperatures by using circular
microscopic fields.
(a)
(i) The phases present are the liquid and solid (L + ).
(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:
Wt % of liquid phase =
Wt % of solid phase =
Smith
74 70
100% = 33.3%
74 62
70 62
100% = 66.67%
74 62
170
(b) At 1500C, the alloy is 100% liquid.

(c) The microstructure of the alloy at these temperatures would look similar to the
following sketches.
Solid
phase
100% Liquid
Liquid
phase L
1350C
8.11
1500C
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.
8.12
Explain how a cored structure is produced in a 70% Cu-30% Ni alloy.

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?
Liquation is the localized melting which occurs if an alloy is heated to a temperature
greater than the lowest melting temperature of the alloys constituents. The result of such
overheating is a liquated structure, in which grain boundaries may be melted. To avoid
liquation, the heat treatment should be performed such that the melting temperature is
approached slowly but never exceeded.
Smith
171
Figure 8.31 The copper-silver phase diagram.

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) 1000C, (b) 800C,
(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 1000C:
Phases present:
Compositions of phases:
liquid
100%
(b) At 800C,
Phases present:
Smith
liquid
78% Ag in liquid phase
beta
93% Ag in phase
172
Amounts of phases:
Wt % liquid phase =
Wt % beta phase =
93 88
100% = 33.3%
93 78
88 78
100% = 66.6%
93 78
(c) At 780o C + T ,
Phases present:
Amounts of phases:
Wt % liquid phase =
Wt % beta phase =
liquid
71.9% Ag in liquid phase
beta
91.2% Ag in phase
91.2 88
100% = 16.6%
91.2 71.9
88 71.9
100% = 83.4%
91.2 71.9
(d) At 780o C T,
Phases present:
Amounts of phases:
Wt % alpha phase =
Wt % beta phase =
8.16
alpha
7.9% Ag in phase
beta
91.2% Ag in phase
91.2 88
100% = 3.84%
91.2 7.9
88 7.9
100% = 96.16%
91.2 7.9
If 500g of a 40 wt % Ag-60 wt % Cu alloy is slowly cooled from 1000C to just below

780C (see Fig. 8.31):
(a) How many grams of liquid and proeutectic alpha are present at 850C?
(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 850C,
Wt % liquid =
Smith
40 7.9
100% = 72.8%
52 7.9
173
Wt % proeutectic =
52 40
100% = 27.2%
52 7.9
Weight of liquid phase = 500 g 0.728 = 364 g

Weight of proeutectic = 500 g 0.272 = 136 g
(b) In the eutectic structure at 780o C + T ,

40 7.9
100% = 50.2%
71.9 7.9
71.9 40
Wt % proeutectic =
100% = 49.8%
71.9 7.9
Wt % liquid =
Weight of liquid phase = 500 g 0.502 = 251 g

Weight of proeutectic = 500 g 0.498 = 249 g
(c) In the eutectic structure at 780o C T, the number of grams of present is,
Wt % total =
91.2 40
100% = 61.5%
91.2 7.9
Weight of total = 500 g 0.615 = 307.5 g
(d) In the eutectic structure at 780o C T, the number of grams of present is,
Wt % total =
40 7.9
100% = 38.5%
91.2 7.9
Weight of = 500 g 0.385 = 192.5 g
8.17
A lead-tin (Pb-Sn) alloy consists of 60 wt % proeutectic and 60 wt % eutectic + at

183o C T . Calculate the average composition of this alloy (see Fig. 8.11).
Since the alloy contains 60 wt % proeutectic , the wt % Sn must lie between 61.9 wt %
and 97.5 wt %:
% proeutectic =
x 61.9
= 0.60
97.5 61.9
x = 0.6(35.6) + 61.9 = 83.3%
Thus, the alloy consists of 83.3 % Sn and 16.7 % Pb.

8.18
A Pb-Sn alloy (Fig. 8.11) contains 40 wt % and 60 wt % at 50C. What is the average
composition of Pb and Sn in this alloy?
Smith
174
At 50C, the phase compositions are 100% Sn for and approximately 2% Sn for .
Thus,
% =
100.0 x
= 0.60, x = 100 0.6(98.0) = 41.2%
100.0 2.0
The alloy consists of 41.2 % Sn and 58.8 % Pb.

8.19
An alloy of 30 wt % Pb and 70 wt % Sn is slowly cooled from 250C to 27C (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 183 C + T ?
(d) What is the amount and composition of each phase that is present at 183 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 containing approximately 98 % Sn.
(c) At 183 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:
Wt % liquid =
Wt % beta =
97.5 70
100% = 77.2%
97.5 61.9
70 61.9
100% = 22.8%
97.5 61.9
(d) At 183 C T , the compositions of the phases present are 19.2 % Sn in phase and
97.5 % Sn in phase. The amounts of the respective phases present are:
Wt % total =
97.5 70
100% = 35.1%
97.5 19.2
Wt % total beta =
70 19.2
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 (20C), equilibrium is not achieved because the diffusion rate is so slow.
Referring to Fig. 8.11, if the solvus line is extrapolated to 20C, the approximate
composition of alpha and beta are 2.0% and 100.0 %, respectively. Thus,
Smith
175
Wt % total =
100 70
100% = 30.6%
100 2
Wt % total beta =
70 2
100% = 69.4%
100 2
Figure 8.32 The iridium-osmium phase diagram.

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) 2600C (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 2600C,
(i) Phases Present:
(ii) Compositions of Phases:
(iii) Amounts of phases:
Liquid and alpha phases

16% Os in liquid phase; 38% Os in alpha phase
30 16
Wt % alpha =
100% = 63.6%
38 16
Wt % liquid =
Smith
38 30
100% = 36.4%
38 16
Solid
phase
Liquid
phase L
176
(b) At 2665o C + T ,
(i) Phases Present:
Wt % beta =
30 23
100% = 18.2%
61.5 23
Wt % liquid =
61.5 30
100% = 81.8%
61.5 23
(c) At 2665o C T ,
(i) Phases Present:
8.21
Liquid and beta phases

23% Os in liquid phase; 61.5% Os in phase
Solid
phase
Liquid
phase L
Liquid and alpha phases

23% Os in liquid phase; 43% Os in phase
Wt % alpha =
30 23
100% = 35.0%
43 23
Solid
phase
Wt % liquid =
43 30
100% = 65.0%
43 23
Liquid
phase L
Consider the binary peritectic iridium-osmium phase diagram of Fig. 8.32. Make phase
analyses of a 40 wt % Ir-60 wt % Os at the temperatures (a) 2600C (b) 2665o C + T ,
and (c) 2665o C T , (d) 2800C. Include in the phase analyses the four items listed in
Prob. 8.20.
(a) At 2600C,
(i) Phases Present:
Alpha and beta phases

43% Os in alpha phase; 61.5% Os in beta phase
61.5 60
Wt % alpha =
100% = 8.1%
61.5 43
Wt % beta =
60 43
100% = 91.9%
61.5 43
(b) At 2665o C + T ,
(i) Phases Present:
Smith
Beta
phase
Liquid and beta phases

23% Os in alpha phase; 61.5% Os in beta phase
61.5 60
100% = 3.9%
61.5 23
Solid
phase
60 23
100% = 96.1%
61.5 23
Liquid
phase
Wt % liquid phase =
Wt % beta phase =
Solid
phase
177
(c) At 2665o C T ,
(i) Phases Present:
61.5 60
100% = 8.1%
61.5 43
Solid
phase
60 43
100% = 91.9%
61.5 43
Beta
phase
Wt % alpha =
Wt % beta =
(d) At 2800C,
(i) Phases Present:
Wt % liquid =
Wt % beta =
8.22

43% Os in liquid phase; 61.5% Os in beta phase

45% Os in liquid phase; 85% Os in beta phase
85 60
100% = 62.5%
85 45
60 45
100% = 37.5%
85 45
Solid
phase
Beta
phase
Describe the mechanism that produces the phenomenon of surrounding in a peritectic

alloy which is rapidly solidified through the peritectic reaction.
Surrounding in a rapidly solidified peritectic alloy is a nonequilibrium phenomenon in
which the alpha phase is encased by the beta phase during the peritectic reaction. As a
result, the solid beta phase acts as a barrier to alpha diffusion and the peritectic reaction
rate decreases continuously.
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 1450C.
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
phases react to form solid :
Wt % =
4.2 4.0
100% = 66.7%
4.3 4.0
At the end of the reaction, there is an excess of phase having a wt % of 33.3 %.

Smith
178
Figure 8.16 The peritectic region of the iron-nickel phase diagram.

The peritectic point is located at 4.3% Ni and 1517C, which is point c.
8.25
Consider an Fe-5.0 wt % Ni alloy (Fig. 8.16) that is slowly cooled from 1550 to 1450C.
What weight percent of the alloy solidifies by the peritectic reaction?
During the peritectic reaction, liquid solidifies to form solid :
Wt % =
8.26
5.4 5.0
100% = 36.4%
5.4 4.3
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 phase
and 5.4 wt % Ni in the liquid phase. The weight percentages of these phases are:
Wt % liquid =
Wt % =
Smith
4.2 4.0
100% = 14.3%
5.4 4.0
5.4 4.2
100% = 85.7%
5.4 4.0
179
8.27
Determine the composition in weight percent of the alloy in the Fe-Ni system (Fig. 8.16)
that will produce a structure of 40 wt % and 60 wt % , just below the peritectic
temperature.
For a 40 wt % composition to exist at 1517 o C T ,
Wt % =
4.3 x
= 0.40
4.3 4.0
x = 4.18%
Thus, the alloy contains 4.18% Ni and 95.82% Fe.

8.28
What is a monotectic invariant reaction? How is the monotectic reaction in the copperlead 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) 1000C (b) 955o C + T , (c)
955o C T , and (d) 200C.
(a) At 1000C,
Compositions of Phases:
Amounts of Phases:
Wt % =
19 10
100% = 47.4%
19 0
(b) At 955o C + T ,
Amounts of Phases:
Wt % =
36 10
100% = 72.2%
36 0
(c) At 955o C T ,
Smith
100% Cu, 0% Pb in phase;

81% Cu, 19% Pb in L1 phase
Wt % L1 =
10 0
100% = 52.6%
19 0

Wt % L1 =
10 0
100% = 27.8%
36 0

180
Amounts of Phases:
Wt % =
87 10
100% = 88.5%
87 0
(d) At 200C,
10 0
100% = 11.5%
87 0
Wt % L2 =
99.995% Cu, 0.005% Pb in phase;

0.007% Cu, 99.993% Pb in phase
Amounts of Phases:
Wt % =
99.99 10
100% = 90%
99.99 0
Wt % =
10 0
100% = 10%
99.99 0
Figure 8.23 The copper-lead phase diagram.

Smith
181
8.30
For an alloy Cu-70 wt % Pb (Fig. 8.23), determine the amounts and compositions in
weight percent of the phases present at (a) 955o C + T , (b) 955o C T , and (c) 200C.
(a) At 955o C + T ,

13% Cu, 87% Pb in L2 phase;
Amounts of Phases:
Wt % L2 =
70 36
100% = 66.7%
87 36
Wt % L1 =
87 70
100% = 33.3%
87 36
(b) At 955o C T ,

Amounts of Phases:
Wt % =
87 70
100% = 19.5%
87 0
Wt % L2 =
70 0
100% = 80.5%
87 0
(c) At 200C,
99.995% Cu, 0.005% Pb in phase;

0.007% Cu, 99.993% Pb in phase
Amounts of Phases:
Wt % =
8.31
99.99 70
100% = 30%
99.99 0
Wt % =
70 0
100% = 70%
99.99 0
What is the average composition (weight percent) of a Cu-Pb alloy that contains 30 wt %
L1 and 70 wt % at 955o C + T ?
For a 30 wt % L1 composition to exist at 955o C + T ,
Wt % L1 =
x0
= 0.30
36 0
x = 10.8%
Thus, the alloy contains 10.8% Pb and 89.2% Cu.
Smith
182
8.32
Write equations for the following invariant reactions: eutectic, eutectoid, peritectic, and
peritectoid. How many degrees of freedom exist at invariant reaction points in binary
phase diagrams?
Eutectic Reaction:
cooling
Eutectoid Reaction:
cooling
Peritectic Reaction:
cooling
+ L
Peritectoid Reaction:
cooling
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.
8.37
Consider the Cu-Zn phase diagram of Fig. 8.25.

(a) What is the maximum solid solubility in weight percent of Zn in Cu in the terminal
solid solution ?
(b) Identify the intermediate phases in the Cu-Zn phase diagram.
Smith
183
(c) Identify the three-phase invariant reactions in the Cu-Zn diagram.

(i) Determine the composition and temperature coordinates of the invariant
reactions.
(ii) Write the equations for the invariant reactions.
(iii) Name the invariant reactions.
(a) The maximum solid solubility in weight percent of zinc in copper in the solid solution
is 39%.
(b) The intermediate phases are , , , and .
(c) The three-phase invariant reactions are:
1. Peritectic reaction at 903C, 36.8% Zn
(32.5% Zn) + L(37.5% Zn)
(36.8% Zn)
(56.5% Zn) + L(59.8% Zn)
(59.8% Zn)
3. Peritectic reaction at 700C, 73% Zn
(69.8% Zn) + L(80.5% Zn)
(73% Zn)
(76.5% Zn) + L(89% Zn)
(78.6% Zn)
(87.5% Zn) + L(98.3% Zn)
(97.3% Zn)
6. Eutectoid reaction at 558C, 73% Zn
(73% Zn)
(69.8% Zn) + (78.6% Zn)
7. Eutectoid reaction at 250C, 47% Zn
(37% Zn) + (59% Zn)
(47% Zn)
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.
(a) and (b):
1. Eutectic reaction at 639C, 0.1% Ni
L (0.1% Ni)
Al (0.05% Ni) + Al3 Ni (42% Ni)
Smith
184
2. Peritectic reaction at 854C, 42% Ni

L (28% Ni) + Al3 Ni 2 (55% Ni)
Al 3 Ni (42% Ni)
L (44% Ni) + AlNi(63% Ni)
Al 3 Ni 2 (59% Ni)
4. Peritectoid reaction at 700C, 81% Ni
AlNi (77% Ni) + AlNi 3 (86% Ni)
Al3 Ni 5 (81% Ni)
L (87% Ni) + AlNi(83% Ni)
AlNi 3 (86% Ni)
6. Eutectic reaction at 1385C, 86% Ni
L (87% Ni)
Ni (90% Ni) + AlNi 3 (86% Ni)
(c) The two-phase regions are identified in Fig. 8.33 below.
Smith
185
Figure 8.34 Nickel-vanadium 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.
(c) The two-phase regions are identified in Fig. 8.34 above.
(a) and (b):
1. Eutectoid reaction at 906C, 29.5% V
Ni (29.5% V)
Ni 3V (25% V) + Ni 2 V(30.5% V)
2. Eutectoid reaction at 890C, 35.2% V
Ni (35.2% V)
Ni 2 V (32% V) + (51% V)
3. Eutectic reaction at 1202C, 47.5% V
Ni (40% V) + (51% V)
L (47% V)
4. Peritectic reaction at 1280C, 64% V
Smith
186
L (58.1% V) + V (73% V)
+ (64% V)
5. Peritectoid reaction at 900C, 75.3% V

(70.7% V) + V (88.1% V)
+ NiV3 (75% V)
Figure 8.35 Titanium-aluminum phase diagram.

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.
(c) The two-phase regions are identified in Fig. 8.35 above.
(a) and (b):
1. Peritectoid reaction at 1285C, 32% Al
Ti (30% Al) + TiAl (35% Al)
Ti (32% Al)
2. Eutectoid reaction at 1125C, 27% Al
Ti (27% Al)
TiAl(34% Al) + Ti 3Al(26% Al)
Smith
187
3. Peritectic reaction at 1380C, 58% Al

L (61% Al) + TiAl(56% Al)
(58% Al)
L (69% Al) + (60% Al)
TiAl 3 (63% Al)
5. Peritectoid reaction at 1240C, 55% Al
TiAl (51% Al) + (57% Al)
TiAl 2 (55% Al)
6. Eutectoid reaction at 1150C, 58% Al
(58% Al)
TiAl 2 (55% Al) + TiAl3 (63% Al)
L (100% Al) + TiAl3 (68% Al)
Al (99% Al)
8.41
What is the composition of point y in Fig. 8.29?

As indicated in the ternary diagram figure below, the composition of point y is 20% A,
30% B and 50% C.
30%
20%
50%
Smith
188

Chapter 4 Solidification, Crystalline Imperfections, and Diffusion in Solids

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Chapter 4 Solidification, Crystalline Imperfections, and Diffusion in Solids

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CHAPTER 4 SOLIDIFICATION, CRYSTALLINE IMPERFECTIONS, AND DIFFUSION IN SOLIDS

The two energies involved in the

Foundations of Materials Science and Engineering

Distinguish between homogeneous and heterogeneous nucleation for the solidification of

where = 240 107 J/cm 2 , H f = 2160 J/cm3 , Tm = 2045 K

2(240 107 J/cm 2 )(2045 K)

Foundations of Materials Science and Engineering

3.574 1023 cm3

Thus, the number of atoms in a critically sized nucleus is:

Foundations of Materials Science and Engineering

Distinguish between equiaxed and columnar grains in a solidified metal structure.

What special techniques must used to produce single crystals?

What is a metal alloy? What is a solid solution?

Distinguish between a substitutional solid solution and an interstitial solid solution.

Foundations of Materials Science and Engineering

2. identical valence of the elements;

(b) very low

(b) very high

Foundations of Materials Science and Engineering

Letting x = Fe atom radius + Interstitial void radius,

The interstitial void radius is thus,

Foundations of Materials Science and Engineering

b) A Schottky imperfection is a cation-anion divacancy which sometimes occurs in

Foundations of Materials Science and Engineering

Why are grain boundaries easily observed in the optical microscope?

Foundations of Materials Science and Engineering

No. of grains at 100 =

Write an equation for the number of vacancies present in a metal at equilibrium at a

Foundations of Materials Science and Engineering

b) The vacancy fraction at 1073 K is,

Substituting and assuming Ev = 1.10 eV for vacancies formed at 1023 K,

Foundations of Materials Science and Engineering

b) The vacancy fraction at 973 K is,

log10 of reaction rate

Describe the substitutional interstitial diffusion mechanisms in solid metals.

Foundations of Materials Science and Engineering

What factors affect the diffusion rate in solid metal crystals?

Type of diffusion mechanism;

Foundations of Materials Science and Engineering

where Cs = surface concentration of element in gas diffusing into the surface;

Cs = 1.15% Co = 0.18% C x = 0.35%

D927 C = 1.28 1011 m 2 / s

Foundations of Materials Science and Engineering

Interpolating from Table 4.5,

The surface of a steel gear made of 1022 steel (0.22 wt % C) is to be gas-carburized at

Interpolating from Table 4.5,

0.9184 0.9103 x 1.2

= 7, 446.6 s = 124 min.

A gear made of 1020 steel (0.20 wt % C) is to be gas-carburized at 927C (1700F).

Foundations of Materials Science and Engineering

1.25(1 C x ) = erf (1.0482)

Interpolating from Table 4.5,

Thus, 0.8608 = erf (1.0482)

A gear made of 1020 steel (0.20 wt % C) is to be gas-carburized at 927C (1700F).

Thus, 0.7959 = erf (0.89798)

Foundations of Materials Science and Engineering

The surface of a steel gear made of 1018 steel (0.18 wt % C) is to be gas-carburized at

Interpolating from Table 4.5,

t = 20, 400 s = 340 min. = 5.67 h

A gear made of 1020 steel (0.20 wt % C) is to be gas-carburized at 927C (1700F).

Foundations of Materials Science and Engineering

Interpolating from Table 4.5,

Thus, 0.7312 = erf (0.7823)