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CHAPTER 4

IMPERFECTIONS IN SOLIDS

PROBLEM SOLUTIONS

Vacancies and Self-Interstitials

4.1 The equilibrium fraction of lattice sites that are vacant in silver (Ag) at 700 C is 2  106. Calculate
the number of vacancies (per meter cubed) at 700C. Assume a density of 10.35 g/cm3 for Ag.

Solution

This problem is solved using two steps: (1) calculate the total number of lattice sites in silver, NAg, using
Equation 4.2; and (2) multiply this number by fraction of lattice that are vacant, 2  106. The parameter NAg is
related to the density, (), Avogadro's number (NA), and the atomic weight (AAg=107.87 g/mol, from inside the front

cover) according to Equation 4.2 as


N A rAg
N Ag =
AAg

(6.022 ´ 1023 atoms/mol)(10.35 g/cm3 )(106 cm3 /m3 )


=
107.87 g/mol

= 5.78  1028 atoms/m3

The number of vacancies per meter cubed in silver at 700C, Nv, is determined as follows:

Nv = (2 ´10 -6 )N Ag

= (2 ´ 10-6 )(5.78 ´ 1028 atoms/m3 ) = 1.156 ´ 1023 vacancies/m3


Impurities in Solids

4.6 Atomic radius, crystal structure, electronegativity, and the most common valence are given in the
following table for several elements; for those that are nonmetals, only atomic radii are indicated.
Element Atomic Radius (nm) Crystal Structure Electronegativity Valence
Ni 0.1246 FCC 1.8 +2
C 0.071
H 0.046
O 0.060
Ag 0.1445 FCC 1.4 +1
Al 0.1431 FCC 1.5 +3
Co 0.1253 HCP 1.7 +2
Cr 0.1249 BCC 1.6 +3
Fe 0.1241 BCC 1.7 +2
Pt 0.1387 FCC 1.5 +2
Zn 0.1332 HCP 1.7 +2

Which of these elements would you expect to form the following with nickel:
(a) A substitutional solid solution having complete solubility
(b) A substitutional solid solution of incomplete solubility
(c) An interstitial solid solution

Solution

For complete substitutional solubility the four Hume-Rothery rules must be satisfied: (1) the difference in
atomic radii between Ni and the other element (R%) must be less than ±15%; (2) the crystal structures must be the
same; (3) the electronegativities must be similar; and (4) the valences should be the same.

Crystal Electro-
Element R% Structure negativity Valence
Ni FCC 2+
C –43
H –63
O –52
Ag +16 FCC -0.4 1+
Al +15 FCC -0.3 3+
Co +0.6 HCP -0.1 2+
Cr +0.2 BCC -0.2 3+
Fe -0.4 BCC -0.1 2+
Pt +11 FCC -0.3 2+
Zn +7 HCP -0.1 2+
(a) Pt is the only element that meets all of the criteria and thus forms a substitutional solid solution having
complete solubility. At elevated temperatures Co and Fe experience allotropic transformations to the FCC crystal
structure, and thus display complete solid solubility at these temperatures.
(b) Ag, Al, Co, Cr, Fe, and Zn form substitutional solid solutions of incomplete solubility. All these metals
have either BCC or HCP crystal structures, and/or the difference between their atomic radii and that for Ni are greater
than ±15%, and/or have a valence different than 2+.
(c) C, H, and O form interstitial solid solutions. These elements have atomic radii that are significantly
smaller than the atomic radius of Ni.

4.17 What is the composition, in atom percent, of an alloy that contains 33 g of copper and 47 g of zinc?

Solution

The concentration of an element in an alloy, in atom percent, may be computed using Equation 4.5a.
However, it first becomes necessary to compute the number of moles of both Cu and Zn, using Equation 4.4. Atomic
weights of copper and zinc (found on the inside of the book's cover) are as follows:
ACu = 63.55 g/mol
AZn = 65.41 g/mol

Thus, the number of moles of Cu is just

m¢ 33 g
nm = Cu = = 0.519 mol
Cu ACu 63.55 g/mol

Likewise, for Zn
47 g
nm = = 0.719 mol
Zn 65.41 g/mol

Now, use of Equation 4.5a yields

nm
¢ =
CCu Cu ´ 100
nm + nm
Cu Zn

0.519 mol
= ´ 100 = 41.9 at%
0.519 mol + 0.719 mol
Also,

0.719 mol
¢ =
CZn ´ 100 = 58.1 at%
0.519 mol + 0.719 mol

4.3FE What is the composition, in weight percent, of an alloy that consists of 94.1 at% Ag and 5.9 at% Cu?
The atomic weights for Ag and Cu are 107.87 g/mol and 63.55 g/mol, respectively.
(A) 9.6 wt% Ag and 90.4 wt% Cu
(B) 3.6 wt% Ag and 96.4 wt% Cu
(C) 90.4 wt% Ag and 9.6 wt% Cu
(D) 96.4 wt% Ag and 3.6 wt% Cu

Solution

To compute composition, in weight percent, of a 94.1 at% Ag-5.9 at% Cu alloy, we employ Equation 4.7 as
follows:
¢ AAg
CAg
CAg = ´ 100
¢ AAg + CCu
CAg ¢ ACu

(94.1)(107.87 g/mol)
= ´ 100
(94.1)(107.87 g/mol) + (5.9)(63.55 g/mol)

= 96.4 wt%

¢ ACu
CCu
CCu = ´ 100
¢ AAg + CCu
CAg ¢ ACu

(5.9)(63.55 g/mol)
= ´ 100
(94.1)(107.87 g/mol) + (5.9)(63.55 g/mol)

= 3.6 wt%

which is answer D (96.4 wt% Ag and 3.6 wt% Cu).