Chap 4 Solns
CHAPTER 5
IMPERFECTIONS IN SOLIDS
PROBLEM SOLUTIONS
Vacancies and Self-Interstitials 5.1 Calculate the fraction of atom sites that are vacant for copper at its melting temperature of 1084°C (1357 K). Assume an energy for vacancy formation of 0.90 eV/atom. Solution In order to compute the fraction of atom sites that are vacant in copper at 1357 K, we must employ Equation 5.1. As stated in the problem, Qv = 0.90 eV/atom. Thus, ⎡ ⎤ ⎛ Q ⎞ 0.90 eV /atom ⎥ = exp ⎜− v ⎟ = exp ⎢− N ⎢⎣ (8.62 × 10−5 eV /atom - K) (1357 K) ⎥⎦ ⎝ kT ⎠
Nv
= 4.56 × 10-4
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.2 Calculate the energy for vacancy formation in silver, given that the equilibrium number of vacancies at 800°C (1073 K) is 3.6 × 1023 m–3. The atomic weight and density (at 800°C) for silver are, respectively, 107.9 g/mol and 9.5 g/cm3. Solution This problem calls for the computation of the activation energy for vacancy formation in silver. Upon examination of Equation 5.1, all parameters besides Qv are given except N, the total number of atomic sites. However, N is related to the density, (ρ), Avogadro's number (NA), and the atomic weight (A) according to Equation 5.2 as
N =
=
N A ρ Pb APb
(6.02 × 1023 atoms / mol)(9.5 g /cm3 ) 107.9 g / mol
= 5.30 × 1022 atoms/cm3 = 5.30 × 1028 atoms/m3
Now, taking natural logarithms of both sides of Equation 5.1, Q ln N v = ln N − v kT
and, after some algebraic manipulation ⎛N ⎞ Qv = − kT ln ⎜ v ⎟ ⎝ N ⎠
Now, inserting values for the parameters given in the problem statement leads to ⎡ 3.60 × 1023 m−3 ⎤ Qv = − (8.62 × 10-5 eV/atom - K) (800°C + 273 K) ln ⎢ ⎥ ⎣ 5.30 × 1028 m−3 ⎦
= 1.10 eV/atom
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Point Defects in Ceramics 5.3 Calculate the fraction of lattice sites that are Schottky defects for cesium chloride at its melting temperature (645°C). Assume an energy for defect formation of 1.86 eV. Solution In order to solve this problem it is necessary to use Equation 5.4 and solve for the Ns/N ratio. Rearrangement of this expression and substituting values for the several parameters leads to Ns N
⎛ Q ⎞ = exp ⎜− s ⎟ ⎝ 2kT ⎠
⎡ ⎤ 1.86 eV = exp ⎢− ⎥ -5 ⎣ (2)(8.62 × 10 eV/K)(645 + 273 K) ⎦
= 7.87 × 10-6
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.4 Using the data given below that relate to the formation of Schottky defects in some oxide ceramic (having the chemical formula MO), determine the following: (a) the energy for defect formation (in eV), (b) the equilibrium number of Schottky defects per cubic meter at 1000°C, and (c) the identity of the oxide (i.e., what is the metal M?)
T (°C)
ρ (g/cm3)
Ns (m–3)
750
3.50
5.7 × 109
1000
3.45
?
1500
3.40
5.8 × 1017
Solution The (a) portion of the problem asks that we compute the energy for defect formation. To begin, let us combine a modified form of Equation 5.2 and Equation 5.4 as ⎛ Q ⎞ N s = N exp ⎜− s ⎟ ⎝ 2kT ⎠ ⎛ N ρ ⎞ ⎛ Q ⎞ A ⎟⎟ exp ⎜− s ⎟ = ⎜⎜ ⎝ 2kT ⎠ ⎝ AM + AO ⎠
Inasmuch as this is a hypothetical oxide material, we don't know the atomic weight of metal M, nor the value of Qs in the above equation. Therefore, let us write equations of the above form for two temperatures, T1 and T2. These are as follows: ⎛ N ρ ⎞ ⎛ ⎞ A 1 ⎟ exp ⎜− Qs ⎟ N s1 = ⎜⎜ ⎟ ⎟ ⎜ ⎝ AM + AO ⎠ ⎝ 2kT1 ⎠
(5.S1a)
⎛ N ρ ⎞ ⎛ ⎞ A 2 ⎟ exp ⎜− Qs ⎟ N s2 = ⎜⎜ ⎟ ⎜ 2kT ⎟ ⎝ AM + AO ⎠ ⎝ 2⎠
(5.S1b)
Dividing the first of these equations by the second leads to
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
⎛ N ρ ⎞ ⎛ A 1 ⎟ exp ⎜− ⎜⎜ ⎟ ⎜ N s1 ⎝ AM + AO ⎠ ⎝ = ⎞ ⎛ N ρ ⎛ N s2 A 2 ⎟ exp ⎜− ⎜⎜ ⎟ ⎜ ⎝ AM + AO ⎠ ⎝
Qs ⎞ ⎟ 2kT1 ⎟⎠ Qs ⎞ ⎟ 2kT2 ⎟⎠
which, after some algebraic manipulation, reduces to the form N s1 N s2
=
⎡ Q ⎛1 1 ⎞⎤ ⎟⎥ exp ⎢− s ⎜⎜ − ρ2 T2 ⎟⎠⎥⎦ ⎢⎣ 2k ⎝ T1 ρ1
(5.S2)
Now, taking natural logarithms of both sides of this equation gives ⎛N ⎞ ⎛ρ ⎞ Q ln ⎜⎜ s1 ⎟⎟ = ln ⎜⎜ 1 ⎟⎟ − s 2k ⎝ N s2 ⎠ ⎝ ρ2 ⎠
⎛1 1⎞ ⎜⎜ ⎟ − T2 ⎟⎠ ⎝ T1
and solving for Qs leads to the expression ⎡ ⎛N ⎞ −2k ⎢ ln⎜⎜ s1 ⎟⎟ ⎢⎣ ⎝ N s2 ⎠ Qs = 1 − T1
⎛ ρ ⎞⎤ − ln⎜⎜ 1 ⎟⎟⎥ ⎝ ρ2 ⎠⎦⎥ 1 T2
Let us take T1 = 750°C and T2 = 1500°C, and we may compute the value of Qs as ⎡ ⎛ 5.7 × 109 m-3 ⎞ ⎛ 3.50 g/cm3 ⎞⎤ − ln −(2)(8.62 × 10-5 eV/K) ⎢ ln ⎜ ⎟ ⎟⎥ ⎜ ⎢⎣ ⎝ 5.8 × 1017 m-3 ⎠ ⎝ 3.40 g/cm3 ⎠⎥⎦ Qs = 1 1 − 750 + 273 K 1500 + 273 K
= 7.70 eV (b) It is now possible to solve for Ns at 1000°C using Equation 5.S2 above. This time let's take T1 = 1000°C and T2 = 750°C. Thus, solving for Ns1, substituting values provided in the problem statement and Qs determined above yields
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
N s1 =
=
(5.7 × 10 9 m-3 )( 3.45 g/cm3) 3.50 g/cm3
N s2 ρ1 ρ2
⎡ Q ⎛1 1 ⎞⎤ ⎟⎥ exp ⎢− s ⎜⎜ − T2 ⎟⎠⎥⎦ ⎢⎣ 2k ⎝ T1
⎡ ⎛ ⎞⎤ 1 1 7.70 eV exp ⎢− − ⎜ ⎟⎥ 750 + 273 K ⎠⎥⎦ ⎢⎣ (2)(8.62 × 10-5 eV/K) ⎝ 1000 + 273 K
= 3.0 × 1013 m-3
(c) And, finally, we want to determine the identity of metal M. This is possible by computing the atomic weight of M (AM) from Equation 5.S1a. Rearrangement of this expression leads to ⎛ N ρ ⎞ ⎛ ⎞ A 1 ⎟ = N exp ⎜ Qs ⎟ ⎜⎜ ⎟ ⎜ 2kT ⎟ s1 ⎝ AM + AO ⎠ ⎝ 1⎠
And, after further algebraic manipulation ⎡ ⎤ ⎢ ⎥ N Aρ1 ⎢ ⎥ = AM + AO ⎢ ⎛ ⎞⎥ ⎢ N exp ⎜ Qs ⎟ ⎥ ⎜ 2kT ⎟ ⎥ ⎢ s1 ⎝ 1 ⎠⎦ ⎣
And, solving this expression for AM gives ⎡ ⎤ ⎢ ⎥ N Aρ1 ⎢ ⎥ AM = ⎢ − AO ⎛ Q ⎞⎥ ⎢ N exp ⎜ s ⎟ ⎥ ⎜ 2kT ⎟ ⎥ ⎢ s1 ⎝ 1 ⎠⎦ ⎣
Now, assuming that T1 = 750°C, the value of AM is
AM
⎧ ⎫ ⎪ ⎪ 23 3 6 3 3 ⎪ ⎪ (6.02 × 10 ions/mol)( 3.50 g/cm )(10 cm / m ) = ⎨ ⎬ − 16.00 g/mol ⎤ ⎡ 7.7 eV ⎪ (5.7 × 109 ions/m3 ) exp ⎪ ⎥⎪ ⎢ -5 ⎪⎩ ⎣ (2)(8.62 × 10 eV/K)(750 + 273 K) ⎦ ⎭
= 24.45 g/mol Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Upon consultation of the periodic table in Figure 2.6, the divalent metal (i.e., that forms M2+ ions) that has an atomic weight closest to 24.45 g/mol is magnesium. Thus, this metal oxide is MgO.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Impurities in Solids 5.5 Below, atomic radius, crystal structure, electronegativity, and the most common valence are tabulated, 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
1.9
+1
Al
0.1431
FCC
1.5
+3
Co
0.1253
HCP
1.8
+2
Cr
0.1249
BCC
1.6
+3
Fe
0.1241
BCC
1.8
+2
Pt
0.1387
FCC
2.2
+2
Zn
0.1332
HCP
1.6
+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 In this problem we are asked to cite which of the elements listed form with Ni the three possible solid solution types. For complete substitutional solubility the following criteria must be met: 1) the difference in atomic radii between Ni and the other element (ΔR%) 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, or nearly the same. Below are tabulated, for the various elements, these criteria.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Element
ΔR%
Ni C H O Ag Al Co Cr Fe Pt Zn
–43 –63 –52 +16 +15 +0.6 +0.2 -0.4 +11 +7
Crystal Structure
ΔElectronegativity
FCC
FCC FCC HCP BCC BCC FCC HCP
Valence 2+
+0.1 -0.3 0 -0.2 0 +0.4 -0.2
1+ 3+ 2+ 3+ 2+ 2+ 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.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.6 (a) Suppose that CaO is added as an impurity to Li2O. If the Ca2+ substitutes for Li+, what kind of vacancies would you expect to form? How many of these vacancies are created for every Ca2+ added? (b) Suppose that CaO is added as an impurity to CaCl2. If the O2– substitutes for Cl–, what kind of vacancies would you expect to form? How many of these vacancies are created for every O2– added? Solution (a) For Ca2+ substituting for Li+ in Li2O, lithium vacancies would be created. For each Ca2+ substituting for Li+, one positive charge is added; in order to maintain charge neutrality, a single positive charge may be removed. Positive charges are eliminated by creating lithium vacancies, and for every Ca2+ ion added, a single lithium vacancy is formed. (b) For O2- substituting for Cl- in CaCl2, chlorine vacancies would be created. For each O2- substituting for a Cl-, one negative charge is added; negative charges are eliminated by creating chlorine vacancies. In order to maintain charge neutrality, one O2- ion will lead to the formation of one chlorine vacancy.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Specification of Composition 5.7 What is the composition, in atom percent, of an alloy that consists of 92.5 wt% Ag and 7.5 wt% Cu? Solution In order to compute composition, in atom percent, of a 92.5 wt% Ag-7.5 wt% Cu alloy, we employ Equation 5.9 as
' = C Ag
=
C Ag ACu C Ag ACu + CCu AAg
× 100
(92.5)(63.55 g / mol) × 100 (92.5)(63.55 g / mol) + (7.5)(107.87g / mol)
= 87.9 at%
' = CCu
=
CCu AAg C Ag ACu + CCu AAg
× 100
(7.5)(107.87 g / mol) × 100 (92.5)(63.55 g / mol) + (7.5)(107.87g / mol)
= 12.1 at%
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.8 Calculate the composition, in weight percent, of an alloy that contains 105 kg of iron, 0.2 kg of carbon, and 1.0 kg of chromium. Solution The concentration, in weight percent, of an element in an alloy may be computed using a modified form of Equation 5.6. For this alloy, the concentration of iron (CFe) is just
C Fe =
=
mFe
mFe + mC + mCr
× 100
105 kg × 100 = 98.87 wt% 105 kg + 0.2 kg + 1.0 kg
Similarly, for carbon CC =
0.2 kg × 100 = 0.19 wt% 105 kg + 0.2 kg + 1.0 kg
CCr =
1.0 kg × 100 = 0.94 wt% 105 kg + 0.2 kg + 1.0 kg
And for chromium
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.9 What is the composition, in atom percent, of an alloy that contains 44.5 lbm of silver, 83.7 lbm of gold, and 5.3 lbm of Cu?
Solution To determine the concentrations, in atom percent, of the Ag-Au-Cu alloy, it is first necessary to convert the amounts of Ag, Au, and Cu into grams. ' = (44.5 lb )(453.6 g/lb ) = 20,185 g mAg m m
' = (83.7 lb )(453.6 g/lb ) = 37, 966 g mAu m m
' = (5.3 lb )(453.6 g/lb ) = 2, 404 g mCu m m
These masses must next be converted into moles (Equation 5.7), as
nm
' mAg
=
=
AAg
Ag
nm
37,966 g = 192.8 mol 196.97 g / mol
=
Au
nm
Cu
20,185 g = 187.1 mol 107.87 g / mol
=
2, 404 g = 37.8 mol 63.55 g / mol
Now, employment of a modified form of Equation 5.8, gives
' = C Ag
nm
Ag
nm
Ag
=
+ nm
Au
+ nm
× 100
Cu
187.1 mol × 100 = 44.8 at% 187.1 mol + 192.8 mol + 37.8 mol
' C Au =
192.8 mol × 100 = 46.2 at% 187.1 mol + 192.8 mol + 37.8 mol
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
' CCu =
37.8 mol × 100 = 9.0 at% 187.1 mol + 192.8 mol + 37.8 mol
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.10 Convert the atom percent composition in Problem 5.9 to weight percent. Solution The composition in atom percent for Problem 5.9 is 44.8 at% Ag, 46.2 at% Au, and 9.0 at% Cu. Modification of Equation 5.10 to take into account a three-component alloy leads to the following
C Ag =
' A C Ag Ag
=
× 100
Ag AAg + C Au AAu + CCu ACu
C'
'
'
(44.8) (107.87 g / mol) × 100 (44.8)(107.87 g / mol) + (46.2) (196.97 g / mol) + (9.0) (63.55 g / mol)
= 33.3 wt%
C Au =
' A CAu Au
CAg AAg + '
=
× 100
Au AAu + CCu ACu
C'
'
(46.2) (196.97 g / mol) × 100 (44.8)(107.87 g / mol) + (46.2) (196.97 g / mol) + (9.0) (63.55 g / mol)
= 62.7 wt%
CCu =
' A CCu Cu
CAg AAg + '
=
Au AAu +
C'
× 100 C'
Cu ACu
(9.0) (63.55 g / mol) × 100 (44.8)(107.87 g / mol) + (46.2) (196.97 g / mol) + (9.0) (63.55 g / mol)
= 4.0 wt%
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.11 Determine the approximate density of a Ti-6Al-4V titanium alloy that has a composition of 90 wt% Ti, 6 wt% Al, and 4 wt% V.
Solution In order to solve this problem, Equation 5.13a is modified to take the following form: ρave =
CTi ρTi
+
100 C Al ρ Al
+
CV ρV
And, using the density values for Ti, Al, and V—i.e., 4.51 g/cm3, 2.71 g/cm3, and 6.10 g/cm3—(as taken from inside the front cover of the text), the density is computed as follows: ρave =
90 wt% 4.51 g /cm3
+
100 6 wt% 2.71 g /cm 3
+
4 wt% 6.10 g /cm3
= 4.38 g/cm3
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.12 Some hypothetical alloy is composed of 25 wt% of metal A and 75 wt% of metal B. If the densities of metals A and B are 6.17 and 8.00 g/cm3, respectively, whereas their respective atomic weights are 171.3 and 162.0 g/mol, determine whether the crystal structure for this alloy is simple cubic, face-centered cubic, or body-centered cubic. Assume a unit cell edge length of 0.332 nm. Solution In order to solve this problem it is necessary to employ Equation 3.5; in this expression density and atomic weight will be averages for the alloy—that is ρave =
nAave VC N A
Inasmuch as for each of the possible crystal structures, the unit cell is cubic, then VC = a3, or
ρave =
nAave a3N A
And, in order to determine the crystal structure it is necessary to solve for n, the number of atoms per unit cell. For n =1, the crystal structure is simple cubic, whereas for n values of 2 and 4, the crystal structure will be either BCC or FCC, respectively. When we solve the above expression for n the result is as follows:
n =
ρave a 3 N A Aave
Expressions for Aave and ρave are found in Equations 5.14a and 5.13a, respectively, which, when incorporated into the above expression yields ⎛ ⎞ ⎜ ⎟ 100 ⎜ ⎟a 3 N A ⎜ CA CB ⎟ + ⎜ ⎟ ρB ⎠ ⎝ ρA n = ⎞ ⎛ ⎟ ⎜ 100 ⎟ ⎜ ⎜ CA CB ⎟ + ⎟ ⎜ AB ⎠ ⎝ AA
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Substitution of the concentration values (i.e., CA = 25 wt% and CB = 75 wt%) as well as values for the other parameters given in the problem statement, into the above equation gives ⎛ ⎞ ⎜ ⎟ 100 ⎜ ⎟(3.32 × 10-8 nm)3 (6.02 × 1023 atoms/mol) ⎜ 25 wt% + 75 wt% ⎟ ⎜ ⎟ 8.00 g/cm3 ⎠ ⎝ 6.17 g/cm3 n = ⎛ ⎞ ⎜ ⎟ 100 ⎜ ⎟ 75 wt% ⎟ ⎜ 25 wt% + ⎜ ⎟ 162.0 g/mol ⎠ ⎝ 171.3 g/mol
= 1.00 atom/unit cell Therefore, on the basis of this value, the crystal structure is simple cubic.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.13
Molybdenum forms a substitutional solid solution with tungsten.
Compute the number of
molybdenum atoms per cubic centimeter for a molybdenum-tungsten alloy that contains 16.4 wt% Mo and 83.6 wt% W. The densities of pure molybdenum and tungsten are 10.22 and 19.30 g/cm3, respectively. Solution To solve this problem, employment of Equation 5.21 (which derivation is called for in problem W5.16 on the book’s Web site) is necessary, using the following values: C1 = CMo = 16.4 wt% ρ1 = ρMo = 10.22 g/cm3 ρ2 = ρW = 19.3 g/cm3 A1 = AMo = 95.94 g/mol Thus
N Mo =
C Mo AMo ρ Mo
=
N AC Mo +
AMo ρW
(100
− CMo )
(6.02 × 1023 atoms / mol) (16.4 wt%) 95.94 g / mol (16.4 wt%)(95.94 g / mol) + (100 − 16.4 wt%) 19.3 g /cm3 10.22 g /cm3
= 1.73 × 1022 atoms/cm3
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.14 Sometimes it is desirable to be able to determine the weight percent of one element, C1, that will produce a specified concentration in terms of the number of atoms per cubic centimeter, N1, for an alloy composed of two types of atoms. This computation is possible using the following expression: C1 =
100 ρ N A ρ2 − 2 1+ N1 A1 ρ1
(5.22)
where NA = Avogadro’s number ρ1 and ρ2 = densities of the two elements A1 and A2 = the atomic weights of the two elements Derive Equation 5.22 using Equation 5.2 and expressions contained in Section 5.6. Solution The number of atoms of component 1 per cubic centimeter is just equal to the atom fraction of component 1
(c ' ) 1
times the total number of atoms per cubic centimeter in the alloy (N). Thus, using the equivalent of
Equation 5.2, we may write
N 1 = c1' N =
c1' N A ρave Aave
Realizing that
c1' =
C1' 100
and
C 2' = 100 − C1'
and substitution of the expressions for ρave and Aave, Equations 5.13b and 5.14b, respectively, leads to
N1 =
c1' N Aρave Aave
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
N AC1' ρ1 ρ 2
=
C1' ρ 2 A1 + (100 − C1' ) ρ1 A2
And, solving for C1'
C1' =
100 N 1 ρ1 A2 N Aρ1 ρ 2 − N 1 ρ 2 A1 + N 1 ρ1 A2
Substitution of this expression for C1' into Equation 5.10a, which may be written in the following form
C1 =
C1' A1
× 100
C1' A1 + C2' A2
C1' A1
=
C'
1 A1
× 100
+ (100 − C1 ) A2 '
yields C1 =
1+
100 N A ρ2
N 1 A1
−
ρ2 ρ1
the desired expression.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.15 Germanium forms a substitutional solid solution with silicon. Compute the weight percent of germanium that must be added to silicon to yield an alloy that contains 2.43 × 1021 Ge atoms per cubic centimeter. The densities of pure Ge and Si are 5.32 and 2.33 g/cm3, respectively.
Solution To solve this problem, employment of Equation 5.22 is necessary, using the following values: N1 = NGe = 2.43 x 1021 atoms/cm3 ρ1 = ρGe = 5.32 g/cm3 ρ2 = ρSi = 2.33 g/cm3 A1 = AGe = 72.64 g/mol A2 = ASi = 28.09 g/mol
Thus CGe =
1+
100 N AρSi
N Ge AGe
−
ρSi
ρGe
100
= 1+
⎛ 2.33 g /cm3 ⎞ × atoms / mol)(2.33 g /cm3 ) − ⎟ ⎜ (2.43 × 1021 atoms /cm3 ) (72.64 g / mol) ⎝ 5.32 g /cm3 ⎠
(6.02
1023
= 11.7 wt%
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.16 Iron and vanadium both have the BCC crystal structure, and V forms a substitutional solid solution for concentrations up to approximately 20 wt% V at room temperature. Compute the unit cell edge length for a 90 wt% Fe–10 wt% V alloy. Solution First of all, the atomic radii for Fe and V (using the table inside the front cover) are 0.124 and 0.132 nm, respectively. Also, using Equation 3.5 it is possible to compute the unit cell volume, and inasmuch as the unit cell is cubic, the unit cell edge length is just the cube root of the volume. However, it is first necessary to calculate the density and average atomic weight of this alloy using Equations 5.13a and 5.14a. Inasmuch as the densities of iron and vanadium are 7.87g/cm3 and 6.10 g/cm3, respectively, (as taken from inside the front cover), the average density is just ρave =
100 CV
ρV
C Fe
+
ρ Fe
100
=
10 wt% 6.10 g /cm3
+
90 wt% 7.87 g /cm3
= 7.65 g/cm3
And for the average atomic weight Aave =
100 CV AV
=
+
C Fe AFe
100 90 wt% 10 wt% + 55.85 g / mol 50.94 g / mole
= 55.32 g/mol Now, VC is determined from Equation 3.5 as
VC =
nAave
ρave N A
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
=
(2 atoms / unit cell)(55.32 g / mol) (7.65 g /cm3 )(6.02 × 1023 atoms / mol)
= 2.40 × 10-23 cm3/unit cell
And, finally a = (VC )1/ 3
= (2.40 × 10 −23cm3/unit cell)1/3 = 2.89 x 10-8 cm = 0.289 nm
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Interfacial Defects 5.17 For an FCC single crystal, would you expect the surface energy for a (100) plane to be greater or less than that for a (111) plane? Why? (Note: You may want to consult the solution to Problem W3.46 at the end of Chapter 3.)
Solution The surface energy for a crystallographic plane will depend on its packing density [i.e., the planar density (Section 3.11)]—that is, the higher the packing density, the greater the number of nearest-neighbor atoms, and the more atomic bonds in that plane that are satisfied, and, consequently, the lower the surface energy. From the 1 1 solution to Problem W3.46, planar densities for FCC (100) and (111) planes are and , respectively— 2 2 4R 2R 3 0.25 0.29 and (where R is the atomic radius). Thus, since the planar density for (111) is greater, it will have that is 2 R R2 the lower surface energy.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.18 (a) For a given material, would you expect the surface energy to be greater than, the same as, or less than the grain boundary energy? Why? (b) The grain boundary energy of a small-angle grain boundary is less than for a high-angle one. Why is this so?
Solution (a) The surface energy will be greater than the grain boundary energy. For grain boundaries, some atoms on one side of a boundary will bond to atoms on the other side; such is not the case for surface atoms. Therefore, there will be fewer unsatisfied bonds along a grain boundary. (b) The small-angle grain boundary energy is lower than for a high-angle one because more atoms bond across the boundary for the small-angle, and, thus, there are fewer unsatisfied bonds.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.19 For each of the following stacking sequences found in FCC metals, cite the type of planar defect that exists: (a) . . . A B C A B C B A C B A . . . (b) . . . A B C A B C B C A B C . . .
Now, copy the stacking sequences and indicate the position(s) of planar defect(s) with a vertical dashed line. Solution (a) The interfacial defect that exists for this stacking sequence is a twin boundary, which occurs at the indicated position.
The stacking sequence on one side of this position is mirrored on the other side.
(b) The interfacial defect that exists within this FCC stacking sequence is a stacking fault, which occurs between the two lines.
Within this region, the stacking sequence is HCP.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Grain Size Determination 5.20 (a) Employing the intercept technique, determine the average grain size for the steel specimen whose microstructure is shown in Figure 10.29(a); use at least seven straight-line segments. (b) Estimate the ASTM grain size number for this material.
Solution (a) This portion of the problem calls for a determination of the average grain size of the specimen which microstructure is shown in Figure 10.29(a). Seven line segments were drawn across the micrograph, each of which was 60 mm long. The average number of grain boundary intersections for these lines was 6.3. Therefore, the average line length intersected is just 60 mm = 9.5 mm 6.3
Hence, the average grain diameter, d, is d =
9.5 mm ave. line length intersected = = 0.106 mm magnification 90
(b) This portion of the problem calls for us to estimate the ASTM grain size number for this same material. The average grain size number, n, is related to the number of grains per square inch, N, at a magnification of 100× according to Equation 5.19.
However, the magnification of this micrograph is not 100x, but rather 90×.
Consequently, it is necessary to use Equation 5.20 ⎛ M ⎞2 NM⎜ ⎟ = 2 n −1 ⎝ 100 ⎠
where NM = the number of grains per square inch at magnification M, and n is the ASTM grain size number. Taking logarithms of both sides of this equation leads to the following: ⎛M ⎞ log N M + 2 log ⎜ ⎟ = (n − 1) log 2 ⎝ 100 ⎠
Solving this expression for n gives ⎛M ⎞ log N M + 2 log ⎜ ⎟ ⎝ 100 ⎠ +1 n= log 2 Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
From Figure 10.29(a), NM is measured to be approximately 4, which leads to ⎛ 90 ⎞ log 4 + 2 log ⎜ ⎟ ⎝ 100 ⎠ +1 n= log 2
= 2.7
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.21 For an ASTM grain size of 6, approximately how many grains would there be per square inch at (a) a magnification of 100, and (b) without any magnification?
Solution (a) This part of problem asks that we compute the number of grains per square inch for an ASTM grain size of 6 at a magnification of 100×. All we need do is solve for the parameter N in Equation 5.19, inasmuch as n = 6. Thus N = 2 n−1
= 2 6−1 = 32 grains/in.2
(b) Now it is necessary to compute the value of N for no magnification. In order to solve this problem it is necessary to use Equation 5.20: ⎛ M ⎞2 NM⎜ ⎟ = 2 n −1 ⎝ 100 ⎠
where NM = the number of grains per square inch at magnification M, and n is the ASTM grain size number. Without any magnification, M in the above equation is 1, and therefore, ⎛ 1 ⎞2 N1 ⎜ ⎟ = 2 6−1 = 32 ⎝ 100 ⎠
And, solving for N1, N1 = 320,000 grains/in.2.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.22 Determine the ASTM grain size number if 25 grains per square inch are measured at a magnification of 75.
Solution In order to solve this problem we make use of Equation 5.20—viz. ⎛ M ⎞2 NM⎜ ⎟ = 2 n −1 ⎝ 100 ⎠
where NM = the number of grains per square inch at magnification M, and n is the ASTM grain size number. Solving the above equation for n, and realizing that NM = 25, while M = 75, we have ⎛M ⎞ log N M + 2 log ⎜ ⎟ ⎝ 100 ⎠ +1 n= log 2 ⎛ 75 ⎞ log 25 + 2 log ⎜ ⎟ ⎝ 100 ⎠ + 1 = 4.8 = log 2
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
DESIGN PROBLEMS
Specification of Composition 5.D1 Aluminum–lithium alloys have been developed by the aircraft industry to reduce the weight and improve the performance of its aircraft. A commercial aircraft skin material having a density of 2.47 g/cm3 is desired. Compute the concentration of Li (in wt%) that is required.
Solution This problem calls for us to compute the concentration of lithium (in wt%) that, when added to aluminum, will yield a density of 2.47 g/cm3. Solution of this problem requires the use of Equation 5.13a, which takes the form ρave =
100 100 − C Li + ρ Li ρ Al
CLi
inasmuch as CLi + CAl = 100. According to the table inside the front cover, the respective densities of Li and Al are 0.534 and 2.71 g/cm3. Upon solving for CLi from the above equation, we get
C Li =
=
100 ρ Li (ρ Al − ρave ) ρave (ρ Al − ρ Li )
(100) (0.534 g /cm3)(2.71 g /cm3 − 2.47 g /cm3)
(2.47 g /cm3)(2.71 g /cm3 − 0.534 g /cm3)
= 2.38 wt%
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.D2 Gallium arsenide (GaAs) and indium arsenide (InAs) both have the zinc blende crystal structure and are soluble in each other at all concentrations. Determine the concentration in weight percent of InAs that must be added to GaAs to yield a unit cell edge length of 0.5820 nm. The densities of GaAs and InAs are 5.316 and 5.668 g/cm3, respectively.
Solution This problem asks that we determine the concentration (in weight percent) of InAs that must be added to GaAs to yield a unit cell edge length of 0.5820 nm. The densities of GaAs and InAs were given in the problem statement as 5.316 and 5.668 g/cm3, respectively. To begin, it is necessary to employ Equation 3.6, and solve for the unit cell volume, VC, for the InAs-GaAs alloy as
VC =
n' Aave
ρave N A
where Aave and ρave are the atomic weight and density, respectively, of the InAs-GaAs alloy. Inasmuch as both of these materials have the zinc blende crystal structure, which has cubic symmetry, VC is just the cube of the unit cell length, a. That is VC = a3 = (0.5820 nm)3 = (5.820 × 10−8 cm)3 = 1.971 × 10−22 cm3
It is now necessary to construct expressions for Aave and ρave in terms of the concentration of indium arsenide, CInAs using Equations 5.14a and 5.13a. For Aave we have Aave =
100 C InAs AInAs
=
+
(100
− C InAs ) AGaAs
100 CInAs 189.74 g / mol
+
(100
− C InAs )
144.64 g / mol
whereas for ρave
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
ρave =
100 C InAs
+
ρ InAs
=
− C InAs ) ρGaAs
(100
100 C InAs 5.668 g /cm3
+
− C InAs ) 5.316 g /cm3
(100
Within the zinc blende unit cell there are four formula units, and thus, the value of n' in Equation 3.6 is 4; hence, this expression may be written in terms of the concentration of InAs in weight percent as follows: VC = 1.971 x 10-22 cm3
=
n' Aave
ρave N A
⎡ ⎤ ⎢ ⎥ 100 ⎥ (4 fu / unit cell) ⎢ C InAs (100 − CInAs ) ⎥ ⎢ ⎢ 189.74 g / mol + 144.64 g / mol ⎥ ⎣ ⎦ = ⎡ ⎤ ⎢ ⎥ 100 ⎢ ⎥ (6.02 × 1023 fu / mol) ⎢ (100 − CInAs ) ⎥ CInAs + ⎢ ⎥ 5.316 g /cm3 ⎦ ⎣ 5.668 g /cm3
And solving this expression for CInAs leads to CInAs = 46.1 wt%.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
IMPERFECTIONS IN SOLIDS
PROBLEM SOLUTIONS
Vacancies and Self-Interstitials 5.1 Calculate the fraction of atom sites that are vacant for copper at its melting temperature of 1084°C (1357 K). Assume an energy for vacancy formation of 0.90 eV/atom. Solution In order to compute the fraction of atom sites that are vacant in copper at 1357 K, we must employ Equation 5.1. As stated in the problem, Qv = 0.90 eV/atom. Thus, ⎡ ⎤ ⎛ Q ⎞ 0.90 eV /atom ⎥ = exp ⎜− v ⎟ = exp ⎢− N ⎢⎣ (8.62 × 10−5 eV /atom - K) (1357 K) ⎥⎦ ⎝ kT ⎠
Nv
= 4.56 × 10-4
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.2 Calculate the energy for vacancy formation in silver, given that the equilibrium number of vacancies at 800°C (1073 K) is 3.6 × 1023 m–3. The atomic weight and density (at 800°C) for silver are, respectively, 107.9 g/mol and 9.5 g/cm3. Solution This problem calls for the computation of the activation energy for vacancy formation in silver. Upon examination of Equation 5.1, all parameters besides Qv are given except N, the total number of atomic sites. However, N is related to the density, (ρ), Avogadro's number (NA), and the atomic weight (A) according to Equation 5.2 as
N =
=
N A ρ Pb APb
(6.02 × 1023 atoms / mol)(9.5 g /cm3 ) 107.9 g / mol
= 5.30 × 1022 atoms/cm3 = 5.30 × 1028 atoms/m3
Now, taking natural logarithms of both sides of Equation 5.1, Q ln N v = ln N − v kT
and, after some algebraic manipulation ⎛N ⎞ Qv = − kT ln ⎜ v ⎟ ⎝ N ⎠
Now, inserting values for the parameters given in the problem statement leads to ⎡ 3.60 × 1023 m−3 ⎤ Qv = − (8.62 × 10-5 eV/atom - K) (800°C + 273 K) ln ⎢ ⎥ ⎣ 5.30 × 1028 m−3 ⎦
= 1.10 eV/atom
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Point Defects in Ceramics 5.3 Calculate the fraction of lattice sites that are Schottky defects for cesium chloride at its melting temperature (645°C). Assume an energy for defect formation of 1.86 eV. Solution In order to solve this problem it is necessary to use Equation 5.4 and solve for the Ns/N ratio. Rearrangement of this expression and substituting values for the several parameters leads to Ns N
⎛ Q ⎞ = exp ⎜− s ⎟ ⎝ 2kT ⎠
⎡ ⎤ 1.86 eV = exp ⎢− ⎥ -5 ⎣ (2)(8.62 × 10 eV/K)(645 + 273 K) ⎦
= 7.87 × 10-6
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.4 Using the data given below that relate to the formation of Schottky defects in some oxide ceramic (having the chemical formula MO), determine the following: (a) the energy for defect formation (in eV), (b) the equilibrium number of Schottky defects per cubic meter at 1000°C, and (c) the identity of the oxide (i.e., what is the metal M?)
T (°C)
ρ (g/cm3)
Ns (m–3)
750
3.50
5.7 × 109
1000
3.45
?
1500
3.40
5.8 × 1017
Solution The (a) portion of the problem asks that we compute the energy for defect formation. To begin, let us combine a modified form of Equation 5.2 and Equation 5.4 as ⎛ Q ⎞ N s = N exp ⎜− s ⎟ ⎝ 2kT ⎠ ⎛ N ρ ⎞ ⎛ Q ⎞ A ⎟⎟ exp ⎜− s ⎟ = ⎜⎜ ⎝ 2kT ⎠ ⎝ AM + AO ⎠
Inasmuch as this is a hypothetical oxide material, we don't know the atomic weight of metal M, nor the value of Qs in the above equation. Therefore, let us write equations of the above form for two temperatures, T1 and T2. These are as follows: ⎛ N ρ ⎞ ⎛ ⎞ A 1 ⎟ exp ⎜− Qs ⎟ N s1 = ⎜⎜ ⎟ ⎟ ⎜ ⎝ AM + AO ⎠ ⎝ 2kT1 ⎠
(5.S1a)
⎛ N ρ ⎞ ⎛ ⎞ A 2 ⎟ exp ⎜− Qs ⎟ N s2 = ⎜⎜ ⎟ ⎜ 2kT ⎟ ⎝ AM + AO ⎠ ⎝ 2⎠
(5.S1b)
Dividing the first of these equations by the second leads to
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
⎛ N ρ ⎞ ⎛ A 1 ⎟ exp ⎜− ⎜⎜ ⎟ ⎜ N s1 ⎝ AM + AO ⎠ ⎝ = ⎞ ⎛ N ρ ⎛ N s2 A 2 ⎟ exp ⎜− ⎜⎜ ⎟ ⎜ ⎝ AM + AO ⎠ ⎝
Qs ⎞ ⎟ 2kT1 ⎟⎠ Qs ⎞ ⎟ 2kT2 ⎟⎠
which, after some algebraic manipulation, reduces to the form N s1 N s2
=
⎡ Q ⎛1 1 ⎞⎤ ⎟⎥ exp ⎢− s ⎜⎜ − ρ2 T2 ⎟⎠⎥⎦ ⎢⎣ 2k ⎝ T1 ρ1
(5.S2)
Now, taking natural logarithms of both sides of this equation gives ⎛N ⎞ ⎛ρ ⎞ Q ln ⎜⎜ s1 ⎟⎟ = ln ⎜⎜ 1 ⎟⎟ − s 2k ⎝ N s2 ⎠ ⎝ ρ2 ⎠
⎛1 1⎞ ⎜⎜ ⎟ − T2 ⎟⎠ ⎝ T1
and solving for Qs leads to the expression ⎡ ⎛N ⎞ −2k ⎢ ln⎜⎜ s1 ⎟⎟ ⎢⎣ ⎝ N s2 ⎠ Qs = 1 − T1
⎛ ρ ⎞⎤ − ln⎜⎜ 1 ⎟⎟⎥ ⎝ ρ2 ⎠⎦⎥ 1 T2
Let us take T1 = 750°C and T2 = 1500°C, and we may compute the value of Qs as ⎡ ⎛ 5.7 × 109 m-3 ⎞ ⎛ 3.50 g/cm3 ⎞⎤ − ln −(2)(8.62 × 10-5 eV/K) ⎢ ln ⎜ ⎟ ⎟⎥ ⎜ ⎢⎣ ⎝ 5.8 × 1017 m-3 ⎠ ⎝ 3.40 g/cm3 ⎠⎥⎦ Qs = 1 1 − 750 + 273 K 1500 + 273 K
= 7.70 eV (b) It is now possible to solve for Ns at 1000°C using Equation 5.S2 above. This time let's take T1 = 1000°C and T2 = 750°C. Thus, solving for Ns1, substituting values provided in the problem statement and Qs determined above yields
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
N s1 =
=
(5.7 × 10 9 m-3 )( 3.45 g/cm3) 3.50 g/cm3
N s2 ρ1 ρ2
⎡ Q ⎛1 1 ⎞⎤ ⎟⎥ exp ⎢− s ⎜⎜ − T2 ⎟⎠⎥⎦ ⎢⎣ 2k ⎝ T1
⎡ ⎛ ⎞⎤ 1 1 7.70 eV exp ⎢− − ⎜ ⎟⎥ 750 + 273 K ⎠⎥⎦ ⎢⎣ (2)(8.62 × 10-5 eV/K) ⎝ 1000 + 273 K
= 3.0 × 1013 m-3
(c) And, finally, we want to determine the identity of metal M. This is possible by computing the atomic weight of M (AM) from Equation 5.S1a. Rearrangement of this expression leads to ⎛ N ρ ⎞ ⎛ ⎞ A 1 ⎟ = N exp ⎜ Qs ⎟ ⎜⎜ ⎟ ⎜ 2kT ⎟ s1 ⎝ AM + AO ⎠ ⎝ 1⎠
And, after further algebraic manipulation ⎡ ⎤ ⎢ ⎥ N Aρ1 ⎢ ⎥ = AM + AO ⎢ ⎛ ⎞⎥ ⎢ N exp ⎜ Qs ⎟ ⎥ ⎜ 2kT ⎟ ⎥ ⎢ s1 ⎝ 1 ⎠⎦ ⎣
And, solving this expression for AM gives ⎡ ⎤ ⎢ ⎥ N Aρ1 ⎢ ⎥ AM = ⎢ − AO ⎛ Q ⎞⎥ ⎢ N exp ⎜ s ⎟ ⎥ ⎜ 2kT ⎟ ⎥ ⎢ s1 ⎝ 1 ⎠⎦ ⎣
Now, assuming that T1 = 750°C, the value of AM is
AM
⎧ ⎫ ⎪ ⎪ 23 3 6 3 3 ⎪ ⎪ (6.02 × 10 ions/mol)( 3.50 g/cm )(10 cm / m ) = ⎨ ⎬ − 16.00 g/mol ⎤ ⎡ 7.7 eV ⎪ (5.7 × 109 ions/m3 ) exp ⎪ ⎥⎪ ⎢ -5 ⎪⎩ ⎣ (2)(8.62 × 10 eV/K)(750 + 273 K) ⎦ ⎭
= 24.45 g/mol Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Upon consultation of the periodic table in Figure 2.6, the divalent metal (i.e., that forms M2+ ions) that has an atomic weight closest to 24.45 g/mol is magnesium. Thus, this metal oxide is MgO.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Impurities in Solids 5.5 Below, atomic radius, crystal structure, electronegativity, and the most common valence are tabulated, 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
1.9
+1
Al
0.1431
FCC
1.5
+3
Co
0.1253
HCP
1.8
+2
Cr
0.1249
BCC
1.6
+3
Fe
0.1241
BCC
1.8
+2
Pt
0.1387
FCC
2.2
+2
Zn
0.1332
HCP
1.6
+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 In this problem we are asked to cite which of the elements listed form with Ni the three possible solid solution types. For complete substitutional solubility the following criteria must be met: 1) the difference in atomic radii between Ni and the other element (ΔR%) 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, or nearly the same. Below are tabulated, for the various elements, these criteria.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Element
ΔR%
Ni C H O Ag Al Co Cr Fe Pt Zn
–43 –63 –52 +16 +15 +0.6 +0.2 -0.4 +11 +7
Crystal Structure
ΔElectronegativity
FCC
FCC FCC HCP BCC BCC FCC HCP
Valence 2+
+0.1 -0.3 0 -0.2 0 +0.4 -0.2
1+ 3+ 2+ 3+ 2+ 2+ 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.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.6 (a) Suppose that CaO is added as an impurity to Li2O. If the Ca2+ substitutes for Li+, what kind of vacancies would you expect to form? How many of these vacancies are created for every Ca2+ added? (b) Suppose that CaO is added as an impurity to CaCl2. If the O2– substitutes for Cl–, what kind of vacancies would you expect to form? How many of these vacancies are created for every O2– added? Solution (a) For Ca2+ substituting for Li+ in Li2O, lithium vacancies would be created. For each Ca2+ substituting for Li+, one positive charge is added; in order to maintain charge neutrality, a single positive charge may be removed. Positive charges are eliminated by creating lithium vacancies, and for every Ca2+ ion added, a single lithium vacancy is formed. (b) For O2- substituting for Cl- in CaCl2, chlorine vacancies would be created. For each O2- substituting for a Cl-, one negative charge is added; negative charges are eliminated by creating chlorine vacancies. In order to maintain charge neutrality, one O2- ion will lead to the formation of one chlorine vacancy.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Specification of Composition 5.7 What is the composition, in atom percent, of an alloy that consists of 92.5 wt% Ag and 7.5 wt% Cu? Solution In order to compute composition, in atom percent, of a 92.5 wt% Ag-7.5 wt% Cu alloy, we employ Equation 5.9 as
' = C Ag
=
C Ag ACu C Ag ACu + CCu AAg
× 100
(92.5)(63.55 g / mol) × 100 (92.5)(63.55 g / mol) + (7.5)(107.87g / mol)
= 87.9 at%
' = CCu
=
CCu AAg C Ag ACu + CCu AAg
× 100
(7.5)(107.87 g / mol) × 100 (92.5)(63.55 g / mol) + (7.5)(107.87g / mol)
= 12.1 at%
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.8 Calculate the composition, in weight percent, of an alloy that contains 105 kg of iron, 0.2 kg of carbon, and 1.0 kg of chromium. Solution The concentration, in weight percent, of an element in an alloy may be computed using a modified form of Equation 5.6. For this alloy, the concentration of iron (CFe) is just
C Fe =
=
mFe
mFe + mC + mCr
× 100
105 kg × 100 = 98.87 wt% 105 kg + 0.2 kg + 1.0 kg
Similarly, for carbon CC =
0.2 kg × 100 = 0.19 wt% 105 kg + 0.2 kg + 1.0 kg
CCr =
1.0 kg × 100 = 0.94 wt% 105 kg + 0.2 kg + 1.0 kg
And for chromium
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.9 What is the composition, in atom percent, of an alloy that contains 44.5 lbm of silver, 83.7 lbm of gold, and 5.3 lbm of Cu?
Solution To determine the concentrations, in atom percent, of the Ag-Au-Cu alloy, it is first necessary to convert the amounts of Ag, Au, and Cu into grams. ' = (44.5 lb )(453.6 g/lb ) = 20,185 g mAg m m
' = (83.7 lb )(453.6 g/lb ) = 37, 966 g mAu m m
' = (5.3 lb )(453.6 g/lb ) = 2, 404 g mCu m m
These masses must next be converted into moles (Equation 5.7), as
nm
' mAg
=
=
AAg
Ag
nm
37,966 g = 192.8 mol 196.97 g / mol
=
Au
nm
Cu
20,185 g = 187.1 mol 107.87 g / mol
=
2, 404 g = 37.8 mol 63.55 g / mol
Now, employment of a modified form of Equation 5.8, gives
' = C Ag
nm
Ag
nm
Ag
=
+ nm
Au
+ nm
× 100
Cu
187.1 mol × 100 = 44.8 at% 187.1 mol + 192.8 mol + 37.8 mol
' C Au =
192.8 mol × 100 = 46.2 at% 187.1 mol + 192.8 mol + 37.8 mol
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
' CCu =
37.8 mol × 100 = 9.0 at% 187.1 mol + 192.8 mol + 37.8 mol
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.10 Convert the atom percent composition in Problem 5.9 to weight percent. Solution The composition in atom percent for Problem 5.9 is 44.8 at% Ag, 46.2 at% Au, and 9.0 at% Cu. Modification of Equation 5.10 to take into account a three-component alloy leads to the following
C Ag =
' A C Ag Ag
=
× 100
Ag AAg + C Au AAu + CCu ACu
C'
'
'
(44.8) (107.87 g / mol) × 100 (44.8)(107.87 g / mol) + (46.2) (196.97 g / mol) + (9.0) (63.55 g / mol)
= 33.3 wt%
C Au =
' A CAu Au
CAg AAg + '
=
× 100
Au AAu + CCu ACu
C'
'
(46.2) (196.97 g / mol) × 100 (44.8)(107.87 g / mol) + (46.2) (196.97 g / mol) + (9.0) (63.55 g / mol)
= 62.7 wt%
CCu =
' A CCu Cu
CAg AAg + '
=
Au AAu +
C'
× 100 C'
Cu ACu
(9.0) (63.55 g / mol) × 100 (44.8)(107.87 g / mol) + (46.2) (196.97 g / mol) + (9.0) (63.55 g / mol)
= 4.0 wt%
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.11 Determine the approximate density of a Ti-6Al-4V titanium alloy that has a composition of 90 wt% Ti, 6 wt% Al, and 4 wt% V.
Solution In order to solve this problem, Equation 5.13a is modified to take the following form: ρave =
CTi ρTi
+
100 C Al ρ Al
+
CV ρV
And, using the density values for Ti, Al, and V—i.e., 4.51 g/cm3, 2.71 g/cm3, and 6.10 g/cm3—(as taken from inside the front cover of the text), the density is computed as follows: ρave =
90 wt% 4.51 g /cm3
+
100 6 wt% 2.71 g /cm 3
+
4 wt% 6.10 g /cm3
= 4.38 g/cm3
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.12 Some hypothetical alloy is composed of 25 wt% of metal A and 75 wt% of metal B. If the densities of metals A and B are 6.17 and 8.00 g/cm3, respectively, whereas their respective atomic weights are 171.3 and 162.0 g/mol, determine whether the crystal structure for this alloy is simple cubic, face-centered cubic, or body-centered cubic. Assume a unit cell edge length of 0.332 nm. Solution In order to solve this problem it is necessary to employ Equation 3.5; in this expression density and atomic weight will be averages for the alloy—that is ρave =
nAave VC N A
Inasmuch as for each of the possible crystal structures, the unit cell is cubic, then VC = a3, or
ρave =
nAave a3N A
And, in order to determine the crystal structure it is necessary to solve for n, the number of atoms per unit cell. For n =1, the crystal structure is simple cubic, whereas for n values of 2 and 4, the crystal structure will be either BCC or FCC, respectively. When we solve the above expression for n the result is as follows:
n =
ρave a 3 N A Aave
Expressions for Aave and ρave are found in Equations 5.14a and 5.13a, respectively, which, when incorporated into the above expression yields ⎛ ⎞ ⎜ ⎟ 100 ⎜ ⎟a 3 N A ⎜ CA CB ⎟ + ⎜ ⎟ ρB ⎠ ⎝ ρA n = ⎞ ⎛ ⎟ ⎜ 100 ⎟ ⎜ ⎜ CA CB ⎟ + ⎟ ⎜ AB ⎠ ⎝ AA
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Substitution of the concentration values (i.e., CA = 25 wt% and CB = 75 wt%) as well as values for the other parameters given in the problem statement, into the above equation gives ⎛ ⎞ ⎜ ⎟ 100 ⎜ ⎟(3.32 × 10-8 nm)3 (6.02 × 1023 atoms/mol) ⎜ 25 wt% + 75 wt% ⎟ ⎜ ⎟ 8.00 g/cm3 ⎠ ⎝ 6.17 g/cm3 n = ⎛ ⎞ ⎜ ⎟ 100 ⎜ ⎟ 75 wt% ⎟ ⎜ 25 wt% + ⎜ ⎟ 162.0 g/mol ⎠ ⎝ 171.3 g/mol
= 1.00 atom/unit cell Therefore, on the basis of this value, the crystal structure is simple cubic.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.13
Molybdenum forms a substitutional solid solution with tungsten.
Compute the number of
molybdenum atoms per cubic centimeter for a molybdenum-tungsten alloy that contains 16.4 wt% Mo and 83.6 wt% W. The densities of pure molybdenum and tungsten are 10.22 and 19.30 g/cm3, respectively. Solution To solve this problem, employment of Equation 5.21 (which derivation is called for in problem W5.16 on the book’s Web site) is necessary, using the following values: C1 = CMo = 16.4 wt% ρ1 = ρMo = 10.22 g/cm3 ρ2 = ρW = 19.3 g/cm3 A1 = AMo = 95.94 g/mol Thus
N Mo =
C Mo AMo ρ Mo
=
N AC Mo +
AMo ρW
(100
− CMo )
(6.02 × 1023 atoms / mol) (16.4 wt%) 95.94 g / mol (16.4 wt%)(95.94 g / mol) + (100 − 16.4 wt%) 19.3 g /cm3 10.22 g /cm3
= 1.73 × 1022 atoms/cm3
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.14 Sometimes it is desirable to be able to determine the weight percent of one element, C1, that will produce a specified concentration in terms of the number of atoms per cubic centimeter, N1, for an alloy composed of two types of atoms. This computation is possible using the following expression: C1 =
100 ρ N A ρ2 − 2 1+ N1 A1 ρ1
(5.22)
where NA = Avogadro’s number ρ1 and ρ2 = densities of the two elements A1 and A2 = the atomic weights of the two elements Derive Equation 5.22 using Equation 5.2 and expressions contained in Section 5.6. Solution The number of atoms of component 1 per cubic centimeter is just equal to the atom fraction of component 1
(c ' ) 1
times the total number of atoms per cubic centimeter in the alloy (N). Thus, using the equivalent of
Equation 5.2, we may write
N 1 = c1' N =
c1' N A ρave Aave
Realizing that
c1' =
C1' 100
and
C 2' = 100 − C1'
and substitution of the expressions for ρave and Aave, Equations 5.13b and 5.14b, respectively, leads to
N1 =
c1' N Aρave Aave
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
N AC1' ρ1 ρ 2
=
C1' ρ 2 A1 + (100 − C1' ) ρ1 A2
And, solving for C1'
C1' =
100 N 1 ρ1 A2 N Aρ1 ρ 2 − N 1 ρ 2 A1 + N 1 ρ1 A2
Substitution of this expression for C1' into Equation 5.10a, which may be written in the following form
C1 =
C1' A1
× 100
C1' A1 + C2' A2
C1' A1
=
C'
1 A1
× 100
+ (100 − C1 ) A2 '
yields C1 =
1+
100 N A ρ2
N 1 A1
−
ρ2 ρ1
the desired expression.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.15 Germanium forms a substitutional solid solution with silicon. Compute the weight percent of germanium that must be added to silicon to yield an alloy that contains 2.43 × 1021 Ge atoms per cubic centimeter. The densities of pure Ge and Si are 5.32 and 2.33 g/cm3, respectively.
Solution To solve this problem, employment of Equation 5.22 is necessary, using the following values: N1 = NGe = 2.43 x 1021 atoms/cm3 ρ1 = ρGe = 5.32 g/cm3 ρ2 = ρSi = 2.33 g/cm3 A1 = AGe = 72.64 g/mol A2 = ASi = 28.09 g/mol
Thus CGe =
1+
100 N AρSi
N Ge AGe
−
ρSi
ρGe
100
= 1+
⎛ 2.33 g /cm3 ⎞ × atoms / mol)(2.33 g /cm3 ) − ⎟ ⎜ (2.43 × 1021 atoms /cm3 ) (72.64 g / mol) ⎝ 5.32 g /cm3 ⎠
(6.02
1023
= 11.7 wt%
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.16 Iron and vanadium both have the BCC crystal structure, and V forms a substitutional solid solution for concentrations up to approximately 20 wt% V at room temperature. Compute the unit cell edge length for a 90 wt% Fe–10 wt% V alloy. Solution First of all, the atomic radii for Fe and V (using the table inside the front cover) are 0.124 and 0.132 nm, respectively. Also, using Equation 3.5 it is possible to compute the unit cell volume, and inasmuch as the unit cell is cubic, the unit cell edge length is just the cube root of the volume. However, it is first necessary to calculate the density and average atomic weight of this alloy using Equations 5.13a and 5.14a. Inasmuch as the densities of iron and vanadium are 7.87g/cm3 and 6.10 g/cm3, respectively, (as taken from inside the front cover), the average density is just ρave =
100 CV
ρV
C Fe
+
ρ Fe
100
=
10 wt% 6.10 g /cm3
+
90 wt% 7.87 g /cm3
= 7.65 g/cm3
And for the average atomic weight Aave =
100 CV AV
=
+
C Fe AFe
100 90 wt% 10 wt% + 55.85 g / mol 50.94 g / mole
= 55.32 g/mol Now, VC is determined from Equation 3.5 as
VC =
nAave
ρave N A
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
=
(2 atoms / unit cell)(55.32 g / mol) (7.65 g /cm3 )(6.02 × 1023 atoms / mol)
= 2.40 × 10-23 cm3/unit cell
And, finally a = (VC )1/ 3
= (2.40 × 10 −23cm3/unit cell)1/3 = 2.89 x 10-8 cm = 0.289 nm
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Interfacial Defects 5.17 For an FCC single crystal, would you expect the surface energy for a (100) plane to be greater or less than that for a (111) plane? Why? (Note: You may want to consult the solution to Problem W3.46 at the end of Chapter 3.)
Solution The surface energy for a crystallographic plane will depend on its packing density [i.e., the planar density (Section 3.11)]—that is, the higher the packing density, the greater the number of nearest-neighbor atoms, and the more atomic bonds in that plane that are satisfied, and, consequently, the lower the surface energy. From the 1 1 solution to Problem W3.46, planar densities for FCC (100) and (111) planes are and , respectively— 2 2 4R 2R 3 0.25 0.29 and (where R is the atomic radius). Thus, since the planar density for (111) is greater, it will have that is 2 R R2 the lower surface energy.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.18 (a) For a given material, would you expect the surface energy to be greater than, the same as, or less than the grain boundary energy? Why? (b) The grain boundary energy of a small-angle grain boundary is less than for a high-angle one. Why is this so?
Solution (a) The surface energy will be greater than the grain boundary energy. For grain boundaries, some atoms on one side of a boundary will bond to atoms on the other side; such is not the case for surface atoms. Therefore, there will be fewer unsatisfied bonds along a grain boundary. (b) The small-angle grain boundary energy is lower than for a high-angle one because more atoms bond across the boundary for the small-angle, and, thus, there are fewer unsatisfied bonds.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.19 For each of the following stacking sequences found in FCC metals, cite the type of planar defect that exists: (a) . . . A B C A B C B A C B A . . . (b) . . . A B C A B C B C A B C . . .
Now, copy the stacking sequences and indicate the position(s) of planar defect(s) with a vertical dashed line. Solution (a) The interfacial defect that exists for this stacking sequence is a twin boundary, which occurs at the indicated position.
The stacking sequence on one side of this position is mirrored on the other side.
(b) The interfacial defect that exists within this FCC stacking sequence is a stacking fault, which occurs between the two lines.
Within this region, the stacking sequence is HCP.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
Grain Size Determination 5.20 (a) Employing the intercept technique, determine the average grain size for the steel specimen whose microstructure is shown in Figure 10.29(a); use at least seven straight-line segments. (b) Estimate the ASTM grain size number for this material.
Solution (a) This portion of the problem calls for a determination of the average grain size of the specimen which microstructure is shown in Figure 10.29(a). Seven line segments were drawn across the micrograph, each of which was 60 mm long. The average number of grain boundary intersections for these lines was 6.3. Therefore, the average line length intersected is just 60 mm = 9.5 mm 6.3
Hence, the average grain diameter, d, is d =
9.5 mm ave. line length intersected = = 0.106 mm magnification 90
(b) This portion of the problem calls for us to estimate the ASTM grain size number for this same material. The average grain size number, n, is related to the number of grains per square inch, N, at a magnification of 100× according to Equation 5.19.
However, the magnification of this micrograph is not 100x, but rather 90×.
Consequently, it is necessary to use Equation 5.20 ⎛ M ⎞2 NM⎜ ⎟ = 2 n −1 ⎝ 100 ⎠
where NM = the number of grains per square inch at magnification M, and n is the ASTM grain size number. Taking logarithms of both sides of this equation leads to the following: ⎛M ⎞ log N M + 2 log ⎜ ⎟ = (n − 1) log 2 ⎝ 100 ⎠
Solving this expression for n gives ⎛M ⎞ log N M + 2 log ⎜ ⎟ ⎝ 100 ⎠ +1 n= log 2 Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
From Figure 10.29(a), NM is measured to be approximately 4, which leads to ⎛ 90 ⎞ log 4 + 2 log ⎜ ⎟ ⎝ 100 ⎠ +1 n= log 2
= 2.7
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.21 For an ASTM grain size of 6, approximately how many grains would there be per square inch at (a) a magnification of 100, and (b) without any magnification?
Solution (a) This part of problem asks that we compute the number of grains per square inch for an ASTM grain size of 6 at a magnification of 100×. All we need do is solve for the parameter N in Equation 5.19, inasmuch as n = 6. Thus N = 2 n−1
= 2 6−1 = 32 grains/in.2
(b) Now it is necessary to compute the value of N for no magnification. In order to solve this problem it is necessary to use Equation 5.20: ⎛ M ⎞2 NM⎜ ⎟ = 2 n −1 ⎝ 100 ⎠
where NM = the number of grains per square inch at magnification M, and n is the ASTM grain size number. Without any magnification, M in the above equation is 1, and therefore, ⎛ 1 ⎞2 N1 ⎜ ⎟ = 2 6−1 = 32 ⎝ 100 ⎠
And, solving for N1, N1 = 320,000 grains/in.2.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.22 Determine the ASTM grain size number if 25 grains per square inch are measured at a magnification of 75.
Solution In order to solve this problem we make use of Equation 5.20—viz. ⎛ M ⎞2 NM⎜ ⎟ = 2 n −1 ⎝ 100 ⎠
where NM = the number of grains per square inch at magnification M, and n is the ASTM grain size number. Solving the above equation for n, and realizing that NM = 25, while M = 75, we have ⎛M ⎞ log N M + 2 log ⎜ ⎟ ⎝ 100 ⎠ +1 n= log 2 ⎛ 75 ⎞ log 25 + 2 log ⎜ ⎟ ⎝ 100 ⎠ + 1 = 4.8 = log 2
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
DESIGN PROBLEMS
Specification of Composition 5.D1 Aluminum–lithium alloys have been developed by the aircraft industry to reduce the weight and improve the performance of its aircraft. A commercial aircraft skin material having a density of 2.47 g/cm3 is desired. Compute the concentration of Li (in wt%) that is required.
Solution This problem calls for us to compute the concentration of lithium (in wt%) that, when added to aluminum, will yield a density of 2.47 g/cm3. Solution of this problem requires the use of Equation 5.13a, which takes the form ρave =
100 100 − C Li + ρ Li ρ Al
CLi
inasmuch as CLi + CAl = 100. According to the table inside the front cover, the respective densities of Li and Al are 0.534 and 2.71 g/cm3. Upon solving for CLi from the above equation, we get
C Li =
=
100 ρ Li (ρ Al − ρave ) ρave (ρ Al − ρ Li )
(100) (0.534 g /cm3)(2.71 g /cm3 − 2.47 g /cm3)
(2.47 g /cm3)(2.71 g /cm3 − 0.534 g /cm3)
= 2.38 wt%
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
5.D2 Gallium arsenide (GaAs) and indium arsenide (InAs) both have the zinc blende crystal structure and are soluble in each other at all concentrations. Determine the concentration in weight percent of InAs that must be added to GaAs to yield a unit cell edge length of 0.5820 nm. The densities of GaAs and InAs are 5.316 and 5.668 g/cm3, respectively.
Solution This problem asks that we determine the concentration (in weight percent) of InAs that must be added to GaAs to yield a unit cell edge length of 0.5820 nm. The densities of GaAs and InAs were given in the problem statement as 5.316 and 5.668 g/cm3, respectively. To begin, it is necessary to employ Equation 3.6, and solve for the unit cell volume, VC, for the InAs-GaAs alloy as
VC =
n' Aave
ρave N A
where Aave and ρave are the atomic weight and density, respectively, of the InAs-GaAs alloy. Inasmuch as both of these materials have the zinc blende crystal structure, which has cubic symmetry, VC is just the cube of the unit cell length, a. That is VC = a3 = (0.5820 nm)3 = (5.820 × 10−8 cm)3 = 1.971 × 10−22 cm3
It is now necessary to construct expressions for Aave and ρave in terms of the concentration of indium arsenide, CInAs using Equations 5.14a and 5.13a. For Aave we have Aave =
100 C InAs AInAs
=
+
(100
− C InAs ) AGaAs
100 CInAs 189.74 g / mol
+
(100
− C InAs )
144.64 g / mol
whereas for ρave
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
ρave =
100 C InAs
+
ρ InAs
=
− C InAs ) ρGaAs
(100
100 C InAs 5.668 g /cm3
+
− C InAs ) 5.316 g /cm3
(100
Within the zinc blende unit cell there are four formula units, and thus, the value of n' in Equation 3.6 is 4; hence, this expression may be written in terms of the concentration of InAs in weight percent as follows: VC = 1.971 x 10-22 cm3
=
n' Aave
ρave N A
⎡ ⎤ ⎢ ⎥ 100 ⎥ (4 fu / unit cell) ⎢ C InAs (100 − CInAs ) ⎥ ⎢ ⎢ 189.74 g / mol + 144.64 g / mol ⎥ ⎣ ⎦ = ⎡ ⎤ ⎢ ⎥ 100 ⎢ ⎥ (6.02 × 1023 fu / mol) ⎢ (100 − CInAs ) ⎥ CInAs + ⎢ ⎥ 5.316 g /cm3 ⎦ ⎣ 5.668 g /cm3
And solving this expression for CInAs leads to CInAs = 46.1 wt%.
Excerpts from this work may be reproduced by instructors for distribution on a not-for-profit basis for testing or instructional purposes only to students enrolled in courses for which the textbook has been adopted. Any other reproduction or translation of this work beyond that permitted by Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner is unlawful.
