Chapter 11
Chapter 11
2
% covalent character = e −0.25 ( X A − X B ) × 100%
Applying this equation, a table can be generated as follows.
Electronegativities % Covalent
Compound (XA –XB)2 -0.25(XA –XB)2
XA XB Character
HfC 1.2 2.5 1.69 -0.4225 65.5
TiC 1.3 2.5 1.44 -0.360 69.8
TaC 1.4 2.5 1.21 -0.3025 73.9
BC 2.0 2.5 0.25 -0.0625 93.9
SiC 1.8 2.5 0.49 -0.1225 88.5
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Foundations of Materials Science and Engineering 4/e
1. The relative size of the ions in the ionic solid, assuming the ions are hard spheres with definite radii;
2. The need to balance the electrostatic charges to maintain electrical neutrality within the ionic solid.
(b) The critical radius ratio is the ratio of the radius of the central cation to the radius of the surrounding anions.
Figure 11.59
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Figure 11.59 (a) Octahedral coordination of six anions (radii = R) around a central cation of radius r. (b)
Horizontal section through center of (a).
[2(r + R)]2 = ( 2 R )2 + ( 2 R )2
(r + R)2 = 2 R 2
r + R = 2R
r = 2 R − R = 0.414 R
r
= 0.414
R
This ratio is greater than 0.732 and greater than 1.0. This is an unusual case in which the cation is
larger than the anion because the elements respectively lie in Periods 6 and 2 of the periodic table. But
if we invert this ratio to represent an anion surrounded by cations, we obtain 0.93. BaO should thus
show cubic coordination (CN = 8). The solid is actually octahedral, CN = 6.
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This ratio is greater than 0.414 and less than 0.732, thus LiF should have an octahedron coordination
number, CN = 6, and it does.
2
a= (0.165 nm + 0.220 nm ) = 0.445 nm = 4.45 ×10−8 cm
3
−
Since the unit cell of CsI contains one Cs+ and one I ion, its mass is
m m 4.32 × 10−22 g
ρ= = 3= −8 3
= 4.90 g/cm 3
V a (4.45 ×10 cm)
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Foundations of Materials Science and Engineering 4/e
2
a= (0.165 nm + 0.196 nm ) = 0.417 nm = 4.17 ×10−8 cm
3
−
Since the unit cell of CsI contains one Cs+ and one Br ion, its mass is
m m 3.53 × 10−22 g
ρ= = 3= −8 3
= 4.87 g/cm 3
V a (4.17 ×10 cm)
2Ni 2+ 2Ni 2+
ρL = = = 3.37 Ni 2+ /nm
2a 2 (0.420 nm )
[ 110 ]
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2O 2− 2O 2−
ρL = = = 3.37 O 2− /nm
2a (
2 0.420 nm )
1O 2− 1O 2−
ρL = = = 1.37 O 2− /nm O 2−
3a 3 (0.420 nm )
1Ni 2+ 1Ni 2+
ρL = = = 1.37 Ni 2+ /nm
3a 3 (0.420 nm )
2Cd 2+ 2Cd 2+
ρL = = = 3.01 Cd 2+ /nm
2a 2 (0.470 nm )
2O 2− 2O 2−
ρL = = = 3.01 O 2− /nm
2a 2 ( 0.470 nm )
1O 2− 1O 2−
ρL = = = 1.23 O 2− /nm
3a (
3 0.470 nm )
1Ni 2+ 1Ni 2+
ρL = = = 1.23 Ni 2+ /nm
3a 3 (0.470 nm )
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Foundations of Materials Science and Engineering 4/e
2−
(a) For CoO, if we consider the O anions to be located at
the FCC positions of a cubic unit cell, then the (111) plane (111)
contains the equivalent of two anions.
The lattice constant is a = 2( r + R ) = 2(0.082 nm + 0.132 nm) = 0.428 nm . The area of the
(111) plane is,
3
A(111) = bh = ( 2a ) a =
1 1 3 2 3
a = (0.428 nm) 2 = 0.159 nm 2
2 2 2 2 2
2−
The planar density for the O anions then becomes,
2(O 2− ions)
ρ planar = 2
= 12.6 O 2- ions/nm 2
0.159 nm
The planar density of the Co2+ cations is the same if we consider them to be located at the FCC
lattice points of the unit cell. Consequently,
A(110) = bh = ( 2a ) ( a ) =
1 1 2 2 2
a = (0.428 nm) 2
2 2 2 2
= 0.13 nm 2
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2(O 2− ions)
ρ planar = 2
= 15.4 O 2- ions/nm 2
0.13 nm
2(Co 2+ ions)
ρ planar = 2
= 15.4 Co 2+ ions/nm 2
0.13 nm
(b) Similarly, for LiCl, the (111) planar densities are calculated as:
1 2 2 2
A(110) = bh = a = (0.518 nm) 2 = 0.19 nm 2
2 2 2
2(Cl− ions)
ρ planar = 2
= 10.5 Cl − ions/nm 2
0.19 nm
2(Li + ions)
ρ planar = 2
= 10.5 Li + ions/nm 2
0.19 nm
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m m 6.89 ×10−22 g
ρ= = 3= −8 3
= 4.96 g/cm 3
V a (5.18 ×10 cm)
m m 4.45 × 10−22 g
ρ= = 3= −8 3
= 7.27 g/cm 3
V a (3.94 ×10 cm)
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(a) For MnO, a = 2(0.091 nm + 0.132 nm) = 0.446 nm and the IPF is
16
3 π (r
3
+ R3 ) 16π (0.091 nm)3 + (0.132 nm)3
IPF = = = 0.577
a3 3(0.446 nm)3
(b) For SrO, a = 2(0.127 nm + 0.132 nm) = 0.518 nm and the IPF is
16
3 π (r
3
+ R3 ) 16π (0.127 nm)3 + (0.132 nm)3
IPF = = = 0.524
a3 3(0.518 nm)3
4 4
a= (r + R) = (0.083 nm + 0.211 nm) = 0.679 nm
3 3
(4Zn 2+ × 65.38 g/mol) + (4Te 2− × 127.6 g/mol)
m unit cell = = 1.28 ×10−21 g
6.02 × 1023 ions/mol
The density is thus calculated as,
m m 1.28 ×10−21 g
ρ= = 3= −8 3
= 4.09 g/cm 3
V a (6.79 ×10 cm)
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4 4
a= (r + R) = (0.034 nm + 0.132 nm) = 0.383 nm
3 3
(4Be 2+ × 9.012 g/mol) + (4O 2− × 16.00 g/mol)
m unit cell = 23
= 1.66 ×10−22 g
6.02 × 10 ions/mol
The density is thus calculated as,
m m 1.66 ×10−22 g
ρ= = 3= −8 3
= 2.95 g/cm 3
V a (3.83 × 10 cm)
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4 4
a= (r + R) = (0.087 nm + 0.132 nm) = 0.506 nm
3 3
(4Zr 2+ × 91.22 g/mol) + (8O 2− × 16.00 g/mol)
m unit cell = 23
= 8.19 ×10−22 g
6.02 ×10 ions/mol
The density is thus calculated as,
m m 8.19 ×10−22 g
ρ= = 3= −8 3
= 6.32 g/cm 3
V a (5.06 ×10 cm)
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1Ce 4+ + 2O 2− 1Ce 4+ + 2O 2−
ρL = =
3a 3 (0.540 nm )
= (1.07Ce4+ + 2.14 O 2− )/nm
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3
A(111) = bh = ( 2a ) a =
1 1 3 2 3
a = (0.559 nm) 2 = 0.270 nm 2
2 2 2 2 2
4+
The planar density for the Th cations on the (111) plane is thus,
2(Th 4+ ions)
ρ planar = 2
= 7.4 Th 4+ ions/nm 2
0.270 nm
For the (110) plane, we have two ions contained within the plane.
The area of the plane is,
A(110) = bh = ( 2a ) ( a ) =
1 1 2 2 2
a = (0.559 nm) 2
2 2 2 2
a
2
= 0.221 nm
The (110) planar densities for ThO are,
2−
Th 4+ O 2−
4(O ions)
ρ planar = = 18.1 O 2− ions/nm 2
0.221 nm 2
2(Th 4+ ions)
ρ planar = 2
= 9.1 Th 4+ ions/nm 2
0.221 nm
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4
where a = (0.127 nm + 0.133 nm) = 0.600 nm . Substituting,
3
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Ca 2+ = 0.106 nm, Ti 4+ = 0.064 nm, and O 2 − = 0.132 nm. Assume the lattice constant
a = 2 ( rTi 4+ + rO2− ).
where a = 2 r ( Ti 4 + )
+ rO2− = 2(0.064 nm + 0.132 nm) = 0.392 nm . Substituting,
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Problems and Solutions to Smith/Hashemi
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For a = 2 r ( Sn 4 + )
+ rO2 − = 2(0.074 nm + 0.132 nm) = 0.412 nm , and a unit cell mass of
m m 4.22 ×10−22 g
ρ= = 3= −8 3
= 6.03 g/cm 3
V a (4.12 ×10 cm)
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1. material preparation
2. forming or casting
3. thermal treatment by drying and firing to a high enough temperature for the particles to bond.
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1. A powdered ceramic material and a liquid are prepared as a stable suspension called a slip.
2. The slip is poured into a porous mold which absorbs some of the slip liquid. The remaining slip forms a
semihard layer on the mold surface.
3. For a drain casting process, excess slip is poured out of the cavity once a sufficient wall thickness has formed.
For a solid casting process, casting is continued until the entire mold cavity is filled.
4. The material in the mold is allowed to dry to provide adequate strength for handling and the subsequent removal
of the part from the mold.
5. Finally, the cast part is fired to attain the required microstructure and properties.
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Figure 11.34
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(b) For a porosity-free ceramic, the flaw size, and thus the strength, is solely a function of grain size; the finer the
grain size, the smaller the flaws at grain boundaries and the greater the ceramic tensile strength.
What is the largest-sized internal flaw that this material can support without fracturing? (Use Y = 1 in the fracture-
toughness equation.)
m m 4.45 × 10 − 22 g
ρ = = 3 = −8
= 7.27 g/cm 3
V a (3.94 × 10 cm ) 3
1 K IC 1 3.7 MPa- m
σf = = = 236 MPa
πa Y π (2.5 × 10−5 m) π
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2 2 2
1 K 1 7.5 MPa- m 7.5 MPa- m −5
a = IC = = = 4.60 ×10 m = 46.0 µ m
π Y σ f π π (352 MPa) π (352 MPa)
(a) If the sample fails at a stress of 450 MPa, what is the size of the largest surface flaw? Assume Y = √π .
(b) The same test is performed with a partially stabilized ZrO2 specimen. This material is transformation-toughened
and has a KIC = 12.5 MPa-√m. If this material has the same flaw distribution as the fully stabilized sample, what
stress must be applied to cause failure?
2 2
1 K 3.8 MPa- m −6
a = IC = = 7.23 × 10 m = 7.23 µm
π Y σ f π (450 MPa)
1 K IC 1 12.5 MPa- m
σf = = = 1480 MPa
π a π π 7.23 × 10−6 m
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The softening point is the temperature which corresponds to a viscosity of 108 poises and which represents the
thermal state at which glass will flow at an appreciable rate under its own weight.
The annealing point is the temperature which corresponds to a viscosity of 1013 poises and which represents the
thermal state at which internal stresses can be relieved.
The strain point is the temperature which corresponds to a viscosity of 1014.5 poises and which represents the
thermal state below which the glass is rigid and stress relaxation only occurs at a slow rate.
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ηstp Q 1 1
= exp −
ηsp R Tstp Tsp
1014.2 P Q 1 1
= exp −
107.5 P 8.314 J/mol ⋅ K 723 K 923 K
106.7 = exp (3.605 × 10−5 ) Q
ln106.7 = (3.605 × 10−5 ) Q
Q = 4.28 ×105 J/mol = 428 kJ/mol
η1 Q 1 1
= exp −
η2 R T1 T2
1014.6 P 430 ×103 J/mol 1 1
= exp −
η2 8.314 J/mol ⋅ K 833 K 948 K
1014.6 P
= exp(7.532) = 1866.6
η2
η2 = 2.133 ×1011 P = 1011.329 P ≈ 1011.33 P
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η1 Q 1 1
= exp −
η2 R T1 T2
1014.3 P 430 ×103 J/mol 1 1
= exp −
8.314 J/mol ⋅ K 843 K T2
9.9
10 P
1 1
ln104.4 = 51, 720 −
843 K T2
T2 = (0.0011862 − 0.0001959) −1 = 1009.7 K = 736.7o C
ηap Q 1 1
= exp −
ηsp R T Tsp
ap
1012.5 P Q 1 1
= exp −
8.314 J/mol ⋅ K 873 K 1073 K
7.4
10 P
105.1 = exp ( 2.568 × 10−5 ) Q
ln105.1 = ( 2.568 ×10−5 ) Q
Q = 4.573 ×105 J/mol = 457.3 kJ/mol
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Problems and Solutions to Smith/Hashemi
Foundations of Materials Science and Engineering 4/e
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