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This problem calls for us to predict crystal structures for several ceramic materials on the basis of ionic
charge and ionic radii.
(a) For CsI, using data from Table 12.3
rCs 0.170 nm
= = 0.773
rI 0.220 nm
Now, from Table 12.2, the coordination number for each cation (Cs +) is eight, and, using Table 12.4, the predicted
crystal structure is cesium chloride.
(b) For NiO, using data from Table 12.3
rNi2 0.069 nm
= = 0.493
rO 2 0.140 nm
The coordination number is six (Table 12.2), and the predicted crystal structure is sodium chloride (Table 12.4).
(c) For KI, using data from Table 12.3
rK 0.138 nm
= = 0.627
rI 0.220 nm
The coordination number is six (Table 12.2), and the predicted crystal structure is sodium chloride (Table 12.4).
(d) For NiS, using data from Table 12.3
rNi2 0.069 nm
= = 0.375
rS 2 0.184 nm
The coordination number is four (Table 12.2), and the predicted crystal structure is zinc blende (Table 12.4).
12.7 Compute the atomic packing factor for the rock salt crystal structure in which rC/rA = 0.414.
Solution
This problem asks that we compute the atomic packing factor for the rock salt crystal structure when rC/rA
VS
APF =
VC
With regard to the sphere volume, VS, there are four cation and four anion spheres per unit cell. Thus,
4 4
VS = (4) rA3 + (4) rC3
3 3
VS =
16 3
r 1 (0.414) 3 = (17.94) rA3
3 A
Now, for rC/rA = 0.414 the corner anions in Table 12.2 just touch one another along the cubic unit cell edges such
that
VC = a 3 = 2 (rA rC )
3
VS (17.94) rA3
APF = = = 0.79
VC (22.62) rA3
12.13 Calculate the density of FeO, given that it has the rock salt crystal structure.
Solution
We are asked to calculate the theoretical density of FeO. This density may be computed using Equation
(12.1) as
nAFe + AO
VC N A
Since the crystal structure is rock salt, n' = 4 formula units per unit cell. Using the ionic radii for Fe2+ and O2- from
Table 12.3, the unit cell volume is computed as follows:
3 3
VC a 3 2rFe 2+ + 2rO 2- 2 (0.077 nm) 2 (0.140 nm)
nm3 cm 3
= 0.0817 = 8.17 10-23
unit cell unit cell
Thus,
= 5.84 g/cm3
12.14 Magnesium oxide has the rock salt crystal structure and a density of 3.58 g/cm3.
(a) Determine the unit cell edge length.
(b) How does this result compare with the edge length as determined from the radii in Table 12.3,
assuming that the Mg2+ and O2- ions just touch each other along the edges?
Solution
(a) This part of the problem calls for us to determine the unit cell edge length for MgO. The density of
MgO is 3.58 g/cm3 and the crystal structure is rock salt. From Equation 12.1
Inasmuch as there are 4 formula units per unit cell for the rock salt crystal structure, and the atomic weights of
magnesium and oxygen are 24.31 and 16.00 g/mol, respectively, when we solve for a from the above equation
= 4.21 10 -8 cm = 0.421 nm
(b) The edge length is determined from the Mg2+ and O2- radii for this portion of the problem. Now for
the rock salt crystal structure
a = 2rMg 2+ + 2rO 2-
12.21 The unit cell for MgFe2O4 (MgO-Fe2O3) has cubic symmetry with a unit cell edge length of 0.836 nm. If the
density of this material is 4.52 g/cm3, compute its atomic packing factor. For this computation, you will need to use
ionic radii listed in Table 12.3.
Solution
This problem asks us to compute the atomic packing factor for MgFe 2O4 given its density and unit cell
edge length. It is first necessary to determine the number of formula units in the unit cell in order to calculate the
sphere volume. Solving for n' from Equation 12.1 leads to
VC N A
n'
AC + AA
Thus, in each unit cell there are 8 Mg2+, 16 Fe3+, and 32 O2- ions. From Table 12.3, r = 0.072 nm, r 3+ =
Mg2+ Fe
0.069 nm, and r 2- = 0.140 nm. Thus, the total sphere volume in Equation 3.2 (which we denote as VS), is just
O
4 4
VS = (8) (7.2 109 cm) 3 + (16) (6.9 109 cm) 3
3 3
4
+ (32) (1.40 108 cm) 3
3
Finally, the atomic packing factor (APF) from Equation 3.2 is just
V 4.02 10-22 cm3
APF S 0.688
VC 5.84 10-22 cm3
Solution
(a) For a Cu2+O2- compound in which a small fraction of the copper ions exist as Cu+, for each Cu+
formed there is one less positive charge introduced (or one more negative charge). In order to maintain charge
neutrality, we must either add an additional positive charge or subtract a negative charge. This may be
accomplished be either creating Cu2+ interstitials or O2- vacancies.
(b) There will be two Cu+ ions required for each of these defects.
(c) The chemical formula for this nonstoichiometric material is Cu1+xO or CuO1-x, where x is
some small fraction.
12.42 A three-point bending test is performed on a glass specimen having a rectangular cross section of height d =
5 mm (0.2 in.) and width b = 10 mm (0.4 in.); the distance between support points is 45 mm (1.75 in.).
(a) Compute the flexural strength if the load at fracture is 290 N (65 lbf).
(b) The point of maximum deflection Δy occurs at the center of the specimen and is described by
FL3
y =
48EI
where E is the modulus of elasticity and I is the cross-sectional moment of inertia. Compute y at a load of 266 N
(60 lbf).
Solution
(a) For this portion of the problem we are asked to compute the flexural strength for a glass specimen that
is subjected to a three-point bending test. The flexural strength (Equation 12.7a) is just
3F f L
fs =
2bd 2
for a rectangular cross-section. Using the values given in the problem statement,
(b) We are now asked to compute the maximum deflection. From Table 12.5, the elastic modulus (E) for
glass is 69 GPa (10 106 psi). Also, the moment of inertia for a rectangular cross section (Figure 12.32) is just
bd 3
I =
12
Thus,
FL3 FL3
y = =
bd 3 4Ebd 3
48E
12
Solution
(a) This portion of the problem requests that we compute the modulus of elasticity for nonporous BeO
given that E = 310 GPa for a material having 5 vol% porosity. Thus, we solve Equation 12.9 for E0, using P = 0.05,
which gives
E
E0 =
1 1.9P 0.9P 2
310 GPa
= = 342 GPa (49.6 106 psi)
1 (1.9)(0.05) (0.9)(0.05) 2
(b) Now we are asked to determine the value of E at P = 10 vol% (i.e., 0.10). Using Equation 12.9 we get
E = E0 (1 1.9P + 0.9P 2 )
= (342 GPa) 1 (1.9)(0.10) + (0.9)(0.10)2 = 280 GPa (40.6 106 psi)
the maximum temperature to which the following two magnesia–alumina refractory materials may be
13.4 Find
heated before a liquid phase will appear.
(a) A spinel-bonded alumina material of composition 95 wt% Al2O3-5 wt% MgO.
(b) A magnesia-alumina spinel of composition 65 wt% Al2O3-35 wt% MgO.
Consult Figure 12.25.
Solution
(a) From Figure 12.25, for a spinel-bonded magnesia material (95 wt% Al2O3-5 wt% MgO), the maximum
temperature without a liquid phase corresponds to the temperature of the eutectic isotherm on the Al 2O3-rich side of
slightly to the left of the congruent melting point at which the two phase boundaries become tangent); this
temperature is approximately 2030C (3685F).
13.13 The viscosity η of a glass varies with temperature according to the relationship
Q
A exp vis
RT
where Qvis is the energy of activation for viscous flow, A is a temperature-independent constant, and R and T are,
respectively, the gas constant and the absolute temperature. A plot of ln η versus l/T should be nearly linear, and
with a slope of Qvis/R. Using the data in Figure 13.7, (a) make such a plot for the borosilicate glass, and (b)
determine the activation energy between temperatures of 500 and 900°C.
Solution
(a) Below is shown the logarithm viscosity versus reciprocal of temperature plot for the borosilicate glass,
using the data in Figure 13.7. The dashed line has been drawn through the data points corresponding to
temperatures between 500 and 900ºC (as stipulated in the problem statement).
ln ln ln 2
Qvis = R R 1
1 1 1
T T1 T2
ln
where R is the gas constant, and is the slope of the dashed line that has been constructed. Taking 1/T1 and
1
T
1/T2 as 0.8 10-3 and 1.3 10-3 K-1, respectively, then the corresponding values of ln 1 and ln 2 are 10.59 and
32.50. Therefore,
ln ln 2 10.59 32.50
Qvis R 1 (8.31 J/mol K)
3 1 3 1
1 1 0.8 10 K 1.3 10 K
T1 T2
= 364,000 J/mol
13.14 For many viscous materials, the viscosity η may be defined in terms of the expression
=
d / dt
where σ and d/dt are, respectively, the tensile stress and the strain rate. A cylindrical specimen of a soda-lime glass
of diameter 5 mm (0.2 in.) and length 100 mm (4 in.) is subjected to a tensile force of 1 N (0.224 lb f) along its axis.
If its deformation is to be less than 1 mm (0.04 in.) over a week’s time, using Figure 13.7, determine the maximum
temperature to which the specimen may be heated.
Solution
This problem calls for us to determine the maximum temperature to which a cylindrical specimen of soda-
lime glass may be heated in order that its deformation be less than 1 mm over a week's time. According to Equation
6.1
F 1 N
= = 2
= 5.09 104 Pa
A0 5 103 m
2
Also,
l
d
l
d 0
=
dt dt
1 mm/100 mm
= = 1.653 10-8 s-1
(1 wk)(7 days
/ week )(24 h / day)(3600 s / h)
Thus,
5.09 10 4 Pa
= = = 3.1 1012 Pa- s
d/ dt 1.653 108 s1
From Figure 13.7, the temperature at which the viscosity of the soda-lime glass is 3.1 1012 Pa-s is about 500C
(930F).