CH 12

CHAPTER 12
STRUCTURES AND PROPERTIES OF CERAMICS
PROBLEM SOLUTIONS
Crystal Structures
12.1 For a ceramic compound, what are the two characteristics of the component ions that determine
the crystal structure?
Solution
The two characteristics of component ions that determine the crystal structure of a ceramic
compound are: 1) the magnitude of the electrical charge on each ion, and 2) the relative sizes of the
cations and anions.
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12.2 Show that the minimum cation-to-anion radius ratio for a coordination number of 4 is 0.225.
Solution
In this problem we are asked to show that the minimum cation-to-anion radius ratio for a
coordination number of four is 0.225. If lines are drawn from the centers of the anions, then a
tetrahedron is formed. The tetrahedron may be inscribed within a cube as shown below.
The spheres at the apexes of the tetrahedron are drawn at the corners of the cube, and designated as
positions A, B, C, and D. (These are reduced in size for the sake of clarity.) The cation resides at the
center of the cube, which is designated as point E. Let us now express the cation and anion radii in
terms of the cube edge length, designated as a. The spheres located at positions A and B touch each
other along the bottom face diagonal. Thus,
AB = 2 rA
But
(AB) 2 = a 2 + a 2 = 2a 2
or
AB = a 2 = 2 rA
And
2rA
a =
2
There will also be an anion located at the corner, point F (not drawn), and the cube diagonal AEF will
be related to the ionic radii as
AEF = 2 (rA + rC )
(The line AEF has not been drawn to avoid confusion.) From the triangle ABF
(AB) 2 + (FB) 2 = ( AEF)2
But,
2rA
FB = a =
2
and
AB = 2 rA
from above. Thus,
⎛ 2r ⎞2 2
(2rA ) 2 + ⎜ A
⎟ = [2 (rA + rC )]
⎝ 2 ⎠
Solving for the rC/rA ratio leads to
rC 6 − 2
= = 0.225
rA 2
12.3 Show that the minimum cation-to-anion radius ratio for a coordination number of 6 is 0.414.
[Hint: Use the NaCl crystal structure (Figure 12.2), and assume that anions and cations are just
touching along cube edges and across face diagonals.]
Solution
This problem asks us to show that the minimum cation-to-anion radius ratio for a coordination
number of 6 is 0.414 (using the rock salt crystal structure). Below is shown one of the faces of the
rock salt crystal structure in which anions and cations just touch along the edges, and also the face
diagonals.
From triangle FGH,
GF = 2 rA
and
FH = GH = rA + rC
Since FGH is a right triangle
(GH )2 + (FH )2 = (FG)2

or
(rA + rC )2 + (rA + rC )2 = (2rA )2
which leads to
2 rA
rA + rC =
2
Or, solving for rC/rA

rC ⎛ 2 ⎞
= ⎜ − 1⎟ = 0.414
rA ⎝ 2 ⎠
12.4 Demonstrate that the minimum cation-to-anion radius ratio for a coordination number of 8 is
0.732.
Solution
This problem asks us to show that the minimum cation-to-anion radius ratio for a coordination
number of 8 is 0.732. From the cubic unit cell shown below
the unit cell edge length is 2rA, and from the base of the unit cell
x 2 = (2 rA ) 2 + (2 rA ) 2 = 8 rA2
Or
x = 2 rA 2
Now from the triangle that involves x, y, and the unit cell edge
x 2 + (2 rA ) 2 = y 2 = (2 rA + 2rC ) 2
(2 rA 2 )2 + 4 rA2 = (2 rA + 2rC ) 2
Which reduces to
2 rA ( 3 − 1) = 2rC
Or
rC
= 3 − 1 = 0.732
rA
12.5 On the basis of ionic charge and ionic radii given in Table 12.3, predict crystal structures for the
following materials:
(a) CsI,
(b) NiO,
(c) KI, and
(d) NiS.
Justify your selections.
Solution
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).
12.6 Which of the cations in Table 12.3 would you predict to form iodides having the cesium
chloride crystal structure? Justify your choices.
Solution
We are asked to cite the cations in Table 12.3 which would form iodides having the cesium
chloride crystal structure. First of all, the possibilities would include only the monovalent cations Cs+,
K+, and Na+. Furthermore, the coordination number for each cation must be 8, which means that 0.732
< rC/rA < 1.0 (Table 12.2). From Table 12.3 the rC/rA ratios for these three cations and the I− ion are as
follows:
rCs + 0.170 nm
= = 0.77
rI− 0.220 nm
rK + 0.138 nm
= = 0.63
rI− 0.220 nm
rNa+ 0.102 nm
= = 0.46
rI − 0.220 nm
Thus, only cesium will form the CsCl crystal structure with iodine.
12.7 Compute the atomic packing factor for the cesium chloride structure in which rC/rA = 0.735.
Solution
This problem asks that we compute the atomic packing factor for the cesium chloride
structure when rC/rA = 0.735. From Equation 3.2
VS
APF =
VC
With regard to the sphere volume, VS, there is one cation and one anion sphere per unit cell. Thus,
⎛4 ⎞ ⎛4 ⎞
VS = (1) ⎜ π rA3 ⎟ + (1) ⎜ π rC3 ⎟
⎝3 ⎠ ⎝3 ⎠
But, since rC/rA = 0.735
4 3
VS = π rA ⎡⎣1 + (0.735)3 ⎤⎦ = (5.85)rA3
3
Now, for rC/rA = 0.735, we can assume that the corner anions in Table 12.2 approximately touch one
another along the body diagonal of the cubic unit cell edges. Hence, 3a = 2 ( ra + rc )
1 3
VC = a 3 = ⎡ 2 (rA + rC )⎤⎦
3 3 ⎣
1 3
= ⎡ 2(rA + 0.735rA )⎤⎦ = (8.04)rA3
3 3⎣
Thus
VS 5.85 rA3
APF = = = 0.73
VC 8.04 rA3
12.8 The zinc blende crystal structure is one that may be generated from close-packed planes of
anions.
(a) Will the stacking sequence for this structure be FCC or HCP? Why?
(b) Will cations fill tetrahedral or octahedral positions? Why?
(c) What fraction of the positions will be occupied?
Solution
This question is concerned with the zinc blende crystal structure in terms of close-packed
planes of anions.
(a) The stacking sequence of close-packed planes of anions for the zinc blende crystal structure will be
the same as FCC (and not HCP) because the anion packing is FCC (Table 12.4).
(b) The cations will fill tetrahedral positions since the coordination number for cations is four (Table
12.4).
(c) Only one-half of the tetrahedral positions will be occupied because there are two tetrahedral sites
per anion, and yet only one cation per anion.
12.9 The corundum crystal structure, found for Al2O3, consists of an HCP arrangement of O2− ions;
the Al3+ ions occupy octahedral positions.
(a) What fraction of the available octahedral positions are filled with Al3+ ions?
(b) Sketch two close-packed O2– planes stacked in an AB sequence, and note octahedral
positions that will be filled with the Al3+ ions.
Solution
This question is concerned with the corundum crystal structure in terms of close-packed
planes of anions.
(a) For this crystal structure, two-thirds of the octahedral positions will be filled with Al3+ ions since
there is one octahedral site per O2− ion, and the ratio of Al3+ to O2− ions is two-to-three.
(b) Two close-packed O2− planes and the octahedral positions between these planes that will be filled
with Al3+ ions are sketched below.
12.10 Iron sulfide (FeS) may form a crystal structure that consists of an HCP arrangement of S2− ions.
(a) Which type of interstitial site will the Fe2+ ions occupy?
(b) What fraction of these available interstitial sites will be occupied by Fe2+ ions?
Solution
(a) This portion of the problem asks that we specify which type of interstitial site the Fe2+ ions will
occupy in FeS if the S2− ions form an HCP arrangement. Since, from Table 12.3, rS2− = 0.184 nm and
rFe2+= 0.077 nm, then
rFe 2+ 0.077 nm
= = 0.418
rS 2− 0.184 nm
Inasmuch as rC/rA is between 0.414 and 0.732, the coordination number for Fe2+ is 6 (Table 12.2);
therefore, tetrahedral octahedral positions are occupied.
(b) We are now asked what fraction of these available interstitial sites are occupied by Fe2+ ions. Since
there is 1 octahedral site per S2− ion, and the ratio of Fe2+ to S2− is 1:1, all of these sites are occupied
with Fe2+ ions.
12.11 Magnesium silicate, Mg2SiO4, forms in the olivine crystal structure that consists of an HCP
arrangement of O2− ions.
(a) Which type of interstitial site will the Mg2+ ions occupy? Why?
(b) Which type of interstitial site will the Si4+ ions occupy? Why?
(c) What fraction of the total tetrahedral sites will be occupied?
(d) What fraction of the total octahedral sites will be occupied?
Solution
(a) We are first of all asked to cite, for Mg2SiO4, which type of interstitial site the Mg2+ ions will
occupy. From Table 12.3, the cation-anion radius ratio is
rMg 2+ 0.072 nm
= = 0.514
rO 2− 0.140 nm
Since this ratio is between 0.414 and 0.732, the Mg2+ ions will occupy octahedral sites (Table 12.2).
(b) Similarly, for the Si4+ ions

rSi 4 + 0.040 nm
= = 0.286
rO 2− 0.140 nm
Since this ratio is between 0.225 and 0.414, the Si4+ ions will occupy tetrahedral sites.
(c) For each Mg2SiO4 formula unit, there are four O2− ions, and, therefore, eight tetrahedral sites;
furthermore, since there is one Si4+ ion per four O2− ions (eight tetrahedral sites), one-eighth of the
tetrahedral sites will be occupied.
(d) Also, inasmuch as the Mg2+ to O2− ratio is 1:2, and there is one octahedral site per O2− ion, one-half
of these sites will be filled.
12.12 Using the Molecule Definition Utility found in both “Metallic Crystal Structures and
Crystallography” and “Ceramic Crystal Structures” modules of VMSE, located on the book’s
web site [www.wiley.com/go/global/callister (Student Companion Site)], generate (and print
out) a three-dimensional unit cell for titanium dioxide, TiO2, given the following: (1) The unit
cell is tetragonal with a = 0.459 nm and c = 0.296 nm, (2) oxygen atoms are located at the
following point coordinates:
1
0.356 0.356 0 0.856 0.144
2
1
0.664 0.664 0 0.144 0.856
2
and (3) Ti atoms are located at the following point coordinates:

0 0 0 1 0 1
1 0 0 0 1 1
0 1 0 1 1 1
1 1 1
0 0 1
2 2 2
1 1 0
Solution
First of all, open the “Molecular Definition Utility”; it may be found in either of “Metallic
Crystal Structures and Crystallography” or “Ceramic Crystal Structures” modules.
In the “Step 1” window, it is necessary to define the atom types, colors for the spheres
(atoms), and specify atom sizes. Let us enter “O” as the name for the oxygen ions (since O is the
symbol for oxygen), and “Ti” as the name for the titanium ions. Next it is necessary to choose a color
for each atom type from the selections that appear in the pull-down menu—for example, “Red” for O
and “Light Cyan” for Ti. In the “Atom Size” window, it is necessary to enter an atom/ion size. In the
instructions for this step, it is suggested that the atom/ion diameter in nanometers be used. From the
table found inside the front cover of the textbook, the atomic radii for oxygen and titanium are 0.140
nm and 0.068 nm, respectively, and, therefore, their ionic diameters are twice these values (i.e., 0.280
nm and 0.136 nm); therefore, we enter the values “0.280” and “0.136” for the two atom types. Now
click on the “Register” button, followed by clicking on the “Go to Step 2” button.
In the “Step 2” window we specify positions for all of the atoms within the unit cell; their
point coordinates are specified in the problem statement. Let’s begin with oxygen. Click on the red
sphere that is located to the right of the “Molecule Definition Utility” box. Some of the point
coordinates for the oxygen ions are fractional ones; in these instances, the unit cell lattice parameters--
a or c (i.e., 0.459 or 0.296) are multiplied by the fraction. For example, one oxygen ion is located at
1
the 0.856 0.144 coordinate. Therefore, the x, y, and z atoms positions are (0.856)(0.459) = 0.393,
2
1
(0.144)(0.459) = 0.066, and (0.296) = 0.148, respectively. Thus, we enter “0.393” in the “x”
2
position box, “0.066” in the “y” position box, and “0.148” in the “z” position box. [Note: the first two
point coordinates relate to the a lattice parameter (0.459 nm), whereas the third applies to the c lattice
parameter (0.296 nm).] Next we click on the “Register Atom Position” button. Now we repeat the
procedure for the remaining oxygen ions
After this step has been completed, it is necessary to specify positions for the titanium ions.
To begin, we click on the light cyan sphere that is located next to the “Molecule Definition Utility”
box. One Ti ion will be positioned at the origin of the coordinate system—i.e., its point coordinates
are 0 0 0, and, therefore, we enter a “0” (zero) in each of the “x”, “y”, and “z” atom position boxes.
Next we click on the “Register Atom Position” button. And the enter the coordinate for all of the other
titanium ions
For the oxygen ions, x, y, and z atom position entries for the 4 sets of point coordinates are as
follows:
0.163, 0.163, 0
0.305, 0.305, 0
0.393, 0.066, 0.148
0.066, 0.393, 0.148
Now, for the titanium ions, the x, y, and z atom position entries for all 9 sets of point
coordinates are as follows:
0, 0, 0
0.459, 0, 0
0, 0.459, 0
0, 0, 0.296
0.459, 0.459, 0
0.459, 0, 0.296
0, 0.459, 0.296
0.459, 0.459, 0.296
0.230, 0.230, 0.148
In Step 3, we may specify which atoms are to be represented as being bonded to one another,
and which type of bond(s) to use (single solid, single dashed, double, and triple are possibilities), or we
may elect to not represent any bonds at all (in which case we are finished). If it is decided to show
bonds, probably the best thing to do is to represent unit cell edges as bonds. Your resulting image may
be rotated by using mouse click-and-drag
Your image should appear as the following screen shot.
Here the darker spheres represent titanium ions, while oxygen ions are depicted by the lighter balls.
[Note: Unfortunately, with this version of the Molecular Definition Utility, it is not possible to save
either the data or the image that you have generated. You may use screen capture (or screen shot)
software to record and store your image.]
12.13 Calculate the theoretical 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
n ′ ( AFe + AO )
ρ=
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
= [ 2 (0.077 nm) + 2 (0.140 nm)]
3
VC = a 3 = 2rFe2+ + 2rO2−
nm3 cm3
= 0.0817 = 8.17 × 10 -23
unit cell unit cell
Thus,
(4 formula units/unit cell)(55.85 g/mol + 16.00 g/mol)

ρ=
( )(
8.17 × 10 −23 cm3 /unit cell 6.022 × 1023 formula units/mol )
= 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
n ′( AMg + AO ) n ′( AMg + AO )
ρ= =
VC N A a3 N A
Or, solving for a
1/ 3
⎡ n ′( AMg + AO ) ⎤
a=⎢ ⎥
⎢⎣ ρ NA ⎥⎦
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 formula units/unit cell)(24.31 g/mol + 16.00 g/mol) ⎤1/ 3

a= ⎢ ⎥
⎣ (3.58 g/cm3)(6.022 × 10 23 formula units/mol) ⎦
= 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 = 2 rMg2+ + 2 rO2−
From Table 12.3
a = 2(0.072 nm) + 2(0.140 nm) = 0.424 nm
12.15 Compute the theoretical density of diamond given that the C—C distance and bond angle are
0.154 nm and 109.5°, respectively. How does this value compare with the measured density?
Solution
This problem asks that we compute the theoretical density of diamond given that the C—C
distance and bond angle are 0.154 nm and 109.5°, respectively. The first thing we need do is to
determine the unit cell edge length from the given C—C distance. The drawing below shows the cubic
unit cell with those carbon atoms that bond to one another in one-quarter of the unit cell.
From this figure, φ is one-half of the bond angle or φ = 109.5°/2 = 54.75°, which means that
θ = 90° − 54.75° = 35.25°
since the triangle shown is a right triangle. Also, y = 0.154 nm, the carbon–carbon bond distance.
Furthermore, x = a/4, and therefore,
a
x = = y sin θ
4
Or
a = 4y sin θ = (4)(0.154 nm)(sin 35.25°) = 0.356 nm
= 3.56 × 10−8 cm
The unit cell volume, VC is just a3, that is
VC = a 3 = (3.56 × 10 -8 cm) 3 = 4.51 × 10−23 cm3
We must now utilize a modified Equation 12.1 since there is only one atom type. There are 8
equivalent atoms per unit cell, and therefore
n ' AC
ρ =
VC NA
(8 atoms/unit cell)(12.01 g/g - atom)

=
(4.51 × 10 -23 cm 3/unit cell)( 6.022 × 10 23 atoms/g - atom)
= 3.54 g/cm3
The measured density is 3.51 g/cm3.
12.16 Compute the theoretical density of ZnS given that the Zn—S distance and bond angle are 0.240
nm and 109.5°, respectively. How does this value compare with the measured density?
Solution
This problem asks that we compute the theoretical density of ZnS given that the Zn—S
distance and bond angle are 0.240 nm and 109.5°, respectively. The first thing we need do is to
determine the unit cell volume from the given Zn—S distance. From the previous problem, the unit
cell volume VC is just a3, a being the unit cell edge length, and
VC = (4 y sin θ )3 = [ (4)(0.240 nm)(sin 35.25°)]

3
= 0.17 nm3 = 1.7 × 10−22 cm3
Now we must utilize Equation 12.1 with n' = 4 formula units, and AZn and AS being 65.41 and 32.06
g/mol, respectively. Thus
n '( AZn + AS )
ρ=
VC NA
(4 formula units/unit cell)(65.41 g/mol + 32.06 g/mol)

=
(1.7 × 10−22 cm3 /unit cell)(6.022 × 1023 formula units/mol)
= 3.80 g/cm3
The measured value of the density is 3.80 g/cm3.
12.17 Cadmium sulfide (CdS) has a cubic unit cell, and from x-ray diffraction data it is known that the
cell edge length is 0.585 nm. If the measured density is 4.82 g/cm3, how many Cd2+ and S2−
ions are there per unit cell?
Solution
We are asked to determine the number of Cd2+ and S2− ions per unit cell for cadmium sulfide
(CdS). For CdS, a = 0.585 nm and ρ = 4.82 g/cm3. Solving for n' from Equation 12.1, we get
ρVC NA ρa 3 NA
n′ = =
ACd + AS ACd + AS
(4.82 g/cm3 )(5.85 × 10 −8 cm)3 (6.022 × 1023 formula units / mol)

=
(112.41 g/mol + 32.06 g/mol)
= 4.02 or almost 4
Therefore, there are four Cd2+ and four S2− per unit cell.
12.18 (a) Using the ionic radii in Table 12.3, compute the theoretical density of CsCl. (Hint: Use a
modification of the result of Problem 3.3.)
(b) The measured density is 3.99 g/cm3. How do you explain the slight discrepancy between
your calculated value and the measured one?
Solution
(a) We are asked to compute the density of CsCl. Modifying the result of Problem 3.3, we
get
2 rCs+ + 2 rCl− 2 (0.170 nm) + 2 ( 0.181 nm)

a = =
3 3
= 0.405 nm = 4.05 × 10−8 cm
From Equation 12.1
n ′ ( ACs + ACl ) n ′( ACs + ACl )

ρ= =
VC NA a 3 NA
For the CsCl crystal structure, n' = 1 formula unit/unit cell, and thus
(1 formula unit/unit cell)(132.91 g/mol + 35.45 g/mol)

ρ=
(4.05 × 10 −8 cm)3 /unit cell (6.022 × 1023 formula units/mol)
= 4.21 g/cm3
(b) This value of the density is greater than the measured density (3.99 g/cm3). The reason
for this discrepancy is that the ionic radii in Table 12.3, used for this computation, were for a
coordination number of six, when, in fact, the coordination number of both Cs+ and Cl− is
eight. The ionic radii should be slightly greater, leading to a larger VC value, and a lower
density.
12.19 From the data in Table 12.3, compute the theoretical density of CaF2, which has the fluorite
structure.
Solution
A unit cell of the fluorite structure is shown in Figure 12.5. It may be seen that there are four
CaF2 units per unit cell (i.e., n' = 4 formula units/unit cell). Assume that for each of the eight small
cubes in the unit cell
2rCa 2+ + 2rF −
a =
3
and, from Table 12.3
2 (0.100 nm) + 2 (0.133 nm)

a = = 0.269 nm = 2.69 × 10 −8 cm
3
The volume of the unit cell is just
[ ]
3
VC = (2a) 3 = (2)(2.69 × 10 -8 cm) = 1.56 × 10−22 cm3
Thus, from Equation 12.1
n ' ( ACa + 2 AF )
ρ =
VC NA
(4 formula units/unit cell) [ 40.08 g/mol + (2)(19.00 g/mol)]

=
(1.56 × 10 −22 cm3 /unit cell)( 6.022 × 1023 formula units/mol)
= 3.33 g/cm3
The measured density is 3.18 g/cm3.
12.20 A hypothetical AX type of ceramic material is known to have a density of 2.31 g/cm3 and a unit
cell of cubic symmetry with a cell edge length of 0.45 nm. The atomic weights of the A and X
elements are 86.6 and 40.3 g/mol, respectively. On the basis of this information, which of the
following crystal structures is (are) possible for this material: rock salt, cesium chloride, or zinc
blende? Justify your choice(s).
Solution
We are asked to specify possible crystal structures for an AX type of ceramic material given
its density (2.31 g/cm3), that the unit cell has cubic symmetry with edge length of 0.45 nm (4.5 × 10−8
cm), and the atomic weights of the A and X elements (86.6 and 40.3 g/mol, respectively). Using
Equation 12.1 and solving for n' yields
ρVC NA
n' =
∑A C + ∑A A
(2.31g/cm3 ) ⎡⎣(4.5 × 10−8 cm)3 /unit cell ⎤⎦ (6.022 × 1023 formula units/mol)
=
(86.6 + 40.3) g/mol
= 0.998
1.00 formula units/unit cell
Of the three possible crystal structures, only cesium chloride has one formula unit per unit cell, and
therefore, is the only possibility.
12.21 The unit cell for MgFe2O4 (MgO-Fe2O3) has cubic symmetry with a unit cell edge length of
0.850 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 MgFe2O4 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
ρVC NA
n' =
∑ C + ∑ AA
A
(4.52 g/cm3 ) ⎡⎣(8.50 × 10-8

cm)3 /unit cell ⎤⎦ (6.022 × 1023 formula units/mol)
=
(1)(24.31 g/mol) + (2)(55.85 g/mol) + (4)(16.00 g/mol)
= 8.3
8.0 formula units/unit cell
Thus, in each unit cell there are 8 Mg2+, 16 Fe3+, and 32 O2− ions. From Table 12.3, rMg2+ = 0.072 nm,
rFe3+ = 0.069 nm, and rO2− = 0.140 nm. Thus, the total sphere volume in Equation 3.2 (which we
denote as VS), is just
⎛4 ⎞ ⎛4 ⎞
VS = (8) ⎜ π ⎟ (7.2 × 10 −9 cm)3 + (16) ⎜ π ⎟ (6.9 × 10 −9 cm)3
⎝3 ⎠ ⎝3 ⎠
⎛4 ⎞
+ (32) ⎜ π ⎟ (1.40 × 10 −8 cm)3
⎝3 ⎠
= 4.02 × 10−22 cm3
Now, the unit cell volume (VC) is just
VC = a 3 = (8.50 × 10 −8 cm)3 = 6.14 × 10 −22 cm3
Finally, the atomic packing factor (APF) from Equation 3.2 is just
VS 4.02 × 10 −22 cm3

APF = = = 0.655
VC 6.14 × 10-22 cm3
12.22 The unit cell for Cr2O3 has hexagonal symmetry with lattice parameters a = 0.5 nm and c = 1.34
nm. If the density of this material is 5.22 g/cm3, calculate its atomic packing factor. For this
computation assume ionic radii of 0.062 nm and 0.140 nm, respectively for Cr3+ and O2−.
Solution
This problem asks for us to calculate the atomic packing factor for chromium oxide given
values for the a and c lattice parameters, and the density. It first becomes necessary to determine the
value of n' in Equation 12.1. This necessitates that we calculate the value of VC, the unit cell volume.
In Problem 3.6 it was shown that the area of the hexagonal base (AREA) is related to a as
2
⎛ a⎞
AREA = 6 R 2 3 = 6 ⎜ ⎟ 3 = 1.5 a 2 3
⎝ 2⎠
inasmuch as, for HCP, a = 2R (where R is the atomic radius). Now, incorporating the value of a
provided in the problem statement into the above expression leads to
AREA = (1.5)(5.0 × 10−8 cm)2 ( 3 ) = 6.49 × 10−15 cm 2
The unit cell volume now is just
VC = (AREA)(c) = (6.49 × 10−15 cm 2 )(1.34 × 10−7 cm)
= 8.70 × 10−22 cm3
Now, solving for n' (Equation 12.1) yields
ρ NA VC
n' =
∑A C + ∑A A
(5.22 g/cm3 )(6.022 × 1023 formula units/mol)(8.70 × 10 −22 cm 3 /unit cell)

=
(2)(52.00 g/mol) + (3)(16.00g/mol)
= 18.0 formula units/unit cell
Or, there are 18 Cr2O3 units per unit cell, or 36 Cr3+ ions and 54 O2− ions. As given in the problem
statement, the radii of these two ion types are 0.062 and 0.140 nm, respectively. Thus, the total sphere
volume in Equation 3.2 (which we denote as VS), is just
⎛4 ⎞ ⎛4 ⎞
VS = (36) ⎜ π ⎟ (rCr3+ )3 + (54) ⎜ π ⎟ (rO2− )3
⎝3 ⎠ ⎝3 ⎠
⎛4 ⎞ ⎛4 ⎞
= (36) ⎜ π ⎟ (6.2 × 10−9 cm)3 + (54) ⎜ π ⎟ (1.4 × 10 −8 cm)3
⎝3 ⎠ ⎝3 ⎠
= 6.57 × 10−22 cm3
Finally, the APF is just
VS 6.57 × 10−22 cm3

APF = = = 0.755
VC 8.70 × 10 −22 cm3
12.23 Compute the atomic packing factor for the diamond cubic crystal structure (Figure 12.15).
Assume that bonding atoms touch one another, that the angle between adjacent bonds is 109.5°,
and that each atom internal to the unit cell is positioned a/4 of the distance away from the two
nearest cell faces (a is the unit cell edge length).
Solution
We are asked in this problem to compute the atomic packing factor for the diamond cubic
crystal structure, given that the angle between adjacent bonds is 109.5°. The first thing that we must
do is to determine the unit cell volume VC in terms of the atomic radius r. From Problem 12.15 the
following relationship was developed
a = 4 y sin θ
in which y = 2r and θ = 35.25°. Furthermore, since the unit cell is cubic, VC = a3; therefore
VC = (4 y sin θ )3 = [ (4)(2 r )(sin 35.25°)]

3
= 98.43 r 3
Now, it is necessary to determine the sphere volume in the unit cell, VS, in terms of r. For this unit cell
(Figure 12.15) there are 4 interior atoms, 6 face atoms, and 8 corner atoms. The entirety of the interior
atoms, one-half of each face atom, and one-eighth of each corner atom belong to the unit cell.
Therefore, there are 8 equivalent atoms per unit cell; hence
⎛4 ⎞
VS = (8) ⎜ π r 3 ⎟ = 33.51 r 3
⎝3 ⎠
Finally, the atomic packing factor is just
VS 33.51 r 3
APF = = = 0.340
VC 98.43 r 3
12.24 Compute the atomic packing factor for cesium chloride using the ionic radii in Table 12.3 and
assuming that the ions touch along the cube diagonals.
Solution
We are asked in this problem to compute the atomic packing factor for the CsCl crystal
structure. This requires that we take the ratio of the sphere volume within the unit cell and the total
unit cell volume. From Figure 12.3 there is the equivalence of one Cs and one Cl ion per unit cell; the
ionic radii of these two ions are 0.170 nm and 0.181 nm, respectively (Table 12.3). Thus, the sphere
volume, VS, is just
4
VS = (π ) ⎡⎣ (0.170 nm)3 + (0.181 nm)3 ⎤⎦ = 0.0454 nm3
3
For CsCl the unit cell edge length, a, in terms of the atomic radii is just
2 rCs + 2 rCl- 2(0.170 nm) + 2(0.181 nm)

a= =
3 3
= 0.405 nm
Since VC = a3
VC = (0.405 nm)3 = 0.0664 nm3
And, finally the atomic packing factor is just
VS 0.0454 nm3
APF = = = 0.684
VC 0.0664 nm3
12.25 For each of the following crystal structures, represent the indicated plane in the manner of
Figures 3.11 and 3.12, showing both anions and cations:
(a) (100) plane for the rock salt crystal structure,
(b) (110) plane for the cesium chloride crystal structure,
(c) (111) plane for the zinc blende crystal structure, and
(d) (110) plane for the perovskite crystal structure.
Solution
(a) A (100) plane for the rock salt crystal structure would appear as
(b) A (110) plane for the cesium chloride crystal structure would appear as
(c) A (111) plane for the zinc blende crystal structure would appear as
(d) A (110) plane for the perovskite crystal structure would appear as
Silicate Ceramics
12.26 In terms of bonding, explain why silicate materials have relatively low densities.
Solution
The silicate materials have relatively low densities because the atomic bonds are primarily
covalent in nature (Table 12.1), and, therefore, directional. This limits the packing efficiency of the
atoms, and therefore, the magnitude of the density.
12.27 Determine the angle between covalent bonds in an SiO 44 − tetrahedron.
Solution
This problem asks for us to determine the angle between covalent bonds in the SiO 44 −
tetrahedron. Below is shown one such tetrahedron situated within a cube.
Now if we extend the base diagonal from one corner to the other, it is the case that
(2 y ) 2 = a 2 + a 2 = 2a 2
or
a 2
y =
2
Furthermore, x = a/2, and
x a/2 1
tan θ = = =
y a 2/2 2
From which
⎛ 1 ⎞
θ = tan −1 ⎜ = 35.26°
⎝ 2 ⎟⎠
Now, solving for the angle φ
φ = 180° − 90° − 35.26° = 54.74°
Finally, the bond angle is just 2φ, or 2φ = (2)(54.74°) = 109.48°.
Imperfections in Ceramics
12.28 Would you expect Frenkel defects for anions to exist in ionic ceramics in relatively large
concentrations? Why or why not?
Solution
Frenkel defects for anions would not exist in appreciable concentrations because the anion is
quite large and is highly unlikely to exist as an interstitial.
12.29 Calculate the fraction of lattice sites that are Schottky defects for sodium chloride at its melting
temperature (801°C). Assume an energy for defect formation of 2.3 eV.
Solution
We are asked in this problem to calculate the fraction of lattice sites that are Schottky defects
for NaCl at its melting temperature (801°C), assuming that the energy for defect formation is 2.3 eV.
In order to solve this problem it is necessary to use Equation 12.3 and solve for the Ns/N ratio.
Rearrangement of this expression and substituting values for the several parameters leads to
Ns ⎛ Qs ⎞
= exp ⎜ − ⎟
N ⎝ 2kT ⎠
⎡ 2.3 eV ⎤
= exp ⎢ − −5 ⎥
⎣ (2)(8.62 × 10 eV/K)(801 + 273 K) ⎦
= 4.03 × 10−6
12.30 Calculate the number of Frenkel defects per cubic meter in zinc oxide at 1000°C. The energy
for defect formation is 2.51 eV, while the density for ZnO is 5.55 g/cm3 at (1000°C).
Solution
This problem asks that we compute the number of Frenkel defects per cubic meter in zinc
oxide at 1000°C. Solution of this problem is possible using Equation 12.2. However, we must first
determine the value of N, the number of lattice sites per cubic meter, which is possible using a
modified form of Equation 4.2; thus
NA ρ
N=
AZn + AO
(6.022 × 10 23 atoms/mol)(5.55 g/cm3 )(10 6 cm3/m3)

=
65.41 g/mol + 16.00 g/mol
= 4.11 × 1028 lattice sites/m3
And, finally the value of Nfr is computed using Equation 12.2 as
⎛ Q fr ⎞
N fr = N exp ⎜− ⎟
⎝ 2kT ⎠
⎡ 2.51 eV ⎤
= (4.11 × 1028 lattice sites/m3 ) exp ⎢ − −5 ⎥
⎣ (2)(8.62 × 10 eV/K)(1000 + 273 K) ⎦
= 4.43 × 1023 defects/m3
12.31 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 5.50 9.21 × 1019
1000 5.44 ?
1250 5.37 5.0 × 1022
Solution
This problem provides for some oxide ceramic, at temperatures of 750°C and 1250°C, values
for density and the number of Schottky defects per cubic meter. 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 4.2 and Equation 12.3 as
⎛ Q ⎞
N s = N exp ⎜− s ⎟
⎝ 2kT ⎠
⎛ NA ρ ⎞ ⎛ Qs ⎞
=⎜ exp ⎜ −
⎝ AM + AO ⎟⎠ ⎝ 2kT ⎟⎠
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 ⎞ ⎛ Qs ⎞
N s1 = ⎜ A 1 ⎟ exp ⎜ − (12.S1a)
⎝ AM + AO ⎠ ⎝ 2kT1 ⎟⎠
⎛ N ρ ⎞ ⎛ Qs ⎞
N s 2 = ⎜ A 2 ⎟ exp ⎜ − (12.S1b)
⎝ AM + AO ⎠ ⎝ 2kT2 ⎟⎠
Dividing the first of these equations by the second leads to
⎛ NA ρ1 ⎞ ⎛ Qs ⎞
N s1 ⎜⎝ A + A ⎟⎠ exp ⎜⎝ − 2kT ⎟⎠
M O 1
=
Ns2 ⎛ NA ρ2 ⎞ ⎛ Qs ⎞
⎜⎝ A + A ⎟⎠ exp ⎜⎝ − 2kT ⎟⎠
M O 2
which, after some algebraic manipulation, reduces to the form
N s1 ρ ⎡ Q ⎛1 1 ⎞⎤
= 1 exp ⎢ − s ⎜ − ⎥ (12.S2)
Ns2 ρ2 ⎣ 2k ⎝ T1 T2 ⎟⎠ ⎦
Now, taking natural logarithms of both sides of this equation gives
⎛N ⎞ ⎛ρ ⎞ Q ⎛1 1⎞
ln ⎜ s1 ⎟ = ln ⎜ 1 ⎟ − s ⎜ − ⎟
⎝ s2 ⎠
N ρ
⎝ 2⎠ 2k ⎝ 1
T T2⎠
and solving for Qs leads to the expression
⎡ ⎛N ⎞ ⎛ ρ ⎞⎤
−2k ⎢ ln ⎜ s1 ⎟ − ln ⎜ 1 ⎟ ⎥
⎣ ⎝ Ns2 ⎠ ⎝ ρ2 ⎠ ⎦
Qs =
1 1
−
T1 T2
Let us take T1 = 750°C and T2 = 1250°C, and we may compute the value of Qs as
⎡ ⎛ 9.2 × 1019 m −3 ⎞ ⎛ 5.50 g/cm3 ⎞ ⎤

− (2)(8.62 × 10 −5 eV/K) ⎢ln ⎜ − ln ⎜⎝ 5.37 g/cm3 ⎟⎠ ⎥
⎣ ⎝ 5.0 × 1022 m −3 ⎟⎠ ⎦
Qs =
1 1
−
750 + 273 K 1250 + 273 K
= 3.40 eV
(b) It is now possible to solve for Ns at 1000°C using Equation 12.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
N s 2 ρ1 ⎡ Q ⎛1 1 ⎞⎤
N s1 = exp ⎢ − s ⎜ − ⎥
ρ2 ⎣ 2k ⎝ T1 T2 ⎟⎠ ⎦
(9.2 × 1019 m −3 )( 5.44 g/cm3 ) ⎡ 3.40 eV ⎛ 1 1 ⎞⎤

= exp ⎢ − ⎜⎝ − ⎟⎥
5.50 g/cm 3 −5
⎢⎣ (2)(8.62 × 10 eV/K) 1000 + 273 K 750 + 273 K ⎠ ⎦⎥
= 4.0 × 1021 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 12.S1a. Rearrangement of this expression leads
to
⎛ NA ρ1 ⎞ ⎛ Qs ⎞
⎜⎝ A + A ⎟⎠ = N s1 exp ⎜⎝ 2kT ⎟⎠
M O 1
And, after further algebraic manipulation
⎡ ⎤
⎢ ⎥
⎢ NA ρ1 ⎥ = A +A
⎢ ⎛ Qs ⎞ ⎥
M O
⎢ N s1 exp ⎜ ⎥
⎢⎣ ⎝ 2kT1 ⎟⎠ ⎥⎦
And, solving this expression for AM gives
⎡ ⎤
⎢ ⎥
NA ρ1
AM = ⎢ ⎥ − A
⎢ ⎛ Qs ⎞ ⎥
O
⎢ N s1 exp ⎜ ⎥
⎢⎣ ⎝ 2kT1 ⎟⎠ ⎥⎦
Now, assuming that T1 = 750°C, the value of AM is
⎧ ⎫
⎪ ⎪
⎪ (6.022 × 10 ions/mol)( 5.50 g/cm )(10 cm / m )
23 3 6 3 3
⎪
AM = ⎨ ⎬ − 16.00 g/mol
⎪ (9.2 × 1019 ions/m 3 ) exp ⎡ 3.40 eV ⎤⎪
⎪⎩ ⎢ (2)(8.62 × 10−5 eV/K)(750 + 273 K) ⎥ ⎪
⎣ ⎦⎭
= 136.7 g/mol
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 136.7 g/mol is barium. Thus, this metal oxide is BaO.
12.32 In your own words, briefly define the term stoichiometric.
Solution
Stoichiometric means having exactly the ratio of anions to cations as specified by the
chemical formula for the compound.
12.33 If cupric oxide (CuO) is exposed to reducing atmospheres at elevated temperatures, some of the
Cu2+ ions will become Cu+.
(a) Under these conditions, name one crystalline defect that you would expect to form in order
to maintain charge neutrality.
(b) How many Cu+ ions are required for the creation of each defect?
(c) How would you express the chemical formula for this nonstoichiometric material?
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.
12.34 (a) Suppose that Li2O is added as an impurity to CaO. If the Li+ substitutes for Ca2+, what kind
of vacancies would you expect to form? How many of these vacancies are created for every Li+
added?
(b) Suppose that CaCl2 is added as an impurity to CaO. If the Cl− substitutes for O2−, what kind
of vacancies would you expect to form? How many of the vacancies are created for every Cl−
added?
Solution
(a) For Li+ substituting for Ca2+ in CaO, oxygen vacancies would be created. For each Li+ substituting
for Ca2+, one positive charge is removed; in order to maintain charge neutrality, a single negative
charge may be removed. Negative charges are eliminated by creating oxygen vacancies, and for every
two Li+ ions added, a single oxygen vacancy is formed.
(b) For Cl− substituting for O2− in CaO, calcium vacancies would be created. For each Cl− substituting
for an O2−, one negative charge is removed; in order to maintain charge neutrality, two Cl− ions will
lead to the formation of one calcium vacancy.
12.35 What point defects are possible for Al2O3 as an impurity in MgO? How many Al3+ ions must be
added to form each of these defects?
Solution
For every Al3+ ion that substitutes for Mg2+ in MgO, a single positive charge is added. Thus,
in order to maintain charge neutrality, either a positive charge must be removed or a negative charge
must be added.
Negative charges are added by forming O2− interstitials, which are not likely to form.
Positive charges may be removed by forming Mg2+ vacancies, and one magnesium vacancy
would be formed for every two Al3+ ions added.
Ceramic Phase Diagrams
12.36 For the ZrO2–CaO system (Figure 12.26), write all eutectic and eutectoid reactions for cooling.
Solution
There is only one eutectic for the portion of the ZrO2–CaO system shown in Figure 12.26. It
occurs at approximately 2250°C and 23.5 wt% CaO, and, upon cooling, the reaction is
Liquid → cubic ZrO 2 + CaZrO3
There are two eutectoids. One occurs at about 1000°C and about 2 wt% CaO; its reaction upon
cooling is as follows:
tetragonal → monoclinic ZrO 2 + cubic ZrO 2
The second eutectoid occurs at about 850°C and 7 wt% CaO. This reaction is
cubic → monoclinic ZrO 2 + CaZr4 O9
12.37 From Figure 12.25, the phase diagram for the MgO–Al2O3 system, it may be noted that the
spinel solid solution exists over a range of compositions, which means that it is
nonstoichiometric at compositions other than 50 mol% MgO–50 mol% Al2O3.
(a) The maximum nonstoichiometry on the Al2O3-rich side of the spinel phase field exists at
about 1198°C (2271 K) corresponding to approximately 82 mol% (92 wt%) Al2O3. Determine
the type of vacancy defect that is produced and the percentage of vacancies that exist at this
composition.
(b) The maximum nonstoichiometry on the MgO-rich side of the spinel phase field exists at
about 1198°C (2271 K) corresponding to approximately 39 mol% (62 wt%) Al2O3. Determine
the type of vacancy defect that is produced and the percentage of vacancies that exist at this
composition.
Solution
(a) For this portion of the problem we are to determine the type of vacancy defect that is produced on
the Al2O3-rich side of the spinel phase field (Figure 12.25) and the percentage of these vacancies at the
maximum nonstoichiometry (82 mol% Al2O3). On the alumina-rich side of this phase field, there is an
excess of Al3+ ions, which means that some of the Al3+ ions substitute for Mg2+ ions. In order to
maintain charge neutrality, Mg2+ vacancies are formed, and for every Mg2+ vacancy formed, two Al3+
ions substitute for three Mg2+ ions.
Now, we will calculate the percentage of Mg2+ vacancies that exist at 82 mol% Al2O3. Let us
arbitrarily choose as our basis 50 MgO–Al2O3 units of the stoichiometric material, which consists of 50
Mg2+ ions and 100 Al3+ ions. Furthermore, let us designate the number of Mg2+ vacancies as x, which
means that 2x Al3+ ions have been added and 3x Mg2+ ions have been removed (two of which are filled
with Al3+ ions). Using our 50 MgO–Al2O3 unit basis, the number of moles of Al2O3 in the
nonstoichiometric material is (100 + 2x)/2; similarly the number of moles of MgO is (50 – 3x). Thus,
the expression for the mol% of Al2O3 is just
⎡ 100 + 2 x ⎤
⎢ 2 ⎥
mol% Al2 O3 = ⎢
100 + 2 x ⎥ × 100
⎢ + (50 − 3 x) ⎥
⎢⎣ 2 ⎥⎦
If we solve for x when the mol% of Al2O3 = 82, then x = 12.1. Thus, adding 2x or (2)(12.1) = 24.2
Al3+ ions to the original material consisting of 100 Al3+ and 50 Mg2+ ions will produce 12.1 Mg2+
vacancies. Therefore, the percentage of vacancies is just
12.1
% vacancies = × 100 = 8.1%
100 + 50
(b) Now, we are asked to make the same determinations for the MgO-rich side of the spinel phase
field, for 39 mol% Al2O3. In this case, Mg2+ ions are substituting for Al3+ ions. Since the Mg2+ ion has
a lower charge than the Al3+ ion, in order to maintain charge neutrality, negative charges must be
eliminated, which may be accomplished by introducing O2− vacancies. For every 2 Mg2+ ions that
substitute for 2 Al3+ ions, one O2− vacancy is formed.
Now, we will calculate the percentage of O2− vacancies that exist at 39 mol% Al2O3. Let us
arbitrarily choose as our basis 50 MgO–Al2O3 units of the stoichiometric material which consists of 50
Mg2+ ions 100 Al3+ ions. Furthermore, let us designate the number of O2− vacancies as y, which means
that 2y Mg2+ ions have been added and 2y Al3+ ions have been removed. Using our 50 MgO–Al2O3
unit basis, the number of moles of Al2O3 in the nonstoichiometric material is (100 – 2y)/2; similarly the
number of moles of MgO is (50 + 2y). Thus, the expression for the mol% of Al2O3 is just
⎡ 100 − 2 y ⎤
⎢ 2 ⎥
mol% Al2 O3 = ⎢ ⎥ × 100
⎢ 100 − 2 y + (50 + 2 y ) ⎥
⎣⎢ 2 ⎦⎥
If we solve for y when the mol% of Al2O3 = 39, then y = 7.91. Thus, 7.91 O2− vacancies are produced
in the original material that had 200 O2− ions. Therefore, the percentage of vacancies is just
7.91
% vacancies = × 100 = 3.96%
200
12.38 When kaolinite clay [Al2(Si2O5)(OH)4] is heated to a sufficiently high temperature, chemical
water is driven off.
(a) Under these circumstances, what is the composition of the remaining product (in weight
percent Al2O3)?
(b) What are the liquidus and solidus temperatures of this material
Solution
(a) The chemical formula for kaolinite clay may also be written as Al2O3–2SiO2-2H2O. Thus, if we
remove the chemical water, the formula becomes Al2O3–2SiO2. The formula weight for Al2O3 is just
(2)(26.98 g/mol) + (3)(16.00 g/mol) = 101.96 g/mol; and for SiO2 the formula weight is 28.09 g/mol +
(2)(16.00 g/mol) = 60.09 g/mol. Thus, the composition of this product, in terms of the concentration of
Al2O3, CAl O , in weight percent is just
2 3
101.96 g/mol
CAl2O3 = × 100 = 45.9 wt%
101.96 g/mol + (2)(60.09 g/mol)
(b) The liquidus and solidus temperatures for this material as determined from the SiO2–Al2O3 phase
diagram, Figure 12.27, are 1825°C and 1587°C, respectively.
Brittle Fracture of Ceramics
12.39 Briefly explain

(a) why there may be significant scatter in the fracture strength for some given ceramic material,
and
(b) why fracture strength increases with decreasing specimen size.
Solution
(a) There may be significant scatter in the fracture strength for some given ceramic material because
the fracture strength depends on the probability of the existence of a flaw that is capable of initiating a
crack; this probability varies from specimen to specimen of the same material.
(b) The fracture strength increases with decreasing specimen size because as specimen size decreases,
the probably of the existence of a flaw of that is capable of initiating a crack diminishes.
12.40 The tensile strength of brittle materials may be determined using a variation of Equation 8.1.
Compute the critical crack tip radius for an Al2O3 specimen that experiences tensile fracture at
an applied stress of 275 MPa. Assume a critical surface crack length of 2 × 10−3 mm and a
theoretical fracture strength of E/10, where E is the modulus of elasticity.
Solution
We are asked for the critical crack tip radius for an Al2O3 material. From Equation 8.1
1/ 2
⎛ a⎞
σ m = 2σ 0 ⎜
⎝ ρt ⎟⎠
Fracture will occur when σm reaches the fracture strength of the material, which is given as E/10; thus
1/ 2
E ⎛ a⎞
= 2σ 0 ⎜ ⎟
10 ⎝ ρt ⎠
Or, solving for ρt
400 a σ 02
ρt =
E2
From Table 12.5, E = 393 GPa, and thus,
(400 ) (2 × 10 −3 mm) (275 MPa) 2

ρt =
(393 × 103 MPa )
2
= 3.9 × 10−7 mm = 0.39 nm
12.41 The fracture strength of glass may be increased by etching away a thin surface layer. It is
believed that the etching may alter surface crack geometry (i.e., reduce crack length and increase
the tip radius). Compute the ratio of the original and etched crack tip radii for an eightfold
increase in fracture strength if two-thirds of the crack length is removed.
Solution
This problem asks that we compute the crack tip radius ratio before and after etching. Let
ρt = original crack tip radius, and

ρt′ = etched crack tip radius
Also,
σ ′f = σ f
a
a′ =
3
σ 0′ = 8σ 0
ρt′
Solving for from the following
ρt
1/ 2 1/ 2
⎛ a⎞ ⎛ a′ ⎞
σ f = 2σ 0 ⎜ ⎟ = σ ′f = 2σ 0′ ⎜ ⎟
⎝ρ ⎠ t ⎝ ρ′⎠
t
yields
2 2
ρt′ ⎛ σ 0′ ⎞ ⎛ a ′ ⎞ ⎛ 8σ 0 ⎞ ⎛ a / 3 ⎞
= = = 21.3
ρt ⎜⎝ σ 0 ⎟⎠ ⎜⎝ a ⎟⎠ ⎜⎝ σ 0 ⎟⎠ ⎜⎝ a ⎟⎠
Stress-Strain Behavior
12.42 A three-point bending test is performed on a glass specimen having a rectangular cross section
of height d = 6 mm and width b = 12 mm the distance between support points is 45 mm.
(a) Compute the flexural strength if the load at fracture is 290 N.
(b) The point of maximum deflection ∆y occurs at the center of the specimen and is described
by
FL3
∆y =
48 EI
where E is the modulus of elasticity and I is the cross-sectional moment of inertia. Compute
∆y at a load of 266 N.
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
σ fs =
2bd 2
for a rectangular cross-section. Using the values given in the problem statement,
(3)(290 N)(45 × 10−3 m)

σ fs = = 4.53 × 107 N/m 2 = 45.3MPa
(2)(12 × 10 −3 m)(6 × 10−3 m)2
(b) We are now asked to compute the maximum deflection. From Table 12.5, the elastic modulus (E)
for glass is 69 GPa. 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 ⎞ 4 Ebd 3
48 E ⎜
⎝ 12 ⎟⎠
(266 N)(45 × 10−3 m)3

=
(4)(69 × 10 N/m 2 )(12 × 10−3 m)(6 × 10−3 m)3
9
= 3.35 × 10−5 m = 3.35 × 10−2 mm
12.43 A circular specimen of MgO is loaded using a three-point bending mode. Compute the
minimum possible radius of the specimen without fracture, given that the applied load is 425 N,
the flexural strength is 105 MPa, and the separation between load points is 60 mm.
Solution
We are asked to calculate the maximum radius of a circular specimen of MgO that is loaded
using three-point bending. Solving for R from Equation 12.7b
1/ 3
⎡ Ff L ⎤
R =⎢ ⎥
⎢⎣ σ fs π ⎥⎦
which, when substituting the parameters stipulated in the problem statement, yields
1/3
⎡ (425 N)(60 × 10−3 m) ⎤
R =⎢ ⎥
⎣ (105 × 10 N/m )(π ) ⎦
6 2
= 4.26 × 10−3 m = 4.26 mm
12.44 A three-point bending test was performed on an aluminum oxide specimen having a circular
cross section of radius 3.8 mm; the specimen fractured at a load of 950 N when the distance
between the support points was 60 mm. Another test is to be performed on a specimen of this
same material, but one that has a square cross section of 12 mm length on each edge. At what
load would you expect this specimen to fracture if the support point separation is 40 mm?
Solution
For this problem, the load is given at which a circular specimen of aluminum oxide fractures
when subjected to a three-point bending test; we are then are asked to determine the load at which a
specimen of the same material having a square cross-section fractures. It is first necessary to compute
the flexural strength of the aluminum oxide, Equation 12.7b, and then, using this value, we may
calculate the value of Ff in Equation 12.7a. From Equation 12.7b
Ff L
σ fs =
π R3
(950 N)(60 × 10 −3 m)
= = 331 × 106 N/m 2 = 331MPa
(π )(3.8 × 10−3 m)3
Now, solving for Ff from Equation 12.7a, realizing that b = d = 12 mm, yields
2 σfs d 3
Ff =
3L
(2)(331 × 106 N / m 2 )(12 × 10−3 m)3

= = 9533 N
(3)(40 × 10−3 m)
12.45 (a) A three-point transverse bending test is conducted on a cylindrical specimen of aluminum
oxide having a reported flexural strength of 390 MPa. If the specimen radius is 2.8 mm and the
support point separation distance is 40 mm, predict whether or not you would expect the
specimen to fracture when a load of 620 N is applied. Justify your prediction.
(b) Would you be 100% certain of the prediction in part (a)? Why or why not?
Solution
(a) This portion of the problem asks that we determine whether or not a cylindrical specimen of
aluminum oxide having a flexural strength of 390 MPa and a radius of 2.8 mm will fracture when
subjected to a load of 620 N in a three-point bending test; the support point separation is given as 40
mm. Using Equation 12.7b we will calculate the value of σ; if this value is greater than σfs (390 MPa),
then fracture is expected to occur. Employment of Equation 12.7b yields
FL
σ =
π R3
(620 N)(40 × 10−3 m)

= = 360 × 106 N/m 2 = 360 MPa
(π )(2.8 × 10 −3 m)3
Since this value is less than the given value of σfs (390 MPa), then fracture is not predicted.
(b) The certainty of this prediction is not 100% because there is always some variability in the flexural
strength for ceramic materials, and since this value of σ (360 MPa) is relatively close to σfs (390 MPa)
then there is some chance that fracture will occur.
Mechanisms of Plastic Deformation
12.46 Cite one reason why ceramic materials are, in general, harder yet more brittle than metals.
Solution
Crystalline ceramics are harder yet more brittle than metals because they (ceramics) have
fewer slip systems, and, therefore, dislocation motion is highly restricted.
Miscellaneous Mechanical Considerations
12.47 The modulus of elasticity for beryllium oxide (BeO) having 5 vol% porosity is 310 GPa
(a) Compute the modulus of elasticity for the nonporous material.
(b) Compute the modulus of elasticity for 10 vol% porosity.
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 − 1.9 P + 0.9 P 2
310 GPa
= = 342 GPa
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 − 1.9 P + 0.9 P 2 )
= (342 GPa) ⎡⎣1 − (1.9)(0.10) + (0.9)(0.10) 2 ⎤⎦ = 280 GPa
12.48 The modulus of elasticity for boron carbide (B4C) having 5 vol% porosity is 290 GPa.
(a) Compute the modulus of elasticity for the nonporous material.
(b) At what volume percent porosity will the modulus of elasticity be 235 GPa?
Solution
(a) This portion of the problem requests that we compute the modulus of elasticity for nonporous B4C
given that E = 290 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 − 1.9 P + 0.9 P 2
290 GPa
= = 320 GPa
1 − (1.9)(0.05) + (0.9)(0.05) 2
(b) Now we are asked to compute the volume percent porosity at which the elastic modulus of B4C is
235 MPa (34 × 106 psi). Since from part (a), E0 = 320 GPa, and using Equation 12.9 we get
E 235 MPa
= = 0.734 = 1 − 1.9P + 0.9P 2
E0 320 MPa
Or
0.9 P 2 − 1.9 P + 0.266 = 0
Now, solving for the value of P using the quadratic equation solution yields
1.9 ± (−1.9) 2 − (4)(0.9)(0.266)

P =
(2)(0.9)
The positive and negative roots are

P+ = 1.96
P− = 0.151
Obviously, only the negative root is physically meaningful, and therefore the value of the porosity to
give the desired modulus of elasticity is 15.1 vol%.
12.49 Using the data in Table 12.5, do the following:
(a) Determine the flexural strength for nonporous MgO assuming a value of 3.75 for n in
Equation 12.10.
(b) Compute the volume fraction porosity at which the flexural strength for MgO is 62 MPa.
Solution
(a) This part of the problem asks us to determine the flexural strength of nonporous MgO assuming
that the value of n in Equation 12.10 is 3.75. Taking natural logarithms of both sides of Equation
12.10 yields
ln σ fs = ln σ 0 − nP
In Table 12.5 it is noted that for P = 0.05, σfs = 105 MPa. For the nonporous material P = 0 and, ln σ 0
= ln σfs. Solving for ln σ 0 from the above equation and using these data gives
ln σ 0 = ln σfs + nP
= ln (105 MPa) + (3.75)(0.05) = 4.841
or σ 0 = e4.841 = 127 MPa
(b) Now we are asked to compute the volume percent porosity to yield a σfs of 62 MPa. Taking the
natural logarithm of Equation 12.10 and solving for P leads to
ln σ 0 − ln σfs
P=
n
ln (127 MPa) − ln (62 MPa)

=
3.75
= 0.19 or 19 vol%
12.50 The flexural strength and associated volume fraction porosity for two specimens of the same
ceramic material are as follows:
σfs (MPa) P
100 0.05
50 0.20
(a) Compute the flexural strength for a completely nonporous specimen of this material.
(b) Compute the flexural strength for a 0.10 volume fraction porosity.
Solution
(a) Given the flexural strengths at two different volume fraction porosities, we are asked to determine
the flexural strength for a nonporous material. If the natural logarithm is taken of both sides of
Equation 12.10, then
ln σfs = ln σ 0 − nP
Using the data provided in the problem statement, two simultaneous equations may be written as
ln (100 MPa) = ln σ 0 − (0.05) n
ln (50 MPa) = ln σ 0 − (0.20) n
Solving for n and σ0 leads to n = 4.62 and σ0 = 126 MPa. For the nonporous material, P = 0, and, from
Equation 12.10, σ0 = σfs. Thus, σfs for P = 0 is 126 MPa.
(b) Now, we are asked for σfs at P = 0.10 for this same material. Utilizing Equation 12.10 yields
σfs = σ 0 exp ( − nP )
= (126 MPa) exp [− (4.62)(0.10)]
= 79.4 MPa
DESIGN PROBLEMS
Crystal Structures
12.D1 Gallium arsenide (GaAs) and gallium phosphide (GaP) both have the zinc blende crystal
structure and are soluble in one another at all concentrations. Determine the concentration in
weight percent of GaP that must be added to GaAs to yield a unit cell edge length of 0.5580 nm.
The densities of GaAs and GaP are 5.316 and 4.130 g/cm3, respectively.
Solution
This problem asks that we determine the concentration (in weight percent) of GaP that must
be added to GaAs to yield a unit cell edge length of 0.5580 nm. The densities of GaAs and GaP were
given in the problem as 5.316 and 4.130 g/cm3, respectively. To begin, it is necessary to employ
Equation (13.1), and solve for the unit cell volume, VC, for the GaP-GaAs alloy as
n ′Aave
VC =
ρave NA
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 = (0.5580 nm)3
= (5.580 × 10 −8 cm)3 = 1.737 × 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 4.11a and 4.10a. For Aave we have
100
Aave =
CGaP (100 − C
GaP
)
+
AGaP AGaAs
100
=
CGaP (100 − CGaP )
+
100.69 g/mol 144.64 g/mol
whereas for ρave
100
ρave =
CGaP (100 − CGaP )
+
ρGaP ρGaAs
100
=
CGaP
+
(100 − CGaP )
4.130 g/cm 3 5.316 g/cm3
Within the zinc blende unit cell there are four formula units, and thus, the value of n' in Equation 12.1
is 4; hence, this expression may be written in terms of the concentration of GaP in weight percent as
follows:
VC = 1.737 × 10−22 cm3
n ′Aave
=
ρave NA
⎡ ⎤
⎢ ⎥
100
(4 formula units/unit cell) ⎢ ⎥
⎢ CGaP (100 − CGaP ) ⎥
⎢ + ⎥
⎣ 100.69 g/mol 144.64 g/mol ⎦
=
⎡ ⎤
⎢ ⎥
⎢ 100 ⎥ (6.022 × 10 23 formula units/mol)
⎢ CGaP (100 − CGaP ) ⎥
⎢ 3
+ ⎥
⎣ 4.130 g/cm 5.316 g/cm3 ⎦
And solving this expression for CGaP leads to CGaP = 20.2 wt%.
Stress-Strain Behavior
12.D2 It is necessary to select a ceramic material to be stressed using a three-point loading scheme
(Figure 12.32). The specimen must have a circular cross section and a radius of 2.8 mm, and
must not experience fracture or a deflection of more than 6.2 × 10−2 mm at its center when a
load of 275 N is applied. If the distance between support points is 50 mm, which of the
materials in Table 12.5 are candidates? The magnitude of the centerpoint deflection may be
computed using the equation supplied in Problem 12.42.
Solution
This problem asks for us to determine which of the ceramic materials in Table 12.5, when
fabricated into cylindrical specimens and stressed in three-point loading, will not fracture when a load
of 275 N is applied, and also will not experience a center-point deflection of more than 6.2 × 10−2 mm.
The first of these criteria is met by those materials that have flexural strengths greater than the stress
calculated using Equation 12.7b. According to this expression
FL
σfs =
π R3
(275 N)(50 × 10 −3 m)
= = 252 × 106 N/m 2 = 199 MPa
(π )(2.8 × 10 −3 m)3
Of the materials in Table 12.5, the following have flexural strengths greater than this value: Si3N4,
ZrO2, SiC, and Al2O3
For the second criterion we must solve for the magnitude of the modulus of elasticity, E, from
the equation given in Problem 12.42 where the expression for the cross-sectional moment of inertia
π R4
appears in Figure 12.32; that is, for a circular cross-section I = . Solving for E from these two
4
expressions
FL3
E =
12 π R 4 ∆y
(275 N)(50 × 10 −3 m)3

=
(12)(π )(2.8 × 10 −3 m) 4 (6.2 × 10 −5 m)
= 239 × 109 N/m2 = 239 GPa
Of those materials that satisfy the first criterion, only Al2O3, Si3N4, MgAl2O4 and SiC have moduli of
elasticity greater than this value (Table 12.5), and, therefore, are possible candidates.

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CHAPTER 12

STRUCTURES AND PROPERTIES OF CERAMICS

(AB) 2 + (FB) 2 = ( AEF)2

from above. Thus,

Solving for the rC/rA ratio leads to

From triangle FGH,

Since FGH is a right triangle

(GH )2 + (FH )2 = (FG)2

Or, solving for rC/rA

(a) For CsI, using data from Table 12.3

(b) For NiO, using data from Table 12.3

(c) For KI, using data from Table 12.3

(d) For NiS, using data from Table 12.3

But, since rC/rA = 0.735

(b) Similarly, for the Si4+ ions

and (3) Ti atoms are located at the following point coordinates:

(4 formula units/unit cell)(55.85 g/mol + 16.00 g/mol)

Or, solving for a

⎡ (4 formula units/unit cell)(24.31 g/mol + 16.00 g/mol) ⎤1/ 3

From Table 12.3

a = 2(0.072 nm) + 2(0.140 nm) = 0.424 nm

θ = 90° − 54.75° = 35.25°

The unit cell volume, VC is just a3, that is

VC = a 3 = (3.56 × 10 -8 cm) 3 = 4.51 × 10−23 cm3

(8 atoms/unit cell)(12.01 g/g - atom)

The measured density is 3.51 g/cm3.

VC = (4 y sin θ )3 = [ (4)(0.240 nm)(sin 35.25°)]

= 0.17 nm3 = 1.7 × 10−22 cm3

(4 formula units/unit cell)(65.41 g/mol + 32.06 g/mol)

The measured value of the density is 3.80 g/cm3.

(4.82 g/cm3 )(5.85 × 10 −8 cm)3 (6.022 × 1023 formula units / mol)

2 rCs+ + 2 rCl− 2 (0.170 nm) + 2 ( 0.181 nm)

= 0.405 nm = 4.05 × 10−8 cm

From Equation 12.1

n ′ ( ACs + ACl ) n ′( ACs + ACl )

(1 formula unit/unit cell)(132.91 g/mol + 35.45 g/mol)

and, from Table 12.3

2 (0.100 nm) + 2 (0.133 nm)

The volume of the unit cell is just

Thus, from Equation 12.1

(4 formula units/unit cell) [ 40.08 g/mol + (2)(19.00 g/mol)]

The measured density is 3.18 g/cm3.

(4.52 g/cm3 ) ⎡⎣(8.50 × 10-8

= 4.02 × 10−22 cm3

Now, the unit cell volume (VC) is just

VC = a 3 = (8.50 × 10 −8 cm)3 = 6.14 × 10 −22 cm3

VS 4.02 × 10 −22 cm3

AREA = (1.5)(5.0 × 10−8 cm)2 ( 3 ) = 6.49 × 10−15 cm 2

The unit cell volume now is just

VC = (AREA)(c) = (6.49 × 10−15 cm 2 )(1.34 × 10−7 cm)

= 8.70 × 10−22 cm3

Now, solving for n' (Equation 12.1) yields

(5.22 g/cm3 )(6.022 × 1023 formula units/mol)(8.70 × 10 −22 cm 3 /unit cell)

= 18.0 formula units/unit cell

= 6.57 × 10−22 cm3

Finally, the APF is just

VS 6.57 × 10−22 cm3

VC = (4 y sin θ )3 = [ (4)(2 r )(sin 35.25°)]

Finally, the atomic packing factor is just