Practice 22
Practice 22
Practice 22
Ceramic materials are inorganic, nonmetallic materials that consist of metallic and
nonmetallic elements bonded together primarily by ionic and/or covalent bonds.
10.2 What are some of the properties common to most ceramic materials?
While the properties of ceramic materials vary greatly, most ceramic materials are hard
and brittle with low toughness and ductility but good electrical and thermal insulating
properties. Also, ceramic materials typically have high melting temperatures and high
chemical stability.
10.3 Distinguish between traditional and engineering ceramic materials and give examples of
each.
Traditional ceramic materials are typically made from three components – clay, feldspar
and silica – whereas engineering ceramics consist of pure or nearly pure compounds
such as aluminum oxide ( Al 2O3 ), silicon carbide (SiC), and silicon nitride ( Si3 N 4 ).
Examples of traditional ceramics include bricks, tiles and electrical porcelain while
applications of engineering ceramics include silicon carbide parts for high temperature
gas turbine engine components, zirconium dioxide crucibles for melting superalloys,
and high performance ball bearing and races made of titanium and carbon nitride.
10.4 Using Pauling’s equation (Eq. 2.10), compare the percent covalent character of the
following compounds: hafnium carbide, titanium carbide, tantalum carbide, boron
carbide, and silicon carbide.
Recall that Pauling’s equation gives the percent covalent character as:
2
% covalent character = e−0.25 ( X A − X B ) × 100%
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
The two main factors which affect the packing of ions in ionic solids are:
1. The relative size of the ions in the ionic solid, assuming the ions are hard
spheres with definite radii;
10.6 Define (a) coordination number and (b) critical radius ratio for the packing of ions in
ionic solids.
(a) The coordination number is the number of anions that surround a central cation.
(b) The critical radius ratio is the ratio of the radius of the central cation to the radius of
the surrounding anions.
10.7 Using Fig. 10.60, calculate the critical radius ratio for octahedral coordination.
Figure 10.60 (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.
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.
10.9 Calculate the density in grams per cubic centimeter of CsI, which has the CsCl
structure. Ionic radii are Cs + = 0.165 nm and I − = 0.220 nm.
For the CsCl structure, 3a = 2(r + R) . Thus, the lattice constant measures,
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)
10.10 Calculate the density in grams per cubic centimeter of CsBr, which has the CsCl
structure. Ionic radii are Cs + = 0.165 nm and Br − = 0.196 nm.
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)
10.11 Calculate the linear densities in ions per nanometer in the [110] and [111] directions for
(a) NiO and (b) CdO. Ionic radii are Ni 2+ = 0.078 nm, Cd 2+ = 0.103 nm, and
O2 − = 0.132 nm.
Since NiO and CdO have the NaCl crystal structure, a = 2(r + R).
2Ni 2+ 2Ni 2+
ρL = = = 3.37 Ni 2+ /nm
2a (
2 0.420 nm )
[ 110 ]
If we shift the origin from (0, 0, 0) to (0, ½, 0), we obtain
2O2− 2O 2−
ρL = = = 3.37 O2− /nm
2a 2 ( 0.420 nm )
1O2− 1O2− O 2−
ρL = = = 1.37 O 2− /nm
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 )
2O2− 2O 2−
ρL = = = 3.01 O 2− /nm
2a 2 ( 0.470 nm )
1O2− 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 )
10.12 Calculate the planar densities in ions per square nanometer on the (111) and (110)
planes for (a) CoO and (b) LiCl. Ionic radii are Co 2+ = 0.082 nm, O2 − = 0.132 nm,
Li + = 0.078 nm, and Cl − = 0.181 nm. (111)
First recognize that both CoO and LiCl have the NaCl structure.
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,
1 1 3 3 2 3
A(111) = bh = ( 2a ) a = a = (0.428 nm)2 = 0.159 nm 2
2 2 2 2 2
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,
2(O 2− ions)
ρplanar = 2
= 15.4 O 2- ions/nm 2
0.13 nm
2(Co 2+ ions)
ρplanar = 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)
ρplanar = 2
= 10.5 Cl − ions/nm 2
0.19 nm
2(Li + ions)
ρplanar = 2
= 10.5 Li + ions/nm 2
0.19 nm
Both SrO and VO have the NaCl structure so a = 2(r + R) and there are four anions and
four cations per unit cell.
m m 4.45 × 10−22 g
ρ= = 3= −8 3
= 7.27 g/cm 3
V a (3.94 ×10 cm)
10.14 Calculate the ionic packing factor for (a) MnO and (b) SrO. Ionic radii are
Mn 2+ = 0.091 nm, Sr 2+ = 0.127 nm, and O2 − = 0.132 nm.
Both MnO and SrO have the NaCl structure. Thus there are four anions and four cations
per unit cell and the ionic packing factor is calculated using the equation:
(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
16
3 π (r
3
+ R3 ) 16π (0.127 nm)3 + (0.132 nm)3
IPF = = = 0.524
a3 3(0.518 nm)3
10.15 ZnTe has the zinc blende crystal structure. Calculate the density of ZnTe. Ionic radii are
Zn 2+ = 0.083 nm and Te 2 − = 0.211 nm.
Since ZnTe has the zinc blende crystal structure (ZnS), there are four zinc ions and four
4
tellurium ions per unit cell. Also, the lattice constant is calculated as a = (r + R) .
3
4 4
a= (r + R) = (0.083 nm + 0.211 nm) = 0.679 nm
3 3
(4Zn 2+ × 65.38 g/mol) + (4Te2− × 127.6 g/mol)
m unit cell = 23
= 1.28 × 10−21 g
6.02 × 10 ions/mol
m m 1.28 × 10−21 g
ρ= = 3= −8 3
= 4.09 g/cm 3
V a (6.79 × 10 cm)
10.16 BeO has the zinc blende crystal structure. Calculate the density of BeO. Ionic radii are
Be 2+ = 0.034 nm and O2 − = 0.132 nm.
Since BeO has the zinc blende crystal structure, there are four zinc ions and four oxygen
4
ions per unit cell. Also, the lattice constant is calculated as a = (r + R) .
3
4 4
a= (r + R) = (0.034 nm + 0.132 nm) = 0.383 nm
3 3
(4Be2+ × 9.012 g/mol) + (4O 2− × 16.00 g/mol)
m unit cell = 23
= 1.66 ×10−22 g
6.02 × 10 ions/mol
m m 1.66 × 10−22 g
ρ= = 3= = 2.95 g/cm 3
V a (3.83 × 10−8 cm)3
The BaF2 unit cell is shown below. With the Ba 2 + ions occupying the FCC lattice sites,
the F − ions occupy the tetrahedral interstitial sites.
10.18 Calculate the density in grams per cubic centimeter of ZrO2, which has the CaF2 crystal
structure. Ionic radii are Zn 4+ = 0.087 nm and O2 − = 0.132 nm.
Since ZrO2 has the CaF2 crystal structure, there are four Zr 4+ ions and eight O2− ions
4
per unit cell. Also, the lattice constant is calculated as a = (r + R) .
3
4 4
a= (r + R) = (0.087 nm + 0.132 nm) = 0.506 nm
3 3
(4Zr 2+ × 91.22 g/mol) + (8O2− × 16.00 g/mol)
m unit cell = 23
= 8.19 × 10−22 g
6.02 × 10 ions/mol
m m 8.19 × 10−22 g
ρ= = 3= −8 3
= 6.32 g/cm 3
V a (5.06 ×10 cm)
10.19 What fraction of the octahedral interstitial sites is occupied in the CaF2 structure?
All eight of the tetrahedral interstitial sites are occupied. However, none of the four
octahedral interstitial sites are occupied; thus the fraction is zero.
Ce4+
4 4
a= (rCe 4+ + RO2− ) = (0.102 nm + 0.132 nm)
3 3
= 0.540 nm
2Ce4+ 2Ce4+
ρL = = = 2.62 Ce4+ /nm
2a 2 ( 0.540 nm )
[ 110 ]
10.21 Calculate the planar density in ions per square nanometer in the (111) and (110) planes
of ThO2 , which has the fluorite structure. Ionic radii are Th 4+ = 0.110 nm and
O2 − = 0.132 nm.
(111) plane
Th 4+
If we consider the Th 4+ cations to be located at
the FCC positions of a cubic unit cell, and the O2− anions a
in the tetrahedral interstitial sites, then the (111) plane
contains the equivalent of two cations.
4 4
The lattice constant is a = (rTh 4+ + RO2− ) = (0.110 nm + 0.132 nm) = 0.559 nm .
3 3
The area of the (111) plane is,
1 1 3 3 2 3
A(111) = bh = ( 2a ) a = a = (0.559 nm) 2 = 0.270 nm 2
2 2 2 2 2
2(Th 4+ ions)
ρplanar = 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,
1 1 2 2 2
A(110) = bh = ( 2a ) ( a ) = a = (0.559 nm) 2
2 2 2 2 a
2
= 0.221 nm
10.22 Calculate the ionic packing factor for SrF2 , which has the fluorite structure. Ionic radii
are Sr 2+ = 0.127 nm and F − = 0.133 nm.
4
where a = (0.127 nm + 0.133 nm) = 0.600 nm . Substituting,
3
10.23 What is the antifluorite structure? What ionic compounds have this structure? What
fraction of the tetrahedral interstitial sites is occupied by cations?
The antifluorite structure consists of an FCC unit cell with anions occupying the FCC
lattice points and cations occupying all eight tetrahedral sites. Thus the cation and anion
positions of the fluorite structure are reversed. Examples of compounds having this
10.24 Why are only two-thirds of the octahedral interstitial sites filled by Al3+ ions when the
oxygen ions occupy the HCP lattice sites in Al 2O3 ?
When the oxygen ions occupy the HCP lattice sites in Al 2O3 , only two-thirds of the
octahedral interstitial sites are filled by Al3+ ions in order to maintain electrical
neutrality. There can only be two Al3+ ions for every three O2− ions.
10.25 Describe the perovskite structure. What fraction of the octahedral interstitial sites is
occupied by the tetravalent cation?
The perovskite structure (CaTiO3) consists of an FCC unit cell with Ca 2+ cations in the
corners, O2− anions in the face centers, and a Ti 4+ cation in the center octahedral
interstitial site. The tetravalent cation Ti 4+ fills one- fourth of the octahedral sites.
10.26 Calculate the ionic packing factor for CaTiO3 , which has the perovskite structure. Ionic
radii are Ca 2+ = 0.106 nm, Ti 4+ = 0.064 nm, and O2 − = 0.132 nm. Assume the lattice
constant a = 2 ( rTi 4+ + rO2 − ) .
In the perovskite structure, there are a total of one calcium ion, one titanium ion, and
three oxygen atoms. The ionic packing factor is therefore calculated as,
( )
where a = 2 rTi4+ + rO2− = 2(0.064 nm + 0.132 nm) = 0.392 nm . Substituting,
10.27 Calculate the density in grams per cubic centimeter of SrSnO3 , which has the
perovskite structure. Ionic radii are Sr 2+ = 0.127 nm, Sn 4+ = 0.074 nm, and
O2 − = 0.132 nm. Assume the lattice constant a = 2 ( rSn 4+ + rO2 − ) .
( )
For a = 2 rSn 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)
The spinel structure has the general form AB2 O4 where A represents a metal ion with a
+2 valence and B is a metal cation with a +3 valence. The oxygen ions form an FCC
lattice in which the A and B ions occupy the octahedral and tetrahedral interstitial sites.
10.29 Draw a section of the graphite structure. Why are the layers of graphite able to slide
past each other easily.
10.30 Describe and illustrate the following silicate structures: (a) island, (b) chain, and (c)
sheet.
(a) Island silicate structures are formed when positive ions, such as Mg 2+ and Fe2+
bond with oxygen anions of the SiO44− tetrahedra.
(b) Chain or ring structures are produced when two corners of each SiO44− tetrahedron
bond with the corners of two other tetrahedra. The result is the SiO32− structure.
(c) Sheet silicate structures form when three corners in the same plane of a silicate
tetrahedron are bonded to the corners of three other silicate tetrahedra. The unit
chemical formula of this structure is Si 2 O52− .
10.32 Describe the bonding arrangement in the cristobalite (silica) network structure.
In the cristobalite silica structure, each silicon atom is bonded to four oxygen atoms and
each oxygen atom forms part of two SiO44− tetrahedra. The resulting network structure
is a common crystalline phase of silica which exists at high temperatures of 1470 to
1710°C.
In the feldspar silicate structural network, some of the Si 4+ ions are replaced by Al3+
ions. The resulting negatively charged network is balanced by large cations of the alkali
and alkaline earth elements, such as Na + , K + , and Ca 2+ , which fit into the interstitial
sites.
10.34 What are the basic steps in the processing of ceramic products by the agglomeration of
particles?
The basic steps in the processing of ceramic products by the agglomeration are:
1. material preparation
2. forming or casting
3. thermal treatment by drying and firing to a high enough temperature for the
particles to bond.
10.35 What types of ingredients are added to ceramic particles in preparing ceramic raw
materials for processing?
Binders, lubricants and other additives are added to ceramic particles to achieve the
desired set of ceramic properties.
10.36 Describe two methods for preparing ceramic raw materials for processing.
Ceramic raw materials are prepared by wet processing, dry processing or a combination
of wet and dry processing. In wet processing, the additives are blended with water while
in dry processing, the additives are ground dry with the raw materials.
10.37 Describe the dry-pressing method for producing such ceramic compounds as technical
ceramic compounds and structural refractories. What are the advantages of dry-pressing
ceramic materials?
In the isostatic process, the ceramic powder is loaded into a flexible airtight container
that is inside a chamber of hydraulic fluid. Pressure is then applied to the fluid to
compact the powder uniformly. The product, which possesses the shape of the
container, is fired to attain the required microstructure and properties.
10.39 Describe the four stages in the manufacture of a spark plug insulator.
In manufacturing a spark plug insulator, four stages are completed: isostatic pressing,
turning the blank, firing to fuse the powder, and glazing.
10.41 Describe the steps in the slip-casting process for ceramic products.
10.42 What is the difference between (a) drain and (b) solid slip casting?
10.44 What types of ceramic products are produced by extrusion? What are the advantages of
this process? Limitations?
10.45 What are the purposes of drying ceramic products before firing?
Ceramics are dried before firing in order to remove water and organic binders.
10.46 What is the sintering process? What occurs to the ceramic particles during sintering?
The sintering process is a thermal treatment which causes ceramic particles to bond
together by solid-state diffusion. This diffusion process, driven by high temperatures,
occurs between the contacting surfaces of the particles and allows them to chemically
bond. As the process proceeds, the sintered particles increase in size until an
equilibrium grain size is attained. The energy of the surfaces of these grain boundaries
is lower than the surface energy associated with the original individual particles.
10.47 What is the vitrification process? In what type of ceramic materials does vitrification
take place?
In the vitrification process, the glass phase of the ceramic liquefies and fills the
material’s pores during firing, and then solidifies during cooling to form a vitreous or
glassy matrix that bonds the particles. This process takes place in ceramic materials
containing a glass phase such as porcelain and structural clay.
The three basic components of traditional ceramics are clay, silica (flint) and feldspar.
The approximate composition of kaolin clay is 45.5 percent SiO2 , 37.4 percent Al2 O3 ,
13.9 percent H 2 O, 1.68 percent Fe2 O3 , 1.30 percent TiO2 , 0.03 percent MgO, 0.011
percent Na 2 O, 0.004 percent CaO, and 0.005 percent K 2 O.
Flint, also called quartz, is silica (SiO2) and serves as the refractory component of
traditional ceramics.
Examples of whiteware ceramic products are bone china, dental porcelain, electrical
insulation ware, vitreous tile and vitreous sanitary ware.
The term triaxial refers to the fact that the whiteware is composed of three primary
materials – clay, feldspar and flint.
10.55 Determine the composition of the ternary compound at point y in Fig. 10.32.
At point y, the ternary compound has the composition 27 percent leucite, 36 percent
silica, and 37 percent mullite.
10.56 Why are triaxial porcelains not satisfactory for use at high frequencies?
Triaxial porcelains are not satisfactory insulators for high frequency applications
because dielectric losses become too large.
10.57 What kinds of ions cause an increase in the conductivity of electrical porcelain?
Most technical ceramics are composed of pure compounds or nearly pure compounds of
chiefly oxides, carbides and nitrides.
10.59 How are pure single-compound technical ceramic particles processed to produce a solid
product? Give an example.
10.60 What are three major applications for ceramic materials in the electrical-electronics
industries?
10.61 Define the terms dielectric, capacitor, and capacitance. What is the SI unit for
capacitance? What units are commonly used for capacitance in the electronics industry?
10.62 What is the dielectric constant of a dielectric material? What is the relationship among
capacitance, dielectric constant, and the area and distance of separation between the
plates of a capacitor?
The dielectric constant represents the ratio of the capacitances achieved when a
capacitor’s plates are separated by a dielectric as compared to a vacuum.
A capacitor’s capacitance, dielectric constant, plate area, and plate separation distance
are related as C = κε 0 A d .
10.63 What is the dielectric strength of a dielectric material? What units are used for dielectric
strength? What is dielectric breakdown?
The dielectric strength is the maximum electric field that a dielectric material can
maintain without experiencing an electrical breakdown. This type of breakdown,
referred to as a dielectric breakdown, causes the passage of current to occur.
The units used to measure dielectric strength are volts per mil in the U.S. Customary
System and kilovolts per millimeter in the SI system.
10.64 What is the dielectric loss angle and dielectric loss factor for a dielectric material? Why
is a high dielectric loss factor undesirable?
The dielectric loss angle, δ, is the angle by which the current’s lead of the voltage is
reduced when a capacitor uses a real dielectric. An ideal or loss-free dielectric causes
zero angular loss and the current leads the sinusoidal voltage by 90°.
10.65 A simple plate capacitor can store 7.0 × 10−5 C at a potential of 12,000 V. If a barium
titanate dielectric material with κ = 2100 is used between the plates, which have an
area of 5 × 10−5 m 2 , what must be the separation distance between the plates?
q 7.0 × 10−5 C
C= = = 5.83 × 10−9 F
V 12,000 V
10.66 A simple plate capacitor stores 6.5 × 10−5 C at a potential of 12,000 V. If the area of the
plates is 3 × 10−5 m 2 and the distance between the plates is 0.18 mm, what must be the
dielectric constant of the material between the plates?
q 6.5 × 10−5 C
C= = = 5.42 × 10−9 F
V 12,000 V
κ=
Cd
=
( 5.42 ×10−9 F) (1.8 ×10−4 m ) = 3675
Aε 0 ( 3.0 × 10−5 m 2 )( 8.85 × 10−12 F/m )
10.68 What is the approximate composition of steatite? What desirable electrical properties
does steatite have as an insulative material?
Steatite porcelains are composed of approximately 90 percent talc and 10 percent clay.
As an electrical insulating material, steatites have the advantageous properties of low
power-loss factors, low moisture absorption and good impact strength.
10.69 What is the composition of fosterite? Why is fosterite an excellent insulator material?
10.70 Why is sintered alumina widely used as a substrate for electronic-device applications?
10.71 Why is BaTiO3 used for high-value, small, flat-disk capacitors? How is the capacitance
of BaTiO3 capacitors varied? What are the four major stages in the manufacture of a
flat-disk ceramic capacitor?
BaTiO3 is used for high-value, small, flat-disk capacitors because its exceptionally high
dielectric constant, 1200 to 1500, allows for very high capacitance. The capacitance of
BaTiO3 capacitors can be further increased through the addition of additives such as
BaZrO3 and CaTiO3 .
The four major stages of flat-disk ceramic capacitors are: (1) firing the ceramic disk; (2)
applying silver electrodes; (3) soldering leads; (4) applying dipped phenolic coating.
NTC thermistors are made from sintered oxides of Mn, Ni, Fe, Co, and Cu.
10.75 How is the electrical conductivity of metal oxide semiconductors for thermistors
changed?
The electrical conductivity of metal oxide semiconductors for thermistors can be varied
in a controlled manner through solid solution addition of a metal oxide having a
different conductivity but a similar structure.
When BaTiO3 is cooled to 120°C, the central Ti 4+ cation and the surrounding O2−
anions shift slightly in opposite directions and thereby create a small electric dipole
moment. At the critical temperature of 120°C, the shifting is accompanied by a
crystalline structural change from cubic to tetragonal. This transformation temperature
is called the Curie temperature.
10.77 What are ferroelectric domains? How can they be lined toward one direction?
Ferroelectric domains are regions within a ferroelectric material in which the small
electric dipoles of the unit cells are aligned in one direction. The orientation of domains
can be lined in one direction by applying an electrical field as the material passes
through its Curie temperature. For example, if a sample of BaTiO3 is held at 120°C
and an electric field is applied, the dipoles within individual domains will orient
themselves toward the negative plate and produce a strong dipole moment per unit
volume of the material.
10.78 Describe the piezoelectric effect for producing an electrical response with the
application of pressure on a ferroelectric material. Do the same for producing a
mechanical response by the application of an electrical force.
When compressive forces are applied across a sample of a ferroelectric material, the
sample length is reduced, and consequently, the distance between dipoles is reduced. As
a result, the overall dipole moment of the material is decreased, which in turn, changes
the charge density at the sample ends and causes a voltage potential to develop.
Similarly, if an electrical field is applied across the sample, the resulting charge density
alteration at the sample ends will cause dimensional changes in the direction of the
applied field. The sample thus produces the mechanical response of physical elongation
or shrinkage.
Two examples of devices which convert mechanical forces into electrical responses are
the piezoelectric compression accelerometer, which measures vibratory accelerations
over a wide range of frequencies, and the phonograph cartridge, which detects electrical
responses via a stylus vibrating in the record grooves. Examples of devices which
convert electrical responses into mechanical output include the ultrasonic cleaning
transducer, which agitates liquid via vibrations induced by ac power, and the
underwater sound transducer, which transmits sound waves through transducer
vibrations stimulated by the application of voltage.
The PZT piezoelectric materials are ceramics made from solid solutions of lead
zirconate (PbZrO3) and lead titanate (PbTiO3). The PZT ceramics have a broader range
of piezoelectric properties, including a higher Curie temperature, than BaTiO3 .
The lack of plasticity in crystalline ceramics is attributed to their ionic and covalent
chemical bonds. In covalent crystals and covalently bonded ceramics, atoms bond
through the exchange of electron charge between pairs of electrons, in a specific and
directional manner. Consequently, if the ceramic is sufficiently stressed, electron-pair
bonds undergo irreparable separation, causing the material to experience brittle fracture.
10.82 Explain the plastic deformation mechanism for some single-crystal ionic solids such as
NaCl and MgO. What is the preferred slip system?
For some single-crystal ionic solids, such as NaCl and MgO, compressive stresses at
room temperature cause considerable plastic deformation prior to fracture because
planes of oppositely charged ions can slip relative to each other. These slip planes,
which maintain their attraction through coulombic forces, typically prefer the
{110}<110> slip system for NaCl-type structures.
10.83 What structural defects are the main cause of failure of polycrystalline ceramic
materials?
10.84 How do (a) porosity and (b) grain size affect the tensile strength of ceramic materials?
(a) Pores serve as a source for stress induced crack initiation/propagation and reduce
the cross-sectional area available for load application. Consequently, as the porosity
of a ceramic material increases, the material tensile strength decreases.
(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.
10.85 A reaction-bonded silicon nitride ceramic has a strength of 250 MPa and a fracture
toughness of 3.4 MPa − m . What is the largest-sized internal flaw that this material
can support without fracturing? (Use Y = 1 in the fracture-toughness equation.)
10.86 The maximum-sized internal flaw in a hot-pressed silicon carbide ceramic is 25 µm. If
this material has a fracture toughness of 3.7 MPa − m , what is the maximum stress
that this material can support? (Use Y = π .)
1 K IC 1 3.7 MPa- m
σf = = = 236 MPa
πa Y π (2.5 ×10−5 m) π
10.87 A partially stabilized zirconia advanced ceramic has a strength of 352 MPa and a
fracture toughness of 7.5 MPa − m . What is the largest-sized internal flaw (expressed
in micrometers) that this material can support? (Use Y = π .)
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)
10.88 A fully stabilized, cubic polycrystalline ZrO2 sample has a fracture toughness of
K IC =3.8 MPa − m when tested on a four-point bend test.
(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 K IC =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 IC 3.8 MPa- m −6
a= = = 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
The two most important industrial abrasives are fused alumina (Al2O3) and silicon
carbide (SiC).
Most ceramic materials have low thermal conductivities because of their strong ionic-
covalent bonding which restricts the motion of electrons required for both thermal and
electrical conduction. Pure metals are excellent electron carriers and thus serve as
important conductors of heat and electricity.
Refractories are materials that have good heat resistance. They are used extensively by
the metals, chemical, ceramic and glass industries for applications such as linings for
various types of furnaces, kilns, ovens, incinerators and reactors.
10.93 What are the two main types of ceramic refractory materials?
The two main types of ceramic refractory materials are acidic refractories and basic
refractories.
10.94 Give the composition and several applications for the following refractories:
(a) silica, (b) fireclay, and (c) high-alumina.
(a) Silica refractories contain 95 to 99 percent SiO2 and are used for chemical reactor
linings, glass tank parts, ceramic kilns and coke ovens.
(b) Fireclays are mixtures of plastic fireclay, flint (silica) clay, and clay grog which give
a combined composition of approximately 51 to 54 percent SiO2 and 37 to 42
percent Al2O3. Their refractory applications include linings for cement, rotary, and
lime kilns, linings for aluminum-melting and blast furnaces, and linings for
incinerators.
(c) High-alumina refractories are composed of 45 to 99+ percent Al2O3 and 0 to 50
percent SiO2. These materials are used in boiler, phosphate, carbon black and spent-
acid furnaces, coke kilns, glass-tank refiner walls, continuous-casting tundish
linings, and coal gasification reactor linings.
Most basic refractories consist of magnesia (MgO), lime (CaO), and chrome ore
(Cr2O3). Some of the important properties associated with these materials are high bulk
densities, high melting temperatures, and good resistance to chemical corrosion by basic
slags and oxides. Consequently, these refractories are used mainly for the linings of
basic-oxygen steelmaking furnaces.
10.98 What are some of the properties of glasses that make them indispensable for many
engineering designs?
Glasses are indispensable to many engineering designs because they possess a unique
combination of special properties – transparency, hardness and sufficient strength at
room temperature, and excellent corrosion resistance to most environments.
Unlike all other ceramic materials, glass constituents are heated to fusion and then
cooled in the rigid state without crystallization. As a consequence, glass has an
amorphous structure rather than crystalline.
10.100 How does the specific volume versus temperature plot for a glass differ from that for a
crystalline material when these materials are cooled from the liquid state?
The plot of specific volume versus temperature for a glass differs from that of a
crystalline material in two ways. First, the glass does not experience a rapid decrease in
specific volume at a temperature associated with a melting point; the glass cooling
curve conveys a gradual decrease in specific volume throughout the cooling range.
Second, the glass curve contains a marked decrease in slope at a glass transition
temperature which other ceramics do not possess.
The glass transition temperature, Tg , is the temperature at which the two slopes of a
glass specific volume versus temperature curve intersect. Physically, this temperature
falls within the narrow temperature range in which a glass changes from a rubbery, soft
plastic state to a rigid, brittle glassy state. Thus, the Tg represents the point at which the
material behaves more like a solid than a liquid.
10.102 Name two glass-forming oxides. What are their fundamental subunits and their shape?
Silica (SiO2) and boron oxide (B2O3) are two glass-forming oxides. Their fundamental
3−
subunits are respectively, the SiO 4-
4 tetrahedron and the BO3 flat triangle.
10.103 How does the silica network of a simple silica glass differ from crystalline (cristobalite)
silica?
In a simple glass, the tetrahedra are joined corner to corner, forming a loose network. In
contrast, a crystalline material, such as cristobalite, has Si-O tetrahedra joined corner to
corner in a regular arrangement, producing a network having a long-range order.
10.104 How is it possible for BO33− triangles to be converted to BO44− tetrahedral and still
maintain neutrality in some borosilicate glasses?
BO33− triangles can be converted to BO44− tetrahedra by adding alkali and alkaline earth
oxides whose cations provide the necessary elecroneutrality.
10.105 What are glass network modifiers? How do they affect the silica-glass network? Why
are they added to silica glass?
Glass network modifiers are oxides that break up the glass network. Examples include
Na2O, K2O, CaO, and MgO. These oxides affect the silica glass network by breaking
the network at the tetrahedra points. As a result, the tetrahedra have oxygen atoms with
an unshared electron while the oxide’s metal cations remain as ions ionically bonded in
the network interstices. Glass modifiers are added to silica glass to facilitate forming
and working the glass by lowering its viscosity.
10.106 What are glass intermediate oxides? How do they affect the silica-glass network? Why
are they added to silica glass?
Glass intermediate oxides are oxides that cannot form a glass network by themselves
but can join an existing one. These oxides may act as modifiers of the structure as well
as become a part of the network chain. In the latter case, they sometimes leave the
network deficient in electrons and alkali cations must be added for electrical neutrality.
The intermediate oxides are added to glass to obtain special properties. For example,
10.107 What is fused silica glass? What are some of its advantages and disadvantages?
Fused silica glass is composed of 99.5 percent SiO2 and is the most important single-
component glass. Its advantageous properties include a high spectral transmission and
the ability to withstand radiation without browning. However, it is expensive and
difficult to melt and fabricate.
10.108 What is the basic composition of soda-lime glass? What are some of its advantages and
disadvantages? What are some applications for soda-lime glass?
10.109 What is the purpose of (a) MgO and (b) Al 2O3 additions to soda-lime glass?
10.110 Define the following viscosity reference points for glasses: working, softening,
annealing, and strain.
The working point is the temperature which corresponds to a viscosity of 104 poises and
which represents the thermal state at which glass fabrication operations can be
performed.
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.
10.111 Distinguish between hard and soft glasses and long and short glasses.
10.112 A soda-lime plate glass between 500°C (strain point) and 700°C (softening point) has
viscosities between 1014.2 and 107.5 P, respectively. Calculate a value for the activation
energy in this temperature region.
ηstp Q 1 1
= exp −
ηsp R Tstp Tsp
1014.2 P Q 1 1
7.5
= exp −
10 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
10.113 A soda-lime glass has a viscosity of 1014.6 P at 560°C. What will be its viscosity at
675°C if the activation energy for viscous flow is 430 kJ/mol?
Let η1 = η0 eQ / RT1 and η2 = η0eQ / RT2 where T1 = 833 K and T2 = 948 K. Then,
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
η1 Q 1 1
= exp −
η2 R T1 T2
1014.3 P 430 ×103 J/mol 1 1
= exp −
109.9 P 8.314 J/mol ⋅ K 843 K T2
1 1
ln104.4 = 51, 720 −
843 K T2
T2 = (0.0011862 − 0.0001959)−1 = 1009.7 K = 736.7o C
10.115 A borosilicate glass between 600°C (annealing point) and 800°C (softening point) has
viscosities of 1012.5 P and 107.4 P, respectively. Calculate a value for the activation
energy for viscous flow in this region, assuming the equation η = η0 eQ / RT is valid.
ηap Q 1 1
= exp −
ηsp R Tap Tsp
1012.5 P Q 1 1
7.4
= exp −
10 P 8.314 J/mol ⋅ K 873 K 1073 K
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
10.116 Describe the float-glass process for the production of flat-glass products. What is its
major advantage?
In the float-glass process, a ribbon of glass flows out of a melting furnace and into a
molten tin bath on which it floats. As the ribbon moves across the bath, it cools under a
chemically controlled atmosphere to prevent oxidation. Once the glass surfaces are
sufficiently hard, the sheet is removed from the float chamber and passed through a lehr
annealing furnace which removes residual stresses. The major advantage of this process
over its predecessor, the rolling process, is that a very flat sheet of glass is produced
which does not require costly grinding or polishing.
10.117 What is tempered glass? How is it produced? Why is tempered glass considerably
stronger in tension than annealed glass? What are some applications for tempered glass?
10.118 What is chemically strengthened glass? Why is chemically strengthened glass stronger
in tension than annealed glass?
Chemically strengthened glass is a glass that has been given a chemical treatment to
introduce large ions, and thus compressive stresses, into the glass surface. Like
tempered glass, chemically strengthened glass is stronger in tension than annealed glass
due to its residual surface stresses.