Chapt 11
Chapt 11
10.1
10.2
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 Paulings 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 Paulings equation gives the percent covalent character as:
2
Electronegativities
XA
XB
1.2
2.5
1.3
2.5
1.4
2.5
2.0
2.5
1.8
2.5
(XA XB)2
-0.25(XA XB)2
1.69
1.44
1.21
0.25
0.49
-0.4225
-0.360
-0.3025
-0.0625
-0.1225
% Covalent
Character
65.5
69.8
73.9
93.9
88.5
223
10.5
What two main factors affect the packing of ions in ionic solids?
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;
2. The need to balance the electrostatic charges to maintain electrical neutrality
within the ionic solid.
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).
From the triangle shown above in Fig. 10.60 (b),
[ 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
Smith
224
10.8
Predict the coordination number for (a) BaO and (b) LiF. Ionic radii are
Ba 2+ = 0.143 nm, O2 = 0.132 nm, Li + = 0.078 nm, F = 0.133 nm.
(a) Using Appendix II, the radius ratio for BaO is
rcation r (Ba 2+ ) 0.143
=
=
= 1.08
ranion
R(O 2 ) 0.132
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.
(b) Using Appendix II, the radius ratio for LiF is
rcation r (Li + ) 0.078
=
=
= 0.59
ranion R(F ) 0.133
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.
2
( 0.165 nm + 0.220 nm ) = 0.445 nm = 4.45 108 cm
3
Since the unit cell of CsI contains one Cs+ and one I ion, its mass is
a=
munit cell =
=
10.10
Smith
m m
4.32 1022 g
= 3=
= 4.90 g/cm 3
8
3
V a
(4.45 10 cm)
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.
225
2
( 0.165 nm + 0.196 nm ) = 0.417 nm = 4.17 108 cm
3
Since the unit cell of CsI contains one Cs+ and one Br ion, its mass is
a=
munit cell =
=
10.11
m m
3.53 1022 g
= 3=
= 4.87 g/cm 3
8
3
V a
(4.17 10 cm)
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).
(a) For NiO in the [110] direction,
a = 2(rNi2+ + RO2 ) = 2(0.078 nm + 0.132 nm)
= 0.420 nm
L =
Ni 2+
2Ni 2+
2Ni 2+
=
= 3.37 Ni 2+ /nm
(
)
2a
2 0.420 nm
[ 110 ]
L =
2O2
2O 2
=
= 3.37 O2 /nm
2a
2 ( 0.420 nm )
Ni 2+
Smith
L =
1O2
1O2
=
= 1.37 O 2 /nm
3a
3 ( 0.420 nm )
L =
1Ni 2+
1Ni 2+
=
= 1.37 Ni 2+ /nm
3a
3 ( 0.420 nm )
[ 111 ]
O 2
226
L =
2Cd 2+
2Cd 2+
=
= 3.01 Cd 2+ /nm
2a
2 ( 0.470 nm )
L =
2O2
2O 2
=
= 3.01 O 2 /nm
2a
2 ( 0.470 nm )
L =
1O2
1O 2
=
= 1.23 O 2 /nm
3a
3 ( 0.470 nm )
1Ni 2+
1Ni 2+
L =
=
= 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.
(a) For CoO, if we consider the O2 anions to be located at
the FCC positions of a cubic unit cell, then the (111) plane
contains the equivalent of two anions.
227
planar =
2(O 2 ions)
= 12.6 O 2- ions/nm 2
2
0.159 nm
The planar density of the Co2+ cations is the same if we consider them to be located
at the FCC lattice points of the unit cell. Consequently,
1
1
2 2
2
(0.428 nm)2
= bh = ( 2a ) ( a ) =
a =
2
2
2
2
= 0.13 nm 2
planar =
planar
(b) Similarly, for LiCl, the (111) planar densities are calculated as:
a = 2(r + R) = 2(0.078 nm + 0.181 nm) = 0.518 nm
1
3 2
3
(0.518 nm)2 = 0.232 nm 2
A(111) = bh =
a =
2
2
2
2(Cl ions)
planar =
= 8.6 Cl ions/nm 2
2
0.232 nm
2(Li + ions)
planar =
= 8.6 Li + ions/nm 2
2
0.232 nm
228
10.13
Calculate the density in grams per cubic centimeter of (a) SrO and (b) VO. Ionic radii
are V 2+ = 0.065 nm, Sr 2+ = 0.127 nm, and O2 = 0.132 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.
(a) For SrO,
a = 2(r + R) = 2(0.127 nm + 0.132 nm) = 0.518 nm
munit cell
munit cell =
=
10.14
m m
4.45 1022 g
= 3=
= 7.27 g/cm 3
8
3
V a
(3.94 10 cm)
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:
IPF =
3
3
Vol. of ions per unit cell 4 ( 4 3 r ) + 4 ( 4 3 R ) 16 3 (r 3 + R3 )
=
=
Vol. of unit cell
a3
a3
(a) For MnO, a = 2(0.091 nm + 0.132 nm) = 0.446 nm and the IPF is
IPF =
Smith
16
3 (r
a3
+ R3 )
229
(b) For SrO, a = 2(0.127 nm + 0.132 nm) = 0.518 nm and the IPF is
IPF =
10.15
16
3 (r
a3
+ R3 )
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
(r + R) .
tellurium ions per unit cell. Also, the lattice constant is calculated as a =
3
a=
4
4
(r + R) =
(0.083 nm + 0.211 nm) = 0.679 nm
3
3
m unit cell =
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
(r + R) .
ions per unit cell. Also, the lattice constant is calculated as a =
3
a=
4
4
(r + R) =
(0.034 nm + 0.132 nm) = 0.383 nm
3
3
m unit cell =
Smith
m m
1.66 1022 g
= 3=
= 2.95 g/cm 3
V a
(3.83 108 cm)3
230
10.17
Draw the unit cell for BaF2, which has the fluorite (CaF2) crystal structure. If the Ba 2 +
ions occupy the FCC lattice sites, which sites do the F ions occupy?
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
(r + R) .
per unit cell. Also, the lattice constant is calculated as a =
3
a=
4
4
(r + R) =
(0.087 nm + 0.132 nm) = 0.506 nm
3
3
m unit cell =
=
10.19
m m
8.19 1022 g
= 3=
= 6.32 g/cm 3
3
8
V a
(5.06 10 cm)
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.
Smith
231
10.20
Calculate the linear density in ions per nanometer in the [111] and [110] directions for
CeO2, which has the fluorite structure. Ionic radii are Ce 4+ = 0.102 nm and
O2 = 0.132 nm.
For CeO2 in the [111] direction, there are two O2
and one Ce4+ along the cube diagonal, which is
3a in length.
O 2
[111]
Ce4+
Ce4+
4
4
a=
(rCe 4+ + RO2 ) =
(0.102 nm + 0.132 nm)
3
3
= 0.540 nm
L =
Ce4+
2Ce4+
2Ce4+
L =
=
= 2.62 Ce4+ /nm
2a
2 ( 0.540 nm )
10.21
[ 110 ]
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.
If we consider the Th 4+ cations to be located at
the FCC positions of a cubic unit cell, and the O2 anions
in the tetrahedral interstitial sites, then the (111) plane
contains the equivalent of two cations.
Th 4+
(111) plane
Th 4+
4
4
(rTh 4+ + RO2 ) =
(0.110 nm + 0.132 nm) = 0.559 nm .
3
3
232
The planar density for the Th 4+ cations on the (111) plane is thus,
planar
2(Th 4+ ions)
=
= 7.4 Th 4+ ions/nm 2
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
= 0.221 nm
4(O 2 ions)
= 18.1 O2 ions/nm 2
0.221 nm 2
2(Th 4+ ions)
=
= 9.1 Th 4+ ions/nm 2
2
0.221 nm
O 2
planar =
planar
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.
Vol. of ions per unit cell (
=
IPF =
Vol. of unit cell
) ( 4rSr3
2+
a3
) + (8R )
3
F
4
(0.127 nm + 0.133 nm) = 0.600 nm . Substituting,
3
where a =
IPF =
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
Smith
233
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,
Vol. of ions per unit cell (
=
IPF =
Vol. of unit cell
) ( rCa3
2+
) + ( r ) + (3r )
3
Ti 4 +
3
O2
a3
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
Smith
234
m unit cell =
=
10.28
m m
4.22 1022 g
= 3=
= 6.03 g/cm 3
3
8
V a
(4.12 10 cm)
10.29
Draw a section of the graphite structure. Why are the layers of graphite able to slide
past each other easily.
The layers of graphite within the
graphite structure can easily slide past
each other because the bonds between
the layers are weak secondary bonds,
as compared to the strong covalent
bonds between the carbon atoms
constituting the layers.
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 .
10.31
Smith
235
10.33
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
Smith
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?
236
In dry pressing, granular ceramic powder, in solution with small amounts of water
and/or organic binder, is simultaneously compacted and shaped in a die. Subsequently,
the parts are typically fired to achieve the desired microstructural properties such as
strength. The advantages of dry-pressing ceramic materials are the ability to rapidly
form a wide variety of shapes and the capability to achieve uniformity and close
tolerances.
10.38
10.39
10.40
10.41
10.42
What is the difference between (a) drain and (b) solid slip casting?
Refer to step (3) in the solution to Problem 10.41.
10.43
Smith
237
Advantages of slip casting include the ability to form parts with thin-walls and complex
shapes and the low cost associated with creating developmental parts and short
production runs.
10.44
What types of ceramic products are produced by extrusion? What are the advantages of
this process? Limitations?
Extrusion is used to produce ceramic products which have a uniform cross-section
(bricks and tiles) and which are hollow (sewer pipes). The advantages associated with
this process include the ability to efficiently form a single long shape which is
subsequently cut to the desired lengths and the ability to achieve close tolerances.
However, the extrusion process is limited by the need to produce a constant crosssection and by the need to cool the extruded part by air-blast or water cooling.
10.45
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
materials 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.
10.48
10.49
10.50
Smith
238
In traditional ceramics, clay constitutes the primary component of the ceramic and
makes the material workable prior to firing.
10.51
10.52
10.53
10.54
10.55
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
10.58
10.59
Smith
How are pure single-compound technical ceramic particles processed to produce a solid
product? Give an example.
239
Technical ceramics are typically cold or hot-pressed and then subjected to a process,
such as sintering or reaction bonding, so that bonding can occur. Examples of technical
ceramic are silicon nitride, alumina, silicon carbide and zirconia.
10.60
What are three major applications for ceramic materials in the electrical-electronics
industries?
Three major applications for ceramic materials in the electrical-electronics industries
are electrical insulators, capacitors and semiconductors.
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?
A dielectric is an electrical insulator. A capacitor is a device that stores electrical charge
while capacitance is a proportionality constant which quantifies the ratio of stored
charge to applied voltage. The SI unit of capacitance is coulombs per volt (C/V) or the
farad (F). In the electronics industry, the smaller units of picofarad and microfarad are
typically used.
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
capacitors plates are separated by a dielectric as compared to a vacuum.
A capacitors capacitance, dielectric constant, plate area, and plate separation distance
are related as C = 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, , is the angle by which the currents 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.
Smith
240
The dielectric loss factor is a measure of the electric energy a capacitor dissipates as
heat in an ac circuit.
10.65
A simple plate capacitor can store 7.0 105 C at a potential of 12,000 V. If a barium
titanate dielectric material with = 2100 is used between the plates, which have an
area of 5 105 m 2 , what must be the separation distance between the plates?
q 7.0 105 C
= 5.83 109 F
C= =
V
12,000 V
A 0 ( 5 105 m 2 ) ( 8.85 1012 F/m ) ( 2100 )
=
= 1.59 104 m = 0.159 mm
d=
9
C
5.83 10 F
10.66
10.67
A simple plate capacitor stores 6.5 105 C at a potential of 12,000 V. If the area of the
plates is 3 105 m 2 and the distance between the plates is 0.18 mm, what must be the
dielectric constant of the material between the plates?
C=
q 6.5 105 C
=
= 5.42 109 F
V
12,000 V
10.68
10.69
Smith
241
higher resistivity and lower electrical losses with increasing temperature, as well as
lower dielectric losses at high frequencies, than the steatite insulators.
10.70
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.
10.72
10.73
10.74
10.75
Smith
242
10.76
What changes occurs in the unit cell of BaTiO3 when it is cooled below 120C? What
is this transformation temperature called?
When BaTiO3 is cooled to 120C, 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 120C, 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 120C
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.
10.79
Smith
243
10.80
What are the PZT piezoelectric materials? In what ways are they superior to BaTiO3
piezoelectric materials?
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 .
10.81
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?
Brittle fracture of polycrystalline ceramics is principally caused by one of four
structural defects: cracks produced during surface finishing; voids; inclusions; and large
grains produced during processing.
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
Smith
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.)
244
2
1 K IC
1 3.4 MPa- m
5
a=
=
= 5.89 10 m = 58.9 m
Y f (1)(250 MPa)
f =
10.87
3.7 MPa- m
1 K IC
1
= 236 MPa
=
a Y
(2.5 105 m)
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 = .)
2
2
7.5 MPa- m
1 K
1 7.5 MPa- m
5
a = IC =
=
= 4.60 10 m = 46.0 m
Y f (352 MPa) (352 MPa)
2
1 K IC 3.8 MPa- m
6
a=
=
= 7.23 10 m = 7.23 m
Y f (450 MPa)
f =
Smith
1 K IC 1 12.5 MPa- m
= 1480 MPa
=
a 7.23 106 m
Foundations of Materials Science and Engineering Solution Manual
245
10.89
10.90
10.91
10.92
10.93
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 spentacid furnaces, coke kilns, glass-tank refiner walls, continuous-casting tundish
linings, and coal gasification reactor linings.
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246
10.95
What do most basic refractories consist of? What are some important properties of basic
refractories? What is a main application for these materials?
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.
10.96
10.97
Define a glass.
While glass is a ceramic material made from inorganic materials at high
temperatures it differs from other ceramics in that its constituents are heated to fusion
and then cooled in the rigid state without crystallization. Thus glass is formally defined
as an organic product of fusion that has cooled to a rigid condition without
crystallization.
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.
10.99
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.
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248
large amounts (60 percent) of lead oxide can be added to produce an ornamental glass
of great brilliance.
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 singlecomponent 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?
Soda-lime glass has a basic composition of 71 to 73 percent SiO2, 12 to 14 percent
Na2O, and 10 to 12 percent CaO. Advantages of soda-lime glass are its low cost and
ease of forming due to a low softening point. Disadvantages include low heat resistance
and chemical durability. Some of its applications are windows, containers, electric
bulbs, and pressed and blown ware.
10.109 What is the purpose of (a) MgO and (b) Al 2O3 additions to soda-lime glass?
(a) MgO is added to soda-lime glass in small quantities of 1 to 4 percent to prevent
devitrification.
(b) Al 2O3 is added in quantities of 0.5 to 1.5 percent to increase durability.
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.
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249
A hard glass has a high softening point as compared to a soft glass. Long glasses have
large temperature differences between their softening and strain points; they solidify
more slowly than a short glass as the temperature decreases.
10.112 A soda-lime plate glass between 500C (strain point) and 700C (softening point) has
viscosities between 1014.2 and 107.5 P, respectively. Calculate a value for the activation
energy in this temperature region.
First, convert the temperatures to absolute values:
Strain point = Tstp = 500o C + 273 = 773 K
Softening point = Tsp = 700o C + 273 = 973 K
Q / RT
Q / RTsp
stp
and sp = 0 e
Using Eq. 10.5, stp = 0e
substituting the temperature and viscosity data,
stp
Q 1
1
= exp
sp
R Tstp Tsp
1014.2 P
Q
1
1
= exp
7.5
10 P
8.314 J/mol K 723 K 923 K
106.7 = exp ( 3.605 105 ) Q
ln106.7 = ( 3.605 105 ) Q
2
8.314 J/mol K 833 K 948 K
1014.6 P
= exp(7.532) = 1866.6
2
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10.114 A soda-lime glass has a viscosity of 1014.3 P at 570C. At what temperature will its
viscosity be 109.9 P if the activation energy for the process is 430 kJ/mol?
Let 1 = 0 eQ / RT1 and 2 = 0eQ / RT2 where T1 = 843 K. Then,
Q 1 1
1
= exp
2
R T1 T2
430 103 J/mol 1
1014.3 P
1
=
exp
109.9 P
8.314 J/mol K 843 K T2
1
1
ln104.4 = 51, 720
843 K T2
10.115 A borosilicate glass between 600C (annealing point) and 800C (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 = 0 eQ / RT is valid.
ap
Q 1
1
= exp
sp
R Tap Tsp
Q
1012.5 P
1
1
= exp
7.4
10 P
8.314 J/mol K 873 K 1073 K
105.1 = exp ( 2.568 105 ) Q
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Tempered glass is a high strength glass due to the compressive stresses developed on its
surface during tempering. It is produced by heating the glass close to its softening
temperature and then rapidly cooling the glass surface with air. Because the surfaces are
rigid during the cooling of the glass interior, tensile stresses are developed in the
interior while compressive stresses form at the surface. Tempered glass is stronger in
tension than annealed glass because with tempered glass, the applied tensile stress must
surpass the surface compressive stress before causing fracture. This glass is used in
applications where safety is paramount, such as automobile windows and safety glass
doors.
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.
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252