Chapter 12

Structures and Properties of Ceramics

Concept Check 12.1

Question: Table 12.3 gives the ionic radii for K+ and O2- as 0.138 and 0.140 nm,
respectively.
(a) What would be the coordination number for each O2- ion?
(b) Briefly describe the resulting crystal structure for K2O.

(c) Explain why this is called the antifluorite structure.

Answer: (a) First, let us find the coordination number of each O2- ion for K2O. Taking

the cation-anion radii ratio

r +
K = 0.138 nm = 0.986
r 2- 0.140 nm
O

From Table 12.2, the coordination number for oxygen is eight.

(b) According to Table 12.4, for a coordination number of eight for both cations and
anions, the crystal structure should be cesium chloride. However, there are twice as many K+ as
O2- ions. Therefore, the centers of the K+ ions are positioned at the corners of cubic unit cells,
while half of the cube centers are occupied by O2- ions.
(c) This structure is called the antifluorite crystal structure because anions and cations
are interchanged with one another from the fluorite structure (Figure 12.5).
Concept Check 12.2

Question: Can Schottky defects exist in K2O? If so, briefly describe this type of defect.

If they cannot exist, then explain why.

Answer: This question can be answered in two ways, as follows:
(1) Yes, Schottky defects can exist in K2O; each defect will consist of one O2- vacancy

and two K+ vacancies.

(2) No, in the strict sense, Schottky cannot exist in K2O if we consider this type of defect

to consist of a cation-anion pair; for every O2- vacancy created there must exist two K+
vacancies.
Concept Check 12.3

Question: What point defects are possible for MgO as an impurity in Al2O3? How many

Mg2+ ions must be added to form each of these defects?

Answer: For every Mg2+ ion that substitutes for Al3+ in Al2O3, a single positive charge

is removed. Thus, in order to maintain charge neutrality, either a positive charge must be added
or a negative charge must be removed.
Positive charges are added by forming Al3+ interstitials, and one Al3+ interstitial would
be formed for every three Mg2+ ions added.
Negative charges may be removed by forming O2- vacancies, and one oxygen vacancy
would be formed for every two Mg2+ ions added.
Concept Check 12.4

Question: (a) For the SiO2-Al2O3 system, what is the maximum temperature that is

possible without the formation of a liquid phase?

(b) At what composition or over what range of compositions will this maximum
temperature be achieved?
Answer: (a) According to Figure 12.27 this maximum temperature is 1890 ± 10°C, (b)
which is possible for compositions between about 77 wt% Al2O3 and virtually 100 wt% Al2O3.
 Chapter 13
Applications and Processing of Ceramics

Concept Check 13.1

Question: Briefly explain why glass-ceramics are generally not transparent. Hint: you
may want to consult Chapter 21.
Answer: Glass-ceramics may not be transparent because they are polycrystalline. Light

will be scattered at grain boundaries in polycrystalline materials if the index of refraction is

anisotropic, and when those grains adjacent to the boundary have different crystallographic

orientations. This phenomenon is discussed in Section 21.10. Also, as noted in Section 21.10,

glass-ceramics may be transparent in the size of the crystals are smaller than the wavelength of

visible light.
Concept Check 13.2

Question: Upon consideration of the SiO2-Al2O3 phase diagram (Figure 12.27) for the

following pair of compositions, which would you judge to be the more desirable refractory?
Justify your choice.
20 wt% Al2O3-80 wt% SiO2

25 wt% Al2O3-75 wt% SiO2

Answer: The 25 wt% Al2O3-75 wt% SiO2 will be more desirable because the liquidus

temperature will be greater for this composition (1740ºC versus 1710ºC); therefore, at any
temperature within the mullite + liquid region on the phase diagram, there will be a lower fraction
of the liquid phase present than for the 20 wt% Al2O3-80 wt% SiO2 composition, and, thus, the

mechanical integrity will be greater.

Concept Check 13.3

Question: Explain why it is important to grind cement into a fine powder.

Answer: It is important to grind cement into a fine powder in order to increase the
surface area of the particles of cement. The hydration reactions between water and the cement
occur at the surface of the cement particles. Therefore, increasing the available surface area
allows for more extensive bonding.
Concept Check 13.4

Question: How does the thickness of a glassware affect the magnitude of the thermal
stresses that may be introduced? Why?
Answer: The thinner the thickness of a glass ware the lower the thermal stresses that are
introduced when it is either heated or cooled. The reason for this is that the difference in
temperature across the cross-section of the ware, and, therefore, the difference in the degree of
expansion or contraction will decrease with a decrease in thickness.
Concept Check 13.5

Question: Thick ceramic wares are more likely to crack upon drying than thin wares.
Why is this so?
Answer: Thick ceramic wares are more likely to crack upon drying than thin wares
because of the differential in shrinkage from the surface to the interior of a cross-section will be
greater for a thick ware. The reason for this is that the water being eliminated during drying has a
longer distance to travel from the interior to the surface for the thicker ware.

Concept Check 13.6

Question: Explain why a clay, once having been fired at an elevated temperature, loses
its hydroplasticity.
Answer: The phenomenon of hydroplasticity results when water molecules form a thin
film around the small clay particles. During firing, these individual particles become fused
together by the viscous liquid that fills in the pore volume between the particles—the pore
volume that was occupied by water in the hydroplastic state. This viscous liquid forms a glass
matrix on subsequent cooling.
 Chapter 14
Polymer Structures

Concept Check 14.1

Question: Differentiate between polymorphism (see Chapter 3) and isomerism.

Answer: Polymorphism is when two or more crystal structures are possible for a material
of given composition. Isomerism is when two or more polymer molecules or repeat units have
the same composition, but different atomic arrangements.
Concept Check 14.2

Question: On the basis of the structures presented in the previous section, sketch the
repeat unit structure for poly(vinyl fluoride).
Answer: Inasmuch as poly(vinyl chloride) has the repeat unit structure shown in Figure
14.2(b), replacing the side-bonded chlorine atom with a fluorine atom will yield a poly(vinyl
fluoride) repeat unit, as shown below.
Concept Check 14.3

Question: What is the difference between configuration and conformation in relation to

polymer chains?
Answer: Relative to polymer chains, the difference between configuration and
conformation is that conformation is used in reference to the outline or shape of the chain
molecule, whereas, configuration refers to the arrangement of atom positions along the chain that
are not alterable except by the breaking and reforming of primary bonds.
Concept Check 14.4

Question: Some polymers (such as the polyesters) may be either thermoplastic or

thermosetting. Suggest one reason for this.
Answer: Thermosetting polyesters will be crosslinked, while thermoplastic ones will
have linear structures without any appreciable crosslinking.
Concept Check 14.5

Question: (a) Compare the crystalline state in metals and polymers. (b) Compare the
noncrystalline state as it applies to polymers and ceramic glasses.
Answers: (a) For crystalline metals, the individual atoms are positioned in a periodic or
ordered arrangement over relatively large atomic distances. The long-range order in polymer
crystals results from the packing of adjacent polymer chains.
(b) For noncrystalline ceramic glasses, the atomic randomness exists outside the SiO 4−
4
unit. The disorder in polymers results from chain misalignment.
 Chapter 15
Characteristics, Applications, and Processing of Polymers

Concept Check 15.1

Question: When citing the ductility as percent elongation for semicrystalline polymers, it
is not necessary to specify the specimen gauge length, as is the case with metals. Why is this so?
Answer: The reason that it is not necessary to specify specimen gauge length when citing
percent elongation for semicrystalline polymers is because, for semicrystalline polymers that
experience necking, the neck normally propagates along the entire gauge length prior to fracture;
thus, there is no localized necking as with metals and the magnitude of the percent elongation is
independent of gauge length.
Concept Check 15.2

Question: An amorphous polystyrene that is deformed at 120°C will exhibit which of the
behaviors shown in Figure 15.5?
Answer: Amorphous polystyrene at 120°C behaves as a rubbery material (Figure 15.8,
curve C); therefore, the strain-time behavior would be as Figure 15.5(c).
Concept Check 15.3

Question: For the following pair of polymers, do the following: (1) state whether it is
possible to decide if one polymer has a higher tensile modulus than the other; (2) if this is
possible, note which has the higher tensile modulus and then cite the reason(s) for your choice;
and (3) if it is not possible to decide, then state why not.
Syndiotactic polystyrene having a number-average molecular weight of 400,000 g/mol
Isotactic polystyrene having a number-average molecular weight of 650,000 g/mol.

Answer: No, it is not possible. Both syndiotactic and isotactic polystyrene have a
tendency to crystallize, and, therefore, we assume that they have approximately the same
crystallinity. Furthermore, since tensile modulus is virtually independent of molecular weight,
we would expect both materials to have approximately the same modulus.

Concept Check 15.4

Question: For the following pair of polymers, do the following: (1) state whether it is
possible to decide if one polymer has a higher tensile strength than the other; (2) if this is
possible, note which has the higher tensile strength and then cite the reason(s) for your choice;
and (3) if it is not possible to decide, then state why not.
Syndiotactic polystyrene having a number-average molecular weight of 600,000 g/mol
Isotactic polystyrene having a number-average molecular weight of 500,000 g/mol.

Answer: Yes, it is possible. The syndiotactic polystyrene has the higher tensile strength.
Both syndiotactic and isotactic polymers tend to crystallize, and, therefore, we assume that both
materials have approximately the same crystallinity. However, tensile modulus increases with
increasing molecular weight, and the syndiotactic PS has the higher molecular weight (600,000
g/mol versus 500,000 g/mol for the isotactic material).
Concept Check 15.5

Question: For the following pair of polymers, plot and label schematic stress-strain
curves on the same graph.
Poly(styrene-butadiene) random copolymer having a number-average molecular weight
of 100,000 g/mol and 10% of the available sites crosslinked and tested at 20°C
Poly(styrene-butadiene) random copolymer having a number-average molecular weight
of 120,000 g/mol and 15% of the available sites crosslinked and tested at –85°C.
Hint: poly(styrene-butadiene) copolymers may exhibit elastomeric behavior.

Answer: Shown below are the stress-strain curves for the two poly(styrene-butadiene)
random copolymers.

The copolymer tested at 20°C will display elastomeric behavior (curve C of Figure 15.1)
inasmuch as it is a random copolymer that is lightly crosslinked; furthermore, the temperature of
testing is above its glass transition temperature. On the other hand, since -85°C is below the glass
transition temperature of the other poly(styrene-butadiene) copolymer, the stress-strain behavior
under these conditions is as curve A of Figure 15.1.

Concept Check 15.6

Question: In terms of molecular structure, explain why phenol-formaldehyde (Bakelite)

will not be an elastomer. (The molecular structure for phenol-formaldehyde is presented in Table
14.3.)
 Answer: The molecules in elastomers must be two-dimensional chains that are lightly
crosslinked and capable of being twisted and kinked in the unstressed state. Phenol-
formaldehyde has a rigid three-dimensional structure consisting of trifunctional repeat units,
which does not meet these criteria for chain conformation and flexibility.
Concept Check 15.7

Question: For each of the following two polymers, plot and label a schematic specific
volume-versus-temperature curve (include both curves on the same graph):
Spherulitic polypropylene, of 25% crystallinity, and having a weight-average molecular
weight of 75,000 g/mol
Spherulitic polystyrene, of 25% crystallinity, and having a weight-average molecular
weight of 100,000 g/mol.
Answer: Shown below are the specific volume-versus-temperature curves for the
polypropylene and polystyrene materials.

Since both polymers are 25% crystalline, they will exhibit behavior similar to curve B in Figure
15.18. However, polystyrene will have higher melting and glass transition temperatures due to
the bulkier side group in its repeat unit structure, and since it has a higher weight-average
molecular weight.

Concept Check 15.8

Question: For the two polymers, (1) state whether is possible to determine whether one
polymer has a higher melting temperature than the other; (2) if it is possible, note which has the
higher melting temperature and then cite reason(s) for your choice; and (3) if it is not possible to
decide, then state why not.
 Isotactic polystyrene that has a density of 1.12 g/cm3 and a weight-average molecular
weight of 150,000 g/mol
Syndiotactic polystyrene that has a density of 1.10 g/cm3 and a weight-average molecular
weight of 125,000 g/mol.
Answer: Yes, it is possible to determine which of the two polystyrenes has the higher
Tm. The isotactic polystyrene will have the higher melting temperature because it has a higher

density (i.e., less branching) and also the greater weight-average molecular weight.
Concept Check 15.9

Question: During the winter months, the temperature in some parts of Alaska may go as
low as –55°C (-65°F). Of the elastomers natural isoprene, styrene-butadiene, acrylonitrile-
butadiene, chloroprene, and polysiloxane, which would be suitable for automobile tires under
these conditions? Why?
Answer: From Table 15.4, only natural polyisoprene, poly(styrene-butadiene), and
polysiloxane have useful temperature ranges that extend to below -55°C. At temperatures below
the lower useful temperature range limit, the other elastomers listed in this table become brittle,
and, therefore, are not suitable for automobile tires.

Concept Check 15.10

Question: Silicone polymers may be prepared to exist as liquids at room temperature.

Cite differences in molecular structure between them and the silicone elastomers. Hint: you may
want to consult Sections 14.5 and 15.9.
Answer: The liquid silicones will have low molecular weights and very little
crosslinking, whereas the molecular weights for the elastomers will be much higher; the
elastomers will also have some crosslinking.
Concept Check 15.11

Question: Cite whether the molecular weight of a polymer that is synthesized by addition
polymerization is relatively high, medium, or relatively low for the following situations:
(a) Rapid initiation, slow propagation, and rapid termination.
(b) Slow initiation, rapid propagation, and slow termination.
(c) Rapid initiation, rapid propagation, and slow termination.
(d) Slow initiation, slow propagation, and rapid termination.
Answer:
(a) For rapid initiation, slow propagation, and rapid termination the molecular weight
will be relatively low.
(b) For slow initiation, rapid propagation, and slow termination the molecular weight
will be relatively high.
(c) For rapid initiation, rapid propagation, and slow termination a medium molecular
weight will be achieved.
(d) For slow initiation, slow propagation, and rapid termination the molecular weight
will be low or medium.
Concept Check 15.12

Question: Nylon 6,6 may be formed by means of a condensation polymerization reaction

in which hexamethylene diamine [NH2—(CH2)6—NH2] and adipic acid react with one another

with the formation of water as a by-product. Write out this reaction in the manner of Equation
15.9. Note: the structure for adipic acid is

Answer: The following represents the reaction between hexamethylene diamine and
adipic acid to produce nylon 6,6 with water as a byproduct:
Concept Check 15.13

Question:
(a) Why must the vapor pressure of a plasticizer be relatively low?
(b) How will the crystallinity of a polymer be affected by the addition of a plasticizer?
Why?
(c) How does the addition of a plasticizer influence the tensile strength of a polymer?
Why?
Answers:
(a) If the vapor pressure of a plasticizer is not relatively low, the plasticizer may
vaporize, which will result in an embrittlement of the polymer.
(b) The crystallinity of a polymer to which has been added a plasticizer will be
diminished, inasmuch as the plasticizer molecules fit in between the polymer molecules, which
will cause more misalignment of the latter.
(c) The tensile strength of a polymer will be diminished when a plasticizer is added. As
the plasticizer molecules force the polymer chain molecules apart, the magnitudes of the
secondary interchain bonds are lessened, which weakens the material since strength is a function
of the magnitude of these bonds.
Concept Check 15.14

Question: For a rubber component that is to be vulcanized in its final form, should
vulcanization be carried out before or after the forming operation? Why? Hint: you may want
to consult Section 15.9.
Answer: Vulcanization of a rubber component should be carried out prior to the forming
operation since, once it has been vulcanized, plastic deformation (and thus forming) is not
possible since chain crosslinks have been introduced.