CHAPTER 12 STRUCTURES AND PROPERTIES OF CERAMICS Page 1/7

CLOSED-BOOK PRACTICE
CHAPTER 12: STRUCTURES AND PROPERTIES OF CERAMICS
CONCEPT CHECK
1. 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) Describe the resulting crystal structure for K 2O .
(c) Explain why this is called the antifluorite structure.
Ans:
(a) First, let us find the coordination number of each O2 ion for K 2O . Taking the cation-anion radii ratio:
rK 0.138 nm
0.986
rO2 0.140 nm
From Table 12.2, the coordination number for oxygen is 8.
(b) According to Table 12.4, for a coordination number of 8 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 (Fig. 12.5).
2. Can Schottky defects exist in K 2O ? If so, describe this type of defect. If they cannot exist, then explain
why.
Ans:
This question can be answered in two ways, as follows:
(1) Yes, Schottky defects can exist in K 2O ; each defect will consist of one O2 vacancy and two K
vacancies.
(2) No, in the strict sense, Schottky cannot exist in K 2O 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.
3. What point defects are possible for MgO as an impurity in Al2O3 ? How many Mg 2 ions must be added to
form each of these defects?
Ans:
For every Mg 2 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.
That is, positive charges are added by forming Al3 interstitials, and one Al3 interstitial would be formed
for every three Mg 2 ions added; whereas negative charges may be removed by forming O2 vacancies,
and one oxygen vacancy would be formed for every two Mg 2 ions added.

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4. (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?
Ans:
(a) According to Fig. 12.25 this maximum temperature is 1,89010C.
(b) The possible for compositions are between about 77 wt% Al2O3 and virtually 100 wt% Al2O3 .

QUESTIONS & PROBLEMS

Crystal Structures
For a ceramic compound, what are the two characteristics of the component ions that determine the crystal
structure?
Ans:
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.
The figure below shows the coordination configuration between a small cation with some of its larger
neighboring anions in a ceramic crystal structure.
(a) What is the coordination number (CN) of this configuration?
r
(b) Derive the minimum cation-to-anion radius ratio: C for the coordination to be stable.
rA

Ans:
(a) The coordination configuration is triangular with a coordination number (CN) = 3.
2 3 2 1 r 2
(b) AB BC CA 2rA ; AO AB rA rC 2rA AO 2rA C 1 0.155
3 2 3 3 rA 3

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The figure below shows the coordination configuration between a small cation with some of its larger
neighboring anions in a ceramic crystal structure.
(a) What is the coordination number (CN) of this configuration?
r
(b) Derive the minimum cation-to-anion radius ratio: C for the coordination to be stable.
rA

Ans:
(a) The coordination configuration is octahedral with a coordination number (CN) = 6.
rC
(b) AC CB 2rA ; AB 2 AC 2 rA rC 2 2rA 2 1 0.414
rA

The figure at right shows the coordination configuration between a small

cation with some of its larger neighboring anions in a ceramic crystal
structure.
(a) What is the coordination number (CN) of this configuration?
r
(b) Derive the minimum cation-to-anion radius ratio: C for the
rA
coordination to be stable.
Ans:
(a) The coordination configuration is D
cubic with a coordination number
(CN) = 8
(b) AB BC CD 2rA
AD 3 AB
2 rA rC 3 2rA
C
A B
r
C 3 1 0.732
rA

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Silicate Ceramics
In terms of bonding, explain why silicate materials have relatively low densities.
Ans:
The silicate materials have relatively low densities because the atomic bonds have a high degree of
covalency (Table 12.1), and, therefore, are directional. This limits the packing efficiency of the atoms, and
therefore, the magnitude of the density.
(a) What type of chemical bond a ceramic usually has if all of its constituent elements are non-metallic? If
one of the constituent elements of the ceramic is metallic while the other is non-metallic, what will the
chemical bond be?
(b) Explain also why ceramic materials are more brittle than metals.
Ans:
(a) Ceramic materials are chemically bonded by either covalent bonds (when all elements are non-metallic)
or ionic bonds (when some of the elements are metallic while others are non-metallic).
(b) Just as in metals, dislocation motion is the main mechanism of plastic deformation in crystalline
ceramics. In highly ionic solids, dislocation motion is difficult since:
few slip systems
resistance to dislocation motion of ions of like charge (e.g., anions) passing one another
Imperfections in Ceramics
Would you expect Frenkel defects for anions to exist in ionic ceramics in relatively large concentrations?
Why or why not?
Ans:
Frenkel defects for anions would NOT exist in appreciable concentrations because the anion (of an anion
vacancy-anion interstitial pair) is quite large and is highly unlikely to exist as an interstitial.
In your own words, briefly define the term stoichiometric.
Ans:
Stoichiometric means having exactly the ratio of anions to cations as specified by the chemical formula for
the compound.
Do the Hume-Rothery rules (Section 4.3) also apply to ceramic systems? Explain your answer.
Ans:
For metals, for appreciable solid solubility of one metal in another, the following characteristics of the
metals must be the same or similar:
1) Atomic size (<15%) 2) Crystal structure
3) Electronegativity 4) Valence
A similar set of rules exist for one ceramics; that is, in order to have appreciable solid solubility of one
ceramic compound in another the following rules must be satisfied:
1) Atomic size factor: similar to that for metallic systems for both cations and anions
2) Valence factor: valences (charges on) anions should be the same; also the same for cations
3) Crystal structures of the two compounds should be the same or similar
4) Other ceramic compounds may form (i.e., solid solubility is limited) when there is a difference in the
electronic structure between the cations and/or anions of the two compounds.

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StressStrain Behavior/Mechanisms of Plastic Deformation

Would you expect a crystalline ceramic material to strain harden at room temperature? Explain why.
Ans:
At room temperature, a crystalline ceramic material is brittle in nature and does NOT strain harden, which
occurs due to plastic deformation. This is from the fact that a crystalline ceramic material is formed by
either ionic bonds or covalent bonds. These bonds are relatively strong and have only limited numbers of
slip systems for dislocation motion. Thus, a crystalline ceramic does not yield nor deform plastically at
room temperature.
Cite one reason why ceramic materials are, in general, harder yet more brittle than metals.
Ans:
Crystalline ceramics are harder yet more brittle than metals because they (ceramics) have fewer slip
systems, and, therefore, dislocation motion is highly restricted.
Brittle Fracture of Ceramics
Compared to plain carbon mild steel, will the data of the fracture strength of a typical ceramic material
tested at room temperature be more or less scatter or about the same statistically? Explain why.
Ans:
The data of the fracture strength of a typical ceramic material will be more scatter since as a brittle material,
a ceramic lacks a plastic-deformation mechanism to dissipate excessive energy. The excessive input energy
thus needs to be consumed by fracture, whose strength depends on the probability of the existence of a
critical flaw that is capable of initiating a crack; this probability varies from specimen to specimen of the
same ceramic material.
As the specimen size of a ceramic material gets smaller, will its fracture strength increase, decrease or
remain about the same? Explain why.
Ans:
The fracture strength increases with decreasing specimen size because as specimen size decreases; hence,
the probability of the existence of a critical flaw that is capable of initiating a fatal crack diminishes.
The figures below show two possible shattering patterns of a piece of window glass of a car struck by a
flying object. From energy dissipation point of view determine which pattern is more dangerous to the
driver? Why?
Ans:
Pattern (a) is more dangerous to the driver
since not only its broken pieces are sharper,
but also it contains less number of broken
pieces, implying smaller fracture surface area
to dissipate the impact energy. Thus, the flying
broken pieces will carry higher velocity,
posing potential injury to the driver.

(a) (b)

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If a thin surface layer of a ceramic specimen is etched away so that the surface becomes polished, will its
fracture strength be (a) increasing, (b) about the same or (c) decreasing? Explain why.
Ans:
Since a ceramic is brittle in nature, it lacks a plastic-deformation mechanism to dissipate excessive energy.
When overloaded, the ceramic fractures when a critical flaw initiate catastrophic crack growth. The
probability of the existence of that critical flaw on the surface in general is higher. When a thin surface layer
of a ceramic specimen is etched away so that the surface becomes polished, the fracture strength of a
ceramic will (a) increase because etching away that surface diminishes the chance of crack initiation.
A ceramic armor is a sandwich structure consisting of one or more outer ceramic facing plates and a
metallic or fiber-reinforced polymeric backing sheet. Explain how a ceramic armor may protect military
personnel and vehicles from ballistic bombardment.
Ans:
As the bullet hits the armor, the hard ceramic strike face begins to break up the bullet while the ceramic
material begins to break into pieces to absorb the energy of the penetration. The round continues to break
apart as the ballistic material extracts energy, decelerating the projectile and catching the fragments by the
metallic or fiber-reinforced polymeric backing sheet while limiting the effect of blunt trauma, the injury
caused by an impacting bullet.

FUNDAMENTALS OF ENGINEERING
Which of the following are the most common coordination numbers for ceramic materials?
(A) 2 and 3
(B) 6, 8, and 12
(C) 6 and 12
(D) 4, 6, and 8
Ans: D. For ceramic materials, the most common coordination numbers are 4, 6, and 8.
A Frenkel defect is composed with which of the following?
(A) A cation interstitial and a cation vacancy
(B) A cation interstitial and an anion interstitial
(C) A cation vacancy and an anion vacancy
(D) An anion interstitial and an anion vacancy
Ans: A. A Frenkel defect is composed of a cation interstitial and a cation vacancy, such that a state of
electroneutrality is maintained.

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A Schottky defect is composed with which of the following?

(A) A cation interstitial and a cation vacancy
(B) A cation interstitial and an anion interstitial
(C) A cation vacancy and an anion vacancy
(D) An anion interstitial and an anion vacancy
Ans: C. A Schottky defect is composed of a cation vacancy and an anion vacancy, such that a state of
electroneutrality is maintained.
Impurity atoms in ceramic materials may form substitutional and interstitial solid solutions.
(A) True
(B) False
Ans: True. Impurity atoms may form substitutional and interstitial solid solutions in ceramic materials.
For noncrystalline ceramics (e.g., glasses), plastic deformation occurs by the motion of dislocations.
(A) True
(B) False
Ans: False. For noncrystalline ceramics, plastic deformation does NOT occur by the motion of dislocations.
Instead these materials deform by viscous flow.
Is it possible for ceramic materials to experience grain growth?
(A) Yes
(B) No
Ans: Yes. Grain growth can take place in polycrystalline ceramics. Grain growth need not be preceded by
recrystallization.

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