CHAPTER 12: STRUCTURE AND MECHANICAL PROPERTIES OF CERAMICS

How do ceramics differ from metals?

Ionic crystal structure depends on charge balance, ion size Vacancies and impurity defects must satisfy charge balance Few dislocations brittle! creep resistant High melting temperature

CERAMIC BONDING
Bonding:
--Mostly ionic, some covalent. --% ionic character increases with difference in electronegativity.

Large vs small ionic bond character:

H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Cs 0.7 Fr 0.7 He Ne Ar Kr Xe Rn -

Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 Ba 0.9 Ra 0.9

Sc 1.3 Y 1.2
Rare earth series Actinide series

Ti 1.5 Zr 1.4 Hf 1.3

V 1.6 Nb 1.6 Ta 1.5

Cr 1.6 Mo 1.8 W 1.7

Mn 1.5 Tc 1.9 Re 1.9

Fe 1.8 Ru 2.2 Os 2.2

Co 1.8 Rh 2.2 Ir 2.2

Ni 1.8 Pd 2.2 Pt 2.2

Cu 1.9 Ag 1.9 Au 2.4

Zn 1.6 Cd 1.7 Hg 1.9

B 2.0 Al 1.5 Ga 1.6 In 1.7 Tl 1.8

C 2.5 Si 1.8 Ge 1.8 Sn 1.8 Pb 1.8

N 3.0 P 2.1 As 2.0 Sb 1.9 Bi 1.9

O 3.5 S 2.5 Se 2.4 Te 2.1 Po 2.0

F 4.0 Cl 3.0 Br 2.8 I 2.5 At 2.2

Table of Electronegativities
12-2

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

12-1

IONIC BONDING & STRUCTURE

Charge Neutrality:

COORDINATION # AND IONIC RADII

How many anions can you arrange around a cation? Coordination #:
r cation r anion < .155 ZnS (zincblende)
Adapted from Fig. 12.4, Callister 6e.

CaF 2 :

Ca 2+ + cation

Fanions F-

Coord # 2 3 4 6 8

A m Xp
Stable structures:

m, p determined by charge neutrality

0.155-0.225 0.225-0.414 0.414-0.732

--maximize the # of nearest oppositely charged neighbors.

NaCl (sodium chloride)

Adapted from Fig. 12.2, Callister 6e.

Adapted from Fig. 12.1, Callister 6e.

0.732-1.0
Adapted from Table 12.2, Callister 6e.

CsCl (cesium chloride)

Adapted from Fig. 12.3, Callister 6e.

Unstable

Stable

Stable

12-3

12-4

EX #1: PREDICTING STRUCTURE

What is the crystal structure of FeO? Ionic radii (nm) Cation Fe2+ 0.077 0.140 Anion O2Data from Table 12.3, Callister 6e.

EX #2: AmXp STRUCTURES

What is the crystal structure of CaF2? Ionic radii (nm) Cation Ca2+ 0.100 0.133 Anion FData from Table 12.3, Callister 6e.

Adapted from Fig. 12.5, Callister 6e.

12-5

12-6

DEFECTS IN CERAMIC STRUCTURES

Vacancies
Frenkel Defect --a cation is out of place (cation vacancy/interstitial pair). Shottky Defect --a paired set of cation and anion vacancies.

DEFECTS IN CERAMIC STRUCTURES

Impurities What if the impurity has a different charge?
Ex: NaCl

Na +

Cl -

Substitutional cation impurity

Na + Na + initial geometry Ca 2+

Ca 2+ impurity

resulting geometry

Substitutional anion impurity

Adapted from Fig. 13.20, Callister 5e. (Fig. 13.20 is from W.G. Moffatt, G.W. Pearsall, and J. Wulff, The Structure and Properties of Materials, Vol. 1, Structure, John Wiley and Sons, Inc., p. 78.) See Fig. 12.21, Callister 6e.

Cl Cl 12-7

Q Equilibrium concentration of defects ~ exp D kT

O 2resulting geometry

initial geometry

O2- impurity

12-8

MEASURING ELASTIC MODULUS

3-Point Bend Testing
(gripping tensile specimens difficult for brittle materials) F cross section
L/2 L/2 d
rect.
Adapted from Fig. 12.29, Callister 6e.

MEASURING STRENGTH
3-point bend test to measure room T flexural strength.
cross section

L/2

L/2

Adapted from Fig. 12.29, Callister 6e.

d
rect.

R
circ. location of max tension

R
circ. = midpoint deflection

Flexural strength:
fail fs = m = Fmax

Typical values:

Determine elastic modulus according to:

1.5Fmax L bd 2

x
slope =

E=

L3

4bd 3
rectangular cross section

or

L3 12 R4

or

Fmax L R3

Material

rectangular circular cross section cross section

fs (MPa) Si nitride 700-1000 Si carbide 550-860 Al oxide 275-550 glass (soda) 69

E(GPa)
300 430 390 69

linear-elastic behavior

circular cross section

12-9

Data from Table 12.5, Callister 6e.

max

12-10

MEASURING ELEVATED T RESPONSE

Creep Test Elevated Temperature Tensile Test (T > 0.4 Tmelt).

SUMMARY
Ceramic materials have mostly ionic & some covalent bonding. Structures are based on: --charge neutrality --maximizing # of nearest oppositely charged neighbors

x
slope = ss = steady-state creep rate

Structures may be predicted based on: --ratio of the cation and anion radii Defects --must preserve charge neutrality --have a concentration that varies exponentially w/T Room T mechanical response is elastic, with brittle fracture and negligible ductility. Elevated T creep properties are generally superior to those of metals (and polymers).
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time

Creep mechanisms in ceramics Diffusion Grain boundary sliding