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CH 12-Structures and Properties of Ceramics

Ceramic materials have ionic and covalent bonding. Their crystal structures are based on charge neutrality and maximizing opposite charges as neighbors. Structures can be predicted from cation-anion radius ratios. Defects preserve neutrality and their concentration varies with temperature. Ceramics have elastic response but brittle fracture with little deformation. They often have better creep properties than metals at high temperatures.

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139 views36 pages

CH 12-Structures and Properties of Ceramics

Ceramic materials have ionic and covalent bonding. Their crystal structures are based on charge neutrality and maximizing opposite charges as neighbors. Structures can be predicted from cation-anion radius ratios. Defects preserve neutrality and their concentration varies with temperature. Ceramics have elastic response but brittle fracture with little deformation. They often have better creep properties than metals at high temperatures.

Uploaded by

Vicces P. Estrada
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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ISSUES TO ADDRESS...

Structures of ceramic materials:


How do they differ from those of metals?

Point defects:
How are they different from those in metals?

Impurities:
How are they accommodated in the lattice and how do they affect properties?

Mechanical Properties:
What special provisions/tests are made for ceramic materials?

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

CaF2: large
SiC: small

Adapted from Fig. 2.7, Callister 7e. (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. 2

1. Charge Neutrality:
--Net charge in the structure should be zero. --General form:

CaF 2 :

Ca 2+ + cation

F-

anions
F-

A m Xp
m, p determined by charge neutrality

2. Size of ionic radii- Stable structures:


--maximize the # of nearest oppositely charged neighbors.

+
stable

Adapted from Fig. 12.1, Callister 7e.

unstable

stable

r cation Coordination # increases with r anion


r cation r anion < 0.155 Coord # linear 2 ZnS (zincblende)
Adapted from Fig. 12.4, Callister 7e.

0.155 - 0.225
0.225 - 0.414 0.414 - 0.732 0.732 - 1.0

3
4 6 8

triangular
TD OH cubic

Adapted from Fig. 12.2, Callister 7e.

NaCl (sodium chloride) CsCl (cesium chloride)

Adapted from Table 12.2, Callister 7e.

Adapted from Fig. 12.3, Callister 7e. 4

rNa = 0.102 nm
rCl = 0.181 nm

rNa/rCl = 0.564
cations prefer OH sites
Adapted from Fig. 12.2, Callister 7e.

rCs rCl

0.170 0.939 0.181

cubic sites preferred So each Cs+ has 8 neighboring ClAdapted from Fig. 12.3, Callister 7e.

Adapted from Fig. 12.4, Callister 7e.

rZn2 rO2

0.074 0.529 OH ?? 0.140

Size arguments predict Zn2+ in OH sites, In observed structure Zn2+ in TD sites

Why is Zn2+ in TD sites? bonding hybridization of zinc favors TD sites

Ex: ZnO, ZnS, SiC

So each Zn2+ has 4 neighboring S28

On the basis of ionic radii, what is the crystal structure of FeO? Cation Ionic radius (nm) 0.053 Al 3+ 0.077 Fe 2+ 0.069 Fe 3+ 0.100 Ca 2+ Anion O2Cl F-

Answer:

rcation 0.077 ranion 0.140 0.550


based on this ratio, --structure = NaCl
Data from Table 12.3, Callister 7e. 9

0.140 0.181 0.133

10

Calcium Fluorite (CaF2) cations in cubic sites ex. UO2, ThO2, ZrO2, CeO2

antifluorite structure cations and anions reversed


Adapted from Fig. 12.5, Callister 7e.

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12

Ex: complex oxide BaTiO3

Adapted from Fig. 12.6, Callister 7e.

13

Number of formula units/unit cell

n( AC AA ) VC N A
Volume of unit cell

14

On the basis of crystal structure, compute the theoretical density for sodium chloride.
n = 4 (FCC)

15

On the basis of crystal structure, compute the theoretical density for sodium chloride.

16

17

Most common elements on earth are Si & O


Si4+
O2Adapted from Figs. 12.9-10, Callister 7e.

crystobalite

SiO2 (silica) structures are quartz, crystobalite, & tridymite The strong Si-O bond leads to a strong, high melting material (1710C)

18

Silica gels - amorphous SiO2 Si4+ and O2- not in well-ordered lattice Charge balanced by H+ (to form OH-) at dangling bonds
very high surface area > 200 m2/g

SiO2 is quite stable, therefore

unreactive
makes good catalyst support
Adapted from Fig. 12.11, Callister 7e. 19

Dense form of amorphous silica


Charge imbalance corrected with counter

cations such as Na+ Borosilicate glass is the pyrex glass used in labs
better temperature stability & less brittle than sodium glass

20

Combine SiO44- tetrahedra by having them share corners,

edges, or faces

Adapted from Fig. 12.12, Callister 7e.

Mg2SiO4

Ca2MgSi2O7

Cations such as Ca2+, Mg2+, & Al3+ act to neutralize & provide

ionic bonding
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Layered silicates (clay silicates) SiO4 tetrahedra connected together to form 2-D plane

(Si2O5)2So need cations to balance charge

Adapted from Fig. 12.13, Callister 7e. 22

Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+ layer

Adapted from Fig. 12.14, Callister 7e.

Note: these sheets loosely bound by van der Waals forces

23

Can change the counterions this changes layer spacing the layers also allow absorption of water Micas KAl3Si3O10(OH)2 Bentonite used to seal wells packaged dry swells 2-3 fold in H2O pump in to seal up well so no polluted ground water seeps in to contaminate the water supply.
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25

tetrahedral carbon hard no good slip planes brittle can cut it


large diamonds jewelry

small diamonds often man made - used for cutting tools and polishing
diamond films hard surface coat tools, medical devices, etc.
Adapted from Fig. 12.15, Callister 7e.

26

layer structure aromatic layers

Adapted from Fig. 12.17, Callister 7e.

weak van der Waals forces between layers planes slide easily, good lubricant
27

Fullerenes or carbon nanotubes wrap the graphite sheet by curving into ball or tube Buckminister fullerenes
Like a soccer ball C60 - also C70 + others

Adapted from Figs. 12.18 & 12.19, Callister 7e. 28

29

Frenkel Defect --a cation is out of place. Shottky Defect --a paired set of cation and anion vacancies.
Shottky Defect:
Adapted from Fig. 12.21, Callister 7e. (Fig. 12.21 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.)

Frenkel Defect

Equilibrium concentration of defects

~e

QD / kT
30

Ex: NaCl

Na +

Cl cation vacancy

Substitutional cation impurity


Ca 2+ Na + Na + initial geometry Ca 2+ impurity

Ca 2+ resulting geometry
an ion vacancy

Substitutional anion impurity


O2-

initial geometry

Cl Cl O2- impurity

resulting geometry
31

32

cross section

L/2

Adapted from Fig. 12.32, Callister 7e.

L/2
d = midpoint deflection

d
rect.

R
circ.

Determine

elastic modulus according to:


F L3 F L3 = E= d 4bd 3 d 12 p R4
rect. cross section circ. cross section
33

F slope = d

linear-elastic behavior

cross section

L/2

L/2

Adapted from Fig. 12.32, Callister 7e.

d
rect.

R
circ.
location of max tension

d = midpoint deflection

Flexural strength:

Ff

s fs x
dfs

1.5Ff L

Ff L

Material

bd 2

pR3

sfs (MPa) E(GPa) Si nitride 250-1000 304 Si carbide 100-820 345 Al oxide 275-700 393 glass (soda) 69 69
34

Typ. values:

Data from Table 12.5, Callister 7e.

35

Ceramic materials have covalent & ionic bonding. Structures are based on:
-- charge neutrality -- maximizing # of nearest oppositely charged neighbors. 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, but fracture is brittle, with negligible deformation. Elevated T creep properties are generally superior to those of metals (and polymers).
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