CHAPTER 12: STRUCTURE AND PROPERTIES OF CERAMICS How do ceramics differ from metals ?

Keramikos ~ burnt stuff

Heat treatment is necessary

Usually a compound between a metal and a non-metal

Bonding displays a mixture of ionic and covalent character

Generally hard and brittle, have high melting temperature

Why ?

Generally thermally and electrically insulating Can be opaque, semi-transparent or transparent Traditional ceramics ~ based on clay (china, porcelain, bricks, tiles) and glasses Hi-tech ceramics => electronic, communication, computer hardware, aerospace industries

Chapter 12- 1

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

Large vs small ionic bond character:

Chapter 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.

Crystal Structure of Ionicly Bonded Ceramics

Crystal structure is defined by 2 criterions

1. Magnitude of the electrical charge on each ion. Charge balance dictates chemical formula (Ca2+ and F- form CaF2). 2. Relative sizes of the cations and anions. Cations wants maximum possible number of anion nearest neighbors and vice-versa.

Stable ceramic crystal structures require anions surrounding a cation to be all in contact with that cation. For a specific coordination number there is a critical or minimum cation/anion radius ratio rC/rA for which this contact can be maintained. Pure geometrical consideration

Chapter 12-

IONIC BONDING & CRYSTAL STRUCTURE

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

--General form:

2. Maximize the # of nearest oppositely charged neighbors

--stable structures:

Adapted from Fig. 12.1, Callister 6e.

Chapter 12- 3

COORDINATION # AND IONIC RADII

Coordination # increases with

Adapted from Fig. 12.4, Callister 6e.

Adapted from Fig. 12.2, Callister 6e.

Adapted from Table 12.2, Callister 6e.

Adapted from Fig. 12.3, Callister 6e.

Chapter 12- 4

EX1: PREDICTING STRUCTURE OF FeO

On the basis of ionic radii, what crystal structure would you predict for FeO? r cation 0.077 Cation Answer: r anion 0.140 3+ Al 0.550 2+ Fe based on this ratio, Fe 3+ --coord # = 6 --structure = NaCl (rocksalt) Ca 2+

Anion O 2Cl FData from Table 12.3, Callister 6e.

Two penetrating FCC units; other examples are MgO, MnS, LiF.

Chapter 12- 5

EX2: AmXp STRUCTURES

Consider CaF2 :
r cation 0.100 0.8 r anion 0.133

Based on this ratio, coord # = 8 and structure = CsCl. Result: CsCl structure w/only half the cation sites occupied.
Only half the cation sites are occupied since #Ca2+ ions = 1/2 # F- ions.

Adapted from Fig. 12.5, Callister 6e.

Empty

Chapter 12- 6

EX3: ZnS - ZincBlende Structure

Zn2+ + S2 What is the CN ? What should be the structure ?

Chapter 12-

Ceramic Density Computations

n: number of formula units in unit cell (all ions that are included in the chemical formula of the compound = formula unit)
AC: sum of atomic weights of cations in the formula unit AA: sum of atomic weights of anions in the formula unit VC: volume of the unit cell NA: Avogadros number, 6.023 X 1023 (formula units)/mol
Chapter 12-

EX4: NaCl density

a n = 4 in FCC lattice AC= ANa= 22.99 g/mol AA= ACl= 35.45 g/mol VC= a3=[2 (rNa + rCl)]3

Chapter 12-

Silicate Ceramics
Composed mainly of silicon and oxygen, the two most abundant elements in earths crust (rocks, soils, clays and sand- SiO2 silica)

Basic building block: SiO44- tetrahedron:

Si-O bonding is largely covalent, but overall SiO4 block has charge of 4 Various silicate structures different ways to arrange SiO44- blocks

Chapter 12-

EX: Crystalline form of SiO2

Three polymorphs of SiO2 : Quartz, Crystobalite, Tridymite
Not a very closed pack structure low density ~ 2.65 g/cm3 3D networks of SiO44- tetrahedra Each O atom is shared by an adjacent tetrahedron

Chapter 12-

Window Glass
Still SiO44- tetrahedra are the basic building block. Most common window glasses are produced by adding other oxides (e.g. CaO, Na2O, B2O3, etc) whose cations are incorporated within SiO4 network. These cations break the tetrahedral network and glasses melt at lower temperature than pure amorphous SiO2 . A lower melting point makes it easy to form glass to make, for instance, bottles. Some other oxides (TiO2, Al2O3) substitute for silicon and become part of the network
Chapter 12-

Carbon/Diamond/Fullerenes/ Nanotubes Read => p399-403

http://www.nas.nasa.gov/Groups/SciTech/nano/

Chapter 12-

DEFECTS IN CERAMIC STRUCTURES

Point defects in ionic crystals are charged. The Coulombic forces that are generated due to defects are very large and any charge imbalance has a strong tendency to balance itself, electroneutrality. To maintain charge neutrality several point defects can be created at the same time:

Frenkel Defect --a cation is out of place. Shottky Defect --a paired set of cation and anion vacancies.

Anion interstitials are unlikely, why ?

Shottky Defect:

Charge neutrality of the crystal is maintained

Frenkel Defect

Equilibrium concentration of defects ~ exp

- QD / kTAdapted from Fig. 13.20, Callister 5e. (Fig. 13.20

is from W.G. Moffatt, G.W. Pearsall, and J. Wulff, The Structure and Properties Chapter 12- of Materials, Vol. 1, Structure, John Wiley and Sons, Inc., p. 78.) See Fig. 12.21, Callister 6e.

IMPURITIES
Impurities must also satisfy charge balance Ex: NaCl

Substitutional cation impurity

Substitutional anion impurity

O 2-

an ion vacancy

initial geometry

Cl Cl O 2- impurity

resulting geometry
Chapter 12- 8

Stoichiometry
A state for ionic solids where there is an exact ratio of anions to cations defined by the chemical formula unit.
NaCl => anion to cation ratio is exactly 1:1 Ca2F => 1:2, otherwise it is called nonstoichiometry FeO => wstite, Fe2+ or Fe3+ may exist depending on temperature and O partial pressure. For any Fe3+, there has to be an extra vacancy so that the charge neutrality is preserved But then, Fe1-xO for x < 1

Chapter 12-

Impurities in Ceramics
Impurity atoms can exist as either substitutional or as interstitial solid solutions in ceramics
Substitutional ions substitute for ions of like type (anion to anion, cation to cation) Interstitial ions are small compared to host structure formation of anion interstitials is unlikely (why?) Solubility is higher if ion radii and charges match closely Incorporation of ion with different charge state requires compensation by point defects to preserve charge neutrality

Chapter 12-

Ceramic Phase Diagrams

Al2O3-Cr2O3 system; often they share a common element in their formula, in many cases it is OXYGEN.
Solubility is achieved by Al3+ substituting Cr3+ Binary Isomorphous system

Chapter 12-

Ceramic Phase Diagrams

Al2O3-SiO2 system
2200 T(C)
3Al 2 O 3 -2SiO 2 Liquid (L) mullite alumina + L mullite +L mullite + crystobalite

20 00 1800
crystobalite +L

1600 1400

alumina + mullite

20

40 60 80 100 Composition (wt% alumina)

Chapter 12-

MEASURING ELASTIC MODULUS

Room T behavior is usually elastic, with brittle failure.

3-Point Bend Testing often used.

--tensile tests are difficult for brittle materials.
Adapted from Fig. 12.29, Callister 6e.

Determine elastic modulus according to:

L3 4bd 3

L3

12 R 4
circ. cross section
Chapter 12- 9

rect. cross section

Mechanical Properties of Ceramics

Ceramics are very brittle. (Fracture Toughness)
For brittle materials fracture stress concentrators are very important. (Chapter 8: measured fracture strengths are significantly smaller than theoretical predictions for perfect materials due to the stress risers) Fracture strength of ceramic may be greatly enhanced by creating compressive stresses in the surface region (similar to shot peening, case hardening in metals, chapter 8)

Compressive strength is typically ten times the tensile strength. This makes ceramics good structural materials under compression (e.g., cement, bricks in building apartments, stone blocks in the pyramids). Generally, tensile test is not used
Hard to machine, grippers may break the piece, fail after 0.1% strain. Size is important due impact of # of cracks on strength, why ?

Chapter 12-

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

F
L/2 R L/2
Adapted from Fig. 12.29, Callister 6e.

d
rect.

circ. location of max tension

Flexural strength:
fail fs m

Typ. values:

1.5Fmax L bd 2 rect.

Fmax L R 3

Material

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

E(GPa)

300 430 390 69

Data from Table 12.5, Callister 6e.

Chapter 12- 10

MEASURING ELEVATED T RESPONSE

Elevated Temperature Tensile Test (T > 0.4 Tmelt).

Generally,
. ceramics . metals . polymers ss ss ss
Chapter 12- 11

SUMMARY
Ceramic materials have mostly covalent & some
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 brittle, with negligible ductility. Elevated T creep properties are generally superior to those of metals (and polymers).
Chapter 12- 12

ANNOUNCEMENTS
Reading: Chapter 12

Core Problems:

Self-help Problems:

Chapter 12- 0