Structure of Crystalline Ceramics

Energy and Packing

Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies.
 Materials and Packing
Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers crystalline SiO2
From Fig. 3.10(a)
Callisters Materials Science and Engineering,
Adapted Version.

Si Oxygen
Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
From Fig. 3.10(b)
Callisters Materials Science and Engineering,
Adapted Version.
 Space (point) lattice: Three dimensional pattern
of points in space

Points in the space lattice with identical

surroundings are called lattice points

Lattice points can be arranges in only 14

different arrangements (arrays) called Bravais
lattice

Don't mix up atoms with lattice points

Lattice points are infinitesimal points in space
Atoms are physical objects
Lattice Points do not necessarily lie at the centre of atoms
Crystal structure can be described in terms a
three-dimensionally periodic arrangement of
points called lattice and an atom or group of
atoms associated with each lattice point called
motif:
Crystal = Lattice + Motif
 Crystal Systems
Unit cell: smallest repetitive volume which contains
the complete lattice pattern of a crystal

7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

Fig. 3.2
Callisters Materials
Science and
Engineering,
Adapted Version.
Primitive cell: Lattice points are only at the corner of the
unit cell; and has only one lattice point per cell
 Bravais Lattices

(Trigonal)
Crystalline material: Material in which the atoms are
situated in a repeating or periodic array over large atomic
distances

Materials with long range order

Materials with short range order

Point Coordinates
Crystallographic directions
Crystallographic planes
 Single crystals
When the periodic and repeated arrangement of atoms is
perfect or extends throughout the entirety of the specimen,
without interruption, such crystalline material is called
Single Crystal.

All unit cells interlock in the same way and have same
orientation
 Crystals as Building Blocks
Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives Fig. 11.33(c)
Callisters Materials
(Courtesy Martin Deakins, Science and Engineering,
GE Superabrasives, Adapted Version.
Worthington, OH. Used with (Fig.11.33(c) courtesy
permission.) of Pratt and Whitney).

Properties of crystalline
materials often related to
crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than others.
(Courtesy P.M.Anderson)
 Polycrystals
most crystalline materials are composed of a collection of
many small crystals or grains; such materials are called
polycrystalline.

Initially, small crystals or nuclei form at various positions

These have random crystallographic orientation
The small grains grow by succesive addtions of atoms from
the surrounding solidyig liquid metal
The extremeties of adjacent grains impinge on one another as
the solidification process completes

The area of atomic mismatch within the region where two

grains meet, is called grain boundary
 Polycrystals Anisotropic
Most engineering materials are polycrystals.

From Fig. K, color inset

pages of Callister 5e.
(Fig. K is courtesy of Paul
E. Danielson, Teledyne
Wah Chang Albany)

1 mm

Nb-Hf-W plate with an electron beam weld. Isotropic

Each "grain" is a single crystal.
If grains are randomly oriented,
overall component properties are not directional.
Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
 Single vs Polycrystals
Single Crystals
-Properties vary with
direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.
E (diagonal) = 273 GPa
Data from Table 3.2,
Callisters Materials
Science and Engineering,
Adapted Version.
(Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics of
Engineering Materials, 3rd
ed., John Wiley and Sons,
1989.)
E (edge) = 125 GPa
200 m From Fig. 5.19(b),
Callisters Materials
Science and Engineering,
Adapted Version.
(Fig. 5.19(b) is courtesy of
L.C. Smith and C. Brady,
the National Bureau of
Standards, Washington,
DC [now the National
Institute of Standards and
Technology, Gaithersburg,
MD].)
 Structure of Ceramics

CERAMICS ARE INORGANIC COMPOUNDS

OXIDES - NITRIDES CARBIDES

Ceramics have more complex crystal structures than metals.

 Structure

The structure has to accommodate anions of different

sizes, and has to preserve chargeneutrality.
IONIC or COVALENT bonds.

The diversity in their properties stems from their

bonding and crystal structures.
 Ceramic Crystal Structures
Atomic bonding : ionic to covalent
Degree of ionic character: depend on EN of
atoms
Ex: CaF2: 89 % ionic; SiC: 12 % ionic

19
For predominantly ionic ceramics, crystal
structures are composed of electrically charged
ions

Crystal structure influenced by

1. Magnitude of the elec. Charge on each of the
component ions
2. Relative sizes of cations and anions
 Electrical charge:
-crystal must be electrically neutral
- chemical formula indicates the ratio of cations to
anions or the composition that achieves this
charge balance

Charge Neutrality:
--Net charge in the F-
structure should CaF 2 : Ca 2+ + anions
be zero.
cation
F-

--General form: A m Xp
m, p determined by charge neutrality
 Site Selection
Which sites will cations occupy?
1. Size of sites
does the cation fit in the site
2. Stoichiometry
if all of one type of site is full the
remainder have to go into other types of
sites.
3. Bond Hybridization
 Ionic Bonding & Structure
1. Size - Stable structures:
--maximize the # of nearest oppositely charged neighbors.
- - - - - - From Fig. 4.10
+ + + Callisters Materials

- - - - - -
Science and Engineering,
Adapted Version.

unstable stable stable

 Coordination # and Ionic Radii
r cation
Coordination # increases with r
anion
Issue: How many anions can you
arrange around a cation?
r cation Coord ZnS
ranion # (zincblende)
From Fig. 4.13
< 0.155 2 linear

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 TD chloride)
From Fig. 4.11

0.414 - 0.732 6 OH CsCl

(cesium
0.732 - 1.0 8 cubic chloride)
From Fig. 4.12
Adapted from Table 4.3

Figures and table from Callisters Materials Science and Engineering, Adapted Version.
 Cation Site Size
Determine minimum rcation/ranion for OH site
(C.N. = 6)
2ranion 2rcation 2a

a 2ranion

2ranion 2rcation 2 2ranion

ranion rcation 2ranion rcation ( 2 1)ranion

rcatio
0.414
n

ranion
2. Stoichiometry
If all of one type of site is full the remainder
have to go into other types of sites.

If for a specific ceramic each unit cell has

6 cations and the cations prefer OH sites
4 in OH
2 in TD
3. Bond Hybridization significant covalent
bonding
the hybrid orbitals can have impact if
significant covalent bond character present
For example in SiC
XSi = 1.8 and XC = 2.5
% ionic character 100 {1- exp[-0.25( X X )2 ]} 11.5%
Si C

ca. 89% covalent bonding

both Si and C prefer sp3 hybridization
Therefore in SiC get TD sites
 Example: Predicting Structure of FeO
On the basis of ionic radii, what crystal
structure would you predict for FeO?
Cation Ionic radius (nm) Answer:
Al 3+ 0.053 rcation 0.077

Fe2+ 0.077 ranion 0.140
Fe3+ 0.069 0.550
Ca 2+ 0.100
based on this ratio,
--coord # = 6
Anion
--structure = NaCl
O2- 0.140
Cl- 0.181
Data from Table 4.4
F- 0.133 Callisters Materials
Science and Engineering,
Adapted Version.
 Coordination # and Ionic Radii
rcation
Coordination # increases with ranion
Issue: How many anionscan you
arrange around acation?
rcation Coord
ranion ZnS
#
(zincblende)
< 0.155 2 linear From Fig. 4.13

0.155 0.225 3 triangular

NaCl
0.225 0.414 4 TD (sodium
chloride)
From Fig. 4.11
0.414 0.732 6 OH
CsCl
(cesium
0.732 1.0 8 cubic chloride)

Figures and table from Callisters Materials Science and Engineering, Adapted Version.
 AX Crystal Structures

AXType Crystal Structures include Rock salt, CsCl,

ZnS
 Rock Salt Structure
NaCl (rock salt) structure

rNa = 0.102 nm
rCl = 0.181 nm

rNa/rCl = 0.564

cations prefer OH sites

22
Callisters Materials Science and Engineering, Adapted Version.
 MgO and FeO
MgO and FeO also have the NaCl structure

O2 rO = 0.140 nm

Mg2+ rMg = 0.072 nm

rMg/rO = 0.514

cations prefer OH sites

Each oxygen has 6 neighboring Mg2+

Callisters Materials Science and Engineering, Adapted Version.
 AX Crystal Structures

Cesium Chloride structure:

r
Cs
0.170
0.939
rCl 0.181

cubic sitespreferred

Each Cs+ has 8 neighboring Cl

Callisters Materials Science and Engineering, Adapted Version.

 AX Crystal Structures
Zinc Blende structure rZn2
0.074 0.529 OH??
rO 2 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

Each Zn2+ has 4 neighboring O2

Ex: ZnO, ZnS, SiC

Callisters Materials Science and Engineering, Adapted Version.

 AX2 Crystal Structures
Fluorite structure

Calcium Fluorite
(CaF2)
cations in cubicsites

UO2, ThO2, ZrO2, CeO2

antifluorite structure
cations and anions
From Fig. 4.14
reversed
Callisters Materials Science and Engineering
Adapted Version.
 ABX3 Crystal Structures
Perovskite structure

Ex: complex oxide

BaTiO3

From Fig. 4.15

Callisters Materials Science and Engineering
Adapted Version.
 Spinel structure
AB2O4 type structure
A is bivalent cation and B is trivalent cation
Oxygen ions occupy the FCC lattice and cations find three
of the available four octahedral and eight tetrahedral
interstities.

MgAl2O4
 Alumina (corundum)
One of the alumina structures: alpha alumina
Oxygen anion pack in a hexagonal arrangemement
Aluminium cation occuy some of the available octahedral
positions

Applications:
Spark plugs, refraactroies, electronic packaging, substrates,
abrasives
 Silicate Ceramics
Mainly of silicon and oxygen, the two most abundant
elements in earths crust (rocks, soils, clays, sand)
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
SiO4-4 blocks

Si4+

O2-

30
 Silica (silicon dioxide) SiO2
Every oxygen shared by adjacent tetrahedra
Silica is crystalline (quartz) or amorphous, as in glass
(fused or vitreous silica)

Si4+

O2-

crystobalite
3D network of SiO4 tetrahedra in cristobalite
High melting temperature of 1710 C
31
 Window glasses
Common window glass is produced by adding oxides (e.g. CaO,
Na2O) whose cations are incorporated within SiO4 network. The
cations break the tetrahedral network. Glasses melt at lower
temperature than pure amorphous SiO2.
Lower melting T makes it easier to form objects (e.g, bottles). Some
other oxides (TiO2, Al2O3) substitute for silicon and become part of
the network

32
 Silicate Ceramics
Most common elements on earth are Si & O

Si4+

O2-

crystobalite

SiO2 (silica) structures are quartz,

crystobalite, & tridymite
The strong Si-O bond leads to a strong,
high melting material (1710C)
 Silica Glass
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
 Carbon Forms
Carbon black amorphous
surface area ca. 1000
m2/g

Diamond
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.
 Carbon Forms - Graphite
layer structure

From Fig. 4.26

Callisters Materials Science and Engineering
Adapted Version.

weak van der Waals forces between layers

planes slide easily, good lubricant
 Carbon Forms
Fullerenes and Nanotubes
Fullerenes or carbon nanotubes
wrap the graphite sheet by curving into ball or tube
Buckminister fullerenes
Like a soccer ball C60 - also C70 + others

From Figs. 4.27 & 4.28

Callisters Materials Science and Engineering
Adapted Version.
Ceramic Density Computation

Number of formula units/unit cell

n( AC AA )

V C NA

Volume of unit cell

 Imperfections in Ceramics
Point defects in ionic crystals are charged. Coulomb forces are large.
Any charge imbalance has a strong tendency to balance itself. To
maintain charge neutrality several point defects can be occur:
Frenkel defect: a pair of cation (positive ion) vacancies and a cation
interstitial. Also be an anion (negative ion) vacancy and anion
interstitial. Anions are larger than cations so not easy for an anion
interstitial to form
Schottky defect is a pair of anion and cation vacancies

Schottky defect
Frenkel defect

39
 Imperfections in Ceramics
Frenkel and Schottky defects do not change ratio of cations to anions
compound is stoichiometric
Non-stoichiometry (composition deviates from the one predicted by
chemical formula) occurs when one ion type can exist in two valence
states, e.g. Fe2+, Fe3+
In FeO, Fe valence state is 2+.
Two Fe ions in 3+ state >an Fe vacancy is required to maintain
charge neutrality
fewer Fe ions non-stoichiometry

40
 Impurities in Ceramics
Impurity atoms can be substitutional or interstitials
Substitutional: substitute for ions of like type
Interstitials: small compared to host structure formation of anion
interstitials is unlikely
Solubilities higher if ion radii and charges match
Incorporation of ion with different charge state requires compensation
by point defects

Interstitial impurity atom

Substitutional impurity ions

41