Lattice, Unit Cells, Basis, and

Crystal Structures
 Lattice - A collection of points that divide space into smaller
equally sized segments.
 Basis - A group of atoms associated with a lattice point.
- it has a chemical composition that is either the same as
the formula unit, or an integer multiple of the formula unit.

Unit cell - A subdivision of the lattice that still retains the overall
characteristics of the entire lattice.

Atomic radius - The apparent radius of an atom, typically

calculated from the dimensions of the unit cell, using close-
packed directions (depends upon coordination number).

Packing factor - The fraction of space in a unit cell occupied by

atoms.
Description and Differentiation of Crystal
Structure:
** assume that all of the atoms in the cell are situated
either at the sites of a prototypical close packed structure
or at one of a few well defined interstitial sites.
*** It is differentiated by the pattern in which these sites
are occupied.
*** So,
Understanding a few geometric principles, it is possible to
describe a vast number of crystal structures.
** Very complex structures can be described by
comparing them to one of a few simple prototypes.
Structure of Ceramics
-- all structures consist of one of the 14 well-known Bravais
lattices plus a collection of atoms, (the basis), that decorates
each lattice point.
--The arrangement of ions and atoms affect the thermal, electrical,
dielectric, optical and magnetic properties of ceramics.
--Exhibit a much wider variety of structures.

3-D arrangement of interstitial sites

The ratio of octahedral sites to atoms is 1:1
The ratio of tetrahedral sites to atoms is 2:1

Cations are usually at

Tetrahedral and
octahedral sites
 Interstitial Sites
 Interstitial sites - Locations between the ‘‘normal’’ atoms or
ions in a crystal into which another - usually different - atom or
ion is placed. Typically, the size of this interstitial location is
smaller than the atom or ion that is to be introduced.

 Cubic site - An interstitial position that has a coordination

number of eight. An atom or ion in the cubic site touches eight
other atoms or ions.

 Octahedral site - An interstitial position that has a coordination

number of six. An atom or ion in the octahedral site touches six
other atoms or ions.

 Tetrahedral site - An interstitial position that has a coordination

number of four. An atom or ion in the tetrahedral site touches
four other atoms or ions.
Interstitial sites in the (a) ccp and (b) bcc structures.
The interstitial sites in the bcc structure do not have the ideal
tetrahedral or octahedral symmetry
(a) When two close-packed planes of spheres are stacked. One on top of the other,
they define the octahedral (B) and tetrahedral (A) sites between them.
(b) Location of tetrahedral and octahedral interstitial sites within the cubic close-
packed arrangement. The number of octahedral sites is always equal to the
number of atoms, while the number of tetrahedral sites is always double the
number of atoms.
(c) Location of octahedral sites in the hexagonal close-packed arrangement.
(d) Location of tetrahedral sites.
 Details of the interstitial
sites in a close packed
structure.
The T+ and T- sites are
not equivalent

Arrangements in which atoms contact at least six other atoms will be referred to as
Close Packed.
 (c) 2003 Brooks/Cole Publishing / Thomson Learning™

The location of the interstitial sites in cubic unit

cells. Only representative sites are shown.
Example 1: Determining Octahedral Sites

Calculate the number of octahedral sites that uniquely

belong to one FCC unit cell.
Example 1 SOLUTION
The octahedral sites include the 12 edges of the unit cell,
with the coordinates
1 1 1 1
,0,0 ,1,0 ,0,1 ,1,1
2 2 2 2
1 1 1 1
0, ,0 1, ,0 1, ,1 0, ,1
2 2 2 2
1 1 1 1
0,0, 1,0, 1,1, 0,1,
2 2 2 2

plus the center position, 1/2, 1/2, 1/2.

Example 1 SOLUTION (Continued)

Each of the sites on the edge of the unit cell is shared

between four unit cells, so only 1/4 of each site belongs
uniquely to each unit cell.

Therefore, the number of sites belonging uniquely to each

cell is:
(12 edges) (1/4 per cell) + 1 center location
= 4 octahedral sites
NAMING CRYSTAL STRUCTURES

**FIRST: name of the prototype for the structure

-- first compound known to have that structure
-- same atomic configurations and connectivity
-- mineral name or the chemical name
-- Example: Structure of NaCl is called Rock Salt Structure or the
Sodium Chloride structure
**SECOND: Structurebericht names
A—is for an element; B– is for a binary compound with 1:1
stoichiometry; C– is a binary compound with 1:2 stoichiometry; D—
signifies a compound with some other stoichiometry; E is for a ternary
compound or more complex composition; L is for an alloy; K is for a
complex alloy.
Example:
NaCl -- B1
 Ceramic crystal structures
• Stability of ceramics depend on two factors:
– Coordination number: maximum number of ions adjacent to
another ion without overlap in electron orbitals
– Electronegativity: how willing atoms are to accept electrons

 Stable crystal structure depends on size ratio of ions.

 Structure is determined by ratios of atomic radii.
Coordination Number: RC/RA
(structure stability)
Tetrahedron maybe
inscribe in a cube
Radius ration= 0.414 for
coordination of six
Radius ration= 0.732
for coordination
number of 8.
 Common ceramic crystal structures
A) AX type

A.1) NaCl structure

Rock salt (e.g., NaCl,

MgO, MnS, LiF, FeO)

• Looks like FCC with atoms in the holes. MgO

and FeO also.
rock salt structure– coordination
number (the number of nearest
neighbors) for cation and anions
is 6.
A.2) CsCl structure

 its cation and anion

coordination is equal to 8.
 Looks like BCC, but center
atom is different than
corners.

8 cubes model

RC/RA =0.8
CN=8
A.3) Zinc Blende structure
• looks like FCC, but with other atoms in different holes.
Also SiC

(c) 2003 Brooks/Cole Publishing / Thomson Learning™

(a) The zinc blende unit cell, (b) plan view.

ZnS structure – it has two polymorphs (zinc blend
and wurtzite) -- all ions are tetrahedrally
coordinated.
they are polytypes of one another, and differ only in the
stacking sequence of tetrahedrally filled close-packed anion
layers.
Polytypism- refers to a special type of polymorphism in
which the different crystalline forms of the compound are
related by different stacking sequence of a 2-D layer.
transformation is reconstructive and requires atom diffusion.
Wurtzite is based on the HCP close-packing of anions.
another polytypic material is Silicon carbide (SiC), which
has more than 74 different polytypes
B) AX2 type crystal structures

B.1 Fluorite structures

-- CaF2
B.2 Antifluorite
structures
-- ZrO2 (cubic), UO2, PuO2,
and ThO2

In the fluorite (CaF2) structure, the cations

occupy the ccp positions and the anions fill the
tetrahedral sites.
FLUORITE STRUCTURE

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™

(a) Fluorite unit cell, (b) plan view.

The cubic unit cell of the fluorite structure: (a)
perspective view; (b) projection down the c-axis.
B.3) AX2-type structures –It has 3 polymorphs (Rutile,
anatase, and brookite) of mineral TiO2.

Unit cell is tetragonal with cations fill one-half of the

available octahedral sites.

The rutile has a large and highly anisotropic

refractive index.

Applications:
opacifying pigment for paints, paper and fabric
B.3 TiO2 unit cell

Ratio of the ions in

the formula unit of
TiO2

Cation balance: Number of cation in

the unit cell

n’ (1) = 2 ; n’ = 2
Anion balance: Number of anion in the unit cell
Therefore, based on
n’ (2) = 4 ; n’ = 2 calculations, the number of
formula units equals 2.
C) AmBnXp structures – Same cations with differing valences
are incorporated in an anion sublattice.
C.1: perovskites
ABO3 is the chemical formula with structure considered
as FCC-derivative.
Titanates and Zirconates are used in electroceramic
applications.
Lead titanate-lead zirconate solid solutions have been
used as speakers and microphones, sonar transducers,
ultrasonic cleaners, and actuators for high precision
positioning.
• A ternary (3 component) structure:
Perovskite.

• Example: BaTiO3, a common piezoelectric

material
• (converts mechanical energy into electrical
signals.)
Learning
(c) 2003 Brooks/Cole Publishing / Thomson

The perovskite unit cell showing the A and B site cations and
oxygen ions occupying the face-center positions of the unit cell.
Note: Ions are not show to scale.
C.2: Spinels
---- normal spinel– cubic close packed anion
arrangement
The unit cell contains eight FCC oxygen
subcells in a cubic array. It has 32 octahedral (1/2
occupied) interstices and 64 tetrahedral interstices
(1/8 occupied).
** where all of the B atoms occupy octahedral sites and all of the A atoms
occupy tetrahedral sites

Highly refractory compound suitable for

structural and optically transmitting applications.
---Soft magnetic ferrites used as inductors,
transformer cores, and read/write heads for magnetic
storage media.
The spinel structure.
(a) and (b) show oblique
views of polyhedral
networks.
(c) is an [001] projection
of the upper half of
the cell.
(d) is an [001] projection
of the lower half of
the cell.
Spinel (garnet) – MgAl2O4

AB2O4 - normal
A: M2+ (Fe, Mg)
B: M3+ (Al, Fe, Cr)
Spinel structure – top view
Inverse-spinels
** all of the A and half of the B atoms (in AB2O4) occupy the octahedral
sites and the other half of the B atoms occupy the tetrahedral sites

** A and B cations could be completely disordered over the octahedral

and tetrahedral sites.

**The exact distribution of the metal atoms is influenced by :

a number of crystal chemical factors including ionic size,
charge, and the crystal field stabilization energy

The degree of disorder in the cation distribution is

represented by the factor λ, which is the fraction of B cations at
tetrahedral sites:

λ =0 specifies an ideal normal spinel. λ =1/2 specifies an ideal inverse

spinel.

Intermediate values indicate some degree of disorder.When 1/3,

the cations are distributed at random
EXAMPLES OF INVERSE-SPINELS

a) (Fe3O4) is the naturally occurring magnetic ore ( lodestone)

Formula is clearly written based on a dual valence: Fe+2Fe2+3O4

b) Defect-spinels such as γ -Al2O3 (thermal decomposition of

Al(OH)3) and γ -Fe2O3
**same framework as the spinel, but some of the octahedral sites that would
normally be occupied are vacant. There are 8/3 Al vacancies per unit cell, with
respect to the ideal spinel.

DEFECT-SPINEL FORMULA:

(Al8+3)T[Al40/3V8/3]OO32, where the V stands for a vacancy

Crystal structure of a new high Tc ceramic
superconductor based on a yttrium barium copper
oxide. These materials are unusual in that they are
ceramics, yet at low temperatures their electrical
resistance vanishes. (Source: ill.fr/dif/3D-
crystals/superconductor.html; © M. Hewat 1998.)
Lattice parameters and density

involve determining the length of unit cell

edges and interaxial angles.
Equals molecular weight
of oxide compound

Density
n' (  M C   M A )

weight of ions within unit cell 
volume of unit cell VC N Av
Where n’= number of formula units within the unit cell
 M C = sum of atomic weights of all cations within unit cell

 M A = sum of atomic weights of all cations within unit cell

VC = unit cell volume

NAv = Avogadro’s number
Try it!
Compute the theoretical density of Rock Salt based on its crystal structure.

Cl- For this NaCl structure, the

crystal lattice parameter is
Na+ a a= 2 ( r Na+ + r Cl -),
where r is ionic radius.

a M 4(A Na  A Cl )
 
V a3 NA
4 ions (22.99  35.45) g/mol

2[(0.102x1 0  7  0.181x10  7 )]cm 3 (6.023x10 23 )ions/mol
 2.14 g/cm 3
(actual  2.16g/cm 3 )
(c) 2003 Brooks/Cole Publishing / Thomson Learning
Corundum structure of alpha-alumina (α-AI203).
Given: a and c and density of alumina
find the APF.
Surprise Quiz:
Solution:
Assignment:
Allotropic or Polymorphic
Transformations

 Allotropy - The characteristic of an element being able to

exist in more than one crystal structure, depending on
temperature and pressure.
 Polymorphism - Compounds exhibiting more than one
type of crystal structure.
Figure 3.17 Oxygen gas sensors used in
cars and other applications are based on
stabilized zirconia compositions. (Image
courtesy of Bosch © Robert Bosch GmbH.)
Example 3
Calculating Volume Changes in Polymorphs
of Zirconia

Calculate the percent volume change as zirconia

transforms from a tetragonal to monoclinic structure.[9]
The lattice constants for the monoclinic unit cells are: a =
5.156, b = 5.191, and c = 5.304 Å, respectively. The
angle β for the monoclinic unit cell is 98.9. The lattice
constants for the tetragonal unit cell are a = 5.094 and c
= 5.304 Å, respectively.[10] Does the zirconia expand or
contract during this transformation? What is the
implication of this transformation on the mechanical
properties of zirconia ceramics?
Example 3 SOLUTION

The volume of a tetragonal unit cell is given by

V = a2c = (5.094)2 (5.304) = 134.33 Å3.

The volume of a monoclinic unit cell is given by

V = abc sin β = (5.156) (5.191) (5.304) sin(98.9) = 140.25 Å3.

Thus, there is an expansion of the unit cell as ZrO2 transforms

from a tetragonal to monoclinic form.

The percent change in volume

= (final volume initial volume)/(initial volume) 100
= (140.25 - 134.33 Å3)/140.25 Å3 * 100 = 4.21%.

Most ceramics are very brittle and cannot withstand more

than a 0.1% change in volume. The conclusion here is that ZrO2
ceramics cannot be used in their monoclinic form since, when
zirconia does transform to the tetragonal form, it will most likely
fracture. Therefore, ZrO2 is often stabilized in a cubic form using
different additives such as CaO, MgO, and Y2O3.
Example 4 Designing a Sensor to
Measure Volume Change

To study how iron behaves at elevated temperatures, we

would like to design an instrument that can detect (with a
1% accuracy) the change in volume of a 1-cm3 iron cube
when the iron is heated through its polymorphic
transformation temperature. At 911oC, iron is BCC, with a
lattice parameter of 0.2863 nm. At 913oC, iron is FCC, with a
lattice parameter of 0.3591 nm. Determine the accuracy
required of the measuring instrument.
Example 4 SOLUTION
The volume of a unit cell of BCC iron before transforming is:
VBCC = a03 = (0.2863 nm)3 = 0.023467 nm3
Example 4 SOLUTION (Continued)

The volume of the unit cell in FCC iron is:

VFCC = a 3 = (0.3591 nm)3 = 0.046307 nm3
0

But this is the volume occupied by four iron

atoms, as there are four atoms per FCC unit cell.
Therefore, we must compare two BCC cells (with a
volume of 2(0.023467) = 0.046934 nm3) with each FCC
cell. The percent volume change during transformation
is:
(0.046307 - 0.046934)
Volume change   100  1.34%
0.046934
The 1-cm3 cube of iron contracts to 1 - 0.0134 =
0.9866 cm3 after transforming; therefore, to assure 1%
accuracy, the instrument must detect a change of:
ΔV = (0.01)(0.0134) = 0.000134 cm3
Factors affecting structure
a) Crystal stoichiometry
-- any crystal has to be electrically neutral. The
sum of the positive charges must be balanced by an
equal number of negative charges.

b) Radius ratio—crystal structure predictor

---Cation and anion tend to maximize attraction
and minimize repulsion to achieve lowest
energy.
c) Propensity for covalency and tetrahedral
coordination
--violation to the structure prediction by the
radius ratio method, which is due to
enhancement of covalency character.
Reasons:
 Cations with high polarizing power (Cu, Al, Zn, Hg) are
bonded to anions that are readily polarizable (I, S, Se)
 Atoms that favor sp3 hybridization such as Si, C, and Ge,
tend to stabilize the terahedral coordination.
Pauling’s Rules
Rule 1. Radius ratio
Around every cation, a coordination polyhedron of anions forms, in which the
cation-anion distance is determined by the radius sums and the coordination
number is determined by the radius ratio.
Rule 2. The electrostatic valency principle
An ionic structure will be stable to the extent that the sum of the strengths of
the electrostatic bonds that reach an ion equal the charge on that ion. e.v. =
charge on the ion/ C.N
Rule 2 continuation……

Isodesmic –bonds are of equal strenghts from all directions.

The bonds are exactly balance for both cations and anions.
Rule 2 continuation……

Rule 3
Shared edges, and particularly faces of two anion polyhedra in a
crystal structure decreases its stability
 Figures for rule 3

Rule 4
In a crystal structure containing several cations, those of high valency
and small coordination number tend not to share polyhedral elements.

Sharing of polyhedral elements for cations of high charge will place cations
close enough together that they may repel one another. Thus, if they do not
share polyhedral elements they can be better shielded from the effects of
other positive charges in the crystal structure.
Rule 5, The principle of Parsimony
The number of different kinds of constituents in a crystal tends to be
small.
- This means that there are only a few different types of cation and anion sites in a
crystal. Even though a crystal may have tetrahedral sites, octahedral sites, and cubic
sites, most crystals will be limited to this small number of sites, although different
elements may occupy similar sites.

Structure of covalent ceramics

--hardness, most refractory and toughest ceramics
--useful as heat sinks, packaging for semiconductor devices
The building block of silicon-based covalent ceramics is the Si tetrahedron in SiC and
Si3N4.
Silicon Nitride exists in two polymorphs α and β. The structure of the β polymorph is
represented by a fraction of the nitrogen atoms are linked to two silicons and others to
thee silicons.
Silicon carbide also exists in in many polymorphs , the simplest of which is cubic SiC,
which has the zinc blende structure.
 Covalent Structures

 Covalently bonded materials frequently

have complex structures in order to
satisfy the directional restraints imposed
by the bonding.
 Diamond cubic (DC) - A special type of
face-centered cubic crystal structure
found in carbon, silicon, and other
covalently bonded materials.
Carbon

1. Diamond
Diamond film by CVD

2. Graphite

Discovered in 1985
3. Fullerenes 20 hexagons + 12 pentagons
FCC packing
Buckytubes, ...
 (c) 2003 Brooks/Cole Publishing / Thomson Learning
(a) Tetrahedron and (b) the diamond cubic (DC) unit
cell. This open structure is produced because of the
requirements of covalent bonding.
A test of the radius ratio rules for binary 1:1 compounds
Reasons for inadequacy of prediction
based on radius ratio:

a)Assumption of spherically symmetric forces

and symmetric coordination
b)Assumption that atoms have the same size
in all chemical environments
c)Underestimation of like-atom repulsions
Structure of silicates

Silicates are abundant mineral in the earth’s crust

and are quite complex.
The basic building block is the SiO4 tetrahedron
The tetrahedral unit has bridging and nonbridging
oxygens.
Bridging oxygens are those bonded to two Si atoms
whereas nonbridging oxygens are bonded to only
one Si atom. NBOs are formed by the addition of
either alkali or alkali-eath metal oxides to silica.
 Silicate ceramics
Building unit

Silica (SiO2)

Quartz,
Cristobailite,
tridymite

Silica glasses: fused silica or

vitreous silica

Schematic representation of ion positions in

a sodium-silicate glass.
Network modifiers: CaO, Na2O; Intermediates: TiO2, Al2O3, etc..
Reduce viscosity stabilizer
 Learning
(c) 2003 Brooks/Cole Publishing / Thomson
The silicon-oxygen tetrahedron and the resultant β-
cristobalite form of silica.
Other types of building units

Layer silicates

Kaolinite clay
Ionic-covalent
Sheet structures!
Van der Wall: between the double-layers e.g., Mica
Salient points for NBOs:
1) The number of NBOs is proportional to the number of moles
of alkali or alkali-earth metal oxide added.
2) The addition of alkali or alkali-earth metal oxides to silica
must increase the overall O/Si ratio of the silicate.
3) Increasing the number of NBOs results in the progressive
breakdown of the silicate structure into smaller units.

Types of silicates according to the repeat units

a) Silica – For a ratio of 2 (SiO2), each oxygen is linked to two
silicons and each silicon is linked to four oxygens, resulting in
a 3-D network.
***Quartz, tridymite, and cristobalite are polymorphs of
silica.
 Silicate Ceramics
Most common elements on earth are Si & O

Si4+

O2-

Adapted 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 (1710ºC)
 Amorphous Silica
• 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.
b) Sheet or Layered silicates ---When three out of four silicons
are shared, a sheet structure results.
examples: Clays, talc and micas.

• (Si2O5)2- Adapted from Fig.

= 12.13, Callister 7e.
• So need cations to balance charge
 Layered Silicates
• 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 Waal’s forces

 Layered Silicates

• 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.
– Used in bonding Foundry Sands and Taconite pellets
c) Chain silicates ---For O/Si ratios of 3.0, infinite chains or
ring structures result.
Examples: Asbestos—is the most notorious mineral. This
results in the stringy, fibrous structures that embed
themselves in the human lung with devastating effect.
d) Island silicates ---When the O/Si ratio is 4,
the structural units are the isolated (SiO4)-4
tetrahedra which cannot join to each other but
are connected by the positive ions in the
structure.
example: Garnets and olivines

e) Aluminosilicates ---Al3+ substitutes Si4+ in the

network and the unbalanced charge is compensated by
cation in the structure.
example: anorthite, orthoclase, spodumen, and albite.