3.

0 Structures of Metals and Ceramics

How do atoms arrange themselves in ordered structures
(crystals)?
- Fundamental concept
-Unit Cells
-Metallic crystal structures
Face-centered cubic
Body-centered cubic
Hexagonal close-pack
-Ceramic crystal structures
-Density computation- Ceramics
-Crystallographic directions and planes
3.1 Fundamental concepts
The properties of some materials are directly
related to their crystal structures. Eg pure Mg is
more brittle than pure Au.

Crystalline material: Atoms self-organize in a

periodic manner.
 Typical of: metals
ceramics
some polymers
crystalline SiO2
Noncrystalline materials: atoms have no periodic
packing.
occurs for: complex structures
rapid cooling
noncrystalline SiO2

Amorphous = Noncrystalline

To discuss crystalline structures, 2 models are used.

Hard-sphere model and lattice points at center
model
1. Hard-sphere model: the shortest distance
between two like atoms is one diameter.

2. Lattice points at sphere center model: Crystal

structure can be considered as lattice of points
at atom/sphere center
3.2 Unit Cell
The unit cell is the smallest structural unit or
building block that can describe the crystal
structure.
The entire crystal is generated by the repetition
of the unit cell
3.3 Metallic crystal structure
 Metals are usually (poly)crystalline; although
formation of amorphous metals is possible by rapid
cooling.
 Atom (hard sphere) radius, R, defined by ion core
radius - typically 0.1 - 0.2 nm.

 The most common types of unit cells are the

faced centered cubic (FCC), the body-centered
cubic (BCC) and the hexagonal close-packed
(HCP).
3.3.1 Face-centered cubic crystal structure
Atoms are located at each of the corners and
on the centers of all the faces of cubic unit cell.
Examples are Cu, Al, Ag, Au have this crystal
structure
 The hard spheres or ion cores touch one another
across a face diagonal ⇒ the cube edge length, a ,
and the atomic radius, R are related by

a= 2R√2

 The coordination number, CN = the number of

closest neighbors to which an atom is bonded =
number of touching atoms, CN = 12

 Number of atoms per unit cell, n = 4.

 For an atom that is shared with m adjacent
unit cells, we only count a fraction of the atom,
1/m. In FCC unit cell we have:
6 face atoms shared by two cells: 6×1/2 = 3
8 corner atoms shared by eight cells: 8×1/8 = 1

 Atomic packing factor, APF = fraction of volume

occupied by hard spheres = (Sum of atomic/sphere
volumes)/(Volume of cell) = 0.74 (maximum
possible)
3.3.2 Body-centered cubic crystal structure
Atom at each corner and at center of cubic
unit cell. Examples are Cr, α-Fe, Mo have this
crystal structure.
 The hard spheres touch one another along cube
diagonal

⇒ the cube edge length, a= 4R/√3

 The coordination number, CN = 8

 Number of atoms per unit cell, n = 2

 Center atom (1) shared by no other cells: 1 x 1 = 1

 8 corner atoms shared by eight cells: 8 x 1/8 = 1

 Atomic packing factor, APF = 0.68

3.3.2 Hexagonal close pack crystal structure (HCP)
 HCP is a common structure of metallic crystals.
Examples are:Cd, Mg, Zn, Ti have this crystal structure

 Six atoms form regular hexagon, surrounding one

atom in the center
 Another plane is situated halfway up unit cell (c
axis), with 3 additional atoms situated at interstices of
hexagonal (close-packed) planes.

 Unit cell has two lattice parameters a and c. Ideal

ratio c/a = 1.633

 The coordination number, CN = 12 (same as in

FCC)

 Atomic packing factor, APF = 0.74 (same as in

FCC)
 Number of atoms per unit cell, n = 6.

 3 mid-plane atoms shared by no other cells:

3x1=3

 12 hexagonal corner atoms shared by 6

cells: 12 x 1/6 = 2

 2 top/bottom plane center atoms shared by 2

cells: 2 x 1/2 = 1
Example 3.1
Show that the APF for FCC crystal structure is 0.74.

Solution
The FCC unit cell is illustrated as:
3.4 Density computation for metals
 The density of a crystalline material, ρ = the
density of the unit cell = (atoms in the unit
cell, n ) × (mass of an atom, M) / (the
volume of the cell, Vc)

 Atoms in the unit cell, n = 2 (BCC); 4 (FCC);

6 (HCP)
 Mass of an atom, M = Atomic weight, A, in
(or g/mol) is given in the periodic table.
NA = 6.023 × 1023 atoms/mol

 The volume of the cell, Vc = a3 (FCC and

BCC)
a = 2R√2 (FCC);
a = 4R/√3 (BCC)

where R is the atomic radius

Example 3.2

Copper has an atomic radius of 0.128 nm

(1.28Ǻ ), a FCC crystal structure, and an
atomic weight of 63.5 g/mol. Compute its
theoretical density and compare the
answer with its measured density of 8.94
g/cm3
3.5 Ceramic crystal structures
Ceramics have complex structures because they are
made up of more than 1 element.

The atomic bonding in these materials ranges from

purely ionic to totally covalent. Many ceramics
exhibit a combination of these two bonding types,
the degree of ionic character being dependent on
the electronegativities of the atoms.
Two characteristics that influence ceramic crystal
structures are: the magnitude of electrical charge
on each of the component ions, and the relative
sizes of the cations and anions.

With the first characteristics, the crystal must be

electrically neutral; that is, all the cation positive
charges must be balanced by an equal number of
anion negative charges.
Example: in formation of calcium fluoride, CaF2.
The second criterion involves the sizes or ionic radii
of the cations and anions, rC and rA, respectively.
Because the metallic elements give up electrons
when ionized, cations are ordinarily smaller than
anions, and, consequently, the ratio rC/rA is less
than unity.

Stable ceramic crystal structures

are formed when the anions
surrounding the cation are all in
contact with that cation.
The coordination number (i.e., number of anion
nearest neighbors for a cation) is related to the
cation–anion radius ratio.

For a specific coordination number, there is a critical

or minimum rC/rA ratio for which this cation–anion
contact is established.

This ratio may be determined from pure

geometrical considerations.
Example 3.3

Show that the minimum cation-to

anion radius ratio for the
coordination number 3 is 0.155.
• Solution
3.5.1 AX Type Crystal Structure
Some of the common ceramic materials are those
in which there are equal numbers of cations and
anions

These are often referred to as AX compounds, where

A denotes the cation and X the anion

There are several different crystal structures for AX

compounds; each is normally named after a common
material that assumes the particular structure.
1. Rock Salt
The most common AX crystal structure is the sodium chloride
(NaCl), or rock salt, type.

The coordination number for both cations and anions is 6, and

therefore the cation–anion radius ratio is between 0.414 and
0.732.

A unit cell for this crystal structure is

generated from an FCC arrangement of
anions with one cation situated at the
cube center and one at the center of
each of the 12 cube edges.
Egs NaCl, MgO, MnS, LiF, and FeO
2. Cesium chloride structure
The coordination number is 8 for both ion types.

The anions are located at each of the corners of a

cube, whereas the cube center is a single cation.
3. Zinc Blende (Sulphide) structure

A third AX structure is one in which the coordination

number is 4; that is, all ions are tetrahedrally
coordinated.

All corner and face positions of the cubic cell are

occupied by S atoms, while the Zn atoms fill interior
tetrahedral positions.

Thus, each Zn atom is bonded to four S atoms, and

vice versa.
Most often the atomic bonding is highly covalent in
compounds exhibiting this crystal structure
Examples include ZnS, ZnTe, and SiC.
3.5.2 AmXp type crystal structure

If the charges on the cations and anions are not the

same, a compound can exist with the chemical
formula AmXp , where m and/or p  1.

An example would be AX2 , for which a common

crystal structure is found in fluorite (CaF2). The ionic
radii ratio rC/rA for CaF2 is about 0.8 which gives a
coordination number of 8.
Calcium ions are positioned at the centers of cubes,
with fluorine ions at the corners.

Other compounds that have this crystal structure

include UO2 , PuO2 , and ThO2
3.5.3 AmBnXp type crystal structure

It is also possible for ceramic compounds to have more

than one type of cation; for two types of cations
(represented by A and B), their chemical formula may
be designated as AmBnXp .

Barium titanate (BaTiO3), having both Ba2+ and Ti4+

cations, falls into this classification. This material has a
perovskite crystal structure.
At temperatures above 120°C, the crystal structure is
cubic.
There is also spinel crystal structures (MgAl2O4).
Ba2+ ions are situated at all eight corners of the cube
and a single Ti4+ is at the cube center, with O2- ions
located at the center of each of the six faces.
Example 3.4

On the basis of atomic radii, what

crystal structure will you predict for
FeO? The atomic radii for Fe2+ and
O are 0.077 and 0.140 nm
2-

respectively.
3.6 Density computations for Ceramics
It is possible to compute the theoretical density of a
crystalline ceramic material from unit cell data in a
manner similar to that for metals.

In this case the density may be determined using

the relation:
n’ = the number of formula units within the unit cell
AC = the sum of the atomic weights of all cations in the formula
unit
AA = the sum of the atomic weights of all anions in the formula
unit
VC = the unit cell volume
NA = Avogadro’s number, 6.023 x 1023 formula units/mol

Example 3.5
On the basis of crystal structure, compute the
theoretical density for sodium chloride if the number
of NaCl units per unit cell is 4. How does this compare
with its measured density of 2.16g/cm3?
Solution
 3.7 General Crystal Systems
By assigning specific values for axial length and
interaxial angles, unit cells of different types can be
constructed.
Crystallographers have shown that only 7 different
types of units cells are necessary to create all space
lattice.
Seven different combinations of a, b, c, α, β and γ
are possible each of which represents a distinct crystal
system.

These are cubic, tetragonal, hexagonal, orthorhombic,

rhombohedral, monoclinic, and triclinic.

The cubic system, for which a = b = c and α = β = γ =90,

has the greatest degree of symmetry.

Least symmetry is displayed by the triclinic system, since

a  b  c and α  β  γ
3.8 Crystallographic directions and planes

Now that we know how atoms arrange themselves to form

crystals, we need a way to identify directions and planes of
atoms.

Why?
 Deformation under loading (slip) occurs on certain crystalline
planes and in certain crystallographic directions. Before we can
predict how materials fail, we need to know what modes of
failure are more likely to occur.

 Other properties of materials (electrical conductivity, thermal

conductivity, elastic modulus) can vary in a crystal with
orientation.
3.8.1 Crystallographic directions (cubic systems)
Three integers or indices are used to designate
directions.
For cubic crystals, the direction indices are the vector
components of the direction resolved along each of
the coordinate axes and reduced to the smallest
integer.
Steps
1. A vector of convenient length is positioned such
that it passes through the origin of the coordinate
system.

2. The length of the vector projection on each of the

three axes is determined; these are measured in
terms of the unit cell dimensions a, b, and c.

3. These three numbers are multiplied or divided by

a common factor to reduce them to the smallest
integer values.
4. The three indices, not separated by commas, are
enclosed in square brackets, thus: [uvw]. The u, v,
and w integers correspond to the reduced
projections along the x, y, and z axes, respectively.

For each of the three axes, there will exist both

positive and negative coordinates.

Thus negative indices are also possible, which are

represented by a bar over the appropriate index.
For example, the [1͞11] direction would have a
component in the -y direction.

Also, changing the signs of all indices will produce an

antiparallel direction; that is, [͞1͞1͞1] is directly
opposite to [111].
For instance, [100], [110], and [111] directions
within a cell are represented as:
Again, the position coordinates shown in this figure is
(1, ½,0) and the direction vector is [210]
Furthermore, the position coordinates in the diagram
below is (-1,-1,0).

The direction vector is [ ]

Example 3.6
Draw the following direction vectors in cubic unit
cells:
a. [112]
b. [ ]
c. [ ]
Hexagonal Crystals
In hexagonal crystal systems, a fourth axis is utilized
or a Miller Bravais coordinate system is used.

The 3 a1, a2, and a3 axes are all contained in a single

plane (basal plane) and at 120o to each other.
The z axis is perpendicular to the basal plane.

Directional indices are denoted by four indices

[uvtw]: by convention, the first three indices
pertain to projections along the respective a1, a2,
and a3 axes in the basal plane.

Conversion from the three-index system to the

four-index system, [u’v’w’] → [uvtw] is given as
n is a factor that may be required to reduce u, v, t,
and w to the smallest integers.
Example 3.8: Convert [010] direction into the
Miller-Bravais four index system.
3.8.2 Crystallographic planes
Steps
• If the plane passes through the origin, select an
equivalent plane or move the origin.
• Determine the intersection of the plane with the
axes in terms of a, b, and c.
• Take the reciprocal (1/∞ = 0)
• Convert to smallest integers (optional)
• Enclose by parentheses
3.8.1 Crystallographic planes

Plane (100) is dawn as

Also, plane (110)

Furthermore, plane (111)

What is the Miller index

for this plane?
Example 3.9
Draw the following crystallographic planes in cubic
unit cells.
a. (101) b.( ) c. (221)
3.9 Linear and planar density
Linear density
– Number of atoms per length whose centers lie on
the direction vector for a specific crystallographic
direction.

Planar density
– Number of atoms per unit area that are centered on
a particular crystallographic plane.
Example 3.10

Calculate the linear density of Aluminum in a [110]

direction if Al is FCC and cube edge length, a = 0.405
nm

[110]
Solution

a
Example 3.11

a. Draw the unit cell for BCC crystal structure and

identify the most densely packed plane.

b. Derive linear density expression for BCC [111] in

terms of the atomic radius R.

c. Derive planer density expression for BCC (110)

plane in terms of atomic radius R.
Solution
a.

b.
c.
3.10 Polymorphism and Allotropy

Some materials may exist in more than one

crystal structure. This is called polymorphism. E.g
Glycerin can be monoclinic and hexagonal
crystals.

If the material is an elemental solid, it is called

allotropy.
An example of allotropy is carbon, which can
exist as diamond, graphite, and amorphous
carbon.