ME2302 CRYSTAL STRUCTURES

CRYSTAL STRUCTURES
Fundamental Concepts

Atoms self-organize in crystals, most of the time. The crystalline lattice is a periodic array of the
atoms. When the solid is not crystalline, it is called amorphous. Examples of crystalline solids are
metals, diamond and other precious stones, ice, graphite. Examples of amorphous solids are glass,
amorphous carbon (a-C), amorphous Si, most plastics.

Packing of atoms in solids

All solid materials (ionic, covalent, metals) may be classified on the basis of their atomic arrangement
as crystalline or amorphous.

Crystalline
Atoms are situated in a repeating or
periodic array over large atomic distances.
Crystalline solids have short range order as
well as long range order (E.g. metals &
ceramics)
Amorphous
Atoms are not packed in definite orderly
arrangement. Amorphous solids have short
range order but there is no long range order.
(E.g. Glass & Polymers)

Above their melting point, metals are liquids, and their atoms are randomly arranged and relatively
free to move. However, when cooled below their melting point, metals rearrange to form ordered,
crystalline structures.

Arrangement of atoms in a
Liquid and a solid

DEPARTMENT OF MME -9-

ME2302 CRYSTAL STRUCTURES

Amorphous solids have one of two atomic arrangements: that is either a

I. Tangled mass of long chained molecules (Polymers) or

II. Three dimensional network of atoms with no long range order (glass)

Crystalline Materials
All most all metals and ceramics are made entirely of small crystals in which atoms are packed in
regular, repeating three dimensional patterns. These are called crystalline materials.

Single Crystals: For a crystalline solid when the periodic and repeated arrangement of atoms extends
throughout the entire specimen it results a single crystal. High technology requires preparing these.
E.g.: tiny semiconductors, single crystal turbine blades (for very high strength).

Polycrystalline Materials: A solid can be composed of many crystalline grains, not aligned with each
other. It is called polycrystalline. The grains can be more or less aligned with respect to each other.
Where they meet is called a grain boundary.

Anisotropy: Different directions in the crystal have a different packing. For instance, atoms along the
edge FCC crystals are more separated than along the face diagonal. This causes anisotropy in the
properties of crystals; for instance, the deformation depends on the direction in which a stress is
applied.

Non-Crystalline Solids

In amorphous solids, there is no long-range order. But amorphous does not mean random, since the
distance between atoms cannot be smaller than the size of the hard spheres. Also, in many cases there
is some form of short-range order. For instance, the tetragonal order of crystalline SiO2 (quartz) is still
apparent in amorphous SiO2 (silica glass.)

Polymers: Long chain polymers made by a process of polymerization. These chains are arranged
randomly and not as regularly repeating 3D patterns and hence they are non crystalline or amorphous.
However some polymers can contain both amorphous and crystalline regions. The atoms within a long
chain molecule are held together by covalent bonding, and the molecules themselves are bonded by
Van der Waals’ forces.

Glass: usually consists of oxides (SiO2) with atoms packed in a non crystalline manner. This is a solid
up to well over 1000˚C because of strong covalent bonds linking the Si to the O atoms. Addition of
soda (Na2O) breaks up the structure and lowers the softening temperature (at which the glass can be
worked) to about 700˚C. Glass is used for bottles, windows,.etc.

Lattice: Atomic arrangements in crystalline solids can be described with respect to a network of lines
in three dimensions. A three dimensional array of points coinciding with atom positions is called as a
lattice. The intersections of the lines are called “lattice sites” (or lattice points). Each lattice site has the
same environment in the same direction.

Unit cell: The unit cell is the smallest structure that repeats itself by translation through the crystal.

We construct these symmetrical units with the hard spheres. The most common types of unit cells are
the faced-centered cubic (FCC), the body-centered cubic (FCC) and the hexagonal close-packed
(HCP). Other types exist, particularly among minerals.

DEPARTMENT OF MME - 10 -
ME2302 CRYSTAL STRUCTURES

s.c. f.c.c b.c.c. h.c.p.

Only Polonium Cu, Pb, Ni, Al Cr, MO, V, W Zn, Mg, Ti
(Po) Fe at temp. > 910C Fe at temp. < 910C

Different types of unit cells available.

e. g.: There are four principle crystal structures for metals

(a) Body-centered cubic (BCC)

The body-centered cubic (BCC) (unit cell has atoms at each of the eight corners of a cube plus one
atom in the center of the cube). Because each of the corner atoms is the corner of another cube, the
corner atoms in each unit cell will be shared among eight unit cells. The BCC unit cell consists of a net
total of two atoms, the one in the center and eight eighths from the corners.

(b) Face-centered cubic (FCC)

In the FCC arrangement, there are eight atoms at corners of the unit cell and one atom centered in each
of the faces. The atom in the face is shared with the adjacent cell. FCC unit cells consist of four atoms,
eight eighths at the corners and six halves in the faces.

DEPARTMENT OF MME - 11 -
ME2302 CRYSTAL STRUCTURES

(c) Hexagonal close-packed (HCP)

Crystal arrangement of close-packed layers of particles where three layers of particles alternate
positions

Important properties of the unit cells are

 The type of atoms and their radii R.

 cell dimensions (side a in cubic cells, side of base a and height c in HCP) in terms of R.
 n, number of atoms per unit cell. For an atom that is shared with m adjacent unit cells, we only
count a fraction of the atom, 1/m.
 CN, the coordination number, which is the number of closest neighbors to which an atom is
bonded.
 APF, the atomic packing factor, which is the fraction of the volume of the cell actually
occupied by the hard spheres. APF = Sum of atomic volumes/Volume of cell.

Unit Cell n CN a/R APF

SC 1 6 2 0.52

BCC 2 8 4/ √3 0.68

FCC 4 12 2×√ 2 0.74

HCP 6 12 0.74

The closest packed direction in a BCC cell is along the diagonal of the cube; in a FCC cell is along the
diagonal of a face of the cube.

Density Computations

The density of a solid is that of the unit cell, obtained by dividing the mass of the atoms (n atoms x
Matom) and dividing by Vc the volume of the cell (a3 in the case of a cube). If the mass of the atom is
given in amu (A), then we have to divide it by the Avogadro number to get Matom. Thus, the formula
for the density is:

DEPARTMENT OF MME - 12 -
ME2302 CRYSTAL STRUCTURES

weight of atoms in a unit cell

Density =
volume of unit cell

Example:
Copper (Cu) has a f.c.c. structure with a lattice parameter of 3.61Å. What is the density of Cu?
(Atomic weight of Cu = 63.5 g/mole)
63.5 g / mole
Weight of atoms = x 4 atoms / unit cell
6.02 x 10 23 atoms / mole
= 4.2192 x 1023 g/unit cell

Volume of unit cell = a3 = (3.61 x 108)3 cm3

4.2192 x 10 22
Therefore, Density =
(3.61x 10  8 )3

= 8.96 g/cm3

Polymorphism and Allotropy

Some materials may exist in more than one crystal structure, this is called polymorphism. 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.

Close-Packed Crystal Structures

The FCC and HCP are related, and have the same APF. They are built by packing spheres on top of
each other, in the hollow sites. The packing is alternate between two types of sites, ABABAB.. in the
HCP structure, and alternates between three types of positions, ABCABC… in the FCC crystals.

To build 3D packing pattern,

- pack atoms two dimensionally in atomic planes

- Stack these planes on top of one another to give crystal.

DEPARTMENT OF MME - 13 -
ME2302 CRYSTAL STRUCTURES

Packing factor (packing Density): Fraction of volumes of the unit cell occupied by the atoms.
Packing factor = volume of atoms in unit cell / volume of the unit cell,
FCC & HCP ≈ 0.74, BCC ≈ 0.68
Coordination Number (CN)
CN is the number of equidistant nearest neighboring atoms for each atom.
BCC → CN= 8
HCP & FCC → CN= 12
Lattice Parameters (constants)
Height, width, Breadth of a unit cell are known as lattice constants or parameters. Consider a unit cell.

Relationship between lattice

parameters (a, b, c) and the atomic
radius (r)

FCC: atoms contact in all the face

diagonals.

4r  a 2  b 2 = 2a

2
r a
4

BCC: Atoms contact along the body diagonal.

AB= √2. a , BC= a

AC2 = AB2 + BC2
=> 4r  2a 2  a 2 4r = 3a
3
r a
4

HCP:

DEPARTMENT OF MME - 14 -
ME2302 CRYSTAL STRUCTURES

Considering top plane,

a
4r = 2a  r 
2

Considering the tetrahedron

Close Packed Planes (CPP) and Close Packed Directions (CPD)

Here parallel planes and directions considered to be similar.
Packing factor = True Volume / Bulk Volume
True Volume = Volume occupied by atoms
Bulk Volume = Volume occupied by unit cell
Miller Indices
Any plane or a direction in a crystal can be specified by a set of three numbers called “Miller Indices.”

Miller Indices for a Plane

The Miller indices for a plane are the reciprocals of the intercepts the plane makes with the three axes,
reduced to the smallest integers.
z
x y z
Intercepts 1 0 
Reciprocals 1/1 1/  1/ 
y Miller indices 1 0 0
x
Miller indices of the plane is (100)

x y z
Intercepts  1 
Reciprocals 1/  1/1 1/ 
Miller indices 0 1 0
Miller indices of the plane is (010)

Miller Indices for a Direction

The Miller indices of a direction are the components of a vector, starting from the origin, along the
direction, reduced to the smallest integer set.

z
P x y Z
a/6 Co – ordinates of P relative to O 1/6 0 1
y
Smallest integers 1 0 6
Miller indices 106
o x

DEPARTMENT OF MME - 15 -
ME2302 CRYSTAL STRUCTURES

z
111

A family of directions is given by the brackets <xyz>.
y

x 100 110
 
Planar Density
Planar density is the number of atoms per unit area within a plane.
a
For a s.c. structure:
a
(1 / 4  4) 1 110
(100) = 2
=
a a2 2a
1 / 4  4 0.707
(110) = = a
2a 2 a2
(1 / 6  3) 1
(111) =  100
3a 2a 3a 2
 2 ]
2a 2a
2 2 2
111
0.577
= 
a2
2a
Therefore, for a simple cubic crystal, planar density of (100) > (110) > (111), and the close-packed
plane in a s.c. structure is the (100) plane.

For a f.c.c. structure:

Therefore, for a f.c.c. crystal
structure the planar density of (111)
> (100) > (110), and the close-
packed plane in a f.c.c. structure is
the (111) plane.

For a b.c.c. structure:

1 Therefore, for a b.c.c. crystal

(100) = 2a structure the planar density of (110)
a2
1.414 > (100) > (111), and the close-
(110) = a packed plane of the b.c.c structure is
a2
the (110) plane.
0.577
(111) =
a2

Linear Density
The linear density is the number of atoms per unit length in particular direction of the unit cell.

DEPARTMENT OF MME - 16 -
ME2302 CRYSTAL STRUCTURES

For the simple cubic structure:

Therefore, for a s.c.c.

structure, the linear
density of 100 >
110 > 111, and
the close-packed
direction of the s.c.c.
structure is [100].

For the f.c.c. structure,

Therefore, for a b.c.c. structure, the linear

Therefore, for a f.c.c. structure, the linear density density of 111 > 100 > 110, and the close-
of 110 > 100 > 111, and the close-packed packed direction of a b.c.c. structure is the [111]
direction of a f.c.c. structure is the [110] direction. direction.

Some Materials have Different Crystal Structures at Different Temperatures.

Crystal Structure for some Metals (at room temperature)

Aluminum FCC Nickel FCC Iron BCC Gold FCC

Cadmium HCP Niobium BCC Lead FCC Vanadium BCC
Chromium BCC Platinum FCC Magnesium HCP Copper FCC
Cobalt HCP Silver FCC Zinc HCP Titanium HCP
Zirconium HCP

Materials choose a crystal structure (bcc, fcc or hcp) that gives minimum energy and this structure
may not necessarily be close packed. Crystal structure may change with temperature. Example: iron
from bcc structure to fcc structure at 911˚C.

˚C
Liquid Fe
1536
δ Fe (BCC) δ - Ferrite
1391

γ Fe (FCC) Austenite
914
α Fe (BCC) Ferrite

DEPARTMENT OF MME - 17 -
ME2302 CRYSTAL STRUCTURES

Unit cell structures determine some of the properties of metals. For example, FCC structures are
more likely to be ductile than BCC, (body centered cubic) or HCP (hexagonal close packed).

Many elements and compounds exist in more than one crystalline form under different conditions of
temperature and pressure. This phenomenon is called polymorphism or allotropy

Crystal Structures in Non-metallic Materials

In non-metallic materials, ionic and covalent bonds are the bases of molecular formation. These bonds
lead to the production of molecules so large that within these molecules exists a repetitive pattern
common to crystalline structures.

(a) (b (c)
)
Crystalline ceramics: (a) covalently bonded silica (SiO2) (b) ionically bonded alumina (Al2O3) and (c) NaCl.

Crystalline solids with directionally bonded atoms and molecules are generally not-close packed due to
the directional requirement of the bonds. Example: Diamond

Carbon exists in three allotropic forms: diamond, graphite, and fullerene.

Diamond:
Diamond which is an allotrope of carbon has a three dimensional structure. Each
carbon atom is connected to four others by covalent bonds and are at the corners
of a regular tetrahedron.

Diamond is mechanically strong and it is the hardest substance known. It has an

extremely high melting point 3500C. Since there are no free electrons, it is not a
conductor of electricity. Materials like Si, Ge and grey tin (an allotrope of tin)
also crystallize in the diamond type of structure.

Graphite:
This has a layer type structure, with each carbon atom surrounded by three other
carbon atoms. Since the fourth electron is free to move from atom to atom, the
graphite conducts electricity. Coordination Number =3. Layers of graphite are held
together by week van der Waals forces. Therefore, sheets of graphite are strong but
they slide over each other very easily. Materials like clay and talc also contain a layer
type structure similar to this.

Fullerenes:
Fullerene consists of a series of large molecules each
containing an even number of carbon atoms arranged in the
form of a closed hollow cage (i & ii). The most stable form
C60 is produced by laser-vaporizing graphite in an inert
atmosphere. It is found that C60 in various compound forms (i) (ii)
can function as an insulator, a conductor, a semiconductor,
and a superconductor.

DEPARTMENT OF MME - 18 -