MME 211

CRYSTALLOGRAPHY AND STRUCTURE OF MATERIALS

MD. MUKTADIR BILLAH, Ph.D. (USA)

Associate Professor
MME, BUET
LATTICE AND MOTIF
Introduction
• Motion of atoms in solids is restricted to small
vibrations about a mean position.
• As temperature is raised, atoms in a solid
become increasingly more mobile until orderly
array in the solid disintegrates and it becomes
a liquid.
• Gas is a state in which atoms have gained so
much freedom of motion that they no longer
bother to stick together at all.
Introduction
• When temperature is lowered sufficiently, a
liquid freezes and a solid results.
• When liquid cools, two types of solids can form.
• If liquid cools sufficiently slowly, atoms can
assume an orderly arrangement and a crystal
results.
• If temperature is dropped abruptly, arresting
motion of the atoms before they can reorganize
themselves, then a mixed-up structure called a
glass or an amorphous solid may result.
Amorphous versus Crystalline Structure
• A crystal may be defined as a solid composed of atoms arranged in a
pattern periodic in three dimensions.
• Crystals differ in a fundamental way from gases and liquids because
atomic arrangements in the latter do not possess the essential
requirement of periodicity.
• Not all solids are crystalline, however; some are amorphous, like glass,
and do not have any regular interior arrangement of atoms.
• There is, in fact, no essential difference between an amorphous solid and
a liquid, and the former is often referred to as an "undercooled liquid."
 An amorphous substance is isotropic, i.e., it exhibits
the same physical and chemical properties when tested
in any direction.
Crystal has many properties that are directional.
Amorphous
versus The basic feature of all crystals is the regularity of their
atomic arrangement.
Crystalline
Structure The first notable feature of the regularity of crystal
structures is the periodicity of their patterns.

In addition to periodicity, most crystal structures

possess the property of symmetry.
Lattice
• Crystal structure means regular
arrangement of atoms or molecules.
“Regular” implies existence of
something that repeats itself,
“arrangement” implies presence of
a pattern.
• It is convenient to ignore actual
atoms composing the crystal and
their periodic arrangement in space,
and to think instead of a set of
imaginary points which has a fixed
relation in space to the atoms of the
crystal and which may be regarded
as a sort of framework or skeleton
on which the actual crystal is built.
 Lattice
• Imagine space to be divided by three
sets of planes, the planes in each set
being parallel and equally spaced.
• This division of space will produce a
set of cells each identical in size,
shape, and orientation to its
neighbors.
• Each cell is a parallelepiped, since its
opposite faces are parallel, and each
face is a parallelogram.
• The space-dividing planes will intersect
each other in a set of lines, and these
lines in turn intersect in the set of
points referred to above.
Lattice
• A set of points so formed has an important
property: it constitutes a point lattice,
which is defined as an array of points in
space so arranged that each point has
identical surroundings.
• By "identical surroundings" we mean that
the lattice of points, when viewed in a
particular direction from one lattice point,
would have the same appearance when
viewed in the same direction from any
other lattice point.
Motif • In a crystal, points of the lattice must be
occupied by atoms, ions, or molecules.
Because the points are all identical, the
collections of objects occupying them must
also be identical. The drawing consists of a
motif which is repeated by translating it
from one point, chosen as the origin, to
other points arranged in a 2-D pattern.
• The set of points constitutes a net in two
dimensions (2-D) and a lattice in three
dimensions (3-D). The motif represents the
decoration of that net or lattice. In the
same way, a crystal structure can be
described as a 3-D lattice, decorated with
atoms or molecules.
Unit Cell • Since all the cells of the lattice shown are
identical, we may choose any one as a unit
cell.
• The size and shape of the unit cell can in
turn be described by the three vectors a, b,
and c drawn from one corner of the cell
taken as origin.
• These vectors define the cell and are called
the crystallographic axes of the cell.
• They may also be described in terms of
their lengths (a, b, c) and the angles
between them (α, β, γ).
• These lengths and angles are the lattice
constants or lattice parameters of the unit
cell.
PATTERN
PATTERN
PATTERN
PATTERN
PATTERN
CRYSTAL SYSTEMS
The Four 2-D
Crystal Systems
• If we take arbitrary values for all
three parameters, then we end up
with oblique net {a, b, γ}.
• When γ = 90◦, the unit cell of a net
becomes a rectangle {a, b, γ = 90◦}.
• When a = b and γ = 90◦, the unit cell
of a net becomes a square {a, a, γ =
90◦}.
• When a = b and γ = 60◦, the unit cell
of a net becomes a hexagonal {a, b,
γ = 60◦}.
THE SEVEN
3-D
CRYSTAL
SYSTEMS
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
TRICLINIC/
ANORTHIC
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
MONOCLINIC
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
HEXAGONAL
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
RHOMBOHEDRAL/
TRIGONAL
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
ORTHORHOMBIC
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
TETRAGONAL
 THE SEVEN
3-D CRYSTAL
SYSTEMS:
CUBIC
SYMMETRY
ELEMENTS
SYMMETRY
ELEMENTS
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System
Cubic Crystal System: Van der Waals Surface
cP, tP & oP Crystal System (Pearson symbol)
cP, tP & oP Crystal System (Pearson symbol)
The Five 2-D Bravais Nets
The Fourteen 3-D Bravais Nets
The Fourteen 3-D Bravais Nets
The Fourteen 3-D Bravais Nets
CRYSTALLOGRAPHIC
CALCULATIONS
 Atomic Packing Factor
• The filling factor of a crystal structure is defined as the fraction of the total crystal
volume filled with atoms considered hard spheres.
• Sometimes instead of filling factor the expressions “atomic packing factor” or
“packing fraction” are used.
• The filling factor gives us an idea how close “the atoms are packed” in the crystal
structure.
• In conclusion, the filling factor together with the coordination number give us an idea
about the degree of filling the crystal volume with atoms, and, at the same time, tells us
how close the atoms in a crystal are packed.
Atomic Packing Factor

SC
Atomic Packing Factor

BCC SC
Atomic Packing Factor

BCC FCC SC
 Nearest Neighbor (NN = 6)

SC
 Next Nearest Neighbor (NNN = 12)

SC
 NN = 8 & NNN = 6

BCC
 NN = 12 & NNN = 6

FCC
LINEAR DENSITY : SC
LINEAR DENSITY : BCC
LINEAR DENSITY : FCC
Planar Density : SC (100) Plane
Planar Density : SC (110) Plane
Planar Density : SC (111) Plane
Planar Density : BCC (100) Plane
Planar Density : BCC (110) Plane
Planar Density : BCC (111) Plane
Planar Density : FCC (100) Plane
Planar Density : FCC (110) Plane
Planar Density : FCC (111) Plane
INTERSTITIAL SITES
INTERSTITIAL SITES: TETRAHEDRAL
INTERSTITIAL SITES: OCTAHEDRAL
EFFECT OF RADIUS RATIO: STABILITY
 EFFECT OF RADIUS RATIO ON CN
NUMBER

There are unfortunately several challenges with using this idea to predict crystal structures:

• Atoms in crystals are not really ions - there is a varying degree of covalency depending
electronegativity differences.
• Bond distances (and therefore ionic radii) depend on bond strength and coordination
number.
• Ionic radii depend on oxidation state (higher charge => smaller cation size, larger anion size).
RADIUS RATIO: <0.155

Radius ratio: 0.10

Radius ratio: 0.155

 RADIUS RATIO: 0.155

Radius ratio: 0.10

Radius ratio: 1.0 Radius ratio: 0.155

RADIUS RATIO: 0.155

Radius ratio: 0.155

 RADIUS RATIO: 0.225

Radius ratio: 0.155

Radius ratio: 1.0 Radius ratio: 0.225

RADIUS RATIO: 0.225

Radius ratio: 0.225

 RADIUS RATIO: 0.414

Radius ratio: 0.225

Radius ratio: 1.0 Radius ratio: 0.414

RADIUS RATIO: 0.414
Sin 45o = (r+ + r-)/2r-
or 2 Sin 45o r- = (r+ + r-)
or r+ = (2 Sin 45o - 1) r-
or r+ /r- = 0.414

Radius ratio: 0.414

 RADIUS RATIO: 0.732

Radius ratio: 0.414

Radius ratio: 1.0 Radius ratio: 0.732

RADIUS RATIO: 0.732

Radius ratio: 0.732

 FCC: OCTAHEDRAL VOID

½ 0 0 and equivalent ½½½

positions
• 4 atoms/unit cell
• 4 octahedral sites/unit cell
• 1 octahedral sites/atom
 FCC: OCTAHEDRAL VOID

½ 0 0 and equivalent ½½½

positions
• 4 atoms/unit cell
• 4 octahedral sites/unit cell
• 1 octahedral sites/atom
FCC: TETRAHEDRAL VOID

¼ ¼ ¼ and equivalent
positions
• 4 atoms/unit cell
• 8 tetrahedral sites/unit cell
• 2 tetrahedral sites/atom
FCC: TETRAHEDRAL VOID

¼ ¼ ¼ and equivalent
positions
• 4 atoms/unit cell
• 8 tetrahedral sites/unit cell
• 2 tetrahedral sites/atom
 BCC: OCTAHEDRAL VOID

½ 0 0 and equivalent ½ ½ 0 and equivalent

positions positions
• 2 atoms/unit cell
• 6 octahedral sites/unit cell
• 3 octahedral sites/atom
 BCC: OCTAHEDRAL VOID

½ 0 0 and equivalent ½ ½ 0 and equivalent

positions positions
• 2 atoms/unit cell
• 6 octahedral sites/unit cell
• 3 octahedral sites/atom
BCC: TETRAHEDRAL VOID

½ ¼ 0 and equivalent
positions
• 2 atoms/unit cell
• 12 tetrahedral sites/unit cell
• 6 tetrahedral sites/atom
BCC: TETRAHEDRAL VOID

½ ¼ 0 and equivalent
positions
• 2 atoms/unit cell
• 12 tetrahedral sites/unit cell
• 6 tetrahedral sites/atom