Introduction to Crystal Structure

Structure of Solids
Properties of a Material are determined by:
 Microstructure: Crystalline and amorphous structures

 Crystal structure and configuration (size and shape of

lattice)

 Grain size
 Phase distribution
 Impurities
 Defects
Microstructural level features & terminology
Grains
 Crystals are of an irregular appearance and size
(1mm – several mm)

Grain boundaries
 where the crystal touch and merge into each other Metal: polycrystalline grain structure

Pores
 Places free of material = voids in the bulk material

Microcracks
 Flaws of less than a micron in size

Impurities
 Atoms and compounds chemically different from the main phase
 Types of Solid

Crystalline Materials Amorphous Materials

Metals Glasses
Ceramics some Polymers
( acrylic, polystyrene,
polycarbonate)

Semi-Crystalline
Materials
i.e. many polymers
( nylon, polyethylene,
polypropylene, PET…. )
Attributes of Solids
Amorphous solids:
considerable disorder in their structures
generally clear transparent materials – polymers, glass.

Crystalline Solids:
highly regular arrangement of their components
table salt (NaCl)
pyrite (FeS2)
metals
sapphire

‘Semi Crystalline’ polymers:

possess some regular structure within a matrix of
amorphous material.
nylon , HDPE, LDPE, PP
An amorphous solid does not possess a well-defined atomic
arrangement and long-range molecular order.

Glass is an example of an amorphous solid. It is an optically

transparent fusion product of inorganic materials that has cooled to a
rigid state without crystallizing

DISORDER -Randomly ordered

structure with some large
spaces between atoms.

Silicon
oxygen

Microscopic representation of
Non-crystalline
silica - glass
 ORDERED
Crystal structure -Perfectly ordered
structure.
‘Crystal structure’ is the manner in which
atoms
Silicon
ions oxygen
molecules
are arranged in space.
Crystalline silica
( quartz, crystobalite)
SiO2

An array of points which describe the ‘regular’ three dimensional

arrangement of atoms in a crystal structure is called a lattice ( or
space lattice).

There are many different types of crystal structure

Metals have simple structures – E.g. BCC, FCC, HCP
Ceramics and polymers can have very complex ones: i.e. intertwined FCC, distorted,

We will only be concerned with crystal structures of metals

 Unit cells
A unit cell is the basic (smallest) repeating
structural unit of a crystalline solid.

Space lattice

lattice
point

Unit Cell Unit cells in 3 dimensions

How to define Crystal Structure : using a point
lattice method

In the unit cell define:

angles a, b, g
and
lengths a, b, c

These are called the lattice parameters of

the unit cell

Vectors a, b, c define the crystal structure.

a,b, c are used in crystallography rather

than conventional orthogonal x, y, z axes.
The Seven Crystal Systems

All crystalline structures

known can be identified
by 1 of these 14 Bravais
lattices – which
essentially belong to
one of 7 systems.
 Planes and Directions in Crystals (FCC)
When lattices in crystalline materials are examined there are often
found to be planes of close packing.
direction

less packed Close packed

planes planes

Interplanar
or d spacing
 BCC Crystal Planes
(Cubic Crystals)

View 2

1 O y
2

Packing along the diagonal

x View 1
Planes and directions in crystals are ‘described’ by a set of numbers
known as Miller indices.
Miller Indexing of Crystal Planes
Assume unit lengths, a = b = c
Example Intercepts Miller indices
x, y, z (h k l)
axes
A , , 1 (001)
A B C
B , 1,  (010)
C -1, ,  (Í00)
D , 1, 1 (011) D E F
E 1, 1,  (110)
F 1, , 1 (101)
G 1, 1, 1 (1 1 1)
G H I

 Do not need to learn the indices - just need to be aware of the

existence of quite a number of planes of close packing.
 Its the, number of & closeness of atoms packed on a plane, that
greatly influence the ductility, strength and hardness of metals.
FCC close-packed planes and directions of maximum packing
Closest packed plane is (111) plane
and has three <110> directions
( i.e. to the apexes of the plane).
Note convention in crystallography:
to denote planes (……) are used
and to denote directions <….> are used.

A z (111) plane What we would see if

we looked head on at
this area

<011>
B
<101>

y
<110> C
D
Closest packed atoms
are on diagonals of the
faces of the cube
 FCC – Packed Planes and Directions = slip systems
FCC has : x
4 off {111} planes in unit cell
these are the 4 diagonals of the cube.
and 3 off <110> directions per plane
z
O y
hence 12 potential ways in
which atoms can slide past one
another = 12 ‘slip systems’
BCC – Packed Planes and Directions = slip systems
z z

O y O y

(110) plane, <111> direction (110) plane, <111> direction

The BCC structure closest packed systems:

2 off {110} planes per unit cell
these are the 2 planes through the cube. hence only 4 slip systems
and 2 off <111> directions per plane of really close pack
Significance of Close Packed planes / directions

- Deformation in metals and alloys occurs by a process of slip

- Slip takes place on specific planes in specific directions:
These are the closest packed planes and directions.
The greater the numbers of planes of closest pack
= more readily atoms slip/slide
= more ductile metal.

Why not in ceramics ?

Structural Level 2: Crystal Structure
Hence there are a restricted number of crystal systems.
We can generalise behaviour for learning purposes that these
fall into either:

 FCC (face centred cubic): Soft, ductile, low melting point,

high electrical & thermal conductivity, low strength and low
modulus, e.g. Al, Cu. Why ?

 BCC (body centred cubic): Hard, brittle, high melting points,

low electrical & thermal conductivity, high strength and high
modulus, e.g. Fe, W. Why ?

 HCP (Hexagonal close packed): Most metals. Properties are

intermediate between FCC & BCC, e.g. Cr, Mo, Zn.

18
Crystal ‘defects’ and their contribution to
properties of materials
 Defects in Crystalline Solids

Real materials do not have the perfect crystal structures

previous described. They contain imperfections.

Three types of structural defects:

 Point defects – defects of size order ~ 1 atom volume defect.

Examples , impurity atom, vacancies.

 Linear defects– disturbances to the crystal structure situated

along a line of atoms. Example : Dislocations

 Surface or planar, (Two-dimensional,) defects – imperfections

associated with interfaces separating 2 crystals.
Examples : grain boundaries, stacking faults, interfaces.
 Point defects
• Point defects are defects that occur only at or around a
single lattice point.

• They are not extended in space in any dimension.

• Typically these defects involve at most a few extra or

missing atoms.

• Point defects in ionic crystals permit ion charge transport (

electric conduction) through the crystals leading to
electrochemical reactions and electrical conductivity.
 Point defect: Vacancies in Crystals
Vacancy defects are lattice sites which would be occupied in a perfect
crystal, but are vacant = the atom or ion is missing.

If a neighboring atom moves to occupy the vacant site, the vacancy moves in
the opposite direction i.e. into the site which used to be occupied by the
moving atom. Vacancy
The stability ( balance of charges) of the surrounding crystal structure
guarantees that neighbouring atoms will not simply collapse around the
vacancy.

Looking at diagram shows the vacancy can be moved & occupy any point in
the crystal, i.e. factorial 8 = a large disorder. Large disorder = higher
entropy = lower free energy.

Vacancies occur in metals and ceramics.

Vacancies are one reason why metals, as an example, have densities less than theoretical for the given
lattice packing ( BCC, FCC, HCP). [ Density also affected by presence of grain boundaries, stacking
faults].
Effects of vacancies:
 promote diffusion through materials,
 alter colour ( in ceramics i.e Ti O2 is pure white, Ti5 O9 is blue)
 promote electrical conductivity.
22
Point defects in Crystals
 Ionic crystals ( ceramics) – consist of two ions with
interpenetrating crystal lattices.

 Potential for at least two types of defect ( vacancy or interstitial) for each ion
type.
 An interstitial is something that is squeezed into a space that is available.
 NaCl as example: we can have a Na cation interstitial & vacancy,
and a Cl Anion interstitial and vacancy.

interstitial

vacancy

vacancy
23
 Schottky Defect: a Pair of Vacancies in Ionic Crystals
Ionic materials are electrically neutral, so must have equal number of +ve charge cations
and -ve charge anions.
Consequently, defects in ceramics do not occur alone, they are ‘paired.’

A cation vacancy with an anion ‘vacancy’ pair

is called a Schottky defect.

‘Charge’ of the vacancy is given by

the missing ion ‘charge ‘ notated on
the surrounding element.

(-ve)anion vacancy
Schottky defect in NaCl: = V Na-
V Na- & V Cl+
Useful application
(+ve) cation vacancy in semi / ionic
= V Cl+ conductors
24
Frenkel defect: An “interstitial + vacancy” pair in
Ionic Crystals
 A nearby pair of a vacancy and an
interstitial is often called a Frenkel defect
or Frenkel pair.

 This is caused when an cation moves into an

interstitial site and creates a cation vacancy.

Frenkel defect in AgBr:

V Ag- + Ag+interstitial
Frenkel defect = cation-vacancy
-ve
charge vacancy create by and a cation interstitial.
move of Ag + to interstitial site.
= still electrically neutral

+ve
charge interstitial create by
move of Ag + to interstitial site.

Vacancies find application in ‘ionic’ conductors = like the Ti5 O9 earlier

25
Point defect: Substitutional defect
Materials are never composed of 100% pure element.
Other elements, present as single atoms, in the crystal , these are classed as impurities.

The direct substitution of an atom of a lattice site in a crystal by an ‘impurity’ atom at a

regular atomic sites is called a substitutional defect.

The substituent atom can be bigger or smaller than the parent atom.
If there is an electron valance difference = we get conduction.

The deliberate addition of dopant atoms is the

basis of the semiconductor industry.

Silicon semiconductors:
silicon atoms are substituted by:

boron, aluminium or gallium = electron deficient

phosphorus, arsenic = an extra electron

26
 Linear ( line) defects: DISLOCATIONS
All metals and alloys contain some line type defects termed dislocations.
Dislocations are linear defects around which some of the
atoms of the crystal lattice are misaligned.

There are two basic types of dislocations:

 edge dislocation
 screw dislocation

An edge dislocation is shown. The dislocation line is

presented in blue.
Burgers vector b in black is a measure of the magnitude and
direction of the dislocation.

Introduced during processing:

 solidification
 during plastic deformation
 as a consequence of thermal stresses from rapid cooling.
Dislocations – allow metals to be malleable =
can be ‘Plastically’ Deformed
When small loads (stresses) are applied to metals
they deform, and they return to their original shape
when the load is released.
Slightly bending a strip of steel is an example
where the bonds are bent or stretched only a small
percentage. This is called elastic deformation and
involves temporary stretching or bending of bonds
between atoms.
[ see Elastic modulus or Youngs’ modulus]
When higher stresses are applied, permanent
(plastic) deformation occurs. For example, when
a paper clip is bent a large amount and then
released, it will remain bent.
Plastic deformation involves the breaking of bonds,
one at a time, by the motion of dislocations.
Dislocations move easily along slip planes in
metals. So the greater the number of slip planes
(i.e FCC crystal structure) the more likely the metal
is to be ductile and soft. This explains why some
metals are ductile, while others are not.

So, permanent deformation of metal = via motion of dislocations.

Linear defects : dislocations
Occurrence of dislocations can be as low as 103/mm2 – for carefully solidified metal
crystals, to as high as 1010/mm2 for heavily deformed metals.

Heat treating a heavily deformed metal can reduce the number of dislocations to
105/mm2. Ceramics have fewer dislocations ~ 103/mm2 .

For well controlled systems i.e. silicon chips the number is only ~ <1 /mm2 .

Normal lattice

Edge dislocation

Screw dislocation

Dislocations = promote ‘plastic’ deformation in metals

Plane ( surface) Defects
Plane defects occur when there is a 2-dimensional surface that disrupts the
crystal lattice.

The surface of a crystal is an obvious imperfection.

A surface defect occurs along the grain boundaries.

A grain is a single crystal. If many seeds are formed when a sample starts to
crystallize, then many crystals are formed at the same time. Each crystal grows
until they meet at the boundaries. Properties along these boundaries are different
from the grains.

Atoms exposed on a surface are different ( more reactive) from those deep in the
crystals = sites of high energy ( exposed electron orbitals ) = electrochemical
activity = potential site of corrosion in metals.

When a solid is used as a catalyst, the catalytic activity depends very much on the
surface area per unit mass of these exposed atoms on the surface of the sample.