MATERIALS SCIENCE 124

Mrs J.T. Kurasha

 Atomic and Ionic Arrangements
Objectives
❖ To understand the way in which atoms or ions are
arranged in materials.
❖Distinguish the different crystal structures &
systems.
❖Classify materials based on atomic/ionic
arrangements.
❖Calculate unit cell volumes & the theoretical density
of materials.
❖Understand allotropy & polymorphism & its
significance in materials.
 Thinking points

1. Does atomic arrangement in a material have any

effect on its properties?
2. How does the three dimensional atomic arrangement
in metals, e.g. copper, differ from the atomic
arrangement in ceramics, e.g. ordinary glass?
3. If you were to pack a cubic box with uniform-sized
spheres, what is the maximum packing possible?
4. Why does lithium have more atoms per unit volume
than lead?
 Introduction
• Arrangement of atoms & ions determine the
microstructure and properties of materials.

• Solid materials may be classified according to the

regularity with which atoms & ions are spatially
arranged.

• Four types of atomic/ionic arrangements may

be distinguished in different states of matter.
MATERIAL TYPE ATOMIC/IONIC
ARRANGEMENT
Monoatomic Gases No order
Amorphous Materials Short range order only
Liquid Crystals Short Range Order with small
volumes of Long Range Order
Crystalline Materials Short and Long Range Order
PROPERTIES EXAMPLES
Randomly fill given space Argon gas
Plasma in fluorescent tube light
Order of atoms extend only to the atom’s Amorphous Si, Silicate glasses,
nearest neighbours, with no order between plastics, steam, ceramics
adjacent molecules. Usually formed when the
kinetics of the formation process does not allow
formation of periodic arrangements
Polymeric materials that behave as amorphous Liquid Crystal Display (LCD)
materials (liquid-like) in one state, but some polymers
polymer molecules align and form small
crystalline regions when an external stimulus eg.
heat , electricity is applied
Single Crystal; Atoms or ions arranged in regular Si, GaAs, Lithium niobate (LiNbO3)
repetitive, 3-dimensional pattern, forming one Metals and alloys
large crystal.
Polycrystalline: consist of many crystals
LIQUID CRYSTAL???

Liquid Crystals
➢ Polymeric materials having a special type of order. Flows like a liquid, but has
some degree of ordering in the arrangement of its molecules.
➢ Behave as amorphous materials (liquid-like) in one state, and when an external
stimulus e.g. electric field or a temperature change is applied, the molecules
undergo alignment and form small crystalline regions.
➢ Used in a lot of commercial applications e.g liquid crystal display (LCD)
technology .
➢ If you were to touch the stuff, it would feel gooey and soapy--in fact, the slimy
mess you find at the bottom of a soap dish is a genuine liquid crystal, not much
different from the material in a laptop screen.

What makes a liquid crystal different from ordinary liquids is the shape of
its molecules: they're long and thin, like fresh chips. Even if the molecules'
positions are random, their orientations can be aligned with one another in a
regular pattern--and that's what creates the ordered structure of a liquid
crystal.
( Courtesy: Einsten’s Legacy)
http://www.iq.usp.br/mralcant/AboutLC.html

Fig 3.1 Images of Liquid Crystals

 Single and Polycrystals

Fig 3.4 Micrograph of a polycrystalline

Fig. 3.3 showing a
metal; grain boundaries evidenced
single Si crystal
by acid etching
 Crystal Structures
• A crystal structure is a unique arrangement of atoms or
molecules in a crystalline liquid or solid.

• The crystal structure consists of a pattern; set of atoms

arranged in a particular way and a lattice exhibiting
long-range order and symmetry.

• The patterns are located upon the lattice which is an

array of points repeating periodically in three
dimensions.
• These points can be thought of as forming identical
tiny boxes called unit cells which fill the lattice space.

• The lengths of the edges of a unit cell and the angles

between them are called the Lattice parameters.

• The crystal structure & symmetry of a material play a

role in determining many of its physical properties,
e.g.
▪Cleavage
▪Optical transparency
 The unit cell
• The crystal structure of a material i.e arrangement of atoms in
the structure can be described in terms of its unit cell.
• It defines the crystal structure by means of its geometry & the
positions of atoms within.
• The collection of unit cells arranged in a periodic 3-D array of
points coinciding with atom positions or sphere centres is
referred to as a lattice.
Unit cell
Lattice parameters (edge lengths & angles between them).
The positions of atoms inside the unit cell are described by the set
of atomic positions (x1, y1 , z1) as measured from a lattice point.
Unit cell geometry defined wholly by
six ‘lattice’ parameters of a crystal
structure; lengths a, b & c and the
interaxial angles α, β, and γ.
• There are seven different combinations of these lattice
parameters, each of which represents a distinct crystal
system. The 7 crystal systems have the following
characteristics.
Table 3.2 Crystal structures & their associated lattice parameters
Crystal Axial Relationships Interaxial Angles
system/structure
Cubic a=b=c α = β= γ =90°
Hexagonal a=b≠c α = β=90° γ =120°
Tetragonal a=b≠c α = β= γ =90°
Rhombohedral/Trig a=b=c α = β= γ ≠90°
onal
Orthorhombic a≠b≠c α = β= γ =90°
Monoclinic a≠b≠c α = γ= 90° ≠ β

Triclinic a≠b≠c α ≠ β≠ γ ≠90°

The fourteen
Bravais
Lattices
Crystal structures in metals, alloys and
ionic solids
• In the description of crystalline structures, atoms/ions are
thought of as being solid spheres having well defined
diameters.
• This is called the atomic hard-sphere model in
which spheres representing nearest-neighbour atoms touch
one another. Each sphere represents an ion core/atom.
•Atomic bonding in metal crystalline structures is metallic and
thus non directional. As a consequence there are minimal
restrictions governing the number & position of nearest –
neighbor atoms; leading to a very large no. of nearest atoms
and very dense atomic packing.
There are four relatively simple crystal structures
commonly found in metals and alloys, and ionic
solid. These are

▪ Face-centred cubic (FCC)

▪Body-centred cubic (BCC)

▪Hexagonal close-packed (HCP)

▪ Simple cubic (SC) (Ionic solids)

 Table 3.1 Atomic Radii & Crystal structures of selected metals

Metal Crystal Structure Atomic Radius

(nm)
Aluminium FCC 0.1431
Cadmium HCP 0.1490
Chromium BCC 0.1249
Cobalt HCP 0.1253
Copper FCC 0.1278
Gold FCC 0.1442
Iron (α) BCC 0.1241
Lead FCC 0.1750
Molybdenum BCC 0.1363
Nickel FCC 0.1246
Platinum FCC 0.1387
Silver FCC 0.1445

N.B To convert nanometres to angstrom units; multiply the nanometre value by 10.
 Face centred Cubic (FCC)

a =(2√2)r vol=16√2r3
where a= cell length and r=atomic radius
In the FCC structure, lattice points are at the corners and faces of
the cube, thus the number of atoms per unit cell
number of atoms 1 1
= ( 8corners ) + ( 6 faces ) = 4
corner 8 2
FCC cont’d
Corner Atoms Are Shared Amongst
8 Unit Cells
 Body centred cubic (BCC)

4
a= r
3
3
 4 
The volume of a BCC unit cell =  r
 3 
For the BCC structure, lattice points are at the corners and the
centre of the cube, thus the number of atoms per unit cell
number of atoms 1
= ( 8corners ) + (1centre )(1) = 2
corner 8
BCC cont’d
 Hexagonal close packed

Number of atoms = 2 (faces) x 6(corners) (1/6) + 2(faces)(1/2) +3 = 6

a = 2r
HCP cont’d
 Simple Cubic (SC)

Number of atoms per unit cell = 8(corners)x (1/8) = 1

a = 2r
Volume of unit cell = 8r3
Simple cubic cont’d
 Coordination number
• This refers to the number of atoms touching a given
atom, or the number of nearest neighbors for the given
atom. This determines how tightly and efficiently atoms
are packed together.
• In a simple cubic (SC) structure, each atom has a
coordination number of 6.
• In a BCC structure each atom has 8 nearest neighbors.
• In FCC and HCP structure the co-ordination number
is 12. This is the maximum.
 Cont’d

https://www.slideshare.net/SachinHariprasad/crystal-structures-40047329
 Atomic packing factor (APF)
• APF- this is the fraction of space within the unit cell, which
is occupied by atoms. It is assumed that the atoms are close
packed hard spheres.
 Cont’d
• For SC, APF is 0.52. This implies that 52% of the
unit cell volume is occupied by atoms, while 48%
is empty space within the unit cell.

• For BCC, APF is 0.68.

• For FCC, APF is 0.74.

• For HCP, APF is also 0.74.

 Theoretical Density
• A knowledge of the crystal structure of a metallic solid
enables us to compute its theoretical density.
• The mass per unit volume of material can be calculated
using crystal structure properties, i.e
( No. of atoms per cell ) ( atomic mass ) nA
Density,  = =
(Volume of unit cell )( Avagadro ' s Number ) Vc N A

Where n = number of atoms associated with each cell

A = atomic weight
Vc= volume of the unit cell
NA= Avogadro’s number (6.023 ×1023
atoms/mol)
 Example
1. Iron has a BCC structure with a lattice parameter of
a= 0.2886nm. It has an atomic mass of 55.847g/mol.
Calculate its theoretical density and compare your answer with its measured density
(7.870g/cm3 ).
 Self Assessment activity 1

1. Iron has a BCC structure with a lattice parameter of a= 0.2886nm. Calculate

the atomic radius of iron.

2. Determine the lattice parameters for the following metals:

(a) Aluminium (FCC, r = 0.1431nm)
(b) Cobalt (HCP, r = 0.1253nm)
(c) Molybdenum. (BCC, r = 0.1363nm)

3. Both copper and aluminium have an FCC structure with atomic radii of
0.1278nm and 0.1431nm respectively. The atomic mass of copper is 63.55
g/mol, while that for aluminium is 26.98 g/mol.
(a) Calculate the lattice parameters of copper and aluminium respectively.
(b) Calculate the theoretical densities of copper and aluminium respectively
and compare them with their measured densities of 8.96g/mol and 2.7
g/mol.
(c) What similarities and differences do copper and aluminium have in terms
of properties.
(a) Why are the densities of copper and aluminium very different?
 Allotropy and Polymorphism
• Materials which exhibit more than one structure
depending on conditions such as temperature and
pressure are called polymorphic.

• This phenomena is termed allotropy when it is

exhibited in elemental solids.

• For carbon, C graphite is the stable allotrope at ambient

conditions, with diamond being formed at extremely
high pressures.
• Several ceramic materials eg. Silica SiO2 and zirconia ZrO2
are polymorphic. The stable form of zirconia at room
temperature is monoclinic. As the temperature is increased
Zirconia transforms to a tetragonal structure at 1170°C and then
to the cubic form at 2370°C before melting at 2680°C.

• Fe has a BCC structure at room temperature which changes

to a FCC structure at 912°C. These polymorphic changes often
Result in changes of density and other physical properties and
this forms the basis of heat treatment of steels and other alloys.

• Zirconia is often stabilized in the cubic phase by doping with

Yttria (Y2O3) or CaO so that it does not transform & fracture at
different temperatures.
 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.

• This is made possible by determining crystallographic

directions and planes.

• Significance??
• 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
depending on orientation.

• For example, the magnetic properties of magnetic

materials depend on crystallographic directions. In the
case of Fe, magnetization is easiest in the [100]
direction compared to other directions.
 Miller indices
• In the study of crystalline materials it is often
important to specify a particular point in the unit
cell, a crystallographic direction or a
crystallographic plane of atoms.
• Miller indices provide a conventional method to
specify planes and directions in a crystal.
• We can locate certain points, e.g. positions of
atoms, by constructing a right-handed coordinate
system.
• Distance is then measured in terms of the lattice
parameters moved along the x, y and z axes.
Right-handed coordinate system
 Direction indices
• In cubic systems, they are specified by three
miller indices [xyz].
• Consider a cartesian coordinate system with
axes parallel to the edges of the unit cell of a
cubic crystal.
• The unit measurement along all the three axes
is a, the lattice parameter.
 Rules for finding miller indices for
directions
1. Draw a vector parallel to the direction whose indices
are desired. Determine the coordinates of two points
that lie on the direction.
2. Subtract the coordinates of the ‘tail’ point from the
coordinates of the ‘head’ point to obtain the number
of lattice parameters travelled in the direction of
each axis of the coordinate system.
3. Reduce the results obtained from subtraction to
lowest integers.
4. Enclose the numbers in square brackets [ ]. If a
negative integer is obtained, represent the negative
sign with a bar over the number.
 Example

https://www.slideshare.net/AbeerKamal1/miller-indecies
 Self Assessment Activity 2
a b c

d e f

Determine the Miller Indices of directions shown above.

 Miller indices for planes
• The orientations of the plane are represented in
terms of a right handed three axes coordinate
system with the unit cell forming the basis.

• In all the crystal systems, except the hexagonal

crystal system, the crystallographic planes are
specified by three Miller indices as (hkl).

• Any two planes which are parallel to each other are

equivalent and have identical indices.
 Rules for determining the Miller
indices for plane
• There is a slight change in the rules when finding Miller
indices for planes in crystal lattices. The rules are:
1. Find the intercepts that the planes make with
coordinate axes. Record the intercepts in x,y,z order.
2. Take the reciprocals of these intercepts.
3. Multiply the intercepts by the smallest overall constant
that yields whole numbers.
4. Enclose the numbers in normal brackets ( ). If a negative
integer is obtained, represent the negative sign with a
bar over the number.
 Example

Determine the Miller indices for the plane shown

below.
 Self Assessment Activity 3
1. Determine the miller indices of the following planes.

2. Sketch the planes represented by the following Miller indices:

(a) (111)
(b) (122)
(c) (101)
 Isotropy and anisotropy
• Anisotropy – When the physical properties of a material depend on
the direction along which they are measured.

• The physical properties of single crystals of some substances

depend on the crystallographic direction in which the
measurements are taken e.g the elastic modulus, refractive index,
and the electrical conductivity may have different values in the
[100] and [111] directions.

• Isotropy – When the properties of material are independent of

direction of measurement.

• Consider a BCC crystal of iron, which has the three most important
directions shown:
• The directions are different because the spacings of atoms
along the three direction are different, i.e. a, √2a, and
√(3/2a), respectively.

• The physical properties measured along these directions

are therefore different.

The three most important directions in a BCC crystal

 Video Links
• https://namibiaust.sharepoint.com/sites/MaterialsScie
nce124MLS521S/Shared%20Documents/General/Recor
dings/MLS521S%20Lecture-%20Crystal%20Structures-
20201103_083242-Meeting%20Recording.mp4?web=1
• https://namibiaust.sharepoint.com/sites/MaterialsScie
nce124MLS521S/Shared%20Documents/General/Recor
dings/MLS521S%20Lecture-%20Unit%20Cells-
20201104_150413-Meeting%20Recording.mp4?web=1
• https://namibiaust.sharepoint.com/sites/MaterialsScie
nce124MLS521S/Shared%20Documents/General/Recor
dings/MLS521S%20Lecture-Unit%20Cells-
20201105_083531-Meeting%20Recording.mp4?web=1
 References
1. Callister, W. D. Jr. & Rethwisch, D. G. (2011). Materials Science
and Engineering – An introduction. 9th Edition. Asia: John Wiley &
Sons.
2. Askeland, D. R. & Fulay, P. P. & Wright, W. J. (2006). The Science
and Engineering of Materials. 6th Edition. Canada: Global
Engineering.
3. Shackleford, J.F. Introduction to Materials Science for Engineers
(1996), S.I Edition. Prentice-Hall, New Jersey.
4. http://www.iq.usp.br/mralcant/AboutLC.html
5. https://www.slideshare.net/SachinHariprasad/crystal-
structures-40047329
6. https://www.slideshare.net/AbeerKamal1/miller-indecies.