Crystal Structure and Analysis

by

Dr. Abdul Faheem Khan

Department of Materials Engineering,

Institute of Space Technology, Islamabad
Textbooks
1. “Introduction to Materials Science for
Engineering” 6th Edition, James F. Shackelford
and Madanapalli K. Muralidhara

2.“Principals of Materials Science and Engineering”

3rd Edition, William F. Smith

3.“Structure and Bonding in Crystalline Solids” 1st

Edition, G.S. Rohrer
Assessment or Evaluation
Quizzes 10%
Assignments 05%
Presentations 05%
OHT Exam 30%
Final Exam 50%
Project Nil
Total 100%
Module/Chapter Topic Week / Lecture

I The structure of the atoms, Types of atomic and molecular 1

bonds, Coordination number, Numerical problems

II Unit Cell, Space lattice, Bravias lattices, Principal metallic 2-3

crystal structures, Numerical problems, Directions in cubic
unit cells.
III Miller indices in cubic and hexagonal unit cell, Numerical 4
problems.
IV Volume density, Planar atomic density, Linear atomic 5
density and related numerical problems
V Brief introduction to reciprocal lattice, Symmetry in 6-7
crystal structures,
VI X-ray diffraction, Numerical problems 8
VII Crystal defects, Solid solution, point defects, Linear defects 9-10
(dislocations), planar defects, Nanocrystalline solids

VIII Diffusion, thermally activated processes, thermal 11

production of point defects, point defects and solid state
diffusion, numerical problems
IX Steady state diffusion, alternate diffusion paths, numerical 12
problems
X Solidification of metals, Homogeneous nucleation, 13
Heterogeneous nucleation, numerical problems
XI Solidification of single crystal, Metallic solid solutions 14

XII Optical Microscopy, Scanning electron microscopy, 15

Transmission electron microscopy
Final Exam 16
PLO2-Problem Analysis
An ability to identify, formulate, research literature and analyse complex
engineering problems reaching substantiated conclusions using first principles of
mathematics, natural sciences and engineering sciences.

PLO2-C2 (Comprehension)

PLO4-Investigation
An ability to investigate complex engineering problems in a methodical way
including literature survey, design and conduct of experiments, analysis and
interpretation of experimental data, and synthesis of information to derive valid
conclusions.

PLO2-C4 (Analysis)
 Space Lattices
 Crystal Structures
 Symmetry, Point Groups and Space Groups
 Crystal = Lattice + Motif

Motif or basis:
an atom or a group of atoms associated with each lattice point
 Space Lattice

An array of points such that every point has identical

surroundings

 In Euclidean space  infinite array

 We can have 1D, 2D or 3D arrays (lattices)

or

Translationally periodic arrangement of points in space is called a lattice

 A 2D lattice
                

                

                

                

                

                

                

                

                 

b 
               

a
 Lattice Crystal

Translationally periodic Translationally periodic

arrangement of points arrangement of motifs

Crystal = Lattice + Motif

Lattice  the underlying periodicity of the crystal
Basis  atom or group of atoms associated with each lattice points

Lattice  how to repeat

Motif  what to repeat
Lattice

Motif
+ 
 Crystal

      
      
      
=       
      
      
      
      
 Cells

Instead of drawing the whole structure I can draw a representative part

and specify the repetition pattern

 A cell is a finite representation of the infinite lattice

 A cell is a parallelogram (2D) or a parallelopiped (3D) with lattice
points at their corners.
 If the lattice points are only at the corners, the cell is primitive.
 If there are lattice points in the cell other than the corners, the cell
is nonprimitive.
 Nonprimitive
cell

Primitive
cell

Primitive
cell

Symmetry of the Lattice or the crystal is not altered by our choice of unit cell!!
Unit Cell: a convenient unit of the space lattice or The unit cell is a tiny box
containing one or more atoms, a spatial arrangement of atoms or an array of
points repeating periodically in three dimensions. The points can be thought of
as forming identical tiny boxes, called unit cells.
The positions of one kind of atoms of ions in inorganic structures
correspond approximately to those of equal spheres in a close-packing
with the other atoms distributed among the voids. All such structures
will be referred to as close-packed structures though they may not be
ideally close-packed.
Voids in a close-packing
In case of close-packed inorganic compounds, the larger atoms or ions occupy
positions approximately corresponding to those of equal spheres in a close- packing
while the smaller atoms are distributed among the voids. Three- dimensional close-
packings of spheres have two kinds of voids:

(i) If the triangular void in a close-packed layer has a sphere directly over it, there
results a void with four spheres around it. Such a void is called a tetrahedral void
since the four spheres surrounding it are arranged on the corners of a regular
tetrahedron. If R denotes the radius of the four spheres surrounding a tetrahedral
void, the radius of the spheres that would just fit into this void is given by 0.225 R.
(ii) If a triangular void pointing up in one close-packed layer is covered by a triangular
void pointing down in the adjacent layer, then a void surrounded by six spheres
results. Such a void is called an octahedral void since the six spheres surrounding it
lie at the corners of a regular octahedron. The radius of the sphere that would just fit
into an octahedral void in a close-packing is given by 0.414 R.
Bravais lattices and crystal systems
 e.g., the cube side of the unit cell of BBC iron is equal to 0.287 nm

No. of unit cells in 1 mm (suppose) = 1 x 10-3 m / 0.287 x 10-9 m = 3.48 x 106

Simple cubic
Body-centered Cubic (BCC) unit cell
 Relation bet. Length
of side of a cube ‘a’
and radius R is

√3a = 4R
 Q. Niobium at 20 C is BCC and has an atomic radius of 0.143 nm. Calculate its
lattice constant “a”.

Atomic packing factor

AFP = (vol. of the atoms in the unit cell) / (vol. of the unit cell)

Face-Centered Cubic (FCC) unit

cell Co-ordination No.

Relation of lattice parameter “a” and radius “R”

for FCC
√2a = 4R
Q. Calculate the atomic pacing factor of FCC.
Q. Calculate the density of FCC Cu in g/cm3. Radius is 0.128 nm. Mass of Cu
Is 63.54 g.

Q. Calculate the density of BCC iron in g/cm3. Radius is 0.220 nm. Mass of iron
Is 55.84.
Q. Gold is FCC and has a lattice constant of 0.40 nm. Calculate a value for
the atomic radius of its atoms.
Hexagonal closed pack structure

c/a ratio = 1.633

Comparison of HCP, CCP and BBC structure
BCT (body centered tetragonal)

a=c
 Miller Indices
Definition
• Miller indices are used to specify directions and
planes.
• These directions and planes could be in lattices or in
crystals.
• The number of indices will match with the dimension
of the lattice or the crystal.
• E.g. in 1D there will be 1 index and 2D there will be
two indices etc
Notation Summary

• (h,k,l) represents a point – note the exclusive

use of commas

• Negative numbers/directions are denoted with

a bar on top of the number

• [hkl] represents a direction

• <hkl> represents a family of directions

• (hkl) represents a plane

• {hkl} represents a family of planes
Miller Indices for Directions

• A vector r passing from the origin to a lattice point

can be written as: r = r1 a + r2 b + r3 c
where, a, b, c → basic vectors and
miller indices → (r1 r2 r3 )

• Fractions in (r1 r2 r3 ) are eliminated by multiplying

all components by their common denominator.

• [e.g. (1, ¾ ,½ ) will be expressed as (432)]

Direction indices are the vector components of the vector and reduces to smallest
integer, closed in a square bracket.

e.g, [100], [010], [001], [111], [210], [-1-10], [-110], [-121], [1-33], 0-12], [-122], [-1-
11], [-103], etc.
Miller Indices for Planes:

Procedure 1. Identify the plane intercepts on the x, y and

z-axes.

2. Specify intercepts in fractional coordinates.

3. Take the reciprocals of the fractional intercepts.

Miller Indices

(100), (010), (001), (111), (110),(101), (1-10), (221)

Family of Directions
Index Members in family for cubic lattice

<100> [100],[-100],[010],[0-10],[001],[00-1]
<110> [110],[-110],[1-10],[-1-10],[101],[-101],[10-1],[-10-1],[011],[0-11],[01-1],[0-1-
1]

<111> do it yourself..
Importance of Miller Indices

• In Materials Science it is important to have a notation

system for atomic planes since these planes influence
• Optical properties
• Reactivity
• Surface tension
• Dislocations
dhkl = a / (h2+k2+l2)1/2
 Volume density

v = mas(unit cell)/ vol. (unit cell)

Q. Calculate the value of vol. density for the FCC platinum from its lattice constant
of 0.39239 nm and its mass 195.09 g/mol?

Q. Copper has an atomic radius of 0.128 nm, an FCC crystal structure. Assuming the atoms to be
hard spheres which touch each other along the face diagonals of the FCC unit cell and an atomic
mass of Cu of 63.5 g/mol. Calcualte its theoretical value and compare the answer with its
measured density.

Given:

Atomic radius = 0.128 nm (1.28 Ǻ)

Atomic mass = 63.5 g/mole

Solution: In the FCC unit cell, there are four atoms per unit cell. Each Cu atom has
a mass of (63.54g/mol)/(6.02x1023 atoms/mol), so the mass of Cu atoms in FCC unit
cell

Unit cell volume = 16 R3√2

4 63.5g/mole
R
ρ= Atomic Radius  8
[16 2 (1.28 10 cm)3 /unit cell](6.023 10 23 )atoms

= 8.89 g/cm3

Close to 8.94 g/cm3 in the literature

Planar density

p = equiv. no. of atoms whose centers are intersected by selected area / selected area

Q. Calculate the planar density of atom in the (110) & (111) plane of
a)Bcc tungsten (R = 0.137 nm)
b)Fcc aluminium (R = 0.404 nm)

Linear density

p = no. of atomic diameter intersected / selected area

Q. Calculate the linear atomic density in the [110] direction in the copper crystal
Lattice in atoms per mm. Copper is FCC and has a lattice constant of 0.361 nm.
 Linear and Planar Atomic Densities
Linear Density:
Directional equivalency is related to the atomic linear density in the
sense that equivalent directions have identical linear densities.
The direction vector is positioned so as to pass through atom centers.
The fraction of line length intersected by these atoms is equal to the
linear density.

Planar Density:
Crystallographic planes that are equivalent have the same atomic planar
density. The plane of interest is positioned so as to pass through atom
centers.
Planar density is the fraction of total crystallographic plane area that is
occupied by atoms.

Linear and planar densities are one- and two-dimensional

analogs of the atomic packing factor.
 FCC: Linear Density
Number of atoms
• Linear Density of Atoms  LD = Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a 2
LD   3.5 nm 1
2a
Calculate the linear density for the length
following directions in terms of R:
a. [100] ----- No. of atoms, 1 ; length ‘a’
54
b. [111] ----- No. of atoms, 1 ; length
3a
P 3.53 (a): Linear Density for BCC
R
2R
[111]
R

3a = 4R
Calculate the linear density for the
following directions in terms of R:
a. [100] ----- No. of atoms, 1, length ‘a’
b. [110] ----- No. of atoms, 1, length 2a’
c. [111] ----- No. of atoms, 2, length 3a
Q. Calculate the linear atomic density in atoms per millimeter for the following
directions in FCC iridium, which has a lattice constant of 0.38389 nm:
(a) [100], (b) [110], (c) [111].

Q. Calculate the linear atomic density in atoms per millimeter for the following
directions in BCC vanadium, which has a lattice constant of 0.3039 nm: (a)
[100], (b) [110], (c) [111].