The Chemistry of Engineering Materials

Basic Concepts of

Crystal Structure
Crystal structure
In crystallography, crystal structure is a description of the
ordered arrangement of atoms, ions or molecules in a crystalline
material.
Crystallography is the experimental science of determining the
arrangement of atoms in crystalline solids

A crystalline solid: Brighter atoms are

atomic resolution image strontium and darker
of strontium titanate. ones are titanium.

Strontium titanate is an oxide of strontium and

titanium with the chemical formula SrTiO3.
An atom is the smallest An illustration
constituent unit of ordinary of the helium
matter that has the atom, depicting
properties of a chemical the nucleus
element. Every solid, liquid, (pink) and the
electron cloud
gas, and plasma is composed distribution
of neutral or ionized atoms. (black).

An ion is an atom or molecule

that has a non-zero net electrical
charge (its total number of
electrons is not equal to its total
number of protons).
A cation is a
positively-charged
ion, while an anion
is negatively
charged.

A molecule is an
electrically neutral
group of two or
more atoms held
together by chemical
bonds.
A crystal or crystalline solid is a
solid material whose constituents
(such as atoms, molecules, or ions)
are arranged in a highly ordered
microscopic structure, forming a
crystal lattice that extends in all
directions.

Ordered structures occur from the

intrinsic nature of the constituent
particles to form symmetric
patterns that repeat along the
principal directions of three-
dimensional space in matter. A representation of a three-dimensional Cartesian coordinate
system with the x-axis pointing towards the observer.
 The smallest group of particles in the material that constitutes the
repeating pattern is the unit cell of the structure.

The unit cell completely

defines the symmetry
and structure of the
entire crystal lattice,
which is built up by
repetitive translation of
the unit cell along its
principal axes.
The repeating patterns
are said to be located at
the points of the Bravais
lattice.
Coordination number = 6

3 1
2 4

6 1/8 atom at each of 8 corners

1
Consider this atom. 𝐴𝑡𝑜𝑚𝑠 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 = × 8 = 1
8
 Why is the Packing Efficiency 52%?

𝑟
𝑙 = 2𝑟

𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑏𝑦 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

P𝑎𝑐𝑘𝑖𝑛𝑔 𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = × 100%
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
1 4 3 1 4 3
𝜋𝑟 × 8 𝜋𝑟 × 8
= 8 3 × 100% = 8 3 × 100%
𝑙 3 2𝑟 3

1 4 3
𝜋𝑟 × 8
= 8 3 × 100% = 52.36% ≈ 52%
2𝑟 3
 10−12 𝑚 1 𝑐𝑚
𝑟 = 125 𝑝𝑚 × × −2
1 𝑝𝑚 10 𝑚

𝑟 = 1.25 × 10−8 𝑐𝑚

For body-centered cubic unit cell:

4𝑟
𝑙=
3
 For the volume, 𝑉:
𝑉 = 𝑙3
3
4𝑟
𝑉=
3
−8 3
4 1.25 × 10 𝑐𝑚
𝑉=
3
𝑉 = 2.4056 × 10−23 𝑐𝑚3
For the mass, 𝑚:
1 𝑚𝑜𝑙𝑒 𝐶𝑟 51.996 𝑔
𝑚 = 2 𝑎𝑡𝑜𝑚𝑠 × 23
×
6.023 × 10 1 𝑚𝑜𝑙𝑒 𝐶𝑟
2 𝑎𝑡𝑜𝑚𝑠
𝑚 = 1.72687 × 10−22 𝑔
 For the density, 𝜌:
𝑚
𝜌=
𝑉
1.72687 × 10−22 𝑔
𝜌=
2.4056 × 10−23 𝑐𝑚3

𝑔
𝜌 = 7.18 Why consider three significant figures?
𝑐𝑚3

From the problem:

 Relating Density to Crystal Structure:

𝑛𝐴
ρ=
𝑉𝑐𝑁

Where: ρ – the density of crystals

n – the number of atoms in a unit cell
A – atomic weight
Vc – Volume of one unit cell
N – Avogadro’s Number
Additional problems:
1. Calculate the radius of Iridium (Ir) atom given that it is a FCC structure,
density of 22.4g/cm3 and atomic weight of 192.2g/mol.
2. Calculate the radius of Vanadium (V) atom given that it is a BCC structure,
density of 5.96g/cm3 and atomic weight of 50.9g/mol.
3. A hypothetical metal has a simple cubic crystal structure. If its atomic
weight is 70.6g/mol and the atomic radius is 0.128nm, compute its density.
4. Zirconium has an HCP crystal structure and a density of 6.51g/cm3. What
is the volume of its unit cell in cubic meters?
5. Rhodium has an atomic radius of 0.1345nm and a density of 12.41g/cm3.
Determine whether it has an FCC or BCC crystal structure.
6. Titanium has an HCP unit cell which has a ratio of lattice parameter c/a=1.58.
If the radius of the Ti is 0.1442nm, (a) Determine the unit cell volume and
(b) calculate the density.
DEFECTS IN CRYSTALS

- Crystal defect, imperfection in the

regular geometrical arrangement of the
atoms in a crystalline solid. These
imperfections result from deformation of
the solid, rapid cooling from high
temperature, or high-energy radiation
(X- rays or neutrons) striking the solid.
Located at single points, along lines, or on
whole surfaces in the solid, these defects
influence its mechanical, electrical, and
optical behaviour.
 IDENTIFICATION OF A CRYSTAL USING
WEISS AND MILLER INDICES
Weiss index
- The Weiss parameters, introduced by Christian Samuel Weiss in 1817,
are the ancestors of the Miller indices. They give an approximate
indication of a face orientation with respect to the crystallographic axes
and were used as a symbol for the face.

Miller Indices
- are a symbolic vector representation for the orientation of an
atomic plane in a crystal lattice and are defined as the reciprocals of
the fractional intercepts which the plane makes with the
crystallographic axes.
Example: Determine the Weiss and Miller index of the plane ℎ𝑘𝑙
𝑧
𝑎 − 𝑢𝑛𝑖𝑡 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒
b − 𝑢𝑛𝑖𝑡 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒
𝑐 − 𝑢𝑛𝑖𝑡 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒
plane ℎ𝑘𝑙
𝑏

𝑦
2𝑎 ℎ = 𝑥 − 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 = 3

3𝑐 k = 𝑦 − 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 = 2
Weiss Index
𝑥
l = 𝑧 − 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 =1
 Multiply the LCD.

Weiss Index Reciprocal Clear Fraction

3 1/3 2
2 1/2 3
1 1/1 6

𝑀𝑖𝑙𝑙𝑒𝑟 𝐼𝑛𝑑𝑒𝑥
Therefore:
𝑊𝑒𝑖𝑠𝑠 𝐼𝑛𝑑𝑒𝑥: (321)

𝑀𝑖𝑙𝑙𝑒𝑟 𝐼𝑛𝑑𝑒𝑥: (236)

 z Weiss (∞ ½ 2)
Reciprocal (0 2 ½)
Miller (0 4 2)
Weiss is the intercept.
Get the reciprocal of
Weiss to determine
the Miller and make
y Miller indices as
whole numbers.
You can have a
fraction on Weiss but
not on Miller indices.
x
 Weiss (∞ ∞ 2)
Reciprocal (0 0 ½)
x Miller (0 0 2)

.
03. Given: Topaz, Al2(PO4)2SiO4
yz

Determine the
y
Weiss and miller
index of topaz.

x
Shortest distance (perpendicular)
from the origin to the plane, dhkl

𝑎
𝑑ℎ𝑘𝑙 =
ℎ2 + 𝑘 2 + 𝑙 2

𝑤ℎ𝑒𝑟𝑒

a − edge length of cubic

ℎ, 𝑘, 𝑙 − 𝑑𝑖𝑔𝑖𝑡𝑠 𝑖𝑛 𝑡ℎ𝑒 𝑀𝑖𝑙𝑙𝑒𝑟 𝑖𝑛𝑑𝑒𝑥

04. 𝑆𝑜𝑙𝑣𝑒 𝑡ℎ𝑒 𝑝𝑒𝑟𝑝𝑒𝑛𝑑𝑖𝑐𝑢𝑙𝑎𝑟 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 0 𝑡𝑜 𝑝𝑙𝑎𝑛𝑒𝑠:
a. 200
b. 400
c. 600
for a 𝑐𝑢𝑏𝑖𝑐 𝑐𝑟𝑦𝑠𝑡𝑎𝑙 𝑤𝑖𝑡ℎ 𝑒𝑑𝑔𝑒 𝑙𝑒𝑛𝑔𝑡ℎ = 2 𝐴0 .

04 𝐷𝑒𝑡𝑒𝑟𝑚𝑖𝑛𝑒 𝑡ℎ𝑒 𝑠ℎ𝑜𝑟𝑡𝑒𝑠𝑡 𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑓𝑟𝑜𝑚 0 𝑡𝑜 𝑝𝑙𝑎𝑛𝑒𝑠:

a. 114
b. 314
c. 121
𝑜𝑓 𝑎 𝑐𝑢𝑏𝑖𝑐 𝑐𝑟𝑦𝑠𝑡𝑎𝑙 𝑤𝑖𝑡ℎ 𝑒𝑑𝑔𝑒 𝑙𝑒𝑛𝑔𝑡ℎ = 3 𝐴0 .
 𝑎
𝑑ℎ𝑘𝑙 =
ℎ2 + 𝑘 2 + 𝑙 2
𝑤ℎ𝑒𝑟𝑒
a − edge length of cubic
ℎ, 𝑘, 𝑙 − 𝑑𝑖𝑔𝑖𝑡𝑠 𝑖𝑛 𝑡ℎ𝑒 𝑀𝑖𝑙𝑙𝑒𝑟 𝑖𝑛𝑑𝑒𝑥
𝐴𝑛𝑠𝑤𝑒𝑟 𝑓𝑜𝑟 𝑛𝑢𝑚𝑏𝑒𝑟 4:
2Å
4𝑎. 𝑑ℎ𝑘𝑙 = = 1Å
22 + 02 + 02
Remember: 1nm = 10Å
2Å
4𝑎. 𝑑ℎ𝑘𝑙 = = 0.5Å
42 + 02 + 02
2Å
4𝑎. 𝑑ℎ𝑘𝑙 = = 0.3333Å
62 + 02 + 02
 POLYMORPHISM
In materials science, polymorphism is the ability of a
solid material to exist in more than one form or crystal
structure. Polymorphism can potentially be found in any
crystalline material including polymers, minerals, and
metals, and is related to allotropy, which refers to
chemical elements.

e.g. glycine, which is able to form monoclinic and hexagonal

crystals. calcite and aragonite, both forms
of calcium carbonate.
End of Lecture 9