2.

Crystal Structures and defects

Teacher: Maitane Gabilondo Nieto ([email protected])

Materials for Engineering 1

INDEX
2.1. Crystal structure
2.1.1. Crystalline and amorphous materials
2.1.2. Unit cell
2.1.3. Crystal systems
2.1.4. Crystal systems of metals
2.1.5. Crystal systems parameters
2.1.6. Allotropy and polymorphism
2.1.7.Single crystal and polycrystalline materials
2.1.8. Anisotropy
2.1.8. Determination of crystal structures

2.2. Imperfections in solids: defects

2.2.1. Point defects (0D)
2.2.2. Lineal defects (1D)
2.2.3. Interfacial defects (2D)
2.2.4. Volumetric defects (3D)
2.2.5. Microscopic examination
2.2.6. Grain size determination

Materials for Engineering 2

2.1. Crystal structure
2.1.1. Crystalline and amorphous materials
Materials can be classified in two groups: crystalline and
noncrystalline (amorphous). Crystalline material=>
atoms are located in an ordered arrangement, periodic
array.
Amorphous=>do not crystallize, do not have an ordered
arrangement.

Crystalline materials
The atoms, ions or molecules repeat themselves periodically in 3D of space.
Different external
forms of aluminum Same crystal structure

Sometimes, crystal structure can be

seen macroscopically

Materials for Engineering 3

2.1. Crystal structure
2.1.2. Unit cell
The atoms in a crystalline material are in an ordered way=> the atoms are in small groups
that are repeated to form a 3D structure (crystal lattice).
These small groups are called unit cells and they are usually parallelepipeds. The unit cell is
the basic structural unit of the crystal structure.

Materials for Engineering 4

2.1. Crystal structure
2.1.3. Crystal systems
There are a lot of crystal structures and in each of them has a different form of unit cell. The
parameters (lattice parameters) that determine the geometry of a unit cell are:
• The three edge lengths a, b and c
• The three interaxial angles α, β and γ
Each combination of these parameters is a different crystal system,
there are 7 types:

Usually in metals

Materials for Engineering 5

Exercise: find a material for each system
2.1. Crystal structure
2.1.3. Crystal systems
Bravais lattices
Body

Materials for Engineering 6

2.1. Crystal structure
2.1.4. Crystal systems of metals

Metallic bonding

Non directional bonding: no restriction in

position and number of neighbours

Atoms are in touch

Large number of neighbour atoms
and high packing densities
The most common crystal structures for metals are: face-centered cubic, body-centered
cubic and hexagonal close-packed.

Materials for Engineering 7

2.1. Crystal structure
2.1.4. Crystal systems of metals
• Face-centered cubic
It is a unit cell of cubic geometry, with atoms located at
each of the corners and the centers of all the cube faces.
The parameters are:

The edge length of the cube is “a” and the atomic radius of
the sphere is R. The relation between them is:

𝑎 = 2𝑅 2

Some common metals that have this crystal structure are

copper, aluminum, silver and gold.

Materials for Engineering 8

2.1. Crystal structure
2.1.4. Crystal systems of metals
• Body-centered cubic
The unit cell is also cubic and it has an atom in the middle of the cube.
The lattice parameters are the same of FCC, but the relation between
the edge length and radii is:
4𝑅
𝑎=
3
Some common metals that have this crystal structure are chromium,
iron or tungsten.
• Hexagonal close-packed
The unit cell is hexagonal, there are 3 planes: 2
with hexagonal form and 1 with triangular
shape.

The parameters are:

Some common metals that have this structure are cadmium, magnesium, titanium…

Materials for Engineering 9

2.1. Crystal structure
2.1.5. Crystal systems parameters
Important parameters in crystal structures:

• Lattice parameters: 3 lengths a, b and c / 3 angles α, β and γ

• Coordination number: the number of nearest neighbor atoms or ions surrounding

an atom or ion.

Exercise: calculate the coordination number of BCC and FCC.

Materials for Engineering 10

2.1. Crystal structure
2.1.5. Crystal systems parameters
• Atomic radius: distance from the centre of the nucleus to the
outer orbital of electrons.

• Atomic packing factor (APF): the sum of the sphere volumes of all atoms in a unit cell
divided by the unit cell volume.
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝐴𝑃𝐹 =
𝑡𝑜𝑡𝑎𝑙 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑣𝑜𝑙𝑢𝑚𝑒

Exercise: calculate the APF for FCC and BCC.

Materials for Engineering 11

2.1. Crystal structure
2.1.5. Crystal systems parameters
• Theoretical density: the theoretical density can be calculated based on the crystal
structure:
𝑛𝐴
𝜌=
𝑉𝑐 𝑁𝐴

n= number of atoms associated with each unit cell

A=atomic weight
Vc= volumen of the unit cell
NA= Avogadro´s number

Exercise: calculate the theoretical density of copper.

Materials for Engineering 12

 2.1. Crystal structure z
2.1.5. Crystal systems parameters
Crystallographic points, directions and planes
• Point coordinates: a point in a unit cell can be determined
by 3 indices or coordinates (fractional multiples of the unit
cell edge lengths)
y

Exercise 1 : for following unit cell, locate the Exercise 2: specify point coordinates for
point having coordinates ¼ 1 ½ all atom positions for a BCC unit cell.

Materials for Engineering 13

2.1. Crystal structure
2.1.5. Crystal systems parameters
Crystallographic points, directions and planes
• Crystallographic direction: a direction can be determined by
3 indices with the following steps:
1. The direction vector with adequate length is
positioned in the origin.
2. The lengths of the vector projection in the 3 axes is
determined.
3. These are expressed by the smallest integer values.
4. The three índices are represented like: [uvw]

Exercise: determine the indices for the direction

shown in the accompanying figure.

Materials for Engineering 14

2.1. Crystal structure
2.1.5. Crystal systems parameters
Crystallographic points, directions and planes
• Crystallographic planes: they are also determined by 3 indices, which are called Miller
indices (hkl). The procedure is:
1. If the plane passes through the origin, a parallel plane must be constructed.
2. The plane intersects or it is parallel to each of the 3 axes; the length in each axis
is determined.
3. The reciprocals of these numbers are taken.
4. The expression is rewritten by the smallest integer values.
5. The indices are enclosed in parentheses: (hkl)

Materials for Engineering 15

2.1. Crystal structure
2.1.5. Crystal systems parameters
Linear and planar densities

Linear density: the number of atoms per unit length whose centers lie on the direction
vector. The units are reciprocal length.
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑐𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑜𝑛 𝑑𝑖𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑣𝑒𝑐𝑡𝑜𝑟
𝐿𝐷 =
𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑑𝑖𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑣𝑒𝑐𝑡𝑜𝑟
Example: [110] in FCC crystal structure

2 𝑎𝑡𝑜𝑚𝑠 1
𝐿𝐷110 = =
4𝑅 2𝑅

Materials for Engineering 16

2.1. Crystal structure
2.1.5. Crystal systems parameters
Linear and planar densities

Planar density: the number of atoms per unit area that are centered on a particular
crystallographic plane. The units are reciprocal area.
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑐𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑜𝑛 𝑑𝑖𝑟𝑒𝑐𝑡𝑖𝑜𝑛 𝑣𝑒𝑐𝑡𝑜𝑟
𝑃𝐷 =
𝑎𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑙𝑎𝑛𝑒

2 𝑎𝑡𝑜𝑚𝑠 1
𝑃𝐷110 = =
8𝑅2 2 4𝑅2 2

Materials for Engineering 17

2.1. Crystal structure
2.1.6. Allotropy and polymorhpism Allotropes of iron

When a pure material can have more than one

crystal structure=> allotropy.

When an alloy can have more than one crystal

structure=> polymorphism.

Allotropes of titanium

Materials for Engineering 18

2.1. Crystal structure
2.1.6. Single crystal and polycrystalline materials
Depending on the arrangement of the atoms:

Single crystal

The arrangement of atoms is perfect, all unit

cells are oriented in the same direction.
They are difficult to grow.

Single crystal Diamond single crystals

Polycrystalline materials Grain boundaries

They are composed of many small crystals or grains.

Each grain is oriented in one direction and the
Regions that separates them is called grain boundary.

Polycrystalline Polycrystalline materials

growth
Crystals or grains
Materials for Engineering 19
2.1. Crystal structure
2.1.8. Anisotropy

Usually the properties of single crystals vary with direction and

this is called anisotropy.
The degree of anisotropy increases with decreasing symmetry

Triclinic structures are highly anisotropic Elastic modulus of BCC iron in

different directions

When the properties are independent of the direction, the material is isotropic.

A polycrystalline material can be isotropic or anisotropic. If the crystals are oriented randomly,
then the material is isotropic.

Materials for Engineering 20

2.1. Crystal structure
2.1.9. Determination of crystal structures
X ray diffraction

Incident Diffracted
beam beam

Bragg’s law:
𝑛λ = 2𝑑ℎ𝑘𝑙 𝑠𝑖𝑛𝜃 dhkl is the interplanar spacing
Miller indices (hkl)=> to
determine the direction
and plane of a crystal

Materials for Engineering

21
2.1. Crystal structure
2.1.9. Determination of crystal structures
X ray diffraction

Characteristic x-ray spectrum of a duplex stainless steel: ferritic and austenitic

α ferrite is BCC (it diffracts at

(110), (200), (211), (220) and
(310) panes

γ austenite is FCC (it diffracts at

(111), (220), (311) and (222).

Materials for Engineering 22

2.1. Crystal structure
2.1.9. Determination of crystal structures
X ray diffraction
Silver with different morphologies

Materials for Engineering 23