MECH 227

Engineering Materials

Lecture 3
The structure of crystalline solids

Dr. Reza Mohammadi

ISSUES TO ADDRESS...

• How do atoms assemble into solid structures? (focus on metals)

• How does the density of a material depend on its structure?

• When do material properties vary with the sample (i.e., part) orientation?

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Atomic arrangement: Ordered vs disordered

Crystalline: Atoms are positioned in a repetitive 3D pattern over a large atomic distances, ‘long-
range order’ (metals, alloys, ceramics & some polymers).

Amorphous or Noncrystalline: random and disordered atomic distribution, ’short-range order’

(amorphous SiO2). Lack of systematic and repeated arrangement of atoms

Crystalline solids are the

most stable solids

Crystal Glass Gas

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Types of crystalline solids

o Single crystals, atoms are organised in a repeating or periodic array over entire extend of
the material.

o Polycrystalline Materials, composed of many small crystals (or grains) in different

orientations.

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Polycrystalline materials
o Polycrystalline materials: comprised of many small crystals or grains. There exist
atomic mismatch within the regions where the grains meet. These regions are called
grain boundaries.
Formation of polycrystalline structures
As a metal cools from the molten state and begins to solidify, individual crystals
nucleate at random positions and orientations throughout the liquid. These
crystals grow and finally interfere with each other at grain boundary

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Why do atoms assemble into ordered structures (crystals) ?

Non-dense, Random Packing Dense, Ordered Packing

Energy of bond
Energy of bond

typical neighbor typical neighbor

bond length bond length

Interatomic distance typical neighbor Interatomic distance

typical neighbor
bond energy
bond energy

Energy of Crystalline Solid < Energy of Amorphous Solid

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Crystal structures

Atomic hard-sphere model: Atoms are hard spheres with well-defined radii. The shortest distance
between two like atoms is one diameter of the hard sphere.

A crystalline structure can be also considered as a lattice, a 3D array of points coinciding with atom
positions (or sphere centers).

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Unit cell

• The unit cell is a structural unit or building block that can describe the crystal structure.
Repetition of the unit cell generates the entire crystal.
• Small groups of atoms form a repetitive pattern

2D crystalline structure 3D crystalline structure

Unit cell showing lattice parameters:

a, b, c – the length of the edges
𝛼, 𝛽, 𝛾 – the angles of the edges

Lattice of a crystalline solid 8

Metallic crystal structures
Metals are usually polycrystalline; although formation of amorphous metals is possible by
rapid cooling.

Atomic bonding in metals is non-directional, therefore there is no restriction on numbers of

nearest neighbour atoms ⇨ Large number of nearest neighbours & dense atomic packing (or
close-packing).

The most common types of crystal structure are

• Simple cubic (SC)
• Body centered cubic (BCC)
• Face centered cubic (FCC)
• Hexagonal close packed (HCP)

SC 9
Packing efficiency

The packing efficiency is the fraction of the crystal (or unit cell) occupied by atoms.
How do the two arrangements compare for efficient use of space?

4R
4R

4R 4R
4R
Square array Close-packed (hexagonal) array occupy 15% less space
Close–packing leads to more energetically stable structures

3D arrangement:

HCP FCC 10
Coordination number

o Number of adjacent atoms surrounding

a reference atoms.
o Coordination number depends directly
on the relative size of foreign atom,
which is characterised by the radius
ratio (r/R).

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Face-Centred Cubic (FCC) structure
Atoms are located at each of the corners and the centres of all the faces of cubic unit cell
(Cu, Al, Ag, Au etc.)

R
a

Unit cell length: 𝑎2 + 𝑎2 = (4𝑅)2 a cube edge length and R the atomic radius
𝒂 = 𝟐𝑹 𝟐
𝑁𝑓 𝑁𝑐 where Ni number of interior atoms,
Number of atoms per unit cell: 𝑁 = 𝑁𝑖 + +
2 8 Nf number of face atoms,
𝟔 𝟖 Nc number of corner atoms,
N= 0 + + =4
𝟐 𝟖

The coordination number, number of nearest-neighbor or touching atoms: 12

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Atomic packing factor of FCC structure

Atomic Packing Factor, APF, (or packing efficiency), the fraction of atom volume in the unit cell. It is
usually represented by a percentage or volume fraction.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑉𝑎 R

𝐴𝑃𝐹 = = a
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝑉𝑐

Unit cell length: 𝒂 = 𝟐𝑹 𝟐

Total volume of FCC unit cell: 𝑽𝒄 = 𝒂𝟑 = 𝟏𝟔𝑹𝟑 𝟐

Number of atoms per FCC unit cell: N=4

𝟒 𝟑
𝟏𝟔
Volume of atoms in FCC unit cell: 𝑽𝒂 = 𝟒 × 𝝅𝑹 = 𝝅𝑹𝟑
𝟑 𝟑
Atomic Packing Factor for FCC crystal:

16 3
𝑉𝑎 𝜋𝑅 𝜋
𝐴𝑃𝐹 = = 3 = = 𝟎. 𝟕𝟒 maximum possible packing factor of hard spheres
𝑉𝑐 3
16𝑅 2 3 2 13
Body-Centred Cubic (BCC) structure
Atoms are located at all eight corners and a single atom at the cube centre (Cr, 𝛂-Fe, Mo, Ta etc.)

Unit cell length: 𝑎2 + 2𝑎2 = (4𝑅)2

𝑎 = 4𝑅/ 3
Number of atoms per unit cell: a

N= 1+ +
0 8
=2 R
2 8

The coordination number: 8

3
4𝑅
Total volume of BCC unit cell: 𝑉𝑐 = 𝑎3 =
3
4 3 8 3
Volume of atoms in BCC unit cell: 𝑉𝑎 = 2 × 𝜋𝑅 = 𝜋𝑅
3 3
𝑉𝑎
Atomic Packing Factor for BCC crystal: 𝐴𝑃𝐹 = = 0.68
𝑉𝑐
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Simple cubic structure

Atoms are situated only at the corners of a cube centre (only Po)

Unit cell length: 𝑎 = 2𝑅

0 8
Number of atoms per unit cell: N= 0+ + =1
2 8

The coordination number: 6

Total volume of SC unit cell: 𝑉𝑐 = 𝑎3 = 8𝑅3

4 3
Volume of atoms in SC unit cell: 𝑉𝑎 = 𝜋𝑅
3
𝑉𝑎
Atomic Packing Factor for SC crystal: 𝐴𝑃𝐹 = = 0.52
𝑉𝑐

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Hexagonal Closed-Packed (HCP) structure
The 1st layer (Layer A) is single layer of close-packed spheres where six
atoms form a regular hexagon, surrounding one atom in center. The 2nd
layer (Layer B), single layer of close-packed spheres, is nesting over the
depressions formed in the 1st layer. The 3rd layer (Layer A) is placed
directly above the atoms in the 1st layer.

Common metallic crystal structure: Cd, Mg, Co, Zn, 𝛂-Ti etc.

2 12
Number of atoms per unit cell: N= 3+ + =6
2 6

The coordination number: 12

Atomic Packing Factor for HCP crystal: 𝐴𝑃𝐹 = 𝟎. 𝟕𝟒

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Density computations
The theoretical density of a crystalline material can be expressed as

𝐴𝑡𝑜𝑚𝑠 𝑖𝑛 𝑡ℎ𝑒 𝑈𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 (𝑁) × 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑎𝑛 𝐴𝑡𝑜𝑚 (𝑀)

𝜌 = 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑈𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑈𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 (𝑉𝐶 )

Mass of an Atom, M: Atomic Weight, A, is given in the Periodic Table in [g/mol] in order to convert to SI
mass [grams] for a single atom:
𝐴
𝑀=
𝑁𝐴
where NA is Avogadro’s number (6.022 x 1023 atoms/mol)

𝑁𝐴
Theoretical density of a crystalline material is 𝜌= [g/cm3] SI unit [kg/m3]
𝑉𝐶 𝑁𝐴

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Numerical problem
A certain element, X, crystallises in a FCC cubic unit cell of dimension a = 405 pm. The density is 𝝆 = 2.71 g
cm-3. Avogadro’s number, NA, is equal to 6.022 x 1023 mol-1. What is the element?
𝑵𝑨
𝝆=
𝑽𝑪 𝑵𝑨
1) An FCC unit cell contains 4 atoms of element X.

2) The Volume of a unit cell of element X is

Vc = a3 = (405 x 10-12)3 m3 = 6.64 x 10-29 m3

3) The mass of a unit cell, containing 4 atoms of element X, is

Mcell = 𝝆 x V = (2.71 x 103 x 6.64 x 10-29) kg = 17.99 x 10-26 kg

4) The mass of one mole of X is

MA = 1/4 (Mcell x NA) = 4.50 x 10-26 x 6.022 x 1023 = 27.1 g

5) The relative atomic mass of element X from the Periodic Table of

Elements corresponds to Aluminium (Al)

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 Densities of material classes
In general
  
metals> ceramics> polymers
Why?
20 Platinum *GFRE, CFRE, & AFRE are Glass,
Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo in an epoxy matrix).
Cu,Ni
• often large atomic masses Steels
Tin, Zinc
Zirconia

 (g/cm 3)
5
Ceramics have... Titanium
4 Al oxide
Diamond
• less dense packing 3 Si nitride
Aluminum Glass -soda Glass fibers
• often lighter elements Concrete
PTFE
2 Silicon GFRE*
Magnesium Carbon fibers
G raphite CFRE *
Polymers have... Silicone Aramid fibers
PVC AFRE *
PET
• low packing density 1 PC
HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Wood
0.4
Composites have...
0.3
• intermediate values
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Polymorphism

o Some materials may have more than one crystal structure, a

phenomenon known as polymorphism. When found in elemental
solids, the condition is often termed allotropy.
o Such change in crystal structure depends on temperature and pressure.

• Examples:
• Carbon: graphite is the stable polymorph at ambient conditions, whereas
diamond is formed at extremely high pressures.
• Pure iron: BCC crystal structure at room temperature and FCC at 912ᵒC

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Crystal systems

There are seven different

crystal systems and fourteen
Bravais lattices

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Point coordinates
z
111 Point coordinates for unit cell center are
c
a/2, b/2, c/2 ½½½

000
y
a b
Point coordinates for unit cell corner are
x 111

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Example

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Crystallographic directions
z Algorithm
1. Vector repositioned (if necessary) to pass through origin.
2. Read off projections in terms of unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
y
[u v w]

e.g.: 1, 0, ½ => 2, 0, 1 => [ 2 0 1 ]

-1, 1, 1 => [ 1 1 1 ] where overbar represents a negative index

families of directions <u v w>

<1 1 1>: [1 1 1], [1 1 1], [1 1 1], [1 1 1], [1 1 1], [1 1 1], [1 1 1], [1 1 1]

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Example

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Crystallographic planes

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Crystallographic planes (cont.)

• Planes are presented by Miller Indices

• All parallel planes have same Miller indices.

• Algorithm
1. Read off intercepts of plane with axes in terms of a, b, c (the plane should not
pass from the origin; if so, select another origin)
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no commas i.e., (h k l)

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Crystallographic planes: Example
z
example a b c
1. Intercepts
c
1 1 
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (1 1 0)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 1 0 0
y
4. Miller Indices (1 0 0) a b
x
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Crystallographic planes: Example (cont.)

z
example a b c
1. Intercepts
c
1/2 1 3/4 •
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 • y
•
3. Reduction 6 3 4 a b
4. Miller Indices (6 3 4) x

Family of Planes {h kl }
e.g.: {100} = (100), (010), (001), (100), (010), (0 0 1)

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Planar density of (1 0 0) Iron
Solution: At T < 912C iron has the BCC structure.

2D repeat unit

(100) 4 3
a= R
3

Radius of iron R = 0.1241 nm

atoms
2D repeat unit 1
1 atoms 19 atoms
Planar Density = = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm2 m2
R
2D repeat unit 3
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X-rays to determine crystal structure
X-ray diffraction (XRD) works by directing X-rays onto a material. When the X-rays interact with the
crystal lattice, they are scattered in specific directions according to the crystal's structure. The
resulting diffraction pattern is recorded, and by analyzing the angles and intensities of the diffracted
beams, the crystal structure, spacing between layers, and other material properties can be
determined.

reflections must
be in phase for
extra a detectable signal
distance  Order of reflection

travelled   X-ray
by wave “2” spacing intensity n
d between d = 2 sin 
planes (from c
detector)

Measurement of critical angle, c, allows computation c
of planar spacing, d. 31
X-ray diffraction pattern
Diffraction pattern for polycrystalline α-iron (BCC)

z
(1 1 0) c
z z
Intensity (relative)

c (2 1 1) c
y
a b
y x y
a b a
(2 0 0) b
x x

Diffraction angle 2

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