Lecture 3:

Crystalline and Amorphous Structure

in Materials
By:
Assoc. Prof. Ir. Dr. Wong Yew Hoong
Department of Mechanical Engineering | Faculty of Engineering
Universiti Malaya| Kuala Lumpur | Malaysia

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Why crystal structure is
important in materials?

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 Elements have very different properties depending on how they are stacked
together or what other elements they are stacked together with.

We wouldn't put salt (composed of sodium and chlorine) on our food if it tasted
like the chlorine that we put into our swimming pools.

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Do you know?

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Solar Panels

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Why is crystal structure important?
• Graphite is the soft, dark colored material that is found
in pencil lead, while diamonds are very hard, often
transparent and colorless, and very expensive
gemstones.
• Both graphite and diamond are made out of only one
element – carbon!
• The reason that graphite and diamond are so different
from each other is because the carbon atoms are
stacked together into two different crystal structures.
• Graphite is composed of carbon that forms loosely
bonded sheets in their crystal structure. These sheets
rub off easily to mark the paper when you write on it.
• Diamond is composed of carbon atoms stacked tightly
together in a cubic crystal structure, making it a very
strong material.
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It is not only important to know what elements are in the mineral,
but it is also very important to know how those elements are
stacked together.

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How do atoms arranged
themselves to form materials

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 Introduction
• In different states of matter (solid, liquid, gas, plasma), there are four (4)
possible types of atomic arrangements:

• No order

• Short-range order (SRO)

• Long-range order (LRO)

• Mixed

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 Introduction
Amorphous Crystalline

Gas / Plasma

Solid

Liquid

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 Fundamental Concept
Classification of solid materials based on atomic arrangement:

• Crystalline: Arranged following a periodic/repetitive array (long-range order)

Example: metals, alloys

• Non-crystalline/amorphous: Arranged in a random manner

Example: polymers

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 Crystalline Solid Materials

Also called monocrystalline.

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Amorphous Solid Materials

No order, random arrangement.

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 Question:
If the solid material has the following atomic arrangement, what
structure should we call it?

semi-crystalline or semi-amorphous
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If the solid material possesses
both crystalline and amorphous
structure, what should we call it?

Semi-crystalline or semi-amorphous

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 Crystal Structure and Unit Cell
• Properties of crystalline solids depends on the crystal structure, i.e. the manner in
which atoms are spatially arranged.

Cubic Hexagonal

• Each crystal structure is composed of unit cells, i.e. small repeat entities.

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 Space lattice
• Imaginary network of lines, with atoms at intersection of lines, representing
the arrangement of atoms is called space lattice.
• Properties of solids depends upon crystal structure and bonding force.

a) Space lattice of ideal crystalline solid b) Unit cell showing lattice constants.
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 Crystal Systems and Bravais Lattice

• Only 7 different types of unit cells are necessary to create all point lattices.

• According to Bravais (1811-1863), 14 standard unit cells can describe all

possible lattice networks.

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Crystal Systems

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Crystal Systems

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Types of Unit Cell
4 types of unit cells:
• Simple
• Body or Volume Centered
• Face Centered
• Base Centered

The fourteen Bravais

lattices in three dimensions.
Source: D.V. Anghel, Bravais
lattice table, 2003.
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 Principal Metallic Crystal Structures
• 90% of the metals have either Body Centered Cubic (BCC), Face
Centered Cubic (FCC) or Hexagonal Close Packed (HCP) crystal
structure.
• HCP is a denser version of simple hexagonal crystal structure.

BCC FCC HCP 22

 BCC Crystal Structure
• Represented as one atom at each corner of cube and one at the center of cube.

• Each central atom is surrounded by 8 nearest neighbors. Therefore, BCC has a

coordination number of 8.

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 BCC Crystal Structure
• Each unit cell has eight ⅛ atom at corners and 1 full atom at the center.

• Therefore each unit cell has (8 x ⅛) + 1 = 2 equivalent number of atoms.

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 BCC Crystal Structure

-Understanding BCC Crystal Structure Video-

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BCC Crystal Structure

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 Atomic Packing Factor (APF) of
BCC Crystal Structure
𝑉𝑎𝑡𝑜𝑚 Vatom = Volume of atoms in unit cell
𝐴𝑃𝐹 = VUC = Volume of unit cell
𝑉𝑈𝐶

4 3
𝑉𝑎𝑡𝑜𝑚 = 2 × 𝜋𝑅 = 8.38𝑅3
3
3
4𝑅
𝑉𝑈𝐶 = 𝑎3 = = 12.32𝑅3
3

8.38𝑅3
𝐴𝑃𝐹 = 3
= 𝟎. 𝟔𝟖
12.32𝑅
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Metals having BCC crystal structure

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 FCC Crystal Structure
• Represented as one atom each at the corner of cube and at the center of each
cube face.

• Each atom is surrounded by 12 nearest neighbors. Therefore, FCC has a

coordination number of 12.

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 FCC Crystal Structure
• Each unit cell has eight ⅛ atom at corners and six ½ atoms at the center of six faces.

• Therefore each unit cell has (8 x ⅛) + (6 x ½) = 4 equivalent number of atoms.

• Atomic Packing Factor (APF) = 0.74.

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 FCC Crystal Structure

-Understanding FCC Crystal Structure Video-

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FCC Crystal Structure

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 Activity 1
Calculate the atomic packing factor (APF) for the FCC unit cell.
𝑉𝑎𝑡𝑜𝑚 Vatom = Volume of atoms in unit cell
𝐴𝑃𝐹 = VUC = Volume of unit cell
𝑉𝑈𝐶

4
𝑉𝑎𝑡𝑜𝑚 = 4 × 𝜋𝑅3 = 16.76𝑅3
3
3
4𝑅
𝑉𝑈𝐶 = 𝑎3 = = 22.63𝑅3
2

16.76𝑅3
𝐴𝑃𝐹 = = 𝟎. 𝟕𝟒
22.63𝑅3

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Metals having BCC crystal structure

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 HCP crystal structure
• Each atom is surrounded by 12 nearest
neighbors.

• HCP has a coordination number of 12.

• Each unit cell has 6 equivalent number

of atoms.

• Atomic Packing Factor (APF) = 0.74.

• Ideal c/a ratio is 1.633

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Metals having HCP crystal structure

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 Theoretical Density
• Ratio between the mass and the total volume of unit cell.

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 Activity 2
Niobium has an atomic radius of 0.143 nm and a theoretical density of 8.57 g/cm3.
Determine whether it has an FCC or BCC crystal structure. Atomic weight of
Niobium is 92.19 g/mol.

If FCC:
4R 4(0.143 × 10−9 m)
a= = = 4.045 × 10−10 m
2 2

VUC = a3 = 6.617 × 10−29 m3

4 (92.19)
Density, ρv = = 9.25 g/cm3
(6.617 × 10 )(6.022 × 10 )
−29 23

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 Polymorphism or Allotropy
• Many elements have more than one
crystal structure under different
temperature and pressure.

• This phenomenon is called

polymorphism or allotropy.

• Example: Iron exists in both BCC and

FCC form depending on the
temperature.

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Polymorphism or Allotropy
Close-Packed Crystal Structures
HCP crystal structures

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Close-Packed Crystal Structures
FCC crystal structures

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 Crystallographic Directions and Planes

• Atoms positions in cubic unit cells

• Crystallographic directions in cubic unit cells

• Miller indices for crystallographic planes

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 Atom Positions in Cubic Unit Cells
• Cartesian coordinate system is used to
locate atoms
• In a cubic unit cell:
• y axis is the direction to the right
• x axis is the direction coming out of
the paper
• z axis is the direction to the top
• Negative directions are to the
opposite of positive directions.
• Atom positions are located using unit
distances along the axes.

BCC
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 Crystallographic Directions
• In cubic crystals, a crystallographic direction is specified by the Direction
Indices.
• Direction indices are the smallest integers of the vector components of the
direction emerging from cell surface.
• They are enclosed by square bracket with no commas.

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Crystallographic Directions
Direction A
1. Origin point = (0,0,0) , Emergence point = (1,0,0)
2. (1,0,0) – (0,0,0) = 1,0,0
3. No fraction to clear or integers to reduce
4. [100]

Direction C
1. Origin point = (1/2,1,0) , Emergence point = (0,0,1)
2. (0,0,1) – (1/2,1,0) = -1/2,-1,1
3. To clear the fraction – 2(-1/2,-1,1) = -1,-2,2
4. 1ത 2ത 2
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 Activity 1
Draw the following direction vectors
in cubic unit cells:

ത
[100], [110], [112], 110 ത 1ത
, 32

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 Crystallographic Miller Indices
• In some cases, the knowledge of crystallographic orientation of a plane in the
lattice is required.

• Miller Indices are used to refer to specific lattice planes of atoms.

• They are reciprocals of the fractional intercepts that the plane makes with the
crystallographic x, y and z axes of three nonparallel edges of the cubic unit
cell.

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Solar Panels

(111)

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 Crystallographic Miller Indices
• Miller Indices are used to refer to specific lattice planes of atoms.

• They are reciprocals of the fractional intercepts (with fractions cleared) that the plane makes
with the crystallographic x, y and z axes of three nonparallel edges of the cubic unit cell.

z Miller Index = (111)

x
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Miller Indices – Procedures

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Miller Indices – Procedures
1. Intercepts of the plane at x, y and z axes are
1, ∞ and ∞
2. By taking reciprocals, we get (1,0,0).
3. Miller indices are (100).
*********************************************
1. Intercepts are 1/3, 2/3 & 1.
2. By taking reciprocals, we get (3, 3/2, 1).
3. Multiplying by 2 to clear fractions, we get
(6,3,2).
4. Miller indices are (632).
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 Activity 2
Determine the Miller indices for the following cubic crystal planes:

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 Activity 3
Draw the cubic crystal planes by using the Miller indices of (101) and (221).

1. To draw the plane (101)

2. By taking reciprocals of the indices, we get
(1 ∞ 1).
3. The intercepts of the plane are x=1, y= ∞
(parallel to y) and z=1.
************************************************
1. To draw the plane (101)
2. By taking reciprocals of the indices, we get
(½ ½ 1).
3. The intercepts of the plane are x = ½, y= ½
and z=1.
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 Miller Indices – Important Relationships
• Planes and their negatives are identical, i.e. ℎ𝑘𝑙 = ℎത 𝑘ത 𝑙 ҧ
• In cubic system, direction indices of a direction perpendicular to a crystal
plane are the same as Miller indices of the plane.

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There is a distance between planes in crystal!

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 Interplanar Spacing
• Interplanar spacing: Distance between two closest parallel planes with the
same Miller indices (hkl)

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What is the importance of
interplanar spacing?

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Quick Recap…

• We know that there is a distance between planes

in crystal.

• The distance between two closest parallel planes

with the same Miller indices (hkl) is called
interplanar spacing.

• Why interplanar spacing is important?

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 Interplanar Spacing
• Interplanar spacing: Distance between two closest parallel planes with the
same Miller indices (hkl)

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Solar Panels

(111)

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Interplanar Spacing, d

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Every crystal material has its own
unique interplanar spacing!

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 Activity 4

Calculate the interplanar spacing of the (110) plane of iron BCC

lattice whose lattice constant is 0.287 nm.

𝑎
𝑑ℎ𝑘𝑙 =
ℎ2 + 𝑘 2 + 𝑙 2
2.87×10−10 𝑚
𝑑110 = = 2.03 × 10−10 𝑚
2

Therefore, 𝑑110 is 2.03 Å or 0.203 nm.

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 Activity 5
Determine the interplanar spacing of (110) plane for FCC copper
(Cu). The lattice constant, a for Cu is 3.61 Å.

𝑎
𝑑ℎ𝑘𝑙 =
ℎ2 + 𝑘 2 + 𝑙 2
3.61×10−10 𝑚
𝑑110 = = 2.55 × 10−10 𝑚
2

Therefore, 𝑑110 is 2.55 Å or 0.255 nm.

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 Crystal Structure Analysis

• Information about crystal structure are obtained

using X-ray diffraction.

• The X-rays used are about the same wavelength

(0.05 – 0.25 nm) as distance between crystal lattice
planes.

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X-ray Diffractometer (XRD)

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 X-Ray Diffraction (XRD) Analysis
• Solid specimens (powder, thin film) can be analyzed using X-ray diffraction
analysis as the random orientation facilitates different angle of incidence.

• Radiation counter detects angle and intensity of diffracted beam.

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Record of the diffraction angles by X-ray diffraction
Tungsten sample
Count per second

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 Activity 6
Question:
If you obtain or record the following XRD pattern, what does it mean?

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 Diffraction Condition for Cubic Cells
• For BCC structure, diffraction occurs only on planes whose Miller indices
when added together total to an even number
i.e. (h+k+l) = even Reflections present
(h+k+l) = odd Reflections absent

• For FCC structure, diffraction occurs only on planes whose Miller indices are
either all even or all odd
i.e. (h,k,l) all even Reflections present
(h,k,l) all odd Reflections present
(h,k,l) not all even or all odd Reflections absent
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 X-Ray Diffraction
For rays reflected from different planes to be in phase, the extra distance
traveled by a ray should be an integral multiple of wave length λ.

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Interpreting Diffraction Data

2𝑎 𝑠𝑖𝑛𝜃
Substituting d into Bragg’s law, 𝜆 =
ℎ2 +𝑘 2 +𝑙 2

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Interpreting Diffraction Data

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Interpreting Experimental Data

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Crystal Structure of Unknown Metal

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 Activity 7
An X-ray diffractometer recorder chart for an element that has either the BCC or the FCC crystal
structure shows diffraction peaks at the following 2θ angles: 40, 58, 73, 86.8, 100.4, and 114.7.
The wavelength of the incoming X-ray used was 0.154 nm.

a. Determine the cubic structure of the element.

b. Determine the lattice constant of the element.

c. Identify the element.

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