Crystal Structure - III

Polymorphism and Allotropy

Polymorphism refers to the existence of more than one crystal structure, commonly found in
both metals and Non – metals.
Eg: AgNO3 exhibit Rhombohedral and Othorhombic crystal structures.

Allotropy: The similar condition found in chemical element is called Allotropy.

Eg: Iron (Fe) at room temperature has BCC crystal structure, while at a temperature of 9120C it
forms FCC crystal structure.

Examples for the three lattice types or crystal structures discussed

9/5/2023 2
 Example
1. The atomic weight, density, and atomic radius for three hypothetical alloys are
listed in the following table. For each, determine whether its crystal structure is FCC,
BCC, or simple cubic and then justify your determination.

Solution

For SC, BCC, and FCC crystal structures,

the respective values of n are 1, 2, and 4

For SC, BCC, and FCC, the values of a are

VC = a3
2R, , and

9/5/2023 3
 Example

2. The accompanying figure shows a unit cell for a hypothetical metal.

(a) To which crystal system does this unit cell belong?
(b) What would this crystal structure be called?
(c) Calculate the density of the material, given that its atomic weight is 141 g/mol.

Solution

9/5/2023 4
 Polymorphism and Allotropy

Some metals, as well as nonmetals, may have more than one crystal structure, a
phenomenon known as polymorphism.  refers to compound

When found in elemental solids, the condition is often termed

allotropy.  refers to element

Crystal structure depends on both the temperature and the external

pressure

Familiar examples are

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
FCC iron at 912 0C (1674 0F)

9/5/2023 5
 Polymorphism and Allotropy
Often a modification of the density and other physical properties accompanies a
polymorphic transformation

Another common metal is tin – Allotropic Change

White tin, having a body-centered tetragonal crystal structure at room temperature,

transforms, at 13.2 0C (55.8 0F), to gray tin, which has cubic crystal structure

The rate at which this transformation happens is very slow

Lower the temperature (below 13.2 0C) the faster the rate

9/5/2023 6
 Crystallographic Points
A crystallographic point is represented using 3 co–ordinates, but as fractional multiples of
unit cell lengths.
No commas or parenthesis.

No commas or parenthesis.
Example: Locate ¼ 1 ½ in the
above unit cell.

the position of P is designated using

coordinates q r s with values that are less than
or equal to unity.

9/5/2023 7
 Crystallographic Points
Specify point coordinates for all atom positions for a BCC unit cell.

BCC unit cell—that is, the eight corner atoms and single center atom

9/5/2023 8
 Crystallographic Points
Specify point coordinates for all atom positions for a FCC unit cell.
Point Point
No Coordinat
5 es
8
1 000
14 2 100
6 7 3 110
4 010
5 001
13
6 101
10 12 7 111
8 011
9 11
11 22
0

10 1 1
0
1 2 2
4 11 11
1
22
2 9
12 1 1
1
3 2 2
13 11
0
22
14 11
FCC unit cell—that is, the eight corner atoms and six atoms on the face 22
1

9/5/2023 9
 Crystallographic Directions
A crystallographic direction is defined as a line between two points, or a vector.

A crystallographic direction is represented using 3 indices,

determined by following the procedure mentioned below:

• Choose a vector of convenient length and origin.

• Determine the projection of vector in 3 direction in terms of the
unit cell dimensions.
• Multiply or divide them with a common factor to reduce them to
smallest possible integers.

NOTE: No commas, but in square brackets

 A vector can be translated throughout the crystal lattice and it would still represent the
same direction. It can be translated to the origin you chose.
 The three components or indices, not separated commas, are kept in square brackets.
 Negative indices are denoted using a ‘bar’ over the number rather than a ‘–ve’ sign.
Eg: [11� 1] or [1� 11� ]

9/5/2023 10
 Exercise

Example 1: Determine the crystallographic direction in the figure shown.

Example 2: Draw the crystallographic direction corresponding to [1 2 1]

and [2 1 1] directions.

9/5/2023 11
 Exercise
Example 2: Draw the crystallographic direction corresponding to [1 2 1]
and [2 1 1] directions in cubic system.

x y z x y z
Projection a/2 b c/2 Projection a b/2 c/2
Fractions of Projection ½ 1 ½ Fractions of Projection 1 ½ ½
Reduction 1 2 1 Reduction 2 1 1
Enclosure [1 2 1] Enclosure [2 1 1]

9/5/2023 12
 Family of Crystallographic Directions

Observation: In a cubic crystal system, all the directions drawn along the lattice or co–
ordinate axes are equivalent. So, 1� 00 , 100 , 01� 0 , 010 , 001� , 001 are all
equivalent.

Points to note:

• All these directions are collectively represented as <100> family of directions.

• Likewise, 2� 13� and 123 are members of the family <123>.

Question 1: Are [200] and [100] same for a cubic system?

True
Question 2: For a tetragonal system [100] and [010] are equivalent, but [100] and [001]
are not. Is this true?
True

9/5/2023 13
 Crystallographic Directions For Hexagonal Crystals
An Activity to Identify the Road Block:

• Choose the co – ordinate system and express all the equivalent

directions within the hexagonal face in terms of indices.

• What do you observe?

Do the following for the same directions and see if you still face
the same problem:

• 𝑢𝑢′ 𝑣𝑣 ′ 𝑤𝑤′ → 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢 : Using four indices instead of three indices,

called Miller–Bravais indices.

𝑢𝑢′ 𝑣𝑣 ′ 𝑤𝑤𝑤 → 𝑢𝑢𝑢𝑢𝑢𝑢𝑢𝑢

9/5/2023 14
 Crystallographic Planes
We would like to express a crystallographic planes in terms of 3 indices (hkl) in a manner similar
to co–ordinate geometry of planes where we use direction cosines of the normal to denote a
plane. These three indices are called Miller Indices.

1. If the plane passes through the selected origin, either another parallel plane must be
constructed within the unit cell by an appropriate translation, or a new origin must be
established at the corner of another unit cell.

2. At this point the crystallographic plane either intersects or parallels each of the three axes;
the length of the planar intercept for each axis is determined in terms of the lattice
parameters a, b, and c.

3. The reciprocals of these numbers are taken. A plane that parallels an axis may be considered
to have an infinite intercept, and, therefore, a zero index.

4. If necessary, these three numbers are changed to the set of smallest integers by
multiplication or division by a common factor.

5. Finally, the integer indices, not separated by commas, are enclosed within parentheses,
thus: (hkl).
9/5/2023 15
 Crystallographic Planes

9/5/2023 16