Mechanical Behavior of Materials

Swarup Bag
Department of Mechanical Engineering
Indian Institute of Technology Guwahati

Module 2
Crystal Structure of Materials

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 Classification of materials

Metals/metallic materials Ceramics & Glasses

•good conductors of electricity and •thermally and electrically
heat insulating
•lustrous appearance •resistant to high temperatures
•susceptible to corrosion and harsh environments
•strong, but deformable •hard, but brittle

Composites Polymers
•consist of more than one material type •very large molecules
•designed to display a combination of •low density, low weight
properties of each component •maybe extremely flexible

Ceramics: Al2O3, SiC, SiO2 (oxides, nitrides and carbides)- bricks, refractories

Polymer: Plastic and rubber materials, organic – C, H2, other non metallic materials

Composites: Concrete, plywood, fiberglass 3

Structure and properties of materials

Structure ->Property->Processing->Performance
Structure: Subatomic, Atomic, microscopic, macroscopic
Property: Mechanical, electrical, thermal, magnetic, optical

Advanced materials – (Magnetic information storage, liquid crystal display, fiber optics)

Semiconductor – Silicon, germanium based, tantalum oxide(Ta2O5) used for ceramic

capacitor (electrical properties between conductors and insulators;
electrical properties can be precisely controlled)

Biomaterials – Bones and teeth – hydroxyapatite (ceramic); artificial organ – plastic;

bone replacement – titanium alloy (implanted in human body)

Smart materials – Respond to change in temperature, stress, humidity or chemical

environment

Shape memory alloy, piezoelectric ceramics, magnetorheological fluid

Nanoengineered materials (High-technology application)

Modern materials need

High performance engine/Nuclear waste processing/Hypersonic flight/
Communication industry/Construction

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 Atomic structure and interatomic bonding

Atom consists of a very small nucleus (protons and neutrons)

with moving electrons
• Electron configurations and electron energy state
• Valance electrons
Valence electrons determine all of the following properties: Chemical,
Electrical, Thermal, and Optical
• Periodic table – electropositive and electronegative elements
Interatomic forces – bind the atoms together
Atomic bonding: Essentially atoms either want to give up (transfer)
or acquire (share) electrons to complete electron configurations;
minimize their energy
Transfer of electrons Ionic bond
Sharing of electrons Covalent bond
Metallic bond Sea of electrons
5

Interatomic bonding
Secondary bonding or Van der Walls bonds
o Formed when atoms or group of atoms have a non-symmetrical
electrical charge, bonding by an electrostatic attraction.
o Arises from interaction between dipoles

Type Bond energy Physical behavior Remarks

(kJ/mol)
Ionic 150-370 Hard and Brittle, High MP, Non directional
(NaCl) Good thermal and electrical
conductor
Covalent 125-300 Very hard, very high MP, Directional (Semiconductors,
(SiC) Usually poor thermal and Ceramics, polymer chains)
electrical conductor
Metallic 25-200 Soft to hard, Low to very high Non directional (metals)
MP and electrical conductor,
Malleable and ductility
Secondary <10 Directional
Inter-chain (polymer) 6
Inter-molecular

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 Crystal structure

Crystalline – regular repetitive arrangement of atoms/ions over

a long range (>100 nm)
Noncrystalline or amorphous material – arrangement of atoms holds
for a short range (glass)
Single crystal – consists of one large crystal (chip made from silicon)
Polycrystalline material – many small crystals with varying
orientations (grains)
Liquid crystal: polymeric materials have a special type of order

- Behaves like amorphous material in one state (liquid-like).

- Some polymer molecules undergo crystalline structure in small zone with external
electric field or temperature change

- Used in liquid crystal display (LCD) technology

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Hard sphere model

Crystal Structure

Lattice points

Identical surrounding
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Crystal structure

Lengths -- (a, b, c)
Angles -- (, , )

Unit cell

• building block of crystal structure

• smallest unit when repeated in space indefinitely
• lattice constants or lattice parameters of the
unit cell
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Crystal structure

NO 7 lattice system 14 Bravais lattice

(from least to most
symmetric) Simple, base-centered, body-centered, face-centered

1 TRICLINIC

2 MONOCLINIC

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NO 7 lattice 14 Bravais lattice
system
(from least to
most
symmetric)
3 ORTHORHOMBIC

4 RHOMBOHEDRAL

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NO 7 lattice system 14 Bravais lattice

(from least to most
symmetric)

5 TETRAGONAL

6 HEXAGONAL

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NO 7 lattice system 14 Bravais lattice
(from least to
most symmetric)

7 CUBIC

• There are 7 unique crystal systems in 3D space

• Total 14 distinct arrangements of lattice points, known as

Bravais lattice 13

Crystal Structure

Crystal structure = lattice + Basis

A group of one or more atoms located in a particular way and

associated with each lattice point, is known as basis

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Crystal Structure

Common crystal structure

• Simple cubic
• Body centered cubic
• Face centered cubic
• Close packed structure
-- HCP and CCP
Simple cubic structure

Examples: Po, α- Mn
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Crystal Structure

Body centered cubic (BCC) structure

Examples: Fe, Ti, W, Mo, Cr

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Crystal Structure

Face centered cubic (FCC) structure

Examples: Fe, Al, Ni, Cu, Ag, Au, Pb

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Crystal Structure

Hexagonal Close packed (HCP) structure

Examples: Ti, Mg, Zn, Co

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 No of atoms per unit cell

 Relation between Atomic radius

and lattice Parameter

 Coordination number

 Packing density or
atomic packing factor

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Crystal Structure

Close packed structure

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 Crystal Structure

Theoretical density of material

Planar densities
No of atoms per unit area whose centers lie on the plane

Planar packing fraction

Allotropic or Polymorphic transformation

• Fe: BCC -> FCC (allotropic – pure element)
• ZrO2: tetragonal -> monoclinic (polymorphism – compounds)

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Crystallographic Directions and Planes

Crystallographic direction

• Cubic systems
– Directions are named based upon the projection of a vector
from the origin of the crystal to another point in the cell.
• Conventionally, a right hand Cartesian coordinate system is
used.
– The chosen origin is arbitrary, but is always selected for
the easiest solution to the problem.

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 Crystallographic Directions and Planes

Procedure for writing directions in Miller Indices

– Determine the coordinates of the two points in the direction.
(Simplified if one of the points is the origin)
– Subtract the coordinates of the second point from those of the
first.
– Clear fractions to give lowest integer values for all coordinates

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Crystallographic Directions and Planes

Miller Indices for crystallographic directions

– Indices are written in square brackets without commas (ex: [hkl])
– Negative values are written with a bar over the integer.
• Ex: if h <0 then the direction is[ h k l]

Direction Indices[h k l] Directions in cubic

OA [1 0 0] crystals having same
indices without regard to
OB [1 1 0] order are equivalent
OC [1 1 1]
OD [2 0 1]
OE [0 1 0]
OF [1 1 2]
CB [0 0 1]
Equivalent directions: <100˃
• Since directions are vector, a direction and its negative are not identical
• A direction and its multiple are identical i.e. [100] = [200]
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• Certain groups of directions are equivalent in a cubic system

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Crystallographic Directions and Planes

Miller indices of Crystallographic Planes

– Identify the coordinate intercepts of the plane
• the coordinates at which the plane intercepts the x, y and z axes.
• If a plane is parallel to an axis, its intercept is taken as α.
• If a plane passes through the origin, choose an equivalent plane, or
move the origin
– Take the reciprocal of the intercepts

– Clear fractions due to the reciprocal, but do not reduce to lowest

integer values.
– Planes are written in parentheses, with bars over the negative indices
• Ex: (hkl) or if h <0 then it becomes ( h kl)

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Crystallographic Directions and Planes

Example: plane A is parallel to x, and intercepts y and z at 1, and therefore is

the (011). Plane B passes through the origin.

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Crystallographic Directions and Planes

• Planes and their negatives are identical

• Planes and their multiples are not identical
• In a cubic system, a direction that has same indices as a plane is
perpendicular to that plane
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Crystallographic Directions and Planes

Equivalent due to
symmetry

{100} 6

{110} 6

Planes with different Miller indices in a cubic crystals

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Crystallographic Directions and Planes

Construction of directions and planes

• Find the intercepts for plane (Projections for direction)

• Take reciprocals for plane (Not necessary for direction)

• Reduction to lowest set of integers (if necessary)

• Plot it

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Crystallographic Directions and Planes

Miller-Bravais Indices for HCP planes

Find the direction opposite to a3 axis from center : [1120] -> [110]

What will it for opposite to a1? [2110] 30

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Crystallographic Directions and Planes

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Crystallographic Directions and Planes

Close-packed planes and directions
atoms are in continuous contact

• Isotropic and anisotropic behaviour

Al – FCC - <111>/<100>

• Interplanar spacing:
distance between two parallel planes having same Miller indices or
belongs to same family
1 h2  k 2  l 2

d2 a2
• Repeat distance: distance between lattice points along the direction 32
that follow similar sequence of atoms

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Comparison of crystal structure

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Interstitial sites

Interstitial sites
• Radius ration ?
• Coordination number

Linear 0.000 – 0.155 2

Triangle 0.155 – 0.225 3 SC – 1 cubic site
Tetrahedron 0.225 – 0.414 4
Octahedron 0.414 – 0.732 6
Cube 0.732 – 1.000 8

No of holes/sites in SC, BCC, FCC ? 34

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Tetrahedral sites

BCC FCC

(6x4)/2 = 12 sites (1/2,1/4,1) 8 sites (3/4,1/4,3/4)

Observation: 2 x no of atoms
35

Octahedral sites

FCC
BCC

12/4 + 6/2 = 6 sites (1/2,1/2,1) 12/4 + 1= 4 sites (1/2,1/2,1/2)

Observation: no of atoms
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Sites in HCP crystal structure

Octahedral sites Tetrahedral sites

6 sites 2 x (6 edgex1/3 + 1 center line + 3 inside)

= no. atoms = 12 sites
= 2 x no. of atoms
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Structure of crystalline solids

Ionic structure: Filling the holes between anions

• Charge Neutrality:
--Net charge in structure
should be zero.

--General form:

--How does geometry determine this?

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 Structure of crystalline solids

How many anions can you arrange around a cation?

39

Structure of crystalline solids

Crystal structure of ionic materials

NaCl
ZnS

Sodium ions - purple (small)

Chloride ions - red (large)
Two interpenetrating FCC Zinc - green (small)
lattice (CN = 6 –> C & A) Sulfur - red (large) - FCC
N = 4 (C & A) Dashed lines -- unit cell
Interatomic distance (min)
CN = 4 -> C & A
Interatomic distance (min)

MgO, MnS, FeO 40

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Structure of crystalline solids

AX structure
• Step 1: Check Valence (Zn2+ and S2-) and Charge Neutrality
Zn2+ : S2- = 1:1 to get Formula Unit  ZnS

r Zn 0.074nm Based on this ratio,

• Consider ZnS: 
rS 0.184nm --coord no. CN = 4
--anion packing = FCC
 0.402
--structure = Zinc Blende
• Result: Must be FCC with only
tetrahedral coordination of cations.

• How many Anions in cell? 4
• How many Tetrahedral sites? 8
• How many Cations to fill holes? 4

This is Zinc Blende Structure

(other zinc blende materials: CdS, SiC etc.)
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Structure of crystalline solids

Crystal structure of diamond
Carbon exists in various polymorphic form
Diamond cubic
• Very hard material
• Very low electrical conductivity

• Combination of two FCC sub-latices

• Silicon and germanium also follow
diamond cubic crystal structure

Dashed lines -- unit cell

• No of atoms per unit cell
Interatomic distance (min) • Coordination number
• Packing density
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 Structure of crystalline solids
Crystal structure of graphite

 Excellent lubricative properties

 Electrical conductivity more than
diamond
 Chemical stability at elevated
temperature

• Layer of hexagonally arranged carbon atoms

• Each carbon atom is bonded to three coplanar neighbour
atoms by covalent bond
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• Fourth bond is weak bond between layers

Structure of crystalline solids

Structure of Fullerenes

Carbon nanotube

C60
extraordinary macroscopic properties:
• Single molecule: 60 carbon atoms
• High tensile strength, high electrical
• Composed of group of carbon atoms
conductivity, high ductility, high heat
– hexagon (20) and pentagon (12)
conductivity
• No two pentagons share a common side

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 Summary
• Classification of materials
• Lattice, Unit cell and Lattice parameters
• Crystal structure of common metals
- SC, BCC, FCC, HCP
- Close packed structure (HCP,CCP)
- atomic radius/coordination number/packing density
- Allotropic or Polymorphic transformation
- Crystal structure of important materials
-- Diamond (two interpenetrating FCC), graphite etc.
• Voids in close-packing cell
- tetrahedral void, octahedral void
•Crystallographic direction and planes
•Stacking sequence of close packed structure

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Problems

1. Theoretical density of BCC iron

2. Theoretical density of compound material
3. Packing fraction of HCP crystal structure
4. Radius ratio of cubic site
5. Packing fraction of diamond crystal structure
6. Planar density and linear density
7. Construction of crystallographic direction and planes
8. Allotropic transformation
9. Interplanar spacing

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Problems

Q1. Theoretical density of BCC iron

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Problems

OA =

48

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Problems

To obtain the intercepts, the reciprocal of the indices is

calculated as x = -1/2; y = 1/1; z = 1/0 = ∞

49

Problems

Q4. Find the interplanar spacing for a (221) plane in a simple

cubic lattice whose lattice constant is 4.12 x 10-10 m.

For a cubic lattice, the interplanar distance is

d = a /√(h2+k2+l2)
where, d = interplanar distance
a = lattice parameter
(h k l) is the Miller indices of the plane.

Therefore,
d = 4.12 * 10-10/√(32+22+12)
= 4.12 * 10-10/√(14)
= 1.10 * 10-10 m
= 0.11 nm
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25
 Problems
Q5. MgO follows similar crystal structure of NaCl. Compute the
theoretical density of MgO. (i) atomic radius of magnesium ion is
0.066 nm and oxygen ion 0.132 nm. (ii) Atomic mass of magnesium
is 24.312 gm/mol and oxygen 16 gm/mol.

The crystal structure of MgO is like NaCl

Theoretical density is defined by
ρ = (n∑A)/ VN where ∑A = AMg+ Ao
For MgO: n = 4

∑A = AMg+ Ao = 24.312+16 = 40.312 gm/mol

The ions touch along the edge of the cube,
Therefore, a = 2(nMg++ + nO--)
= 2(0.066+0.132) nm = 0.396 nm
= 0.396x10-8 cm
Therefore, ρ = 4 * 40.312/[(0.396 *10-8)3 *(6.023*1023)] 51
= 4.31 gm/cm3

Problems
Q6. What is the packing density or atomic packing factor of HCP
crystal structure?
In HCP crystal structure, a = 2r
where a = lattice parameter, and r = atomic radius
Therefore, number of atoms per unit cell
= (1/6)* 6 + ½ + 3 + ½ + (1/6)* 6
=1+½+3+½+1=6
Relation between c and a (c is the height of hexagon):
G
OG is the half of height and normal
E’
to base.

X
OX = 2/3 OE’
= (2/3) * (√3/2) * a
A
J O = a/√3
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26
 Problems

Again,
OG2 = OX2 + GX2
i.e. a2 = a2/3 + (c/2)2
2a2/3= c2 / 4
c/a = √ (8/3) = 1.63

Packing density = volume occupied by atoms / volume of unit cell

= [6 * (4/3) * pi * r3] / [6 * (√3/4) * a2 * c ]
= pi / 3√2
= 0.74

53

Problems
Q7. Above 8820C, titanium has a BCC crystal structure, with lattice
parameter a = 0.332 nm. Below this temperature, titanium has a HCP
structure with a = 0.2978 nm. Determine the percent volume change
when BCC titanium transforms to HCP titanium. Is this contraction
or expansion?

Since the crystal structure changes with temperature as well as the

density, we consider a fixed mass M as a reference to compare the
volume change.

For BCC crystal structure (above 882º C), the density

ρ = n A /Vc NA
= 2A / (0.332 nm)3 * NA
= 54.65 (A/ NA) nm-3
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 Problems
For HCP crystal structure (below 882º c), the density
ρ = n A /Vc NA = 6A / (3√3 /2) * a2 * c * NA
( where, c = √ (8/3) * a)
= 6A / (3√3/2) * (0.2978 nm)2 * √(8/3)*0.2978 nm * NA
= 55.02 (A/ NA) nm-3
For given mass M:
VBCC = M/ (54.65A/ NA )
VHCP = M/ (55.02A/ NA )

Volume is lesser for HCP structure compared to BCC structure for

same mass. Material contracts on changing from BCC to HCP.

% change in volume = [(VHCP -VBCC)/ VHCP] * 100

= [(1/55.02–1/54.65)x55.02] * 100
= - 0.68%
55

Problems

28
 Problems
Q9. Determine the packing density or atomic packing factor of
diamond cubic crystal structure.

Corner atom = 8
Face centered atom = 6
Atom lying on the body diagonal = 4
No of atoms = 8×(1/8) + 6×(1/2) + 4 = 8
Coordination No = 4
2R = (1/4)×body diagonal = (1/4) × √3a
57

Problems

58

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 Problems
Q11. Determine the minimum radius of an atom that will just fit into
the tetrahedral interstitial site in FCC nickel. The lattice parameter
of Nickel is 0.352 nm.
A P

O
O A
B C
D
Center of the tetrahedron = ¾ OP
AD = (√3/2)x2R =√3 R
OA = ⅔ AD =2R/√3 Now, OP = √(AP2-OA2)
Therefore, ¾ OP = R + r = √(4R2-4R2/3) = √(8/3)R
=> 3/4 x √(8/3)R = R + r
=> 1.225 R = R + r r/R = 0.225 59

Problems

For FCC,
√2 x a = 4R
=> R = √2/4 a (where a = 0.352 nm)
=> R = 0.12445 nm

Therefore,
r = R x 0.225 = 0.028 nm,

which is the required minimum radius of an atom

60

30
 Problems
Q12. Calculate the repeat distance and linear atomic density of
copper in the [110] direction. Also find out planar density (no. of
atoms/unit area) and planar packing fraction for the (010) plane of
Copper. Copper follows FCC structure and has a lattice parameter of
a = 0.361 nm.

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Thank you
for your kind attention

End of Module 2

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