The Structure of Crystalline Solids

Dr. Madan Lal Chandravanshi

Assistant Professor
Mechanical Engineering
Department, IIT(ISM) Dhanbad
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 What is solid state physics?

• Explains the properties of solid materials.

• Explains the properties of a collection of

atomic nuclei and electrons interacting with
electrostatic forces.

• Formulates fundamental laws that govern the

behavior of solids.
 CLASSIFICATION OF SOLIDS

SOLID MATERIALS

CRYSTALLINE POLYCRYSTALLINE AMORPHOUS

(Non-crystalline)

Single Crystal

Crystal Structure
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 Crystal Structures

Groups

Lattice

Unit cell

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 Crystalline Solids
• Crystalline materials are solids with an atomic
structure based on a regular repeated pattern.

• The majority of all solids are crystalline.

• More progress has been made in understanding

the behavior of crystalline solids than that of non-
crystalline materials since the calculation are
easier in crystalline materials.

• Understanding the electrical properties of solids is

right at the heart of modern society and
technology.
 Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy
• Dense, ordered packing
Energy

typical neighbor
bond length

typical neighbor r
bond energy
a. Dense, ordered packed structures tend to have lower
energies in molecules (not bond energy).
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Electrochemical energy storage materials

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 Materials and Packing

Crystalline materials...
• atoms pack in periodic, 3D arrays
• typical of: -metals
-many ceramics
-some polymers crystalline SiO2

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Plastics, glass, rubber, metallic glass, polymers, gel, fused silica, tar, thin
layer lubricants, and wax are examples of amorphous solids 8
 SINGLE CRYSTALS
 Single crystals have a periodic atomic structure across its
whole volume.
 At long range length scales, each atom is related to every
other equivalent atom in the structure by translational or
rotational symmetry

Single Pyrite
Crystal

Amorphous
Solid
Single Crystals
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 POLYCRYSTALLINE SOLIDS
 Polycrystalline materials are made up of an aggregate of many
small single crystals (also called crystallites or grains).

 Polycrystalline materials have a high degree of order over many

atomic or molecular dimensions.

 Grains (domains) are separated by grain boundaries. The atomic

order can vary from one domain to the next.
 The grains are usually 100 nm - 100 microns in diameter.
 Polycrystals with grains less than 10 nm in diameter are Nano
crystalline

Polycrystalline
Pyrite form
(Grain)

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 AMORPHOUS SOLIDS
• Amorphous (Non-crystalline) Solids are made up of
randomly orientated atoms , ions, or molecules that do not form
defined patterns or lattice structures.

• These materials have order only within a few atomic or molecular

dimensions and do not have any long-range order,

Example: amorphous materials include amorphous

silicon, plastics which can be used in solar cells and thin
film transistors.

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 CRYSTAL LATTICE
What is a crystal lattice?
In crystallography, only the geometrical properties of the
crystal are of our interest, therefore one replaces each
atom by a geometrical point located at the equilibrium
position of that atom.

Platinum Platinum surface

(scanning tunneling microscope)
Crystal lattice and
structure of Platinum
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Three common Unit Cells in 3D

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Unit cell

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Definition of Reciprocal Lattice

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Types of Lattice

Crystal Structure
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 Metallic Crystal Structures

• Tend to be densely packed.

• Reasons for dense packing:
- Typically, only one element is present, so all
atomic radii are the same.
- Metallic bonding is not directional.
- Nearest neighbor distances tend to be small in
order to lower bond energy.
- Electron cloud shields cores from each other

• Have the simplest crystal structures.

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 Simple Cubic Structure (SC)

• Rare due to low packing density (only Po (Polonium) has this

structure)
• Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

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 Atomic Packing Factor (APF)

Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.24, Callister & Rethwisch 8e. 19
 Body Centered Cubic Structure (BCC)

• Atoms touch each other along cube diagonals.

--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

ex: Cr, W, Fe (), Tantalum, Molybdenum

• Coordination # = 8

Adapted from Fig. 3.2,

Callister & Rethwisch 8e.
(Courtesy P.M. Anderson)
2 atoms/unit cell: 1 center + 8 corners x 1/8
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 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
R length = 4R = 3 a
a
atoms volume
4
unit cell 2 p ( 3a/4) 3
3 atom
APF =
volume
a3
unit cell 21
 Face Centered Cubic Structure (FCC)

• Atoms touch each other along face diagonals.

--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

• Coordination # = 12

Adapted from Fig. 3.1, Callister & Rethwisch 8e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

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 Atomic Packing Factor: FCC

• APF for a face-centered cubic structure = 0.74

maximum achievable APF
Close-packed directions:
length = 4R = 2 a
2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
atoms volume
4
unit cell 4 p ( 2a/4) 3
3 atom
APF =
3 volume
a
Adapted from Fig. 3.1(a), Callister & Rethwisch 8e. unit cell
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Common Crustal Structures

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 FCC Stacking Sequence

• ABCABC... Stacking Sequence

• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

A
• FCC Unit Cell B
C

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Hexagonal Close-Packed Structure (HCP)

• ABAB... Stacking Sequence

• 3D Projection
• 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister & Rethwisch 8e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 26
Hexagonal Close-Packed Structure (HCP)

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 Theoretical Density, 

• Ex: Cr (BCC)
A = 52.00 g/mol (Atomic weight)
R = 0.125 nm
n = 2 atoms/unit cell
R
a a = 4R/ 3 = 0.2887 nm

atoms
g
unit cell 2 52.00 theoretical = 7.18 g/cm3
mol
= actual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol 28
Miller indices

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Miller indices – Example

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 X-Ray Diffraction Pattern
z z z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x (211)

(200)

Diffraction angle 2q

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.22, Callister 8e. 32
Crystallographic planes

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Crystallographic planes

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Hexagonal Crystals

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Planes and Directions in Hexagonal Unit Cells –
MILLER Bravais Indices

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Planes and Directions in Hexagonal Unit Cells

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Planes and Directions in Hexagonal Unit Cells

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Hexagonal Unit Cell- Example

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Hexagonal Unit Cell- Examples

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 Hexagonal Crystal
The first three indices pertain to projections
along the respective a1, a2, and a3 axes in the
basal plane the four values of miller bravaias
may be obtained from equation:

Conversion and Construction of Miller Bravais Directional

Indices for a Hexagonal Unit Cell from Miller Indices [111] for
hexagonal crystals.

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X-RAY DIFFRACTION: DETERMINATION OF CRYSTAL
STRUCTURES
• Our understanding regarding the atomic and molecular arrangements in
solids has resulted from x-ray diffraction investigations; furthermore, x-rays
are still very important in developing new materials.

• Diffraction occurs when a wave encounters a series of regularly spaced

obstacles that

• (1) are capable of scattering the wave, and

• (2) have spacings that are comparable in magnitude to the wavelength.

Furthermore, diffraction is a consequence of specific phase relationships
established between two or more waves that have been scattered by the
obstacles.

https://www.youtube.com/watch?v=xBA09PXPPR4
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diffraction is a consequence
of specific phase
relationships established
between two or more waves
that have been scattered by
the obstacles.

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 X-Ray Diffraction and Bragg’s Law
• X-rays are a form of electromagnetic radiation that have
high energies and short wavelengths—wavelengths on the
order of the atomic spacings for solids.
• When a beam of x-rays impinges on a solid material, a
portion of this beam will be scattered in all directions by
the electrons associated with each atom or ion that lies
within the beam’s path.
• Two parallel planes of atoms A– and B– in Figure 3.20, the
same h, k, and l Miller indices are separated by the
interplanar spacing dhkl.
• Now assume that a parallel, monochromatic, and
coherent (in-phase)

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 The diffractometer used to
determine the angles at which
X-ray Diffraction diffraction occurs for powdered
specimens

Figure 3.20 Diffraction of x-rays

by planes of atoms (A–A’ and B–B’). 45
Bragg’s law

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Relative Sizes and Microscopy Examination tools

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 Theoretical Density, 

Mass of Atoms in Unit Cell

Density =  =
Total Volume of Unit Cell

nA
 =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro’s number
= 6.022 x 1023 atoms/mol

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Linear and Planer densities

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Linear Density- Example

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 Densities of Material Classes
In general Graphite/
metals > ceramics > polymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
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Based on data in Table B1, Callister
20 Platinum *GFRE, CFRE, & AFRE (Aramid Fiber-
Gold, W
Metals have... Tantalum Reinforced Epoxy composites) are Glass,

• close-packing
10 Silver, Mo
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

 (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
• often lighter elements Concrete
Silicon PTFE
Glass fibers
2 GFRE
Polymers have... Magnesium Graphite
Silicone Carbon* fiber
PVC
• low packing density PET
PC
CFRE
1 HDPE, PS Aramid fibers
(often amorphous) PP, LDPE
• lighter elements (C,H,O) AFRE

0.5 PET-polyethylene Terephthalate. Wood

Composites have... 0.4 Polycarbonates (PC)

• intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 8e.
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 Crystals as Building Blocks
• Some engineering applications require single crystals:

-- diamond single
crystals for abrasives

-- Ex: Quartz fractures more easily

along some crystal planes than
others. -- Turbine blades

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 Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa

-Properties vary with direction:

anisotropic.
-Example: the modulus of elasticity (E)
in BCC iron:
E (edge) = 125 GPa
• Polycrystals
-Properties may/may not 200 mm
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-

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 Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)

titanium Iron system

, -Ti
liquid
1538ºC
carbon
BCC -Fe
diamond, graphite,
Uckyball – C60 1394ºC
FCC -Fe
912ºC
BCC -Fe

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Polymer structures

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 Polymer Structures
Linear

Branched

Cross-Linked

Network
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Thermo-sets – Thermo-plasts

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 Ceramic crystal structures
Ceramic Crystal structures

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 Ceramic crystal structures
Ceramic Crystal structures

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 Ceramic crystal structures
Silicates

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Carbon

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Thanks
For

Your
Attention 63