Crystal Structure and Classification of Solids

UES 012 Engineering Materials
Crystal Structure
Disclaimer: The above material is purely for teaching purpose

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CLASSIFICATION OF SOLIDS
SOLID MATERIALS
AMORPHOUS
CRYSTALLINE POLYCRYSTALLINE
(Non-crystalline)
Single Crystal
Disclaimer: The above material is purely for teaching

purpose only
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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SINGLE CRYSTALS
A garnet single crystal that was found in Tongbei, Fujian Province, China

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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 nanocrystalline
Polycrystalline
Pyrite form
(Grain)

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Various stages in the solidification of a polycrystalline
material

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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.
• Amorphous materials have order only within a few atomic or molecular dimensions.
• Amorphous materials do not have any long-range order, but they have varying degrees
of short-range order.
• Examples to amorphous materials include amorphous silicon, plastics, and glasses.
• Amorphous silicon can be used in solar cells and thin film transistors.

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Amorphous vs Crystalline solids
Crystalline silicon dioxide Non-crystalline silicon dioxide
Quartz Glass-Silicate

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Schematic representation of ion positions in a sodium–silicate glass

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Crystalline solids
 There is a long range order in crystals.
 Melt at a sharp temperature.
 Crystalline solids can be cleaved along definite planes.
 Crystalline solids, in general are anisotrophic (It means that, their properties
such as electrical conductivity, refractive index, thermal expansion etc. will
be different directions).
Examples of Crystalline solids: Copper, Potassium nitrate, NaCl

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Amorphous solids
 There is only a short range order in amorphous solids
 Amorphous solids do not have a sharp melting point; they are softened
in a range of temperature.
 Amorphous solids undergo irregular or conchoidal breakage.
 Amorphous solids are isotrophic-the properties will be independent of

the direction in which they are measured.
 Less rigid.
Examples of Amorphous solids: Fibre glass, Cellophane, Teflon, Polyurethane,

Naphthalene, Polyvinyl chloride

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Significance of Crystal Structure in understanding
material Properties
Iron: BCC: soft and malleable

Cu, Al, Ag: FCC: hard , ductile, malleable
Mg, Na: hexagonal: brittle, non malleable, non ductile

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Crystal Lattice
What is a crystal lattice?
In crystallography, only the geometrical properties of the crystal
are of interest, therefore one replaces each atom by a
geometrical point located at the equilibrium position of that
atom.
Platinum Platinum surface Crystal lattice and

(scanning tunneling microscope) structure of Platinum

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Crystal Lattice-definition
y
 An infinite array of points in
space, B C D E
b α
 Each point has identical O a A x

surroundings to all others.
 Arrays are arranged in a

periodic manner.

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Crystal Lattice
• A 3-dimensional periodic array of points in space is

called as Space Lattice.
• For a particular solid, the smallest structural unit,
which when repeated for every point in the lattice is
called the Basis.
• Crystal Structure ≡ Lattice + Basis

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Crystal Structure
Crystal structures can be obtained by attaching atoms,
groups of atoms or molecules which are called basis (motif)
to the lattice sides of the lattice point.
Crystal Structure = Crystal Lattice + Basis

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Crystal Lattice
Karthiselva et. al., PhilosoPhical Magazine, 2017

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A two-dimensional Bravais lattice with
different choices for the basis

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Unit Cell in 2D
The smallest component of the crystal (group of atoms, ions or
molecules), which when stacked together with pure translational
repetition reproduces the whole crystal.

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Unit Cell in 2D
Part of an infinite lattice: the numbers are the indices, u, v, of
each lattice point.
Position of any other lattice point is defined by the vector P(uv)

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Nonprimitive cell
Primitive
cell
Primitive
cell

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Nonprimitive cell
Primitive
cell
Primitive
cell
Double
Triple
Symmetry of the Lattice or the crystal is not altered by our choice of unit cell!!
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Hypothetical case that two-dimensional (2D) crystals
of NaCl could form
(a) Section through the NaCl structure, showing (b) to (e) possible repeat units and
(f) incorrect units. Disclaimer: The above material is purely for teaching purpose
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Unit Cell in 2D

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Five Bravais Lattices in 2D

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Five Bravais Lattices in 2D

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Unit Cell in 3D
Crystals are built up of regular arrangements of atoms in three

dimensions; these arrangements can be represented by a repeat unit
or motif called the unit cell.
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Unit Cell in 3D
The unit cell is defined as the smallest repeating unit which shows the
full symmetry of the crystal structure.
• The unit cell and, consequently, the

entire lattice, is uniquely determined
by the six lattice constants: a, b, c, α, β
and γ.
• Only 1/8 of each lattice point in a unit
cell can actually be assigned to that
cell.
• Each unit cell in the figure can be
associated with 8 x 1/8 = 1 lattice
point.

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Primitive Unit Cell
Primitive Unit Cell:

A unit cell will be called as Primitive Unit Cell if number of atoms per
unit cell is equal to one.
Every primitive cell is a unit cell but the reverse may not be true.
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Sodium Chloride Structure
• Sodium chloride also crystallizes in a

cubic lattice, but with a different unit
cell.
• Sodium chloride structure consists of
equal numbers of sodium and
chlorine ions placed at alternate
points of a simple cubic lattice.
• Each ion has six of the other kind of
ions as its nearest neighbours.

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Sodium Chloride Structure

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1. Cubic (Isometric) System
Symmetry elements: Four 3-fold rotation axes along
cube diagonals c
a=b=c   b
a 
 =  =  = 90 o
3 Bravais lattices

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2. Tetragonal System
2 Bravais lattices
Symmetry element: One 4-fold rotation axis

a=bc
a=  =  = 90o

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3. Orthorhombic System
Four Bravais lattices
Symmetry element: Three mutually perpendicular

2-fold rotation axes
abc
a =  =  = 90o

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4. Hexagonal System
Symmetry element: One
6-fold rotation axis
a=bc
a= 120o
 =  = 90o
Only 1 Bravais lattice

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5. Trigonal (Rhombohedral) System
One Bravais lattice

a=b=c
a=  =   90o

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6. Monoclinic System
Two Bravais lattices

abc
a =  = 90o,   90o

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7. Triclinic System
One Bravais lattice
Symmetry element: None

abc
a      90o

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Typical Crystal Structures in 3D
3D – 14 BRAVAIS LATTICES AND SEVEN CRYSTAL TYPES
Rhombohedral

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Crystal Symmetry
 If an object is brought into self-coincidence after some

operation it said to possess symmetry with respect to that
operation.
SYMMETRY OPERATOR
 Given a general point a symmetry operator leaves a finite set of

points in space.
 A symmetry operator closes space onto itself.

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Rotation Axis
If an object come into self-coincidence through smallest non-zero rotation

angle of  then it is said to have an n-fold rotation axis where
360 0
n

=180 n=2 2-fold rotation axis

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The rotations compatible with translational symmetry are  (1, 2, 3, 4, 6)

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Symmetry Elements
(a) Two-, three-, and fourfold axes and (b, c) mirror planes of a cube.

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Absence of 5-fold Symmetry in regular
crystals
 We have seen earlier that the crystalline solids show only 1,2,3,4
and 6-fold axes of symmetry and not 5-fold axis of symmetry or
symmetry axis higher than 6.
 The reason is that, a crystal is a one in which the atoms or

molecules are internally arranged in a very regular and periodic
fashion in a three dimensional pattern, and identical repetition of
an unit cell can take place only when we consider 1,2,3,4 and 6-
fold axes.

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Absence of 5-fold and 7, 8 and higher order
symmetry
Packing of objects displaying 5- and 8-fold symmetry. Note that they do not fill completely
space and therefore they are not compatible with crystals.

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Why 5-fold symmetry is not possible in crystal system?
Geometric proof of the impossibility of a lattice with 5-fold symmetry
 Assume that 5-fold symmetry is possible.
 Draw the grid points shown below as small gray

circles.
 The shortest translation vectors t1 = t2 = t3 = t4 =

t5.
 The sum of any two lattice vectors must also be

a lattice vector, but no lattice vector can be
shorter than the shortest lattice vectors we have
just set up.
 if we take the sum of the t1 and t4 vectors we will

get a new vector (t1 + t4, shown in red) whose
magnitude is less than our “shortest” lattice
vectors, what destroys the hypothesis.
Disclaimer: The above material is purely for teaching purpose only

 Consider a grid line with lattice points
(gray circles) separated by a translation
vector t.
 If we rotate the line around a symmetry

axis of order n (perpendicular to the
drawing)
𝟑𝟔𝟎𝒐
𝜶=
𝒏
 We will get the line with blue circles. similarly, applying the reverse rotation, -α
we will get the line of red circles.
 If the α rotation is a lattice symmetry operation.
 Any distance between blue and red circles must be equal to an integral multiple
of the lattice translation (t): m.t, m'.t, etc., where m is an integer.
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In the isosceles triangle
cos α = (1/2) m.t / t
cos α = m / 2
m -2 -1 0 1 2
cos α -1 -1/2 0 1/2 1
α 180 120 90 60 0
n 2 3 4 6 1

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Simple Cubic

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Face Centered Cubic

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Body Centered Cubic

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Coordination Number
Coordination Number is equal to the number of

equidistant nearest neighbours.
• SC : Coordination Number is 6, PF = 0.52
• BCC: Coordination Number is 8, PF = 0.68
• FCC: Coordination Number is 12, PF = 0.74
• HCP: Coordination Number is 12, PF = 0.74
PF = Packing fraction

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Close-packed lattices in 2D

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Hexagonal Close packing and unit cell

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Putting atoms in the B position in the II layer and in C positions in the III layer we get a stacking sequence  ABC ABC
ABC….  The CCP (FCC) crystal
CCP
+ + =
A B C FCC
A
A
C
B
C
B

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Interstitial Void Spaces
Octahedral holes
Tetrahedral holes

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Interstitial Void Spaces

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Hexagonal Close Packed Structure
Shown displaced for clarity HCP
+ + =
A B A HCP
The C position is vacant and we can pass a line
through this position without intersecting any
atoms.

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• A hexagonal lattice decorated with a two atom/ion motif (at (0,0,0), (⅔, ⅓,½)) gives rise to
the HCP structure  In this ideal structure with spherical motifs the c/a ratio is ~1.632.
• Real HCP crystal often (mostly!) have c/a ratios differing from this ideal value. Only Mg
comes close .
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Question: For the HCP crystal structure, show that the ideal c/a ratio is 1.633 ?
Parallelopiped unit cell of HCP
The atom at point M is midway between the top and bottom faces of the unit cell
MH = c/2
Since atoms at J, K and L positions are touching each other
JM = MK = JK = 2R = a only Where R is the atomic radius
In right angle triangle JHM Metal c/a

Cd 1.886
(JM)2 = (JH)2 + (HM)2 Zn 1.856
Mg 1.624
a2 = (JH)2 + (c/2)2
Zr 1.590
Ti 1.588
ΔJKL is a equilateral triangle
Be 1.586
Substituting this value for JH in the above expression, yields

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Atomic Packing Fraction: HCP
APF is the ratio of the total sphere volume, VS, to the unit cell volume, VC
Number of atoms in HCP = 6
The unit cell volume is the product of the base area times the cell height, c
The base area is equal to six times

Disclaimer: thematerial
The above areais purely
of the equilateral
for teaching purpose triangle, OAB
only

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Cesium Chloride (CsCl) Crystal Structure
 Unit cell: Simple cubic lattice.
 No. of atoms per unit cell: 2
 The coordination number is 8 for

both ion types.
 This is not a BCC crystal structure

because ions of two different kinds
are involved.

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Zinc Blende (ZnS) Crystal Structure
 The coordination number is 4.
 All ions are tetrahedrally coordinated.
 All corner and face positions of the

cubic cell are occupied by S atoms,
while the Zn atoms fill interior
tetrahedral positions.

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Carbon base Crystal Structure
Carbon is an element that exists in various polymorphic forms
graphite
A unit cell for the
diamond cubic
crystal structure

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Carbon base Crystal Structure
The structure of a carbon nanotube.
Fullerenes
(C60 molecule)

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Diamond Cubic Structure
 The diamond cubic structure is a
combination of two interpenetrating FCC sub
lattices displaced along the body diagonal of
the cubic cell by 1/4th length of that
diagonal.
z
 Every carbon atom is surrounded by four
other carbon atoms situated at the corners of
y
X regular tetrahedral by the covalent linkages.
 One sublattice has its origin at the point (0,

0, 0) and the other at a point quarter of the
way along the body diagonal (at the point
a/4, a/4, a/4)
 The point at 0 and ½ are on the fcc lattice,

those at ¼ and ¾ are on a similar lattice
displaced among the body diagonals by ¼ of
the cube edge.
 No. of atoms present in a diamond cubic unit

cell is 1 + 3 + 4 = 8.
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APF: Diamond Cubic Structure
Thus it is a loosely packed structure. Example: C, Si, Ge, ZnS

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Numerical problem
1. Sodium crystallises in a cubic lattice. The edge of the unit cell is
4.16 Å. The density of sodium is 975kg/m3 and its atomic weight is 23.
What type of unit cell does sodium form ? (Take Avagadro number as
6.023 1023 atoms/mole)
2. A metallic element exists in a cubic lattice. Each side of the unit cell
is 2.88 Å. The density of the metal is 7.20 gm/cm3. How many unit
cells will be there in 100gm of the metal?

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Edge of the unit cell, a = 2.88Å = 2.88 × 10-10m
Density of the metal, ρ = 7.20 gm/cm3
= 7.2 ×103 kg/m3
mass of the metal = 100gm = 0.1kg
Volume of the unit cell = a3 = (2.88 × 10-10)3
= 23.9 × 10-30m3
Mass 0.1
Volume of 100gm of the metal = 
Density 7.2  103
= 1.39 × 10-5m3
Number of unit cells in the volume =
= 5.8 × 1023
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Crystal Structure and Classification of Solids

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Crystal Structure and Classification of Solids

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UES 012 Engineering Materials

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching

 Single crystals have a periodic atomic structure across its

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

 There is a long range order in crystals.

 Melt at a sharp temperature.

 Crystalline solids can be cleaved along definite planes.

Examples of Crystalline solids: Copper, Potassium nitrate, NaCl

Disclaimer: The above material is purely for teaching purpose

 There is only a short range order in amorphous solids

 Amorphous solids undergo irregular or conchoidal breakage.

 Amorphous solids are isotrophic-the properties will be independent of

Examples of Amorphous solids: Fibre glass, Cellophane, Teflon, Polyurethane,

Disclaimer: The above material is purely for teaching purpose

Iron: BCC: soft and malleable

Disclaimer: The above material is purely for teaching purpose

Platinum Platinum surface Crystal lattice and

Disclaimer: The above material is purely for teaching purpose

 Each point has identical O a A x

 Arrays are arranged in a

Disclaimer: The above material is purely for teaching purpose

• A 3-dimensional periodic array of points in space is

Disclaimer: The above material is purely for teaching purpose

Crystal Structure = Crystal Lattice + Basis

Disclaimer: The above material is purely for teaching purpose

Karthiselva et. al., PhilosoPhical Magazine, 2017

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Position of any other lattice point is defined by the vector P(uv)

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Crystals are built up of regular arrangements of atoms in three

• The unit cell and, consequently, the

Disclaimer: The above material is purely for teaching purpose

Primitive Unit Cell:

• Sodium chloride also crystallizes in a

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Disclaimer: The above material is purely for teaching purpose

Symmetry element: One 4-fold rotation axis

Disclaimer: The above material is purely for teaching purpose

Symmetry element: Three mutually perpendicular

Disclaimer: The above material is purely for teaching purpose

Only 1 Bravais lattice

Disclaimer: The above material is purely for teaching purpose

Symmetry element: One 3-fold rotation axis

Disclaimer: The above material is purely for teaching purpose

Two Bravais lattices

Symmetry element: One 2-fold rotation axis

Disclaimer: The above material is purely for teaching purpose

Symmetry element: None

Disclaimer: The above material is purely for teaching purpose