Unit III Crystollography

ST.
JOSEPH UNIVERSITY IN TANZANIA
ST. JOSEPH COLLEGE OF ENGINEERING

&TECHNOLOGY
DEPARTMENT OF BASIC ENGINEERING
DEGREE SEMESTER I
MODULE NAME: PH1103

MODULE CODE: ENGINEERING PHYSICS
LECTURE NOTES
ENGINEERING PHYSICS-PH1103 ----------Ms. MINA--------
UNIT III -CRYSTALLOGRAPHY

Crystallography: Crystalline and amorphous solids – Forces between atoms - Cohesion of
atoms and equilibrium atomic spacing- cohesive energy - lattice and unit
cell – seven crystal system and Bravais lattices – Miller indices – d-spacing in cubic lattice
- Calculation of number of atoms per unit cell – Atomic radius – Coordination number –
Packing factor for SC, BCC, FCC and HCP structures – Crystal preparation by slow
evaporation and Czochralski method - Bragg ‘s law for X-ray diffraction – Laue method –
Powder method. – Crystal structure of NaCl and Diamond.
INTRODUCTION
Crystallography is the term applied to the field which studies crystalline structures. Many
crystalline structures exist in nature, such as gemstones and rocks. In the field of life sciences,
however, crystallography is primarily used to study proteins and other important biological
molecules which do not crystallize naturally.
Matter is normally divided into three states namely solid, liquid & gas; plasma is considered
as the fourth state of matter. Some of the substances exhibit an additional state intermediate to
solid and liquid states. It is known as liquid crystal state. Each of the state consists of some
characteristic’s distribution of atoms (or molecules) in it. Finally, matter is classified as follows.
 Solid State: - A solid consist of atoms or cluster of atoms arranged in close proximity.
The physical structure of a solid and its properties are closely related to the scheme of
arrangement of atoms within the solid. Solids can be classified into two categories
namely crystalline and amorphous solids.
DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~2~

 Crystalline solids: In crystalline solids, the atoms, ions or molecules of which they are
composed of are arranged in regular repeated three-dimensional pattern having a definite
geometrical shape. Crystalline solids may occur in single crystal form or polycrystalline
form.
 Single Crystal: Single crystals are polyhedrons that have a distinctive shape for each
material. They have smooth faces and straight edges. A large single crystal of regular
shape is called monocrystal. Quartz, alum, diamond and rock salt are examples of solids
that occurs as large size single crystal.
 Polycrystalline Solids: Polycrystalline solids consist of fine grains having size of 10 3 to
104 A o, separated by well-defined boundaries and oriented in different directions. Each
such grain is a single crystal of an irregular shape. Majority of natural solids have
polycrystalline structure. Metals are example of polycrystalline solids.
 Non-Crystalline (Amorphous) Solid: Some material maintains a fixed volume, shape
and resemble in their external features, but internally they do not have the ordered
crystalline state. Such materials are known as amorphous solids. The atomic arrangement
in these materials exhibit only short-range order as in liquids. They are in fact considered
as super cooled liquids having very high viscosity in which atoms have become fixed in a
random arrangement. Glass, rubber and polymers are examples of amorphous substance.
CRYSTOLLOGRAPHY
Crystallography is used to study atomic structures because optical microscopy is unsuitable for
this purpose. This is because visible light’s wavelength is several magnitudes larger than the
length of atomic bonds and atoms. The shorter wavelength of electromagnetic radiation is,
therefore, more suited to the analysis of structures at this scale.
SOLID STATE
 A solid state is simply one of the states of matter. One of the many different states of
matter is solid. Solids have a distinct volume, mass, and shape. Solids differ from liquids
and gases in that they exhibit unique characteristics.

 These solid states or shapes depending on how the particles are arranged in a specific or
indeterminate geometry. There are, however, a few exceptions when it comes to the
particles that make up the solid material.
 These particles are held together by powerful forces between them, irrespective of
whether they are molecular, ionic, metallic, or covalent. Crystalline solids are made up of
an array of particles that are uniformly arranged and kept together by intermolecular
forces. On the other hand, the particles are not arranged in regular arrays in amorphous
solids.
TYPES OF SOLIDS
Solids are classified into two types based on the arrangement of constituent particles:
1. Crystalline solid
2. Amorphous Solid
1.CRYSTALLINE SOLIDS
A crystalline solid has a well-arranged large small crystal. A crystal is an ordered

arrangement of constituent particles (atoms, molecules, or ions).
Crystalline solid has a long-range order which means that there is a consistent pattern of
particle arrangement that repeats itself on a regular basis across the entire crystal. Typical
crystalline solids examples are sodium chloride and quartz.
PROPERTIES OF CRYSTALLINE SOLIDS

 Crystalline solids have a sharp melting point and begin to melt at a specific
temperature.
 The shapes are well defined and also particle arrangements of crystalline solids are
well-defined.
 Crystalline solid has cleavage property, which means that when cut with the edge of a
sharp tool, they split into two pieces and the newly formed surfaces are smooth and
plain.
 They have a distinct heat of fusion (amount of energy needed to melt a given mass of
solid at its melting point).
 Crystalline solids are anisotropic. Anisotropic solids have physical properties, such as
electrical resistance or refractive index, that differ when measured in different
directions within the same crystal.
 True solids are crystalline solids.
TYPES OF CRYSTALLINE SOLIDS
Crystalline solids are classified into four types based on the nature of their intermolecular forces:
molecular, ionic, metallic, and covalent solids. Let us now learn more about these classifications.
 Molecular Solids: In molecular solids, molecules are constituent particles. Molecular

solids are further divided into three categories-
 Non-polar Molecular Solids – These are made up of either atoms, such as argon and
helium, or molecules formed by non-polar covalent bonds, such as H2, Cl2, and I2. The
atoms or molecules in these solids are held together by weak dispersion forces or London
forces.
 Polar Molecular Solids – Polar covalent bonds form the molecules of substances such as
HCl, SO2, and others. The molecules of these solids are held together by relatively
stronger dipole-dipole interactions. These soft solids are electrically inactive. Examples
of such solids include solid SO2 and solid NH3.
 Hydrogen-Bonded Molecular Solids – These solids’ molecules have polar covalent
bonds between H and F, O, or N atoms. Strong hydrogen bonding holds molecules of
solids like H2O together (Ice).

 Ionic Solids: Ions are the particles that make up ionic solids. Ionic solids are three-
dimensional arrangements of cations and anions held together by strong electrostatic
forces. These solids are naturally hard and brittle. Their melting and boiling points are
both very high. Because the ions cannot move freely, they are electrical insulators in the
solid state. When the ionic solid is molten or dissolved in water, the ions become free to
move and conduct electricity.
 Metallic Solids: Metals are a well-organized collection of positive ions that are
surrounded and held together by a sea of free electrons. These electrons are mobile and
are distributed evenly throughout the crystal. Each metal atom adds one or more electrons
to the sea of mobile electrons. Metals’ high electrical and thermal conductivity is due to
these free and mobile electrons. These electrons flow through the network of positive
ions when an electric field is applied.
 Covalent or Network Solids: The formation of covalent bonds between adjacent atoms
throughout the crystal results in a wide range of nonmetal crystalline solids. They are also
known as giant molecules. Because covalent bonds are strong and directional in nature,
atoms are held very tightly in their positions. These solids are extremely hard and brittle.
They have extremely high melting points and may decompose prior to melting. They are
electrical insulators that do not conduct electricity. Diamond and silicon carbide are two
well-known examples of such solids.
2. AMORPHOUS SOLIDS
Amorphous solids (Greek amorphous = no form) are made up of irregularly shaped particles.
Short-range order exists in the arrangement of constituent particles (atoms, molecules, or ions) in
such a solid. Only over short distances are a regular and periodically repeating pattern observed
in such an arrangement.

PROPERTIES OF AMORPHOUS SOLID
 Amorphous solids soften gradually over a temperature range and can be shaped into
various shapes when heated.
 Amorphous solids are pseudo-solids or supercooled liquids, which means they move very
slowly. If you look at the glass panes that are fixed to the windows of old buildings, you
will notice that they are slightly thicker at the bottom than at the top.
 Amorphous solids have an irregular shape, indicating that the constituent particles do not
have a definite geometry of arrangement.
 When amorphous solids are cut with a sharp edge tool, irregular surfaces are formed.
 Because of the irregular arrangement of the particles, amorphous solids do not have
definite heat of fusion.
 Because of the irregular arrangement of particles, amorphous solids are isotropic in
nature, which means that the value of any physical property would be the same along any
direction.
DIFFERENCE BETWEEN CRYSTALLINE SOLIDS AND AMORPHOUS SOLIDS
CRYSTALLINE SOLID AMORPHOUS SOLID
A crystalline solid has well-arranged Constituent particles of amorphous solids

constituent particles. are not well arranged
Crystalline solids are true solids. Amorphous solids are pseudo-solids.
Crystalline solids are anisotropic. Amorphous solids are isotropic.
Crystalline solids have a sharp melting point Amorphous solids soften gradually over
and begin to melt at a specific temperature. a temperature range and can be shaped
into various shapes when heated.

The shapes are well defined and also particle The shape of amorphous solids is
arrangements of crystalline solids are well- irregular and also particle arrangement
defined. is not well defined.
Crystalline solids when cut with the edge of When amorphous solids are cut with a
a sharp tool, they split into two pieces and sharp edge tool, irregular surfaces are
the newly formed surfaces are smooth and formed.
plain.
Quartz, calcite, sugar, mica, diamonds, Plastics, glass, rubber, metallic glass,
snowflakes, rock, calcium fluoride, silicon polymers, gel, fused silica, pitch tar,
dioxide, and alum are examples of thin layer lubricants, and wax are
crystalline solids. examples of amorphous solids.
FORCES BETWEEN ATOMS AND MOLECULES
(or)
INTERMOLECULAR FORCES
An intermolecular force is the force that arises from the interaction between molecules.
Intermolecular attractions are not nearly as strong as the intramolecular attractions that hold
compounds together (covalent or ionic bonds).

There are three main types of intermolecular force:
 Permanent dipole-dipole forces

 Induced dipole-dipole forces – Also known as van der Waals, dispersion or London
forces.
 Hydrogen bonding
1. Permanent Dipole-Dipole Forces
Permanent dipole-dipole forces are the weak intermolecular forces of attraction that arise
between permanently polar molecules. These forces are between the delta positive end of one
polar bond with the delta negative end of another polar bond. The more polar the molecules, the
stronger the force of attraction between them.
2. Induced Dipole-Dipole Forces
Induced dipole-dipole forces are weak intermolecular forces of attraction present between all
atoms and all molecules that exist – whether polar or non-polar – as a result of the present of
electrons in the molecule and the formation of temporary dipoles. They are the weakest type of
intermolecular force.
This causes a sudden displacement of electrons in one atom to one side causing the atom to have
a temporary dipole: a transient asymmetry of charge distribution around an atom.

Once a temporary dipole is formed, it induces temporary dipoles in neighboring atoms and
molecules in a domino like effect. The two temporary dipoles are attracted towards each other by
induced dipole- dipole forces also known as London or Van der Waals forces.
The dipoles are called temporary because as electrons are constantly moving, dipoles are
constantly being created and destroyed. However, there is always a dipole present at any given
time, so overall effect is for the atoms in the molecule to remain attracted to each other.
3. Hydrogen Bonding
Hydrogen bonds are a special type of permanent dipole-dipole forces that only form when
hydrogen forms a covalent bond with a very electronegative element: either nitrogen, oxygen or
fluorine. They are the strongest type of intermolecular force.
DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 10 ~

As nitrogen, oxygen and fluorine are more electronegative hydrogen, they attract the electron
pair in the covalent bond with hydrogen towards themselves. This forms a polar bond – hydrogen
is δ+, and the other atom is δ-.
Hydrogen atoms have a very high charge density because the hydrogen atoms only have 1 shell
of electrons. Therefore, the δ+ hydrogen can be attracted to the lone pair of electrons on the
nitrogen, oxygen or fluorine atoms in nearby molecules.
COHESION OF ATOMS AND EQUILIBRIUM ATOMIC SPACING
A crystal consists of atoms or molecules bound together by certain forces. These forces or
bonds determine the arrangement of the constituent atoms i.e., crystal structure. Forces that hold
the crystalline atoms/molecules together are called cohesive forces.

The total energy of a crystal consists of its kinetic energy and potential energies. It is called
the crystal energy. It includes the energy of interaction when the atoms come together.
COHESIVE ENERGY
The energy of the same atoms that constitute the crystal when free (i.e. infinitely far apart) is
called the free atom energy. The difference between the free atom energy and the crystal energy
is called the cohesive energy.
The inert gas crystals like He, Ne, and Xe have cohesive energies in the range 3-4kJ/mol.
They are weakly bound. Carbon silicon and Germanium are strongly bound. Their cohesive
energies are in the range 370 – 700 kJ/mol.

CRYSTAL LATTICE
A regular three-dimensional arrangement of points (ions, atoms, etc.) in space is called a

crystal lattice. There are 14 possible three-dimensional lattices. These are called Bravais
lattices.
CHARACTERISTICS OF CRYSTAL LATTICE
 Each point in the crystal lattice is called a lattice point or lattice site.
 Each point in the crystal lattice represents a constituent particle which can be an
atom, a molecule (a group of atoms) or an ion.
 Three-dimensional distribution of lattice points representing a crystal lattice.
 The lattice points are joined by straight lines to bring out the geometry of the lattice.
UNIT CELL
 The unit cell is the smallest part of the crystal lattice, which when repeated in
different directions produces the entire lattice, e.g., Primitive unit cells and
concentrated unit cells.
 A unit cell is the smallest unit that when stacked together repeatedly without any gaps
can reproduce the entire crystal.

The unit cell for sodium chloride is shown in figure 1. In figure 1a the green and red spheres
represent the center of the Cl– and Na+ ions respectively. Figure 1b provides a more realistic
representation with the sodium and chloride ions touching each other along the cell edges.
PARAMETERS OF A UNIT CELL
A unit cell is characterized by:
 Its dimensions (length) are of form a, b, and c with three edges. These edges may or
may not be mutually perpendicular.
 angles α, ß, and γ between the pair of edges. The angle α is between the edges b and
c, angle ß is between the edges c and a and angle γ is between the edges a and b.

Thus, a unit cell is characterized by six parameters, a, b, c, α, ß and γ. The complete

crystal lattice can be obtained by expanding the unit cell in all three directions.
TYPES OF UNIT CELLS
Unit cells can be broadly divided into two categories,
1. primitive unit cell

2. non- primitive unit cell
1. primitive unit cell-A unit cell that contains only one lattice point is called a primitive
unit cell, which is made up from the lattice points at each of the corners. In primitive unit
cells, the constituent particles are present only at the corner positions of the unit cell
whereas, in concentrated unit cells, one or more component particles are present at
locations other than the corners.
2. non- primitive unit cell-In case of non-primitive unit cells, there are additional lattice
points, either on a face of the unit cell or with in the unit cell. Centered unit cell is
classified as the body-centered unit cell (bcc), face-centered unit cell (fcc), end centered
unit cell (ECC).

There are seven primitive crystal systems; cubic, tetragonal, orthorhombic, hexagonal,
monoclinic, triclinic and rhombohedral. They differ in the arrangement of their
crystallographic axes and angles. Corresponding to the above seven, Bravis defined 14
possible crystal systems as shown in the figure.

14 BRAVIS LATTICES

Bravais introduced the concept of space lattice in the study of crystal structures. One would
expect that many lattices can be generated in three dimensions with different primitives and
non-primitive cells. However, in 1848.
Aauguste Bravais, the French Crystallographer proved that there are only 14 different
ways of arranging identical points in three-dimensional space, satisfying the condition of
periodicity so that they are in every way equivalent in their surroundings. These fourteen
types of arrangement are called Bravais Lattices.
Crystal System: The sets of the values that the six lattice parameters a, b, c, α, β and γ can
take are limited to 7 only and accordingly all the crystal structures can be classified into 7
crystal system. So, the total 14 lattices form 7 crystal system. They are Cubic, tetragonal,
orthorhombic, monoclinic, Triclinic, Hexagonal and rhombohedral.
THE UNIT CELL CHARACTERISTICS
(i) UNIT CELL VOLUME, V
The volume of a unit cell is given by
V= abc [1-cos 2 α-cos 2 β-cos 2 γ + 2cos αcos βcos γ]1/2
If α= β= γ = 90o, then V = abc
Further, when a=b=c, as in the case of cubic cells

V= a3
(ii) EFFECTIVE NUMBER OF ATOMS PER UNIT CELL (Z) / RANK OF UNIT CELL
The effective number of atoms per unit cell is equal to the product of the number of atoms
per lattice point and the number of lattice points per unit cell. Unit cell is a part of an infinite
scheme and is not an isolated entity. Therefore, the Lattice points do not exclusively belong to
one unit cell but each one is shared by several adjacent cells. As a result, an atom located at a
lattice site contributes only a fraction of its mass and volume to one unit cell.
(iii) ATOMIC RADIUS, (r):
The relationship between the apparent size of the atom and the edge of the unit cell can be
determined where one atom is attached to a lattice site.
(iv) NEAREST NEIGHBOUR DISTANCE, (2r)
The nearest neighbour distance, in metallic structures is the distance between the centers of
the atoms in contact expressed in terms of the length of the edge of the unit cell.
(v) COORDINATION NUMBER (CN)
The coordination number of an atom in a crystal is the number of nearest neighbour atoms
which are simultaneously in contact with that atom. It signifies the tightness of packing of atoms
in the crystal.
(vi) ATOMIC PACKING FRACTION (APF)
The fraction of the space occupied by atoms in the unit cell is known as atomic packing
fraction. It is defined as the ratio of the volume of effective number of atoms in the unit cell to
the total volume of the unit cell. Thus,
No.of atoms /unit cell (Volume of each atom)

𝐀𝐏𝐅 =
Volume of the unit cell
Zv
Therefore, 𝐀𝐏𝐅 =
𝑣

The atomic packing fraction denotes the efficiency with which the available space in a unit cell is
utilized.
(vii) VOID SPACE
The void space in the unit cell is the vacant space left unutilized in the cell. It is equal to (1-
APF). It is often expressed as %. It is commonly known as interstitial space.
Thus, %Void space= (1 – APF) x 100
(viii) DENSITY
The density of unit cell must be the same as that of bulk crystal. Thus,
𝑀𝑎𝑠𝑠 𝑍𝑊
Density, ρ = =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑉
𝑀
Where, W is the mass of each atom. W is given by W = N𝐴
Where, M →the molecular weight of the material
NA→ the Avogadro number.
𝑍𝑀
Therefore, ρ =
N𝐴 V
𝑍𝑀
ρ=
N𝐴 𝑎3
CUBIC LATTICE (Or) CUBIC CRYSTAL SYSTEM
The lattice for which the unit cell is a cube is called a cubic lattice. In this case a=b=c and α=β=
γ=90.There are three types of unit cells in the cubic structure.
They are:
1) Simple Cubic Cell (SC)

2) Body Centered Cubic Cell (BCC)
3) Face Centered Cubic Cell (FCC)

1. PRIMITIVE (or) SIMPLE CUBIC UNIT CELL. (SC)
In the simple cubic unit cell, each corner is occupied by an identical atoms or ions or
molecules. And they touch along the edges of the cube, do not touch diagonally. A simple
Cubic Cell is a primitive Cell with lattice points located at eight corners of the cube.

(i) Unit cell Volume
If α= β= γ=90o, then V = abc
V= a3
(ii) Atomic radius
In a SC cell the atoms would be in contact along the edges of the cube, as shown in fig. If ‘a’ is
the edge of the cubic cell & r be the radius of the atom.
a = 2 r or r = a / 2
(iii) Effective number of atoms per unit cell (Z)
A simple cubic cell has eight lattice point at its eight corners, which are occupied by eight
atoms. In the three-dimensional array, each corner atom is linked to eight surrounding cells,
hence in effect, each corner atom contributes 1/8th of its content to a unit cell. The total
contribution (Z) from all the corner atoms to the unit cell is given by,

(iv) Coordination Number (CN)
Around an atom in a SC cell, there would be six equally spaced nearest neighbour atoms each
at a distance ‘a’ from that atom. Four atoms lie in the plane of the atom while one is vertically
above it and one vertically below. Therefore, coordination number, CN=6
(v) Atomic Packing Fraction (APF)
APF = (Z )/V
For SC cell, Z = 1
 = Volume of spherical atom
 = 4/3r 3
V = Volume of the unit cell
= a 3 = (2r)3 = 8r3
APF = [1 x (4/3r 3)] / (8r3)
APF = /6 = 0.52
(vi) Percentage void space
% Void space= (1 – APF) x 100
= (1-0.52) x100
= 48%
(vii) Density
𝑍𝑀
ρ=
N𝐴 𝑎3
In case of SC cell, Z= 1
1𝑀
Hence, ρ =
N𝐴 𝑎3

2. Body centered cubic unit cell. (BCC)
The Body Centered Cubic Cell is a non-primitive cell having a lattice point within the cell in
addition to the eight lattice points at eight corners of the cube.
(i) Unit cell Volume
V= abc [1-cos2 α-cos2 β-cos2 γ + 2cos αcos βcos γ]1/2
V= a3
ii) Atomic Radius

In a BCC cell atom are in contact along the body diagonal. From
iii) Effective Number of atoms per unit cell (Z)
In a body centered cubic unit cell, each corner is occupied by an identical particle and in
addition to that one atom occupies the body center. Those atoms which occupy the corners do
not touch each other, however they all touch the one that occupies the body centre. Hence,
each atom is surrounded by eight nearest neighbors and coordination number is 8. An atom
present at the body centre belongs to only to a particular unit cell i.e., unshared by another
unit cell.

iv) Coordination Number (CN)
In the BCC cell each corner atom is in contact with the body centre atom. As there are
eight-unit cells around each corner, the atom located at each corner would be simultaneously
touching the eight-body centre atom around it. Therefore, coordination number is eight.
v) Atomic Packing Fraction
APF = (Z )/V
For BCC cell, Z = 2
 = volume of spherical atom
 = 4/3r 3
V = volume of the unit cell
= a 3 = (4r/3) 3 = 64r3 /33
APF = [2 x (4/3r 3)] / [64r3 / 33]
APF =  3 /8 = 0.68
vi) % Void space
Void Space = [1- APF] x 100
Void Space = [1-0.68] x 100 = 32%
(vii) Density
𝑍𝑀
ρ=
N𝐴 𝑎3
In case of BCC cell, Z= 2
2𝑀
ρ=
N𝐴 𝑎3

3. FACE CENTERED CUBIC UNIT CELL. (FCC)

The Face Centered Cubic Cell is a non-primitive cell having six lattice points at the
centers of its six faces and eight lattice points at eight corners of the cube.
i) Unit cell Volume
V= abc [1-cos2 α-cos2 β-cos2 γ + 2cos αcos βcos γ]1/2
V= a3

ii) Atomic Radius
In an FCC cell, atoms are in contact along the face diagonal of the cube, as shown in fig.
iii) Effective Number of atoms per unit cell (Z)
In a face centered cubic unit cell, identical atoms lie at each corner as well as in the centre of
each face. Those atoms in the corners touch those in the faces but not each other. The atoms in
the face centre is being shared by two unit cells, each atom in the face centers makes ( 1/2 )
contribution to the unit cell.

iv) Coordination number
In FCC cell, each corner atom is in contact with face centre atom. It would be simultaneously
touching 4 atoms in the xy-plane,4 atoms in the yz-plane,4 atoms in zx-plane, making up a total
of 12 atoms.
Coordination Number = 4+ 4 + 4 = 12
v) Atomic Packing Fraction
APF = (Z ) /V
For FCC cell, Z = 4
 = Volume of spherical atom
 = 4/3r 3
V = volume of the unit cell
= a 3 = (22r)3
APF = [4 x (4/3r 3)] / [162r 3]
APF =  /32 = 0.74
vi) % Void space
% Void space= (1 – APF) x 100
= (1- 0.74) x100 =26%
vii) Density
𝑍𝑀
ρ=
N𝐴 𝑎3
For FCC cell, Z =4 Hence,
4𝑀
ρ=
N𝐴 𝑎3

4.HEXAGONAL CLOSELY PACKED STRUCTURE (HCP)
The hexagonal closely packed (hcp) is shown in the figure 1.1.8. In the hcp structure of a unit
cell contains three types of atoms as three layers.
12 corner atoms, one at each and every corner of the Hexagon.2 base centered atoms, one at the
top face of the hexagon and another at the bottom face of the hexagon.
In addition to corner and base atoms, 3 atoms are situated in between the top and bottom face
of the hexagon, in alternate vertical faces. Also note that these atoms are situated inside the face
so that they can’t be shared by other cells as shown in the figure.
(i) Number of atoms per unit cell
To calculate the number of atoms per unit cell, first consider the bottom layer. The bottom
layer consists of six corner atoms and one face centered atom. Each and every corner atom
contributes 1/6 of its part to one unit cell. The total number atoms contributed by the corner
atoms is 1/6 x 6 = 1.
The face-centered atom contributes ½ of its part to one unit cell. Therefore, the total
number of atoms contributes ½ of its part to one unit cell. Therefore, total number of atoms
present in the case of the bottom layer is 1 + ½ = 3/2

Similarly, the number of atoms present in the upper layer is 1 + ½ = 3/2
The total number of atoms present in the unit cell = 3/2 + 3/2 + 3 = 6 atoms
(ii) Atomic Radius
To find the atomic radius of the hcp structure, consider any two-corner atoms. It has to be
noted that, each and every corner atom touches with each other, therefore they are nearest
neighbor.
we can write,
Atomic Radius – HCP Structure
(iii) Coordination Number
The coordination number of the hcp structure can be calculated as follows. Let us consider
two-unit cells as shown in the figure.

The hcp structure is considered to have three layers viz, 1) Bottom Layer [B1],2) Top Layer [T1]
and 3) Middle Layer [M1] as shown.
In the top and bottom layers, the base centered atom is surrounded by six corner atoms. In the
middle layer we have 3 atoms stacked inside the unit cell as shown.
Let us consider two-unit cells let ‘X’ be the reference atom taken in the bottom layer BL1 of unit
cell 1(or top layer [TL2] of unit cell 2). This atom has 6 neighboring atoms in its own plane.
Further at a distance of c/2 it has 3 atoms in the middle layer (ML1) of unit cell -1 and 3 more
atoms in the middle layer (ML2) of unit cell -2. Therefore, the total number of neighboring
atoms is 6+3+3=12
Thus, the coordination number is 12.
We know that ‘c’ is the height of the unit cell of HCP structure and ‘a’ is the distance between
two neighboring atoms. Now consider a triangle ABO in the bottom layer.
Here A, B, and O are the lattice points and exactly above these atoms at a perpendicular distance
‘c’/2 the next layer atom lies at C.


(iv) Atomic Packing factor
Volume of all atoms in a unit cell(v)
Atomic radius r = a/2
No of atoms per unit cell, n =6
Volume of all the six atoms in the unit cell

The volume of the unit cell of the HCP = base area x height

Thus, the packing density is 74% and hence, it is a closed packed structure.
Example. Zinc, Beryellium and Magnesium
MILLER INDICES
A crystal lattice may be considered as an assembly of a number of equidistant parallel planes

passing through the lattice points and are called lattice planes. For a given lattice, these sets of
planes can be selected in a number of ways. The inter-planar spacing for a set of parallel planes
is fixed but for different sets of planes the inter-planar spacing varies as also the density of lattice
points.

Figure. Intercepts along x, y and z axes
The equation of plane in three dimensions having the intercepts a, b and c (Bravis lattice) along
the axes x, y, z respectively will be,
x y z
a
+b+c =1
1 1 1
Let h = 𝑎 , k = 𝑏 and l = 𝑐 then the above equation becomes
h x ky  lz 1. This equation describes the first lattice plane, nearest to the origin, in a set of
parallel, identical and equally spaced planes. The set of three integers h, k and l are expressed as
(hkl) called Miller indices.
x y z
Then the equation can be written as 1
⁄a
+ 1⁄ + 1⁄ =1.
b c
Where 1/h ,1/k and 1/l are intercepts along x, y and z axes respectively.
To obtain Miller indices of a plane the following procedure will be adopted:
1. Determine the intercepts of the plane along x, y, z axes in terms of lattice parameters.
2. Divide these intercepts by the proper unit translations.
3. Find their reciprocals.
4. If Fraction results, multiply each of them by the smallest common divisor.
5. Put the final integers in parenthesis (hkl) to get the required Miller Indices.

Definition: Miller Indices are the reciprocals of the intercepts, made by the plane on the
crystallographic axes, when reduced to smallest integers.
THE PROCEDURE FOR FINDING THE MILLER INDICES
STEP 1: Identify the intercepts of planes along three crystallographic axes (The coordinates of
the points of interception are expressed as integral multiples of the axial lengths in the respective
directions)
STEP 2: Determine the reciprocals of the integers.
STEP 3: Reduce the reciprocals to the smallest set of integers h, k, l by taking LCM.
STEP 4: The integers are written as (hkl) by enclosing in a parenthesis.
EXAMPLE
Find the Miller indices for the given plane ABC The plane ABC has intercepts of 2a on x-axis,
2b on y-axis and 1c on z axis.
STEP 1; The intercepts are 2, 2, 1
STEP 2: The reciprocals of the intercepts are ½, ½, 1
STEP 3: Taking LCM, we get 1, 1, 2
STEP 4: The miller Indices of the planes are (1 1 2)

IMPORTANT FEATURES OF MILLER INDICES
 Parallel planes spaced equally have the same miller indices.

 A plane parallel to one coordinate axis has miller index zero for that direction.
 When the intercepts of a plane are negative on an axis, a bar is placed on the
corresponding miller index.
D-SPACING IN CUBIC LATTICE
(or)
INTERPLANER DISTANCE IN A CUBIC CRYSTAL
The distance between successive members of a series of a parallel plane is known as a

interplanar distance. Let dhkl represents the distance between two adjacent parallel planes having
Miller Indices (hkl). Let the plane ABC be one of the planes that has intercepts OA=a/h, OB=b/k
and OC=c/l. The origin of the coordinates O is in next plane of set parallel to ABC. The
perpendicular OD in fig. from the origin to the plane is equal to d hkl. Let the direction cosines of
OD be cosα, cosβ, cosγ. The intercepts of the plane on the coordinate axes are
OA= a/h; OB=a/k; OC=a/l (As a=b=c= Unit length of edge a)
Where ‘a’ is the length of the cube edge.
Denoting OD=d
OD ℎ𝑑
cos α = =
OA 𝑎

OD 𝐾𝑑
cos β= OB = 𝑎
OD 𝑙𝑑
cos γ = OC = 𝑎
Since, cos2 α+ cos2 β+ cos2 γ= 1

h²d² 𝑘²𝑑² 𝑙²𝑑²
+ + =1
a² 𝑎² 𝑎²
𝑑2 2
(ℎ + 𝑘 2 + 𝑙 2 ) = 1
𝑎2
𝑎²
d² =
(ℎ2 +𝑘 2 +𝑙2 )
𝑎
d=
(ℎ2 +𝑘 2 +𝑙 2)
CRYSTAL GROWTH
Crystal growth is an important field of material technology. Growth of crystal ranges from a
small inexpensive technique to a complex expensive technique. Crystallization time ranges from
minutes, hours, days and to months. Nucleation is an important phenomenon in crystal growth.
The growth of synthetic crystals is very much useful in the field of solid-state physics,
electronics, photonics, high efficiency photovoltaic cells, etc.
METHODS OF CRYSTAL GROWTH
Crystal growth techniques are classified into three categories namely,

 Solid growth: Solid to solid phase transformation.

 Liquid growth: Liquid to solid phase transformation.
 Solution growth:
1. Low temperature solution growth.
2. High temperature solution growth.
 Melt growth:
1. Bridgman technique
2. Verneuil technique
3. Czochralski technique
4. Zone melting technique.
5. Heat exchanger method
 Vapour growth: Vapor to solid phase transformation.
1. Physical Vapour Deposition (PVD)
2. Chemical Vapour Deposition (CVD)
SOLUTION GROWTH
In this method, crystals are grown from aqueous solution. This method is widely used for
producing bulk crystals. There are two methods in solution growth depending upon the solvents
and the solubility of solute.
 Low temperature solution growth

Example: Growth from aqueous solution, gel growth
 High temperature solution growth
Example: Flux growth, hydrothermal growth.
LOW TEMPERATURE SOLUTION GROWTH
In the low temperature solution growth, single crystals can be grown solution if the solution is
supersaturated. The useful techniques used
 Slow cooling of the solution

 Slow evaporation of the solvent.
 Temperature gradient method

SLOW COOLING OF THE SOLUTION
A saturated solution above the room temperature is filled in a crystallizer and it is thermally
sealed. A seed crystal is suspended in the solution. The crystallizer is kept in a water thermostat
and allowed to cool slowly. As the temperature decreases solubility decreases and single crystals
start growing.
Advantages
Easy, works best for soluble substances. Crystallization begins usually from room
temperature to 750C.
Disadvantages
 Needs lot of material

 Range of temperatures
 Disordered or twinned crystals start growing
SLOW EVAPORATION OF THE SOLVENT
This method is similar to the slow cooling method. Super saturated solution of the compound
is prepared in a suitable solvent. The prepared solution is transferred into a clean container. The
temperature is fixed constant and provision is made for evaporation. The container is set aside
and the solvent is allowed to evaporate over for few days. The super saturated solution is slowly
evaporated and small crystals grow. The crystals get bigger as the solution becomes more
concentrated.
Advantages
Easy and the crystals grow at a fixed temperature.
Disadvantages
 Needs a lot of material, too much nucleation leading to simultaneous growth of many
crystals.
 It requires temperature stabilization of about ±0.005oC and rates of evaporation of a few
ml/hr.

Application of low temperature solution growth
Excellent quality crystals of ferroelectric and piezoelectric materials ADP, KDP and TGS are
grown.
MELT GROWTH
Crystal growth from melt is the most widely used for growing single crystals. The materials
which don’t decompose at the melting point and don't undergo any phase transformation between
the melting point and room temperature can be grown from melt growth technique.
BRIDGMAN TECHNIQUE
In Bridgman technique, the temperature gradient of the furnace plays an important role in
growing single crystal.
• It consists of a vertical cylindrical container made by platinum or quartz, tapered conically

with a point bottom.
• The crystal to be grown is kept inside the container.
• The container is surrounded by two furnaces namely upper furnace and lower furnace.

• The container is slowly lowered from hot zone of the furnace into the cold zone by using
an electric motor.
 The temperature of the lower furnace is maintained below the melting temperature of the
melt inside the container.
• The rates of movement slowly range from about 1-30 mm/hr.
• Crystallization begins at the tip and continues usually growth from the first formed
nucleus.
Advantages
• Simpler technology.
• Relatively cheaper.
• Control of shape and size of growing crystals.
• Easy control and maintenance.
• No radial temperature gradients are needed to control the crystal shape.
Disadvantages
 This technique can’t be used for materials, which decompose before melting. This is the
best suited for materials with low melting point.
 Dislocation crystals can be grown.
 Growth rate is low.
 difficult to observe seeding and growing processes.
Applications
It is popular method of producing single crystal semiconductors such as GaAs, ZnSe, CdS,
CdTe and ZinS.
CZOCHRALSKI METHOD
Czochralski crystal pulling method is the most common technique of crystal growth from
melt. A refractory container contains the pure material heated by magnetic induction, under a
controlled atmosphere. By controlling the furnace temperature, the material is melted. A seed
crystal is attached to a rod in the desired orientation. The seed is slightly lowered into the surface

of the molten material. When the temperature of the seed is maintained very low compared to the
temperature of the melt by suitable cooling effect. The molten charge in contact with the seed
will solidification on the seed. By activating a pulling mechanism, the seed is withdrawn from
the melt. If the rod is pulled up slowly, the diameter increases because, crystal grows on the sides
and on the end of the crystal.
Advantages
• Growth rate is high.

• Growth of large oriented single crystals. High crystalline perfection can be achieved.
Disadvantages
• Possible contamination of the melt by the crucible.

• Problems in temperature maintenance.
• cannot grow materials with high vapor pressure.
Applications
• Used in industry to grow semiconductor materials. [Si, GaAs, InP]

• Silicon grown by this method is for the production of IC's used in TV, Computers,
Cellphones, Laptops, etc.
DIFFRACTION OF X-RAYS BY CRYSTAL PLANES

The visible light rays when pass through a sharp edge of an object can form some bright
regions inside the geometrical shadow of the object. This is due to the bending nature of light,
called diffraction.
Diffraction of visible light rays can also be produced using plane-ruled grating. This grating
consists of about 6000 lines/cm; so that the spacing between any two consecutive lines in the
grating is of the order of the wavelength of visible light used to produce diffraction.
The wavelength of X-rays is of the order of an angstrom, so X-rays are unable to produce
diffraction with plane optical grating. To produce diffraction with X-rays, the spacing between
the consecutive lines of grating should be of the order of few angstroms. Practically, it is not
possible to construct such a grating. In the year 1912, a German physicist Laue suggested that the
three-dimensional arrangement of atoms in a crystal can serve as a three-dimensional grating for
X-rays. Inside the crystal, the spacing between the crystal planes can work as the transparent
regions as between lines in a ruled grating.
Laue’s associates Friedrich and Knipping succeeded in diffracting X-rays by passing through a
thin crystal. In 1913, W.L. Bragg and his son W.H. Bragg gave a simple interpretation of the
diffraction pattern. According to Bragg, the diffraction spots produced are due to the reflection of
some of the incident X-rays by various sets of parallel crystal planes. These planes are called
Bragg’s planes. The Bragg’s interpretation is explained in the following topic.
BRAGG ‘S LAW FOR X-RAY DIFFRACTION
William Henry Bragg and William Lawrence Bragg, the team of son & father of British
Physicist derived in1913, a simple equation relating the wavelength of X-ray to the angular
position of the scattered beams and the separation of the atomic plane in the crystal.
A crystal may be regarded as a stack of the parallel planes of atoms, the atomis planes are
often called Bragg planes. Every crystal has several sets of Bragg’s planes oriented in different
directions and each plane in a given set has the same distribution of atoms.
When an X-ray beam impinges on the crystal, each atom in a given Bragg plane scatters a
portion of the incident beam. The scattered waves proceed in all directions.

The condition for constructive interference of waves is obtained by treating the crystal as a set
of equally spaced parallel semitransparent planes and by regarding the complex phenomenon of
diffraction of X-ray as a simple reflection at the Bragg’s planes.
Let us consider a series of Bragg planes separated by a distance, d. let a beam of

monochromatic X-rays represented by the parallel lines AB and DE be incident on these planes.
The scattered beam emerges along BC and EF as shown in fig.
The rays BC and DE are coherent and reinforce each other, if they are in phase. In fig. the
contribution of two adjacent atoms in successive planes MN and PQ are considered. The path
difference, Δ between the rays reflected along BC and EF is,
Δ =GE + EH -------------(A)
The rays BC and EF will be in phase only when their path difference, Δ is an integral multiple of
wavelength. Thus,
Δ =GE + EH = mλ (m= 1, 2, 3,……..)
From the figure,
< ABG = θ + α = 900 ------------------(1)

BE is normal to the plane MN, therefore,
< MBE = α+< GBE = 90---------------(2)
Comparing (1) & (2), we get
<GBE = θ
In the ΔBGE, BE = d sinθ
sinθ = GE/ BE
∴ GE = BE. Sinθ = d sinθ
Similarly, EH = d sinθ
∴ the path difference,
Δ =GE + EH = 2d sinθ------------------(B)
Combining equations (A) & (B), we obtain the condition for reinforcement of scattered waves as,
2d sinθ =mλ (m=1, 2, 3………….)
This equation is known as Bragg’s law or Bragg’s equation. The angle θ in the above equation
represents the angle between the Bragg plane and the direction of the incident beam. It is known
as glancing angle or Bragg angle.
The angle 2θ is called diffraction angle.
For a given set of atomic planes, d has a fixed value and the reinforcement of reflected waves
depend on the value of θ. As θ is increased gradually, a number of positions will be found at
which the reflections are intense. These positions correspond to m=1, 2, 3…. Values. Thus, m
denotes the order of reflection.
If the value of θ is determined experimentally, and knowing the wavelength λ, the interplanar
spacing ‘d’ can be determined with help of Bragg’s law.
APPLICATIONS OF BRAGG’S LAW/ X-RAY DIFFRACTION TECHNIQUES
Bragg’s law made a breakthrough in the field of crystallography. It has some useful applications.

 In X-ray diffraction, the interplanar spacing of a crystal is used for the identification
purposes.
 It is useful for conducting the measurements of the wavelength of different families of
crystals.
 In X-ray fluorescence spectroscopy (XRS), the crystals with known interplanar spacings
are used to analyses the crystals in the spectrometer.
IMPORTANCE OF BRAGG’S LAW:
1. Bragg’s law is the essential condition to be satisfied by crystal planes in order to get
diffraction pattern from a crystal.
2. It is used to calculate inter-planar spacing. Knowing the values of inter-planar spacing, lattice
parameters can be determined.
1. The Laue method: - applicable for single crystals
2. The Rotating crystal method: - applicable for single crystals
3. The Powder method: - used for finely divided crystalline or polycrystalline powers
THE LAUE METHOD
The Laue method is mainly used to determine the orientation of large single crystals while
radiation is reflected from, or transmitted through a fixed crystal. The diffracted beams form
arrays of spots, which lie on curves on the film.

The Bragg angle is fixed for every set of planes in the crystal. Each set of planes picks out and
diffracts the particular wavelength from the white radiation that satisfies the Bragg law for the
values of d and θ involved.
SCHEMATIC REPRESENTATION OF LAUE TECHNIQUE
In the back-reflection method, the film is placed between the x-ray source and the crystal. The
beams which are diffracted in a backward direction are recorded. One side of the cone of Laue
reflections is defined by the transmitted beam. The film intersects the cone, with the diffraction
spots generally lying on a hyperbola.
In the transmission Laue method, the film is placed behind the crystal to record beams
which are transmitted through the crystal. One side of the cone of Laue reflections is defined by
the transmitted beam. The film intersects the cone, with the diffraction spots generally lying on
an ellipse.
The symmetry of the spot pattern reflects the symmetry of the crystal when viewed along the
direction of the incident beam. Laue method is often used to determine the orientation of single
crystals by means of illuminating the crystal with a continuous spectrum of X-rays;

Therefore, the Laue method is mainly used to determine the crystal orientation.  Although the
Laue method can also be used to determine the crystal structure, several wavelengths can reflect
in different orders from the same set of planes, with the different order reflections superimposed
on the same spot in the film. This makes crystal structure determination by spot intensity
difficult. Rotating crystal method overcomes this problem.
ROTATING CRYSTAL METHOD
In the rotating crystal method, a single crystal is mounted with an axis normal to a
monochromatic x-ray beam. A cylindrical film is placed around it and the crystal is rotated about
the chosen axis.
SCHEMATIC REPRESENTATION OF ROTATING CRYSTAL TECHNIQUE
As the crystal rotates, sets of lattice planes will at some point make the correct Bragg angle for
the monochromatic incident beam, and at that point a diffracted beam will be formed.
Lattice constant of the crystal can be determined by means of this method; for a given
wavelength if the angle θ at which a dh k l reflection occurs is known, can be determined.
The reflected beams are located on the surface of imaginary cones. By recording the diffraction
patterns (both angles and intensities) for various crystal orientations, one can determine the shape
and size of unit cell as well as arrangement of atoms inside the cell.

THE POWDER METHOD
If a powdered specimen is used, instead of a single crystal, then there is no need to rotate the
specimen, because there will always be some crystals at an orientation for which diffraction is
permitted. Here a monochromatic X-ray beam is incident on a powdered or polycrystalline
sample. This method is useful for samples that are difficult to obtain in single crystal form.
The powder method is used to determine the value of the lattice parameters accurately.
Lattice parameters are the magnitudes of the unit vectors a, b and c which define the unit cell for
the crystal. For every set of crystal planes, by chance, one or more crystals will be in the correct
orientation to give the correct Bragg angle to satisfy Bragg's equation. Every crystal plane is thus
capable of diffraction. Each diffraction line is made up of a large number of small spots, each
from a separate crystal. Each spot is so small as to give the appearance of a continuous line.
EXPERIMENTAL ARRANGEMENT IN POWDER METHOD
A sample of some hundreds of crystals (i.e., a powdered sample) show that the diffracted beams
form continuous cones. A circle of film is used to record the diffraction pattern as shown. Each
cone intersects the film giving diffraction lines. The lines are seen as arcs on the film.
A very small amount of powdered material is sealed into a fine capillary tube made from glass
that does not diffract x-rays. The specimen is placed in the Debye Scherrer camera and is
accurately aligned to be in the centre of the camera. X-rays enter the camera through a

collimator. The powder diffracts the x-rays in accordance with Braggs law to produce cones of
diffracted beams. These cones intersect a strip of photographic film located in the cylindrical
camera to produce a characteristic set of arcs on the film.
CONES OF DIFFRACTED BEAMS OF X RAY
When the film is removed from the camera, flattened and processed, it shows the diffraction lines
and the holes for the incident and transmitted beams.
APPLICATION OF XRD
 Differentiation between crystalline and amorphous materials;

 Determination of the structure of crystalline materials;
 Determination of electron distribution within the atoms, and throughout the unit cell;
 Determination of the orientation of single crystals;
 Determination of the texture of polygrained materials;
 Measurement of strain and small grain size…. etc.
ADVANTAGES
 Powerful and rapid (< 20 min) technique for identification of an unknown mineral
 In most cases, it provides an unambiguous mineral determination
 Minimal sample preparation is required
 XRD units are widely available
 Data interpretation is relatively straight forward
 X-ray is the cheapest, the most convenient and widely used method.
 X-rays are not absorbed very much by air, so the specimen need not be in an evacuated
chamber.

DISADVANTAGE
 Homogeneous and single-phase material is best for identification of an unknown.

 Must have access to a standard reference file of inorganic compounds (d-spacings, hkl).
 Requires tenths of a gram of material which must be ground into a powder.
 For mixed materials, detection limit is ~ 2% of sample.
 For unit cell determinations, indexing of patterns for non-isometric crystal systems is
complicated.
 Peak overlay may occur and worsens for high angle 'reflections.
 They do not interact very strongly with lighter elements.
CRYSTAL STRUCTURES
1. SODIUM CHLORIDE STRUCTURE

The Sodium Chloride Structure is shown in figure. It consists of equal number 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 nearest neighbours. The lattice is face centered cubic. The basis consists of
one Sodium (Na) ion and one Chlorine ion (Cl) separated by one half the body diagonal of a
unit cube.
There are four units of NaCl in each cube, with ions in the positions:
Na: 0 0 0, ½½0, ½0½, 0½½
Cl: ½½½, 00½, 0½0, ½00

the Sodium Chloride structure, Na+ and Cl-are shown by small and big circles respectively. Big
and small circles from interpenetrating fcc lattice.
2. CESIUM CHLORIDE STRUCTURE

The Cesium chloride (CsCl) structure is shown in fig. It consists of equal number of Cesium
and Chlorine ions. This is described as simple cubic lattice with a basis consisting of a Cesium
ion at the corners or origin (000) and a chlorine ion at the body centered position (½ ½ ½). One
type of ions is situated at the body centred positions so that each ion has eight other type of ions
as nearest neighbour. The value of a is 4.11Ǻ
In figure Shows the Cesium Chloride structure the filled circle ● and the hollow circle ○
represents two different ions which form interpenetrating simple cubic lattice.
3. DIAMOND STRUCTURE
The space lattice of Diamond is fcc. The primitive basis has two identical atoms at 000, ¼ ¼
¼ associated with each lattice point. It is characterized by a tetrahedral bond arrangement as
shown in fig. Each atom has four nearest neighbours and twelve next nearest neighbours. The
diamond structure is relatively empty, i.e., the proportion of available volume filled by hard
spheres is 0.34 (the atomic packing factor) only. It has 46% of filling factor for closest structure of
fcc or hcp.
Example
Carbon, Silicon, Germanium and Tin with lattice constant a = 3.56, 5.43, 5.65 and 6.46 Ǻ

In figure, (a) denotes the crystal structure of diamond showing the tetrahedral bond arrangement
and (b) shows the atomic positions in the cubic cell of diamond structure projected on a cube face.
ZINC BLENDE STRUCTURE:
The Zinc Blende (ZnS) has equal number of Zinc and Sulphur ions distributed on a Diamond
lattice so that each has four of the opposite kind as nearest neighbours. Zinc atoms are placed on
one fcc lattice and S atoms on the other fcc lattice.
The coordinates of Zn atoms are 000, 0 ½ ½, ½ 0 ½, ½ ½ 0
The coordinates of S atoms are ¼ ¼ ¼, ¼ ¾ ¾, ¾ ¼ ¾, ¾ ¾ ¼
The Diamond structure allows centre of inversion symmetry but the Zinc Blende structure does
not have inversion symmetry.
Example: CuF, CuCl, AgI, GaAs with a = 4.26, 5.41, 6.47, 5.65 Ǻ

Unit III Crystollography

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Unit III Crystollography

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ST.

JOSEPH UNIVERSITY IN TANZANIA

ST. JOSEPH COLLEGE OF ENGINEERING

DEPARTMENT OF BASIC ENGINEERING

MODULE NAME: PH1103

UNIT III -CRYSTALLOGRAPHY

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~2~

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~3~

A crystalline solid has a well-arranged large small crystal. A crystal is an ordered

PROPERTIES OF CRYSTALLINE SOLIDS

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~4~

TYPES OF CRYSTALLINE SOLIDS

 Molecular Solids: In molecular solids, molecules are constituent particles. Molecular

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~5~

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~6~

PROPERTIES OF AMORPHOUS SOLID

DIFFERENCE BETWEEN CRYSTALLINE SOLIDS AND AMORPHOUS SOLIDS

CRYSTALLINE SOLID AMORPHOUS SOLID

A crystalline solid has well-arranged Constituent particles of amorphous solids

Crystalline solids are anisotropic. Amorphous solids are isotropic.

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~7~

FORCES BETWEEN ATOMS AND MOLECULES

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~8~

There are three main types of intermolecular force:

 Permanent dipole-dipole forces

1. Permanent Dipole-Dipole Forces

2. Induced Dipole-Dipole Forces

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~9~

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 10 ~

COHESION OF ATOMS AND EQUILIBRIUM ATOMIC SPACING

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 11 ~

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 12 ~

A regular three-dimensional arrangement of points (ions, atoms, etc.) in space is called a

CHARACTERISTICS OF CRYSTAL LATTICE

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 13 ~

PARAMETERS OF A UNIT CELL

A unit cell is characterized by:

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 14 ~

Thus, a unit cell is characterized by six parameters, a, b, c, α, ß and γ. The complete

TYPES OF UNIT CELLS

Unit cells can be broadly divided into two categories,

1. primitive unit cell

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 15 ~

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 16 ~

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 17 ~

THE UNIT CELL CHARACTERISTICS

(i) UNIT CELL VOLUME, V

The volume of a unit cell is given by

V= abc [1-cos 2 α-cos 2 β-cos 2 γ + 2cos αcos βcos γ]1/2

If α= β= γ = 90o, then V = abc

Further, when a=b=c, as in the case of cubic cells

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 18 ~

(iii) ATOMIC RADIUS, (r):

(iv) NEAREST NEIGHBOUR DISTANCE, (2r)

(v) COORDINATION NUMBER (CN)

(vi) ATOMIC PACKING FRACTION (APF)

No.of atoms /unit cell (Volume of each atom)

DEPARTMENT OF BASIC ENGINEERING UNIT-III CRYSTOLLOGRAPHY ~ 19 ~

(vii) VOID SPACE

Thus, %Void space= (1 – APF) x 100

Where, M →the molecular weight of the material

NA→ the Avogadro number.

CUBIC LATTICE (Or) CUBIC CRYSTAL SYSTEM

1) Simple Cubic Cell (SC)