Structure of Materials

Introduction: -
- The structure of materials refers to the arrangement of their internal components, such as atoms,
molecules, or grains.
• The structure of materials determines virtually everything about a material: its properties,
its potential applications, and its performance within those applications.
• The structure of materials can be studied at different length scales, from the atomic level to
the macroscopic level.
• The structure of materials can be classified into two main categories: amorphous and
crystalline.
- Amorphous materials have no long-range order in their atomic arrangement. They
include glasses and polymers.
- Crystalline materials have a periodic and repeating pattern of atoms in their structure.
They include metals, ceramics, and semiconductors.
• The structure of materials can be measured and described by various techniques, such as
microscopy, spectroscopy, and x-ray diffraction.
• Microscopy allows us to observe the morphology and features of materials at different
magnifications.
• Spectroscopy allows us to identify the chemical composition and bonding of materials by
analyzing their interaction with electromagnetic radiation.
• X-ray diffraction allows us to determine the crystal structure and lattice parameters of
materials by analyzing the diffraction pattern of x-rays scattered by the atoms.

Classification of materials: -
• Classification of materials is a process of grouping materials based on their similarities and
differences in properties, structure, composition, and performance. Some of the benefits of
classification of materials are:
• It helps to identify and select suitable materials for specific applications and purposes.
• It helps to understand the relationship between the properties and structure of materials,
and how they can be modified or improved by processing or treatment.
• It helps to organize and categorize the vast diversity of materials available in nature and
industry, and to facilitate communication and research among different fields of science
and engineering.
• There are different ways to classify materials, depending on the criteria and level of detail
used. Some of the common methods of classification of materials are:
- Based on the state of matter: solid, liquid, gas, plasma
- Based on the chemical composition: metals, ceramics, polymers, composites
- Based on the atomic structure: crystalline, amorphous, nanomaterials
- Based on the electrical properties: conductors, semiconductors, insulators
- Based on the magnetic properties: ferromagnetic, paramagnetic, diamagnetic
- Based on the optical properties: transparent, translucent, opaque
- Based on the mechanical properties: elastic, plastic, brittle, ductile
Metals: -
• In this group are composed of one or more metallic elements and often also non-metallic
elements in relatively small amounts.
• Atoms in metals and their alloys are arranged in a very orderly manner, and in comparison,
to the ceramics and polymers, are relatively dense.
• With regard to mechanical characteristics, these materials are relatively stiff and strong, yet
are ductile and are resistant to fracture, which accounts for their widespread use in
structural applications.
• Metallic materials have large numbers of nonlocalized electrons; that is, these electrons are
not bound to particular atoms.
• Many properties of metals are directly attributable to these electrons.
• For example, metals are extremely good conductors of electricity and heat, and are not
transparent to visible light.
Ceramics: -
• Ceramics are inorganic and non-metallic materials that are typically hard, brittle and
resistant to heat and corrosion.
• Ceramics can be classified into four main categories based on their composition, structure,
properties and applications: traditional ceramics, advanced ceramics, glass and glass-
ceramics, and refractories.
• Traditional ceramics are made from natural raw materials such as clay, sand and feldspar.
They include products such as pottery, bricks, tiles, cement and porcelain. Traditional
ceramics have low to moderate strength and toughness, high thermal expansion and low
electrical conductivity.
• Advanced ceramics are made from synthetic or engineered materials such as alumina,
zirconia, silicon carbide and silicon nitride. They have superior mechanical, thermal, optical
and electrical properties than traditional ceramics. Advanced ceramics are used for
applications such as biomedical implants, aerospace components, electronic devices and
cutting tools.
• Glass-ceramics are amorphous or semi-crystalline materials that are formed by rapid
cooling of molten mixtures of silica and other additives. Glass has high transparency, low
thermal conductivity and high chemical durability. Glass-ceramics are partially crystallized
glass that have improved strength, hardness and thermal stability. Glass and glass-ceramics
are used for applications such as windows, lenses, cookware and dental restorations.
• Refractories are ceramics that can withstand very high temperatures (above 1500°C) and
corrosive environments. They are composed of oxides, carbides, nitrides or borides of
metals or non-metals. Refractories are used for applications such as lining furnaces, kilns,
reactors and boilers.
Polymers: -
• Polymers are materials composed of long chains of repeating units called monomers.
• Polymers can be classified into three main categories based on their structure, properties
and applications: thermoplastics, thermosets and elastomers.
 • Thermoplastics are polymers that can be melted and reshaped by heating and cooling. They
have linear or branched structures that allow them to flow when heated. Examples of
thermoplastics are polyethylene, polypropylene, polystyrene and nylon.
• Thermosets are polymers that undergo irreversible chemical reactions when heated and
cured. They have cross-linked structures that prevent them from flowing when heated.
Examples of thermosets are epoxy, phenolic, polyester and silicone.
• Elastomers are polymers that can stretch and return to their original shape when released.
They have coiled or network structures that allow them to deform under stress. Examples
of elastomers are rubber, latex, silicone and polyurethane.
Composite: -
• A composite material is a combination of two or more materials with different properties
that produce a new material with enhanced performance and functionality.
• Composite materials can be classified based on the type of matrix, reinforcement, and
fabrication method.
• Matrix: The matrix is the continuous phase that binds the reinforcement and transfers the
load to it. The matrix can be polymer, metal, ceramic, or carbon-based.
• Reinforcement: The reinforcement is the dispersed phase that provides strength, stiffness,
and resistance to the composite. The reinforcement can be fibers, particles, flakes, or
whiskers.
• Fabrication method: The fabrication method is the process of combining the matrix and the
reinforcement to form the composite. The fabrication method can be molding, laminating,
winding, weaving, or additive manufacturing.
Semiconductors: -
• Classification of materials in Semiconductors is based on the electrical conductivity and the
band gap of the materials.
• Electrical conductivity is the measure of how easily electrons can flow through a material
when an electric field is applied.
• Band gap is the energy difference between the highest occupied energy level (valence band)
and the lowest unoccupied energy level (conduction band) of a material.
• Materials can be classified into three categories: insulators, semiconductors and
conductors.
• Insulators have a very large band gap and a very low electrical conductivity. They do not
allow any electrons to flow through them even at high temperatures or voltages. Examples
of insulators are glass, rubber and diamond.
• Conductors have a very small or zero band gap and a very high electrical conductivity. They
allow many electrons to flow through them even at low temperatures or voltages.
Examples of conductors are metals, such as copper, silver and gold.
• Semiconductors have a moderate band gap and a moderate electrical conductivity. They
allow some electrons to flow through them depending on the temperature, voltage and
impurities. Examples of semiconductors are silicon, germanium and gallium arsenide.
Biomaterials: -
 • Classification of materials in Biomaterials is based on their interaction with living tissues and
cells.
• There are three main types of materials in Biomaterials: bioinert, bioactive and
biodegradable.
- Bioinert materials are those that do not elicit any significant biological response from
the host tissue. They are usually used for implants that require mechanical stability and
durability, such as artificial joints and dental implants.
Examples of bioinert materials are metals (e.g. titanium, stainless steel) and ceramics
(e.g. alumina, zirconia).
- Bioactive materials are those that form a chemical bond with the host tissue and
stimulate its growth and regeneration. They are usually used for implants that require
integration with the surrounding tissue, such as bone grafts and coatings.
Examples of bioactive materials are glasses (e.g. bioactive glass) and ceramics (e.g.
hydroxyapatite, bioglass-ceramic).
- Biodegradable materials are those that degrade over time in the body and are replaced
by natural tissue. They are usually used for temporary implants that support tissue
healing and regeneration, such as sutures, stents and scaffolds.
Examples of biodegradable materials are polymers (e.g. polyglycolic acid, polylactic
acid) and natural materials (e.g. collagen, silk).

Crystalline Non-Crystalline
1. The basic structural unit is a crystal [a slid The basic structural unit is a molecule & chains of
whose constituent molecules or atoms are these molecule come together to form an amorphous
arranged in a systematic geometric solids.
pattern.
2. Each crystal [also called as a grain] is made The chains of molecules are random within the solid
up of a number of respective blocks called & occur in no particular relation to each other. They
unit cells[ the smallest group of atoms are irregular & lack symmetry.
possessing the symmetry of the crystal]
which are arranged neatly in relation to
each other.
3. Compare crystalline solid with a military In this, crowd where people are random & not
parade where all soldiers are arranged in arranged in order with respect to each other.
order with respect to each other.
4. A crystalline solid therefore is made up of In this it is made up of millions of molecules
millions of unit cells orderly arranged. disorderly arranged.
Each unit cell is itself made up of atoms &
the number of atoms depends on the type
of unit cell.
5. Metals, alloys, some salts like NaCl, KCl, Glass, polymers, rubber & plastics.
many oxides & ceramics, non metals like
diamond, Gem stones.
6. Density of crystalline solids is generally Generally low because molecules cannot be
high. They have higher melting point & compacted. They have lower melting point &
strength. strength.
7. Structures are stable & materials are Structures are unstable & materials are less stronger.
stronger.
Atomic bonding: -
• Atomic bonding is the process of joining atoms together to form molecules or compounds.
• There are three main types of atomic bonding: ionic, covalent and metallic.
Ionic bond: -
- An ionic bond is a type of chemical bond that involves the transfer of electrons from one
atom to another, resulting in the formation of ions.
- Ions are atoms or groups of atoms that have a net electric charge due to the loss or gain of
electrons.
- Ionic bonds usually occur between metals and nonmetals, or between polyatomic ions.
- Ionic compounds are held together by the electrostatic attraction between oppositely
charged ions, forming a lattice structure.
- Ionic compounds have high melting and boiling points, are brittle and hard, and conduct
electricity when dissolved in water or molten.
Covalent bond: -
- A covalent bond is a type of chemical bond that involves the sharing of electrons between
two or more atoms.
- Covalent bonds are formed when atoms have similar electronegativities, meaning they
have similar tendencies to attract electrons.
- Covalent bonds can be classified into single, double, or triple bonds, depending on how
many pairs of electrons are shared between the atoms.
- Covalent bonds can also be classified into polar or nonpolar bonds, depending on how
evenly the electrons are distributed between the atoms.
- Covalent bonds are important for the formation of molecules and compounds, such as
water, carbon dioxide, methane, and DNA.

Metallic bond: -
- A metallic bond is a type of chemical bond that occurs between atoms of metallic
elements.
- It involves the sharing of free electrons among a lattice of metal atoms.
- It is the collective attraction between these free electrons and metal ions that results in
the strength and durability of metals.
- Some properties of metals that are explained by metallic bonding are:
- High electrical and thermal conductivity: The free electrons can move easily through
the metal, carrying electric current or heat energy.
- Malleability and ductility: The metal atoms can slide past each other without
breaking the bond, allowing metals to be hammered into thin sheets or drawn into
wires.
- Luster: The free electrons reflect light, giving metals a shiny appearance.
- High melting and boiling points: A lot of energy is required to overcome the strong
attraction between the free electrons and metal ions.
 Geometrical Crystallography
• Geometrical Crystallography is a branch of science that studies the shapes and symmetries of
crystals and their relation to the atomic structure.
• Crystals are solids that have a regular and repeating arrangement of atoms, ions or molecules
in three dimensions.
• The basic unit of a crystal is called a unit cell, which is the smallest repeating pattern that
defines the crystal structure.
• The unit cell can be described by six parameters: three edge lengths (a, b, c) and three angles
(α, β, γ) between the edges. These parameters are called the lattice constants or lattice
parameters of the crystal.
• The shape of the unit cell is determined by the type of lattice system that the crystal belongs
to. There are seven lattice systems: triclinic, monoclinic, orthorhombic, tetragonal, hexagonal,
rhombohedral and cubic.
• The symmetry of the crystal is determined by the type of point group or space group that the
crystal belongs to. A point group is a set of symmetry operations that leave a point unchanged.
A space group is a set of symmetry operations that leave a unit cell unchanged.
• There are 32 possible point groups and 230 possible space groups in three dimensions. Each
space group belongs to one of the seven lattice systems and one of the 32 point groups.
• Geometrical Crystallography uses mathematical tools such as matrices, vectors and tensors to
represent and manipulate the symmetry elements and operations of crystals.
• Geometrical Crystallography also uses graphical tools such as stereographic projections,
crystallographic planes and directions, Miller indices and reciprocal lattice to visualize and
analyze the crystal structure and properties.

Symmetry elements: -
• Symmetry elements are geometrical features that relate different parts of a molecule or a
crystal to each other by symmetry operations.
• Symmetry operations are transformations that leave an object unchanged when applied to it.
For example, rotation, reflection, inversion and translation are symmetry operations.
• The most common symmetry elements are:
- A point of inversion (i), which is a point at the center of an object that maps every atom
to its opposite position when inverted through it.
- A plane of symmetry (σ), which is a plane that divides an object into two halves that are
mirror images of each other when reflected through it.
- An axis of rotation (Cn), which is a line that passes through an object such that rotating
the object by 360/n degrees around it brings the object back to its original configuration.
The value of n is called the order of the axis.
- A center of symmetry (S), which is a point that combines inversion and rotation. An
object has a center of symmetry if rotating it by 180 degrees around a point and then
inverting it through that point leaves it unchanged.
- A translation vector (t), which is a vector that shifts an object by a fixed distance and
direction without changing its orientation or shape.
• Symmetry elements can be used to classify molecules and crystals into different symmetry
groups, which describe their overall symmetry properties. Symmetry groups can help predict
 physical and chemical properties of molecules and crystals, such as polarity, optical activity,
bonding and reactivity.

The operation of rotation: -

Operation of rotation is the process of turning an object around an axis or a point.
• Rotation can be described by the angle of rotation, the direction of rotation, and the point
or axis of rotation.
• The angle of rotation is the measure of how much an object has turned from its initial
position. It is usually expressed in degrees or radians.
• The direction of rotation is the way an object is turning: clockwise or counter clockwise.
Clockwise rotation means that the object is turning in the same direction as the hands of a
clock. Counter clockwise rotation means that the object is turning in the opposite direction.
• The point or axis of rotation is the fixed point or line that an object rotates around. For
example, a wheel rotates around its center, and a door rotates around its hinge. The point
or axis of rotation can be inside or outside the object.

Proper rotation axes: -

1-Fold Rotation. A 1(E)-fold rotation operation implies either a 0° rotation or a 360° rotation, and
is referred to as the identity operation
2-Fold Rotation. A 2-fold(C2) rotation operation moves the object by (360/2) ° = 180 °. The symbol
used to designate a 2-fold axis is a solid oval.
3-Fold Rotation. A 3-fold(C3) rotation operation moves the object by (360/3) ° = 120 °. The symbol
used to designate a 3-fold axis is a solid equilateral triangle.
4-Fold Rotation. A 4-fold(C4) rotation operation moves the object by (360/4) ° = 90 °. The symbol
used to designate a 4-fold axis is a solid square.
6-Fold Rotation. A 6-fold(C6) rotation operation moves the object by (360/6) ° = 60 °. The symbol
used to designate a 6-fold axis is a solid hexagon.

Improper rotation axes: -

• Improper rotation axes are a type of symmetry operation in crystallography that combine a rotation
and an inversion.
• An improper rotation axis is denoted by the symbol n̅, where n is the order of the rotation (the
number of times the operation must be performed to return to the original configuration).
• For example, a 4̅ axis means a four-fold rotation followed by an inversion through the center of the
axis.
• Improper rotation axes can be found in some point groups and space groups, such as 2̅, 3̅, 4̅, and 6̅.
• Improper rotation axes are different from proper rotation axes, which only involve rotations
without inversions.
Screw axes: -
• Screw axes are a type of symmetry element in crystals that combine a rotation and a translation
along the same direction.
• Screw axes are denoted by a number and a letter, where the number indicates the order of rotation
(2, 3, 4 or 6) and the letter indicates the fraction of translation (a, b, c, n or d).
• Screw axes can be visualized as a helix that traces out a lattice point after each rotation-translation
operation.
• Screw axes are important for describing the structure and properties of some materials, such as
quartz and chiral molecules.

Glide planes: -
• Glide planes are a type of symmetry operation in crystallography that combine a reflection and a
translation.
• Glide planes are denoted by a letter that indicates the direction of the translation vector: a, b, c, n,
or d.
• Glide planes are important for understanding the structure and properties of materials, especially
those with layered structures such as graphite or mica.
• Glide planes can also be used to classify the space groups of crystals, which are the sets of
symmetry operations that leave the crystal invariant.
• Glide planes are one of the five types of symmetry elements in two dimensions, along with rotation
axes, mirrors, centres of symmetry, and screw axes.
 Crystal Structure
• Crystal structure is the arrangement of atoms or molecules in a solid material.
• The crystal structure determines many physical properties of the material, such as density,
hardness, melting point, electrical conductivity, etc.
• The crystal structure can be described by a unit cell, which is the smallest repeating unit
that defines the pattern of atoms or molecules.
• The unit cell has a specific shape and size, defined by its lattice parameters (a, b, c, α, β, γ).
• The unit cell also has a specific symmetry, defined by its crystal system (cubic, tetragonal,
orthorhombic, etc.) and its space group (Pm3m, P4/mmm, etc.).
• The crystal structure can be represented by a crystallographic model, which shows the
positions of atoms or molecules within the unit cell and their bonds or interactions.
• The crystal structure can be determined by various experimental techniques, such as X-ray
diffraction, electron microscopy, neutron scattering, etc.

Crystal Lattice: -
• A space lattice is a three-dimensional arrangement of points that represents the positions
of atoms or molecules in a crystal.
• The points in a space lattice are called lattice points or nodes. Each lattice point is
equivalent to any other in terms of its environment and symmetry.
• A space lattice can be described by a set of three vectors called the primitive vectors or
basis vectors, which define the unit cell of the lattice. The unit cell is the smallest repeating
unit of the lattice that contains all the information about its structure and symmetry.
• There are 14 possible types of space lattices in three dimensions, called the Bravais lattices.
They are classified according to their symmetry and shape of the unit cell.
The Bravais lattices are:
- cubic (simple, body-centred, face-centred)
- tetragonal (simple, body-centred)
- orthorhombic (simple, body-centred, face-centred, base-centred)
- monoclinic (simple, base-centred)
- triclinic (simple)
- hexagonal (simple)
- rhombohedral (simple).
• The structure and properties of a crystal depend not only on the type of space lattice, but
also on the arrangement of atoms or molecules within the unit cell. This is called the crystal
basis or motif. The crystal basis can be described by a set of coordinates relative to the
lattice points. The combination of the space lattice and the crystal basis forms the crystal
structure.

Unit Cell: -
• A unit cell is the smallest repeating unit of a crystal structure that can be used to describe
the entire lattice.
• A unit cell has a fixed shape and size, and can be defined by three lattice vectors that span
the cell and six lattice parameters that specify the angles and lengths of the vectors.
• A unit cell can be primitive or non-primitive. A primitive unit cell contains only one lattice
point, while a non-primitive unit cell contains more than one lattice point.
• There are seven types of primitive unit cells based on their symmetry:
- Cubic - Rhombohedral
- Tetragonal - Monoclinic
- Orthorhombic - triclinic.
- Hexagonal
Each type has a different number of possible lattice systems and Bravais lattices.
• A unit cell can also be classified by its centring:
- simple (no additional lattice points)
- body-centred (one additional lattice point at the centre)
- face-centred (one additional lattice point at each face)
- base-centred (one additional lattice point at each pair of opposite faces).
• The volume of a unit cell can be calculated by taking the scalar product of one lattice vector
with the cross product of the other two lattice vectors. The volume of a unit cell is
proportional to the density of the crystal.
Unit cell Space lattice Abb Examples of materials
[Crystal System] [Atomic arrangement]
1. Simple cubic SC Mn, Po, NaCl
Atoms only at the 8 corners of the unit cell.
2. Body centred cubic BCC Na, V, Cr, Mo, W, Fe,
Atoms at the 8 corners plus one at the centre Cscl
of the body.
3. Face centred cubic FCC Ni, Cu, Ag, Al, Pb, Pt,
Atoms at the 8 corners plus one each at the Fe
centre of 6 faces.

2.Tetragonal 1. Simple Tetragonal ST Pa, In

Atoms only at the 8 corners of the unit cell
2. Body centred Tetragonal BCT Sn, U, Martensite
Atoms at the 8 corners & 1 atom at centre

3.Orthorombic 1. Simple Orthorhombic SO As, Bi, Sb

Atoms at the 8 corners
2. End centred Orthorhombic ECO Mg, So4, Kno3
Atom at 8 corners & at 2 face centres opp. To
each other.
3. Body centred Orthorhombic BCO Cementite
Atoms at 8 corners & one at body centre
4. Face centred Orthorhombic FCO Ga, S
Atoms at 8 corners & at 6 face centres
 4.Rhombohedral Simple Rhombohedra SR B, CaCo3, SiO2
Atoms at 8 corners

5.Hexagonal Hexagonal close packed HCP Mg, Be, Ti, Hf, Co

Atoms each at 6 corners of top face, 6 corners
of base, 2 hexagonal face centres & 3 within
the body

6.Monoclinic 1. Simple Monoclinic SM FeSO4, NaSO4

Atoms at 8 corners
2. End centred Monoclinic ECM
Atoms at 8 corners & at 2 face centres
opp. To each other

7.Triclinic Simple triclinic STC CuSo4, K2Cr2O2

Planes and directions in a lattice: -

• Planes and directions in a lattice are used to describe the geometric features of a crystal structure.
• A plane in a lattice is a set of points that lie on a flat surface that extends infinitely in two dimensions.
A plane can be defined by three non-collinear points or by a normal vector that is perpendicular to
the plane.
• A direction in a lattice is a line that passes through a point and extends infinitely in both directions. A
direction can be defined by two points or by a vector that indicates the magnitude and direction of
the line.
• Planes and directions in a lattice are usually expressed in terms of the unit cell parameters, which are
the lengths and angles of the edges of the smallest repeating unit of the crystal structure. The unit
cell parameters are denoted by a, b, c, α, β, and γ.
• To specify a plane in a lattice, the Miller indices are used. The Miller indices are three integers (h, k, l)
that are inversely proportional to the intercepts of the plane with the three unit cell axes. The Miller
indices are written in parentheses as (hkl).
 • To specify a direction in a lattice, the direction indices are used. The direction indices are three
integers [u, v, w] that are proportional to the components of the direction vector along the three unit
cell axes. The direction indices are written in square brackets as [uvw].

Planar Atomic Density: -

• Planar Atomic Density (PAD) is a measure of how many atoms are present in a unit area of a crystal
plane.
• PAD can be calculated by dividing the number of atoms in the plane by the area of the plane.
• PAD is useful for comparing the packing efficiency and bonding strength of different crystal
structures and orientations.
• PAD depends on the type of crystal structure (cubic, hexagonal, etc.), the Miller indices of the plane
(hkl), and the atomic radius of the element.

(a) Reduced-sphere FCC unit cell with the plane.

(b) Atomic packing of an FCC plane.

Packing of atoms: -
• Packing of atoms refers to how atoms are arranged in a solid material, such as a metal or a crystal.
• The packing of atoms affects the physical properties of the material, such as its density, strength,
electrical conductivity and thermal expansion.
• There are two main types of packing of atoms: close-packed and non-close-packed.
• Close-packed structures have the highest possible density for a given type of atom. They are formed
by stacking layers of atoms in a regular pattern. Examples of close-packed structures are hexagonal
close-packed (HCP) and cubic close-packed (CCP) or face-centred cubic (FCC).
 • Non-close-packed structures have lower density than close-packed structures. They are formed by
stacking layers of atoms in a less regular pattern. Examples of non-close-packed structures are body-
centered cubic (BCC) and simple cubic (SC).
• The packing of atoms can be characterized by the coordination number, which is the number of
nearest neighbors for each atom, and the packing factor, which is the fraction of space occupied by
the atoms in the unit cell.

(a) A portion of a close-packed plane of atoms; A, B, and C positions are indicated.

(b) The AB stacking sequence for close-packed atomic planes.

Packing fraction: -
• Packing fraction is a measure of how efficiently the atoms or molecules of a substance occupy the
available space in a given volume.
• It is defined as the ratio of the volume of the atoms or molecules to the total volume of the
substance.
• It can vary depending on the shape, size and arrangement of the atoms or molecules, as well as the
temperature and pressure of the substance.
• It is an important parameter in determining the density, mechanical and thermal properties of
materials, especially in nuclear engineering and solid-state physics.
• A high packing fraction means that the atoms or molecules are closely packed and have less empty
space between them, while a low packing fraction means that they are loosely packed and have
more empty space between them.

• The maximum possible packing fraction for spherical atoms or molecules in a regular arrangement is
0.74, which is achieved by a face-centered cubic or a hexagonal close-packed structure. The
minimum possible packing fraction for spherical atoms or molecules in a regular arrangement is
0.52, which is achieved by a simple cubic structure.

Classification and Coordination of voids: -

Voids:
In close packing of spheres, some hollows or voids are left blank. These vacancies in the crystal are
called interstitial Voids or interstitial sites or simply, voids. The two essential interstitial voids are
Tetrahedral Voids and Octahedral Voids.
Tetrahedral voids:
• Tetrahedral voids are the spaces between four atoms or ions arranged in a tetrahedral
shape.
• They are found in close-packed structures such as hexagonal close packing (hcp) and cubic
close packing (ccp).
 • The radius ratio of the smaller atom or ion that can fit into a
tetrahedral void is 0.225 to 0.414 of the larger atom or ion.
• There are two tetrahedral voids per atom in a close-packed
structure, so the number of tetrahedral voids is twice the number of
atoms.
• Tetrahedral voids are important for understanding the properties
and formation of compounds such as ionic solids and alloys.
Octahedral void:
• Octahedral void is a type of interstitial site in a crystal structure
where an atom can fit into a gap surrounded by six other atoms.
• The name octahedral comes from the fact that the six surrounding
atoms form the vertices of an octahedron, a polyhedron with eight
triangular faces.
• Octahedral voids are common in close-packed structures such as
face-centered cubic (fcc) and hexagonal close-packed (hcp) lattices,
where each sphere has 12 nearest neighbors.
• The size of the octahedral void is determined by the radius ratio of the interstitial atom and
the host atom. The radius ratio is defined as r/R, where r is the radius of the interstitial
atom and R is the radius of the host atom.
• The radius ratio for an octahedral void is 0.414, which means that the interstitial atom can
fit into the void if its radius is less than 41.4% of the host atom's radius.
• Some examples of compounds that have octahedral voids are sodium chloride (NaCl), zinc
sulfide (ZnS), and magnesium oxide (MgO).

Tetrahedral voids Octahedral voids

Tetrahedral voids are unoccupied empty Octahedral voids are unoccupied empty spaces
spaces present in substances having a present in substances having an octahedral
tetrahedral crystal system. crystal system.
It can be found in substances having a It can be found in substances having an
tetrahedral arrangement in their crystal octahedral arrangement in their crystal system
system.
Tetrahedral voids can be observed in the edges Octahedral voids can be observed in the center
of the unit cell. of the unit cell.
Four is the coordination number of the Six is the coordination number of the
tetrahedral void. Octahedral void.
In the space lattice, there are two tetrahedral There are two octahedral voids per sphere in
voids per sphere. the crystal lattice
Tetrahedral voids are smaller. Octahedral voids are larger as compared to
tetrahedral voids.
Bragg’s Law: -
• Bragg's law is a formula that relates the wavelength of X-rays to the angle of incidence and the
interplanar spacing of a crystalline material.
• It can be used to determine the structure of crystals by measuring the diffraction patterns produced
by X-rays passing through them.
• The law states that nλ = 2dsinθ, where n is an integer, λ is the wavelength of X-rays, d is the
interplanar spacing, and θ is the angle of incidence.
• When Bragg's law is satisfied, constructive interference occurs between the X-rays reflected by
different planes of atoms in the crystal, resulting in a peak in the intensity of the diffracted beam.
 Imperfections in Solids
All the different types of crystal structures with their arrangement of atoms are true only under
ideal conditions. This means that all real crystals generally have imperfections among their unit
cells. These are important because they affect many structure-sensitive properties of the material.
Ex: tensile strength, shear strengths of materials.

Types of imperfections: -
• Surface imperfections:
- Surface imperfections are deviations from the ideal shape or structure of a material.
- They can be classified into four types: point defects, line defects, surface defects and
volume defects.
- Point defects are localized disruptions of the atomic arrangement, such as vacancies,
interstitials or impurities.
- Line defects are one-dimensional defects that involve the misalignment of atoms
along a line, such as dislocations or grain boundaries.
- Surface defects are two-dimensional defects that occur at the boundaries between
different phases or materials, such as interfaces, free surfaces or cracks.
- Volume defects are three-dimensional defects that affect a large region of the
material, such as pores, voids or inclusions.
- Surface imperfections can have significant effects on the mechanical, electrical, optical
and chemical properties of materials. They can also influence the processing and
fabrication of materials.
• Point imperfections:
- Point imperfections are defects that occur at or around a single lattice point in a crystalline
material.
- They can be classified into three types: vacancies, interstitials and substitutional atoms.
- Vacancies are empty lattice sites where an atom is missing. They can be created by
thermal vibrations, irradiation or chemical reactions. They affect the density, electrical
conductivity and diffusion of the material.
- Interstitials are atoms that occupy the spaces between the regular lattice sites. They
can be introduced by doping, irradiation or mechanical deformation. They cause
distortion and strain in the lattice and affect the mechanical and electrical properties
of the material.
- Substitutional atoms are atoms of a different element that replace the original atoms at
the lattice sites. They can be introduced by alloying, doping or surface deposition. They
alter the chemical composition, crystal structure and physical properties of the material.

Line imperfections
 • Line imperfections:
- Line imperfections are defects in the crystal structure of a material that occur along one-
dimensional lines.
- They are also called dislocations and can be classified into two types: edge dislocations
and screw dislocations.
- Edge dislocations occur when an extra half-plane of atoms is inserted into the crystal
lattice, creating a step-like distortion along the line of the dislocation.
- Screw dislocations occur when the crystal lattice is sheared along a plane parallel to
the line of the dislocation, creating a spiral-like distortion.
- Line imperfections affect the mechanical properties of materials, such as strength, ductility
and hardness. They also influence the electrical and thermal conductivity of materials.
- Line imperfections can be introduced into materials by various processes, such as plastic
deformation, solidification, phase transformation and irradiation.
• Volume imperfections:
- Volume imperfections are defects in the crystal structure of a solid material that affect a
large number of atoms or molecules.
- They can be classified into two types: point defects and extended defects.
- Point defects are localized deviations from the ideal arrangement of atoms or
molecules in a crystal lattice. They include vacancies, interstitials, substitutional
impurities, and Frenkel defects.
- Extended defects are linear, planar, or three-dimensional regions of distorted or
disordered atoms or molecules in a crystal lattice. They include dislocations, grain
boundaries, stacking faults, twins, and precipitates.
- Volume imperfections can affect the physical and chemical properties of a material, such
as its strength, ductility, conductivity, diffusion, corrosion resistance, and optical behavior.
• Screw dislocation: -
- Screw dislocation is a type of line defect in a crystalline material that results from a shear
stress applied parallel to a crystal plane.
- It can be visualized as a helical ramp that connects two adjacent and parallel crystal
planes, creating a mismatch along the line of the defect.
- The direction of the ramp is called the Burgers vector, and its magnitude is equal to the
lattice spacing along the direction of shear.
- Screw dislocations are important for plastic deformation of materials, as they allow atoms
to slip past each other along the direction of the Burgers vector without breaking many
bonds.
- Screw dislocations can also interact with other defects, such as vacancies, interstitials,
grain boundaries, or other dislocations, and affect the mechanical properties of the
material.
Edge dislocation: -
- Edge dislocation is a type of line defect in a crystalline material
that occurs when an extra half-plane of atoms is inserted or
removed from the crystal lattice.
- The edge dislocation can be visualized as a wedge-shaped
distortion that creates a step at the surface of the crystal.
- The edge dislocation has a Burgers vector that is perpendicular
to the dislocation line and points in the direction of the extra
half-plane of atoms.
- The edge dislocation can move along its slip plane by gliding or climbing when subjected to an
external stress or a change in temperature.
- The edge dislocation affects the mechanical, electrical and optical properties of the material
by creating strain fields, scattering carriers and altering the band structure.

2-D and 3D-defects: -

Grain boundaries: -
• Grain boundaries are those regions which separate crystals of different conditions. A Grain
boundary is formed when two adjoining growing crystals (grains) meet at their surfaces.
• The thickness of these regions is only a few atomic diameters.
• The atoms in these regions are highly distorted & are caught between the two crystals &
pulled apart by each to its own configuration.
Tilt / Twin boundaries: -
• It is a type of low angle grain boundary where the orientation difference between two
neighbouring crystals is less than 10˚.
• The distortion in the boundary is less, & is limited to a few edge dislocations, located one below the other.
Twin boundaries: -
• In this type the atomic arrangement on one side of the twin boundary is a mirror reflection of
the arrangement on the other side.
• Twin boundaries occur in pairs so that change in orientation of two grains introduced by one
boundary is restored by the other grain boundary.
• Twins are generally formed during annealing or mechanical working of metals.
3D defects: -
Volume defects:
Volume imperfections are those defects like blow holes, cracks, foreign inclusions etc. Which are 3
dimensional & are much larger than other types of imperfections. They are normally introduced
into solids during processing & fabrication techniques & have a considerable effect on the
properties of materials.

Concept of free volume in amorphous solids: -

Concept of free volume in amorphous solids Free volume in a polymer can be defined as the
volume of the total mass, that is not occupied by polymer chains themselves and hence diffusing
molecules can be situated there. It can generally be said to the gap or pores occupied between the
chains of polymers as shown in the Figure.

Similarly in the case of glass and gel the atoms do not have long range order and possesses space
between the molecules/atoms which constitute to free volume