Solid State Definition: Solids are a state of matter characterized by structural rigidity and

resistance to changes in shape or volume.

Key Characteristics:
• Definite mass, volume and shape; Short intermolecular distances & strong intermolecular
forces; Constituent particles (atoms, molecules, or ions) have fixed positions and can only
oscillate about their mean positions; Incompressible and rigid.
Bonding in materials: Atomic bonding in materials determines their physical, mechanical, and
electrical properties, generally categorized into strong primary (ionic, covalent and metallic) and
weak secondary (Van der Waals) bonding.
1. Primary bonding:
(a) Ionic Bonding: Occurs between metal and non-metal atoms
(e.g., NaCl or salts) through electron transfer, creating
electrostatic attraction.
(b) Covalent Bonding: Occurs by sharing valence electrons
between atoms, commonly seen in polymers, diamond and
silicon.
(c) Metallic Bonding:
Valence electrons are
delocalized, forming a
"cloud" that surrounds
positively charged metal ions,
typical of metals and alloys.

2. Secondary bonding:
Van der Waals/Molecular Bonds: Weak attraction forces that exist in
many materials (e.g., polymers) and are often responsible for melting
points, although overshadowed by primary bonds.
Crystalline vs. Amorphous
Feature Crystalline Solids Amorphous Solids
Shape Characteristic geometrical shape Irregular shape
Order Long-range order Short-range order
Melting Point Sharp and characteristic Soften over a range of temperature
Cleavage Split into plain, smooth pieces Cut into irregular surfaces
Examples Quartz, Diamond, NaCl Glass, Rubber, Plastics
Parameters: A unit cell is characterized by its dimensions
along the three edges (a, b, c) and the angles between them
(, , ).

: Angle between edges b and c

: Angle between edges a and c.
: Angle between edges a and b.
Crystalline NaCl Amorphous Silica
Crystal lattice: A lattice is an ordered array of points describing the
arrangement of particles that form a crystal.
Unit cell: The smallest portion of a crystal lattice which, when repeated in
different directions, generates the entire lattice
 • Primitive (Simple) Unit Cell: Particles are present only at the corners.
• Body-Centered Unit Cell (BCC): Contains one constituent particle at the
center of the body, in addition to particles at the corners.

• Face-Centered Unit Cell (FCC): Contains one particle at the

center of each face, in addition to particles at the corners.
• End/Base-Centered Unit Cell: Contains particles at all
corners, plus one at the center of any two opposite faces.

Characteristics of Primitive crystal system

➢ A primitive crystal structure, or primitive unit cell, is the smallest, simplest and most fundamental repeating unit in a
crystal lattice, containing exactly one lattice point (or one net atom/molecule).
➢ It defines the entire structure through translation without gaps or overlaps. Primitive cells such as the simple cubic
structure have lattice points only at the corners.
➢ The primitive cell contains only one, or a net total of one, lattice point per unit cell. While 8 corners exist in a simple
cubic lattice, each is shared by 8 neighbors, resulting in 1/8x8=1
➢ Of the 14 3-D Bravais lattices, seven are considered "primitive" systems (e.g., Simple Cubic, Simple Orthorhombic,
Simple Triclinic).
➢ In a Simple Cubic (SC) structure, atoms are only located at the 8 corners, making it the most basic primitive cell. Ex. Po,
ZnO
Bravais lattice: A French mathematician, Bravais showed that there are only 14 possible 3-D
lattices, and called them as Bravais lattices.
Unit Cells of Cubic, Tetragonal, Orthorhombic and Monoclinic
Unit Cells of Hexagonal, Rhombohedral and Triclinic
Atomic packing factor (APF) of Primitive crystal system (Simple Cubic)
Characteristics of BCC crystal system
▪ BCC crystal structure features atoms at each of the
eight corners of a cube plus one atom in the center.
▪ It has a coordination number of 8, an Atomic
Packing Factor (APF) of 0.68, and contains 2 atoms
per unit cell.
▪ Common in metals like Fe, Cr, and W.
▪ BCC is less closely packed than FCC, often resulting
in higher strength and lower ductility.
▪ Unit Cell Composition: 8 corner atoms (each
shared by 8 cells) + 1 central atom= 1/8x8=1 +1=
2 atoms per unit cell.
▪ Coordination Number: 8 (each central atom
touches 8 corner atoms).
▪ Atomic Radius &Lattice Parameter: Atoms in
BCC structure touch along body diagonal of cube.

▪ The relationship between the edge length (a) and the atomic radius is 4r=a3
▪ BCC metals are generally harder and less malleable than more densely packed structures like FCC.
▪ Temperature Sensitivity: Many BCC metals undergo a ductile-to-brittle transformation (DBTT). They are ductile at higher
temperatures but can become quite brittle in cold conditions.
▪ High Melting Points: Due to the strong bonding influence of next-nearest neighbors (which are only 15% further away than
nearest neighbors), BCC metals often have high melting points.
Characteristics of BCC crystal system
Characteristics of FCC Structure
• Atomic Positions: Atoms are located at the 8 corners (shared by 8 cells, shared by 8 cells, 8x1/8=1 atom) and 6 face-centers
(shared by 2 cells, 6X1/2=3 atoms totalling 4 atoms per unit cell.
• Packing Density: It is a close-packed structure with an Atomic Packing Factor (APF) of 0.74 (74%) and 26% void space.
• Coordination Number: 12 (each atom touches 12 nearest neighbors).
• Stacking Sequence: The stacking sequence is ABCABC, which is a close-packed arrangement.
• Properties: FCC metals (e.g., copper, aluminium, nickel, silver, gold) are generally ductile and tough.
• Common Examples: Aluminium, Copper, Gold, Lead, Nickel, Platinum, Silver.
Atomic packing factor FCC crystal system
Seven Crystal System
▪ Inspection of a wide variety of crystals leads to the conclusion that all can be regarded as conforming to one of
the seven regular figures. These basic regular figures are called seven crystal systems.
▪ The crystal system is defined by the angles between its faces and deciding how many axis are needed to define
the principal features of its shape.
Closed packing of Solid materials
In solids, the constituent particles are close-packed, leaving the minimum vacant space. Let us consider the constituent particles as
identical hard spheres and consider building up the three-dimensional structure in three steps.
Close Packing in One Dimension

Close Packing in Two Dimensions

Square close packing in two

dimensions, a non closed packed
structure with coordination no: 4
hexagonal close packing in
two dimensions
Representation of void space
If no of close packed sphere is N
No of tetrahedra void is 2N
No of octahedral is N
Closed packing of Solid materials
Placing third layer over second layer Covering octahedral hole

Covering Tetrahedral Voids: Tetrahedral voids of 2nd layer Covering octahedral hole: The 3rd layer may be placed above 2nd
may be covered by spheres of 3rd layer. In this case, the spheres layer in a manner such that its spheres cover the octahedral voids.
of 3rd layer are exactly aligned with those of 1st layer. Thus, the When placed in this manner, the spheres of 3rd layer are not
pattern of spheres is repeated in alternate layers. This pattern is aligned with those of either 1st or 2nd layer. This arrangement is
often written as ABAB pattern. This structure is called HCP called ‘C’ type. Only when 4th layer is placed, its spheres are
structure. aligned with those of 1st layer .This pattern of layers is often
written as ABCABC & structure called CCP or FCC.
Numerical on cubic system
Q. 1. Copper crystallizes into FCC lattice. Edge length of unit cell is 361 pm. Calculate the atomic radius of a Cu atom.
Ans: (i). Identify the given information: Lattice type = FCC & Edge length (a) = 361 pm
(ii). State the relevant formula: For FCC unit cell, relationship between edge length (a) and atomic radius (r) = a/ 22
(iii). Perform the calculation: Atomic radius of copper (r) = 361/(2x1.414) = 127.6 pm.

Q. 2. Sodium crystallizes in a body-centered cubic (BCC) unit cell. If the atomic radius of sodium is 186 pm, calculate the edge
length of the unit cell.
Ans: (i). Identify the given information: Atomic radius (r) = 186 pm & Lattice type = BCC
(ii). Recall the relationship between a and r for BCC: a = 4r /3
(iii). Substitute the values: Edge length of sodium unit cell (a) = 4 x 186/1.732 = 429.56 pm

Q. 3. Polonium is the only element known to crystallize in a simple cubic structure at room temperature. If the atomic radius of
polonium is 167 pm, calculate the edge length and volume of its unit cell in cm³.
Ans: (i). Find the edge length (a): For a simple cubic unit cell, the edge length is twice the atomic radius; a = 2r
a = 2 x 167 pm = 334 pm
(ii). Convert edge length to cm (pm = 10-10 cm): a = 334 x 10 -10 cm = 3.34 x 10-8 cm
(iii). Calculate the volume (V = a3): V = (3.34 x 10-8)3 cm3 = 3.73 x 10-23 cm3
 Types of Volume Defects
Precipitate: May be fraction or micron in size
Dispersants: May be large precipitates, grains or polygranular particles distributed through microstructure.
Inclusions: Foreign particles or large precipitate particles, undesirable, harmful.
Voids: Trapped gases, decreases mechanical strength.
Principle and applications of powder X-Ray Diffraction (XRD) technique
• Principle: XRD is a technique used to determine the crystallographic structure of a material. XRD works by irradiating a
material with incident X-rays and then measuring the intensities and scattering angles of the X-rays that leave the material.
• XRD is a versatile, non-destructive technique (NDT) widely used in materials science and engineering for identifying unknown
crystalline materials. XRD is also used to determine structural properties (lattice parameters, strain, grain size, epitaxy, phase
composition, orientation, atomic arrangement) and to measure film thickness.
How XRD pattern is produced? Bragg model of diffraction
• Crystals are regular arrays of atoms, whilst X-rays are waves of EM radiation. Crystal atoms scatter incident X-rays, primarily
through interaction with the atom’s electrons, known as elastic scattering; the electron is known as the scatterer.
• A regular array of scatterers produces a regular
array of spherical waves. In the majority of
directions, these waves cancel each other
through destructive interference, but they add
constructively in a few specific directions, as
determined by Bragg’s law.
• nλ = 2dsinθ, where “n” is an integer, and “λ” is
the beam wavelength, “d” is the spacing
between diffracting planes and “θ” is the
incident angle.
• X-rays scattered from adjacent crystalline
planes will combine constructively (constructive
interference) when angle θ between plane and
X-ray results in path-length difference that is
integer multiple “n” of X-ray wavelength “λ”.
What is diffraction?
• Diffraction refers to a phenomena when a wave encounters an obstacle.
• In classical physics, the diffraction phenomenon is described as the apparent bending
of waves around small obstacles and the spreading out of waves past small openings.
Interference of diffracted waves
• Interaction between diffracted waves is called interference.
• Constructive Interference: Waves are in-phase when each of their crests and troughs occur exactly at the same time.
Those type of waves stack together to produce a resultant wave that has a higher amplitude. For constructive
interference, path difference should be multiples of n*λ.
• Destructive Interference: If the waves are out of phase by multiples of (n/2)*λ, then destructive interference occurs and
the amplitude of the resultant wave will be reduced.

path difference = multiple of n*λ path difference = multiple of (n/2)*λ

Components of a XRD instrument
Incident-beam optics Receiving-side optics • X-ray tube: source of X-rays
• Incident-beam optics:
condition the X-ray beam before it hits the
sample.
• Goniometer: platform that holds and moves
the sample, optics, detector, and/or tube.

• Sample holder
• Receiving-side optics: condition the X-ray beam after it has
encountered the sample.
• Detector: count the number of X-rays scattered by the
sample.

• Incident angle (w) is defined between the X-ray source

and sample.
• Diffracted angle (2q) is defined between the incident
beam and the detector angle.

(Interference
pattern)
• Incident angle (w) is always ½ of the detector angle 2q
i.e. q.
• In a typical XRD instrument, the X-ray tube is fixed,
the sample rotates at q°/min and detector rotates at
2q°/min.
P-XRD Pattern Parameters and Analysis
➢ XRD Plot: Signal intensity at 2θ positions.
➢ Peak Intensity and Peak position
• 2θ positions atoms within a lattice structure.
• Intensity of peaks correlates with number of atoms in phase.
• Greater peak intensity indicates more crystals or molecules with specific spacing.
➢ Peak Width and Crystal Size
• Peak width inversely proportional to crystal size. Thinner peak indicates larger crystal.
• Broader peak suggests smaller crystal, defect, or amorphous nature.
➢ Diffraction Pattern Database Confirmation
• Matches unknown compound patterns with literature
and experimental values (Joint Committee on Powder
Diffraction Standards (JCPDS) and International
Crystal Structure Database (ICSD).
• Verifies element identity by matching location, width,
and relative heights of diffraction patterns.

➢ Crystallite size: D = kλ/βcosθ

• k = Scherrer constant (depends on shape).
• λ = X-ray wavelength.
• β = FWHM in radians
• θ = Bragg’s angle
XRD Numericals
Q. 1. In a NaCl crystal, there is a family of planes 0.252 nm apart. If the first-order maximum is observed at an
incidence angle of 18.1°, what is the wavelength of the X-ray scattering from this crystal?
Ans.: Use the Bragg equation nλ = 2dsinθ to solve for θ.
For the first-order, n=1. Then λ = 2dsinθ/n = 2dsinθ/1
λ = 2(0.252×10−9 m)sin(18.1°)/1
= 0.504*0.31068 = 1.57×10−10m or 0.157 nm.
Q. 2. Estimate the crystallite size of the given nanomaterial using p-XRD data:
Peak position 2 = 21.61o, FWHM of sample = 2.51o, k = 0.9 and λ = 1.5406 Å (degree to radian = Degree × π/180).
Ans.: 2θ = 21.61o (θ = 10.805o) and FWHM = 2.51o (0.043825 radian)
Crystalline grain size calculation by Scherrer’s equation: k*/β*cos θ
k = 0.9,  = 1.5406 Å (0.15406 nm), β = FWHM in radian and 2 = Bragg’s angle in o obtained from p-XRD data.
Crystallite size = (0.9*0.15406)/(0.043825*0.982271) nm = 3.22 nm