CRYSTAL STRUCTURES

Without materials, there is no engineering.

Examples
Ceramics - Bottles
Metal - Cans
Polymer - Bottles
Ceramics
Bricks
Polymers
Safety applications
Helmets
Spoons & Fork
Die
NOTE: Engineers will be exposed to design problems involving materials
STRUCTURE
Subatomic Level - Electronic structure of individual atoms that define interaction
among atoms (Interatomic Bonding)
atomic Level - arrangement of atoms in Materials (for the same atoms can have
different properties, e.g. two forms of Carbon: Graphite & Diamond)
Microscopic Structure - Arrangement of small grains of Materials that can be
identified by Microscopy
Macroscopic Structure - Structural Elements that can be viewed with the Naked
Eye
PROPERTY
Mechanical - Strength, Hardness, Toughness, Ductility, Fatigue, Creep, Wear
Resistance
Physical - Density, Thermal Conductivity, Thermal Expansion, Electricity,
Magnetism, Optical Behavior, Color
Chemical - Corrosion Resistance, Alloying Element
CREEP
Progressive Plastic Deformation under constant stress with time
Important in high temperature applications
PROCESS
CRYSTAL STRUCTURE
Matter in universe is mainly classified into 3 kinds
SOLIDS: all atoms or Molecules are arranged in a fixed manner and have definite
shape and size
LIQUIDS & GASES: Atoms or Molecules are not fixed and cannot form any shape
and size. They gain the shape and size of the Container
In selecting materials for Engineering, we use ones in Solid State to have better
performance in Engineering Output
Ex. Gloves, Insulators, Beakers, Tanks, Steels, Alloys, etc.
SOLID
Atoms are closely packed. They are not stationary but are vibrating around fixed
points, giving rise to orderly arrangement of Crystal Structures
TYPES: Amorphous (Non-Crystalline) & Crystalline
CRYSTALLINE
Greek Word 'Krustallos' meaning Ice & Crystal
State of solid material in which Atoms, Ions or Molecules are situated in a
repeating or periodic array over large atomic distances
Characterised by presence of long-range order, such that upon Solidification,
atoms will position themselves in a repeating Geometric arrangement in which
each atom is bonded to its nearest-neighbor atoms
Diamond, Quartz, Table Salt
NON-CRYSTALLINE
From Greek Words 'a' meaning without and 'morphe' meaning Shapeless or
Without Form
Solid Materials that lack a systematic and regular arrangement of atoms or Ions
over relatively large atomic distances
Atomic Structure resembles that of a Liquid
Characterised by absence of long-range order
When cut, break into uneven pieces because of the random and disorderly
arranged atoms, Ions or Molecules
Rubber, Glass, and several Polymers belong to this classification
PROPERTIES CRYSTALLINE SOLID AMORPHOUS SOLID

The crystals of every

Do not have any orderly
crystalline solid have defined
pattern of arrangement of
Geometrical geometrical shape due to
particles and therefore, does
Shape definite and orderly
not have any definite
arrangement of particles in 3D
geometrical shape
Shape

Crystalline Solids which

directly change into Liquid Like Glass, they do not have
Melting Point
State have definite Melting any definite Melting Point
Point

Have definite Cleavage Planes

which are inclined to one Do not have such well-defined
Cleavage Planes
another at a particular angle Cleavage Plates
for a given Crystalline Solid

The orderly arranged particles

Similar to Liquids & Gases, the
Anisotropic & in Crystalline Solids are
arrangement of particles is
Isotropic different in different
Random, these solids show
Properties directions, these solids show
Isotropic Properties
anisotropic Properties

Symmetry Have Crystal Symmetry Do not have Symmetry

Tensile Strength Very High Low

They fracture in a Ductile They fracture in a Brittle

Fracturing
Manner Manner

Metals - NaCl, KCl, CsCl

Glass, Plastics, Polymers,
Examples Carbon
Rubbers, Silica, etc.
etc.
CRYSTAL STRUCTURE
Way Atoms, Ions or Molecules are spatially arranged in a Crystalline Material
Defined in terms of the Unit Cell Geometry and atom Positions within the Unit Cell
Lattice - 3D Dimensional array of Points coinciding with atom positions (or Sphere
Centers) or an Infinite, Regular array of Points in Space
PLANE LATTICE
Consider an array of points in such that the environment about any point is
identical to the environment about any other point
This array is of 2D

For constructing a 2D Lattice, choose any two convenient axis that the points lie at
equal intervals 'a' and 'b' along these axis as shown in the figure
There are 5 Lattices in 2D: Oblique, Square, Hexagonal, Rectangular and Centered
Rectangular Lattice
SPACE LATTICE
If array of Points is extended to 3D
For constructing the Space Lattice the points are arranged at equal intervals 'c' in
the third direction also. There are 14 Space Lattices called the Bravais Lattice
Lattices may also be defined as a Parallel Net like arrangement of points such that
the environment bout any point is identical with the environment about any other
point
BASIS
Assembly of atoms, Ions or Molecules identical in Composition, arrangement and
Orientation
Consists of the simplest arrangement of atoms which is repeated at every point in
the Lattice to build up the Crystal Structure
Number of atoms in a basis may be one as in case of many Metals and Inert Gases
In Ionic Crystals a basis is composed of two distinct types of Ions. For example
Na+ and Cl-
 When Basis is attached identically to each Lattice Point, the actual Crystal Structure
is formed as shown

Relation can be written as Lattice + Basis = Crystal Structure

UNIT CELL
Describes Crystal Structure
Smallest portion of Crystal Lattice that shows the 3D Pattern of the entire Crystal
Basic Structural Unit or Building Block of the Crystal Structure and defines the
Crystal Structure by virtue of Geometry and atom positions within
Geometry of the Unit Cell is defined as parallelepiped, providing six Lattice
Parameters taken as the lengths of the Cell Edges (a, b, c) and the angles between
them
Region of Space which when repeated by Primitive Translation vectors fills all space

Choice of the Unit Cell is not unique. It can be constructed in a number of ways
but the Unit Cell should be chosen in such a way that it conveys all the symmetry
of a Crystal Lattice, by having shortest possible size, which makes mathematical
calculations easy
Each atom or Molecule in the Unit Cell is considered as a Lattice Point. The
distance between the two atoms or ions of the same type is the 'Length of the Unit
Cell'
Figure below illustrates the relationship of a Unit Cell to the entire Crystal Lattice.
The lengths (a, b, c) of the principal axis or edges of the Unit Cell and the angles
between them are the Lattice Constants, are also called Lattice Parameters
an xyz Coordinate System is established with its origin at one of the Unit Cell
corners; each of the x, y, z axes coincides with one of the three parallelepiped
edges that extend from the corner
WAYS OF REPRESENTING CRYSTAL STRUCTURES
Atomic-Site Cell Unit Cell (Ball & Stick Model)
Hard Sphere Unit Cell (Ball Method)
Isolated Unit Cell
PRINCIPAL METALLIC STRUCTURE
Simple Crystal Structure / Primitive
Unit cell with atomic packing arrangement in which one atom is located at the
corners of a Geometrical Figure
atoms are present only at the corners. The edge length of the cube becomes equal
to the Diameter of one atom, allowing the Corner atoms to touch one another
an atom at the corner is equally shared by 8 Unit Cells. So the contribution of one
atom is 1/8

Body-Centered Cubic (BCC)

There is one atom at the center along with 8 Corner atoms
This corner atom is shared by 8 Unit Cells and the atom at the Center is not a
shared one
Face-Centered Cubic (FCC)
One atom is located at each corner of the Cube, and additional atoms are placed
at the center of each of the six faces of the Cube
The atoms at the faces are equally shared by 2 Unit Cells. Corner atoms by 8 Unit
Cells.
BRAVAIS LATTICE
In 1948, Bravais showed that there are 4 ways of arranging points in Space Lattice
under the seven crystal systems to describe Crystals. They are classified on the
basis of the following Crystal Lattices
Crystals of different substances have similar shapes and hence the crystals are
classified into the so-called Crystal Systems depending on their axial ratio and the
interfacial angles. In 3D, there are 7 Crystal Systems
Bravais showed that throughout the 7 Crystal Systems, there are fourteen Lattice
Types possible. These are known as Bravais or Space Lattices
The 7 Crystal Systems are:
Cubic (CsCl, NaCl, Cu)
Tetragonal (SnO2)
Orthorhombic (PbSO4, MgSO4)
Monoclinic (FeSO4, LiSO4, H2O)
Triclinic (FeSO4, 5H2O, K2Cr2O7)
Trigonal (Rhombohedral) (Sb, As, CaCO3)
Hexagonal (Zn, Cd, Ni, As, SiO2)
HOW MANY ATOMS ARE CONTAINED IN THE UNIT CELL
We need to realise than an individual atom is frequently shared between multiple
Unit Cells
The atoms on the faces, for example, will be in the Unit Cell that we are looking as
well as the adjacent one
Each of the corner atoms will appear in a total of 8 Unit Cells because the corners
of 8 Cubes would meet if we were to stack the unit Cells up like Blocks
COORDINATION NUMBER
Characteristic of the Crystal Structure
Refers to number of nearest neighbors to an atom or Ion. For metals, each atom
has the same number of nearest-neighbor or touching atoms
For particle of the same size, the higher the Coordination Number, the greater the
number of particles in each volume
Simple Crystal Structure / Primitive
The centers of 8 Identical Particles define the corners of a Cube
The particles touch along the cube edges but they do not touch diagonally along
the cube faces or through its Center
The Coordination Number for Simple Structure is 6: 4 in its own Layer, one in the
layer above and one below

Body-Centered Cubic (BCC)

Identical atoms lie at each corner and in the center of the Cube
 Those at the corners do not touch each other, but all touch the One in the center
Each atom is surrounded by 8 nearest neighbors, 4 above and 4 below, so the
Coordination Number for the BBC Crystal Structure is 8

Face-Centered Cubic (FCC)

Identical atoms lie at each corner and in the center of each face but not in the
Center of the Cube
The atoms at the corners touch those in the faces but not each other
The Coordination Number is 12; the front face atom has four corner nearest-
neighbor atoms surrounding it, four face atoms that are in contact from behind,
and four other equivalent face atoms residing in the next Unit Cell to the front (not
shown)

ARRANGEMENT OF ATOMS IN A CRYSTALLINE STRUCTURE

Unit Cells result from the way atoms pack together
Since atoms can be thought of as spheres, arranging them into a Crystalline Solid
is loosely like stacking a collection of marbles into a box
It is intuitively clear that no matter how we arrange the marbles in the box, there
will always be some gaps between; the spheres can never completely fill the
volume of the box
 But it should also be clear that the amount of empty space among the marbles
could be minimised by carefully arranging them
We can illustrate the difference in a way the atoms may be packed by using a 2D
Model. It is easy to see the gaps can be reduced if the rows or marbles are offset
from one another
The marbles in the picture are arranged in a very orderly pattern, but significant
gaps remain. If our aim is to place as many marbles as possible into a given area,
we would do better by staggering the rows, as shown in the panel (a). Both
pictures are of same size, but the arrangement on the right (b) allows more
marbles to fit in the area. It is easy to see that the gaps can be reduced if the rows
or marbles are offset from one another.

Simple Crystal Structure / Primitive

The first layer of Spheres is arranged in vertical and horizontal rows to form large
diamond-shaped spaces. If we place the next layer of spheres directly above the
first, we obtain the arrangement based on the Simple Cubic Unit Cell
Body-Centered Cubic (BCC)
This is arranged by placing the second layer directly above the first and use the
space more efficiently by placing it on the diamond-shaped spaces in the first
layer. Then we pack the third layer onto the diamond-shaped spaces in the second,
which makes the first and third layers line up vertically

Close-Packed Crystal Structures

Cubic Close-Packing (CCP) or Face-Centered Cubic (FCC)
Hexagonal Close-Packing (HCP)
The two arrangements differ in a way that the layers line up with one another
The cubic structure is said to feature an "a, b, c, a, b, c...." stacking pattern
The hexagonal structure has an "a, b, a, b..." stacking pattern
Both structures occupy roughly 74% of the available space, which is the most
efficient packing of equal-sized spheres or atoms
METALLIC CRYSTAL STRUCTURES
3 Relatively Simple Crystal Structures are found for most of the common metals:
Face-Centered Cubic (FCC)
Body-Centered Cubic (BCC)
Hexagonal-Close Packed (HCP)
PACKING EFFICIENCY OF THE STRUCTURE OR ATOMIC PACKING FACTOR
Percentage of Space occupied in each arrangement
Ratio of volumes of atoms occupying the Unit Cell to the volume of the Unit Cell
Related to the density of a Material because an increase in the Packing Efficiency
will put more atoms into the same Volume
The shading in the Periodic Table indicates the most stable Crystal Structure for the Solid
state of the Elements. Most of the elements display one of the structures we have
discussed, but a few less common Crystal arrangements
DENSITY CALCULATION