CRYSTAL STRUCTURE

• A Crystal is defined as an orderly array of

atoms in space. Crystalline materials have
crystal structure.
• Also defined as regular repetition of 3 D
pattern of atoms in space
 Unit cell
• The simplest repeating unit of any structure that can be
stacked to fill space is the unit cell
Lattice Points
• Lattice Parameters are a, b, c are axial length.
, ,  interaxial angles
•The cubic shape has, of course, the highest
symmetry.
• By adding additional lattice points to some of these
seven basic shapes, the 14 Bravais lattices are
generated which compactly describe all of the
possible geometric packing arrangements with the
greatest symmetry and simplicity.
• Most metals and many other solids have unit cell
structures described as body center cubic (bcc),
face centered cubic (fcc) or Hexagonal Close
Packed (hcp).
Body-Centered Cubic (BCC) Structure

• Atoms at each of the eight corners of a cube (like the cubic unit cell) plus one
atom in the center of the cube (middle image)
• Co-ordination number of 8, The packing factor is 0.68
• Total of two atoms;
atoms one in the center and eight eighths from corners atoms
as shown in the middle image below (middle image).

• The bcc structure is often the high temperature form of metals that are
close-packed at lower temperatures.

• Bcc structure include lithium, sodium, potassium, chromium, barium, vanadium,

alpha-iron and tungsten.

• Metals which have a bcc structure are usually harder and less malleable than
close-packed metals such as gold.
 Face Centered Cubic (FCC) Structure

 The face centered cubic structure has atoms located at each of the corners and the
centers of all the cubic faces (middle image).

 All corner atoms are shared among eight unit cells & six face centered atoms is shared
with an adjacent Unit cell

 coordination number of 12.

In the fcc structure (and the hcp structure) the atoms can pack closer together than
they can in the bcc structure.

The packing factor (the volume of atoms in a cell per the total volume of a cell) is 0.74

Ex: aluminum, copper, gold, iridium, lead, nickel, platinum and silver.
 Hexagonal Close Packed (HPC) Structure

• HCP structure has three layers of atoms.

• The coordination number of the atoms in this structure is 12
•The packing factor is 0.74
• Ex: beryllium, cadmium, magnesium, titanium, zinc and zirconium.

Packing Factor:
 Crystal Structure Characteristics of some Metal

Struct. a0 versus r Atoms Co-ordination Packing Examples

per No Factor
Cell
SCS a0=2r 1 6 0.52 Polonium, alpha Mn

BCC a0=2r√2 2 8 0.68 Fe,Ti,W,Mo,Nb,Ta,K,N

a,V,Zr,Cr

FCC a0=4r/√3 4 12 0.74 Fe, Cu, Au, Pt,Ag, Pb,

Ni

HCP a0=2r 6 12 0.74 Ti,Mg,Zn,Be,Co,Zr,Cd

C0=1.6333a0
 Assignment No-1
• Define Materials Science, Metallurgy,
Crystallography, Millers Indices, Atomic
Packing Factor, co-ordination Number
• Calculate the atomic radius, co-ordination
number & packing factor for BCC, FCC,
HCP crystal structure.
 Imperfections in Crystal Structure
• Definition of crystal: A crystal is a solid composed of
atoms, ions, or molecules are arranged in a pattern which is
repetitive in 3D
• A perfect crystal, with every atom of the same
type in the correct position, does not exist.

• Real Crystals (as in cast/welded objects) are never perfect,

lattice distortions, various imperfections, irregularities/defects.
• Defects give rise to discrepancies in computed & real yield
stresses.
• Imperfections affects mechanical, physical properties of
metals & alloys.
 Types of imperfections
lattice vacancies
Interstitial atoms
Point Defects Impurity atoms
Electronic Defects

Line Defects Edge dislocations

Screw dislocations
Planar/Surface, interfacial/ Grain Grain boundary
boundaries defects Tilt boundary
Twin Boundary
Volume Defects
POINT DEFECTS

A point defect is a localized imperfection that disrupts the

lattice.
The properties of materials may be controlled by
intentionally creating and controlling point defects through
heat treatment, strain hardening, solid solution strengthening,
and other related processes.
Point defects hamper the movement of dislocations by
disrupting the atom positions and making the slip planes bent
or bumpy, and therefore strengthen the material.
They also affect optical and electrical properties and
diffusion rates.
In the perfect lattice, all of the atoms line up
evenly, and there is no distortion.

1. When an atom is missing from

the lattice, there is a vacancy. In
Creep phenomenon atoms are
transported through lattice with the
help of vacancies
Self interstitial atom
•A self interstitial atom is an extra atom
that has crowded its way into an interstitial
void in the crystal structure.
• Self interstitial atoms occur only in low
concentrations in metals because they distort
and highly stress the tightly packed lattice
structure.
• The substitutional atoms may be either
larger or smaller than the surrounding atoms.

• A substitutional impurity atom is an atom of a different type than

the bulk atoms, which has replaced one of the bulk atoms in the
lattice. Types: are substitutional impurity or interstitial
impurity
• Substitutional impurity atoms are usually close in size (within
approximately 15%) to the bulk atom. Ex. zinc atoms in brass. In
brass, zinc atoms with a radius of 0.133 nm have replaced some of
the copper atoms, which have a radius of 0.128 nm.
 Compositional defects :ex Slag inclusions
 Solid state processes like diffusion, phase transformation,
electrical & Thermal conductivity impurities play a major role.
 Controlled introduction of impurities can create electronic devices
 In an ionic material, an ion can be displaced from a normal site to
an interstitial site, causing a Frenkel defect.

 A Schottky defect can also occur in an ionic material - both an

anion and a cation are missing.
 These "pairs" of defects stay close together, in the one case
because of lattice strain, and in the other because of their charge
differences
Interstitial Carbon in Steels is vital importance in strengthening of iron,
Iron being an allotropic metal, its crystal structure changes
with temperature. Above 910°C, the structure is FCC . The
largest site between the iron atoms has a radius of 0.052
nm, somewhat smaller than the carbon atom. A maximum of
about 2.1% carbon by weight can dissolve in FCC iron,
limited by distortion of the lattice due to the presence of the
interstitial atoms.

Below 910°C, the iron structure changes to BCC . Even

though this is a less close-packed structure, the largest
available interstitial site is smaller than in FCC; only about
0.026 nm. Because of the greater lattice distortion the atoms
cause, less carbon can be dissolved in the BCC iron (a
maximum of about 0.02%).

Heat treating steels often involves heating the alloy so that it

transforms to FCC and dissolves all the carbon, then cooling
it so that the carbon atoms are either trapped in the BCC
structure (causing distortion) or forcing the atoms out of
solution to form iron carbides.
LINE IMPERFECTIONS
Dislocations are line imperfections where the three-
dimensional lattice is offset.
Two types dislocations 1. Screw dislocation, 2.Edge dislocation –
The presence and movement of these imperfections provide
ductility (deformability) of the specimen and can lead to failure of a
material.
Controlling the number of dislocations in material by forming the
object and by heat treatment is an important tool for the control of
the properties of the material.

The screw dislocation

occurs when atoms are
displaced in a direction
parallel to the line of the
dislocation
As the dislocation (the
vertical line) moves to the
left through the sample,
the atoms are displaced
downward by one unit cell.
An edge dislocation can be most easily visualized as the insertion of
an extra plane of atoms into the lattice, so that where it ends, the
orderly rows of atoms are offset. The edge of the half-plane of atoms
is the actual dislocation line
Burgers vector of the dislocation is perpendicular to the dislocation line for an
edge dislocation.
Dislocations arise in the crystals as a result of

• Growth accidents
• Thermal Stress
• External stresses causing plastic flow
• Phase Transformation
• Segregation of solute atoms causing mismatches
etc
Explaining SLIP through Dislocation

Applying a shear force to a sample can cause a

dislocation to move, producing overall deformation
The movement of a dislocation produces a step, one
atom high, at the surface or at a grain boundary

Creep
Strengthening a material can be accomplished by placing obstacles in the path
of the moving dislocation.
A precipitate particle in the matrix, for example, either stops the dislocation
completely or forces it to "climb over" which requires energy (it happens more
easily at higher temperatures which is why materials "creep" under load at high
temperature,
•Grain Boundaries:
Boundaries Imperfect Ions in polycrystalline
materials separate grains of different orientation
• Grain boundaries form when 2 grain surfaces meet
• At Grain Boundaries atomic packing is imperfect
• Grain Boundaries transition zone has atoms which are
not aligned with either grain
• GB highly strained distorted positions free energy is high
• Few atoms thick width (Impurities concentrate at the GB during solidification)
STACKING FAULTS: occur in a number of crystal structures, but the common
example is in close-packed structures. Face-centered cubic (fcc) structures differ
from hexagonal close packed (hcp) structures only in stacking order: both
structures have close packed atomic planes with six fold symmetry—the atoms
form equilateral triangles.

When stacking one of these layers on top of another, the atoms are not directly on
top of one another—the first two layers are identical for hcp and fcc, and labelled
AB.

If the third layer is placed so that its atoms are directly above those of the first
layer, the stacking will be ABA—this is the hcp structure, and it continues
ABABABAB.

However there is another location for the third layer, such that its atoms are not
above the first layer. Instead, the fourth layer is placed so that its atoms are
directly above the first layer.

This produces the stacking ABCABCABC, and is actually a cubic arrangement of

the atoms.

A stacking fault is a one or two layer interruption in the stacking sequence, for
example if the sequence ABCABABCAB were found in an fcc structure
A Tilt Boundary, between two
slightly mis-aligned grains appears
as an array of edge dislocations.
 BULK /VOLUME DEFECTS :
Voids are small regions where there are
no atoms, and can be thought of as
clusters of vacancies.
 Impurities can cluster together to form
small regions of a different phase.
 Shrinkages, Porosity

Twin boundaries are a particular type of

boundary where one portion of the lattice is Porosity
a mirror image of the other; the mirror is
the twinning plane growth
 Diffusion in Solids
Definition: Diffusion is the primary method by which atoms "mix" in
materials. It can be used to introduce selected atoms into materials.
Examples include "doping" of semiconductors with atoms to control
conductivity and carburization of steels to harden the surface.
 By being able to move in the lattice, vacancies produce diffusion, and
dislocations produce deformation
Rate of Diffusion
The rate at which atoms move in diffusion is given by:
slope = -Q / R
This is represented by a
straight line on an Arrhenius plot of
Log(Rate) vs. 1/T.
where
c = constant
Q = activation energy (cal/mol)
R = gas constant (1.987 cal/mol°K)
T = absolute temperature (°K)
Log is the natural logarithm
 Activation Energy
Q is the activation energy required for the given diffusion
mechanism, (1) volume, (2) grain boundary, and (3) surface.
It is energy that must be borrowed in order for the atom to move
but is given back afterward. Thermal energy is the usual source
for this borrowing.
The height of the activation energy barrier is a measure of the
effect of temperature on how fast diffusion proceeds.

Volume diffusion, where the atoms 1

move through the lattice structure,
includes vacancy and interstitial diffusion.
Diffusion of this type tends to have large 2
activation energy.
The height of the barrier represents the
3
energy needed for atoms to squeeze past
their neighbors into the new position.
The activation energy depends on the
atom size and the lattice structure.
 Diffusion Mechanism
Surface Diffusion is the easiest of the three (having the lowest activation energy)
because there is less constraint on the diffusing surface atoms. Ex: Solid Liquid
interface

Vacancy Diffusion
Vacancy diffusion is the most common method for the motion of atoms within
material. Any of the atoms adjacent to a vacant site in the lattice can move into
that site with relatively little effort. This leaves a vacancy at its previous location,
and the procedure can be repeated. Other bulk diffusion mechanisms in which
atoms must swap positions are much more difficult.

Interstitial Diffusion
Diffusion mechanism in bulk material is interstitial diffusion in which a relatively
small atom (such as carbon in iron) squeezes into the interstitial spaces between
the regular lattice atoms. Since there are relatively few carbon atoms and lots of
spaces, this is also a fast method of diffusion. However, it does require some
energy for the moving atom to squeeze between neighbors to get to the new site.
 Diffusion Mechanism
• Grain boundary diffusion is easier than volume diffusion
because the atom packing is mixed up at the grain boundaries
leaving more space for the atoms to move. The atoms can move
more easily, so the activation energy is lower.

• Diffusion down grain boundaries , or along a surface , can also

be fast because there are many more sites than atoms moving,
and the disorder of the atoms near such surfaces makes it easier
for the moving atom to squeeze past. Grain boundary diffusion is
important for grain growth, and surface diffusion is important for
sintering. These methods do not affect the bulk of properties of
most materials.
Fick's First Law
Fick's first law describes the rate at which atoms diffuse in a material:

where:
J = net flux (atoms per square cm per second)
D = diffusion coefficient (cm2/s)
= concentration gradient, the change in composition with distance
(atoms/cm4)
D can be calculated from the equation:

where:
Do is a constant for the given diffusion system (atoms and structure).
Q and D both depend on the atomic species and the structure. :
To calculate D (the diffusion coefficient), you use the equation

where Q, R, T, and Do, It is important to remember that D depends on both Do

and Q. A species can have a lower Q than another but still have a slower diffusion
rate if its Do is lower than the other's. These constants can be read from tables or
graphs.