MM102 Notes

1. The Structure of Crystalline Solids

A crystalline material is one in which the atoms are situated in a repeating or periodic
array over large atomic distancesthat is, long-range order exists. A crystal forms a cube
which has 6 faces, 12 edges and 8 corners. Atoms sit on each of these places and
sometimes in the center as well.

2. Imperfections in Solids
Imperfections improve materials in terms of use. Classification of crystalline imperfections
is frequently made according to the geometry or dimensionality of the defect. There are
Point defects (those associated with one or two atomic positions); linear (or one-
dimensional) defects; and interfacial defects, or boundaries, which are two-dimensional. In
Solids, impurity atoms may exist as point defects.
If an atom is missing from a lattice structure, there is a vacancy there. In self-interstitial
imperfection, the atom of the lattice itself becomes smaller and can move to a new
position. In substitutional impurity, atoms of the current lattice get replaced by atoms of a
different element. In interstitial impurity, a new smaller atom of a different element comes
and occupies free interstitial locations.
Q
Nv v

=e kT Nv
N where is the number of free vacancies, N is the total number of

vacancies, Qv is the energy required to create 1 vacancy, k is the Boltzmann

constant 8.62 105 and T is the temperature in kelvin.

Solid solutions are formed if the following conditions are met:
o Atomic size close (Cu 128 pm and Ni 125 pm)
o Crystal structure same (Both FCC or BCC or any other)
o Electronegativity Close (Cu = 1.9 and Ni = 1.8)
o Valences same or in +2 or -2 range (Cu 2+ and Ni 2+)
If these conditions are satisfied, A will dissolve fully in B and B will dissolve in A. Saturation
wont be reached and the two components will be miscible in all ratios.
A portion of a plane is missing when crystallization occurs as all bonds are not made.
These missing planes are called dislocation/line defects. This is
known as an edge dislocation.
A screw dislocation, may be thought
of as being formed by a shear stress
that is applied to produce the
distortion. The upper front region of
the crystal is shifted one atomic
distance to the right relative to the
bottom portion.
Cohesive energy is the energy required to make or
break all bonds.
Burgers vector is 1 atomic distance either left or right and is perpendicular to the
dislocation lines in edge dislocation and parallel to the dislocation lines in screw
dislocation. The dislocation line is in and out of the plane. Linear dislocations store stress
energy inside materials which also modify the materials properties. Ductile materials are
 made by linear dislocations. If ductile, linear dislocations can move whereas they are fixed
in brittle materials.
Some points about dislocation line:
o Ease of motion of dislocations mean ductile material.
o Cold working creates dislocations and this strengthens metals because dislocation
lines interfere with other dislocation motion.
o Foreign atoms also block dislocation motion and strengthen crystals.
o Second phase precipitates block dislocations and further strengthen crystals.
Interfacial defects are boundaries that have two dimensions and normally separate regions
of the materials that have different crystal structures and/or crystallographic orientations.
These imperfections include external surfaces, grain boundaries, phase boundaries, twin
boundaries, and stacking faults:
o On surface, atoms dont have bonds on top, thus they are imperfections. Surface
atoms are not bonded to the maximum number of nearest neighbors and are
therefore in a higher energy state than the atoms at interior positions.
o Grain boundaries are surfaces and if one grain grows, the other has to decrease in
size hence grain number decreases. Following are properties of grain boundaries:
Can be several atomic distances wide.
Characterized by atomic mismatch.
Bond lengths and angles are larger than normal and some bonds are not
satisfied.
Energy is stored on grain boundaries, hence they are more reactive.
Small grains mean larger surface and more energy.
If kept at high Temperature (half of melting point), grains grow, surface
reduces, energy releases and coarse structure is made.
Impurity atoms accumulate at boundaries.
They separate small grains.
o A twin boundary is a special type of grain boundary across which there is a specific
mirror lattice symmetry; that is, atoms on one side of the boundary are located in
mirror image positions to those of the atoms on the other side. Twins result from
atomic displacements that are produced from applied mechanical shear forces
(mechanical twins) and also during annealing heat treatments following deformation
(annealing twins). Twinning occurs on a definite crystallographic plane and in a
specific direction, both of which depend on the crystal structure
o Low angle tilt boundary between grains resulting from edge dislocations.
As some crystals are very small, they need to be seen with a microscope. Following are the
types of microscopes:
 There are two methods to determine the grain size:
o In the intercept method, straight lines of equal length are drawn across grains. Then
we count number of borders 1 line crosses for each line. Measure length of line with
ruler and convert it to microns. Then use formula,
Length of originalline
Magnification=
Scale given on diagram . Now use following formula to find mean

l=
Lt
=
of length of all lines
intercept length
PM Number of intercepts with grain boundaries Magnification .

Now use G=6.6457 log l3.298 ( mm ) to find the number G which is the grain size

number. Now use formula n=2G1 to get the average number of grains per square
inch.
o If we have the grain size number, we can find average number of grains per square
G1
inch using n=2 .

3. Diffusion in Solids
Copper and Nickel (alloy) are diffusing into each other.

This type of diffusion is called interdiffusion or impurity diffusion because

atoms of 2 different metals have been diffused together. There is a net drift or
transport of atoms from high- to low-concentration regions. This is known as the
concentration gradient.
When atoms of the same element diffuse into each other, it is known as self-
diffusion but this is very slow.
For diffusion to occur i.e. an atom to move from one lattice site or interstitial site to
another, it is necessary that there be a vacancy adjacent to that atom and the
 atom must have sufficient energy to break bonds with its neighbor atoms and then
cause some lattice distortion during the displacement. This energy comes from
external heat or internal energy of atom (Rotational Energy, Translational Energy
and Vibrational Energy)
There are two mechanisms of diffusion:
o Vacancy diffusion process requires
the presence of vacancies, and the
extent to which vacancy diffusion
can occur depends on the number
of vacancies that are present;
significant concentrations of
vacancies may exist in metals at
elevated temperatures. Because
diffusing atoms and vacancies
exchange positions, the diffusion
of atoms in one direction corresponds to the motion of vacancies in the
opposite direction. Both self-diffusion and interdiffusion occur by this
mechanism; for the latter, the impurity atoms must substitute for host atoms.
o Interstitial Diffusion involves
atoms that migrate from an
interstitial position to a
neighboring one that is empty.
This mechanism is found for
interdiffusion of
impurities such as
hydrogen, carbon,
nitrogen, and oxygen,
which have atoms that
are small enough to fit
into the interstitial
positions. Host or
substitutional impurity
atoms rarely form
interstitials and do not
normally diffuse via this
mechanism. In most
metal alloys, interstitial diffusion occurs much more rapidly than diffusion by
the vacancy mode, because the interstitial atoms are smaller and thus more
mobile. Furthermore, there are more empty interstitial positions than
vacancies; hence, the probability of interstitial atomic movement is greater
than for vacancy diffusion.
Ficks 1st law for steady state diffusion. In this, Concentration is only a function of x i.e.
distance of sheet. Also, number of atoms diffusing in is equal to the number of atoms
M
diffusing out. Flux is calculate using the following equation J= where J is the flux
At
(kg/m^2.s), M is the mass diffusing, A is the surface area and t is the time. The
concentration gradient is the slope at a particular point on the concentration profile. It is
 dC C C B
calculate using the following equation J =D =D( A ) where D is the Diffusion
dx X A X B

J Mass L4
D= = 2 = L2 T 1 .
Constant. The units of D are calculated as follows dC L . T Mass
dx
Ficks 2nd law for non-steady state diffusion.
After sometime concentration profile may
become independent of time. Same graph of t3
will repeat again and again.

Distance and Time are the independent

variable C(x,t) and concentration is the
dependent variable.
Where Cx is the final concentration, C0 is

the initial concentration, Cs is the

source concentration, x is the distance of the
diffusing medium, D is the diffusion constant
and t is the time.

The derivation of T from this formula:

To get unknown value from erf(z),

use ration of Z values = erf(Z)
values.
Diffusion constant D depends on the following factors:
o Diffusion mechanism: Interstitial diffusion is faster because interstitial atoms are
lightly bonded with surrounding atoms hence less activation energy is required to
 break the bond. Also, there are more vacancies available for interstitial atoms to
move too.
o Temperature: Diffusion rate increases with increasing temperature because more
vacancies become available and activation energy in atoms increase, which means
they can break their bond easily.
o Grain boundaries and dislocation areas provide faster pathways for diffusing
species, hence diffusion is faster in polycrystalline vs single crystal materials
because there are no grain boundaries in single crystal materials whereas there are
a lot in polycrystalline structures. Excess vacancies will enhance diffusion.

4. Mechanical Properties of Metals

When we stretch polycrystalline material, grains get elongated. Stress is induced,
deformation takes place and grain size, shape and orientation may also change. Phase
might also change (e.g. Tin). Now energy is stored inside the material and dislocation
density changes.
Strain is given by and stress is

l il o
=
l0

Force
given by = =E
Area . So, where E is the modulus

of elasticity/Young Modulus.