Defects in Solids (Nikhil Sir)

A perfect crystalline structure have an ordered repetition of the lattice in every direction in
space. But, real crystals are not perfect, they always have a considerable number of
imperfections, or defects, that affect their physical, chemical, mechanical, and electrical
properties.
These defects are classified under four main divisions:
 Point Defects
 Line Defect
 Surface/Planar Defects
 Volume Defects

Point Defects:
A point defect is an irregularity in the lattice associated with a missing atom (vacancy), an extra
atom (interstitial), or an impurity (substitutional) atom. Sub classification of point defects are:
Vacancy:
Vacancies are the simplest defect. A vacancy is simply missing from the
crystalline lattice, as illustrated in the figure. Vacancies are created
during solidification due to imperfect packing. They also occur during
processing at elevated temperatures, the atoms are constantly being
displaced from their ideal locations by thermal vibrations. As the
temperature is increased, the lattice vibrations become larger, and atoms
have a tendency to jump out of their normal positions, leaving a vacant
lattice site behind.
Schottky:
Schottky defects consists of unoccupied anion and
cation sites in a stoichiometric ratio and it occurs in
ionic lattice. Schottky defects are observed most
frequently when there is a small difference in size
between cations and anions. The lattice undergoes
thermal vibration and thermal expansion when the
temperature is raised above 0 K. When it happens the
pair of vacancies are incorporated in the crystal. So
electrical neutrality is maintained inside the crystals.
Substitutional:
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.
Substitutional impurity atoms are usually close in size (within
approximately 15%) to the bulk atom. An example of substitutional
impurity atoms is the 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.
Interstitial:
Interstitial impurity atoms are much smaller than the atoms in the bulk
matrix. Interstitial impurity atoms fit into the open space between the bulk
atoms of the lattice structure. An example of interstitial impurity atoms is
the carbon atoms that are added to iron to make steel. Carbon atoms, with a
radius of 0.071 nm, fit nicely in the open spaces between the larger (0.124
nm) iron atoms.
Frenkel:
A Frenkel defect or dislocation defect occurs in
crystalline solids where an atom is displaced from its
lattice position to an interstitial site, creating a vacancy
at the original site and an interstitial defect at the new
location without any changes in chemical properties.
This defect appears in ionic solids, and the smaller ion
(usually cation) is dislocated. Frenkel defects are often
shown by ionic substances with a large difference in
the size of ions. For exp, in ZnS, AgCl, AgBr, and AgI.
Electronic:
When there is a charge misbalance in the ionic crystal.
Effects of point defects:
Point defects influence solid-state processes such as diffusion, dislocation motion, phase
transformations, and electrical conductivity. Point defects typically strengthen a metal and
decrease its ductility by impeding the motion of dislocations. Vacancies enhance atomic
diffusion. Vacancy diffusion is the movement of a vacancy through the lattice, thereby assisting
the diffusion of atoms. The number of dislocations is reduced when the vacancies diffuse to
grain boundaries or surfaces, which act as sinks. Point defects also decrease electrical
conductivity, because they interfere with the flow of electrons through the lattice.

Line Defects:
The existence of line defects in crystals, called dislocations, provides the mechanism that
allows mechanical deformation. A crystalline metal without dislocations, although will be
extremely strong, but would also be extremely brittle and practically useless as an engineering
material. Thus, dislocations play a central role in the determination of such important properties
as strength and ductility. There are two types of dislocations:
Edge dislocation:
The edge defect can be easily visualized as an extra half-plane of
atoms in a lattice. The dislocation is called a line defect because the
locus of defective points produced in the lattice by the dislocation,
lie along a line. This line runs along the top of the extra half-plane.
The inter-atomic bonds are significantly distorted only in the
immediate vicinity of the dislocation line. The lattice below the
dislocation is in a state of tension, while above the dislocation,
there is a compressive stress field. Preferred dislocation direction
is closest pack direction.
 Burger vector:
A quantitative description of dislocations is given by the Burgers vector, b. This vector
is defined using what is called the Burgers circuit, which is an atom-to-atom path that makes a
closed loop in a dislocation-free part of the crystal lattice. Now, if the same Burgers circuit is
made to encircle a dislocation, the loop does not close. The vector needed to close the loop (the
vector from the end of the Burgers circuit to its starting point) is the Burgers vector, b,
describing the dislocation.

The displacement vector between the two parts of the crystal is denoted by u, and the axis of
the dislocation (dislocation line) is t. For an edge dislocation, the Burgers vector, b, is
perpendicular to the axis of the dislocation (dislocation line), t (b⊥t), and parallel to the
displacement vector, u (b||u).
Screw dislocation:
The term screw dislocation is used because of the spiral surface formed by the atomic planes
around the screw dislocation line. When a Burgers circuit is used to determine the Burgers
vector of a screw dislocation, the vector is found to be parallel to the dislocation. A screw
dislocation is somewhat like a spiral ramp with an imperfection line running down its axis. In
a screw dislocation, the Burgers vector, b, is parallel to both the axis of the dislocation, t, and
the displacement vector, u; that is, (b|| t ||u).

An important characteristic of a dislocation is that it cannot end inside the crystal, it must end
at a surface such as a grain boundary or at a surface of the crystal. This dislocation is highly
glissile (highly movable). The dislocations move along the densest planes of atoms in a
material, because the stress needed to move the dislocation increases with the spacing between
the planes. FCC and BCC metals have many dense planes, so dislocations move relatively easy
and these materials have high ductility. Metals are strengthened by making it more difficult for
dislocations to move. This may involve the introduction of obstacles, such as interstitial atoms
or grain boundaries, to “pin” the dislocations. Also, as a material plastically deforms, more
dislocations are produced and they will get into each other’s way and impede movement. This
is why strain or work hardening occurs.
Surface Imperfections/Defects:
Surface, or planar, defects occur whenever the crystalline structure of a metal is discontinuous
across a plane. Surface defects extend in two directions over a relatively large surface with a
thickness of only one or two lattice parameters. Grain boundaries and phase boundaries are
independent of crystal structure, while coherent phase boundaries, twin boundaries, and
stacking faults depend on the crystalline structure.

Grain Boundary:
The most important surface defect is the grain boundary. Most metals are polycrystalline and
consist of many small crystallites called grains. The interfaces between these grains are called
grain boundaries and are only one or two atoms thick, since the system wants to reduce the free
energy as much as possible. Atoms within the grain boundaries are highly strained and
distorted; therefore, grain boundaries are high energy sites. Grain boundaries are preferential
regions for accumulation and segregation of many types of impurities. Weakening or
embrittlement can also occur by preferential phase precipitation or absorption of environmental
species, such as hydrogen or oxygen, in the grain boundaries.
Tilt Boundary:
Small-angle tilt grain boundaries occur when the
misorientation between grains is small, usually less than 5
degrees. These small-angle misorientations can be
represented by a row of somewhat parallel edge
dislocations, as shown for the low-angle tilt boundary in the
figure. If the misorientation is greater than approximately
10 to 15 degrees, then high-angle grain boundaries will
form. Tilt boundaries have angle less than 20 degrees.
 Twin Boundary:
Twin boundary or Mechanical twinning is the
coordinated movement of large numbers of atoms that
deform a portion of the crystal by an abrupt shearing
motion. Atoms on each side of the twinning plane, or habit
plane, form a mirror image with those on the other side of
the plane. Twinning occurs on a definite crystallographic
plane and in a specific direction that depends on the
crystalline structure. Twins can occur as a result of plastic
deformation (deformation twins) or during annealing
(annealing twins). Mechanical twinning occurs in bcc and
hcp metals, while annealing twins are fairly common in fcc
metals.
Stacking fault:
A stacking fault is a one or two layer interruption in the stacking sequence of atom planes.
Stacking faults occur in a number of crystal structures, but it is easiest to see how they occur
in close packed structures. If the HCP structure is going along as ABABAB and suddenly
switches to ABABABCABAB, there is a stacking fault present. Alternately, in the FCC
arrangement the pattern is ABCABCABC. A stacking fault in an FCC structure would appear
as one of the C planes missing. In other words the pattern would become
ABCABCAB_ABCABC.
The total energy of a perfect lattice is lower than one with a stacking fault. Thus, a stacking
fault has an energy associated with it. The difference in energy between a perfect lattice and
one with a stacking fault is known as the stacking fault energy (SFE). Stacking fault energy
plays a role in determining deformation textures in FCC and HCP metals. Stacking faults also
influence plastic deformation characteristics. Metals with wide stacking faults (low SFE) strain
harden more rapidly and twin more readily during annealing than those with narrow stacking
faults (high SFE).

Volume Defects:
Volume defects, such as porosity, impurity inclusions and micro-cracks, almost always
reduce strength and fracture resistance. Shrinkage during solidification can result in
microporosity, that is, porosity having diameters on the order of micrometers. In metals,
porosity is much more likely to be found in castings than in wrought products. The extensive
plastic deformation during the production of wrought metals is usually sufficient to heal or
close microporosity. Porosity in powder metallurgy products can be reduced if pressure is used
during the sintering process by either hot pressing in a press or hot isostatic pressing under gas
pressure.
Diffusion (Nikhil Sir)

Diffusion is the movement of atoms through the crystalline lattice. At all temperatures above
absolute zero, the atoms in gases, liquids, and solids are in a constant state of motion. In gases,
the atomic movement is very rapid. In solids, atomic movements are restricted by the crystal
lattice. However, thermal vibrations in solids allow atoms to diffuse, and as the temperature
increases, the vibrations of the atoms about their equilibrium positions in the crystal lattice also
increase. Thus, atomic vibrations are necessary for diffusion to take place, and as the amplitude
of atomic vibrations increases with increasing temperature, the rate of diffusion increases.

Mechanism of Diffusion:
There are two main types of diffusion that can occur in solids: interstitial diffusion and
substitutional diffusion. Whether diffusion occurs interstitially or substitutionally depends on
the relative sizes of the atoms in the solute and solvent.
Interstitial diffusion:
If the solute atom is sufficiently small, it will locate in an interstice between the larger solvent
atoms, forming an interstitial solid solution. Diffusion of interstitial atoms occurs by atoms
jumping from one interstitial site to another without permanently displacing any other atoms
in the crystal lattice. For interstitial diffusion to occur, the size of the diffusing atoms must be
very small compared to that of the matrix atoms. Therefore, only small atoms such as carbon,
nitrogen, hydrogen, oxygen, and boron can diffuse interstitially. For example, carbon diffuses
interstitially in both face-centered cubic (FCC) γ iron and body-centered cubic (BCC) α iron.
Substitutional diffusion:
Various mechanisms have been proposed to explain substitutional diffusion. Direct exchange
diffusion involves two adjacent atoms merely exchanging places. Zener ring diffusion is
similar but involves the simultaneous rotation of four atoms. Vacancy diffusion involves the
migration of an atom from a lattice position to an adjacent vacancy (vacant lattice site).
The vacancy diffusion mechanism requires less energy than either the direct exchange or Zener
ring mechanisms, and therefore, it is now accepted that vacancy diffusion is the major
mechanism for substitutional diffusion. As the temperature increases, both thermal vibrations
on the lattice and the number of vacancies increase, greatly facilitating diffusion. Thus,
diffusion occurs much more rapidly at higher temperatures.
Flick’s Laws of Diffusion:
Adolf Fick, a German physiologist, developed his laws of diffusion in 1855. In addition to
describing the diffusion behaviour in metals, equations based on Fick’s laws have been used to
model transport processes in foods, neurons, biopolymers, pharmaceuticals, porous soils, and
semiconductor doping processes.

Flick’s first law of diffusion:

Fick’s first law states that in a solution with a concentration gradient, there will be a net flux
of atoms from regions of high solute concentration to regions of low solute concentration, and
furthermore, the net flux of solute is proportional to the concentration gradient. The flux, J, is
defined as the number of atoms (n) of the diffusing species that pass through a plane of unit
area, A, which is normal to the diffusion direction per unit time t. there for flux J is:
𝐽 = 𝑑𝑛/𝐴𝑑𝑡
The flux of atoms across the plane at x=x’ in the figure is the number of atoms crossing the
plane area per unit time and is proportional to the gradient dc/dx at that location (x=x’). This
type of diffusion is governed by Fick’s first law of diffusion:
𝑑𝑐 𝑑𝑐
𝐽 = −𝐷 𝑑𝑥 ; 𝑑𝑥
= concentration gradient
Where, J is the flux or net flow of solute atoms, D is the diffusion coefficient or diffusivity, c
is the solute concentration, and x is the distance. The proportionality constant, D, is the
diffusivity or diffusion coefficient. The negative sign is used because the diffusion is from a
higher concentration to a lower concentration.

Flick’s first law of diffusion:

Steady-state diffusion, as defined by Fick’s first law, where conditions do not change with
time, is not commonly encountered. In most cases, non-steady-state diffusion takes place,
where the concentration of solute atoms at any point in the material changes with time. The
difference between steady-state and no steady - state diffusion conditions can readily be
visualized in figure:
Fick’s second law equation takes into account how the concentration at a point changes with
𝑑𝑐 𝑑 𝑑𝑐
time: 𝑑𝑡 = 𝑑𝑥 (𝐷 𝑑𝑥 )
This law states that the rate of compositional change is equal to the diffusivity times the rate of
change of the concentration gradient. In this form, the diffusivity is a function of concentration
and distance, x. However, it is often appropriate to treat the diffusivity as independent of the
𝑑𝑐 𝑑2 𝑐
concentration. In this case, Fick’s second law can be written as: = 𝐷 𝑑𝑥2
𝑑𝑡
𝑑𝑐 𝑑2 𝑐 𝑑2 𝑐 𝑑2 𝑐
Now for 3 dimension it can be written as: = 𝐷( 𝑑𝑥2 + + )
𝑑𝑡 𝑑𝑦 2 𝑑𝑧 2

Applications of Flick’s law:

Carburizing: One application of the second law is calculating the carbon depth obtained during
carburization of steel. Case hardening of gears is done by this process.
Diffusion couple: If two blocks of metals with different compositions, c1 and c2 are joined.
Application of a diffusion couple is when two metal interfaces are joined by diffusion bonding
at high pressures and temperatures.
Homogenization: During solidification of an ingot during casting, microsegregation occurs,
resulting in local compositional variations that are often removed by thermal aging at high
temperatures.
Doping: doping in the semiconductors is done.

Temperature dependence of Diffusion:

The temperature at which diffusion occurs greatly affects the value of the diffusion coefficient.
As the temperature increases, the diffusion coefficient increases exponentially. The diffusion
coefficient, D, is given by an Arrhenius equation:
𝐷 = 𝐷𝑜 𝑒 −𝑄/𝑅𝑇
Where, Do is the constant for a given diffusion system (cm2/s), Q is the activation energy for
the diffusion process (kJ/mol), R is the ideal gas constant (8.31 J/mol ᴼ K), and T is the absolute
temperature (K).