UNIT - I

Material Technology:

Materials technology is a relatively comprehensive discipline that begins with the production of
goods from raw materials to processing of materials into the shapes and forms needed for
specific applications.

Materials - metals, plastics and ceramics - typically have completely different properties, which
means that the technologies involved in their production are fundamentally different. Materials
technology is a constantly evolving discipline, and new materials with interesting properties lead
to new applications. For example, the combination of different materials into composites gives
rise to entirely new material properties.

Material Science:

Materials Science is closely related to materials technology. Materials Science is a

multidisciplinary field that connects material properties to the material’s chemical composition,
micro-structure and crystal structure. Crystal structure is a description of the ordered
arrangement of atoms, ions or molecules in a crystalline material. The crystalline lattice, is a
periodic array of the atoms. When the solid is not crystalline, it is called amorphous. Examples
of crystalline solids are metals, diamond and other precious stones, ice, graphite. Examples of
amorphous solids are glass, amorphous carbon (a-C), amorphous Si, most plastics

Polymorphism and Allotropy:

Some materials may exist in more than one crystal structure, this is called polymorphism. If the
material is an elemental solid, it is called allotropy. An example of allotropy is carbon, which
can exist as diamond, graphite, and amorphous carbon.

Anisotropy:

Different directions in the crystal have a different packing. For instance, atoms along the edge
FCC crystals are more separated than along the face diagonal. This causes anisotropy in the
properties of crystals; for instance, the deformation depends on the direction in which a stress is
applied.

Crystal Structure:

It is the manner in which atoms, ions, or molecules are spatially arranged.

Lattice:

It is a 3D collection of points that divide space into smaller equally sized units.

Basis:

It is a group of atoms associated with a lattice point. This may be one single atom or a group of
atoms.

Atomic Radius:

Atomic radius is the apparent radius of an atom, typically calculated from the dimensions of the
unit cell, using close-packed directions

Unit Cells:

It is the basic building block of the crystal structure. It defines the entire crystal structure with the
atom positions within. The unit cell is the smallest structure that repeats itself by translation
through the crystal. The most common types of unit cells are the faced-centered cubic (FCC), the
body-centered cubic (BCC) and the hexagonal close-packed (HCP).

FCC BCC HCP

The properties of the unit cells are

 The type of atoms and their radii R.

 cell dimensions (side a in cubic cells, side of base a and height c in HCP) in terms of R.
 n, number of atoms per unit cell. For an atom that is shared with m adjacent unit cells, we
only count a fraction of the atom, 1/m.
 CN, the coordination number, which is the number of closest neighbors to which an atom
is bonded.

Space lattice:
A space lattice is a set of points such that a translation from any point P in the lattice by a
vector.
 Rlmn = la + mb +nc ( l, m, n integers)

locates an exactly equivalent point, i.e. a point with the same environment as P. This is
translational symmetry. The vectors a, b, c are known as lattice vectors

Coordination number:

The number of nearest neighbor atoms or ions surrounding an atom or ion.

The Atomic Packing Factor (APF):

APF is the fraction of the volume of the cell actually occupied by the hard spheres.
APF = Sum of atomic volumes/Volume of cell.

Miller indices:

The plane of atoms in a crystal are defined using mathematical notation known as Miller
indices.
Procedure for finding millers indices:
(i) Find the intercepts of the plane with the 3 crystal directions or axes in terms of
primitive vectors a , b , c
(ii) Take the reciprocals
(iii) Multiply the resulting 3 numbers by the smallest number that makes the result equal
to 3 integers h, k, l. The plane is then defined by the notation ( h k l ).
Thus, in the above example :

intercepts = 2 , 4 , 3
reciprocals = 1/2 , 1/4 , 1/3
x 12 = 6 , 3 , 4 and so the plane is ( 6 3 4 ).
In a crystal with true cubic symmetry the choice of which of the three axes to label the .x-axis.,
and which the .y. and the .z., is entirely arbitrary. Thus the (100) plane is physically equivalent to
the mathematically distinct (010) and (001) planes. This leads to the grouping of various
numbers of planes into sets, or families
___
(001) (010) (100) (100) (010) (100) 3 x 2 = 6
(110) (011) .... 3 x 2 x 2 = 12
(111) .... .... 2 x 2 x 2 = 8
(210) .... .... 6 x 2 x 2 = 24
(321) .... .... 6 x 2 x 2 x 2 = 48
The sets of planes are denoted { h k l }.
For directions in a crystal, take components (or projections) on axes a , b and c . For example,
the direction whose components are 2a, 3b, 2c is denoted [ 2 3 2 ]. Directions also occur in sets,
and are denoted < h k l >.
For a cubic lattice, the direction [ h k l ] is perpendicular to the plane ( h k l ).

Body Centred Cubic:

In BCC atoms are arranged at the corners of the cube with another atom at the cube center. The
BCC structure is commonly found for the elements at the lighter end of all the rows of the
periodic table, from the alkali metals (Li, Na, K, Rb, Cs) through to the start of the transition
metals (V, Cr, Fe, Nb, Mo, Ba, Ta, W).

Face Centred Cubic:

Atoms are arranged at the corners and center of each cube face of the cell. The FCC structure is
adopted by a large number (~ 20) of metals, including the heavier end of the transition metals
(Ni, Rh, Pd, Ir, Pt), the noble metals (Cu, Ag, Au), and some of the rare gases (Ne, Ar, Kr, Xe).
In addition, many compounds and alloys are based on the cubic structure. Two examples of
general interest are NaCl and CsCl, and these compounds have given their names to these
generic types of structure.

Hexagonal Close-Packed:
The HCP structure is based on the simple hexagonal lattice and has a two-atom basis. The
second atom of the basis is positioned half way up the cell and so forms another
hexagonal layer of close-packed atoms half-way between the top and bottom layers of the unit
cell.

The Bravais Lattice:

Crystals possess a regular, repetitive internal structure. The concept of symmetry describes the
repetition of structural features. Symmetries are most frequently used to classify the different
crystal structures. In general one can generate 14 basic crystal structures through symmetries.
These are called Bravais lattices. Any crystal structures can be reduced to one of these 14
Bravias lattices. A Bravais Lattice is a three dimensional lattice. A Bravis Lattice tiles space
without any gaps or holes. There are 14 ways in which this can be accomplished. Lattices are
characterized by translation symmetry.
Crystal Structure Determination:

The determination of an unknown structure proceeds in three major steps: 1. The shape and size
of the unit cell are deduced from the angular positions of the diffraction lines. 2. The number of
atoms per unit cell is then computed from the shape and size of the unit cell, the chemical
composition of the specimen, and its measured density. 3. Finally, the position of the atoms
within the unit cell are deduced from the relative intensities of the diffraction lines. The third
step is generally the most difficult and there are many structures which are known only
incompletely, in the sense that this final step has not yet been made. Size and Shape of the Unit
Cell

Bragg's Law:

When x-rays are scattered from a crystal lattice, peaks of scattered intensity are observed which
correspond to the following conditions:

1. The angle of incidence = angle of scattering.

2. The path length difference is equal to an integer number of wavelengths.

The condition for maximum intensity contained in Bragg's law above allow us to calculate
details about the crystal structure, or if the crystal structure is known, to determine the
wavelength of the x-rays incident upon the crystal.
X-ray diffraction:
Powder diffraction method:

A crystalline powder consist of small grains; each grain is a single crystal. In general the
orientation of the grains in a powder sample is random. Grains with anisotropic shapes tend to
show some ordering. The diffraction pattern consists of discrete cones, with top angle 4θ,
dictated by Bragg’s law. When projected on a plane perpendicular to the incident beam, a series
of concentric circles is obtained. The diffraction pattern of a single crystal will change when the
sample is rotated. The diffraction pattern of a powder will keep the same appearance when the
sample is rotated, although other powder grains will contribute to the pattern.
In a powder diffraction pattern large numbers of reflections will overlap, causing problems with
indexing (determination of the unit cell) and intensity measurement. Powder diffraction can be
used to identify materials without solving the structure.
 In the powder sample there are crystallites in different ‘random’ orientations (a
polycrystalline sample too has grains in different orientations)
 The coherent x-ray beam is diffracted by these crystallites at various angles to the
incident direction
 All the diffracted beams (called ‘reflections’) from a single plane, but from different
crystallites lie on a cone.
 Depending on the angle there are forward and back reflection cones.
 A diffractometer can record the angle of these reflections along with the intensities of the
reflection
 The X-ray source and diffractometer move in arcs of a circle- maintaining the Bragg
‘reflection’ geometry as in the figure (right)
Diffusion:
Diffusion is a process of mass transport by atomic movement under the influence of
thermal energy and a concentration gradient. Atoms move from higher to lower concentration
region. If this movement is from one element to another e.g. Cu to Ni, then it is termed inter-
diffusion. If the movement is within similar atoms as in pure metals, it is termed self-diffusion.

Diffusion Mechanism:
Diffusion of atoms involves movement in steps from one lattice site to the another. An
empty adjacent site and breaking of bonds with the neighbor atoms are the two necessary
conditions for this.
1.Vacancy Diffusion:
This mechanism involves movement of atoms from a regular lattice site to an adjacent
vacancy. Since vacancy and atoms exchange position, the vacancy flux is in the opposite
direction.

2. Interstitial Diffusion:
This mechanism involves migration of atoms from one interstitial site to a neighbouring
empty interstitial site. This mechanism is more prevalent for impurity atoms such as hydrogen,
carbon, nitrogen, oxygen which are small enough to fit in to an interstitial position. For
substitutional diffusion atoms exchange their places directly or along a ring (ring diffusion
mechanism).

3. Inter Diffusion or Impurities Diffusion:

Interdiffusion (or impurity diffusion) occurs in response to a concentration gradient.

Factors that influence diffusion:

1. Diffusing species
2. Host solid
3. Temperature
4. Microstructure
The Phase Rule:

The Phase Rule expresses the relation between phases, phase compositions, and intensive
variables (temperature and pressure) in a system of a given composition at equilibrium.

Gibbs Phase Rule: The Gibbs phase rule describes the degrees of freedom available to describe
a particular system with various phases and substances.

System: An assemblage of materials that is isolated in some manner from rest of the universe.

 isolated system: one that does not exchange matter or energy with its surroundings.
 closed system: one that exchanges only energy with its surroundings.
 open system: one that exchanges both matter and energy with its surroundings.
 adiabatic system: a system with changes in energy caused only by a change in volume as
pressure changes.

Equilibrium: The lowest energy state of a system in which there is no tendency for a
spontaneous change.

Metastable Equilibrium: state of a system which is not in its lowest energy state at the imposed
conditions, but cannot spontaneously change due to high activation energy for change.

Phase Rule:

F=C-+2
 (# of phases): a phase is any portion of a system that is chemically and physically
homogenous and can be mechanically isolated from any other portion of the system.

C (# of components): minimum number of chemically distinct constituents necessary to describe

the composition of each phase in the system.

“2” stands for temperature and pressure. Temperature (T) and pressure (P) are intensive
parameters of a system. Intensive parameters do not depend on amount or mass. Extensive
parameters (e.g., volume, number of moles) depend on mass.

F (degrees of freedom; variance):

 number of attributes of a system (T, P, phase composition) that can be changed

independently without creating or destroying a phase, or ...
 number of parameters (T, P, system composition) that need to be described to completely
define the composition and identity of each phase.

F = 3 : trivariant

F = 2 : divariant

F = 1 : univariant

F = 0 : invariant

if F < 0 then there must be disequilibrium.

The meaning of “C” - minimum number of components necessary to describe each phase in
a system:

One-component system (unary):

Consider the minerals andalusite, kyanite, and sillimanite. The formula of each is Al2SiO5. The
chemical constituents we could choose to describe all three minerals could be:

Al, Si, O … 3 components

Al2O3, SiO3 … 2 components

Al2SiO5 … 1 component

Thus we can describe all the phases in the system in terms of one component.

To calculate the variance or F at a given position in the P-T diagram, we have

F=1-+2

 In any one-phase field, F = 2. To be able to state which phase is present, we need to

specify two parameters. Also, within a divariant field both P and T can change without
loosing or gaining a minerals.
  Along any reaction curve, two phases are present. Thus, F = 1. To be able the state which
minerals are present, we need to define only either P or T. Or, if we know that two of the
minerals are present, if we know P, we can deduce T, or vice-versa. Or, if T is changed,
to keep the two phases coexisting, P has to change accordingly to keep the system along
the univariant line.
 At the intersection of the three reaction curves, three phases are present. Thus, F = 0. This
means, that if all three phases are present, both T and P are fixed. If either of the intensive
parameters is changed, at least one phase will be lost.

Two-component system:

Consider the minerals muscovite and orthoclase. We could describe them in terms of the
following components:

K, Al, Si, O, H ... 5 components

K2O, Al2O3, SiO2, H2O ... 4 components

KAlSi3O8, Al2O3, H2O ... 3 components

KAlSi3O8, KAl3Si3O10(OH)2 ... 2 components

So the phase rule would work properly, we would choose the two-component option.

Three-component system:

Let us add corundum and water to the above system. We can describe all the phases in this
system in terms of the following components:

K, Al, Si, O, H ... 5 components

K2O, Al2O3, SiO2, H2O ... 4 components

KAlSi3O8, Al2O3, H2O ... 3 components

 corundum consists of 0 KAlSi3O8, 1 Al2O3, 0 H2O

water consists of 0 KAlSi3O8, 0 Al2O3, 1 H2O

So the phase rule would work properly, we would choose the three-component option.

KAlSi3O8
K-feldspar

muscovite

corundum water

Al2O3 H2O

Two-component system with a solution:

Consider the melting reaction

0.5 quartz + 0.5 K-feldspar  1 melt .

Quartz is made-up of the SiO2 component, K-feldspar of the KAlSi3O8 component. The fraction
of SiO2 in the melt is 0.5 and the fraction of KAlSi3O8 in the melt is also 0.5. Thus, all three
phases can be described by some combination of the two components SiO2 and KAlSi3O8.

The eutectoid reaction:

The eutectoid reaction describes the phase transformation of one solid into two different solids.
In the Fe-C system, there is a eutectoid point at approximately 0.8wt% C, 723°C. The phase just
above the eutectoid temperature for plain carbon steels is known as austenite or gamma. We now
consider what happens as this phase is cooled through the eutectoid temperature (723°C).
The phase diagram which we will be considering throughout this section is shown below:

Definitions

Component: pure metal or compound (e.g., Cu, Zn in Cu-Zn alloy, sugar, water, in a
syrup.)

Solvent: host or major component in solution.

Solute: dissolved, minor component in solution.

System: set of possible alloys from same component (e.g., iron-carbon system.)

Solubility Limit: Maximum solute concentration that can be dissolved at a given

temperature.

Phase: part with homogeneous physical and chemical characteristics

Solubility Limit:

Effect of temperature on solubility limit. Maximum content: saturation. Exceeding

maximum content (like when cooling) leads to precipitation.
Phases:

One-phase systems are homogeneous. Systems with two or more phases are
heterogeneous, or mixtures. This is the case of most metallic alloys, but also happens in
ceramics and polymers.

A two-component alloy is called binary. One with three components, ternary.

Microstructure

The properties of an alloy do not depend only on concentration of the phases but how they are
arranged structurally at the microscopy level. Thus, the microstructure is specified by the number
of phases, their proportions, and their arrangement in space.

A binary alloy may be

a. a single solid solution

b. two separated, essentially pure components.
c. two separated solid solutions.
d. a chemical compound, together with a solid solution.

The way to tell is to cut the material, polish it to a mirror finish, etch it a weak acid (components
etch at a different rate) and observe the surface under a microscope.

Phase Equilibrium:

Equilibrium is the state of minimum energy. It is achieved given sufficient time. But the time to
achieve equilibrium may be so long (the kinetics is so slow) that a state that is not at an energy
minimum may have a long life and appear to be stable. This is called a metastable state.

A less strict, operational, definition of equilibrium is that of a system that does not change with
time during observation.

Equilibrium Phase Diagrams

Give the relationship of composition of a solution as a function of temperatures and the

quantities of phases in equilibrium. These diagrams do not indicate the dynamics when one
phase transforms into another. Sometimes diagrams are given with pressure as one of the
variables. In the phase diagrams we will discuss, pressure is assumed to be constant at one
atmosphere.
Binary Isomorphous Systems

This very simple case is one complete liquid and solid solubility, an isomorphous system. The
example is the Cu-Ni alloy of Fig. 9.2a. The complete solubility occurs because both Cu and Ni
have the same crystal structure (FCC), near the same radii, electronegativity and valence.

The liquidus line separates the liquid phase from solid or solid + liquid phases. That is, the
solution is liquid above the liquidus line.

The solidus line is that below which the solution is completely solid (does not contain a liquid
phase.)

Interpretation of phase diagrams

Concentrations: Tie-line method

a. locate composition and temperature in diagram

b. In two phase region draw tie line or isotherm
c. note intersection with phase boundaries. Read compositions.

Fractions: lever rule

a. construct tie line (isotherm)

b. obtain ratios of line segments lengths.

Note: the fractions are inversely proportional to the length to the boundary for the particular
phase. If the point in the diagram is close to the phase line, the fraction of that phase is large.

Development of microstructure in isomorphous alloys

a) Equilibrium cooling

Solidification in the solid + liquid phase occurs gradually upon cooling from the liquidus line.
The composition of the solid and the liquid change gradually during cooling (as can be
determined by the tie-line method.) Nuclei of the solid phase form and they grow to consume all
the liquid at the solidus line.

b) Non-equilibrium cooling

Solidification in the solid + liquid phase also occurs gradually. The composition of the liquid
phase evolves by diffusion, following the equilibrium values that can be derived from the tie-line
method. However, diffusion in the solid state is very slow. Hence, the new layers that solidify on
top of the grains have the equilibrium composition at that temperature but once they are solid
their composition does not change. This lead to the formation of layered (cored) grains (Fig.
9.14) and to the invalidity of the tie-line method to determine the composition of the solid phase
(it still works for the liquid phase, where diffusion is fast.)
Eutectic or invariant point. Liquid and two solid phases exist in equilibrium at the eutectic
composition and the eutectic temperature.

Alloys which are to the left of the eutectic concentration (hipoeutectic) or to the right
(hypereutectic) form a proeutectic phase before reaching the eutectic temperature, while in the
solid + liquid region. The eutectic structure then adds when the remaining liquid is solidified
when cooling further. The eutectic microstructure is lamellar (layered) due to the reduced
diffusion distances in the solid state.

A terminal phase or terminal solution is one that exists in the extremes of concentration (0 and
100%) of the phase diagram. One that exists in the middle, separated from the extremes, is called
an intermediate phase or solid solution.

An important phase is the intermetallic compound, that has a precise chemical compositions.
When using the lever rules, intermetallic compounds are treated like any other phase, except they
appear not as a wide region but as a vertical line.

The eutectoid (eutectic-like) reaction is similar to the eutectic reaction but occurs from one solid
phase to two new solid phases. It also shows as V on top of a horizontal line in the phase
diagram. There are associated eutectoid temperature (or temperature), eutectoid phase, eutectoid
and proeutectoid microstructures.

Solid Phase 1 à Solid Phase 2 + Solid Phase 3

The peritectic reaction also involves three solid in equilibrium, the transition is from a solid +
liquid phase to a different solid phase when cooling. The inverse reaction occurs when heating.

Solid Phase 1 + liquid à Solid Phase 2

Congruent transformation is one where there is no change in composition, like allotropic

transformations (e.g., a-Fe to g-Fe) or melting transitions in pure solids.

Ternary phase diagrams are three-dimensional. Example: Ceramic phase diagrams