MT-201B MATERIALS SCIENCE

Why Study Materials Science?

1. Application oriented Properties 2. Cost consideration 3. Processing route

Classification of Materials
1. Metals 2. Ceramics 3. Polymers 4. Composites 5. Semiconductors 6. Biomaterials 7. Nanomaterials

Syllabus

1. 2. 3. 4. 5. 6. 7.

Introduction to Crystallography Principle of Alloy Formation Binary Equilibria Mechanical Properties Heat Treatments Engineering Materials Advanced Materials

Recommended Books
1. Callister W.D., Materials Science and Engineering an Introduction 2. Askeland D.R., The Science and Engineering of Materials 3. Raghavan V.,Materials Science and Engineering- A first Course, 4. Avener S.H, Introduction to Physical Metallurgy,

The Structure of Crystalline Solids

CRYSTALLINE STATE
Most solids are crystalline with their atoms arranged in a regular manner. Long-range order: the regularity can extend throughout the crystal. Short-range order: the regularity does not persist over appreciable distances. Ex. amorphous materials such as glass and wax. Liquids have short-range order, but lack long-range order. Gases lack both long-range and short-range order. Some of the properties of crystalline solids depend on the crystal structure of the material, the manner in which atoms, ions, or molecules are arranged.

Lattice
Sometimes the term lattice is used in the context of crystal structures; in this sense lattice means a threedimensional array of points coinciding with atom positions (or sphere centers).

A point lattice

Unit Cells
The unit cell is the basic structural unit or building block of the crystal structure and defines the crystal structure by virtue of its geometry and the atom positions within.
This size and shape of the unit cell can be described in terms of their lengths (a,b,c) and the angles between then (,,). These lengths and angles are the lattice constants or lattice parameters of the unit cell.

A point lattice

A unit cell

Bravais Lattice
Table 1: Crystal systems and Bravais Lattices

Crystal systems and Bravais Lattice

Types of crystals Three relatively simple crystal structures are found for most of the common metals; body-centered cubic, face-centered cubic, and hexagonal close-packed. 1. Body Centered Cubic Structure (BCC) 2. Face Centered Cubic Structure (FCC) 3. Hexagonal Close Packed (HCP)

1. Body Centered Cubic Structure (BCC) In these structures, there are 8 atoms at the 8 corners and one atom in the interior, i.e. in the centre of the unit cell with no atoms on the faces.

2. Face Centered Cubic Structure (FCC) In these structures, there are 8 atoms at the 8 corners, 6 atoms at the centers of 6 faces and no interior atom.

3. Hexagonal Close Packed (HCP)

In these structures, there are 12 corner atoms (6 at the bottom face and 6 at the top face), 2 atoms at the centers of the above two faces and 3 atoms in the interior of the unit cell.

Average Number of Atoms per Unit Cell Since the atoms in a unit cell are shared by the neighboring cells it is important to know the average number of atoms per unit cell. In cubic structures, the corner atoms are shared by 8 cells (4 from below and 4 from above), face atoms are shared by adjacent two cells and atoms in the interior are shared by only that one cell. Therefore, general we can write: Nav = Nc / 8 + Nf / 2 + Ni / 1 Where, Nav = average number of atoms per unit cell. Nc = Total number of corner atoms in an unit cell. Nf = Total number of face atoms in an unit cell. Ni = Centre or interior atoms.

 Simple cubic (SC) structures: In these structures there are 8 atoms corresponding to 8 corners and there are no atoms on the faces or in the interior of the unit cell. Therefore, Nc = 8, Nf = 0 and Ni = 0 Using above eqn. we get, Nav = 8/8 + 0/2 + 0/1 = 1

2. Body centered cubic (BCC) structures: In these structures, there are 8 atoms at the 8 corners and one atom in the interior, i.e. in the centre of the unit cell with no atoms on the faces. Therefore Nc = 8, Nf = 0 and Ni = 1 Using above eqn. we get, Nav = 8/8 + 0/2 + 1/1 = 2

3. Face Centered Cubic Structure (FCC): In these structures, there are 8 atoms at the 8 corners, 6 atoms at the centers of 6 faces and no interior atom Therefore Nc = 8, Nf = 6 and Ni = 0 Using above eqn. we get, Nav = 8/8 + 6/2 + 0/1 = 4

4. Hexagonal Close Packed (HCP) Structures: In these structures, there are 12 corner atoms (6 at the bottom face and 6 at the top face), 2 atoms at the centers of the above two faces and 3 atoms in the interior of the unit cell. For hexagonal structures, the corner atoms are shared by 6 cells (3 from below and 3 from above), face atoms are shared by adjacent 2 cells and atoms in the interior are shared by only one cell. Therefore, in general the number of atoms per unit cell will be as: Nav = Nc / 6 + Nf / 2 + Ni / 1 Here Nc = 12, Nf = 2 and Ni = 3 Hence, Nav = 12 / 6 + 2 / 2 + 3 / 1 = 6

Co-ordination Number
Co-ordination number is the number of nearest equidistant neighboring atoms surrounding an atom under consideration 1. Simple Cubic Structure:

Simple cubic structure has a coordination number of 6

2. Body Centered Cubic Structure:

Body centered cubic structure has a coordination number of 8

3. Face Centered Cubic Structure:

Face centered cubic structure has a coordination number of 12

4. Hexagonal Close Packed Structure:

Hexagonal close packed structure has a coordination number of 12

Stacking Sequence for SC, BCC, FCC and HCP

Lattice structures are described by stacking of identical planes of atoms one over the other in a definite manner Different crystal structures exhibit different stacking sequences 1. Stacking Sequence of Simple Cubic Structure: Stacking sequence of simple cubic structure is AAAAA..since the second as well as the other planes are stacked in a similar manner as the first i.e. all planes are stacked in the same manner.
A

2. Stacking Sequence of Body Centered Cubic Structure: Stacking sequence of body centered cubic structure is ABABAB. The stacking sequence ABABAB indicates that the second plane is stacked in a different manner to the first. Any one atom from the second plane occupies any one interstitial site of the first atom.

Third plane is stacked in a manner identical to the first and fourth plane is stacked in an identical manner to the second and so on. A B This results in a bcc structure.
A B

3. Stacking Sequence of Face Centered Cubic Structure: Stacking sequence of face centered cubic structure is ABCABC. The close packed planes are inclined at an angle to the cube faces and are known as octahedral planes The stacking sequence ABCABC indicates that the second plane is stacked in a different manner to the first and so is the third from the second and the first. The fourth plane is stacked in a similar fashion to the first

4. Stacking Sequence of Hexagonal Close Packed Structure: Stacking sequence of HCP structure is ABABAB..

HCP structure is produced by stacking sequence of the type ABABAB..in which any one atom from the second plane occupies any one interstitial site of the first plane.
Third plane is stacked similar to first and fourth similar to second and so on.

Atomic Packing Factor (APF) Atomic packing factor is the fraction of volume or space occupied by atoms in an unit cell. Therefore,

APF = Volume of atoms in unit cell Volume of the unit cell

Since volume of atoms in a unit cell = Average number of atoms/cell x Volume of an atom

APF = Average number of atoms/cell x Volume of an atom Volume of the unit cell

1. Simple Cubic Structures:

In simple cubic structures, the atoms are assumed to be placed in such a way that any two adjacent atoms touch each other. If a is the lattice parameter of the simple cubic structure and r is the radius of atoms, it is clear from the fig that: r = a/2

APF = Average number of atoms/cell x Volume of an atom Volume of the unit cell = 1 x 4/3 r3 a3 = 4/3 r3 (2r)3 = 0.52

APF of simple cubic structure is 0.52 or 52%

2. Body Centered Cubic (BCC) Structures:

In body centred cubic structures, the centre atom touches the corner atoms as shown in fig.

If a is the lattice parameter of BCC structure and r is the radius of atoms, we can write (DF)2 = (DG)2 + (GF)2 Now (DG)2 = (DC)2 + (CG)2 and DF = 4r Therefore, (DF)2 = (DC)2 + (CG)2 + (GF)2

(4r)2 = a2 + a2 + a2 Therefore, r = a3 / 4 APF = Average number of atoms/cell x Volume of an atom Volume of the unit cell 2 x 4/3 (a3 / 4)3 a3 = 0.68

APF of body centered cubic structure is 0.68 or 68%

3. Face Centered Cubic (FCC) Structures:

In face centred cubic structures, the atoms at the centre of faces touch the corner atoms as shown in figure.

If a is the lattice parameter of FCC structure and r is the atomic radius (DB)2 = (DC)2 + (CB)2 i.e. (4r)2 = a2 + a2 Therefore, r = a / 22 APF = Average number of atoms/cell x Volume of an atom Volume of the unit cell = 4 x 4 / 3 x (a/22)3 = 0.74 a3

APF of face centered cubic structure is 0.74 or 74%

4. Hexagonal Close Packed (HCP) Structures

The volume of the unit cell for HCP can be found by finding out the area of the basal plane and then multiplying this by its height This area is six times the area of equilateral triangle ABC Area of triangle ABC = a2 sin 60 Total area ABDEFG = 6 x a2 sin 60 = 3 a2 sin 60 Now volume of unit cell = 3 a2 sin 60 x c
For HCP structures, the corner atoms are touching the centre atoms, i.e. atoms at ABDEFG are touching the C atom. Therefore a = 2r or r = a / 2

APF = Average number of atoms/cell x Volume of an atom Volume of the unit cell APF = 6 x 4/3 r3 3 a2 sin 60 x c APF = 6 x 4/3 (a/2)3 3 a2 sin 60 x c APF = a 3 c sin 60 The c/a ratio for an ideal HCP structure consisting of uniform spheres packed as tightly together as possible is 1.633. Therefore, substituting c/a = 1.633 and Sin 60o = 0.866 in above equation we get: APF = / 3 x 1.633 x 0.899 = 0.74

APF of face centered cubic structure is 0.74 or 74%

Atomic Packing Factor

1. Simple cubic structure: 0.52 2. Body centered cubic structure: 0.68 3. Face centered cubic structure: 0.74 4. Hexagonal close packed structure: 0.74

Crystallographic Points, Planes and Directions

1. Point Coordinates
When dealing with crystalline materials it often becomes necessary to specify a particular point within a unit cell.
The position of any point located within a unit cell may be specified in terms of its coordinates as fractional multiples of the unit cell edge lengths.

2. Plane Coordinates
1. Find out the intercepts made by the plane at the three reference axis e.g. p,q and r. 2. Convert these intercepts to fractional intercepts by dividing with their axial lengths. If the axial length is a, b and c the fractional intercepts will be p/a, q/b and r/c. 3. Find the reciprocals of the fractional intercepts. In the above case a/p, b/q and c/r. 4. Convert these reciprocals to the minimum of whole numbers by multiplying with their LCM. 5. Enclose these numbers in brackets (parenthesis) as (hkl) Note: If plane passes through the selected origin, either another
parallel plane must be constructed within the unit cell by an appropriate translation or a new origin must be established at the corner of the unit cell.

1. 2. 3. 4. 5.

Intercepts: p,q and r. Fractional intercepts: p/a, q/b and r/c. Reciprocals: a/p, b/q and c/r. Convert to whole numbers Enclose these numbers in brackets (parenthesis) as (hkl)

Step 1 : Identify the intercepts on the x- , y- and z- axes. In this case the intercept on the x-axis is at x = 1 ( at the point (1,0,0) ), but the surface is parallel to the y- and z-axes so we consider the intercept to be at infinity ( ) for the special case where the plane is parallel to an axis. The intercepts on the x- , y- and z-axes are thus Intercepts : 1 , , Step 2 : Specify the intercepts in fractional co-ordinates Co-ordinates are converted to fractional co-ordinates by dividing by the respective cell-dimension - This gives Fractional Intercepts : 1/1 , /1, /1 i.e. 1 , , Step 3 : Take the reciprocals of the fractional intercepts This final manipulation generates the Miller Indices which (by convention) should then be specified without being separated by any commas or other symbols. The Miller Indices are also enclosed within standard brackets (.). The reciprocals of 1 and are 1 and 0 respectively, thus yielding Miller Indices : (100) So the surface/plane illustrated is the (100) plane of the cubic crystal.

Intercepts : 1 , 1 , Fractional intercepts : 1 , 1 , Reciprocal: 1,1,0 Miller Indices : (110)

Intercepts : 1 , 1 , 1 Fractional intercepts : 1 , 1 , 1 Reciprocal: 1,1,1 Miller Indices : (111)

Intercepts : , 1 , Fractional intercepts : , 1 , Reciprocal: 2,1,0 Miller Indices : (210)

Intercepts : 1/3 , 2/3 , 1 Fractional intercepts : 1/3 , 2/3 , 1 Reciprocal: 3, 3/2, 1 Miller Indices : (632)

Exercise

Exercise

Exercise

Exercise

Exercise

If the plane passes through the origin, the origin has to be shifted for indexing the plane

Miller Indices of Planes for Hexagonal Crystals

Crystal Plane in HCP unit cells is commonly identified by using four indices instead of three. The HCP crystal plane indices called Miller-Bravis indices are denoted by the letters h, k, i and l are enclosed in parentheses as (hkil) These four digit hexagonal indices are based on a coordinate system with four axes.

The three a1, a2 and a3 axes are all contained within a single plane (called the basal plane), and at 1200 angles to one another. The z-axis is perpendicular to the basal plane.
The unit of measurement along the a1, a2 and a3 axes is the distance between the atoms along these axes. The unit of measurement along the z- axis is the height of the unit cell. The reciprocals of the intercepts that a crystal plane makes with the a1, a2 and a3 axes give the h, k and I indices while the reciprocal of the intercept with the z-axis gives the index l.

Miller Indices of Directions for Cubic Crystals

A vector of convenient length is positioned such that it passes through the origin of the coordinate system.

The length of the vector projection on each of the three axes is determined.
These three numbers are multiplied or divided by a common factor to reduce them to the smallest integer values. The three indices, not separated by commas, are enclosed in square brackets [uvw] If a negative sign is obtained represent the ve sign with a bar over the number

For direction not originating from origin the origin has to be shifted

Examples of directions with shift of origin

Family of Symmetry Related Planes

_ (1 1 0) _ (101) _ (011)

(110) (101) (011)

{110}
{ 1 1 0 } = Plane ( 1 1 0 ) and all other planes related by symmetry to ( 1 1 0 )

Family of Symmetry Related Directions

[001]

Identical atomic density

_
[100]

Identical properties

100
[010]

[010] [100] z y x

_
[001]

1 0 0= [ 1 0 0 ] and all other directions related to [ 1 0 0 ] by symmetry

SUMMARY OF MEANINGS OF PARENTHESES

q r s represents a point

(hkl) represents a plane {hkl} represents a family of planes

[hkl] represents a direction

<hkl> represents a family of directions

Anisotropy of crystals
191.1 GPa

Youngs modulus of FCC Cu

130.3 GPa

66.7 GPa

Anisotropy of crystals (contd.)

Different crystallographic planes have different atomic density

And hence different properties

Si Wafer for computers

Linear and Planar Densities

Linear Density
Linear density (LD) is defined as the number of atoms per unit length whose centers lie on the direction vector
LD = number of atoms centered on direction vector length of direction vector

The [110] linear density for FCC is: LD110 = 2 atoms/4R = 1/2R

Planar Density
Planar density (PD) is defined as the number of atoms per unit area that are centered on a particular crystallographic plane PD = number of atoms centered on a plane area of plane Planar density on (110) plane in a FCC unit cell Number of atoms on (110) plane is 2 Area of (110) plane (rectangular section) is 4R (length) x 22R (height) = 8R22 PD = 2 atoms / 8R22 = 1 / 4R22

Planar density on (100) plane in a Simple Cubic Structure: Number of atoms on (100) plane is 1 Area of (100) plane (square section) is a x a = a2 PD = 1 atom / a2 = = 1 / a2 Planar density on (110) plane in a Simple Cubic Structure: Number of atoms on (110) plane is 1 Area of (110) plane (rectangular section) is 2a2 PD = 1 atom / 2 a2 = = 1 / 2 a2

Planar density on (111) plane in a Simple Cubic Structure: Number of atoms on (111) plane is 1/6 x 3 = 0.5 Area of (111) plane (triangle DEF) is 1/2 x (2a) x (0.866 x 2a) = 0.866a2 PD = 0.5 atom / 0.866a2 = = 0.577 / a2 Planar density on (100) plane in a Body Centred Cubic Structure: Number of atoms on (100) plane is 1 Area of (100) plane (square section) is a x a = a2 PD = 1 atom / a2 = 1 / a2

Planar density on (110) plane in a Body Centered Cubic Structure: Number of atoms on (110) plane is 1/4 x4+1=2 Area of (110) plane (rectangle AFGD) is a x 2a = 2a2 PD = 2 atoms / 2a2 = = 2 / a2 = 1.414 / a2 Planar density on (111) plane in a Body Centered Cubic Structure: Number of atoms on (111) plane is 1/6 x 3 + 1 = 1.5 Area of (111) plane (triangle DEG) is x 2a 2a sin60o = 0.866 a2 PD = 1.5 atoms / 0.866a2 = = 1.732 / a2

Voids in crystalline structures

We have already seen that as spheres cannot fill entire space the atomic packing fraction (APF) < 1 (for all crystals) This implies there are voids between the atoms. Lower the PF, larger the volume occupied by voids. These voids have complicated shapes; but we are mostly interested in the largest sphere which can fit into these voids The size and distribution of voids in materials play a role in determining aspects of material behaviour e.g. solubility of interstitials and their diffusivity The position of the voids of a particular type will be consistent with the symmetry of the crystal In the close packed crystals (FCC, HCP) there are two types of voids tetrahedral and octahedral voids (identical in both the structures as the voids are formed between two layers of atoms) The tetrahedral void has a coordination number of 4 The octahedral void has a coordination number 6

Interstitial sites / voids

Tetrahedral sites in HCP

Octahedral sites in HCP

Voids: Tetrahedral and Octahedral Sites

Tetrahedral and octahedral sites in a close packed structure can be occupied by other atoms or ions in crystal structures of alloys.

Thus, recognizing their existence and their geometrical constrains help in the study and interpretation of crystal chemistry.
The packing of spheres and the formation of tetrahedral and octahedral sites or holes are shown below.

What is the radius of the largest sphere that can be placed in a tetrahedral void without pushing the spheres apart?
To solve a problem of this type, we need to construct a model for the analysis. Use the diagram shown here as a starting point, and construct a tetrahedral arrangement by placing four spheres of radius R at alternate corners of a cube. What is the length of the face diagonal fd of this cube in terms of R? Since the spheres are in contact at the centre of each cube face, fd = 2 R. What is the length of the edge for such a cube, in terms of R? Cube edge length a = 2 R What is the length of the body diagonal bd of the cube in R? bd = 6 R Is the center of the cube also the center of the tetrahedral hole? Yes Let the radius of the tetrahedral hole be r, express bd in terms of R and r If you put a small ball there, it will be in contact with all four spheres. bd = 2 (R + r). r = (2.45 R) / 2 - R = 1.225 R - R = 0.225 R What is the radius ratio of tetrahedral holes to the spheres? r / R = 0.225

Derive the relation between the radius (r) of the octahedral void and the radius (R) of the atom in a close packed structure (Assume largest sphere in an octahedral void without pushing the parent atom)

A sphere into the octahedral void is shown in the diagram. A sphere above and a sphere below this small sphere have not been shown in the figure. ABC is a right angled triangle. The centre of void is A.
Applying Pythagoras theorem. BC2 = AB2 + AC2 (2R)2 + (R + r)2 + (R + r)2 = 2(R + r)2 4R2/2 = (R + r)2 2R2 = (R + r)2 2R = R + r r = 2R R = (1.414 1)R r = 0.414 R

Single Crystal and Polycrystalline

Stages of solidification of a polycrystalline material
Single Crystal

silicon single crystal

Micrograph of a polycrystalline stainless steel showing grains and grain boundaries

Polymorphism

Ceramic Crystal Structures

Ceramics are compounds between metallic & nonmetallic elements e.x. Al2O3, FeO, SiC, TiN, NaCl They are hard and brittle Typically insulative to the passage of electricity & heat

Crystal Structures Atomic bonding is mostly ionic i.e. the crystal structure is composed of electrically charged ions instead of atoms. The metallic ions, or cations are positively charged because they have given up their valence electrons to the nonmetallic Ions or anions, which are negatively charged

Ionic bonding

 In a ceramic material two characteristics of the component ions influence the crystal structure: 1. Charge neutrality

2. The relative sizes of the cations and anions

1. Charge neutrality: each crystal should be electrically neutral e.x. NaCl and CaCl2

2. The relative sizes of the cations and anions

Because the metallic elements give up electrons when Ionized, cations are smaller than anions

Hence rc / ra is less than unity Stable ceramic crystal structures form when those anions surrounding a cation are all in contact with the that cation

 Coordination number is related to the cation-anion ratio For a specific coordination number there is a critical or minimum rc / ra ratio

Predicting Structure of FeO

AX-TYPE STRUCTURES
Equal number of cations and anions referred to as AX compounds A denotes the cation and X denotes the anion
rNa = 0.102 nm rCl = 0.181 nm

rNa / rCl = 0.564

Cations prefer octahedral sites

Rock Salt Structure

AX-TYPE STRUCTURES continued

MgO also has a NaCl type structure

rO = 0.140 nm

rMg = 0.072 nm

rMg / rO = 0.514
Cations prefer octahedral sites

AX-TYPE STRUCTURES continued

AmXp-TYPE STRUCTURES
number of cations and anions are different, referred to as AmXp compounds Calcium Fluorite Structure

AmBnXp-TYPE STRUCTURES
Ceramic compound with more than two types of cations, referred to as AmBnXp compounds

Crystal defects (Imperfections in Solids)

Perfect order does not exist throughout a crystalline material on an atomic scale. All crystalline materials contain large number of various defects or imperfections. Defects or imperfections influence properties such as mechanical, electrical, magnetic, etc. Classification of crystalline defects is generally made according to geometry or dimensionality of the defect i.e. zero dimensional defects, one dimensional defects and two dimensional defects.

Crystal defects / imperfections are broadly classified into three classes:

1. Point defect (zero dimensional defects)
Vacancy, Impurity atoms ( substitutional and interstitial) Frankel and Schottky defect

2. Line defect (one dimensional defects)

Edge dislocation Screw dislocation, Mixed dislocation

3. Surface defects or Planer defects (two dimensional defects)

Grain boundaries Twin boundary Stacking faults

Vacancy

1. Point defects

Vacancy
If an atom is missing from its regular site, the defect produced is called a vacancy All crystalline solids contain vacancies and their number increases with temperature The equilibrium concentration of vacancies Nv for a given quantity of material depends on & increases with temperature according to
Where: N is the total number of atomic sites Qv is the energy required for the formation of a vacancy T is the absolute temperature & k is the gas or Boltzmanns constant i.e. 1.38 x 10-23 J/atom-K or 8.62 X 10-5 eV/atom-K

Vacancies aid in the movement (diffusion) of atoms

Impurity atoms ( substitutional and interstitial)

 Impurity point defects are of two types 1. Substitutional 2. Interstitial For substitutional, solute or impurity atoms replace or substitute for the host atoms

For interstitial, solute or impurity atoms fill the void or interstitial space among the host atoms
Both the substitutional and interstitial impurity atoms distort the crystal lattice affecting the mechanical and electrical / electronic properties

 Impurity atoms generate stress in the lattice by distorting the lattice The stress is compressive in case of smaller substitutional atom and tensile in case of larger substitutional atom These stresses act as barriers to movement of dislocations and thus improve the strength / hardness of a material These stresses also act as barriers to the movement of electrons and lower the electrical conductivity (increases resistivity) of the material

Frankel and Schottky defects

 Frenkel and Schottky defects occur in ionic solids like ceramics An atom may leave its regular site and may occupy nearby interstitial site of the matrix giving rise to two defects simultaneously i.e. one vacancy and the other self interstitial. These two defects together is called a Frenkel defect. This can occur only for cations because of their smaller size as compared to the size of anions.

When cation vacancy is associated with an anion vacancy, the defect is called Schottky defect. Schottky defects are more common in ionic solids because the lattice has to maintain electrical neutrality

Dislocations

2. Line defects

A missing line or row of atoms in a regular crystal lattice is called a dislocation Dislocation is a boundary between the slipped region and the unslipped region and lies in the slip plane Movement of dislocation is necessary for plastic deformation There are mainly two types of dislocations (a) Edge dislocations and (b) Screw dislocations

Edge Dislocation

Dislocation line and b are perpendicular to each other

Movement of edge dislocation

Elastic stress field responsible for electron scattering and increase in electrical resistivity

lattice strain around dislocation

Screw Dislocation

Dislocation line and b are parallel to each other

Movement of Screw Dislocation

When Dislocations Interact

Mixed Dislocations

By resolving, the contribution from both types of dislocations can be determined

Dislocations as seen under Transmission Electron Microscope (TEM)

Grain Boundary

3. Surface defects

Grain boundary is a defect which separates grains of different orientation from each other in a polycrystalline material.

When this orientation mismatch is slight, on the order of a few degrees (< 15 degrees) then the term small- (or low- ) angle grain boundary is used. When the same is more than 15 degrees its is know as a high angle grain boundary. The total interfacial energy is lower in large or coarse-grained materials than in fine-grained ones, since there is less total boundary area in the former. Mechanical properties of materials like hardness, strength, ductility etc are influenced by the grain size.
Grains grow at elevated temperatures to reduce the total boundary energy.

Coarse and fine grain structure Grain boundaries acting as barriers to the movement of dislocations

Deformation of grains during cold working (cold rolling in this case)

Twin Boundary
Twin boundary Atoms on one side of the boundary are located in Mirror image positions of the atoms on the other side

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 of the atoms on the other side.
The region of material between these boundaries is appropriately termed a twin. 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. Annealing twins are typically found in metals that have the FCC crystal structure, while mechanical twins are observed in BCC and HCP metals. Twins contribute to plastic deformation in a small way

Stacking fault
Occurs when there is a flaw in the stacking sequence Stacking fault results from the stacking of one atomic plane out of sequence on another and the lattice on either side of the fault is perfect BCC and HCP stacking sequence: ABABABAB with stacking fault: ABABBABABor ABABAABABAB.. FCC stacking sequence: ABCABCABC. with stacking fault: ABCABCABABCABC

Stacking fault

FCC Stacking

Plastic Deformation

Principles of Alloy Formation

Solid Solution: A homogeneous crystalline phase that contains two or more chemical species It is an alloy in which the atoms of solute are distributed in the solvent and has the same structure as that of the solvent Types of Solid Solutions: 1. Interstitial solid solution, ex. Fe-C 2. Substitutional solid solution, ex. Au-Cu

Interstitial Solid Soln

Substitutional Solid Soln

1. Interstitial Solid Solution Alloys

Parent metal atoms are bigger than atoms of alloying metal. Smaller atoms fit into spaces, (Interstices), between larger atoms.

Interstitial sites

2. Substitutional Solid Solution Alloys

Atoms of both metals are of almost similar size. Direct substitution takes place.

Some Solid Solution Alloys

Alloy Copper - Nickel Copper - Gold Gold - Silver Nickel - Platinum Molybdenum - Tungsten Iron - Chromium Unit Cell Structure FCC FCC FCC FCC BCC BCC

Hume-Rotherys Rules of Solid Solubility

1. Atomic size factor

2. Crystal structure factor 3. Electronegativity factor

4. Relative valency factor

1. Atomic size factor: If the atomic sizes of solute and solvent differ by less than 15%, it is said to have a favourable size factor for solid solution formation. If the atomic size difference exceeds 15% solid solubility is limited

2. Crystal Structure factor: Metals having same crystal structure will have greater solubility. Difference in crystal structure limits the solid solubility

+
A (fcc) B (fcc) AB solid solution (fcc)

3. Electronegativity factor: The solute and solvent should have similar electronegativity. If the electronegativity difference is too great, the metals will tend to form compounds instead of solid solutions. If electronegativity difference is too great the highly electropositive element will lose electrons, the highly electronegative element will acquire electrons, and compound formation will take place.
4. Relative Valency factor: Complete solubility occurs when the solvent and solute have the same valency. If there is shortage of electrons between the atoms, the binding between them will be upset, resulting in conditions unfavourable for solid solubility

Phase Diagrams
Phase diagrams: Phase or equilibrium diagrams are diagrams which indicate the phases existing in the system at any temperature, pressure and composition.

Why study Phase Diagrams? Used to find out the amount of phases existing in a given alloy with their composition at any temperature.
From the amount of phases it is possible to estimate the approximate properties of the alloy. Useful in design and control of heat treatment procedures

Terms: System: A system is that part of the universe which is under consideration. Phase: A phase is a physically separable part of the system with distinct physical and chemical properties. (In a system consisting of ice and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the humid air over the water is a third phase. The glass of the jar is another separate phase.) Variable: A particular phase exists under various conditions of temperature, pressure and concentration. These parameters are called as the variables of the phase Component: The elements present in the system are called as components. For ex. Ice, water or steam all contain H2O so the number of components is 2, i.e. H and O.

Gibbs Phase Rule: The Gibbs phase rule states that under equilibrium conditions, the following relation must be satisfied: P+ F=C+2 Where, P = number of phases existing in a system under consideration. F = degree of freedom i.e. the number of variables such as temperature, pressure or composition (concentration) that can be changed independently without changing the number of phases existing in the system. C = number of components (i.e. elements) in the system, and 2 = represents any two variables out of the above three i.e. temperature pressure and composition.

Most of the studies are done at constant pressure i.e. one atmospheric pressure and hence pressure is no more a variable. For such cases, Gibbs phase rule becomes: P+ F=C+1 In the above rule, 1 represents any one variable out of the remaining two i.e. temperature and concentration.

Hence, Degree of Freedom (F) is given by

F=CP+1

Application of Gibbs Phase Rule

C At point A P = 1, C = 2 F=CP+1 F = 2 1 +1 F=2 The meaning of F = 2 is that both temperature and concentration can be varied independently without changing the liquid phase existing in the system At point B P = 2, C = 2 F=CP+1 F = 2 2 +1 F=1 The meaning of F = 1 is that any one variable out of temperature and composition can be changed independently without altering the liquid and solid phases existing in the system

At point C P = 1, C = 2 F=CP+1 F = 2 1 +1 F=2 The meaning of F = 2 is that both temperature and concentration can be varied independently without changing the liquid phase existing in the system

Types of Phase Diagrams:

Unary phase diagram

Binary phase diagram

Ternary phase diagram

1. Unary Phase diagram (one component)

The simplest phase diagrams are pressure-temperature diagrams of a single simple substance, such as water. The axes correspond to the pressure and temperature.

2. Binary Phase diagram (two components) A phase diagram plot of temperature against the relative concentrations of two substances in a binary mixture called a binary phase diagram Types of binary phase diagrams: 1. Isomorphous 2. Eutectic 3. Partial Eutectic

3. Ternary Phase diagram (three components)

A ternary phase diagram has three components. It is three dimensional put plotted in two dimensions at constant temperature Stainless steel (Fe-Ni-Cr) is a perfect example of a metal alloy that is represented by a ternary phase diagram.

Binary phase diagram The binary phase diagram represents the concentration (composition) along the x-axis and the temperature along the y-axis. These are plotted at atmospheric pressure hence pressure is constant i.e. 1 atm. pressure. These are the most widely used phase diagrams.

Types of binary phase diagrams: Binary isomorphous system: Two metals having complete solubility in the liquid as well as the solid state. Binary eutectic system: Two metals having complete solubility in the liquid state and complete insolubility in the solid state. Binary partial eutectic system: Two metals having complete solubility in the liquid state and partial solubility in the solid state. Binary layer type system: Two metals having complete insolubility in the liquid as well as in the solid state.

Cooling curve for Pure Metal (one component)

Cooling curve for an alloy / solid solution (two components)

Plotting of Phase Diagrams

Binary isomorphous system:

These phase diagrams are of loop type and are obtained for two metals having complete solubility in the liquid as well as solid state. Ex.: Cu-Ni, Au-Ag, Au-Cu, Mo-W, Mo-Ti, W-V.

Lever rule
Finding the amounts of phases in a two phase region : 1. Locate composition and temperature in phase diagram 2. In two phase region draw the tie line or isotherm 3. Fraction of a phase is determined by taking the length of the tie line to the phase boundary for the other phase, and dividing by the total length of tie line

% of Solid = LO / LS X 100= (Wo-Wi) / (Ws-Wi) X 100 % of Liquid = OS / LS X 100= (Ws-Wi) / (Ws-Wi) X 100 or simply % Liquid = 100 - % of Solid or vice versa

Development of Microstructure during slow cooling in isomorphous alloys

Properties of alloys in Isomorphous systems with variation in composition

(a) Phase diagram of the Cu-Ni alloy system. Above the liquidus line only the liquid phase exists. In the L + S region, the liquid (L) and solid (S) phases coexist whereas below the solidus line, only the solid phase (a solid solution) exists.

(b) The resistivity of the Cu-Ni alloy as a Function of Ni content (at.%) at room temperature

Binary Eutectic System:

These diagrams are obtained for two metals having complete solubility (i.e. miscibility) in the liquid state and complete insolubility in the solid state. Examples: Pb-As, Bi-Cd, Th-Ti, and Au-Si.

What is a Eutectic?
A eutectic or eutectic mixture is a mixture of two or more phases at a composition that has the lowest melting point Eutectic Reaction: Liquid Solid A + Solid B

Cooling Curves in Eutectic System

Plotting of Eutectic Phase Diagrams

Binary Partial Eutectic System

These diagrams are obtained for two metals having complete solubility (i.e. miscibility) in the liquid state and partial solubility in the solid state. Examples: Pb-Sn, Ag-Cu, Sn-Bi, Pb-Sb, Cd-Zn and Al-Si.

Development of microstructure in binary partial eutectic alloys during equilibrium cooling 1. Solidification of the eutectic composition

2. Solidification of the off - eutectic composition

3. Solidification of compositions that range between the room temperature solubility limit and the maximum solid solubility at the eutectic temperature

Uses of Eutectic / Partial Eutectic Alloys

Alloys of eutectic compositions have some specific properties which make them suitable for certain applications: Since they fuse at constant temperature, they are used for electrical and thermal fuses. They are used as solders due to their lower melting temperature. Since eutectic alloys have low melting points, some of them are used coatings by spraying techniques Since they melt at constant temperature they can be used for temperature measurement. Majority of the eutectic alloys are superplastic in character. Superplasticity is the phenomenon by which an alloy exhibits large extension (ductility) when deformed with certain rate at some temperature. The alloy behaves like plastic and can be formed into many shapes.

The Iron Carbon System

Allotrophic Transformations in Iron

Iron Carbon Phase Diagram

Phases in Iron-Carbon Phase Diagram

1. Ferrite: Solid solution of carbon in bcc iron

2. Austenite: Solid solution of carbon in fcc iron

3. -iron: Solid solution of carbon in bcc iron 4. Cementite (Fe3C): Intermetallic compound of iron and carbon with a fixed carbon content of 6.67% by wt. 5. Pearlite: It is a two phased lamellar (or layered) structure composed of alternating layers of ferrite and cementite

Austenite

Ferrite and -iron

Cementite

The iron-carbon system exhibits three important transformations / reactions as described below:
Eutectoid Reaction: Solid1 Solid2 + Solid3 Austenite Ferrite + Cementite Eutectic Reaction: Liquid Solid1 + Solid2 Liquid Austenite + Cementite Peritectic Reaction: Solid1 + Liquid Solid2 -iron + Liquid Austenite

What is Pearlite?
Pearlite is a two phased lamellar (or layered) structure composed of alternating layers of ferrite and cementite that occurs in some steels and cast irons 100% pearlite is formed at 0.8%C at 727oC by the eutectoid reaction / Pearlitic transfromation Eutectoid Reaction: Solid1 Solid2 + Solid3 Austenite Ferrite + Cementite

Development of microstructures in steel during slow cooling

Eutectoid Steel

Hypoeutectoid Steel

Hypereutectoid Steel

Non-Equilibrium Cooling
Non-equilibrium cooling leads to shift in the transformation temperatures that appear on the phase diagram Leads to development of non-equilibrium phases that do not appear on the phase diagram

Some common binary phase diagrams and important alloys belonging to these systems
Cooper Zinc (Cu-Zn) Cooper Tin (Cu-Sn)

Copper Nickel (Cu-Ni)

Aluminum Silicon (Al-Si)

Lead Tin (Pb-Sn)

Copper and copper alloys

Properties: 1. It has good ductility and malleability 2. It has high electrical and thermal conductivity 3. It is non-magnetic and has a pleasing reddish colour 4. It has fairly good corrosion resistance 5. It has good ability to get alloyed with other elements Major copper alloys 1. Brass: Alloys of copper and zinc 2. Bronzes: Alloys of copper containing elements other than zinc ex. Copper-Tin alloys Copper-Nickel alloys

Cooper Zinc (Cu-Zn)

Cu-Zn alloys exhibit good ductility at lower amounts of Zn.
These alloys are mostly cast and formed Widely used for tubes in heat exchangers, cartridge cases, fixtures, springs, utensils, pump parts, propeller shafts, etc

Cooper Tin (Cu-Sn)

Cu-Sn alloys exhibit good ductility and malleability along with good corrosion resistance.
Widely used for pumps, gears, marine fittings, bearings, coins etc

Copper Nickel (Cu-Ni)

Cu-Ni Complete solubility in each other Copper alloy containing about 45% Nickel has very high electrical resistivity Hence used for resistors and thermocouple wires

Aluminium and aluminium alloys

Properties: 1. It is ductile and malleable 2. It is light in weight 3. It has good thermal and electrical conductivity 4. It has excellent ability to get alloyed with other elements like Cu, Si, Mg, etc. 5. It has excellent corrosion and oxidation resistance 6. It is non-magnetic and non-sparking Major Aluminium Alloys: 1. Aluminium- silicon 2. Aluminium copper 3. Aluminium- Magnesium

Aluminum Silicon (Al-Si)

Al-Si alloys widely used for castings due to their excellent fluidity and casting characteristics.

Higher silicon content gives better mechanical properties, better corrosion resistance, Improved fludity Widely used for automobile castings like engine block etc

Lead Tin (Pb-Sn)

Pb-Sn alloys form a eutectic at 61.9% Sn at 183oC.

These alloys widely used as solders because of their low melting point and flow characteristics