Manav Rachna College of Engg.

ME III SEM

Material Science Unit-1

Manav Rachna College of Engg.

Crystallography

The Electronic Structure of Hydrogen

A simple atom of one electron surrounding the nucleus of one proton Only definite orbits( energy levels) are allowed Energy can be absorbed or emitted

During transition a discrete amount (quanta) of energy is released in the form of a photon Energy is directly related to the frequency Plancks constant (h) is the constant of proportion-ality. h = 6.63 x 10-34 Js

Manav Rachna College of Engg.

Energy and the Hydrogen Atom

DE=hf EH=-13.6/n2 eV n= principal quantum number n represents the energy level for electrons in atoms The position of the hydrogen electron cannot be predicted due to Heisenbergs uncertainty principle. The highest electron density is at a radius of

Manav Rachna College of Engg.

Quantum Numbers Principal and Subsidiary

Principal Quantum Number n Principal Quantum Numbern

Manav Rachna College of Engg.

Positive integers from 1-7 Represents the shell or energy level Higher number = more energy and farther distance from the nucleus

Subsidiary Quantum number l

Subenergy level or subshell l =0,1,2,3n-1 orbitals: s(0),p(1),d(2),f(3)

Quantum Numbers Magnetic and Electron Spin

Magnetic Quantum Number ml

Spatial orientation Permissible values of l to +l In general, ml=2l+1

Electron Spin Quantum Number ms

Specifies whether the electron is

spinning CW or CCW Permissible values of 1/2 to +1/2

Inter-ionic Forces for an Ion Pair

Fnet = F attractive + Frepulsive The forces that hold atoms together are governed by Coulombs Law

Manav Rachna College of Engg.

Fe=electric force q = charge r or a = interionic separation distance eo=permittivity of free space = 8.85 x 10-12 C2/(Nm2)

Crystal Geometry

Manav Rachna College of Engg.

It is possible to map the surface of conducting solids by using an STM (scanning tunneling microscope). It works by placing a small amount of current through an extremely small tip (single atom tungsten nanotip). The current is then amplified and used to measure the size of the gap between the tip and the atomic surface

Atom Manipulation using the STM

One innovative applications of STM recently found is manipulation of atoms. Here is an example, Iron atoms are placed on Cu(111) surface at very low temperature (4K), Iron atoms are first physisorbed on the Cu surface, then the tip is placed directly over a physisorbed atom and lowered to increase the attractive force by increasing the tunneling current, the atom was dragged by the tip and moves across the surface to a desired position. Then, the tip was withdrawn by lowering the tunneling current.

Manav Rachna College of Engg.

TYPES OF SOLIDS
Crystalline material: atoms self-organize in a periodic array Single crystal: atoms are in a repeating or periodic array over the entire extent of the material Polycrystalline material: comprised of many small crystals or grains

Manav Rachna College of Engg.

Amorphous: disordered lack of systematic atomic arrangement Crystalline Amorphous

CRYSTAL STRUCTURES
Why do atoms assemble into ordered structures (crystals)?
Manav Rachna College of Engg.

Energy Of Interatomic Bond 0

Interatomic Distance

Energy of the crystal < Energy of the amorphous solid

CRYSTAL STRUCTURE

To discuss crystalline structures it is useful to consider atoms as being hard spheres with welldefined radii. In this hard-sphere model, the shortest distance between two like atoms is one diameter of the hard sphere.
2R

Manav Rachna College of Engg.

- hard-sphere model

We can also consider crystalline structure as a lattice of points at atom/sphere centers

LATTICE
In crystalline structures, atoms are considered as being solid spheres having well-defined diameters Atomic hard sphere model -> in which spheres representing nearest-neighbor atoms touch one another Lattice is a regularly spaced array of points that represents the structure of a crystal

The Unit Cell

The unit cell is a structural unit or building block that can describe the crystal structure. Repetition of the unit cell generates the entire crystal
Manav Rachna College of Engg.

The size and shape of the unit cell are described by three lattice vectors a,b,c, originating from one corner of the unit cell. The axial lengths a,b,c and the inter axial angles , , and are lattice

Crystal Systems and Bravais Lattices

Crystal System Cubic Axial Lengths and angles a = b = c, a = b = g = 90 Tetragonal Space Lattice Simple Body-centered Face-centered a = b c, a=b=g=90 Simple, BC
Manav Rachna College of Engg.

Orthorhombic

a b c, a=b=g=90 Simple,BC, FC, Base Centered

Rhombohedral Hexagonal

a = b = c, a =b =g 90 a = b c, a=b=90, g=120

Simple Simple

Monoclinic Triclinic

a b c, a=g=90 Simple, Base-C b a b c,a b g Simple 90

METALLIC CRYSTAL STRUCTURES

Metals are usually (poly)crystalline; although formation of amorphous metals is possible by rapid cooling The atomic bonding in metals is non-directional no restriction on numbers or positions of nearestneighbor atoms large number of nearest neighbors and dense atomic packing Atomic (hard sphere) radius, R, defined by ion core radius - typically 0.1 - 0.2 nm The most common types of unit cells are faced-centered cubic (FCC) body-centered cubic (BCC) hexagonal close-packed (HCP).

Manav Rachna College of Engg.

FACE-CENTERED CUBIC STRUCTURE (FCC)

FCC -> a unit cell of cubic geometry, with atoms located at each of the corners and the centers of all the cube faces For the fcc crystal structure, each corner atom is shared among eight unit cells, whereas a facecentered atom belongs to only two Therefore, one-eighth of each of the eight corner atoms and one-half of each of the six face atoms, or a total of four whole atoms, may be assigned to a given unit cell copper, aluminum, silver, and gold have fcc The cell comprises the volume of the cube, which is generated from the centers of the corner atoms

FCC - EXERCISE
Derive: Where a = side length of the unit cell cube And R = Radius of the atom sphere

FCC COORDINATION NUMBER AND APF

For metals, each atom has the same number of touching atoms, which is the coordination number For fcc, coordination number is 12 The APF (Atomic Packing Factor) is the sum of the sphere volumes of all atoms within a unit cell divided by the unit cell volume

For fcc, APF is 0.74

BODY-CENTERED CUBIC STRUCTURE (BCC)

BCC -> a cubic unit cell with atoms located at all eight corners and a single atom at the cube center Center and corner atoms touch one another along cube diagonals

BCC - EXERCISE

Derive:

Where a = side length of the unit cell cube And R = Radius of the atom sphere

BCC
Chromium, iron, tungsten exhibit bcc structure Two atoms are associated with each BCC unit cell The coordination number for the BCC is 8 the atomic packing factor for BCC lower 0.68 versus 0.74 (FCC)

PACKING FACTOR FCC VS BCC

HEXAGONAL CLOSE-PACKED CRYSTAL (HCP)

The top and bottom faces of the unit cell consist of 6 atoms that form regular hexagons and surround a single atom in the center Another plane that provides 3 additional atoms to the unit cell is situated between the top and bottom planes The atoms in this mid-plane have as nearest neighbors atoms in both of the adjacent two planes

HEXAGONAL CLOSE-PACKED CRYSTAL (HCP)

The equivalent of six atoms is contained in each unit cell If a and c represent, respectively, the short and long unit cell dimensions the c/a ratio should be 1.633 The coordination number and the APF for the HCP are the same as for FCC: 12 and 0.74, respectively The HCP metals include cadmium, magnesium, titanium, and zinc, etc

DENSITY COMPUTATIONS
Density of a material can be computed from its crystalline structure n = number of atoms associated with each unit cell A = atomic weight VC = volume of the unit cell

NA = Avogadros number (6.023 X 1023 atoms/mol)

2. CRYSTALLOGRAPHIC DIRECTIONS
A crystallographic direction is defined as a line between two points, or a vector a vector of convenient length is placed parallel to the required direction. - the length of the vector projection on each of three axes are measured in unit cell dimensions. - these three numbers are made to smallest integer values, known as indices, by multiplying or dividing by a common factor. - the three indices are enclosed in square brackets, [uvw]. A family of directions is represented by <uvw>.

Atom Positions in the Unit Cell

To locate atoms we use a rectangular x,y, and z axis. In crystallography, x is defined as coming out of the page, y axis to the right, and z is the direction to the top.

Atom Positions are defined by using parenthesis as shown to the right

Directions in Cubic Unit Cells

For cubic crystal systems, direction indices are vectors resolved along each coordinate axes and REDUCED to the smallest integers. Brackets are used to symbolize directions. [111] Negative values are written with a line over the number.

2. CRYSTALLOGRAPHIC DIRECTIONS
The [100], [110], and [111] directions within a unit cell the [ 11] direction would have a component in Y the direction Changing the signs of all indices produces an antiparallel direction

2. CRYSTALLOGRAPHIC DIRECTIONS
For some crystal structures, several nonparallel directions with different indices are actually equivalent For example, in cubic crystals, all the directions represented by the following indices are equivalent

Equivalent directions are grouped together into a family, which are enclosed in angle brackets, thus: <100>

3. CRYSTALLOGRAPHIC PLANES
In all but the hexagonal crystal system, crystallographic planes are specified by three Miller indices as (hkl). Any two planes parallel to each other are equivalent and have identical indices 1. If the 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 another unit cell

3. CRYSTALLOGRAPHIC PLANES
2.

3.

The length of the planar intercept for each axis is determined in terms of the lattice parameters a, b, and c. The reciprocals of these numbers are taken. A plane that parallels an axis may be considered to have an infinite intercept, and, therefore, a zero index.

3. CRYSTALLOGRAPHIC PLANES
4.

5.

If necessary, these three numbers are changed to the set of smallest integers by multiplication or division by a common factor Finally, the integer indices, not separated by commas, are enclosed within parentheses, thus: (hkl). For cubic crystals the planes and directions having the same indices are perpendicular to one another

Miller Indices for Planes in Cubic Unit Cells

Indices for planes are defined as the RECIPROCAL of the fractional intercepts(with fractions cleared) that the plane makes with the x,y, and z axes. This procedure is used: Choose a plane that does NOT pass through the origin. Determine the intercepts Form the reciprocal Clear fractions and reduce to smallest set of whole numbers.

For example, if the x-, y-, and z- intercepts of a plane are 2, 1, and 3. The Miller indices are calculated as: - take reciprocals: 1/2, 1/1, 1/3. - clear fractions (multiply by 6): 3, 6, 2. - reduce to lowest terms (already there). => Miller indices of the plane are (362). Figure 2.2 depicts Miller indices for number of directions and planes in a cubic crystal.

Manav Rachna College of Engg.

Miller indices in a cubic crystal

Some useful conventions of Miller notation: - If a plane is parallel to an axis, its intercept is at infinity and its Miller index will be zero. - If a plane has negative intercept, the negative number is denoted by a bar above the number. Never alter negative numbers. For example, do not divide -1, -1, -1 by -1 to get 1,1,1. This implies symmetry that the crystal may not have! - The crystal directions of a family are not necessarily parallel to each other. Similarly, not all planes of a family are parallel to each other.
Manav Rachna College of Engg.

- By changing signs of all indices of a direction, we obtain opposite direction. Similarly, by changing all signs of a plane, a plane at same distance in other side of the origin can be obtained. - Multiplying or dividing a Miller index by constant has no effect on the orientation of the plane.

- The smaller the Miller index, more nearly parallel the plane to that axis, and vice versa. - When the integers used in the Miller indices contain more than one digit, the indices must be separated by commas. E.g.: (3,10,13)

- By changing the signs of all the indices of (a) a direction, we obtain opposite direction, and (b) a plane, we obtain a plane located at the same distance on the other side of the origin.

Interplanar spacing
As the position of the atoms in a unit cell are defined as (x,y,z), the position of the planes will use ( h,k,l ) as their notation. Suppose we have 2 planes parallel To the (110) plane. These planes are separated by a distance dhkl . It can be shown that : dhkl = distance between planes a = lattice constant ( edge of unit cell) h,k,l = Miller indices of planes being considered

CRYSTALLINE AND NON CRYSTALLINE MATERIALS

1. 2. 3.

Single Crystal Polycrystalline Materials Anisotropy

1. SINGLE CRYSTAL
For a crystalline solid, when the repeated arrangement of atoms is perfect or extends throughout the entirety of the specimen without interruption, the result is a single crystal If the extremities of a single crystal are permitted to grow without any external constraint, the crystal will assume a regular geometric shape having flat faces Within the past few years, single crystals have become extremely important in many of our modern technologies.

2. POLYCRYSTALLINE MATERIALS
Most crystalline solids are composed of a collection of many small crystals or grains; such materials are termed polycrystalline Initially, small crystals or nuclei form at various positions. These have random crystallographic orientations

2. POLYCRYSTALLINE MATERIALS
Growth of the crystallites; the obstruction of some grains that are adjacent to one another Upon completion of solidification, grains having irregular shapes have formed The grain structure as it would appear under the microscope; dark lines are the grain boundaries there exists some atomic mismatch within the region where two grains meet; this area, called a grain boundary

3. ANISOTROPY
The

physical properties of single crystals of some substances depend on the crystallographic direction in which measurements are taken This directionality of properties is termed anisotropy The extent and magnitude of anisotropic effects in crystalline materials are functions of the symmetry of the crystal structure

3. ANISOTROPY
For many polycrystalline materials, the crystallographic orientations of the individual grains are totally random. Under these circumstances, even though each grain may be anisotropic, a specimen composed of the grain aggregate behaves isotropically Sometimes the grains in polycrystalline materials have a preferential crystallographic orientation, in which case the material is said to have a texture.

3. ANISOTROPY
The

magnetic properties of some iron alloys used in transformer cores are anisotropic that is, grains (or single crystals) magnetize in a <100>-type direction easier than any other crystallographic direction Energy losses in transformer cores are minimized by utilizing polycrystalline sheets of these alloys into which have been introduced a magnetic texture

How do you measure the inter-planar distance?

Answer: X-Ray Diffraction! X-Ray radiation is sent towards the sample. X-rays are reflected off of the planes at an angle. The detector sweeps out a circular area measuring the intensity of the reflected rays.

X-Ray Bragg Diffraction

The X-Rays released have a specific wavelength. The Xrays hit the planes at a specific angle and are reflected at the same angle. Thus they sweep an angle of 2q. The value 2dsinq is equal wavelength of the X-rays.

2dsinq = l If we can determine d, we can solve for the lattice constant a and then IDENTIFY the

Manav Rachna College of Engg.