Crystal Structure

why study the structure of crystalline solids?

The properties of some materials are directly related to their crystal structures For example, pure and undeformed magnesium and beryllium, having one crystal structure, are much more brittle (i.e., fracture at lower degrees of deformation) than are pure and undeformed metals such as gold and silver that have yet another crystal structure

 Furthermore, significant property differences exist between crystalline and non crystalline materials having the same composition. For example, non crystalline ceramics and polymers normally are optically transparent; the same materials in crystalline (or semi crystalline) form tend to be opaque or, at best, translucent.

Type of Materials
Crystalline: A crystalline material is one in which the atoms are situated in a repeating or periodic array over large atomic distances All metals, many ceramic materials, and certain polymers form crystalline structures under normal solidification conditions
E.g.:-Iron, Copper, Aluminum

Amorphous or Non crystalline: For those that do not crystallize, this long-range atomic order absent; these non crystalline or amorphous materials
E.g.:- Wood, paper, plastics, glass

is

 Crystal structure: the manner in which atoms, ions, or molecules are spatially arranged. When describing crystalline structures, atoms (or ions) are thought of as being solid spheres having well-defined diameters

What is a unit cell

The unit cell is the smallest structural unit or building block that can describe the crystal structure. Repetition of the unit cell generates the entire crystal.

Metallic Crystal Structures

Three relatively simple crystal structures are found for most of the common metals: simple cubic (SC), face centered cubic (FCC), bodycentered cubic (BCC), and hexagonal closepacked (HCP). SC :

Metallic Crystal Structures

BCC : Chromium, iron, tungsten

Metallic Crystal Structures

FCC: copper, aluminum, silver, and gold
a 2R 2

unit cell edge length for FCC :

Atomic packing factor

APF is the sum of the sphere volumes of all atoms within a unit cell divided by unit cell volume.

Let atomic radius be R. 4 3 Volume of sphere is R , 4 atoms per FCC unit cell, the total FCC atom 3 ( or sphere) volume is 4 3 16 3 V 4 R R S 3 3 16 3 R to find VC VS 2 2 2 APF 3 3 0.74 a a 4R VC 16 R 2 solv i ng for a, a 2 R 2
Vc a 2 R 2
3

Vs Vc

16 R3 2

Coordination number
Refers to the number of atoms touched by the given atoms inside a lattice structure.

1. SC:
1 vertex atom touches 3 other atoms along 3 edges of the cell. To see the remaining atoms we must see outside the single cell. The same atom also touches the 3 other atoms along the edges of the 3 other cells for a coordination number of 6

 BCC: any body atom touches 8 vertex atoms for a coordination number 8

 FCC:
Atom touch along the side diagonal of the cell. First consider the coordination number of the face atom. Face atom touches 4 vertex atoms

 also touches 8 other face atoms 4 above and four below for a total coordination number 12. Now consider coordination number of vertex atom. Each vertex atom touches four face atoms within same plane, four face atoms below and four face atoms above again giving coordination number 12

 The coordination number s same regardless of which atom is chosen. There fore we can also say the each vertex atom is surrounded by 8 body atoms again giving coordination number 8.

 The top and bottom faces of the unit cell consist of six atoms that form regular Hexagonal Close Pack Structures (HCP) hexagons and surround a single atom in the center. Another plane that provides three additional atoms to the unit cell is situated between the top and bottom planes. The equivalent of six atoms is contained in each unit cell; one-sixth of each of the 12 top and bottom face corner atoms, one-half of each of the 2 center face atoms, and all 3 mid plane interior atoms. The coordination number and the atomic packing factor for the HCP crystal structure are the same as for FCC: 12 and 0.74, respectively. The HCP metals include cadmium, magnesium, titanium, and zinc

In addition to the 3 cubic structures there are 2 close pack structures. It consists of closely packed layers of atoms within which each atom is surrounded by 6 others.

TYPES OF CRYSTAL LATTICES

Crystallographic Points, Directions, and Planes

When dealing with crystalline materials, it often becomes necessary to specify a particular point within a unit cell, a crystallographic direction, or some crystallographic plane of atoms.

Three numbers or indices are used to designate point locations, directions, and planes.
The basis for determining index values is the unit cell, with a right-handed coordinate system consisting of three (x, y, and z) axes situated at one of the corners and coinciding with the unit cell edges

POINT COORDINATES

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 (i.e., in terms of a, b, and c)

For the unit cell shown in the accompanying sketch (a), locate the point having coordinates 1

a = 0.48nm, b = 0.46nm, c = 0.40nm. Fractional lengths: q = , r = 1, s = First we move from the origin of the unit cell (pt M) qa = (0.48) = 0.12nm along x axis to point N, Similarly rb = 1 ( 0.46) = 0.46nm parallel to Y axis from N to O,

sc = (0.40) = 0.20 units parallel to Z axis to point P.

This point P corresponds to 1 .

CRYSTALLOGRAPHIC DIRECTIONS
A crystallographic direction is defined as a line between two points, or a vector.
Any vector may be translated throughout the crystal lattice without alteration, if parallelism is maintained. The length of the vector projection on each of the three axes is determined, these are measured in terms of the unit cell dimensions a, b, and c. 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, thus [uvw]. The u, v, and w integers correspond to the reduced projections along the x, y, and z axes, respectively There will exist both positive and negative coordinates. Thus negative indices are also possible, which are represented by a bar over the appropriate index. For example, the direction would have a component in the -Y direction.

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

CRYSTALLOGRAPHIC PLANES

Layers of planes along which atoms are arranged are known as crystallographic planes. Here one corner of the unit cell is assumed to be origin. w.r to this coordinates all planes are considered. Steps:
Position a plane in a convenient coordinate system. Plane shouldnt pass through origin. If it passes, shift the origin to adjacent unit cell. Find point of intersection of plane on the axis. If the plane does not intersect on any axis then the intercept distance or unit cell dimension w.r.to this axis is infinite. ( i.e., we assume that if plane is parallel it will intersect at infinity.) Take reciprocal of unit cell dimension. If it is a fraction then multiply or divide by same value and write as[u v w].

If unit cell dimension is negative the represent as [u v w].

Plane surface parallel to X axis , unit cell distance/pt. of intersection = Plane surface parallel to Z axis , unit cell distance = Y But @ Y axis there is intersection point, therefore distance of unit cell = 1. We can write ( 1 ) =(1/0 1 1/0) Miller indices = [0 1 0]

Hexagonal crystals
For crystals having hexagonal symmetry, it is desirable that equivalent planes have the same indices. This convention leads to the four-index (hkil) scheme Where I = - ( h + k)

 Furthermore, its intersections with the a2 and z axes are -a and c, respectively. Therefore, in terms of the lattice parameters, these intersections are 1, -1 and 1. To determine these Miller Bravais indices, consider the plane in the figure referenced to the parallelepiped labeled with the letters A through H at its corners. This plane intersects the a1axis at a distance a from the origin of the a1 a2-a3-zcoordinate axes system (point C) Furthermore, the reciprocals of these numbers are also 1, -1 and 1. hence h = 1, k = -1, l = 1. From i = - ( h + k ) = - (1 1) = 0 therefore the (hkil) indices are ( 1 -1 0 1) Notice that the third index is zero (i.e., its reciprocal = ), which means that this plane parallels the a3 axis