X- RAY DIFFRACTION

INTRODUCTION:So far we have seen ideal crystal which is obtained by combining a basis with an infinite space lattice. In real crystal, the periodicity is not continuous within a crystal. So many properties of crystalline materials are structure sensitive. To explain this sensitivity the only possible way is X-Ray Diffraction. Lattice Planes: A crystal is made up of a large number of parallel equidistant planes passing through lattice points called Lattice Planes. Interplanar Distance: The perpendicular distance between any two adjacent crystal planes is called Interplanar distance (d). Orientation of Planes:In crystal analysis it is necessary to indicate the orientation of planes. The orientation of the planes can be described in terms of their intercepts on three axes(X, Y, and Z). This is shown in the figure. In the figure the intercepts along X, Y and Z are pa, qb and rc respectively. Miller Indices: The reciprocals of the intercepts made by a plane on the co-ordinate axis or crystallographic axis are called Miller Indices. Procedure for finding Miller Indices: 1) Find the intercepts of the desired plane on the three co-ordinate axis. i.e., (pa, qb and rc) 2) Divide with primitives (a, b, c) then the intercepts are (p, q, r) 3) Take the reciprocals of the intercepts. i.e., (1/p, 1/q, 1/r). 4) Find the LCM of Denominators. 5) Reduce the reciprocals into integers by multiplying each of them with LCM. 6) Enclose these integers in brackets, which represent the Miller indices (h, k, l) of a given plane. Important Features of Miller Indices: 1) Miller indices represent the Orientation of Crystal Planes in a crystal. 2) A Plane parallel to any one of the co-ordinate axis will have infinite intercept, and the corresponding Miller index is Zero. 3) All equally parallel planes have the same Miller Indices (h, k, l). 4) When an intercept of plane is negative, the index is represented by bar over it. 5) If (h, k, l) are Miller Indices of a crystal plane, then the intercepts made by the plane with co-ordinate axis are a/h, b/k and c/l where a, b, c are lattice parameters. 6) A Plane passing through the origin is defined in terms of parallel planes having non zero intercepts.

PEC

Name of the Faculty: P.V.V.Satyanarayana

Equation for Interplanar Distance (d) or Separation Between Successive [h, k, l] Planes (or) Relation between interplanar spacing and Miller indices:
Let us consider three mutually perpendicular coordinate axis, OX, OY, and OZ and assume that a plane (hkl) parallel to the plane passing through the origin makes intercepts a/h, b/k and c/l on the three axes at A. B and C respectively as shown in figure.

In the case of Simple cubic system a = b = c; then equation 2 becomes dhkl =

1 h + k +l
2 2 2

dhkl =

h +k +l

PEC

Name of the Faculty: P.V.V.Satyanarayana

Braggs Law: Braggs Law studied the diffraction of X-Rays from various parallel planes of a crystal and
obtained condition called Braggs Condition. Let us consider a set of parallel lattice planes of a crystal in which spacing between any two successive planes is d. A narrow beam of XRay of wave length be incident on the planes with glancing angle , at which the diffraction occurs. This angle also called Braggs Angle. Consider the rays XO and X1O1 are incident on two consecutive planes AA1 and BB1. They are reflects along OY, O1Y1 respectively. Let OP and OQ are perpendiculars drawn from O on the rays X1O1 and O1Y1 respectively. Then the path difference between the incident and reflected ray is = PO1+O1Q------- (1)

For the reflected light intensity to be maximum when the path difference = n Therefore 2d sin = n, this is called Braggs Law. So Braggs law states that the X-Ray reflection from different parallel planes of a crystal, interfere constructively when the path difference is integral multiple of wave length of X-Rays. i.e.,

2d sin = n
Where n = 1,2,3............etc for first order, second order, third order maxima etc respectively. For first maxima sin 1 = /2d For second maxima sin 2 = 2/2d For third maxima sin 3 = 3/2d Therefore Sin 1 : sin 2 : sin 3 = 1:2:3

PEC

Name of the Faculty: P.V.V.Satyanarayana

X-Ray diffraction Methods

The Laue Method (Single fixed Crystal, Poly chromatic Source)

The Powder Method (Poly crystal in form of Powder, and Monochromatic Source)

The Rotating Crystal Method (Single crystal at different angles, and Monochromatic Source)

The Laue Method: Laue method is used to study the crystal orientation and to verify the
symmetry. The experimental arrangement consists of X-Ray Source, Collimating slits (S1 and S2), Crystal holder and Photographic Plate as shown in the figure.
The Source produce the continues X-Rays of NaCl

wave length (0.2 to 2Ao). These X-Rays are allowed to pass through two collimating slits S1 and S2 to form a fine and sharp beam. This fine sharp beam allowed to fall on a single crystal specimen which is held at fixed angle. The X-Rays diffracted through the crystal is made to fall on photographic film placed in its front as shown in the figure.

Apparatus used by Max von Laue

In Laues method diffraction pattern caused, by scattering of X-Rays at different atomic diffraction centers, and the wave lengths which satisfy the Braggs equation (2d sin = n). The diffraction pattern consists of central spot surrounded by concentric circular spots. The Symmetrical pattern of spots is called Laue Pattern. Each spot in the Laue pattern corresponds to an interference maximum for a set of planes satisfying the Braggs condition. The atomic arrangement can be understood from the position and intensities of the Laues Spots as shown in the figure. From Laue method it is possible to find the lattice constant and Interplanar spacing. This method is useful for determine the crystal orientation, symmetry and also to study the crystal imperfections. Limitations: 1. Laue method is used to determine the structure of single crystal only. 2. Determination of Unit cell Dimensions is not possible.

X-ray diffraction pattern of rock salt (common salt).

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Name of the Faculty: P.V.V.Satyanarayana

Powder Method (Debye- Seherrer Method):

The powder method was developed by Debye and Sherrer in Germany and by Hill in America simultaneously. This method is used to study the structure of crystals which cannot be obtained in the form of perfect crystals in shapes and sizes. This method can be used for pure metals, compounds and alloys also. Basic Principle The basic principle in this powder technique is that, the specimen contains a large number of micro crystals (~1012 in 1mm3 of powder sample) with random orientations, almost all the possible and d values are available. The diffraction takes place for these values of and d which satisfy Braggs condition, i.e., 2d sin = n Experimental arrangement:The experimental arrangement is shown in figure. The finely powdered sample is filled in a thin capillary tube and mounted at the center of the drum shaped camera with photographic film at the inner circumference which Collect the monochromatic Xrays from the X-ray tube. This monochromatic (or homogenous) x-rays can be converted into fine pencil beam by passing through the collimator. The pencil beam of X-rays is allowed to fall on the powder specimen (sample) as shown in the figure.1

Figure-1

Figure-2

Theory: The basic principle in this powder technique is that, the specimen contains a large number of micro crystals with random orientations, so almost all the possible and d values are available. The diffraction takes place for these values of and d which satisfy Braggs condition, i.e., 2d sin = n . Reflection takes place at the lattice planes, which satisfy the Braggs condition. For the value of , the beam appears at the corresponding 2 deviation. When the film is laid flat the pattern recorded on the photographic film is shown in the figure-2. Due to the narrow width of the film, only parts of circular rings are register on it. The curvature of arcs reverses when the angle of diffraction exceeds900.
The glancing angles () corresponding to the rings on the films can be calculated by measuring the diameter of the rings (s) and knowing the camera radius R. It is shown in the figure. From the figure Diameter of the ring S = 4 x R

4 (radians) =

S R

Using the above expression, can be calculated. Then the interplanar spacing for various sets of parallel planes can be evaluated from the Braggs law as follows. i.e., d =

. 2 sin By knowing all parameters, the crystal structures can be determined.

PEC

Name of the Faculty: P.V.V.Satyanarayana