AUTONOMOUS

X-Ray Diffraction
Photographic plate

slits X-rays

crystal

X-ray pattern

Diffraction of X-rays:

y In 1912 German Physicist Laue suggested that a crystal

which consists of a 3-D array of regularly spaced atoms can the serve the purpose of a grating.
y Laue ,and his associates Friedrich and Knipping

succeeded in diffracting X-rays by passing through a thin crystal

Screen

Slits X-rays NaCl P O

y A simple explanation of the diffraction pattern

was given by W.L.Bragg ,the spots are produced due to the reflection of some of incident X-rays from the various sets of parallel crystal which contain the large number of atoms.

Diffraction of X-rays

y X-ray diffraction techniques are very useful for

crystal structure analysis and identification of different types of crystals.  Experimental study of crystalline materials became possible only after the discovery of xrays.
y In crystal analysis it is essential to indicate

certain directions inside the crystal. direction dependent.

y A large number of properties of crystals are

Diffraction of X-rays
y X-rays are the EM radiation. y The wavelengths of x-rays lies between 0.1A

and 100A y The dimensions of atoms and inter atomic spacing is about 1A to 2A y The crystals produce the diffraction of x-rays when wavelength matches with the values 1A to 2A

y Bragg while studying the properties of x-rays,

studied the x-ray diffraction pattern of a few crystals. y This discovery lead to understand the crystal structures which subsequently helped in the fields of chemistry, solid state etc.

y Braggs law:(Statement)

y Braggs law states that, the path difference between

the two reflected rays by the crystal planes should be an integral multiple of wavelength of incident xxrays for producing maxima or constructive interference. planes.

y The crystal act as a series of parallel reflecting y Consider a ray PA reflected at a atom A, in the

direction AR from plane 1 and another ray QB reflected at another atom B in the direction BS.

P Q

A Plane 1
90 90

C Plane 2 Plane 3 B

y The path difference between these two rays is

CB+BD
y The two rays will reinforce each other and produce

an intense spot , when path difference is an integral multiple of wave length.

y CB+BD=n y CB=BD=d sin y 2d sin = n y Where n = 1,2,3,..first , second order etc. y For 1st order

sin 1 = /2d. y For 2nd order sin 2 = 2 / 2d. y For 3rd order sin 3 = 3 / 2d. y where 1, 2 and 3 are the glancing angles for n=1,2 and 3 respectively.

Importance of Braggslaw

For cubic:

For BCC

For FCC

y Experimental Methods in X-ray Diffraction. Xy Introduction:

y X-ray diffraction techniques are very useful for crystal

structure analysis and identification of different types of crystals.

y Experimental study of crystalline materials became possible

only after the discovery of x-rays.

y Diffraction occurs when waves traveling through an object

whose dimensions are order of wavelength.

y Typical inter atomic spacing in crystals is 2-3A. y The x-rays have wavelengths (0.02A to 100A) in this range .

Hence x-ray diffraction is utilized to study the crystal structures.

X-ray Diffraction Techniques:

y There are three main experimental X-ray X-

diffraction methods by which the crystal structure can be analyzed. 1.Laue method. 2.Powder method. 3.Rotating crystal method.

Laue method:


Consider beam of x-rays in the wavelength of 0.2A to 2A x0.2 2 originating from a suitable source. source. In this technique, the crystal is held stationary in the beam of x-rays. xAfter passing through the crystal ,the X-rays are Xdiffracted and recorded on the photographic plate. The diffraction pattern consists of a bright central spot and a set of spots arranged in a definite pattern about the central spot. The symmetrical pattern caused by diffraction of x-rays by xcrystal planes is called the Laue pattern.

Photographic plate

slits X-rays

crystal

Laue pattern

Photographic film

P
White x-radiation

crystal

y The crystal is fixed, for an incident angle

, the diffracted angle becomes 2 .

y Consider, D is the distance between the

crystal and photographic film and OP = R.

 From

COP, Tan2 = OP/OC OP = OC tan2 R = D tan2

y By the interpretation of the reflection spots in the

photographic film, the crystal structure of the given specimen can be determined. y This method is used to study the orientation of the crystal and verify crystal symmetry.

y Different laue pattern

Powder method (Debye scherrer method):

y Powder crystal method is a standard technique to study the structure of micro

crystals.

y This method gives the information regarding the size of crystals, presence of

impurities,distortion,etc impurities,distortion,etc

y It is used for accurate determination of lattice parameters in crystals

y The powdered specimen is kept inside a small capillary tube y If a monochromatic X-ray beam is directed on to a single crystal, then only one X-

or two diffracted beams may result.

y If the sample consists of few tens of randomly oriented

single crystal ,the diffraction beams are seen to lie on the surface of several cones. The cones may emerge in all direction ,forward and backward y A sample of few hundred of crystals(i.e Powdered sample) show that the diffracted beams form continuous cones .

powderCrystal

Incident x-ray beam

X-Ray
2 2

Exit hole S

w1

Entrancehole

w2

Photographic film Camera

Entrance point Exit point

Tr
S

Photographic Film

y The full opening angle of the diffraction cone 4 is

determined by measuring the distance s between two corresponding arc.

y The distance s on the film between two diffraction

lines corresponding to a particular plane is related to the Braggs angle by the equation.

4U ! s
y

U ! s

4r

y Where r is the specimen to film distance.

y Applications of X-ray Diffraction:

1. Laue diffraction method is most used for mounting the single crystals in a precisely known orientation. It is very much useful for study of crystal symmetry. 2. X-ray powder diffraction has large number of applications. y Study of d-spacing. y Study of alloys. y Stress determination in metals. y Determination of particle size. 3. Rotating crystal method is generally used to align the crystals and measure lattice parameters and determine the crystal structure.