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Prepared by: Ms.M.Shalini
(i) Laue Method
The Laue method is mainly used to determine the orientation of large single crystals while radiation is reflected from, or transmitted through a fixed crystal Laue Studied The phenomena of crystal diffraction by two methods: (a). Transmission method (b). Back reflection method
(a). Transmission method
(b). Back reflection method
Back Reflection Laue
• In the transmission Laue method, the film is placed behind the crystal to record beams which are transmitted through the crystal.
• In the back-reflection method, the film is placed between the xray source and the crystal. The beams which are diffracted in a backward direction are recorded.
• One side of the cone of Laue reflections is defined by the transmitted beam. The film intersects the cone, with the diffraction spots generally lying on an ellipse.
• One side of the cone of Laue reflections is defined by the transmitted beam. The film intersects the cone, with the diffraction spots generally lying on an hyperbola.
Bragg X-ray spectrophotometer method
vBragg analyzed the structure of crystals of NaCl, KCl, and ZnS using the Laue’s Photographs. vHe devised a spectrophotometer to measure the intensity of X-ray beam. vThe Bragg’s equation is as follows:
The Bragg Equation
nλ = 2d sinθ
where n is an integer is the wavelength of the x-rays d is the interplanar spacing in the specimen is the diffraction angle
The Bragg equation is the fundamental equation, valid only for monochromatic X-rays, that is used to calculate interplanar spacings used in XRD analysis
WORKING OF BRAGG SPECTROPHOTOMETER
• The crystal is mounted in such a position that θ= 0ο and the ionization chamber is adjusted to receive x-rays. • The crystal and ionization chamber are moved in steps so that the angle through which the chamber is rotated is twice the angle through which the crystal is rotated. • The ionization at first fall as θ rises but for certain values of θ it rises sharply. • This corresponds to the direction of X-ray spectrum. • X-ray spectrum are obtained by plotting a graph between ionization current and the glancing angle θ1, θ2 and θ3. • With known values of d and n and from observed
The following figures show experimental x-ray diffraction patterns of cubic SiC
An X- ray spectrum showing variation of ionization current as a function of glancing angle θ
Measurement of λ
Ø The wavelength of the x-rays can be determined by employing the eqn: n λ= 2 d si Θ n Ø The value of θ for various order spectra produced by crystal was measured. Ø The mean value of λ/d was calculated. The value of λ/d is known as lattice constant. Ø Knowing d, the wavelength is thus
Measurement of d
• • • •
d= a(2)0.5 /2 for simple cubic lattice d= a/2 for fcc lattice d= a(3)0.5 /2 for bcc crystal lattice Where a= ( Mol.wtXNo.Of atoms in unit cell)0.333 (Avogadro’s NoX Density)
BODY CENTERED CUBIC
FACE CENTERED CUBIC
Determination of crystal structure by Bragg’s law
From Bragg’s eqn the ratio of lattice spacing for various groups of plane is recorded. This ratio is different for different crystals. d100:d110:d111= 1:1/√2: 1/√3 for simple cubic d100:d110:d111= 1:1/√2: 1/√3 for fcc crystal d100:d110:d111= 1:1/√2: 1/√3 for for bcc crystal
3. Powder crystal Method
What is X-ray Powder Diffraction (XRD)?
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase identification of a crystalline material and can provide information on unit cell dimensions. The analyzed crystal is finely ground, homogenized, and average bulk composition is determined. It was devised independently by Debye and Scherrer in Germany and by Hull in America at the same time. The experimental setup was shown in figure below:
Powder Crystal method
THE POWDER METHOD
If a powdered specimen is used, instead of a single crystal, then there is no need to rotate the specimen, because there will always be some crystals at an orientation for which diffraction is permitted. Here a monochromatic X-ray beam is incident on a powdered or polycrystalline sample. This method is useful for samples that are difficult to obtain n single crystal form.
The powder method is used to determine the value of the lattice parameters accurately . Lattice parameters are the magnitudes of the unit vectors a, b and c which define the unit cell for the crystal. For every set of crystal planes, by chance, one or more crystals will be in the correct orientation to give the correct Bragg angle to satisfy Bragg's equation. Every crystal plane is thus capable of diffraction. Each diffraction line is made up of a large number of small spots, each from a separate crystal. Each spot is so small as to give the appearance of a continuous line.
ROTATING CRYSTAL METHOD
Lattice constant of the crystal can be determined by means of this method; for a given wavelength if the angle θat which a d known, reflection occurs is hkl can be determined.
d = a h 2 + 2+l 2 k
The reflected beams are located on the surface of imaginary cones. By recording the diffraction patterns (both angles and intensities) for various crystal orientations, one can determine the shape and size of unit cell as well as arrangement of atoms inside the cell.
XRD is a nondestructive technique. Some of the uses of x-ray diffraction are;
Application of XRD
between crystalline and amorphous materials; 2.Determination of the structure of crystalline materials; 3.Determination of electron distribution within the atoms, and throughout the unit cell; 4.Determination of the orientation of single crystals; 5.Determination of the texture of polygrained materials; 6.Measurement of strain and small grain size…..etc