Solid matter can be classified as: Amorphous: The atoms are arranged in a random way similar to the disorder

we find in a liquid. Glasses are amorphous materials. Crystalline: The atoms are arranged in a regular pattern, and there is as smallest volume element that by repetition in three dimensions describes the crystal. This smallest volume element is called a unit cell. The dimensions of the unit cell are described by three axes: a, b, c and the angles between them alpha, beta, gamma. A crystal consists of a periodic arrangement of the unit cell into a lattice. The unit cell can contain a single atom or atoms in a fixed arrangement. Crystals consist of planes of atoms that are spaced a distance d apart, but can be resolved into many atomic planes, each with a different spacing. a, b and c (length) and angles between a, b and c are lattice constant or parameters which can be determined by XRD. About 95% of all solids can be described as crystalline. Miller Indices: Miller indices are the reciprocals of the fractional intercepts which the plane makes with crystallographic axes. E.g.

abc 100 100

abc 110 110

abc 111 111

abc 01 012

Black numbers-fractional intercepts, Blue numbers-Miller indices An electron in an alternating electromagnetic field will oscillate with the same frequency as the field. When an X-ray beam hits an atom, the electrons around the atom start to oscillate with the same frequency as the incoming beam. In almost all directions we will have destructive interference, that is, the combining waves are out of phase and there is no resultant energy leaving the solid sample. However the atoms in a crystal are arranged in a regular pattern, and in a very few directions we will have constructive interference. The waves will be in phase and there will be well defined X-ray beams leaving the sample at various directions. Hence, a diffracted beam may be described as a beam composed of a large number of scattered rays mutually reinforcing one another. To decide whether interference is constructive or destructive Sir William Henry Bragg and William Lawrence Bragg had given a law. Bragg Law: In 1913 these English physicists developed a relationship to explain why the cleavage faces of crystals appear to reflect X-ray beams at certain angles of incidence (theta, q). The variable d is the distance between atomic layers in a crystal, and the variable lambda l is the wavelength of the incident X-ray beam, n is an integer. n= 2dsin

X-ray 1 X-ray 2

Fig: Braggs Law

X-ray Diffraction (XRD): The atomic planes of a crystal cause an incident beam of X-rays to interfere with one another as they leave the crystal. The phenomenon is called X-ray diffraction. With the help of XRD technique we can: Measure the average spacing between layers or rows of atoms. Determine the orientation of a single crystal or grain. Find the crystal structure of an unknown material. Measure the size, shape and internal stress of small crystalline regions. Working principle of XRD: X-rays are diffracted by electron clouds. Firing x-rays at electron clouds that are around ordered atoms (in crystals) gives a diffraction pattern. We can interpret the diffraction pattern to calculate the 3-dimensional position of the atoms in the crystals. The reflection of x-rays off of repeating planes of atoms creates a series of spots called a diffraction pattern. The orientation of the x-ray and the crystal is of utmost importance. As the angle between the x-ray beam and the crystal face is varied, the diffraction pattern will change as well. By collecting data from a series of orientation angles, the three dimensional atomic structure can be calculated.

The sample used in x-ray diffraction must not only be crystalline, but it must also be a single crystal. In reality, there can be small defects within the lattice, and crystals often fuse together. Both of these situations imply that repeating planes of atoms are interrupted. To get good x-ray diffraction data, chemists use only single crystals with minimum defects. A schematic of an x-ray diffractometer is shown in Figure 3.12. The main components are an x-ray source, a goniometer, a detection system, and a computer control system. The x-ray source is a high-vacuum tube, and the x-ray beam passes out of the tube through a thin window. A single crystal is generally mounted on the end of a glass fiber. This fiber is then attached to a metal pin which is secured to the goniometer head. The goniometer precisely orients the sample in the x-ray beam. As the x-rays pass through the crystal, the detector collects information to generate a diffraction pattern. Finally, the computer control system processes the information from the detector, and the structure of the crystal is solved.

Fig: XRD Technique

In a crystal, x-rays are reflected from the different planes of atoms that are present. If two x rays travel to two different planes, then one x-ray must travel further than the other. The x-rays may end up out of phase after they are reflected. Only at certain angles of reflection do the two rays remain in phase. In the diffraction pattern, dark areas are caused by constructive interference while lighter areas are caused by destructive interference. Thus, the diffraction pattern can be related to the structure of the crystal, and the position of each atom in a

molecule as well as the type and size of a unit cell can be determined by using xray diffraction. Diffraction is the bending of rays off the sharp edges. Regarding this technique two types of diffractions are mainly famous. Single Crystal (Laue) Diffraction a beam of X-rays of all wavelengths is directed at a single crystal, which sits stationary in front of a photographic plate. A series of diffraction spots surround the central point of the beam, corresponding to diffraction from a given series of atomic planes

Fig: Single crystal diffraction Powder Diffraction A powder is used to ensure completely random crystal orientation to get diffraction from all possible planes. The diffraction pattern can be recorded on a flat photographic film or on a CRT (cathode ray tube). When the incident beam satisfies the Bragg condition, a set of planes forms a cone of diffracted. Since the cone of X-rays intersects the flat photographic filmstrip in two arcs equally spaced from the direct X-ray beam, two curved lines will be recorded on the photographic film. The distance of the lines from the center can be used to determine the angle , which can then be used to determine the interplanar d spacing. The pattern of diffracted X-rays is unique for a particular structure type and can be used as a fingerprint to identify the structure type. Different minerals have different structure types, thus X-ray diffraction is an ideal tool for identifying different minerals.

Applications: Following are the some applications of XRD technique. Identification : The most common use of powder (polycrystalline) diffraction is chemical analysis. This can include phase identification (search/match), investigation of high/low temperature phases, solid solutions and determinations of unit cell parameters of new materials. Polymer crystallinity : A polymer can be considered partly crystalline and partly amorphous. The crystalline domains act as a reinforcing grid, like the iron framework in concrete, and improves the performance over a wide range of temperature. However, too much crystallinity causes brittleness. The crystalline parts give sharp narrow diffraction peaks and the amorphous component gives a very broad peak (halo). The ratio between these intensities can be used to calculate the amount of crystallinity in the material. Residual stress: Residual stress is the stress that remains in the material after the external force that caused the stress have been removed. Stress is defined as force per unit area. Positive values indicate tensile (expansion) stress, negative values indicate a compressive state. The deformation per unit length is called strain. The residual stress can be introduced by any mechanical, chemical or thermal process. e.g. machining, plating and welding. The principals of stress analysis by the X-ray diffraction is based on measuring angular lattice strain distributions.