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Mphil thesis cristal

Mphil thesis cristal

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Published by: Balaji Rao N on Dec 20, 2009
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01/07/2013

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CHAPTER - 1
INTRODUCTION
Crystals have been attracting mankind in the past due to their aesthetic beauty.Examples for them are the most valuable diamond to artificial stones like Americandiamond. Though the things are like above, their scientific applications were understoodonly in the last century, i.e., 20
th
century. Recently, single crystals have been usedextensively in solid state devices.The search for new materials and their single crystal growth have always beengiven top priority by the scientists throughout the world. Since 1970, one could see thatthere are lot of developments in science and technology, especially in the fields of electronics, fiber-optic communications and lasers. These things became possible due tothe availability of single crystals. Nowadays, it is possible to synthesis artificially in thelaboratory almost all naturally occurring crystals, and new crystals from the elements inthe periodic table and organic crystals.Their smooth surfaces with scintillating reflections of light, their enchantingcolours, and their definite and varied shapes with sharp edges, their deep transparencyaltogether aroused the aesthetic since of early men who used these crystals as ornaments.As science and technology grows, the curiosity of mankind to understand quantitativelyabout crystals also grows. Thus their utility range from ornaments to several usefulapplications in fiber-optics, etc.The fantasy of their external beauty was understood by the natural laws of mathematics, physics and chemistry. Their contents and [inside] were probed, analyzedand understood by the modern methods of diffraction and spectroscopic techniques.Their external plane, shape and colours are correlated with the internal atomic contentand their arrangement. Thus grew a separate field of science, the study of crystals -crystal growth of characterization. The word crystal originates from the Greek wordCRYSTTALOS, which means clear transparent ice. In the middle ages, this word wasextended to include quarts are rock crystals which were believed to have been formed bythe intense freezing of water on the Alps mountains into permanent form of ice. To a
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 present day of student of crystal growth, the crystal is a chemical compound in the shapeof a solid polyhedron bounded by definite planes. Their shape and symmetry is amanifestation of the internal atomic arrangements extending in three dimensions, in anorderly way. Nowadays crystal growth technology is largely on crystals such as NLO crystals, piezo-electric crystals, Ferro-electric crystals, sensitive crystals and crystalline films.Preparation of single crystals of such materials has resulted in growing realization for theimportance of crystal growth, in the theoretical and experimental aspects. The preparation of single crystal is mainly based on the availability and nature of the startingmaterials and their physico-chemical properties. Fields as diverse as physics, chemistry,chemical engineering, mineralogy and biology have contributed much to the field of crystal growth, also these fields benefited from crystal growth. Crystal growth concepthas been fundamental to many areas of science and technology.We can grow crystals in any one of the following four transformations. [Pamplin,B.R., 1979].1.Solid-state reaction involving solid-solid phase transition.2.Solution growth process involving Liquid-solid phase transition.3.Vapour growth process involving vapour-solid phase transition.4.Melt growth process involving liquid- solid phase transition.The general condition for all the above mentioned process is that the growingcrystals must have lower free energy than the initial state of the system.
1.1 SOLID GROWTH TECHNIQUES
Solid state growth requires atomic diffusion except in case of martenstictransformations. At normal temperatures such diffusion is usually very slow except in thecase of superionic materials where the small cation is quite mobile. Thus solid stategrowth techniques are seldom employed when other methods can be used. Fig. 1.1 showsthat most of these techniques were known and used before 1900 and compared with theother growth methods, have not been changed very substantially this century. Solid stategrowth techniques for the production of single crystal are of very small significance;however, annealing, heat treatment, sintering, and quenching are, of course,
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metallurgical processes of great importance in tailoring the properties of materials.[Brice J.C., 1986].
Fig. 1.1. Evolution of solid growth technique1.2 ANNEALING TECHNIQUES
If a polycrystalline metal rod is held at an elevated temperature below the melting point for many hours some grains may grow at the expense of their neighbors. Sincegrain boundaries contain more free energy than bulk crystal. This process can be seen tolower the free energy of the rod. However, such growth is unreliable and incomplete.Two main techniques were introduced early this century to improve it.
1.3 STRAIN ANNEALING
It was found that cold worked metals showed more grain growth than unstrainedsamples. Some favoured grains grow at the expense of others occasionally the wholesample may become a single crystal. Thirteen “laws of grains growth” were enunciatedin a book published in 1924. It became clear that a critical strain can induce nucleationand growth of new grains. Secondary recrystallization: Below the critical strain onlynormal coarsening or primary crystallization occurs. Above it, many new grainsnucleate and grow. At the critical strain ideally one grain nucleates and grows toencompass the whole specimen before there is time for any substantial statistical chance
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