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Without crystals, there would be no electronic industry, no photonic industry, no fibre optic communication, which depend on materials/crystals such as semiconductors, superconductors, polarizer’s, transducers, radiation detectors, ultrasonic amplifiers, ferrites, magnetic garnets, solid state lasers, ocousto-optic, photosensitive, refractory of different grades, crystalline films for microelectronics and computer industries. A most remarkable feature of matter in the solid is the tendency of the constituent atoms of a great many solids to arrange themselves in an ordered periodic pattern. A solid material with such a regular atomic arrangement is said to be crystalline. A solid material without such a structure is called non-crystalline or amorphous. The properties of amorphous bodies are distinctly different from those of crystalline substance. The term ‘crystal’ and ‘amorphous’ have been adapted from the Greek and mean ‘clear ice’ and ‘shapeless’ respectively. When a solid is described as ‘amorphous’, it means that the substance has no regular internal structure. If the substance is having a definite geometrical shape, it is artificially created and is not formed from the natural conditions of growth. In between the two extremes exist polycrystalline, which is made up of a number of smaller crystals known as crystallites, and paracrystalline phases. Liquid crystals are another state of matter that has properties between those of a conventional liquid and those of a solid crystal. . Most crystals in nature, such as those in sugar, salt or diamonds, are symmetrical and all have the same orientation throughout the entire crystal. Quasi crystals represent a new state of matter that was not expected to be found, with some properties of crystals and others of non-crystalline matter, such as glass. Quasi crystals behave differently than other crystals. They have an orderly pattern that includes pentagons, five fold shapes, but unlike other crystals, the pattern never repeats itself exactly. They were first observed in 1982 in an aluminum-manganese alloy (Al6Mn). On 5 Oct 2011, Daniel Shechtman, 70, a researcher at Technion-Israel Institute of Technology in Haifa, received the award for discovering quasi crystals. Crystallography is a tool that is often employed by material scientists. It is the experimental science of the arrangement of atoms in solids. The word “crystallography” derives from the Greek words crystallon = cold drop/frozen drop, with its meaning extending to all solids with some degree of transparency, and grapho =write. 
Most solid matter is crystalline i.e., nature favors the crystalline state of solids. There are over 20,000 crystalline substances in the crystal kingdom. The scientific use of the term ‘crystal’ is limited to the description of any solid with an ordered atomic arrangement for a given structure. Crystals are used in our day today life for a number of purposes. When ever we add common salt in cooking foods, we are ingesting salt crystals. On the contrary, precious and some semiprecious crystals are worn as jewelries. Another use of crystals is metaphysical healing. Likewise, several types of crystals are identified, which are categorized according to their shape and properties. Crystal Types: Based on shape As per the shape or structure, there are seven types of crystal lattice systems; Cubic- Precisely known as isometric crystal (e.g. halite), this type comprises crystals that measure the same length in all axes. They may be four sided (cubic), eight sided (octahedron) and twelve sided (dodecahedron). Monoclinic- Monoclinic crystals (e.g. orthoclase) are characterized by lattice vectors of different lengths. Their structure resembles a rectangular prism having a parallelogram base. Triclinic- In triclinic crystals (e.g. microcline), all the three vectors have different lengths, thus exhibiting some what strange shapes. Trigonal- Simply speaking, trigonal crystals (e.g. dolomite), are cubic crystals, when the latter is stretched along the body diagonal. Tetragonal- Tetragonal crystals (e.g. wulfenite), are more or less similar to cubic type, except that one lattice vector is stretched to a certain length. Structurally, a tetragonal crystal resembles a rectangular prism having a square shaped base. Orthorhombic- This type of crystal appears like a tetragonal crystal, when viewed from the side. An orthorhombic crystal (e.g. aragonite) has a rectangular prism and a rectangular base. Hexagonal- The structural symmetry of a hexagonal crystal (e.g. beryl) is similar to a right prism. When viewed in cross section, it has a regular hexagonal shape. Crystal Types: Based on properties Crystals can be divided into four types, according to their physical and chemical properties.
Ionic Crystals- Crystals in which the constituent atoms are bound together by strong ionic or electrostatic bonds. Example of ionic crystal type is common salt (NaCl); the sodium ion and chloride ion are bonded non-covalent, electrostatic bonds. Covalent Crystals- As the name signifies, the component particles of covalent crystals exhibit strong covalent bonding. The most precious stone, diamond is an example of covalent crystal. Metallic Crystals- In general, metallic crystals (e.g. nickel and copper) have a very high melting and boiling points. In this type of crystal, the atoms are present in the lattice sites, which enable the outer electrons to move freely. Molecular Crystals- Unlike the ionic and covalent crystals, the constituents of molecular type are bonded by weak hydrogen or Van der Waals forces. Thus, a molecular crystal (e.g. sugar) usually has a low melting point.
Crystallization is the (natural or artificial) process for the formation of ‘solid crystals’ from a uniform solution. Crystallization is also defined as a process of arranging atoms or molecules that are in fluid or solution state into an ordered solid state. All crystallizing methods change the physical state of a material by transforming the system from some non-equilibrium state towards an equilibrium state. Crystallization methods are divided into two broad categories viz., concentration gradient and thermal gradient, based upon how system performs the transformation. Concentration gradient methods typically involve concentrating the sample by either removal of solvent or transport of material to another solvent system in which the material is less soluble. Thermal gradient methods rely upon the fact that the crystals form when the material is cooled. The choice of crystallization method for a particular sample depends greatly upon the physical and chemical properties of the sample. Growing crystals is more of an art than a science and luck is a major factor, there are some things to do and some other things not to do. Some theoretical background about crystallization:Saturation and Super saturation A key parameter for crystallization is supersaturation. It is the driving force of crystallization. Theoretically, crystallization should starts when the concentration of a compound in a solvent is higher than the solubility product of this compound. Generally, however, crystallization is
kinetically hindered process and crystals grow only from supersaturated solutions. There are several ways to achieve this metastable state of super saturation. The easiest is increasing the concentration by evaporation of the solvent until crystallization sets in. This can be achieved by not closing the lid of tube or flask very tightly and simply wait. Another way of obtaining a supersaturated solution is by making use of the fact that many compounds are better soluble in hot solvents than in cold ones. A hot solution that is almost saturated is likely to yield crystals at room temperature or, if appropriate, below. However crystals that grow at higher temperature are frequently twinned or show static disorder. Another way to super saturation, frequently the best way to grow quality crystals, is the use of binary solvent systems. Nucleation Nucleation process is a conglomeration of atoms or molecules to form the first submicroscopic speck or nucleus of the solid crystal. It may also be defined as the appearance of little ordered domain amidst of randomness. Theory of nucleation: Considering the total free energy for a group of atoms, a theory for the formation of nucleus was put forward by Volmer and Weber . Fluctuations with in the supersaturated solution give rise to small clusters of molecules known as “embryos”. The probability that an embryo will grow to form a stable nucleus depends on the change in free energy associated with its formation. If the free energy change between the solid and liquid is ∆Gv, the free energy of the system decreases by this amount for each unit volume of the solid created, but increases by an amount equal to the interfacial free energy σ , for each unit area of the solid-liquid interface formed. Hence the change in Gibbs free energy associated with the formation of a spherical embryo of radius r is given by
ΔG = The surface energy increases with r2 and energy term decreases with r3. The net free energy change increases with increase in size, attaining a maximum and decreases for the further increase in size of the nucleus. The size of the nucleus corresponding to the minimum free
energy change is known as the “critical nucleus”. It is the smallest sized embryo which can grow further effecting the reduction in free energy of the system. On the other hand, if the size of the nucleus formed is below the critical dimension, no further growth is possible and it will redissociate into the mother system. Types of nucleation: There are two possible types of crystalline phase nuclei in liquids, namely, molecular clusters of fluctuation origin having certain properties of the crystalline phase (homogeneous nucleation) and easily-activated solid impurities (heterogeneous nucleation).So, nucleation can be classified into two types as: 1) Primary (homogeneous) nucleation - which takes place without the involvement of any foreign substance i.e. which takes place on its own. Homogeneous nucleation occurs spontaneously and randomly, but it requires superheating or super cooling. 2) Secondary (heterogeneous) nucleation - which takes place only in the presence of foreign substances. Heterogeneous nucleation is faster than homogeneous nucleation. In homogeneous nucleation, the solution is totally uniform, and the process occurs spontaneously, usually in response to something like a change in pressure or temperature. Heterogeneous nucleation involves a solution which is mixed in nature. Nucleation tends to occur much more quickly in such mixtures. As an example of the difference between heterogeneous and homogeneous nucleation, ‘purified water’ freezes at a lower temperature than conventional water, because the purified water lacks small particles which can be used as “seeds” to start the nucleation process.
Crystal growth: Introduction.
The subsequent step after nucleation is crystal growth. Crystal growth is an interdisciplinary subject covering physics, chemistry, material science, chemical engineering, metallurgy, crystallography, mineralogy, etc. In the past few decades, there has been a growing interest on crystal growth processes, particularly in view of the increasing demands of materials for technological applications. Crystal growth generally takes place by means of the following four processes occurring in series-
1) Diffusion of the atoms (or molecules, in the case of molecular crystals such as hydrocarbons or polymers) of the crystallizing substance through the surrounding environment (or solution to the surface of the crystal. 2) Diffusion of these atoms over the surface of the crystal to special sites on the surface. 3) Incorporation of atoms into the crystal at these sites, and 4) Diffusion of the heat of crystallization away from the crystal surface.
History of crystal growth
The art of crystallization extends for back in the past and antedates considerably the written history of man. The crystallization of salt from sea water by evaporation was already practiced at many places in prehistoric time and can be considered as one of the oldest technical methods of transforming materials. Crystallization procedures were recorded in written documents well before the Christian era. The Roman Plinius in his “Naturalis historia” mentioned the crystallization of a number of salts, for instance of vitriols. The medieval alchemists, European as well as Arabian, had arrived at a stage of detailed knowledge about many crystallization processes and phenomenon. The alchemist Geber, whose papers are dated in the 12th of 13th century, described the precipitation and purification of various materials by recrystallization as well as by sublimation and distillation. Towards the end of the Middle Ages, the general technical progress led to corresponding progress in techniques of material production and transformation, too, In the middle of the 16th century, Birringuccio (1540) recorded in detail the leaching of salt petre and its purification by recrystallization, and the Saxonian scientist Agricola (1556) in his famous, extensive work “De re metallica” gave instruction how to produce various salts, alums and vitriols. In the following century, the word “crystal” came in use more and more in the modern, general sense. Originally, Homer had used the expression “crystallos” for ice crystals (rock crystals). Also in the 17th century, the denotation “crystallization” came in use, replacing earlier expressions like “condensation” or “coagulation”.
Need to grow artificial crystals
The first step in the transition of crystals from museum to technology was the development of the methods of producing large crystals artificially. ‘Geneva’ rubies, Which appeared in 1900, are possible the first case of commercial exploitation. Before world war 2nd there was little use of
synthetic crystals except in scientific instruments. However, the period 1900 to 1940 saw enoromous advances in the field of crystal growth. During world war 2nd, crystals were widely used as piezoelectric transducers, as resonant devices to control radiofrequencies in point contact diodes for radar and other high frequency applications. Natural crystals have been used for both as gems and for a few devices such as crystal controlled oscillators. The systematic production of artificial crystals might be viewed as new “agriculture that began to flourish”. The need of artificial crystals is growing day by day due to their commercial uses like: 1) frequency controlled oscillators (quartz) 2) polarizer’s (calcite, sodium nitrate) 3) transducers (quartz, Rochelle salt, ammonium dihydrogen phosphate) 4) grinding (diamond) 5) radiation detectors (aluminum oxide) 6) transistors (Ge and Si) 7) magnetic devices (garnets) 8) strain gauges (Si) 9) ultrasonic amplifiers (cadmium sulphate) 10) masers and lasers (ruby, gadolinium arsenide, calcium tungstate) 11) lenses (fluorite) 12) melting crucibles (MgO) 13) tunnel diodes (GaAs)
Crystal Growth Technology Now
The world crystal production is estimated at more than 20,000 tons per year, of which the largest fraction of about 60% are semiconductors silicon, GaAs, InP, GaP, CdTe and its alloys. Optical crystals, scintillator crystals, and acousto-optic crystals have about equal shares of 10%, whereas lasers and non-linear optic crystals and crystals for jewelry and watch industry have shares of a few % only. This scale of crystal production and the fact that most crystals are produced in factories specialized in silicon or GaAs or LiNbO3, etc. has caused an increasing degree of specialization. Furthermore, crystal growth has split into five major areas so that crossfertilization and communication are more and reduced. 1) Fundamental theoretical and experimental crystal growth studies.
2) Laboratory crystal growth for preparing research samples. 3) Industrial fabrication of single crystals and their machining and characterization. 4) Fabrication of metallic/dendritic crystals (e.g., turbine blades). 5) Mass crystallization (salt, sugar, chemicals).
Thermodynamics of Crystal Growth
Thermodynamics is an important practical tool for crystal growers. It helps to derive the most effective phase transition, i.e. growth method, and the value of driving force of crystallization. From thermodynamic principles one can estimate the nucleation and existence conditions of a given crystalline phase, the width of compound homogeneity regions, and optimize the in-situ control of crystal composition during growth. In a word, no technological optimum can be found without considering thermodynamic relationships. In general, crystal growth involves first order phase transitions. This means there is a coexistence of two distinct uniform phases that are stable at the equilibrium point and separated by a phase boundary i.e. an interface. Close to the equilibrium point the phases can still exist, one as thermodynamically stable, the other as thermodynamically metastable phase, whereas the metastable phase is supersaturated (super cooled) w.r.t. the stable (equilibrium) phase. As a result, a thermodynamic driving force of crystallization will appear leading at a critical value of supersaturation to spontaneous nucleation of the crystalline phase with in the metastable fluid phase.
Crystal growth methods:
The process of crystal growth is a controlled change of state or phase change, to the solid state. This transition may occur from the solid, liquid or vapor state. Depending on the phase transitions involved in the process, the crystal growth methods can generally be classified into four main categories [4-7] 1) Solid growth (solid-solid) 2) Vapor growth (vapor-solid) 3) Melt growth (liquid-solid) 4) Solution growth (liquid-solid)
The growth of crystals from the liquid phase is treated as two categories due to the independent behaviour of melt and solution.
Growth from solids
Growth from melt The first detailed study of crystal growth phenomenon was by Tamman (1899)who measured the rate of crystal growth of augite from a melt. He found that the rate is zero at the liquidus, increases to a maximum, and then decreases with increasing under cooling (decreasing temp.) Volmer and Marder (1931) developed a simple theory to explain this relationship. Other theoretical work includes that of Eilson (1900) and Frenkel (1932)
Growth in gels: Introduction
A systematic study of crystallization in gels begins with Liesegang’s famous discovery of periodic crystallization in gels. This method has gained considerable attention because of its simplicity and effectiveness in growing single crystal of certain compound. This method is an alternative technique to solution growth with controlled diffusion. This growth process is free from convection. Henisch explained the use f gel to grow the crystals . Chemical reduction, complex dilution and reduction of solubility are the popular methods of crystal growth in gels. Gel media prevents turbulence and helps in formation of crystal by providing a framework of nucleation site. This media is unique place due to its characteristics of suppression of nucleation centre. Optimum conditions are established by varying various process parameters such as pH, concentration of gel solution, setting time of the gel solution and concentration of the reactants. What are gels? The materials which are ordinarily called gels are not only silica gels (e.g. as usually grown from sodium metasilicate), but also agar (a carbohydrate polymer derived from sea weed), gelatin (a substance closely related to proteins), soft soaps (potassium salts of higher fatty acids), a variety of oleates and stearates, polyvinyl alcohol, various hydroxides in water, and even (waterinsoluble) tetraethoxysilene in the presence of electrolytes and co-solvents (e.g. methanol) or surface-active agents (Caslavska and Gron, 1984) A gel (from the lat. Gelu-freezing, cold, ice or gelatus-frozen, immobile) is a solid, jelly-like material that can have properties ranging from soft and weak to hard to tough. Gels are defined as a substantially dilute cross-linked system, which exhibits no flow when in the steady state . By weight gels are mostly liquid, yet they behave like solids due to a three dimensional cross-linked network with in the liquid. It is the crosslink’s with in the
fluid that gives a gel its structure (hardness) and contribute to stickiness (tack). In this way gels are a dispersion of molecules of a liquid with in a solid in which the solid is the continuous phase and the liquid is the discontinuous phase. Composition and types of gels Gels consist of a solid 3D network that spans the volume of a liquid medium and ensnares it through surface tension effects. This internal network structure may result from physical bonds (physical gels) or chemical bonds (chemical gels), as well as crystallites or other junctions that remain intact with in the extending fluid. Virtually any fluid can be used as an extender including water (hydro gels also called aqua gels), oil or an organic solvent (organo gels), and air (aero gels). Both by weight and volume, gels are mostly fluid in composition and thus exhibit densities similar to those of their constituent liquids. Edible jelly is a common example of a hydro gel and has approximately the density of water.
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