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Crystal Growth by Sol Gel Method: A Historical Review The latest developments in the field like high temperature optical spectroscopy, high-voltage electron microscopy, laser annealing techniques, new laser techniques for fast and accurate measurements of growth rate, computer solutions of problems in liquid flow, and of heat and mass transfer etc. have caused immense increase in our knowledge as to how crystals grow and have transformed 'crystal growth' into a pure branch of science. Now, technological progress in this branch of science is such that it is possible to prepare pure, defect-free, economically viable and shapely crystals which are preferred by scientists. The earliest use of colloids to prepare functional materials is seen in the cave painting at Lascaux in France, dating back 17,000 years. The pigments used were based on iron oxide, carbon and clays, ground into fine powders, graded by sedimentation and dispersed in water using natural oils as surface active stabilisers. In the 19th century two major developments occurred which were to prove foundation stones for solgel processing: the physical properties of colloids came under intensive study by such giants as Becquerel and Faraday (his gold sols were so stable that they are still in existence at the Royal Institution in London); and the chemistry became very sophisticated. In 1846 Ebelmen [i] prepared the first silicon alkoxides by the reaction between silicon tetrachloride and alcohol, observing that the product gelled on prolonged exposure to atmosphere with normal humidity. In 1876 Troost and Hautefeuille [ii] made hydrolysed derivates of silicon alkoxides. In 1884 Grimaux [ iii] hydrolysed tetramethoxysilane to prepare silicic acid sols, and made colloidal iron oxides from iron alkoxide. However, for the next 50 years these developments had little scientific impact for the development of the sol-gel materials field. The one notable exception in this period was the work of W.A. Patrick, who pioneered the field of silica gel desiccants, catalysts and absorbent materials, starting with the drying and firing of a homogeneous silica gel at up to 700C to produce a very porous form of silica [ iv]. In 1923 he went on to show that impregnation of the partially dried materials with metal salts led to the formation of supporting catalysts [v], and by 1930 he had filed many patents for supporting catalysts, including the use of sol-gel methods [vi]. This signaled the beginning of an intensive period of technological development using sol-gel methods, which produced a very large number of patents, many useful materials, and a large body of data and experience. Only later, with the advent of modern characterisation methods, could a set of firmly-based theoretical principles begin to be established to interpret all these data. Indeed it could be said that despite the new methods now available, the subject is still strongly influenced by this empirical approach. It is therefore important that the large amount of early work in the field is not overlooked, only to be re-discovered as the topics attract interest for a new reason The growth of crystals in gel media is a relatively old method of crystal growth that gained some prominence about 60 years ago. Much of the earlier work on the subject has been reviewed by Holmes vii .After this initial interest the subject remained nearly dormant, except as a curiosity, until a paper by Henisch et al viii revived interest in this type of crystal growth. Since then, approximately 100 papers have been published on the subject. The most commonly used medium is silica gel. Numerous other gels have been used but with limited success, apparently because of the structural differences in the gels. A more detailed description of the

various gels is given by Henisch? There are several chemical requirements that must be fulfded to grow crystals by this method. First, the reactants employed must be soluble in the solvent (usually water), and the product must be relatively insoluble in the same solvent. Some solubility of the product crystal is required to grow crystals of appreciable size. While it is believed that this is related to supersaturation of the product, the exact mechanism is not yet understood. A second requirement is that the gel must remain stable in the presence of the reacting solutions and must not react with these solutions or the product formed. Silica gels are most stable in acid solutions and tend to dissolve at pH values much greater than 8. This can create problems with chelating agents, since these agents are most useful in highly basic solutions where the gel is unstable. If the pH is only slightly higher than 8 (up to 10) some crystals may still form, but the gel near the alkaline solution gel interface will start to decompose and sometimes one must race with time to get the crystals grown and out of the gel before the gel itself dissolves. The influence of the gel in crystal growth is not fully understood. It appears that the main effect of the gel is to slow down the rate of diffusion, which allows the crystal to grow at a slower rate. It is generally believed that the gel does not actually react with the solutions involved, but there is a possibility that it may have some effect on the degree of saturation that is attainable in the solution. The role the gel plays on the nucleation process is also unknown, but some observations on nucleation have been made by Henisch and Armington et al ix The procedure for growing crystals in gels has been known since the end of the last century, tut the method had fallen into virtual oblivion until it was revived by modern interest in these materials, and more generally, in the room temperature method. The importance of this method lies in the simplicity with which strain-free perfect crystals can be obtained at low temperatures. Apart from stabilizing the patterns of concentration gradients in the neighbourhood of the growing crystal by suppressing the convection currents, an important function of the gel medium is the suppression of nucleation. The gel acts as a "three-dimensional crucible" which supports the crystal and at the same time, yields to its growth without exerting major forces upon it. 2 Sol-gel process Flow: Sol-gel synthesis encompasses a wide range of organic, inorganic and organic-inorganic porous materials which share a common preparation strategy. Sol-gel process means the synthesis of an inorganic network by a chemical reaction in solution at low temperatures or it also means the formation of an amorphous network in opposition to the crystallization process from the solution. The most obvious feature of this reaction is the transition from a colloidal solution (liquid) into a di or multi phase gel (solid) that led to the expression Sol-gel process. The first step of any sol-gel process consists in selecting the precursor of the required material. It is the precursor that, by its chemistry, leads the reaction towards the formation of colloidal particles. The precursors for synthesizing these colloids consist of a metal or metalloid element surrounded by various reactive ligands. Also, alkoxides are most popular because they react readily with water. The most widely used alkoxides are the alkoxysilanes, such as tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS). However, other alkoxides such as methyltrimethoxysilane (MTMS) and methyltriethoxysilane (MTES) are also commonly used in the sol-gel process. Compared to the precursors of other elements, the network forming power of the Si is more to build up a gel. Moreover, silicon is the most abundant material in the earths crust and its oxide is well known material in naturally occurring crystalline and amorphous states. The evidence of silicate hydrolysis and condensation to form polysilicate is seen in many natural systems like opals and agates [x]. Therefore, the silica precursors are mostly used for the preparation of the alcogels. The most of the work in the sol-gel field has been done by the use of alkoxides as precursors because

the alkoxide precursors provide a convenient source for "inorganic" monomers which in most cases are soluble in common solvents. Another advantage of the alkoxide route is the possibility to control the reaction rates by controlling the hydrolysis and condensation by chemical means (and not by surface or colloid chemistry). The main compounds which come under this category are silicon alkoxides e.g. Si(OR)4, where R= CH3, C2H5 [8-9] and silicon tetrachloride (SiCl4). The general hydrolysis and condensation reactions of silicon alkoxide precursors are given below: Hydrolysis: M X + H2O M OH + HX (1.1) M = metal or Si ; X = reactive ligand like halogen, OR, NR2, acylates Condensation: Alcohol condensation: M OH + XM M O M + HX (1.2) Water condensation: M OH + HOM M O M + H2O (1.3) The chemistry of processes like this should be more easily to be controlled than the colloid chemistry phenomena like surface charges or species adsorbed on the surfaces of particles. It means that at least within the first step of the reactions, the alkoxide route or better spoken, the route of using latent reactive monomers could be advantageous compared to the route using colloids as starting materials. Another advantage of the latent monomer route is the solubility of these monomers (e.g. alkoxides, halogenides, acylates) in a variety of organic solvents especially alcohols. Alcohols enable a convenient addition of water to start the hydrolysis reaction. 2.1 Sol A sol is a dispersion of colloidal particles suspended in Brownian motion within a fluid matrix. Suspension of particles of linear dimensions between 1nm (10 Ao) and 1m (104 Ao) are called colloids [xi]. The particles in this proper size range can be divided into three categories. They can be either composed of subdivided parts of bulk mater (e.g. small particles of -alumina), or real macromolecules that are big enough to be colloidal (such as proteins), or of small particles that can be considered both macromolecules and as tiny parts of macroscopic matter (e.g. lacy particles). In the case of subdivided parts of bulk material, there are two thermodynamic phases and the sol is considered as lyophobic, or hydrophobic if water is the main solvent used. The formation of uniform suspensions of colloidal particles can be understood by calculation of the sedimentation rates assuming that the particles are spherical so that Stokes law can be applied. Sedimentation rate, dx/dt = [(4r3/3) (- ) g] / 6 r = [2r2 (- ) g] / 9 (1.4) Where, = Viscosity of surrounding medium r = radius of colloid particle = Density of colloid particle material = Density of surrounding material For a sol to exist, the solid particles, denser than the surrounding liquid, must be small enough for the forces responsible of dispersion to be greater than those of gravity. Moreover, these particles must include a number of atoms macroscopically significant. In fact, if the particles were too small, then it would be more accurate to speak of molecules in solution. Originally, colloid only referred to macroscopic particles that could not pass through a dialysis membrane. This definition, however, did not give the accurate values of the size ranges of the particles concerned. Therefore, the characteristics feature of colloidal system lies in relative importance which is attached to the various physico-

chemicals properties of the systems being studied. The factors which contribute most to overall nature of colloidal system are: a) Particle size b) Particle shape and flexibility c) Surface properties d) Particle-particle interactions e) Particle-solvent interactions 2.2 Gel A gel is a porous 3-dimentionally interconnected semi-solid network that expands in a stable fashion throughout a liquid medium and is only limited by the size of the container. If the solid network is made of colloidal sol particles, the gel is said to be colloidal. If the solid network is made up of subcolloidal chemical units then the gel is polymeric. A polymer, as defined by the Flory is a group of molecules whose structure can be generated through repetition of one or a few elementary units [xii]. The nature of gels depends on the coexistence between the solid network and the liquid medium. Several remarks, therefore, have been made on the equilibrium. The liquid is present between the mesh of the solid network that composes the gel; it does not flow out spontaneously and is in thermodynamic equilibrium with the solid network. If the liquid is mostly composed of water, and if that aqueous phase is present in more proportion, then the corresponding gel is an aquagel or hydrogel. An aquagel is a soft material that can be easily cut with a knife. If the liquid phase is largely composed of an alcohol then the gel is an alcogel. 2.3 Gelation Gelation occurs when links form between silica sol particles, produced by hydrolysis and condensation reactions, to such an extent that a giant spanning cluster reaches across the containing vessel. At this point, although the mixture has a high viscosity so that it does not pour when the vessel is tipped. Many sol particles are still present as such, entrapped and entangled in the spanning cluster. This initial gel has a high viscosity but low elasticity. Following gelation, further cross-linking and chemical inclusion of isolated sol particles into the spanning cluster continues, leading to an increase in the elasticity of the sample. Precise definition of the term gel-point is the time interval starting from the moment of sol preparation to the moment no more fluidity of the sol [xiii]. Under controlled conditions, the pH change reduces the electrostatic barrier to agglomerate and promotes the formation of the 3D network. Before the gel point, the colloidal solution can be stabilized and used directly to coat various substrates by classical techniques like dip coating, spin coating, or spray coating. This provides a low cost and efficient way to produce nanometric thin films with good homogeneity. Colloid is a system of two distinct phases in which one phase (solid/liquid) is divided into fine particles (called colloidal particles) and dispersed throughout in a second phase. This system is called a colloidal system, colloidal solution or colloidal dispersion. For example, fog, smoke, homogenized milk and ruby colored glasses are some of the examples of the colloidal systems. The colloidal particles are larger in size (1 to 1000 nm) than the molecules of the dispersion medium but too small to be observed with an optical microscope. However, their shape and size can be determined by an electron microscope. The Scottish chemist Thomas Graham [xiv] found that certain materials, which are dispersed through the solvent, are very much larger than the molecules of the solvent, such systems are called as colloidal dispersion. The following two conditions are essential to form a colloidal dispersion of a solid in a given liquid. (a) The solid must be insoluble in the liquid. (b) The solid must have certain definite size of the particles. Hence, depending upon the particle sizes the solutions are classified into

three types as, (1) True solution (common salt dissolved into water) (2) Colloidal solution (3) Suspension 2.4 Gel Growth Methods Crystal growth in gel has been mainly divided into the following five different methods: 1. Reaction Method. 2. Chemical Reduction Method. 3. Complex Decomplexion Method. 4. Solubility Reduction of solubility. 5. Electrolytic Method. 2.4.1 Crystal Growth by Reaction Crystals which are insoluble or slightly soluble in water and decompose before reaching their melting points can be conveniently grown by this method. The basic requirements to grow single crystals by this method are, (1) The reactants used must be soluble in the solvent (usually water) and the product crystal must be relatively less soluble. (2) The gel must remain stable in the presence of the reacting solutions and must not react with these solutions or with the product formed. (3) Some solubility of the product crystal is needed in order to grow crystals of any size. xv Two aqueous solutions of soluble salts are suitably chosen and allowed to diffuse through the gel, so that there can be a slow and controlled segregation of ions and molecules resulting into the precipitation of an insoluble phase as the crystal. The gel affords to limit the number of critical size nuclei and decreases the rate of crystal growth either by controlling the diffusion of reacting ions or by governing the reaction velocity on the surfaces of the growing crystals. 2.4.2 Chemical Reduction Method This method is suitable for growing only metal crystals from gel media. Hatschek and Simons19xvi were the first to report the growth of gold crystals by adding 8 % oxalic acid solution over a set gel containing gold chloride solution. By this particular method crystals of Nickel, Cobalt, Selenium, Lead and Copper have been obtained. 2.4.3 Complex Decomplexion Method This method requires first forming a chemical complex of the material of the crystals to be grown with aqueous solutions of some suitable substance, called complexing agent, in which the former is homogeneously mixable and then providing externally a condition conducive to de-complexing or dissociation of the complex formed. A standard procedure adopted for decomplexion is to increase the dilution steadily, while complex solution is diffused through the gel. Crystal growth by this method was first attempted by O Connor et al xvii for the growth of cupric halide crystals.

2.4.4 Solubility Reduction Method In this method, the substance to be grown is dissolved in water and is incorporated with the gel forming solution. Then a solution, which reduces the solubility of the substance is added over the set gel to induce crystallization . For instance, potassium dihydrogen phosphate (KDP) crystals have been grown by adding ethyl alcohol over the gel containing a saturated solution of KDP xviii. Crystals are grown due to the reduction of solubility of KDP in the liquid phase by the diffusing alcohol. This method is applicable to grow single crystals of highly water-soluble substances. The growth of ammonium dihydrogen phosphate (ADP) single crystals by this method has been first reported by Gloker and Soest. xix 2.4.5 Electrolytic Method The electrolytic method can also be used for the growth of metallic crystals by selecting the gel medium for controlled growth. In this method a very low d.c. electric current, usually of the order of 210 mA, is passed through a silica gel charged with suitable acid or electrolytic solution. 3 Advantages of sol-gel process ~ The temperature required for all stages apart from' densification are low, frequently close to room temperature. Thus thennal degradation of both the material itself and any entrapped species is minimized, and high purity and stoichiometry can be achieved. ~ Precursors such as metal alkoxides and mixed alkyl! alkoxides are frequently volatile and easily purified to very high levels (e.g., by distillation or sublimation) using techniques developed for the microelectronics industry. This fiuther contributes to high purity products. ~ Since organometallic precursors involving different rretals are frequently miscible, homogeneous controlled doping is easy to achieve. ~ The chemical conditions are mild. Hydrolysis and condensation are catalyzed by acids and bases, but extreme pH conditions may easily be avoided, especially by the use of "two step" methods in which acid catalyzed hydrolysis is followed by rapid neutralization or buffering. In this way pH sensitive organic species (e.g. dyes) and even biological species including enzymes and whole cells may be entrapped and still retain their functions. ~ Highly porous materials and nanocrystalline materials may be prepared in this way. ~ By appropriate chemical modification of the precursors, control may be achieved over the rates of hydrolysis and condensation, and over colloid particle size and the pore size, porosity and pore wall chemistry of the final material. ~ Using functionalised precursors, covalent attachment of organic and biological species to porous silicate glass structures is possible. ~ By controlling the ageing and drying conditions, further pore sIZe and mechanical strength control may be achieved. ~ By using organometallic precursors containing polymerisable orgaruc ligands, materials may be produced which contain both inorganic and organic polymer networks. ~ Entrapped organic species may serve as templates for creation of pores with controlled size and shape. Subsequent removal of these species (for example by heat or strong acid treatment) leaves "molecular footprints" with potential as catalytic sites. ~ Since liquid precursors are used f is possible to cast ceramic materials in a range of complex shapes and to produce thin films or fibres as well as monoliths without the need for machining or melting.

~ The optical quality of the materials is often good, leading to applications for optical components. ~ The low temperature of sol-gel process is generally below the crystallization temperature for oxide materials, and this allows the production of unusual amorphous matetials xx,xxi 4 Limitations Of Sol-Gel Process Despite all these advantages, sol-gel materials are not without limitations. The precursors are often expensive and sensitive to moisture, limiting large scale production plants to specialized applications such as optical coatings. The process is also time conswning particularly where careful ageing and <hying are required. Although this need not be a limiting factor where long continuous production runs are envisaged, it does mean that the total volume of material in the processing line is inevitably significantly higher than in faster processes. Finally the problem of dimensional change on densification, and of shrinkage and stress cracking on <hying, although not insuperable, do require careful attention. These significant limitations emphasize the need to optimize the sol-gel materials to exploit their advantages to the maximum in applications where they can provide properties not attainable by other methods vi,v, 5 Review on the Tartrate crystals grown by gel Sol-Gel method Most of the tartrate compounds are in soluble in water and decompose before melting. Hence single crystals of such type of compounds cannot be grown by either slow evaporation or melt technique. In this situation gel method is the appropriate one for their growth. The growth of single crystals oh Calcium tartrate was reported [xxii] and single crystals of strontium tartrate was reported [xxiii].thermal studies on tartrate crystals grown by gel method were reported by many investigators [ xxiv,xxv,xxvi]. Tartrate crystals are of considerable interest, particularly for basic studies of some of their interesting physical properties. Some crystals of this family are ferroelectric [xxvii,xxviii,xxix], some others are piezoelectric [xxx] and quite a few of them have been used for controlling laser emission [xxxi]. As tartrates are sparingly soluble in water and decompose before melting, the gel method is found to be more promising than the high temperature crystal growth methods. Many tartrates salts with monovalent cations; such as rubidium hydrogen tartrate [xxxii], sodium tartrate [xxxiii], and ammonium tartrate [xxxiv] and divalent cations; such as calcium tartrate [xxxv], cadmium tartrate [xxxvi], manganese tartrate [xxxvii], zinc tartrate [xxxviii] and strontium tartrate [xxxix,xl] have been studied for their dielectric and thermal properties. Mixed crystal of tartrate have several applications in medicine, optics etc. and hence; it was thought work while to undertake investigation on growth of crystals of mixed tartrate and their characterization by different methods. The purpose of the present paper is to report for the first time (to the best of our knowledge) the growth of mixed single crystals of Calcium Barium tartrate in silica gel at ambient temperature.
The formation of crystals of potassium acid tartrate in silica gels was described by Holmes (1917) xli. He reported that when a gel, made from equal volumes of 1.16 sp gr sodium silicate and 3N tartaric acid, was covered with a dilute solution of a potassium salt, blocks 5 mm wide formed and ". . . in several hours crystals of notable size could be counted on. Changing the concentrations somewhat, wide-branching fern growths were obtained". Holmes' experiment was repeated, using four different 1.16 sp gr sodium silicates. In each instance, volunteer sodium acid tartrate crystals, NaHC4H4O6.H2O, formed in the gel before any external reactant was placed on the gel. All four gels contained axialities of NaHT.H2O. One gel contained free H2T and no Na2T; the volunteer growths in it were unsymmetrical axialities. The three other gels contained no free H2T

and only small amounts of Na2T; in these, NaHT.H2O crystals volunteered as symmetrical axialities. This acid salt formed also in other 3N tartaric acid 1.10 to 1.20 sp gr sodium silicate gels, but not in gels made with 1.08 or lower sp gr silicate solutions. Therefore, it is concluded that Holmes' figure of 1.16 for the specific gravity of his sodium silicate is a typographical error.
PHILIP F. KURZ xliiinvestigated the methods for growing potassium acid tartrate (KHT) crystals by chemical reaction in acidic gels prepared with tartaric acid (H2T) and sodium silicate and reacted with K+. H2T ranging from IN to 18N was used, and remarkable changes in size and perfection of shape of KHT crystals formed were noted as the concentration of H2T was increased. KC1, KBr, KNO3, and K2SO4 appear equally useful as external reactants. KI permits growth of excellent crystals also, but forms HI, which reduces tartrate progressively to malate and succinate, releases I2, and produces an increasingly intense background color. K2Cr04 consumes tartrate in redox and prevents KHT formation. Potassium acetate causes gel cleavage and produces multitudes of clusters of tiny needles.

Objectives of the present work To prepare titania, transition metal as well as rare earth metal incoIporated titania catalysts through particulate so~ gel route. To investigate the surface properties of the prepared systems by techniques such as XRD, TGIDTG, FTIR., SEM, UV-Vis DRS and BET surface area-pore volume measurements. To explore the surface acidic properties of the prepared catalysts using various independent techniques such as TPD of ammonia, TG analysis of adsorbed 2,6-DMP and test reactions like cumene cracking and cyc1ohexanol decomposition. To study the catalytic activity of the systems towards liquid phase epoxidation of cyclohexene as well as hydroxylation of phenol. To study the catalytic activity of the prepared systems ID the industrially important alkylation reactions such as tert-butylation of phenoL methylation of aniline and anisole. To evaluate the catalytic activity of the prepared systems towards the dehydrogenation of cyclohexane and cyc1ohexene. Effect of various parameters like gel pH, and gel aging, gel density and concentration of reactants on the growth of these crystals were studies. Crystals having different morphologies and habits were obtained.The crystals grown were characterized by PL, SEM, and UV. XRD studies reveal that the crystal lattice of the Calcium Barium tartrate is orthorhombic and crystalline perfection of the crystals is extremely good. Photoluminescence spectrum shows Cyan, green, orange, and red emissions. SEM image showed plate like morphology and further plate like growth was observed on some plates.

i J.J. Ebelman, Ann. Chim. Phys., 16, 129 (1846) ii L. Troost and P. Hautefeuille, Ann. Chim. Phys., 7, 452 (1876) iii E. Grimaux, Bull. Soc. Chim., 41, 50, 157 (1884)

iv W.A. Patrick, Silica gel and process of making same U.S. patent 1,297,724 (1919) v W.A. Patrick, Catalyst British Patent 208,656 (1923) vi (a selection) W.A. Patrick, Adsorbent and catalyst oxides U.S. Patent 1,520,305 (1924); Porous catalytic gels U.S. Patent 1,577,186 (1926); Gels for catalytic and absorbent purposes U.S. Patent 1.577,190 (1926); Tungstic oxide gel U.S. Patent 1,682,239 (1928); Stannic oxide gel U.S. Patent 1,682,240 (1928); Aluminum oxide gel U.S. Patent 1,682,241 (1928); Titanium oxide gel U.S. Patent 1,682,242 (1928); Catalytic and absorbent gel U.S. Patent 1,696,644 (1928); Tungsten oxide gel U.S. Patent 1,848,266 (1932) vii Holmes, H. N. (1917) J.Phys. Chem. 21, 709
viii H HEKTISCH, J DENNIS, J HANOKA, "Crystal growth in gels", Journal of Physics and Chemistry of Solids - J PHYS CHEM SOLIDS , vol. 26, no. 3, pp. 493-496, 1965 ix H. K. Henisch, Crystal Growth in Gels, The Pennsylvania State University Press, University Park, London, UK, 1970.

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September, 1969

III. FORMATION OF POTASSIUM ACID TARTARATE CRYSTALS, THE OHIO JOURNAL OF SCIENCE 69(5): 296,

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