A Novel Method to Enhance Metastable Zone Width for Crystal Growth from Solution

A novel method has been found to enhance the metastable zone width of solutions in their supersaturated region in order to grow large size crystals. In which, the incorporation of a small quantity of Ethylenediamine tetra acetic acid (EDTA), a well‐known chelating agent, enhances the zone width significantly due to its chelating action. Also this incorporation reduces the nucleation rate and enhances the growth rate of the crystal. X‐ray rocking curve experiment for the grown crystals reveals that EDTA addition does not affect the crystalline quality. This concept was first realized with Potassium acid phthalate (KAP) solutions and then confirmed with Potassium dihydrogen phosphate (KDP) and Triglycine Sulphate (TGS).     

An Investigation on the Lattice Distortion in Urea and KCl Doped KDP Single Crystals by X‐ray Diffraction Studies

Potassium dihydrogen phosphate (KDP) doped with different mole concentrations of Urea and KCl were grown using low temperature solution growth technique. X‐ray diffraction studies were carried out on the grown crystals using a Shimadzu X‐ray diffractometer with CuKD radiation. X‐ray study revealed that the structures of the doped crystals are slightly distorted compared to the pure KDP crystal. This may be attributed to strains on the lattice by the adsorption of urea and KCl.     

Application of Track Membranes to Fabricate Potassium Dihydrogen Phosphate Microstructures

A method to fabricate insulator microstructures from aqueous solutions using track membranes as a template has been developed by an example of potassium dihydrogen phosphate. It is shown that microstructures are formed in pores of a track membrane under conditions of forced flow of supersaturated crystallization solution through this membrane. These microstructures continue to grow beyond the pore volume, mainly on the membrane side facing the flow. Their transverse sizes and growth direction are determined by the direction and diameter of membrane pores.

     

Growth and properties of dyed KDP crystals

Potassium dihydrogen phosphate (KDP) crystals doped with xylenol orange (XO) and methylthymol blue (MTB) are grown from aqueous solutions by the method of solvent evaporation at room temperature under the conditions of natural convection and by the method of temperature lowering. Studied is the influence of the mother solution acidity on the character of the crystal coloration. The color and coloration intensity of the grown crystals are shown to strongly depend on the solution's pH. It is revealed that the crystal habit changes in the presence of organic dyes. The optical transmission spectra and the luminescence spectra of KDP:XO solutions and of the grown crystals are measured. The effect of thermal treatment and UV‐irradiation on the coloration stability of the crystals is studied. It is found that the laser damage threshold in the prismatic impurity rich colored sectors of KDP:XO is the same as that in the prismatic sectors of pure KDP crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Reduction of crystal surface roughness to augment anti-Caking Properties

Ammonium bromide crystals were grown in quiescent and stirred batch systems and in a continuous laboratory crystallizer at steady state. Urea was added in concentration of 5–20 ppm. The crystals were filtered out, dried, sieved and inspected by Scanning Electron Microscope. The effect of urea was evaluated by comparison between crystals grown by one of the techniques without an admixture and those grown within the presence of urea. In quiescent batch solution pure ammonium bromide crystals grow in fern-like large dendritic forms. Urea suppresses the characteristic branching. Stirring changes the habit into aggregates of small globular crystals. The addition of urea to a stirred batch system causes growth of separate ovoid crystals. In a continuous crystallizer, at steady state conditions seemingly loose agglomerates of ammonium bromide are formed. No change visible at low magnification is brought forward by the addition of urea. However, at high magnifications the crystal surface of the pure ammonium bromide is brush-like and rough, retaining the dendritic tendencies in the range of microscopic sizes. The addition of urea smoothes the surface. The roughness of the pure ammonium bromide surfaces may explain its strong caking tendencies. Reduction of the roughness will probably decrease the caking in the polycrystaline mass. This assumption has to be checked in industrial production.     

Synergy of organic dyes for KDP crystal growth

Single potassium dihydrogen phosphate (KDP) crystals were grown in a supersaturated solution containing an organic dye (sunset yellow FCF, brilliant blue FCF, and sky blue). The growth rate, morphology, and impurity dye distribution of faces, (100) and (101) in a KDP crystal were measured as dye concentration and the supersatutation of KDP were changed. Complete expressions for the effect of dye on all aspects of the growth of KDP crystals were discussed. The growth rates of (100) and (101) faces were well correlated by the empirical equation, and resulted in good estimation of the morphology. The distribution of dye in a KDP crystal was represented by the distribution model containing the minimum growth rate for coloring. The growth rate equation and distribution equation were expressed by functions of the supersaturation and dye concentration, and they could effectively provide the operational conditions with coloring the KDP crystal. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth imperfections in oriented grown KDP crystals by X‐ray topographic analysis

Potassium dihydrogen phosphate (KDP) crystals were restrained to grow in two dimensions only, using a specially designed platform. This enables us to grow the blanks of frequency conversion elements that satisfy type‐II phase matching direction out of a type‐II phase‐matched seed crystal. Synchrotron radiation topography was used to study the growth mechanism of these profiling grown KDP crystals. It is found that both dislocation growth mechanism and layer growth mechanism were involved in the growing process. Inclusions, growth striations and dislocations were the main defects that influenced the crystalline quality of these crystals. High‐resolution X‐ray diffraction was employed to study the lattice integrality of the crystal.     

Growth and thermal studies on pure ADP,KDP and mixed K1‐x(NH4)xH2PO4 crystals

The investigations on the formation of mixed crystals of ammonium dihydrogen orthophosphate (ADP) and potassium dihydrogen orthophosphate (KDP) i.e. potassium ammonium dihydrogen phosphate, K_1‐x(NH₄)_xH₂PO₄ have been presented in this paper. Pure and mixed crystals of ADP and KDP have been grown by slow evaporation technique from the supersaturated solution at an ambient temperature 26±1 °C for ammonium concentration x in the range 0.0 ≤ x ≤ 1.0 in the case of mixed crystals. Crystal compositions were determined by flame atomic absorption spectroscopy and chemical analysis. The results of the X‐ray analysis of the grown crystals are also reported. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the kinetic process of dehydration and the high temperature phase behaviour. DTA showed the distinct thermal events attributed to dehydration of ADP, KDP and K_1‐x(NH₄)_xH₂PO₄. The results of thermal analysis and chemical analysis are consistent with each other. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Habit modification and improvement in properties of potassium hydrogen phthalate (KAP) crystals doped with metal ions

Potassium hydrogen phthalate (KAP) single crystals were grown by slow evaporation and slow cooling techniques. The growth procedure like temperature cooling rate, evaporation rate, solution pH, concentration of the solute, supersaturation ratio etc., has been varied to have optically transparent crystals. Efforts were made to dope the KAP crystals with rubidium, sodium and lithium ions. The dopant concentration has been varied from 0.01 to 10 mole percent. Good quality single crystals were grown with different concentrations of dopants in the mother phase. Depending on the concentration of the dopants and the solution pH value, there is modification of habit. Rubidium ions very much improve the growth on the prismatic faces. The transparency of the crystals is improved with rubidium and sodium doping. The role of the dopants on the non‐linear optical performance of KAP indicates better efficiency for doped crystals. The grown crystals were characterized with XRD, FT‐IR, chemical etching, Vickers microhardness and SHG measurements. The influence of the dopants on the optical, chemical, structural, mechanical and other properties of the KAP crystals was analysed. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Synthesis,bulk growth,polarizability and nonlinear optical properties of γ‐glycine single crystals

The role of sodium acetate, sodium nitrate, sodium hydroxide and malonic acid as additives in assisting the nucleation of γ‐polymorph from solution has been investigated. For the first time large dimensional bulk single crystals of γ‐glycine have been grown at the optimized concentration of the additives by the top seeded slow cooling technique. The bulk growth of single crystals elucidates well the unidirectional growth characteristics and the existence of merohedral twinning in γ‐ glycine. Polarizability, plasmon energy and Fermi energy has been evaluated for the first time for γ‐glycine single crystals based on an analytical approach. Structural affirmation of the nucleated polymorph has been carried out by Powder x‐ray diffraction and the thermal characteristics of the nucleated polymorph are well revealed by Differential Scanning Calorimetry. The non linear optical characteristics of γ‐glycine studied by Kurtz and Perry technique revealed increased SHG efficiency with the highest of about 2.2 in the presence of malonic acid compared to the standard Potassium dihydrogen orthophosphate (KDP).     

Conduction mechanisms in TlSbSe2 chalcogenides

TlSbSe₂ samples used for electrical measurements were cleaved from larger crystals grown by using the Bridgman ‐ Stockbarger method. Electrical properties of the samples are investigated with a view of determining the dominant conduction mechanism. DC conduction studies reveal that Poole – Frenkel conduction is predominant. The DC conduction studies revealed the non‐ohmic type conduction. The activation energies are also calculated. It is seen that the activation energy decreases with increase of applied voltage. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A mechanism for the habit modification of ammonium dihydrogen phosphate crystals in the presence of ionic species in aqueous solution

Ammonium dihydrogen phosphate (ADP) crystals develop new high index faces when grown from aqueous solution containing up to 1000 ppm of added CrCl₃ · 6 H₂O. The crystallographic nature of these faces has been studied as a function of the CrCl₃ · 6 H₂O concentration in the growth solution (24.0°C, σ = 0.06) and their high morphological importance is explained, using a modification of the Hartman-Perdok theory of crystal morphology, but postulating that the adsorption of impurity species at specific sites transform K-faces into pseudo-F-faces.     

Precipitation of sparingly soluble salts in packed sandbeds in the presence of miscible and immiscible organic substances

Sparingly soluble salts precipitation, e.g. calcium carbonate or calcium sulfate, results in pore clogging in rock formations and in the concomitant reduction of the local permeability of oil wells during the oil extraction processes. On the other hand, in situ controlled salt precipitation is desirable in various applications e.g. waterproofing of concrete constructions suffering from leakages, etc. In the present study, calcium carbonate (CaCO₃) precipitation in sandbeds was investigated, in the presence of organic solvents simulating the conditions prevalent in oil‐well zones. CaCO₃ precipitation was investigated from supersaturated solutions prepared by in‐situ mixing of NaHCO₃ and CaCl₂.2H₂O solutions before the inlet of sandbeds. The solution resulting from the mixing of the two solutions was supersaturated with respect to all calcium carbonate polymorphs. Three types of experiments were performed depending on the supersaturated solutions: a) aqueous solutions b) aqueous supersaturated solutions in contact with sandbeds pre‐saturated with n‐dodecane c) aqueous solutions containing monoethylene glycol (MEG). Results showed that oil–water interfaces enhanced the heterogeneity of the supersaturated solutions and accelerated crystal growth of calcium carbonate at the inlet of the sandbed, resulting in early pore clogging and limitation of local permeability. Maximum sandbed consolidation was obtained with the solutions containing MEG.     

Kinetics of crystal growth of mirabilite in aqueous supersaturated solutions

The crystallization of sodium sulfate decahydrate (Na₂SO₄·10H₂O, mirabilite) from supersaturated solutions was investigated using stable supersaturated solutions seeded with mirabilite seed crystals. The experiments were done in batch, stirred reactors in which the supersaturated solutions were prepared either by dissolution of sodium sulfate anhydrous at 32 °C followed by cooling to 18 or 20 °C or by mixing equal volumes of equimolar ammonium sulfate and sodium hydroxide solutions at 20 °C. Inoculation of the solutions supersaturated only with respect to mirabilite with seed crystals was accompanied with temperature increase of the thermostated solution. Despite the fact that crystal growth was initiated with seed crystals, the process started past the lapse of induction times inversely proportional to the solution supersaturation. The rates of crystal growth were measured both from the temperature rise and from the concentration–time profiles, which were linearly correlated. The measured crystal growth rates showed a parabolic dependence on supersaturation at low supersaturations. For higher values this dependence changed to linear, a behavior consistent with the BCF spiral crystal growth model. The morphology of the crystals growing at 20 °C showed typical prismatic habit, while at 18 °C when crystallized from cooled sodium sulfate solutions changes in the crystal habit to a leaf like morphology were observed.     

Distribution of metallic ions in a single KDP crystal grown from aqueous solution

A single KDP (potassium dihydrogen phosphate) crystal was grown in a supersaturated solution containing a metallic ion (Al³⁺, Fe³⁺, or Cr³⁺). The growth rate, morphology, and distribution of the metallic ions into the KDP crystal were measured as the ionic concentration and supersaturation in the solution changed. It was found that in the KDP crystal, Al³⁺ and Fe³⁺ were greatly concentrated, but Cr³⁺ was diluted. Complete expressions for the effect of metallic ions on all aspects of the growth of KDP crystal were suggested. The growth rates of (100) and (101) faces were well correlated by the empirical equation and resulted in good estimation of morphology. The distribution of metallic ions into KDP crystal was also correlated by the distribution model. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enhancement of stability of growth,structural and NLO properties of KDP crystals due to additive along with seed rotation

Potassium Acetate (CH₃COOK) and Potassium Citrate (K₃C₆H₅O₇) as new additives were added into the potassium dihydrogen phosphate (KDP) solutions in different molar ratios. The metastable zone width and induction period with and without these additives were determined and compared. Dielectric measurements on pure and doped KDP crystals at various temperatures ranging from 313 to 423 K were carried out by the conventional parallel plate capacitor method which results low dielectric constant value dielectrics in doped crystals. The high resolution XRD studies show that CH₃COOK doped KDP crystal and K₃C₆H₅O₇ doped KDP crystal do not contain any internal structural grain boundaries and indicates that the crystalline perfection is very good. Moreover, the addition of these potassium additives improves the quality of the crystal and yields highly transparent crystals with well defined features. The effect of additives on the growth, nucleation kinetics, structural, NLO and optical properties has been investigated. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase transformation in the system TlBi(Te1‐xSex)2

TlBiTe₂ and TlBiSe₂ ‐ that are ternary analogs of the IV‐VI semiconductors ‐, although they crystallize in the same space group R m (D⁵_3d), exhibit different behaviour during heating. The observed phase transformation depends on Se content (x) in the system TlBi(Te_1‐xSe_x)₂ and the transformation disappears by increasing Se content after a certain value (x = 0.25). This dependence is examined through the analysis of the DSC non‐isothermal measurements and an attempt for the explanation of the observed behaviour is undertaken through the consideration of off‐center atoms. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of the temperature and the oxygen partial pressure on the phase formation in the system Cu – Fe – O

Copper iron oxides, Cu_1‐xFe_2+xO₄ (0 ≤ x ≤ 0.5), have been synthesized by thermal oxidation of copper ‐ iron mixtures. In this process, the phase formation and the phase stability were investigated as function of the temperature (800°C – 1200°C) and the oxygen partial pressure (1.013 x 10¹ – 1.013 x 10⁵ Pa). The phase formation starts with the reaction of the metallic components to simple oxides (Fe₃O₄, Fe₂O₃, CuO). From these simple oxides, the formation of complex oxides requires a minimum temperature of 800°C. The synthesis of single phase spinel compounds Cu²⁺_1‐2x Cu¹⁺_xFe_2+xO_4±δ is realized for 0.1 ≤ x ≤ 0.5, using specific temperature – p(O₂) – conditions for a given value of x. Remarkably, to achieve our goal, we found that the increase of x implies that of the reaction temperature and/or a decrease of the p(O₂) in the reaction gas stream. Besides, a single phase spinel CuFe₂O₄ does not exist in the temperature / p(O₂)‐field investigated. Using the results of XRD ‐ phase analysis, T ‐ p(O₂) – x – diagrams were constructed. These diagrams allow the prediction of phase compositions expected for different synthesis conditions. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and electrical characterization of L‐arginine added KDP and ADP single crystals

Potassium dihydrogen orthophosphate (KDP) and ammonium dihydrogen orthophosphate (ADP) single crystals added with L‐arginine have been grown by the solution methods. DC and AC electrical measurements were carried out at various temperatures along both a‐ and c‐ directions. Results indicate an increase of the electrical parameters with the increase of temperature which can be attributed mainly to the increase of thermally generated hydrogen bond vacancies (L. defects). Also, the present study indicates that L‐arginine addition leads to reduction of electrical parameters of KDP and ADP single crystals which can be attributed mainly to the decrease of L‐defects due to creation of additional hydrogen bonds by the impurity in random directions. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth,spectral and thermal properties of KAP single crystals in the presence of DL‐Alanine and L‐Methionine amino acid dopants

Single crystals of potassium acid phthalate (KAP) and amino acid (DL‐Alanine, L‐Methionine) doped KAP were grown from aqueous solutions by slow cooling method. The grown crystals were characterized using powder X Ray diffraction (XRD) and Fourier Transform Infrared (FTIR) analysis. The thermal stability of KAP in the presence of dopants was analysed using Thermogravimetric and Differential Scanning caloriemetric (TGA/ DSC) studies and the maximum temperature for non linear optical application of this compound in the presence of dopants was found out. The transmittance of KAP was found to increase in the presence of dopants. Etch pits were observed for all the crystals using different etchants. Vickers microhardness tests were performed to study the mechanical stability of the crystals. The hardness of DL‐alanine doped KAP is more than that of L‐alanine doped KAP crystal. The dielectric constant and loss were determined as a function of temperature. Frequency response of the dielectric constant and dielectric loss factor have been studied over the frequency range of 50Hz – 5MHz. Second harmonic generation (SHG) was confirmed in all the crystals using the Kurtz and Perry powder technique. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)