Periodic crystallization of barium oxalate in silica hydrogel

The experimental conditions for obtaining periodic crystallization of barium oxalate in silica hydrogel are investigated. The Liesegang rings formed by the reaction of oxalic acid and barium chloride are studied. The dependence of velocity constant and the spacing coefficient on pH, concentrations of inner and outer electrolytes and temperature have also been studied and a possible mechanism for the behaviour is suggested. The deviations from Isemura’s general observations are interpreted by considering the microcrystals constituting the rings and the irreversibility of inner and outer electrolytes.     

Growth and study of barium oxalate single crystals in agar gel

Barium oxalate was grown in agar gel at ambient temperature. The effect of various parameters like gel concentration, gel setting time and concentration of the reactants on the growth of these crystals was studied. Prismatic platy shaped spherulites and dendrites were obtained. The grown crystals were characterized by X-ray powder diffractometry, infrared spectroscopy, thermogravimetric and differential thermal analysis. An attempt is made to explain the spherulitic growth mechanism.     

Growth of single crystals of some complex salts in silica gels

Single crystals of ammonium nickel sulphate, potassium nickel sulphate, ammonium alum and potassium alum are grown in sodium-metasilicate gels. The method of gel preparation and growth procedure are described. Both single diffusion and double diffusion methods are used. Studies on nucleation and characterisation of crystals are also reported. Crystals grown are illustrated.     

Structural characterization of gel-grown neodymium copper oxalate single crystals

Sparingly soluble neodymium copper oxalate (NCO) single crystals were grown by gel method, by the diffusion of a mixture of neodymium nitrate and cupric nitrate into the set gel containing oxalic acid. Tabular crystal, revealing well-defined dissolution figures has been recorded. X-ray diffraction studies of the powdered sample reveal that NCO is crystalline. Infrared absorption spectrum confirmed the formation of oxalato complex with water of crystallization, while energy dispersive X-ray analysis established the presence of neodymium dominant over copper in the sample. X-ray photoelectron spectroscopic studies established the presence of Nd and Cu in oxide states besides (C₂O₄)²⁻ oxalate group. The intensities of Nd (3d _5/2) and Cu (2p _3/2) peaks measured in terms of maximum photoelectron count rates also revealed the presence of Nd in predominance. The inductively coupled plasma analysis supports the EDAX and XPS data by the estimation of neodymium percentage by weight to that of copper present in the NCO sample. On the basis of these findings, an empirical structure for NCO has been proposed. The implications are discussed.     

Surface topographical studies of prism faces of barium copper oxalate single crystals

The present paper reports observations made on microstructures of gel-grown barium copper oxalate crystals. Growth spirals, growth layers, liquid inclusions and growth of microcrystallites are described and discussed in relation to the mechanism and conditions of crystal growth.     

Growth and characterization of glycinium oxalate (GOX) single crystals

Glycinium oxalate (GOX) single crystals were grown by slow cooling solution growth method. The X-ray diffraction and Fourier transform infra red studies confirm the grown crystal. The hardness values of GOX are found to be higher than glycine. The increase in hardness may be due to the C-H---O bonding. The UV-Visible studies show that GOX crystals can be used for nonlinear applications. The dielectric measurement indicates that the GOX crystals have domains of varying sizes and varying relaxation time. The SHG output of GOX was 210 mV at given pulse energy of 5 mJ/s and KDP was 240 mV.     

Growth and physico chemical characterization of lanthanum neodymium oxalate single crystals

Single crystals of lanthanum neodymium oxalate (LNO) are grown in sodium meta silicate gels, by the diffusion of a mixture of aqueous solutions of lanthanum nitrate and neodymium nitrate into the test tube having the set gel containing oxalic acid. The bluish pink coloured tabular crystals of LNO having well defined hexagonal basal planes appear either as ‘foggy’ or ‘clear’, the latter at the greater depths inside the gel. The colouration of LNO visually observed is evidenced in UV-visible spectrum, by the revelation of well pronounced characteristic peaks in the visible region (500–900 nm). X-ray diffraction (XRD) of powdered LNO is ordered, meaning crystalline in nature, besides its ‘isostructurality’ with similarly grown lanthanum samarium oxalate crystals. The single crystallinity of LNO is established by its oscillation XRD pattern. Thermogravimetric analysis (TGA) and differential scanning colorimetry (DSC) support that LNO loses water of crystallization around 120°C and CO and CO₂ around 350–450°C, while the infrared absorption (IR) spectrum of LNO establishes the presence of oxalate (C₂O₄)²⁻ ions. Energy dispersive X-ray analysis (EDAX) confirms the presence of La and Nd in the sample. X-ray photoelectron spectroscopic (XPS) studies of LNO establish the presence of La and Nd in their respective oxide states. An empirical structure for LNO has been proposed on the basis of these findings. The ‘smokiness’ in the foggy LNO crystal has been attributed due to the ‘gel inclusion’ during the growth process.     

Characterization and thermal behaviour of lanthanum tartrate crystals grown from silica gels

Results obtained on characterization of lanthanum tartrate crystals, grown by the gel method, using chemical analysis, x-ray and electron diffraction, infra-red and mass spectroscopy are reported. The thermal behaviour is studied using DTA, TGA and DTG. The decomposition pattern is reported to be typical of a hydrated metal tartrate. Kinetic parameters like order of reaction, frequency factor and activation energy are evaluated. Contracting cylinder kinetic model is found to be the best fit for the decomposition processes involved. Magnetic susceptibility measurements indicate the material to be diamagnetic.     

Growth and characterization of rare-earth mixed single crystals of samarium barium molybdate

Molybdate crystals doped with rare-earth ions are finding immense use as laser materials. Rare-earth mixed single crystals of samarium barium molybdate grown in silica gel are important for use in optical equipment and electronic and acoustic studies. These octahedral bipyramidal crystals of samarium barium molybdates are characterized by IR, EDAX and thermal analyses.     

Growth,characterization and dielectric property studies of gel grown barium succinate single crystals

. Single crystals of barium succinate (BaC4H4O4) were grown in silica gel medium using controlled chemical reaction method. Plate-like single crystals of size up to 3 × 2 × 0·2 mm³ was obtained. Single crystal X-ray diffraction (XRD) studies confirmed that structure of the title compound is tetragonal. Powder X-ray diffraction (PXRD) pattern of the grown crystal and the Fourier transform infrared (FT–IR) spectrum in the range 400–4000 cm^–1 are recorded. The vibrational bands corresponding to different functional groups are assigned. Thermal stability of the grown crystals is confirmed by differential scanning calorimetry (DSC). Dielectric constant and dielectric loss have been calculated and discussed as a function of frequency at different temperatures.     

Growth of strontium tartrate tetrahydrate single crystals in silica gels

Growth of single crystals of strontium tartrate tetrahydrate by controlled diffusion in silica gels has been narrated. In the field of material science, there is always a keen and competitive race to grow perfect single crystals with sufficient purity and perfection. Successful attempts to larger as well as more perfect crystals of SrTr are described in this paper and thus probably the largest (about 2 in. across) ever grown size of gel-grown products is reported here. The effect of several parameters, e.g. crystallization apparatus, environmental temperature, reactant concentration, gel density, gel-ageing and gel pH, on the size, quality and morphology of the crystals has also been studied.     

Some structural aspects of neodymium praseodymium oxalate single crystals grown in hydro silica gels

The mixed crystals of neodymium praseodymium oxalate are grown by the diffusion of a mixture of aqueous solutions of neodymium nitrate and praseodymium nitrate (as an upper reactant) into the set gel embedded with oxalic acid. By varying the concentration (by volume) of rare earth nitrates in the upper reactant, the incorporation of Nd and Pr in the mixed crystals has been studied. Tabular crystals with the well defined hexagonal basal planes are observed in the mixed crystals of varying concentrations. X-ray diffraction patterns of these powdered samples reveal that these mixed crystals are ‘isostructural’, while IR and FTIR spectra establish the presence of oxalate groups. TGA and DSC analyses show the correctness of the chemical formula for the mixed crystals, by the release of water molecules (endothermic) and of CO and CO₂ (exothermic), with the rare earth oxides as the stable residue. X-ray fluorescence (XRF) and energy dispersive X-ray analyses (EDAX) establish the presence of heavy rare earth elements qualitatively and to a good extent quantitatively. X-ray photoelectron spectroscopic (XPS) studies confirm the presence of rare earth elements (Nd and Pr) as their respective oxides. The findings of these techniques of characterization are in excellent agreement with the proposed empirical structure for the mixed rare earth oxalates. The implications are discussed.     

Studies on etching of gel-grown barium oxalate dihydrate crystals

Etch pits produced by selective etchants such as 1 M HCl, 1 M HNO₃, 4 M BaCl₂, 4 M NH₄Cl and 4 M NH₄Cl-1 M HCl solutions on the as-grown {110} faces of barium oxalate dihydrate crystals are illustrated and explained. The kinetics of etching is studied. From Arrhenius plots, the activation energy of etching and the pre-exponential factor are computed. An empirical equation governing the kinetics has been suggested.     

Growth and characterization of nonlinear optical diglycinehydrobromide single crystals

Diglycinehydrobromide (DGHB) a semi-organic nonlinear optical material with the molecular formula C₄H₁₁N₂O₄⁺Br⁻ has been synthesized at ambient temperature. Chemical composition of the synthesized material was confirmed by CHN analysis. Functional groups present in the sample were identified by FT-IR and Raman spectral analysis. Bulk single crystals of DGHB were grown by slow evaporation method at constant temperature. Powder X-ray diffraction pattern of the grown DGHB has been indexed. Unit cell parameters of the grown DGHB crystals were determined. Thermal stability of DGHB was determined from TGA/DTA and DSC response curves. Mechanical hardness of the grown crystal DGHB was determined and Vickers hardness number was calculated. The optical transparency and the lower cutoff of UV transmission were identified from the recorded UV-vis-IR spectrum of DGHB. The Kurtz powder second harmonic generation test shows that the crystal is a potential candidate for optical second harmonic generation.     

Growth and characterization of 4-methyl benzene sulfonamide single crystals

Single crystals of 4-methyl benzene sulfonamide (4MBS) were successfully grown from aqueous solution by low temperature solution growth technique. The grown crystal was characterized by single crystal XRD and powder XRD methods to obtain the lattice parameters and the diffraction planes of the crystal. UV–vis–NIR absorption spectrum was used to measure the range of optical transmittance and optical band gap energy. The optical transmission range was measured as 250–1200 nm. FTIR spectral studies were carried out to identify the presence of functional groups in the grown crystal. The thermal behavior of the crystal was investigated from thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC) study. The absence of SHG was noticed by Kurtz and Perry powder technique. The third order NLO behavior of the material was confirmed by measuring the nonlinear optical properties using Z-scan technique and it was found that the crystal is capable of exhibiting saturation absorption and self-defocusing performance.     

Nucleation and growth of CdC2O4·3H2O single crystals in silica gels

As part of our work on growth of cadmium oxalate single crystals in gels, we describe here variation of nucleation density and growth of these crystals as a function of concentration of feed solution, gel ageing, gel density, gel pH and intermediate neutral gel column. While high density and high pH gels have been found to produce opaque crystals, good quality transparent single crystals have been obtained in low density and low pH gels. It was observed that the intermediate neutral gel column and gel ageing considerably reduced the number of nucleation sites and increased the size of the crystals without affecting their quality. By concentration programming the size of the crystals increased.     

Physico-chemical characterization of BaHPO4 crystals

Characterization of the gel-grown barium hydrogen phosphate (BHP) crystals was performed by utilizing the techniques of chemical analysis, X-ray diffraction, infrared and thermal behaviour. The results show that BHP crystals had chemical composition BaHPO₄ at room temperature. TG and DTA studies revealed the BHP crystals to be anhydrous at room temperature and decomposed at temperatures above 370°C and the decomposition was an endothermic process. Magnetic susceptibility measurements indicate the material to be diamagnetic.