Study on the Growth of Triglycinsulphate Single Crystals

Crystallization of TGS at 52.0°C - above the transition point - has been studied in a wide range of supersaturation of the solution (σ = 0 to 10⁻²). The rates of growth of {110} and {001} faces were measured as a function of supersaturation at constant hydrodynamical conditions (Re = 3.4 · 10⁻³). Further, the influence of hydrodynamical conditions on the growth of {110} faces at constant supersaturation (σ = 4.2 · 10⁻³) was established. The parameters of the experimentally found dependences are determined on the basis of the surface-diffusion model of BURTON . CABRERA and FRANK . From these dependences follows that the growth rate of the {110} faces is already almost limited by the volume diffusion of TGS molecules towards the crystal surface, while in the case of {001} faces the surface diffusion mechanism of crystallization is clearly manifested. Dislocation densities in the crystals have been determined by means of etching technique. The number of dislocations increases with increasing supersaturation; hence, supersaturation of the solution together with the processes taking place in the regeneration zone surrounding the seed determine the number of dislocations in the crystal volume and thus the resulting structural perfection of single crystals. Investigation of the spontaneous redistribution of domains showed that the growth rate of TGS crystals influences the dielectric properties to much smaller extent than does chemical purity.     

Calcium Oxalate Monohydrate Crystal Growth

The growth rate of calcium oxalate monohydrate seed representing aggregates of highly irregular crystals from solutions of the stoichiometric composition with I = 100 mol m⁻³ in the range of supersaturation Δc = 0.056 to 0.353 mol m⁻³ was measured at 37 °C by the constant composition method. The crystal growth rate decreased during the initial period of experiment, then reached a value constant over a considerable time and later increased again. The initial decrease of the growth rate resulted from crystal perfection whereas the later increase was caused by formation of new crystals by secondary nucleation. The supersaturation dependence of the kinetic growth rate satisfied the power law with the growth order equal to 2 and 4 at supersaturations lower and higher than about Δc = 0.150 mol m⁻³, respectively.     

Kinetics of growth of calcite crystals in presence of ammonium ions

The growth of calcite crystals from an aqueous supersaturated solution of initial concentration 0.15 mol m⁻³ containing 10 mol m⁻³ of (NH₄)₂CO₃ has been studied at 298 K. The progress of growth has been followed through determining the composition of the solution by chemical analysis. The crystal growth is controlled by the surface reaction mechanism and satisfies a kinetic equation of the second order with the rate constant 3.7 × 10⁻⁶ m⁴ mol⁻¹ s⁻¹ that is independent on the surface area of the present solid. NH₄⁺ ions do not change the crystal growth mechanism but decrease the growth rate of calcite crystals.     

Kinetics of sodium fluosilicate precipitation

The formation of Na₂SiF₆ by discontinuous precipitation of dilute H₂SiF₆ with a 40% excess of an aqueous solution of NaCl under various conditions was studied. The values of induction time, number of crystals formed, their final size and their habit were determined during precipitation from solutions, whose initial supersaturation was 2 < S < 11. At S < 7–8 the crystals were formed by heterogeneous nucleation, whereas at S ≳ 7–8 homogeneous nucleation mechanism began to prevail. Once formed, the Na₂SiF₆ crystals were growing according to the screw-dislocation mechanism till they reached visible size; the corresponding values of kinetic order of nucleation and of the growth rate constant were g = 1.35 and k_g = 4.32 × 10⁻⁸ cm^2.05 sec⁻¹ g^−0.35, resp. The value of interfacial tension on the phase boundary Na₂SiF₆ crystal — saturated solution was determined (σ ∼ 52 erg/cm²). The resulting Na₂SiF₆ crystals conformed to log-normal distribution irrespective of conditions of precipitation. The dependence of the final size of crystals on supersaturation exhibited a maximum at S ∼ 6. Crystals of Na₂SiF₆ had a hexagonal habit, which was near to a spherical form at lower supersaturations, while dendritic crystals were formed at higher supersaturations.     

Enhancement of thermoelectric efficiency in vapor deposited Sb2Te3 and Sb1.8In0.2Te3 crystals

Pure and indium doped antimony telluride (Sb₂Te₃) crystals find applications in high performance room temperature thermoelectric devices. Owing to the meagre physical properties exhibited on the cleavage faces of melt grown samples, an attempt was made to explore the thermoelectric parameters of p‐type crystals grown by the physical vapor deposition (PVD) method. The crystal structure of the grown platelets (9 mm× 8 mm× 2 mm) was identified as rhombohedral by x‐ray powder diffraction method. The energy dispersive analysis confirmed the elemental composition of the crystals. The electron microscopic and scanning probe image studies revealed that the crystals were grown by layer growth mechanism with low surface roughness. At room temperature (300 K), the values of Seebeck coefficient S (⊥ c) and power factor were observed to be higher for Sb_1.8In_0.2Te₃ crystals (155 μVK⁻¹, 2.669 × 10⁻³ W/mK²) than those of pure ones. Upon doping, the thermal conductivity κ (⊥ c) was decreased by 37.14% and thus thermoelectric efficiency was improved. The increased figure of merit, Z = 1.23 × 10⁻³ K⁻¹ for vapour grown Sb_1.8In_0.2Te₃ platelets indicates that it could be used as a potential thermoelectric candidate.     

Crystal growth of FeCO3 in mixed monoethylene glycol and water solvent

The transportation of natural gas in long subsea pipelines is a challenge when it comes to hydrate prevention, corrosion and mineral scaling. When monoethylene glycol (MEG) is injected into carbon steel pipelines to prevent formation of gas hydrates, the solubility of the corrosion products is altered. Understanding the kinetics of FeCO₃ precipitation may make it possible to avoid deposition in the gas liquid separation process and improve solids removal in MEG recovery units. In this work, the growth kinetics of iron carbonate (siderite) has been studied in seeded batch experiments in MEG‐water solutions with 0 and 40 wt% MEG at 50 and 70 °C. Precautions were taken to keep anaerobic conditions and avoid oxidation of ferrous ions. The growth rate (G) was measured as function of supersaturation (S) and fitted to the equation: G = k_r(S‐1)^g. The growth order (g) was approximately 2 independent of the MEG concentration at the two temperatures. The growth rate constant (k_r) was in the range of 6 × 10⁻¹¹ to 1 × 10⁻¹⁰ m/s. Temperature increase from 50 to 70°C had no measurable effect on the growth rate while in the presence of 40 wt% MEG the growth rate constant decreased.     

Growth aspects of barium oxalate monohydrate single crystals in gel medium

Single crystals of barium oxalate monohydrate (BaC₂O₄.H₂O, BOM) were grown in pure form by controlled diffusion of Ba²⁺ using the gel technique at different temperatures. Starting from aqueous Ba²⁺ chloride (BaCl₂) and acetic acid (C₂H₂O₄) in gel, this method offers a low‐cost and an easiest alternative to other preparation methods for the production of barium oxalate bulky single crystals. The optimal conditions for the growth of BOM crystals in silica gel were found by investigating different growth parameters such as gel pH, gel aging and crystallization temperature. Irrespective of all such crystallization environments, growth rate of the crystals were initially less and then exhibited supersaturation effect leading to non‐linearity. Gel aging and temperature has profound effect on nucleation density that resulted less number of crystals of maximum size in the gel matrix. Perfect single crystals were grown on gels of higher pH. The macropore morphology and porosity was controlled by changing age of the gel. It has been found that temperature has a fabulous effect in controlling the nucleation density by altering the supersaturation conditions for the formation of critical nuclei. The entire growth kinetics informed that the grown crystals were derived by the one dimensional diffusion controlled process. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth mechanism of crystals from aqueous solutions

Microscopic processes occurring on the surface of a growing crystal or a dissolving one were observed by microcinematography. The crystals under observation were grown either in a drop of solution by evaporation or in a constant-temperature microscope stage at a chosen supersaturation. Small (approx. 0.1 mm) and large (approx. 10 mm) crystals of NaCl, Pb(NO₃)₂, NaNO₃, CdI₂, KDP and ADP were studied. It is concluded qualitatively that the layers, in general polygonal, originating in one or several active centres, are formed on the crystal face, never at the corners or edges. – The average velocity of layer motion was studied quantitatively in dependence on their thickness and supersaturation. The layer motion at constant supersaturation considerably fluctuated. – Surface patterns created by moving layers agree in most cases with predictions of the dislocation theory. Two categories of steps were found on the surface: ”︁real”︁ macrosteps and shock waves. – The velocity of layer motion for most compounds lies within (1–10) · 10⁻⁴ cm · s⁻¹.     

Growth of Nd:Sr3Ga2Ge4O14 crystals by a modified Bridgman method

Bridgman growth of Nd:SGG (Sr₃Ga₂Ge₄O₁₄) crystals has been investigated for the first time. Pt crucible of ∅︁25mm×250mm with a seed well of ∅︁10mm×80 mm is used, and seed is SGG crystal of ∅︁10mm×50mm grown by Bridgman method in advance. The growth parameters are optimized as the furnace temperature is set to 1450∼1500°C, temperature gradient in the crystal‐melt interface is less than 25 K/cm and growth rate is less than 0.5mm/h. The Nd:SGG crystals with 25mm in diameter and 60mm in length are grown successfully from 1.5 to 8at% Nd³⁺ doped stoichiometric Sr₃Ga₂Ge₄O₁₄ melt. The distribution coefficient and concentration of Nd³⁺ in Nd:SGG crystals are obviously higher than those of Nd:YAG crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Semiconducting Properties of TI2Te3 Single Crystals

Electrical conductivity and Hall effect measurements were performed on single crystals of TI₂Te₃ to have the general semiconducting behaviour of this compound. The measurements were done at the temperature range 160–350 K. All crystals were found to be of p-type conductivity. The values of the Hall coefficient and the electrical conductivity at room temperature were 1.59 × 10³ cm³/coul and 3.2 × 10⁻² ω⁻¹ cm⁻¹, respectively. The hole concentration at the same temperature was driven as 39.31 × 10¹¹ cm⁻³. The energy gap was found to be 0.7 eV where the depth of impurity centers was 0.45 eV. The temperature dependence of the mobility is discussed.     

Growth Kinetics of Adenine Sulphate Crystals

The kinetics of growth and dissolution of adenine sulphate in 1.5 mol · 1⁻¹ H₂SO₄ at different super- and undersaturations has been studied. The solubility of adenine sulphate in H₂SO₄ was determined over the temperature range 20–50 °C. The growth rate of the (100) face is by about 25% higher than that of (111) and the crystal habit is changed by a high supersaturation almost to a bipyramide. The surface diffusion was determined as a prevailing processes and the BaS model gives the best fit with experimental data.     

Electric Characterization of Indium Sesquiselenide Single Crystals

Conductivity, Hall-effect measurements were performed on δ-phase In₂Se₃ single crystals, grown by the Bridgman method over the temperature range 150–428 K, in the directions perpendicular and parallel to the c-axis. The anisotropy of the electrical conductivity and of the Hall coefficient of n-type In₂Se₃ had been investigated. The values of the Hall coefficient and electrical conductivity at room temperature spreads from an order of R_H11 = 1.36 × 10⁴ cm³/coul, σ₁₁ = 4.138 × 10⁻³ Ω⁻¹ cm⁻¹ and R_H = 66.55 × 10⁴ cm³/coul, σ = 0.799 × 10⁻³ Ω⁻¹ cm⁻¹ for parallel and perpendicular to c-axis, respectively. The temperature dependence of Hall mobility and carrier concentration are also studied.     

Synthesis and characterization of ferroelectric magnesium hydrogen phosphate single crystals

Ferroelectric Magnesium Hydrogen Phosphate MgHPO₄ (MHP) single crystals are grown by slow diffusion of magnesium chloride in sodium metasilicate gels impregnated with orthophosphoric acid. Bright and transparent prismatic, tabular, and isometric habit MHP crystals upto 3 × 2 × 1 mm³ are obtained. Results of chemical, X-ray diffraction, EDAX, microhardness and magnetic analysis are reported. The average etch pit density is determined by chemical etching to be 7 × 10³ cm⁻². Microtopographic investigations revealed the mechanism of crystal growth.     

Crystal growth and spectral properties of Nd:Ca5(BO3)3F

A neodymium doped Ca₅(BO₃)₃F single crystal with size up to 51×48×8 mm³ has been grown by the top seeded solution growth (TSSG) technique with a Li₂O‐B₂O₃‐LiF flux. The spectra of absorption and fluorescence were measured at room temperature. According to Judd‐Ofelt (J‐O) theory, the spectroscopic parameters were calculated and the J‐O parameters Ω₂, Ω₄, Ω₆ were obtained as follows: Ω₂ = 1.41×10⁻²⁰cm², Ω₄ = 3.18×10⁻²⁰cm², Ω₆ = 2.11×10⁻²⁰cm². The room temperature fluorescence lifetime of NCBF was measured to be 51.8 μs. According to the J‐O paramenters, the emission probabilities of transitions, branching ratios, the radiative lifetime and the quantum efficiency from the Nd^{3+ 4}F_3/2 metastable state to lower lying J manifolds were also obtained. In comparasion with other Nd‐doped borate crystals, the calculated and experimental parameters show that NCBF is a promising SFD crystal.     

Growth of corundum single crystals by the top-seeded solution growth technique (TSSG)

Single crystals of corundum were grown by the top-seeded solution growth technique from a cryolite, Na₃AlF₆, solvent. The relationship between the growth rate (mg/h) of a crystal and the temperature difference (= supersaturation) or the rotation rate of a seed crystal was investigated, and optimum growth conditions for obtaining single crystals with good quality are discussed.     

Crystal growth of PbTe and (Pb,Sn)Te by the bridgman method and by THM

Synthesis and growth of PbTe and (Pb, Sn)Te single crystals by the Bridgman method and by the Travelling Heater Method (THM) from Te-rich solutions are described. It is to be seen from comparative investigations that seeded THM growth reproducibly provides oriented single-crystalline ingots free of low-angle grain boundaries and with etch pit densities of 8–12 × 10⁴ cm⁻². All the materials were p-type with carrier concentrations from 1 to 2 × 10¹⁸ cm⁻³.     

The growth of high-quality MCT films by MBE using in-situ ellipsometry

The ellipsometry and RHEED study of high-quality MCT films grown on (112)- and (130) CdTe and GaAs by MBE was carried out. The dependence of the ellipsometric parameter ψ on MCT composition is evaluated. It was shown that such parameters as growth rate, the surface roughness, initial substrate temperature, and film composition may be measured by the in-situ ellipsometry. The appearance of surface roughness was observed in the initial stage of MCT growth under various compositions (x_CdTe = 0 ÷ 0.4). The further growth at optimum conditions leads to the smoothing of the surface and supplies us with high-quality MCT films. The concentration, mobility, and life time of carriers in MCT films were respectively: n = 1.8 × 10¹⁴ ÷ 8.2 × 10¹⁵ cm⁻³, μ_n = 44000 ÷ 370000 cm² V⁻¹ s⁻¹, τ_n = 40 ÷ 220 ns; p = 1.8 × 10¹⁵ ÷ 8.4 × 10¹⁵ cm⁻³, μ_p = 215 ÷ 284 cm² V⁻¹ s⁻¹, τ_p = 12 ÷ 20 ns.     

TSM-gewachsene Halbleiter-Einkristalle aus (Pb0,8Sn0,2)Te

By means of the Travelling Solvent Method (TSM) the authors succeeded in growing PbSnTe solid solution crystals using a simple working growing principle. Imperfections and constitution as well as electrical properties of the crystals have been investigated. The results lead to the conclusion that one can grow homogeneous, nearly perfect crystals having low carrier densities and high carrier mobilities in a relatively short time which seems to be the main advantage of the experimental techniques used. Representative values of electrical crystal parameters are p₇₇ ≦ 10¹⁷ cm⁻³, n₇₇ ≦ 10¹⁷ cm⁻³; pμ₇₇ ⋍ 1,6 × × 10⁴cm²/Vs; dimensions: 1 × 4 × 4 mm³.     

A study of primary nucleation of calcium oxalate monohydrate: I‐Effect of supersaturation

There are various organic and inorganic constituents in kidney stones. Among them, calcium oxalate monohydrate (COM) is the primary inorganic constituent of kidney stones. However, the mechanisms of formation of kidney stones are not well understood. In this regard, a basic study is carried out for better understanding of nucleation, crystal growth and/or aggregation of formed COM crystals. The primary nucleation of calcium oxalate monohydrate is studied at the laboratory scale using turbidity measurements. Calcium chloride and potassium oxalate solutions are mixed and then added to a Turbidimeter tube for continuous recording of turbidity. Induction time (time to induce formation of detectable crystals) is estimated from time‐turbidity graphs. The effect of some urinary species, such as oxalate and calcium, on nucleation and crystallization characteristics of COM is determined by particle size distribution analysis, measuring weight of crystals and calculation of relative supersaturation. The classical nucleation theory is applied at high supersaturation ratios (SR) ranging from 1.6 to 2.2. The results indicate that nucleation rate increases with increasing supersaturation ratio from 0.81 × 10²⁸ nuclei/cm³.sec at 1.6 SR, to 18.02 × 10²⁸ nuclei/cm³.sec at 2.2 SR. On the other hand, free energy change and radius of critical nucleus are decreased as supersaturation ratio is increased. The nucleation rates are higher than those reported in literature. Such discrepancy is discussed on the bases of differences in experimental techniques. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.