Calcite crystallization on oxadiazole-terpyridine copolymer

The nucleation and further crystallization of calcite on oxadiazole-terpyridine copolymer were investigated by the constant composition method. The apparent order of the crystallization process was found to be 2.3±0.2 indicative of a surface diffusion-controlled spiral growth mechanism. The number of ions forming the critical nucleus was found experimentally to be (n^*=) 3 in accordance with the simulation by the PM3 method included in the MOPAC program package. The surface energy of the growing phase was found to be 29.5 mJ m⁻².     

Monte Carlo simulation of a cluster model for the chirality conversion of crystals with grinding

By means of Monte Carlo simulation of a cluster model, we study statistical aspect of the chirality conversion of crystals. The chirality conversion is known to occur in a saturated solution by grinding crystals, and the enantiomeric excess increases exponentially. In the simulation, with crystallization and dissolution of monomers alone, the behavior of the enantiomeric excess observed in experiment cannot be reproduced although the homochirality is realized as a result of statistical fluctuation. By allowing crystallization and dissolution of dimers, the exponential amplification of enantiomeric excess can be realized.     

Investigation of the growth rate of β-cyclodextrin in water during both flow-cell and batch experiments

Growth rate measurements of β-cyclodextrin in water were performed both ways. Firstly, experiments were conducted with single monocrystals located in a supersaturation-controlled flow cell. Diffusional limitations and perturbations due to a competition between surface secondary nucleation and growth at high level of supersaturation have been put in evidence. The evolution of the growth rate with supersaturation has been modelled with a BCF law, assuming a screw dislocation mechanism. Secondly seeded cooling batch trials have been carried on in a well-mixed suspension crystallizer in order to assess the growth rate of the seeds. Refractometry was used as an in situ sensor for measuring the evolution of the concentration of the solute. Measurements of the crystals size distribution of the seeds and of the final crystals are performed off line with laser diffraction technique. A kinetic law with three parameters allows a consistent assessment of the growth of the seeds. The comparison of the two sets of data shows that overall growth rate of the seed is partially limited by diffusion. Nevertheless, the estimation of a surface integration growth kinetic coefficient from batch trials is rather difficult. The theoretical framework of nucleation models developed by Mersmann et al. (Crystallization Technology Handbook, second ed., Marcel Dekker, New York, 2001, pp. 45–80 and 81–144) coupled with the estimated growth kinetics can therefore be used to better monitor the seeding process during batch crystallization operations so as to favor the growth of the seed crystals.     

Simulation of metastable zone width and induction time for a seeded aqueous solution of potassium sulfate

The metastable zone width (MSZW, ΔT_m) and induction time (t_ind) were determined with computer simulation for seeded batch crystallization of potassium sulfate from aqueous solution. The MSZW and induction time determined with simulation showed the same behavior as experimental values reported in the literature; log (ΔT_m) increased linearly with an increase in log R (R: cooling rate) and t_ind decreases in proportion to (ΔT)⁻ⁿ (ΔT: supercooling, n: nucleation order in the secondary rate expression of B=k_n(ΔT)ⁿ). The secondary nucleation parameters (k_n and n) were deduced both from the simulated MSZW and induction times by using the previously proposed model [J. Cryst. Growth, 2010, 312, 548–554]. The secondary nucleation rate calculated with the deduced parameters was in agreement with that calculated with the parameters input for simulation.     

Effects of pH and temperature on CaCO3 crystallization in aqueous solution with water soluble matrix of pearls

Water soluble matrix (WSM) was extracted from pearls originated from Hyriopsis cumingii in Zhuji, Zhejiang province, China. WSM was regarded as an additive in mineralization experiments in order to study the effect of WSM on CaCO₃ crystallization. The experiments were carried out at different pH and temperatures by gas diffusion method and solution titration method, respectively. Scanning electron microscopy (SEM) and Raman spectroscopy (Raman) were used as powerful techniques to analyze the co-effect of pH value, temperature and WSM on crystal growth of CaCO₃. The results showed that WSM could induce aragonite at different pH values of mineralization solution, and the pH value had remarkable influence on morphology of calcite rather than aragonite due to distinct supersaturation and ionic strength related to various pH values. At different solution temperatures, WSM had little effect on crystal growth of calcium carbonate while the solution temperature had notable effect on polymorph and morphology of CaCO₃ crystals. This work can provide some basic information for the polymorph and morphology control of calcium carbonate.     

Computational analysis of three-dimensional flow and mass transfer in a non-standard configuration for growth of a KDP crystal

Computational analysis of three-dimensional flow and mass transfer in a non-standard configuration for growth of a KDP crystal was conducted. The results show that the surface shear stress is mainly affected by the inlet velocity, and the distribution of the surface supersaturation is determined by the bulk supersaturation and the inlet velocity. By adjusting the inlet velocity, the homogeneity of surface supersaturation can be improved, which is helpful for reducing the occurrence of inclusions and enhancing the crystal quality. The thickness of solute boundary layer is closely related to the flow intensity, but it is almost free from the impact of the bulk supersaturation.     

Thermal stationarity criteria for a proper study on growth (dissolution) kinetics in systems with small volumes of solutions in melts

It is shown that an application of theories developed on the assumption of the stationary thermal conditions for discussing the results on kinetic experiments with small volumes of solutions in melts is incorrect if the strong measures on eliminating temperature oscillations in these experiments are not taken. The results on an analysis of the influence of various temperature changes on the velocity of migration of liquid interlayers through a crystalline wafer are presented and discussed. Criteria for thermally stationary conditions in kinetic experiments are deduced.     

In-situ observations of dissolution process of GaSb into InSb melt by X-ray penetration method

Dissolution process of GaSb into InSb melt was observed by an X-ray penetration method. The intensity of X-rays penetrated through the rectangular shaped GaSb (seed)/InSb/GaSb (feed) sandwich sample was recorded by the CdTe line sensor detector. The penetrated X-ray intensities and images of the sample were obtained as a function of time and temperature. The gallium (Ga) composition profile of the sample was calculated as a function of time by making the calibration line with the penetrated X-ray intensities of GaSb and InSb standard samples. The calculated Ga composition profile of the grown sample agreed well with the data measured by energy dispersive X-ray spectroscopy analysis. The result suggested that lower GaSb seed dissolved faster than upper GaSb feed despite of the low temperature at the lower GaSb seed. It clearly indicates that the solutal transport induced by gravity strongly affects the dissolution process.     

Decisive role of Au layer on the oriented growth of ZnO nanorod arrays via a simple aqueous solution method

Vertically aligned arrays of ZnO nanorod were synthesized on the Au/SiO₂/Si(1 0 0) substrate by a simple aqueous solution growth process, without pre-prepared ZnO seed layer. For comparison, glass and SiO₂/Si were also used as substrates, and the results show that the Au layer plays a decisive role in orienting the growth of the ZnO nanorod. The effects of other growth parameters, including Zn²⁺ concentration and growth time, on morphology, density, and orientation of the ZnO nanostructure were also studied and with longer reaction time, a new structure namely ZnO nanotip was obtained. Moreover, the growth mechanism of ZnO nanorod arrays grown on the Au/SiO₂/Si substrate was proposed.     

Numerical simulation of a new SiC growth system by the dual-directional sublimation method

A new SiC growth system using the dual-directional sublimation method was investigated in this study. Induction heating and thermal conditions were computed and analyzed by using a global simulation model, and then the values of growth rate and shear stress in a growing crystal were calculated and compared with those in a conventional system. The results showed that the growth rate of SiC single crystals can be increased by twofold by using the dual-directional sublimation method with little increase in electrical power consumption and that thermal stresses can be reduced due to no constraint of the crucible lid and low temperature gradient in crystals.     

Hydroxyapatite crystallization in the presence of acetaminophen

The effect of acetaminophen; a widely used analgesic and fever reducing medicine; in supersaturated solutions of calcium phosphate was investigated under plethostatic conditions, at 37 °C, 0.15 M NaCl, pH 7.40. The rates of crystal growth measured in the presence of acetaminophen 1.654×10⁻⁴ mol dm⁻³ to 6.616×10⁻⁴ mol dm⁻³ were reduced by 43% to 79%, respectively. The inhibition effect on the crystal growth rate may be explained through adsorption onto the active growth sites. Kinetic analysis suggested Langmuir-type adsorption of acetaminophen on the HAP surface with a affinity value of 2.4×10⁻⁴ dm³ mol⁻¹, for the substrate in the concentration range investigated. The electrophoretic mobility measurements showed that in the presence of acetaminophen the charge of the acetaminophen covered HAP particles was shifted to more negative values as compared to bare HAP. In the presence of acetaminophen no changes observed in the HAP overgrown morphology or in the apparent order of crystallization.     

Determination of kinetic parameters of crystal growth rate of borax in aqueous solution by using the rotating disc technique

Growth rate of polycrystalline disc of borax compressed at different pressure and rotated at various speed has been measured in a rotating disc crystallizer under well-defined conditions of supersaturation. It was found that the mass transfer coefficient, K, increased while overall growth rate constant, K_g, and surface reaction constant, k_r, decreased with increasing smoothness of the disc. It was also determined that kinetic parameters (k_r,r,K,g) of crystal growth rate of borax decreased with increasing rotating speed of the polycrystalline disc. The effectiveness factor was calculated from the growth rate data to evaluate the relative magnitude of the steps in series bulk diffusion through the mass transfer boundary layer and the surface integration. At low rotating speed of disc, the crystal growth rate of borax is mainly controlled by integration. However, both diffusion and integration steps affect the growth rate of borax at higher rotating speed of polycrystalline disc.     

Influence of polyethylenimine on the precipitation process of lead sulfate crystals

Crystals of lead sulfate were precipitated in a solution of polyethylenimine (PEI) using a double-jet crystallizer. PEI controlled both the nucleation rate and the growth rate, and enabled to produce fine monodispersed crystals. This effect is considered to be due to a complexation between PEI and lead ion. The on-line measurement of the variation in the lead ion concentration indicated PEI lost its effect when a certain amount of reactants was supplied. And the duration in which PEI could control the precipitation rate and the amount of PEI had a strong correlation. In addition, it was suggested that their relationship could be utilized in order to produce monodispersed particles.     

Scale-up synthesis of zinc borate from the reaction of zinc oxide and boric acid in aqueous medium

Synthesis of zinc borate was conducted in a laboratory and a pilot scale batch reactor to see the influence of process variables on the reaction parameters and the final product, 2ZnO·3B₂O₃·3.5H₂O. Effects of stirring speed, presence of baffles, amount of seed, particle size and purity of zinc oxide, and mole ratio of H₃BO₃:ZnO on the zinc borate formation reaction were examined at a constant temperature of 85 °C in a laboratory (4 L) and a pilot scale (85 L) reactor. Products obtained from the reaction in both reactors were characterized by chemical analysis, X-ray diffraction, particle size distribution analysis, thermal gravimetric analysis and scanning electron microscopy. The kinetic data for the zinc borate production reaction was fit by using the logistic model. The results revealed that the specific reaction rate, a model parameter, decreases with increase in particle size of zinc oxide and the presence of baffles, but increases with increase in stirring speed and purity of zinc oxide; however, it is unaffected with the changes in the amount of seed and reactants ratio. The reaction completion time is unaffected by scaling-up.     

Growth of nanofibrous barium carbonate on calcium carbonate seeds

Fibrous barium carbonate (BaCO₃/witherite) crystals 50–100 nm in diameter and several microns in length were grown on calcium carbonate (CaCO₃) seeds at temperatures as low as 4 °C. The BaCO₃ fibers were deposited onto calcite rhombs or CaCO₃ films using the polymer-induced liquid-precursor (PILP) process, which was induced with the sodium salt of polyacrylic acid (PAA). The structure and morphology of the resultant fibers were investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and polarized light microscopy (PLM). Fibers were successfully grown on calcite seeds of various morphologies, with a range of barium concentrations, and PAA molecular weight and concentration. Two categories of fibers were grown: straight and twisted. Both types of fibers displayed single-crystalline SAED diffraction patterns, but after examining high-resolution TEM lattice images, it was revealed that the fibers were in fact made up of nanocrystalline domains. We postulate that these nanocrystalline domains are well aligned due to a singular nucleation event (i.e., each fiber propagates from a single nucleation event on the seed crystal) with the nanocrystalline domains resulting from stresses caused by dehydration during crystallization of the highly hydrated precursor phase. These BaCO₃ fibers grown on calcite substrates further illustrate the robustness and non-specificity of the PILP process.     

Homogeneous SiGe crystals grown by using the traveling liquidus-zone method

It is indispensable to estimate a diffusion coefficient in a solution zone in order to grow a homogeneous crystal by using the traveling liquidus-zone (TLZ) method. To estimate the diffusion coefficient of Ge in the SiGe solution zone, result of a two-dimensional numerical simulation is compared with an experimental result. From the comparison, the diffusion coefficient is estimated to be 9.5×10⁻⁵ cm²/s. By using this coefficient, a sample translation rate for obtaining a homogeneous SiGe crystal is determined. By translating samples with appropriate rates, homogeneous Si_0.5Ge_0.5 crystals are successfully grown. The typical Ge composition is 0.496±0.006 for more than 13 mm long. The experimental result shows the homogeneity of ±1.2% in the mole fraction. This deviation corresponds to the variation of less than ±0.03% in the lattice constant. Since this variation is negligibly small, the homogeneity is excellent. Thus it is found that the TLZ method is the universal growth technique, which is applicable to the crystal growth of not only the III–V compounds but also the IV–IV compounds.     

Analysis of SiC crystal sublimation growth by fully coupled compressible multi-phase flow simulation

A fully coupled compressible multi-phase flow solver was developed to effectively design a large furnace for producing large-size SiC crystals. Compressible effect, convection and buoyancy effects, flow coupling between argon gas and species, and the Stefan effect are included. A small and experimental furnace is used to validate the solver. First, the essentiality of 2D flow calculation and the significance of incorporating buoyancy effect and gas convection, the Stefan effect, and flow interaction between argon gas and species were investigated by numerical results. Then the effects of argon gas on deposition rate, growth rate, graphitization on the powder source, and supersaturation and stoichiometry on the seed were analyzed. Finally, the advantages of an extra chamber design were explained, and improvement of growth rate was validated by the present solver.     

Variation of crystallization mechanisms in flash-lamp-irradiated amorphous silicon films

Flash lamp annealing (FLA) can form polycrystalline silicon (poly-Si) films with various microstructures depending on the thickness of precursor amorphous Si (a-Si) films due to the variation of crystallization mechanisms. Intermittent explosive crystallization (EC) takes place in precursor a-Si films thicker than approximately 2 μm, and the periodicity of microstructure formed resulting from the intermittent EC is independent of the thickness of a-Si films if their thickness is 2 μm or greater. In addition to the intermittent EC, continuous EC and homogeneous solid-phase crystallization (SPC) also occur in thinner films. These crystallization mechanisms are governed by the ignition of EC at Si film edges and the homogeneous heating of interior a-Si. The results obtained in this study could be applied to control the microstructures of flash-lamp-crystallized poly-Si films.     

On favorable thermal fields for detached Bridgman growth

The thermal fields of two Bridgman-like configurations, representative of real systems used in prior experiments for the detached growth of CdTe and Ge crystals, are studied. These detailed heat transfer computations are performed using the CrysMAS code and expand upon our previous analysis [C. Stelian, A. Yeckel, J.J. Derby, Influence of thermal phenomena on crystal reattachment during the dewetted Bridgman growth, J. Cryst. Growth, in press] that posited a new mechanism involving the thermal field and meniscus position to explain stable conditions for dewetted Bridgman growth. Computational results indicate that heat transfer conditions that led to successful detached growth in both of these systems are in accordance with our prior assertion, namely that the prevention of crystal reattachment to the crucible wall requires the avoidance of any undercooling of the melt meniscus during the growth run. Significantly, relatively simple process modifications that promote favorable thermal conditions for detached growth may overcome detrimental factors associated with meniscus shape and crucible wetting. Thus, these ideas may be important to advance the practice of detached growth for many materials.