Determination of metastable zone width for combined anti-solvent/cooling crystallization

The metastable zone width (MSZW), induction time and primary nucleation kinetics have been measured and estimated for simultaneous anti-solvent and cooling crystallization of paracetamol in iso-propanol/water solution. ATR-FTIR spectroscopy and laser back-scattering are used to measure the solute concentration and primary nucleation event, respectively. Response surface analysis was applied to find the contribution of the crystallization mechanism on the MSZW and obtain a statistical model for quick estimation of the MSZW. Two theoretical approaches for the estimation of nucleation rate kinetic parameters from experimental data are presented. The methods are obtained by modifying the classical Nyvlt's correlation for simultaneous cooling/anti-solvent crystallizations. The nucleation order n for primary nucleation was deduced from the slope of a linear plot of log(MSZW) vs. log(cooling and anti-solvent rates). The induction time was also estimated by changing the classical methods for combined cooling and anti-solvent crystallization.     

Nucleation kinetics of paracetamol–ethanol solutions from metastable zone widths

A study of the nucleation kinetics for a cooling crystallisation of paracetamol–ethanol solutions in a batch reactor is described in this paper. Metastable zone width (MSZW) experiments were conducted in order to estimate the nucleation kinetics of the system. Measured MSZWs can be affected by numerous process parameters, such as cooling rate, concentration, agitation rate, and working volume. Two theoretical approaches were employed to estimate the nucleation kinetics, the classical mass based approach of Nývlt, and a more recent approach by Kubota, which also considers number density. Both approaches were found to produce similar estimates for the nucleation rates of the paracetamol–ethanol solutions as a function of supersaturation for an assumed nucleus size of 10 μm. The theory of Kubota was found to predict satisfactory estimates for the induction time of the nucleation process from MSZW data. The induction time was observed to be independent of the solution temperature as suggested by Kubota’s theory. This is a novel finding and serves to validate the induction time theory of Kubota. In this investigation, MSZWs were observed to decrease with increased levels of agitation and found to be independent of working volume.     

Solubility and metastable zone width of DL‐tartaric acid in aqueous solution

Solubility and metastable zone width (MSZW) of DL‐tartaric acid (DL‐TA) in aqueous solution have been determined. Solubility of DL‐TA was measured in the temperature range from 0 to 50 °C at atmospheric pressure by means of the conventional polythermal method using Turbidity Monitoring Technique, which was verified by a gravimetric method. The dissolution enthalpy and entropy of DL‐TA were then calculated from the solubility data using van't Hoff equation. Two approaches was used to estimate the nucleation kinetics from the measured metastable zone width data, the self‐consistent approach and the approach based on 3D nucleation. In addition, the metastable zone width slightly decreases with increasing agitation rate and was independent of working volume.     

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.     

Investigation of metastable zone width of ammonium oxalate aqueous solutions

The metastable zone width of pure ammonium oxalate aqueous solutions, as represented by maximum supercooling ΔT_max, is investigated as functions of cooling rate R and saturation temperature T₀ by the polythermal method. The experimental results are discussed by using two recently advanced approaches: (1) self‐consistent Nývlt‐like approach based on a power‐law relationship between nucleation rate J and maximum supersaturation lnS_max, and (2) a novel approach based on the relationship between J and lnS_max described by the classical three‐dimensional nucleation theory. Analysis of the experimental data revealed that both approaches describe the experimental data on metastable zone width by the polythermal method reliably and provide useful information about the physical processes and parameters involved in nucleation kinetics. The values of various physical quantities predicted by both of these approaches are reasonable for a fairly‐soluble compound. A careful examination of the data on ΔT_max as a function of T₀ obtained by polythermal method and from density measurements showed that ΔT_max has a slight tendency to decrease with increasing saturation temperature T₀. The values of lnS_max at saturation temperature 303 K suggest that the metastable zone width of ammonium oxalate aqueous solutions is determined by primary nucleation in the polythermal method and by secondary nucleation during density measurements. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Metastable zone width and nucleation threshold of aluminium hydroxyfluoride hydrate

This paper considers the metastable zone width (MSZW) of aluminium hydroxyfluoride hydrate (AHF, AlF₂OH.H₂O) crystallizing solution, with a view to identifying suitable conditions for crystal growth. Speciation calculations combined with experimental validations have been used to estimate the degree of saturation at varying pHs leading to the identification of the metastable zone width (MSZW). From the results obtained, the solutions are saturated at pH 3.0 ± 0.3 and remain metastable until the nucleation threshold is reached at pH 5.0 ± 0.3. A narrowing of the MSZW at elevated temperatures has been observed and is attributed to the decrease in AHF solubility with increasing temperatures. This phenomenon was applied to obtain a tripling of the crystal particles in 30 minutes. The pH profile of the crystallizing solution is similar to that of acid/base titration curves and is found to be a quick and accurate method of estimating the MSZW. Using similar terminologies, the equivalent point corresponds to solution saturation while the mid‐point corresponds to the nucleation threshold. These results are applicable in the recovery of fluoride values of spent pot lining.     

Effect of Mn(II) ions on the growth of ammonium oxalate monohydrate crystals from aqueous solutions: I. Growth habit and surface morphology

The effect of concentration of Mn(II) ions on the growth habit and the surface micromorphology of different as‐grown faces of ammonium oxalate monohydrate (AO) single crystals grown from aqueous solutions was studied at a constant temperature of 30 °C and predefined supersaturations up to 20%. It was observed that the growth habit and the surface morphology of the crystals strongly depend on the supersaturation used for growth and the impurity concentration in the solution. The experimental results were analysed in terms of connected nets determined from different projections of the structure of AO crystals. Analysis of the observations revealed that: (1) the directions of connected nets corresponding to basic growth units composed of single (NH₄)₂C₂O₄ · H₂O molecules are in excellent agreement with the low‐index crystallographic directions of the orientations of growth layers, (2) all faces appearing in the growth morphology of AO crystals are F faces, and (3) the {001} face growing from pure aqueous solutions is essentially a kinetically rough face but the presence of Mn(II) impurity leads to their appearance in the morphology due to increase in the strength of bonds of the connected nets composing the surface graph.     

γ-氨基丁酸晶体成核动力学、晶体生长及热力学性质研究

本文研究了γ-氨基丁酸的热力学及成核动力学性质.对γ-氨酪酸晶体的热力学性质进行研究,γ-氨基丁酸的差示扫描量热研究表明:γ-氨基丁酸的熔点为190.6 ℃,熔化焓为-343.4 J/g.测定了不同温度下γ-氨基丁酸在水中的溶解度及不同过饱和度下的诱导期.结果表明:γ-氨基丁酸的诱导期随着过饱和度的增加而降低.通过经典成核理论计算了固-液表面张力、成核自由能和临界成核半径.     

In situ monitoring and control of lysozyme concentration during crystallization in a hanging drop

Fiber optic Raman spectroscopy combined with a partial least-squares regression model was demonstrated as a monitor of lysozyme concentration during crystallization in a hanging drop experiment in real time. Raman spectral features of the buffer and protein were employed to build the regression model. The use of fiber optic technology coupled with Raman spectroscopy, which is ideal for use with aqueous solutions, results in a powerful noninvasive probe of the changing environment within the solution. Lysozyme concentrations were monitored in experiments at a constant reservoir ionic strength. Data from these uncontrolled experiments were used to determine rates of supersaturation, induction times, and the number and size of the resultant lysozyme crystals. Control experiments were performed by introducing step changes in the reservoir ionic strength. The step changes were initiated by comparing in situ rates of supersaturation with the rates of supersaturation calculated from the uncontrolled data. Monitoring the concentration changes of the lysozyme within the hanging drop permits a measurement of the level of supersaturation of the system and enhances the possibility of dynamic control of the crystallization process.     

Determination of nucleation kinetics of potassium tetraborate tetrahydrate

In this study, the metastable zone width of potassium tetraborate tetrahydrate was determined for four different temperatures and cooling rates. The induction period of potassium tetraborate tetrahydrate in aqueous solution was examined according to polythermal method by using visual observation. The induction period, which changes inversely proportional to the nucleation rate has been used to determine the interfacial tension between the potassium tetraborate tetrahydrate and aqueous solution. By using interfacial tension, the nucleation parameters such as Gibbs free energy change for the formation of critical nucleus, ΔG*, free energy of formation, ΔG, radius of critical nucleus, r and number of molecules in the critical nucleus, i* has been calculated. The effect of Li⁺ and Ca²⁺ impurities on metastable zone width has been studied. The metastable zone width of aqueous solution of potassium tetraborate tetrahydrate decreases with increasing impurity concentrations. The equilibrium saturation concentration change is high in the presence of Ca²⁺ ions while it is low in the presence of Li⁺ ions. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Induction time in crystallization of gas hydrates

The kinetics of the initial stage of crystallization of one-component gas hydrates in aqueous solutions are analyzed. The temporal evolution of the volume of hydrate crystallized and the moles of gas consumed are determined. Expressions are derived for the supersaturation dependence of the hydrate crystallite growth rate and the induction time in hydrate crystallization. These expressions are used for revealing how additives in the solution that act as kinetic inhibitors of hydrate crystallization can affect the induction time of the process. The results obtained are applied to crystallization of methane, ethane and cyclopropane hydrates.     

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.     

Antisolvent crystallization of aqueous ammonium dihydrogen phosphate solutions by addition of acetone at different rates

Results of an investigation of in situ measurements of laser‐beam intensity I_s and I_m transmitted through aqueous ammonium dihydrogen phosphate (ADP) solutions saturated at 30 °C and water, respectively, and temperature T_s of solution and T_m of water during feeding of antisolvent acetone at different rates R_A, using an indigenously designed experimental setup, are presented and discussed. It was found that: (1) for the measurement of MSZW, defined as the maximum volume fraction of acetone content Δx_max in the solution, obtained from temperature measurements are more reliable than transmitted laser‐beam intensity measurements for solutions, (2) two minima ΔT_min1 and ΔT_min2 associated with endothermic reactions, separated by a maximum ΔT_max due to exothermic reactions appear in the plots of temperature difference ΔT = T_s−T_m against acetone feeding time t, and (3) in the ΔT(t) plots there are time intervals Δt of constant rates R_T of increase in ΔT of aqueous ADP solutions, and these values of R_T increase linearly with acetone feeding time rate R_A. The experimental data on the observed dependence of MSZW on antisolvent feeding rate R_A, the appearance of minima ΔT_min1 and ΔT_min2 and maximum ΔT_max and their dependence on R_A, and the relationship between R_T and R_A are discussed from consideration of processes of nucleation and growth of crystallites.     

Formation of partially ordered organic planar systems based on the in situ control of their structural organization

The possibilities of significantly improving the quality of planar systems based on photoactive porphyrin–fullerene dyads, layers based on cytochrome c and cardiolipin, and lysozyme crystals and films using a complex of in situ X-ray methods and simulation are described. The potential of X-ray phase-sensitive and surface-sensitive methods developed by M.V. Koval’chuk and researchers from his school in monitoring all stages of synthesis of partially ordered organic structure is demonstrated. This approach shows its efficiency for in situ studies: starting from the formation of complexes in solutions up to the growth of protein films and crystals.     

Determination of nucleation kinetics of lovastatin in acetone solution

The metastable zone widths of lovastatin in acetone solution were determined at different temperatures, cooling rates and initial concentrations by polythermal method. It decreases with the increase of temperature and initial concentration, increases with the increase of cooling rate. The induction periods of lovastatin in acetone solution were also investigated as a function of supersaturation ratios. The crystal‐liquid interfacial tension, thus the fundermental nucleation parameters including Gibbs free energy change for the formation of critical nucleus, radius of critical nucleus and number of molecules in the critical nucleus have been gotten based on the classical homogeneous nucleation theory. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and properties of epoxy/polyaniline nanocomposites

Epoxy/polyaniline nanocomposites have been prepared by in situ polymerization of aniline carried out in hydrophilic epoxy networks based on polyoxyethylene (POE) swollen in aqueous solutions of aniline hydrochloride. Formation of polyaniline (PANI) nanoparticles in water-rich phase of swollen networks has been revealed by transmission electron microscopy and infrared spectroscopy. The nanoparticles are dispersed in elastomeric matrix, suppress effectively crystallization of POE and increase glass transition temperature of the matrix.     

Characterization of potash-glass corrosion in aqueous solution by ion beam and IR spectroscopy

In this work the corrosion processes of potash-glass surfaces in contact with aqueous solutions were studied using ion beam spectroscopic techniques, optical microscopy (OM) and Fourier transform infra-red (FTIR) spectroscopy. In order to follow the corrosion progress these surface studies were combined with the evaluation of the changes taking place in the aqueous solution. In particular, the hydrogen profiles obtained from the attacked surface region of glass were compared with the variation of pH values of the aqueous solutions, in order to extract information about the ion exchange processes. It is shown that pH values may also be a good parameter for studying corrosion kinetics in high humidity conditions. The two tests conditions explored (with and without stirring of the aqueous solution) proved to lead to different surface morphologies associated with different corrosion rates. Stirring results in a more fine grained and uniform morphology of the corrosion products and a higher corrosion rate.     

An investigation of the growth of β-BaB2O4 crystals in the BaB2O4-NaF system and new fluoroborate Ba2Na3[B3O6]2F

Crystallography Reports - The phase formation in the BaB2O4-NaF cut has been investigated by the methods of solid-phase synthesis, visual polythermal analysis, and spontaneous crystallization on a...     

Time resolved fluorescence and anisotropy of 1-pyrene butyric acid and pyranine as probes of solvent organization in sucrose solutions

The microenvironment of solute-solvent interactions in aqueous sucrose solutions, ranging from 0 to 80 wt% in concentration, was investigated using time resolved fluorescence techniques. The fluorescence lifetimes and rotational correlation times of the trace fluorescent probes, PBA (1-pyrene butyric acid) and pyranine (trisodium 8-hydroxy-1,3,6-pyrenetrisulfonate), were measured in sucrose solutions. The behavior of the fluorescence lifetimes and the increase in the rotational correlation times with increasing sucrose concentration provided no evidence for the formation of water exclusive solute clusters in the metastable solutions. Instead, the results indicated the formation of a network of hydrogen bonding interactions between dispersed sucrose molecules.     

Novel synthesis of gibbsite by laser-stimulated nucleation in supersaturated sodium aluminate solutions

Laser-induced localized density fluctuations are shown to stimulate primary nucleation of nano-sized aluminum trihydroxide seed crystals in flowing supersaturated industrial sodium aluminate solutions (Bayer liquor). The post-nucleation mass deposition rate is greatly increased over rates attainable through more traditional seeding methods. Near-ideal single-crystal gibbsite is formed under diffusion-limited growth conditions. Laser-stimulated nucleation represents an in situ method for the active local modulation of the supersaturation state, so that the stimulated nucleation occurs under macroscopic solution conditions that are unfavorable for spontaneous nucleation.