The influence of additives on the crystal habit of gibbsite

Crystallization of gibbsite (Al(OH)₃) is an important stage of the Bayer process, production of alumina from bauxite ores. In both pure or industrial supersaturated sodium aluminate solutions, gibbsite crystals are always agglomerated. In the present paper, we present results of a study concerning the influence of different polycarboxylic acids as crystal habit modifier for gibbsite. In pure solution, agglomerated hexagonal plates are observed. Whereas acicular and tabular morphologies are found in the presence of different additives. These results are discussed referring to the crystallographic structure of gibbsite. It is found that only oxygen atoms are present on gibbsite surface. This observation leads us to propose an additive way of acting by formation of a molecular complex between the growth unit and the carboxylic groups of the additive.     

Influence of solvent and crystallization method on the crystal habit of metronidazole

In the present study, metronidazole was crystallized in several solvents, according to both the “cooling crystallization” and the “crystallization by non‐solvent addition”. Particle properties, such as crystal habit, elongation ratio, and mean particle size, were determined by SEM analysis. Structural changes and development of polymorphic forms were excluded by both Differential Scanning Calorimetry (DSC) and X‐Ray Powder Diffractometry (XRPD). Crystal habit (and thus elongation ratio) was typically influenced by both the solvent polarity index and the crystallization method: solvents with higher polarity index tended to promote acicular or stick‐shaped crystals with a high elongation ratio, while isodimensional crystals were promoted by decreasing the polarity index, as was particle aggregation. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of solvents and crystallization conditions on crystal habit of cholesterol

The effect of various organic solvents as well as the crystallization conditions on the crystal habit of anhydrous cholesterol have been studied. Both plates and needle-like crystals can be obtained in a particular solvent depending on the degree of supersaturation of the solution. However, the crystals grown at about the same supersaturation, from different solvents, show differences in their habit indicating dependence on the solvent-solute interaction. Thus, it is advisable not to identify needle-like crystals with anhydrous-cholesterol and plates with mono-hydrate cholesterol without specifying the crystallization conditions. A prediction on the crystal habit length to width ratios can be made using those parameters.     

Crystal habit prediction ‐ Including the liquid as well as the solid side

Commercially available methods of morphology prediction utilize molecular dynamics to estimate the crystal growth rates but predominantly consider the solid side. For the extension of these methods to a multi‐component solid‐liquid system the diffusion coefficient is required. Since, the diffusion coefficient enables the calculation of crystal growth rates and the morphology in presence of additives and solvents. Modeling the diffusion coefficient is achieved by conducting MD on a system consisting of the crystal surface and the liquid phase. The achieved results match very well with the calculated diffusion coefficient (Wilke‐Chang). In this case study benzoic acid is used as model substance with water as solvent.     

The effect of fluoride ion concentration on apatite formation and on its crystal habit

The effect of fluoride ions on the rate of apatite [ca_10(PO4)6(F,OH)₂] formation and on its crystal habit was investigated. It was found that both at high and at low fluoride concentrations the rate formations is retarded. At two optimal concentrations, namely at 3.4 and 5.5 fluoride: apatite excess of the stoichiometric ratio, the rate is the highest. The crystal habit of the apatite formed at high fluoride concentrations is hexagonal plate-like, while the apatite formed at low fluoride concentrations is dendritic or needle-like. The concentrations of fluoride in the crystals were determined by specific fluoride electrode technique.     

Stability of growth conditions and α-HgI2 crystal habit during growing by temperature oscillation method

On the basis of analysis of the experimental data, it is shown that:

• the crystal growth rate is mainly determined by diffusion in vapour phase;
• the limitation of the growth process by transport leads to an unremitting change of the growth conditions, being the cause of slowing down the growth and the change of the growth rates ratio of the crystallographically different facets, the latter evokes refaceting;
• the limitation of the growth by the transport process is the factor reducing the perfection of the structure and the maximum sizes of single crystals.

     

Lactose particle engineering: Influence of ultrasound and anti-solvent on crystal habit and particle size

This study focuses on ultrasound-assisted anti-solvent crystallization of lactose, expanding on previous studies and presenting, for the first time, the results of large scale implementation of sonocrystallization for lactose. The results further clarify the interplay between solution chemistry – namely the role of β-lactose – and crystallization, representing a step forward in the fine tuning of lactose properties for pharmaceutical manufacturing applications. Batches manufactured at laboratory and pilot scales were extensively characterised, including an approach for the quantification of β-lactose in α-lactose based on powder X-ray diffraction (PXRD), which is described here.     

Improvement of growth habit and optical properties of rapidly grown KDP crystal by adding diethylene triamine pentacetate acid in growth solution

By altering the concentration of a new additive ‐ diethylene triamine pentacetate acid (DTPA) in the growth solution, a series of KDP crystals were obtained by the “point seed” rapid growth method. The growth rates up to about 20 mm/day. Effects of DTPA on the growth habit and optical properties of these as‐grown KDP crystals were investigated. The results reveal that, with the increase of DTPA concentration in growth solution, the contents of impurity metal ions incorporated into crystal and aspect ratio of crystal morphology were both decreased gradually, while the UV transmittance of crystal was enhanced continually. In the presence of moderate concentration of DTPA (100–200 ppm), the solution stability was increased and optical properties of crystal (including optical homogeneity, light scattering and laser damage threshold) were all improved. However excessive doping (>500 ppm) has opposite effects. The impact mechanism was also analyzed combining with the structure of KDP crystal and chemical characteristics of DTPA molecular.     

On the influence on tracht and habit of urea crystals (II)

It is shown that during crystallization urea forms mixed crystals, adsorption mixed crystals, and epitaxial growth from aqueous solutions with inorganic salts, the lattice parameters of which are lying within the tolerance of efficiency parameters of urea. The extent of the formation of mixed crystals is determined by the composition of the solution. The slats added to the solution affect changes of tracht and habit of urea and thus are important for improving storage and transport properties. Similar results can be found for modified melts of urea.     

Influence of SiO32‐ impurity on growth habit of potassium dihydrogen phosphate crystal

By altering the concentration of silicate (SiO₃^2‐) impurity in the solution, a series of potassium dihydrogen phosphate (KDP) crystals was obtained by the conventional temperature cooling and the rapid growth methods, respectively. It was observed that the presence of SiO₃^2‐ made KDP crystals tapering in conventional cooling method, while more SiO₃^2‐ induced inclusions at prismatic sectors in the rapid growth method. Laser‐polarization‐interference results showed that SiO₃^2‐ extended the dead zone and reduced the growth rate of (100) face of KDP crystals. The negative influence of SiO₃^2‐on the growth was considered absolutely similar to the effect of cations. It was also suggested that the stability of solution doped with SiO₃^2‐ was improved without seed crystals, while it was destructed with seed crystals. The inhibition mechanism was analyzed in terms of SiO₃^2‐ absorption on (100) face. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the surface mechanism of crystal melting

A crystal melting mechanism is proposed. The melting is caused by enhanced thermal expansion of the lattice on the surface and around structure defects. For the microcrystallites formed this way an approximate calculation of parameters is made. The microcrystallites surface area per mole is shown to be thousands of m², the radius within 1.5 to 10 nm, the gaps between microcrystallites — by 30 percent more than the lattice interatomic distance. The mean thermal linear expansion coefficients determined on the crystal surface are roughly ten times as much as the bulk values.     

Magnetic crystal structure of iron as revealed by electron interference

Crystallographic axis of a magnetic domain found in iron crystals has been revealed to be [100] by means of electron interference. An empirical formula for the magnetic analysis was proposed which permitted to treat quantitatively the experimental results obtained. It was necessary for carrying out the magnetic analysis by electron diffraction to utilize an electron beam of rather high energy, i.e. accelerated with about 200 kV. Representation of Ewald's reciprocal lattice was applicable suitably to the magnetic analysis of ferromagnetics in terms of electron interference.     

On the thermodynamics of homogeneous crystal nucleation

A correct phenomenological consideration is given to the change in the Gibbs thermodynamic potential in the course of crystal nucleation. It is proved that this process is described by two activation barriers.     

On the mechanisms of modulation of crystal structures

Based on the assumption that crystal structures of a number of sulfides are the result of modulation of cationic lattices by anionic lattices, the versions of their conjugation in direct and reciprocal spaces have been analyzed using common translational lattices. The concept of this phenomenon, developed within the superspace formalism, is supplemented by a proposed interpretation of the real modulation of the structures.     

On the bindings in the crystal phases of Mn

The heterotypism of Mn may be interpreted energetically when a temperature dependent valence electron concentration is supposed which takes on values between 2.2 and 0.6 electrons per atom. The room temperature phase Mn.r (= αMn) belongs to a series of structural types: Cr₃Si, U.h₁ (= βU), Mn.r, which occur in alloy systems such as MoRe_M (M = undetermined mole number) at certain values of the averaged group number (AGN) of the perodic system of chemical elements (rule of Raub). An interpretation of the series by means of the plural-correlations model becomes possible when instead of the (Ekmanian) AGN count another (non-Ekmanian) electron count is used. The phase Mo₃Re (Cr₃Si-type) yields a simple bonding type (binding) which undergoes moderate transformations to form the phases Mo₂Re₃(U.h₁) and MoRe₃(Mn.r) and the binding of MoRe₃ may be taken to be valid also for Mn.r; it corresponds to the valence electron concentration N′^A_b = 2.16. For the high temperature phases Mn.h₁ (= βMn) and Mn.h₂ (= γMn) the values N′^A_b = 1.6 and 1.0 are probable and allow the brass-like structures Mn.h₁ (C20) and Cu(Fl). The binding of Mn.h₂, incidentally, explains the occurrence of the tetragonal metastable phase Mn.m. finally Mn.h₃ (= δMn) crystallizing in the W-type is isodesmic to Fe.h₂ (= δFe), i.e. of the same binding.     

On the initial stages of skeletal crystal growth

The transition from isometric into skeletal form of a crystal growing under diffusion control is explained as a result of the transition from a global compensation of the super-saturation nonhomogeneity, i.e. in the framework of the whole crystal face, to a spatially limited one. The said compensation is now possible only in the region of the macroscopically flat margin surrounding the gross morphological defect (in the form of a depression) which is the immediate result of the uneven, and unsufficient matter supply.     

On the crystal structure stability of calcite-type carbonates

The preparation of carbonates of the bivalent metals (Mg, Ca, Ba, Sr, Mn, Fe, Co, Ni, Cu and Zn) by two methods under ordinary conditions has been investigated. The stability of calcite type carbonates has been discussed. The shortest O—O distance (d*_O—O) between two neighbouring octahedra has been proposed as a criterion for the formation of stable calcite type carbonates. The lower stereochemical boundary of the calcite carbonate stability has been found to be d*_O−O ∼ 2.9 Å. The relative stability of carbonates with d_O−O* < 2.9 Å (Zn, Co and Ni) has been studied with respect to their isomorphous incorporation into MnCO₃.     

Understanding the effect of solvent polarity on the habit modification of monoclinic paracetamol in terms of molecular recognition at the solvent crystal/interface

The habit change of monoclinic paracetamol crystallized from solutions with different solvents such as water, ethanol, methanol, acetone, isopropyl alcohol, tetrahydrofuran, cyclohexanone, acetonitrile and 1, 4 ‐ dioxane was investigated. Change in solubility, pH and nucleation time of paracetamol in these solvents at ambient condition was studied. The polymorphic form of the nucleated paracetamol was observed under in‐situ optical microscopy. Solutions with different solvents having different chemical nature and polarity yielded paracetamol crystals with different habits: columnar morphology from polar protic water and prismatic morphology from other selected polar protic, aprotic and in non‐polar solvents. The significant differences on the growth rate of various crystal habit faces of the monoclinic paracetamol grown from different solvents are attributed in context with the solubility of the solute, solvent polarity, evaporation number of the solvent, rate of generation of supersaturation and the role of hydrogen bonding interaction between the solvent molecules and protruding solute molecules on the crystal surface. Among the solution with different solvents, bulk monoclinic paracetamol single crystal was grown from ethanolic solution using seed rotation technique by controlled cooling method.     

Anomalous small-angle scattering as a way to solve the Babinet principle problem

X-ray absorption spectra (XAS) have been used to determine the absorption edges of atoms present in a sample under study. A series of small-angle X-ray scattering (SAXS) measurements using different monochromatic X-ray beams at different wavelengths near the absorption edges is performed to solve the Babinet principle problem. The sizes of clusters containing atoms determined by the method of XAS were defined in SAXS experiments. In contrast to differential X-ray porosimetry, anomalous SAXS makes it possible to determine sizes of clusters of different atomic compositions.