Microwave assisted synthesis of hydroxyapatite nano strips

Synthesis of hydroxyapatite (HAP) nano strips was carried out by chemical precipitation method followed by microwave irradiation. The microwave assisted reactions proceed at fast rates. It is found that the presence of the complex reagent EDTA plays an important role in the morphological changes of nanostructure hydroxyapatite. EDTA acts as a hexadentate unit by wrapping itself around the Ca²⁺ metal ion with, four oxygen and two nitrogen atoms and forms several five member chelate rings. The relative specific surface energies associated with the facets of the crystal determines the shape of the crystal. Scanning electron microscopy revealed the presence of hydroxyapatite nano strips with the range 50‐100 nm in EDTA influenced HAP powders. Fourier transform‐infrared spectroscopy (FT‐IR) result combined with the X‐ray diffraction (XRD) indicates the presence of amorphous hydroxyapatite (HAP) in the as‐prepared material. X‐ray patterns collected on the powder after heat‐treatment at 1100 °C for 2 h in air exhibits single phase of HAP. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation and characterization of monodispersed PbSe nanocubes

Monodispersed PbSe nanocubes were synthesized through a simple hydrothermal method by using Pb²⁺‐EDTA complex and Na₂SeSO₃. Composition and morphology of the samples were characterized by means of XRD, TEM and SEM. The gradually releasing of Pb²⁺ from Pb²⁺‐EDTA complex, and the adopting of PVP can adjust the growth rate in <100> and <111> directions of PbSe. Both Pb²⁺‐EDTA complex and PVP played important roles in the crystal growth of the monodispersed PbSe nanocubes. In addition, UV‐vis and photoluminescence properties were characterized. E_g of the PbSe nanocubes is 1.5 eV approximately, which is much larger than that of bulk PbSe. Under PL excitation at 406 nm, a red emission peak at 696 nm is observed, showing that the synthesized PbSe is luminescent nanomaterials. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of cationic impurities on solubility and crystal growth processes of ammonium oxalate monohydrate: Role of formation of metal‐oxalate complexes

The effect of different bi‐ and trivalent cationic impurities on the solubility of ammonium oxalate and the composition and distribution of chemical complexes formed in saturated ammonium oxalate aqueous solutions as a function of impurity concentration are investigated. The knowledge of the composition and stability of complexes formed in saturated aqueous solutions is then employed to explain the appearance of dead zones of supersaturation for growth and the difference in the effective segregation coefficient of the impurities. Analysis of the experimental results revealed that: (1) at a constant temperature, the dependence of concentration of complex species formed in saturated solutions on the concentration of different impurities can be described by an equation similar to that of the concentration dependence of density of solutions, (2) the dominant metal‐containing species present in saturated solutions are negatively‐charged, most stable oxalato complexes like Cu(C₂O₄)₂²⁻, Mn(C₂O₄)₃⁴⁻, Zn(C₂O₄)₃⁴⁻, Cr(C₂O₄)₃³⁻ and Fe(C₂O₄)₃³⁻, (3) in the investigated range of impurity concentration, the solubility of ammonium oxalates increases linearly with the concentration of all impurities and the increase is associated with the stability of dominant complexes, (4) appearance of dead supersaturation zones in the presence of impurities is associated with instantaneous adsorption of all growth sites by dominant oxalato complexes in relatively short adsorption time, and (5) the segregation coefficient of an impurity cation M of charge z + increases with a decrease in the solubility product constant K_sp for the hydrolysis products of reactions of the type: M^{z +} ↔ M₁^{(z −1)+} + H⁺ (where the cation M has z + charge, and H⁺ is hydrogen ion). (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Distribution of metallic ions in a single KDP crystal grown from aqueous solution

A single KDP (potassium dihydrogen phosphate) crystal was grown in a supersaturated solution containing a metallic ion (Al³⁺, Fe³⁺, or Cr³⁺). The growth rate, morphology, and distribution of the metallic ions into the KDP crystal were measured as the ionic concentration and supersaturation in the solution changed. It was found that in the KDP crystal, Al³⁺ and Fe³⁺ were greatly concentrated, but Cr³⁺ was diluted. Complete expressions for the effect of metallic ions on all aspects of the growth of KDP crystal were suggested. The growth rates of (100) and (101) faces were well correlated by the empirical equation and resulted in good estimation of morphology. The distribution of metallic ions into KDP crystal was also correlated by the distribution model. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gas bubble associated mass transport in Bridgman-Stockbarger melt growth system

Experimental evidence has been obtained showing that gas bubbles may be responsible for melt stirring in Bridgman-Stockbarger growth system which results in Pfann type impurity distribution profiles along the crystal length. The hypothesis of the gas bubble associated mass transfer mechanism is supported by the production of Y₃Al₅O₁₂–Nd³⁺ single crystals under conditions which eliminate or limit gas bubble nucleation in the melts with Nd³⁺ distribution profiles similar to those generally observed in melt growth systems where the mass transport in the melts is limited to diffusion.     

Characterization of defects generated by di-and trivalent cations in the potassium-dihydrophosphate structure and their influence on growth kinetics and face morphology

Different types of defect sites generated by the impurities of divalent (M²⁺) and trivalent (M³⁺) metals in the structure of potassium dihydrophosphate KH₂PO₄ (KDP) were revealed by crystal-chemical analysis and computer simulation. These sites cause different deformations of the crystal matrix by generating different local strains, which enhance the inhibiting effect of impurity atoms adsorbed on the surface. This fact accounts for the different influence of di-and trivalent cations on the growth kinetics and face morphology of KDP crystals. The effect of the M³⁺ ions is associated primarily with their adsorption on the face surfaces, whereas the influence of the M²⁺ ions results from their insertion into the surface layer of the crystal.     

Optical absorption spectra of LiNbO3, Fe:LiNbO3, and Zn:Fe:LiNbO3 single crystals grown by Bridgman method

The optical absorption spectra of LiNbO₃ (LN), Fe:LiNbO₃ (Fe:LN), and Zn:Fe:LiNbO₃ (Zn:Fe:LN) single crystals grown by Bridgman method were measured and compared. The absorption characteristics of the samples and the effects of growth process conditions on the absorption spectra were investigated. The Fe, Zn and Li concentrations in the crystals were analyzed by inductively coupled plasma (ICP) spectrometry. The results indicated that the overall Fe ion and Fe²⁺ concentration in Fe:LN and Zn:Fe:LN crystals increased along the growing direction. The incorporation of ZnO in Fe:LN crystal induced increase of Fe²⁺ in the crystal. Among Fe‐doped and Zn:Fe‐codoped LN single crystals, 3 mol% ZnO doped Fe:LN had a biggest change of Fe²⁺ ion concentration from bottom to top part of crystal. The effects of technical conditions (atmosphere and thermal history) on Fe²⁺ ion concentration were discussed. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of zinc doping on pentaerythritol tetranitrate single crystals

In this study, the effect of zinc impurity on the organic high explosive pentaerythritol tetranitrate (PETN) single crystal has been investigated with optical microscopy and ex situ atomic force microscopy (AFM). The optical images show that the crystal shape has a transition with a predictable trend from long crystal to compact one as the zinc concentration is increased. Also, the 2‐dimentional (2‐D) growth hillocks are observed clearly on (110) face with contact AFM. The crystal growth occurs on monomolecular steps generated by 2‐D nucleation and followed by layer‐by‐layer expansion, and the macro‐steps formed onto the surface before spreading laterally as step bunches. The zinc ions are incorporated in growth steps as the zinc concentration is increased. The mechanism of inorganic impurity on molecular crystallization growth is still unclear. However, the incorporation of impurities may significantly affect growth kinetics of defect structure, and the bulk properties of molecular crystals. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Internal stress in doped NH<Subscript>4</Subscript>Cl:Mn<Superscript>2+</Superscript> crystals

The relationship of the effect of impurity on crystal growth and morphology, along with the internal stress and anomalous birefringence arising upon impurity trapping by a growing crystal, is considered. The NH₄Cl-MnCl₂-H₂O-CONH₃ model system and the heterostructural NH₄Cl:Mn²⁺ crystals formed in it are experimentally studied. It is found that up to 6.63 wt % Mn²⁺ impurity is effectively captured by growing NH₄Cl crystals at an impurity trapping coefficient only slightly below unity. The effect of Mn impurity stabilizes the full-face growth of NH₄Cl crystals with a rhombododecahedral habit in aqueous solutions and a cubic habit in water-formamide solutions. The trapping of manganese impurity by ammonium chloride crystals causes high internal stress (up to 4 GPa) in them, which manifests itself in the form of anomalous birefringence and leads to splitting, twinning, and cracking in NH₄Cl crystals.     

Cr3+‐doped LiNbO3 crystals grown by the Bridgman method

The growth of LiNbO₃ crystals doped with Cr³⁺ ions in 0.1, 0.2, and 0.5 mol % concentrations by Bridgman method were reported. The Cr³⁺ ion concentrations in crystals were measured by inductively coupled plasma spectrometry. Electron paramagnetic resonance had been used to investigate the sites occupied by the Cr³⁺ ions. Two Cr³⁺ ion centers located at Li⁺ and Nb⁵⁺ sites (Cr_Li³⁺ and Cr_Nb³⁺ centers, respectively) were observed. Optical absorption and temperature‐dependence emission spectra of the Cr³⁺ ions were reported. The crystal‐field parameters and Racah parameters of the Cr³⁺ ion defect sites were reported and compared with those grown by Czochralski technique. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Impurity adsorption mechanism of borax for a suspension growth condition: A comparison of models and experimental data

A fluidized bed crystallizer is employed to investigate the growth and dissolution rates of MgSO₄·7H₂O from aqueous solutions in the presence of borax as impurity at 25°C. By adding 0.5, 1, 2 and 5 wt % of impurity the pH value changes from 6.7 to 7.11, while the saturation temperature shifts to 24.8, 24.4, 24 and 23.1°C, respectively. The data on crystal growth rates from aqueous solutions as a function of impurity concentration are discussed from the standpoint of Cabrera and Vermileya, and Kubota and Mullin. The value of the impurity effect, αθ_eq, determined from analysis of the data on growth kinetics was found to be in good agreement with the value obtained from direct adsorption experiments. The estimated value of the average spacing between the adjacent adsorption active sites and the average distance between the neighbouring impurity‐adsorbed sites are also reported. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Impurity effect of iron(III) on the growth of potassium sulfate crystal in aqueous solution

Growth rates of the {1 1 0} faces of a potassium sulfate crystal were measured in a flow cell in the presence of traces of impurity Fe(III) (up to 2 ppm) over the range of pH=2.5–6.0. The growth rate was significantly suppressed by the impurity. The effect became stronger as the impurity concentration was increased and at pH<5. It became weaker with increasing supersaturation. It also became weaker as the pH was increased and at pH>5 it finally disappeared completely. The concentration and supersaturation effects on the impurity action were reasonably explained with a model proposed by Kubota and Mullin [J. Crystal Growth, 152 (1995) 203]. The surface coverage of the active sites by Fe(III) is estimated to increase linearly on increasing its concentration in solution in the range examined by growth experiments. The impurity effectiveness factor is confirmed to increase inversely proportional to the supersaturation as predicted by the model. Apart from the discussion based on the model, the pH effect on the impurity action is qualitatively explained by assuming that the first hydrolysis product of aqua Fe(III) complex compound, [Fe(H₂O)₅(OH)]²⁺, is both growth suppression and adsorption active, but the second hydrolysis product, [Fe(H₂O)₄(OH)₂]⁺, is only adsorption active.     

The role of hydration and complexing in the mechanism of impurity influence on crystal growth

The influence of impurities of chlorides and nitrates of divalent Ca²⁺ and Ba²⁺ cations on the kinetic growth of potassium dihydrophosphate KH₂PO₄ crystals at a saturation temperature of 323 K and relative supersaturation of 0.03 has been investigated experimentally. It is established that the impurity acts differently, depending on the face index, the impurity concentration, cation hydration, and the stability of the complexes formed in the solution by impurity salt ions. A model is proposed to explain the different influence of impurity ions on the growth of crystal faces. This influence is determined by the different hydration of cations and enhanced association of cations and anions of impurity salts in the surface layer with a lower dielectric constant.     

KDP晶体中包裹体形成机制的探讨

本文介绍了包裹体对KDP晶体质量的影响,并从两个方面探讨了KDP晶体生长过程中包裹体的形成机制.通过分析KDP晶体表面原子结构研究了不同杂质的吸附情况以及杂质对生长台阶的阻碍作用,通过分析晶体生长过程中流体动力学和质量输运条件的变化研究了旋转晶体的流体切应力和表面过饱和度,结果表明吸附杂质对生长台阶的阻碍和表面过饱和度的不均匀造成了生长台阶的弯曲和宏观台阶的形成,导致生长台阶形貌的不稳定是包裹体形成的重要原因.     

Temperature‐concentration oscillations of crystal‐solution phase equilibria in the presence of trace impurities of surface‐active agents

Using the examples of aqueous salt solutions NaNO₃, KNO₃, RbNO₃, K₂SO₄, NaBr·2H₂O, KBr, and NH₄NO₃, it was experimentally proven that the new phenomena, i.e. temperature‐concentration oscillations of crystal‐solution phase equilibria detected previously in the range of 15–45 °C remain in the presence of trace impurities (10^‐4–10^‐3 wt. %) of ion‐active organic matters. The signs of breaks transformation into pair oscillations of “maximum‐minimum” type are established for the K₂SO₄, NaBr, KBr solutions. The efficiency of influence of trace impurities on phase equilibria sharply rises in the areas of the temperature‐concentration oscillations (the saturation temperature ranges up to 10 K). The impurity efficiency is promoted by the presence of the amides in its content (as compared with the sulphates) and an increase in length of the hydrocarbon radical. The phenomenon is absent in case of an addition of ion‐inactive compounds. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the origin of supersaturation barriers during the growth of single crystals from aqueous solutions containing impurities – a review

A generalised treatment of the appearance of supersaturation barriers σ_d, σ* and σ** during the growth of single crystals is outlined from the standpoint of well‐defined critical values of relative step velocities on a face. The final theoretical expressions are based on the premise that: (1) there are critical values of the relative step velocities associated with different average distances between adsorbed impurity particles during instantaneous, time‐dependent and time‐independent adsorption of the impurity on the growing surface, (2) the growth rate of a face is proporptional to velocity of steps on the growing face, and (3) Freundlich and Langmuir adsorption isotherms apply for different impurities. The theoretical expressions are then used to critically analyse the experimental data on supersaturation barriers observed during the growth of ammonium oxalate monohydrate and potassium dihydrogen phosphate single crystals from aqueous solutions containing different impurities. It was found that: (1) Langmuir adsorption isotherm is more practical for the analysis of the experimental data of the dependence of supersaturation barriers σ_d, σ* and σ** on the concentration c_i of an impurity, and (2) the ratios σ_d/σ* and σ*/σ** of successive supersaturation barriers for an impurity either increases or remains constant with an increase in impurity concentration c_i, and may be explained in terms of the mechanism of adsorption of impurity particles. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of impurity adsorption on the growth of Rochelle salt crystals

The influence of impurities of copper compounds on the growth of Rochelle salt crystals of the composition KNaC₄H₄O₄ · 4H₂O is studied. The growth rates of the faces of various simple forms experimentally measured as functions of the CuCO₃ concentration in solution at a constant supersaturation and temperature are compared with the theoretical models of impurity adsorption on the faces of a growing crystal. Deceleration of the growth of various faces of a Rochelle salt crystal is satisfactorily described by the Bliznakov equation with the use of the Langmuir, Frumkin-Fowler, and de Boor adsorption isotherms for all the faces except for {010}. However, such a comparison does not allow one to reveal the cause of adsorption or its type on different faces. Photometric scanning of Rochelle salt solutions with copper-compound impurity showed that a small addition of alkali (0.06–0.4 g/l) to the solution results in the appearance in the absorption spectra of both the solution nd the crystal grown from it of a maximum at the wavelength 660–670 nm. The intensity of this maximum increases with an increase in the copper concentration. The EPR data, the absorption spectra of the solution and the crystal, and the modified crystal shape showed that the addition of alkali to the solution results in the formation of new copper complexes that more actively decelerate the growth of Rochelle salt faces.     

Impurity effects on low-angle boundary formation in silicon single crystals

The combined effects of crystal growth conditions and impurity (Sb, P, B, Ga) concentration on low-angle boundary (LAB) formation in silicon single crystals growing by Czochralski technique was investigated. The dependence of LAB formation frequency and LAB parameters on crystal growth conditions and impurity content was found. Impurity effects on LAB formation become apparent at concentrations of about 10¹⁸ cm⁻³. – All impurity investigated decreases the probability of LAB formation, the acceptor impurity influence is stronger. At B concentration exceeding 2 · 10¹⁹ cm⁻³ LAB formation does not occur. – Results are interpreted in terms of scheme of LAB formation in thermal stress field of growing crystal. To explain observed impurity effects assumptions about dislocation drag and about raising of critical stresses for dislocation generation with doping are made.     

The catalytic effect of impurity. The effect of benzene, acetone, organic acids, iron, and chromium on growth of KH2PO4 and C8H5O4K crystals

The effect of benzene, acetone, acetic, formic, and oxalic acids, iron, and chromium on the growth kinetics of KH₂PO₄ and C₈H₅O₄ K crystal faces has been studied. It is found that low concentrations of organic impurities increase growth rates of some crystal faces (the so-called catalytic effect of impurity). This effect is rather weak in the case of organic acids, however, it is clearly seen in the presence of inorganic impurity (Fe³⁺). The analysis of two models of growth (dislocation-free and B + S) under the assumption that the main cause of the catalytic effect is a decrease in the step energy showed that the calculated and experimental data are consistent only under certain assumptions that should be additionally verified both theoretically and experimentally.     

Fluorescence properties of Nd3+ doped stoichiometric LiNbO3 fiber single crystals by micro‐pulling down method

Using the micro‐pulling down (μ‐PD) method, 1 and 3 mol% Nd₂O₃ doped near stoichiometric lithium niobate (LiNbO₃) single crystal fibers were grown in 1 mm diameter and 35∼40 mm length. The grown crystal fibers were free of cracks and the homogeneous distribution of Nd³⁺ ion concentrations were confirmed by the electron probe micro analysis. The changes of fluorescence spectra were measured with respect to the Nd³⁺ ion doping concentration. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)