On the kinetics of crystal growth from a supercooled melt

We present a theoretical analysis of the dynamics of crystal growth from a supercooled melt. A molecular theory of crystal growth that pays proper attention to the structure at the liquid-solid interface is discussed.

Crystal growth, transport and magnetic properties of rare-earth manganite Pr1-xPbxMnO3

Crystal growth, electrical and magnetic properties are reported for mixed valence manganite Pr1-xPbxMnO3 (x = 0.2, 0.23, and 0.3). The crystals with x = 0.2 and 0.23 are ferromagnetic and insulating, whereas that with x = 0.3 is ferromagnetic below 200 K and shows an insulator-metal transition at 235 K. This composition shows a magnetoresistance of 90% in a field of 5 T. In the paramagnetic region, the temperature dependence of magnetic susceptibility of the crystals follows a Curie-Weiss behavior. The thermal evolution of magnetization in the ferromagnetic phase varies as T-3/2, in accordance with Bloch's law. The spin-stiffness constant D obtained from the Bloch constant is found to increase linearly with x. The magnetization does not reach complete saturation upto a field of 5 T. A possible contribution of the Pr spins to the total magnetic moment is discussed.

Crystal growth and defects characterization of zinc tris (thiourea) sulfate: a novel metalorganic nonlinear optical crystal

Single crystals of the metalorganic nonlinear optical material zinc tris (thiourea) sulfate (ZTS) were grown from aqueous solution. The morphology of the crystals was indexed. The grown crystals were characterized by recording the powder X-ray diffraction pattern and by identifying the diffracting planes. Spectrophotometric studies on ZTS reveal that it has good transparency for the Nd: YAG laser fundamental wavelength. Differential thermal analysis of ZTS indicates that the material does not sublime before melting but decomposes immediately after melting. The defect content of the crystals was estimated using etching and X-ray topography. The mechanical hardness anisotropy was evaluated in the (100) plane, which indicates the presence of soft directions.

Crystal growth and nonlinear optical properties of sodium D-isoascorbate monohydrate

Optical quality single crystals of sodium D-isoascorbate monohydrate were grown by a slow cooling technique. The crystal possesses a bulky prismatic morphology. Thermal analyses indicate that the crystals are stable up to 125 degrees C. The optical transmission window ranges from 307 nm to 1450 nm. The principal refractive indices have been measured employing Brewster's angle method. The crystallographic and the principal dielectric axes coincide with each other such that a lies along Z, b along X and c along Y. The optic axis is oriented 58 degrees (at 532 nm) to the crystallographic a axis in the XZ plane and the crystal is negative biaxial. Type 1 and type 2 phase matching curves are generated and experimentally verified. No polarization dependence of the light absorption was observed confirming the validity of Kleinman's symmetry conjecture, leading to a single nonvanishing nonlinear tensor component. According to Hobden's classification the crystal belongs to class 3. The crystal also exhibits second order noncollinear conic sections. The single shot and multiple shot surface laser damage thresholds are determined to be 32.7 GW cm(-2) and 6.5 GW cm(-2) respectively for 1064 nm radiation.

Computer simulation of polytypes

Polytypes have been simulated, treating them as analogues of a one-dimensional spin-half Ising chain with competing short-range and infinite-range interactions. Short-range interactions are treated as random variables to approximate conditions of growth from melt as well as from vapour. Besides ordered polytypes up to 12R, short stretches of long-period polytypes (up to 33R) have been observed. Such long-period sequences could be of significance in the context of Frank's theory of polytypism. The form of short-range interactions employed in the study has been justified by carrying out model potential calculations.

Crystal growth and characterization of two-leg spin ladder compounds: Sr14Cu24O41 and Sr2Ca12Cu24O41

Single crystals of Sr14−xCaxCu24O41 (x=0 and 12) are grown by the travelling solvent floating zone technique using an image furnace. The grown crystals are characterized for their single crystallinity by the X-ray and Neutron Laue method. The magnetic susceptibility measurements in Sr14Cu24O41 show considerable anisotropy along the main crystallographic axes. Low-temperature specific heat measurement and DC susceptibility measurement in Ca-doped crystal showed antiferromagnetic ordering at 2.8 K at ambient pressure. High-pressure AC susceptibility measurement on Ca-doped crystal showed a sharp superconducting transition at 2 K under 40 kbars. Tc onset reached a maximum value of 9.9 K at 54 kbars. The bulk superconductivity of the sample is confirmed by the high-pressure AC calorimetry with Tc max=9.4 K and TN=5 K at 56 kbars.

Crystal structure from packing studies: application to the triclinic structure of the cyclic hexapeptide cyclo-(gly-tyr-gly)2

The paper describes a novel method of finding the position and orientation of a relatively rigid molecule in the unit cell from criteria concerning allowed contact distances between atoms. On application to the crystal structure of a hexapeptide, C25H31N6O8.2H2O, it was possible to solve the structure from this starting point, by a series of SFLS refinements with an increasingly larger number of reflexions at successive stages. The packing analysis succeeded, even though the water molecules were not included to start with.

Exceptionally long crystal formation from 4-(3-bromopropyloxy)salicylaldehyde. X-ray crystallographic investigation

Unusually long (>14 cm) crystalline needles grow from 4-(3-bromopropyloxy)salicylaldehyde 1 presumably as a consequence of Br ... Br interactions; the powdered form of 1 shows one order of magnitude greater SHG activity realtive to urea.

Directional grain growth from anisotropic kinetic roughening of grain boundaries in sheared colloidal crystals

The fabrication of functional materials via grain growth engineering implicitly relies on altering the mobilities of grain boundaries (GBs) by applying external fields. Although computer simulations have alluded to kinetic roughening as a potential mechanism for modifying GB mobilities, its implications for grain growth have remained largely unexplored owing to difficulties in bridging the widely separated length and time scales. Here, by imaging GB particle dynamics as well as grain network evolution under shear, we present direct evidence for kinetic roughening of GBs and unravel its connection to grain growth in driven colloidal polycrystals. The capillary fluctuation method allows us to quantitatively extract shear-dependent effective mobilities. Remarkably, our experiments reveal that for sufficiently large strains, GBs with normals parallel to shear undergo preferential kinetic roughening, resulting in anisotropic enhancement of effective mobilities and hence directional grain growth. Single-particle level analysis shows that the mobility anisotropy emerges from strain-induced directional enhancement of activated particle hops normal to the GB plane. We expect our results to influence materials fabrication strategies for atomic and block copolymeric polycrystals as well.

Crystal engineering: from molecule to crystal

How do molecules aggregate in solution, and how do these aggregates consolidate themselves in crystals? What is the relationship between the structure of a molecule and the structure of the crystal it forms? Why do some molecules adopt more than one crystal structure? Why do some crystal structures contain solvent? How does one design a crystal structure with a specified topology of molecules, or a specified coordination of molecules and/or ions, or with a specified property? What are the relationships between crystal structures and properties for molecular crystals? These are some of the questions that are being addressed today by the crystal engineering community, a group that draws from the larger communities of organic, inorganic, and physical chemists, crystallographers, and solid state scientists. This Perspective provides a brief historical introduction to crystal engineering itself and an assessment of the importance and utility of the supramolecular synthon, which is one of the most important concepts in the practical use and implementation of crystal design. It also provides a look to the future from the viewpoint of the author, and indicates some directions in which this field might be moving.

Nucleation of a Stable Solid from Melt in the Presence of Multiple Metastable Intermediate Phases: Wetting, Ostwald's Step Rule, and Vanishing Polymorphs

In many systems, nucleation of a stable solid may occur in the presence of other (often more than one) metastable phases. These may be polymorphic solids or even liquid phases. Sometimes, the metastable phase might have a lower free energy minimum than the liquid but higher than the stable-solid-phase minimum and have characteristics in between the parent liquid and the globally stable solid phase. In such cases, nucleation of the solid phase from the melt may be facilitated by the metastable phase because the latter can ``wet'' the interface between the parent and the daughter phases, even though there may be no signature of the existence of metastable phase in the thermodynamic properties of the parent liquid and the stable solid phase. Straightforward application of classical nucleation theory (CNT) is flawed here as it overestimates the nucleation barrier because surface tension is overestimated (by neglecting the metastable phases of intermediate order) while the thermodynamic free energy gap between daughter and parent phases remains unchanged. In this work, we discuss a density functional theory (DFT)-based statistical mechanical approach to explore and quantify such facilitation. We construct a simple order-parameter-dependent free energy surface that we then use in DFT to calculate (i) the order parameter profile, (ii) the overall nucleation free energy barrier, and (iii) the surface tension between the parent liquid and the metastable solid and also parent liquid and stable solid phases. The theory indeed finds that the nucleation free energy barrier can decrease significantly in the presence of wetting. This approach can provide a microscopic explanation of the Ostwald step rule and the well-known phenomenon of ``disappearing polymorphs'' that depends on temperature and other thermodynamic conditions. Theory reveals a diverse scenario for phase transformation kinetics, some of which may be explored via modem nanoscopic synthetic methods.

Carbon nanoflake growth from carbon nanotubes by hot filament chemical vapor deposition

We report the growth of carbon nanoflakes (CNFs) on Si substrate by the hot filament chemical vapor deposition without the substrate bias or the catalyst. CNFs were grown using the single wall carbon nanotubes and the multiwall carbon nanotubes as the nucleation center, in the Ar-rich CH4-H-2-Ar precursor gas mixture with 1% CH4, at the chamber pressure and the substrate temperature of 7.5 Ton and 840 degrees C, respectively. In the H-2-rich condition, CNF synthesis failed due to severe etch-removal of carbon nanotubes (CNTs) while it was successful at the optimized Ar-rich condition. Other forms of carbon such as nano-diamond or mesoporous carbon failed to serve as the nucleation centers for the CNF growth. We proposed a mechanism of the CNF synthesis from the CNTs, which involved the initial unzipping of CNTs by atomic hydrogen and subsequent nucleation and growth of CNFs from the unzipped portion of the graphene layers. (C) 2013 Elsevier Ltd. All rights reserved.