Observation of Combined Effect of Temperature and Pressure on Cubic to Hexagonal Phase Transformation in ZnS at the Nanoscale

The temperature of allotropic phase transformation in ZnS (cubic to wurtzite) changes with pressure and particle size. In this paper we have explored the interrelation among these through a detailed study of ZnS powders obtained by a temperature-controlled high energy milling process. By employing the combined effect of temperature and pressure in an indigenously built cryomill, we have demonstrated a large-scale, low-temperature synthesis of wurtzite ZnS nanoparticles. The synthesized products have been characterized for their phase and microstructure by the use of X-ray diffraction and transmission electron microscopic techniques. Further, it has been demonstrated that the synthesized materials exhibit photoluminescence emissions in the UV-visible region with an unusual doublet pattern due to the presence of both cubic and hexagonal wurtzite domains in the same particles. By further fine-tuning the processing conditions, it may be possible to achieve controlled defect related photoluminescence emissions from the ZnS nanoparticles.

Temperature-Induced Reversible First-Order Single Crystal to Single Crystal Phase Transition in Boc-gamma(4)(R)Val-Val-OH: Interplay of Enthalpy and Entropy

Crystals of Boc-gamma y(4)(R)Val-Val-OH undergo a reversible first-order single crystal to single crystal phase transition at T-c approximate to 205 K from the orthorhombic space group P22(1)2(1) (Z' = 1) to the monoclinic space group P2(1) (Z' = 2) with a hysteresis of similar to 2.1 K. The low-temperature monoclinic form is best described as a nonmerohedral twin with similar to 50% contributions from its two components. The thermal behavior of the dipeptide crystals was characterized by differential scanning calorimetry experiments. Visual changes in birefringence of the sample during heating and cooling cycles on a hot-stage microscope with polarized light supported the phase transition. Variable-temperature unit cell check measurements from 300 to 100 K showed discontinuity in the volume and cell parameters near the transition temperature, supporting the first-order behavior. A detailed comparison of the room-temperature orthorhombic form with the low-temperature (100 K) monoclinic form revealed that the strong hydrogen-bonding motif is retained in both crystal systems, whereas the non-covalent interactions involving side chains of the dipeptide differ significantly, leading to a small change in molecular conformation in the monoclinic form as well as a small reorientation of the molecules along the ac plane. A rigid-body thermal motion analysis (translation, libration, screw; correlation of translation and libration) was performed to study the crystal entropy. The reversible nature of the phase transition is probably the result of an interplay between enthalpy and entropy: the low-temperature monoclinic form is enthalpically favored, whereas the room-temperature orthorhombic form is entropically favored.

Stabilization of the high-temperature and high-pressure cubic phase of ZnO by temperature-controlled milling

The reversible transition of wurtzite to rock salt phase under pressure is well reported in literature. The cubic phase is unstable under ambient conditions both in the bulk and in nanoparticles. This paper reports defect-induced stabilization of cubic ZnO phase in sub 20 nm ZnO particles and explores their optical properties. The size reduction was achieved by ball milling in a specially designed mill which allows a control of the milling temperature. The process of synthesis involved both variation of milling temperature (including low temperature similar to 150 K) and impact pressure. We show that these have profound influence in the introduction of defects and stabilization of the cubic phase. A molecular dynamics simulation is presented to explain the observed results. The measured optical properties have further supported the observations of defect-induced stabilization of cubic ZnO and reduction in particle size.

Review: Overcoming the paradox of strength and ductility in ultrafine-grained materials at low temperatures

Ultrafine-grained (UFG) materials with grain sizes in the submicrometer or nanometer range may be prepared through the application of severe plastic deformation (SPD) to bulk coarse-grained solids. These materials generally exhibit high strength but only very limited ductility in low-temperature testing, thereby giving rise to the so-called paradox of strength and ductility. This paradox is examined and a new quantitative diagram is presented which permits the easy insertion of experimental data. It is shown that relatively simple procedures are available for achieving both high strength and high ductility in UFG materials including processing the material to a very high strain and/or applying a very short-term anneal immediately after the SPD processing. Significant evidence is now available demonstrating the occurrence of grain boundary sliding in these materials at low temperatures, where this is attributed to the presence of non-equilibrium grain boundaries and the occurrence of enhanced diffusion along these boundaries.

Synthesis of ZnO nanorods on a flexible Phynox alloy substrate: influence of growth temperature on their properties

A novel flexible alloy substrate (Phynox, 50 mm thick) was used for the synthesis of zinc oxide (ZnO) nanorods via a low-temperature solution growth method. The growth of ZnO nanorods was observed over a low temperature range of 60-90 degrees C for a growth duration of 4 hours. The as-synthesized nanorods were characterized using field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) for their morphology, crystallinity, microstructure and composition. The as-grown ZnO nanorods were observed to be relatively vertical to the substrate. However, the morphology of the ZnO nanorods in terms of their length, diameter and aspect ratio was found to vary with the growth temperature. The morphological variation was mainly due to the effects of the various relative growth rates observed at the different growth temperatures. The growth temperature influenced ZnO nanorods were also analyzed for their wetting (either hydrophobic or hydrophilic) properties. After carrying out multiple wetting behaviour analyses, it has been found that the as-synthesized ZnO nanorods are hydrophobic in nature. The ZnO nanorods have potential application possibilities in self-cleaning devices, sensors and actuators as well as energy harvesters such as nanogenerators.

Temperature dependent compressive behavior of graphene mediated three-dimensional cellular assembly

Mechanical behavior of three-dimensional cellular assembly of graphene foam (GF) presented temperature dependent characteristics evaluated at both low temperature and room temperature conditions. Cellular structure of GF comprised of polydimethyl siloxane polymer as a flexible supporting material demonstrated 94% enhancement in the storage modulus as compared to polymer foam alone. Evaluation of frequency dependence revealed an increase in both storage modulus and tan delta with the increase in frequency. Moreover, strain rate independent highly reversible behavior is measured up to several compression cycles at larger strains. It is elucidated that the interaction between graphene and polymer plays a crucial role in thermo-mechanical stability of the cellular structure. (C) 2015 Elsevier Ltd. All rights reserved.