Size and temperature dependent stability and phase transformation in single-crystal zirconium nanowire

A novel size dependent FCC (face-centered-cubic) -> HCP (hexagonally-closed-pack) phase transformation and stability of an initial FCC zirconium nanowire are studied. FCC zirconium nanowires with cross-sectional dimensions < 20 are found unstable in nature, and they undergo a FCC -> HCP phase transformation, which is driven by tensile surface stress induced high internal compressive stresses. FCC nanowire with cross-sectional dimensions > 20 , in which surface stresses are not enough to drive the phase transformation, show meta-stability. In such a case, an external kinetic energy in the form of thermal heating is required to overcome the energy barrier and achieve FCC -> HCP phase transformation. The FCC-HCP transition pathway is also studied using Nudged Elastic Band (NEB) method, to further confirm the size dependent stability/metastability of Zr nanowires. We also show size dependent critical temperature, which is required for complete phase transformation of a metastable-FCC nanowire.

Perovskite phase transformation in 0.65Pb(Mg1/3Nb2/3)O-3-0.35PbTiO(3) nanoparticles derived by sol-gel

Fabrication of 0.65Pb(Mg1/3Nb2./3)O-3-0.35PbTiO(3) (PMN-PT) nanoparticles with an average size of about 40 nm and their phase transformation behavior from pyrochlore to perovskite phase is investigated. A novel sol-gel method was used for the synthesis of air-stable and precipitate-free diol-based sol of PMN-PT which was dried and partially calcined at 450 degrees C for 1 h to decompose organics and bring down the free energy barrier for perovskite crystallization and then finally annealed in the temperature range 600 to 700 degrees C. Annealed at around 700 degrees C for 1 h, PMN-PT gel powder exhibited nanocrystalline morphology with perovskite phase as confirmed by the transmission electron microscopy and X-ray diffraction techniques. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3677974]

Nano Al2O3-Pb AND SiO2-Pb cermets by sol-gel technique and the phase transformation study of the embedded Pb particles

Sol-gel processing followed by H2 reduction is used to produce dispersions of nanosized Pb in amorphous SiO2 and ultrafine γ Al2O3 matrices. A depression of 3–5K in Pb melting point is reported. The size and shape of these metastable particles in molten and solid state are discussed in the light of the experimental observations and expectations from the intersection group theory for equilibrium shape.

Tracing a common ``origin'' of phase transformation, polymorphism, disorder, isosterism, and isostructuralism in fluorobenzoylcarvacryl thiourea

The terms phase transformation, polymorphism, disorder, isosterism, and isostructuralism are often the keywords used in the design and engineering of molecular crystals. Three benzoylcarvacryl thiourea derivatives with -NH-C(S)-NH-C(O)-] cores generate molecular crystals, which provide the basis for exploring a common link between the structures related by aforementioned terms. The apparent ``origin'' of all these structural modifications has been traced to the formation of a planar molecular dimeric chain built with homomeric R-2(2)(12) and R-2(2)(8) synthons occurring in tandem, one formed with N-H center dot center dot center dot O and the other with N-H center dot center dot center dot S hydrogen bonds.

Pressure induced structural phase transformation in TiN: a first-principles study

Titanium nitride (TiN), which is widely used for hard coatings, reportedly undergoes a pressure-induced structural phase transformation, from a NaCl to a CsCl structure, at similar to 7 GPa. In this paper, we use first-principles calculations based on density functional theory with a generalized gradient approximation of the exchange correlation energy to determine the structural stability of this transformation. Our results show that the stress required for this structural transformation is substantially lower (by more than an order of magnitude) when it is deviatoric in nature vis-a-vis that under hydrostatic pressure. Local stability of the structure is assessed with phonon dispersion determined at different pressures, and we find that CsCl structure of TiN is expected to distort after the transformation. From the electronic structure calculations, we estimate the electrical conductivity of TiN in the CsCl structure to be about 5 times of that in NaCl structure, which should be observable experimentally. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4798591]

Pressure-Induced Bond Rearrangement and Reversible Phase Transformation in a Metal-Organic Framework

Pressure-induced phase transformations (PIPTs) occur in a wide range of materials. In general, the bonding characteristics, before and after the PIPT, remain invariant in most materials, and the bond rearrangement is usually irreversible due to the strain induced under pressure. A reversible PIPT associated with a substantial bond rearrangement has been found in a metal-organic framework material, namely tmenH(2)]Er(HCOO)(4)](2) (tmenH(2)(2+) = N,N,N',N'-tetramethylethylenediammonium). The transition is first-order and is accompanied by a unit cell volume change of about 10%. High-pressure single-crystal X-ray diffraction studies reveal the complex bond rearrangement through the transition. The reversible nature of the transition is confirmed by means of independent nanoindentation measurements on single crystals.

Phase transformation, improved ferroelectric and magnetic properties of (1-x) BiFeO3-xPb(Zr0.52Ti0.48)O-3 solid solutions

The authors prepared (1 - x) BiFeO3 - (x)Pb(Zr0.52Ti0.48)O-3 for x <= 0.30 by sol-gel method and investigated the material's structures, magnetic and electrical properties. Detailed Rietveld analysis of X-ray diffraction data revealed that the system retains distorted rhombohedral R3c structure for x <= 0.10 but transforms to monoclinic (Cc) structure for x > 0.10. Disappearance of some Raman modes corresponding to A1 modes and the decrease in the intensities of the remaining A1 modes with increasing x in the Raman spectra, which is a clear indication of structural modification and symmetry changes brought about by PZT doping. Enhanced magnetization with PZT doping content may be attributed to the gradual change and destruction in the spin cycloid structure of BiFeO3. The leakage current density at 3.5 kV/cm was reduced by approximately three orders of magnitude by doping PZT (x = 0.30), compared with BFO ceramics. (C) 2014 AIP Publishing LLC.

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.

Polymorphism and Phase Transformation Behavior of Solid Forms of 4-Amino-3,5-dinitrobenzamide

We report the preparation, analysis, and phase transformation behavior of polymorphs and the hydrate of 4-amino-3,5-dinitrobenzamide. The compound crystallizes in four different polymorphic forms, Form I (monoclinic, P2(1)/n), Form II (orthorhombic, Pbca), Form III (monoclinic, P2(1)/c), and Form IV (monoclinic, P2(1)/c). Interestingly, a hydrate (triclinic, P (1) over bar) of the compound is also discovered during the systematic identification of the polymorphs. Analysis of the polymorphs has been investigated using hot stage microscopy, differential scanning calorimetry, in situ variable-temperature powder X-ray diffraction, and single-crystal X-ray diffraction. On heating, all of the solid forms convert into Form I irreversibly, and on further heating, melting is observed. In situ single-crystal X-ray diffraction studies revealed that Form II transforms to Form I above 175 degrees C via single-crystal-to-single-crystal transformation. The hydrate, on heating, undergoes a double phase transition, first to Form III upon losing water in a single-crystal-to-single-crystal fashion and then to a more stable polymorph Form I on further heating. Thermal analysis leads to the conclusion that Form II appears to be the most stable phase at ambient conditions, whereas Form I is more stable at higher temperature.

Phase transformation of ZrO2:Tb3+ nanophosphor: Color tunable photoluminescence and photocatalytic activities

The current study involves synthesis of a series of Tb3+ doped ZrO2 nanophosphors by solution combustion method using oxalyl dihydrazide as fuel. The as-formed ZrO2:Tb3+ nanophosphors having different concentrations of Tb3+ (1-11 mol%) were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-Visible spectroscopic techniques and the materials were subjected to photoluminescence and photocatalytic dye decolorization studies. The PXRD analysis indicates the formation of tetragonal symmetry up to 5 mol% concentration of Tb3+. Further increase in Tb3+ concentration has lead to cubic phase formation and the same was confirmed by Rietveld refinement analysis. SEM images revealed that material was highly porous in nature comprising of large voids and cracks with irregular morphology. TEM and SAED images clearly confirm the formation of high quality tetragonal nanocrystals. The emissive properties of nanophosphors were found to be dependent on Tb3+ dopant concentration. The green emission of the material was turned to white emission with the increase of Tb3+ ion concentration. The photocatalytic activities of these nanophosphors were probed for the decolorization of Congo red under UV and Sunlight irradiation. All the photocatalysts showed enhanced activity under UV light compared to Sunlight. The photocatalyst with 7 mol% Tb3+ showed enhanced activity attributed to effective separation of charge carriers due to phase transformation from tetragonal to cubic. The influence of crystallite size and PL on charge carrier trapping-recombination dynamics was investigated. The study successfully demonstrates synthesis of tetragonal and cubic ZrO2:Tb3+ green nanophosphors with superior photoluminescence and photocatalytic activities. (C) 2014 Elsevier B.V. All rights reserved.

Metastable monoclinic and orthorhombic phases and electric field induced irreversible phase transformation at room temperature in the lead-free classical ferroelectric BaTiO3

For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family, namely, BaTiO3, KNbO3, PbTiO3, and Na1/2Bi1/2TiO3, the dielectric and piezoelectric properties of BaTiO3 are considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibit anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural standpoint. In this work, we have used high-resolution synchrotron x-ray powder diffraction, atomic resolution aberration-corrected transmission electron microscopy, in conjunction with a powder poling technique, to reveal that at 300 K (i) the equilibrium state of BaTiO3 is characterized by coexistence of metastable monoclinic Pm and orthorhombic (Amm2) phases along with the tetragonal phase, and (ii) strong electric field switches the polarization direction from the 001] direction towards the 101] direction. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds at room temperature. Pure BaTiO3 at room temperature is therefore more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play a fundamental role in influencing the dielectric and piezoelectric behavior.

Partial rotation of the isopropyl group in the solid state: single-crystal-to-single-crystal phase transformation in a carvacrol derivative

A hitherto unseen rotation of the isopropyl group in the solid state, predicted to be forbidden based on theoretical investigations, is reported. This C-C rotation observed during the temperature dependent single-crystal-to-single-crystal transformation is attributed to the concomitant changes in molecular structure and intermolecular packing.

Monoclinic to cubic phase transformation in combustion synthesized gadolinium oxide

Gadolinium oxide, cerium oxide, and 10 mol% gadolinia doped ceria ceramic powders have been synthesized using combustion technique. Though the cubic gadolinia phase is stable at room temperature, single phase monoclinic gadolinia was obtained as a result of combustion synthesis using fuel lean and stoichiometric precursor compositions. This powder was subjected to calcination treatment and ceria doping to study the stability of phases and the rate of phase transformation from monoclinic to cubic gadolinia. It was found that monoclinic gadolinia transforms to cubic gadolinia upon calcination at temperatures less than 1200 degrees C. It was also found that rate of phase transformation is more for powder produced using fuel lean compositions; and the rate is enhanced upon ceria doping. (C) 2015 Elsevier Ltd. All rights reserved.

Deformation, Phase Transformation and Recrystallization in the Shear Bands Induced by High-Strain Rate Loading in Titanium and its Alloys

alpha-titanium and its alloys with a dual-phase structure (alpha+beta) were deformed dynamically under strain rate of about 10(4) s(-1). The formation and microstructural evolution of the localized shear bands were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results reveal that both the strain and strain rate should be considered simultaneously as the mechanical conditions for shear band formation, and twinning is an important mode of deformation. Both experimental and calculation show that the materials within the bands underwent a superhigh strain rate (9 x 10(5) s(-1)) deformation, which is two magnitudes of that of average strain rate required for shear band formation; the dislocations in the bands can be constricted and developed into cell structures; the phase transformation from alpha to alpha(2) within the bands was observed, and the transformation products (alpha(2)) had a certain crystallographic orientation relationship with their parent; the equiaxed grains with an average size of 10 mu m in diameter observed within the bands are proposed to be the results of recrystallization.