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.

Nanostructuration via solid state transformation as a strategy for improving the thermoelectric efficiency of PbTe alloys

The approach taken in this paper in order to modify the scattering features of electrons and phonons and improve the figure of merit (ZT) of thermoelectric PbTe is to alter the microstructure at constant chemistry. A lamellar pattern of PbTe/GeTe at the nano- and microscale was produced in Pb(0.36)Ge(0.64)Te alloy by the diffusional decomposition of a supersaturated solid solution. The mechanism of nanostructuration is most likely a discontinuous spinodal decomposition. A simple model relating the interface velocity to the observed lamellar spacing is proposed. The effects of nanostructuration in Pb(0.36)Ge(0.64)Te alloy on the electrical and thermal conductivity, thermopower and ZT were investigated. It was shown that nanostructuration through the formation of a lamellar pattern of PbTe/GeTe is unlikely to provide a significant improvement due to the occurrence of discontinuous coarsening. However, the present study allows an analysis of possible strategies to improve thermoelectric materials via optimal design of the microstructure and optimized heat treatment. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Usefulness of in Situ Single Crystal to Single Crystal Transformation (SCSC) Studies in Understanding the Temperature-Dependent Dimensionality Cross-over and Structural Reorganization in Copper-Containing Metal-Organic Frameworks (MOFs)

Two copper-containing compounds [Cu(3)(mu(3)-OH)(2)-(H(2)O)(2){(SO(3))-C(6)H(3)-(COO)(2)}(CH(3)COO)] , I, and [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, II, were prepared using sulphoisophthalic and nitroisophthalic acids. The removal of the coordinated water molecules in the compounds was investigated using in situ single crystal to single crystal (SCSC) transformation studies, temperature-dependent powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA). The efficacy of SCSC transformation studies were established by the observation of dimensionality cross-over from a two-dimensional (I) to a three-dimensional structure, Cu(6)(mu(3)-OH)(4){(SO(3))-C(6)H(3)-(COO)(2)}(2)(CH(3)COO)(2), Ia, during the removal of the coordinated water molecules. Compound H exhibited a structural reorganization forming Cu(5)(mu(2)-OH)(2){(NO(2))C(6)H(3)-(COO)(2))(4)], Ha, possessing trimeric (Cu(3)O(12)) and dimeric (Cu(2)O(8)) copper clusters. The PXRD studies indicate that the three-dimensional structure (Ia) is transient and unstable, reverting back to the more stable two-dimensional structure (I) on cooling to room temperature. Compound Ha appears to be more stable at room temperature. The rehydration/dehydration studies using a modified TGA setup suggest complete rehydration of the water molecules, indicating that the water molecules in both compounds are labile. A possible model for the observed changes in the structures has been proposed. Magnetic studies indicate changes in the exchanges between the copper centers in Ha, whereas no such behavior was observed in Ia.

Matrix Processors Using p-adic Arithmetic for Exact Linear Computations

A unique code (called Hensel's code) is derived for a rational number by truncating its infinite p-adic expansion. The four basic arithmetic algorithms for these codes are described and their application to rational matrix computations is demonstrated by solving a system of linear equations exactly, using the Gaussian elimination procedure.

Influence of Tempered Microstructures on the Transformation Behaviour of Cold Deformed and Intercritically Annealed Medium Carbon Low Alloy Steel

This research is focused on understanding the role of microstructural variables and processing parameters in obtaining optimised dual phase structures in medium carbon low alloy steels. Tempered Martensite structures produced at 300, 500, and 650 degrees C, were cold rolled to varied degrees ranging from 20 to 80% deformation. Intercritical annealing was then performed at 740, 760, and 780 degrees C for various time duration ranging from 60 seconds to 60 minutes before quenching in water. The transformation behaviour was studied with the aid of optical microscopy and hardness curves. From the results, it is observed that microstructural condition, deformation, and intercritical temperatures influenced the chronological order of the competing stress relaxation and decomposition phase reactions which interfered with the rate of the expected alpha -> gamma transformation. The three unique transformation trends observed are systematically analyzed. It was also observed that the 300 and 500 degrees C tempered initial microstructures were unsuitable for the production of dual structures with optimized strength characteristics.

On the athermal nature of the beta to omega transformation

One characteristic feature of the athermal beta -> omega transformation is the short time scale of the transformation. So far, no clear understanding of this issue exists. Here we construct a model that includes contributions from a Landau sixth-order free energy density, kinetic energy due to displacement, and the Rayleigh dissipation function to account for the dissipation arising from the rapid movement of the parent product interface during rapid nucleation. We also include the contribution from omega-like fluctuations to local stress. The model shows that the transformation is complete on a time scale comparable to the velocity of sound. The estimated nucleation rate is several orders higher than that for diffusion-controlled transformations. The model predicts that the athermal omega phase is limited to a certain range of alloying composition. The estimated nucleation rate and the size of ``isothermal'' particles beyond 17% Nb are also consistent with experimental results. The model provides an explanation for the reprecipitation process of the omega particles in the ``cleared'' channels formed during deformation of omega-forming alloys. The model also predicts that acoustic emission should be detectable during the formation of the athermal phase. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

An extension of Mangler transformation to a 3-D problem

Considering the linearized boundary layer equations for three-dimensional disturbances, a Mangler type transformation is used to reduce this case to an equivalent two-dimensional one.

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.

Shape Transformation of ZnO Nanorods/Nanotubes at Low Temperature

We report the shape transformation of ZnO nanorods/nanotubes at temperatures (similar to 700 degrees C) much lower than the bulk melting temperature (1975 degrees C). With increasing annealing temperature, not only does shape transformation take place but the luminescence characteristics of ZnO are also modified. It is proposed that the observed shape transformation is due to surface diffusion, contradicting the previously reported notion of melting and its link to luminescence. Luminescence in the green-to-red region is observed when excited with a blue laser, indicating the conversion of blue to white light.

Estimation of the shear transformation zone size fin a bulk metallic glass through statistical a analysis of the first pop-in stresses during spherical nanoindentation

The size of the shear transformation zone (STZ) that initiates the elastic to plastic transition in a Zr-based bulk metallic glass was estimated by conducting a statistical analysis of the first pop-in event during spherical nanoindentation. A series of experiments led us to a successful description of the distribution of shear strength for the transition and its dependence on the loading rate. From the activation volume determined by statistical analysis the STZ size was estimated based on a cooperative shearing model. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A novel oxidative transformation of alcohols to nitriles: an efficient utility of azides as a nitrogen source

An efficient methodology to oxidize benzylic and cinnamyl alcohols to their corresponding nitriles in excellent yields has been developed. This methodology employs DDQ as an oxidant and TMSN3 as a source of nitrogen in the presence of a catalytic amount of Cu(ClO4)(2)center dot 6H(2)O.

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.

Electric-field-driven monoclinic-to-rhombohedral transformation in Na1/2Bi1/2TiO3

The lead free ferroelectric Na1/2Bi1/2TiO3 (NBT) is shown to exhibit electric-field-induced monoclinic (Cc) to rhombohedral (R3c) phase transformation at room temperature. This phenomenon has been analyzed both from the viewpoint of the intrinsic polarization rotation and adaptive phase models. In analogy with the morphotropic phase boundary systems, NBT seems to possess intrinsic competing ferroelectric instabilities near room temperature.