DSC studies on the phase transformation of hydrazonium sulfate

The high temperature phase transformation of hydrazonium sulfate, N2H6SO4 has been studied using DSC. The enthalpy of phase transition is found to be 3.63 ± 0.1 kJ mole−1. The phase transition temperature is found to decrease with the increase of particle size. It appears that the strain energy and not surface energy, is responsible for the phase transformation. The molar volume of the salt increases during the transformation as found by the dilatometric experiment involving percentage of linear thermal expansion. On cooling, the transformation from the high temperature modification to orthorhombic form is incomplete and extends over a wide range of temperature.

EPR observation of phase transitions in calcium cadmium acetate hexahydrate: Using Mn2+ and Cu2+ ions as probe

Results of temperature dependence of EPR spectra of Mn2+ and Cu2+ ions doped calcium cadmium acetate hexahydrate (CaCd(CH3COO)4•6H2O) have been reported. The investigation has been carried out in the temperature range between room temperature ( 300 K) and liquid nitrogen temperature. A I-order phase transition at 146 ± 0.5 K has been confirmed. In addition a new II-order phase transition at 128 ± 1 K has been detected for the first time. There is evidence of large amplitude hindered rotations of CH3 groups which become frozen at 128 K. The incorporation of Cu2+ and Mn2+ probes at Ca2+ and Cd2+ sites respectively provide evidence that the phase transitions are caused by the molecular rearrangements of the common coordinating acetate groups between Ca2+ and Cd2+ sites. In contradiction to the previous reports of a change of symmetry from tetragonal to orthorhombic below 140 K, the symmetry of the host is concluded to remain tetragonal in all the three observed phases between room temperature and liquid nitrogen temperature.

Dynamics of the ammonium ion in the ferroelectric transition in sodium ammonium selenate, NaNH4SeO4·2H2O-an E.S.R. study

E.S.R. investigations of γ-irradiated ferroelectric Sodium ammonium selenate, NaNH4SeO4•2H2O and its deuteriated analogue in powder and single crystal forms have led to a deeper understanding of the nature of the ferroelectric transition of 180 K. A number of paramagnetic species formed due to γ-irradiation have been identified on the basis of their g-factors and hyperfine features from 77Se. The radical SeO4 has been used as a microprobe in studying the phase transition.

A fluctuation-based probe to athermal phase transitions

We focus on athermal phase transitions where in discrete and dissipative avalanches are observed in physical observables as the system jumps from one metastable state to another, when driven by an external field. Using higher order statistics of time dependent avalanches, or noise, in electrical resistivity during temperature-driven martensite transformation in thin nickel-titanium films, we demonstrate evidence suggesting the existence of a singular `global instability' or divergence of the correlation length as a function of temperature at the transition. These results not only establish a mapping of non-equilibrium first order phase transition and equilibrium critical phenomena, but perhaps also call for a re-evaluation of many existing experimental claims of self-organized criticality.

Universality class of the reversible-irreversible transition in sheared suspensions

Collections of non-Brownian particles suspended in a viscous fluid and subjected to oscillatory shear at very low Reynolds number have recently been shown to exhibit a remarkable dynamical phase transition separating reversible from irreversible behavior as the strain amplitude or volume fraction are increased. We present a simple model for this phenomenon, based on which we argue that this transition lies in the universality class of the conserved directed percolation models. This leads to predictions for the scaling behavior of a large number of experimental observables. Non-Brownian suspensions under oscillatory shear may thus constitute the first experimental realization of an inactive-active phase transition which is not in the universality class of conventional directed percolation.

Photoacoustic investigation of phase transitions in solids

The use of the photoacoustic effect in the investigation of first- and second-order phase transitions has been examined. Changes in the amplitude of the photoacoustic signal across the phase transition are compared with changes in thermal properties such as specific heat and thermal diffusivity. The systemsstudied include NaN02, TlN03, CsN03, NH4N03, BaTiO,, COO, Cu,HgI,, V02 andV305. The current photoacoustic studies are discussed in the light of the theoretical models available.

In Situ Phase Separation Following Dehydration in Bimetallic Sulfates: A Variable-Temperature X-Ray Diffraction Study

Phase separation resulting in a single-crystal-single-crystal transition accompanied by a polycrystalline phase following the dehydration of hydrated bimetallic sulfates [Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O and K4Cd3-(SO4)(5)center dot 3H(2)O] has been investigated by in situ variable-temperature single-crystal X-ray diffraction. With two examples, we illustrate the possibility of generating structural frameworks following dehydration in bimetallic sulfates, which refer to the possible precursor phases at that temperature leading to the mineral formation. The room-temperature structure of Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O is trigonal, space group R (3) over bar. On heating the crystal in situ on the diffractometer, the diffraction images display spherical spots and concentric rings suggesting phase separation, with the spherical spots getting indexed in a monoclinic space group, C2/c. The structure determination based on this data suggests the formation of Na2Mn(SO4)(2). However, the diffraction images from concentric rings could not be indexed. In the second example, the room-temperature structure is determined to be K4Cd3(SO4)(5)center dot 3H(2)O, crystallizing in a monoclinic space group, P2(1)/n. On heating the crystal in situ, the diffraction images collected also have both spherical spots and diffuse rings. The spherical spots could be indexed to a cubic crystal system, space group P2(1)3, and the structure is K4Cd3(SO4)(3). The possible mechanism for the phase transition in the dehydration regime resulting in this remarkable single-crystal to single-crystal transition with the appearance of a surrogate polycrystalline phase is proposed.

Mixed valency in the high-temperature phases of transition metal molybdates,AMoO4 (A=Fe, Co, Ni)

Transition metal molybdates of the formulaAMoO4 whereA=Fe, Co or Ni exhibit a first-order phase transition between 670K–970K. An investigation of the lowtemperature (lt) and high-temperature (ht) phases by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, magnetic susceptibility and other physical methods shows that the phase transition is associated with a valence change of the typeA 2++Mo6+αA 3++Mo5+ in the cases of iron and cobalt molybdates.

Phase transitions in (NH4)2SO4 and (NH4)2SO4---K2SO4 mixed crystals as studied by EPR of CrO3- radicals

A study of the phase transitions in (NH4)2SO4 and (NH4)2SO4---K2SO4 mixed crystals by EPR of the CrO3- ion is reported. The results indicate a bilinear coupling of the order parameter with spontaneous polarization and a crossover from a discontinuous to a continuous nature of the phase transition in mixed crystals.

Synthesis of wurtzite-phase ZnS nanocrystal and its optical properties

The wurtzite phase of ZnS nanocrystal has been prepared by annealing in 200-600 degrees C temperature range, its cubic phase of 2-3 nm size. prepared through soft chemical method. Results of isochronal experiments of 2 h at different temperatures indicate that visible transformation to wurtzite from cubic ZnS appears at a temperature of 400 degrees C, which is about three times smaller than that of bulk ZnS phase transition temperature. The phases, nanostructures, and optical absorption characteristics are obtained through X-ray diffraction. transmission electron microscopy, and UV-visible absorption spectroscopy. A stable and green photoluminescence emission peaked at 518 nm is observed from the 600 degrees C annealed samples, under ultraviolet light excitation.

Rate Model and Mechanism of Liquid-Phase Oxidation of Propionaldehyde

A rate equation is developed for the liquid-phase oxidation of propionaldehyde with oxygen in the presence of manganese propionate catalyst in a sparged reactor. The equation takes into account diffusional limitations based on Brian's solution for mass transfer accompanied by a pseudo m-. nth-order reaction. Sauter-mean bubble diameter, gas holdup, interfacial area, and bubble rise velocity are measured, and rates of mass transfer within the gas phase and across the gas-liquid interface are computed. Statistically designed experiments show the adequacy of the equation. The oxidation reaction is zero order with respect to oxygen concentration, 3/2 order with respect to aldehyde concentration, and order with respect to catalyst concentration. The activation energy is 12.1 kcal/g mole.

A fluctuation-based characterization of athermal phase transitions:Application to shape memory alloys

We employ a fluctuation-based technique to investigate the athermal component associated with martensite phase transition, which is a prototype of temperature-driven structural transformation. Statistically, when the phase transition is purely athermal, we find that the temporal sequence of avalanches under constant drive is insensitive to the drive rate. We have used fluctuations in electrical resistivity or noise in nickel titanium shape memory alloys in three different forms: a thin film exhibiting well-defined transition temperatures,a highly disordered film, and a bulk wire of rectangular cross-section. Noise is studied in the realm of dynamic transition,viz.while the temperature is being ramped, which probes into the kinetics of the transformation at real time scales,and could probably stand out as a promising tool for material testing in various other systems, including nanoscale devices.

Quantum phase analysis of 1D superconducting quantum dot lattice using extended Bose-Hubbard model

We have obtained the quantum phase diagram of a one-dimensional superconducting quantum dot lattice using the extended Bose-Hubbard model for different commensurabilities. We describe the nature of different quantum phases at the charge degeneracy point. We find a direct phase transition from the Mott insulating phase to the superconducting phase for integer band fillings of Cooper pairs. We predict explicitly the presence of two kinds of repulsive Luttinger liquid phases, besides the charge density wave and superconducting phases for half-integer band fillings. We also predict that extended range interactions are necessary to obtain the correct phase boundary of a one-dimensional interacting Cooper system. We have used the density matrix renormalization group method and Abelian bosonization to study our system.

An investigation of first-order transition across charge ordered and ferromagnetic phases in Gd0.5Sr0.5MnO3 single crystals by magnetic and magnetotransport studies

Gadolinium strontium manganite single crystals of the composition Gd0.5Sr0.5MnO3 were grown using the optical float zone method. We report here the magnetic and magnetotransport properties of these crystals. A large magnetoresistance similar to 10(9)% was observed at 45 K under the application of a 110 kOe field. We have observed notable thermomagnetic anomalies such as open hysteresis loops across the broadened first-order transition between the charge order insulator and the ferromagnetic metallic phase while traversing the magnetic field-temperature (H-T) plane isothermally or isomagnetically. In order to discern the cause of these observed anomalies, the H-T phase diagram for Gd0.5Sr0.5MnO3 is formulated using the magnetization-field (M-H), magnetization-temperature (M-T) and resistance-temperature (R-T) measurements. The temperature dependence of the critical field (i.e. H-up, the field required for transformation to the ferromagnetic metallic phase) is non-monotonic. We note that the non-monotonic variation of the supercooling limit is anomalous according to the classical concepts of the first-order phase transition. Accordingly, H-up values below similar to 20 K are unsuitable to represent the supercooling limit. It is possible that the nature of the metastable states responsible for the observed open hysteresis loops is different from that of the supercooled ones.

Melting of an Anchored Bilayer: Phase Transitions in the Organic-Inorganic Hybrid Pervoskite (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 (n=11, 13, 15, 17)

The conformation, organization, and phase transitions of alkyl chains in organic-inorganic hybrids based on the double pervoskite-slab lead iodides, (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 (n = 11, 13, 15, 17) have been investigated by X-ray diffraction, calorimetry, and infrared vibrational spectroscopy. In these hybrid solids, double pervoskite (CH3NH3)Pb2I7 slabs are interleaved with alkyl ammonium chains with the anchored alkyl chains arranged as tilted bilayers and adopting a planar all-trans conformation at room temperature. The (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 compounds exhibit a single reversible phase transition above room temperature with the associated enthalpy change varying linearly with alkyl chain length. This transition corresponds to the melting in two-dimensions of the alkyl chains of the anchored bilayer and is characterized by increased conformational disorder of the methylene units of the chain and loss of tilt angle coherence leading to an increase in the interslab spacing. By monitoring features in the infrared spectra that are characteristic of the global conformation of the alkyl chains, a quantitative relation between conformational disorder and melting of the anchored bilayer is established. It is found that, irrespective of the alkyl chain length, melting occurs when at least 60% of the chains in the anchored bilayer of (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 have one or more gauche defects. This concentration is determined by the underlying lattice to which the alkyl chains are anchored.