On the existence of a nickel hydroxide phase which is neither alpha nor beta

A novel phase of nickel hydroxide with an average interlayer spacing 5.4-5.6 Angstrom has been synthesized which is neither ct nor beta type but is an interstratification of both. It ages to the beta form in strong alkali. These observations have implications on the dissolution-reprecipitation mechanism suggested for the alpha-->beta transformation of nickel hydroxide.

Mean-field theory of charge ordering and phase transitions in the colossal-magnetoresistive manganites

We study phase transitions in the colossal-magnetoresistive manganites by using a mean-field theory both at zero and non-zero temperatures. Our Hamiltonian includes double-exchange, superexchange, and Hubbard terms with on-site and nearest-neighbour Coulomb interaction, with the parameters estimated from earlier density-functional calculations. The phase diagrams show magnetic and charge-ordered (or charge-disordered) phases as a result of the competition between the double-exchange, superexchange, and Hubbard terms, the relative effects of which are sensitively dependent on parameters such as doping, bandwidth, and temperature. In accord with the experimental observations, several important features are reproduced from our model, namely, (i) a phase transition from an insulating, charge-ordered antiferromagnetic to a metallic, charge-disordered ferromagnetic state near dopant concentration x = 1/2, (ii) the reduction of the transition temperature TAF-->F by the application of a magnetic field, (iii) melting of the charge order by a magnetic field, and (iv) phase coexistence for certain values of temperature and doping. An important feature, not reproduced in our model, is the antiferromagnetism in the electron-doped systems, e.g., La1-xCaxMnO3 over the entire range of 0.5 less than or equal to x less than or equal to 1, and we suggest that a multi-band model which includes the unoccupied t(2g) orbitals might be an important ingredient for describing this feature.

Pressure-induced phase transitions in alpha-ZrMo2O8

We report high-pressure Raman, infrared (IR), and optical-absorption spectra of alpha-ZrMo2O8 (trigonal) up to 38 GPa at room temperature. The spectroscopic studies are consistent with diffraction results that show that alpha-ZrMo2O8 transforms into delta-ZrMo2O8 (monoclinic) at about 1 GPa and the delta phase converts to the epsilon phase (trielinic) at about 2.0 GPa. Optical-absorption measurements give an estimate of the band gap of about 0.6 eV at the lowest pressure. Band-gap changes with pressure are confirmed with visual observations. ZrMo2O8 changes from transparent at 5 GPa to yellow at 10 GPa, red at 18 GPa, and at about 30 GPa it becomes opaque.

Characterization of phase transformation behaviour and microstructural development of electroless Ni-B coating

Phase transformation behaviour of amorphous electroless Ni-B coating with a targeted composition of Ni-6wt% B is characterized in conjunction with microstructural development and hardness. Microscopic observations of the as-deposited coating display a novel microstructure which is already phase separated at multiple length scales. Spherical colonies of similar to 5 mu m consist of 2-3 mu m nodular regions which are surrounded by similar to 2-3 mu m region that contains fine bands ranging from 10 to 70 nm in width. The appearance of three crystalline phases in this binary system at different stages of heat treatment and the concomitant variation in hardness are shown to arise from nanoscale fluctuations in the as-deposited boron content from 4 to 8 wt%. High temperature annealing reveals continuous crystallization up to 430 degrees C, overlapping with the domain of B loss due to diffusion into the substrate. The implications of such a microstructure for optimal heat treatment procedures are discussed. (C) 2011 Elsevier B.V. All rights reserved.

Nanocrystalline TiO(2) preparation by microwave route and nature of anatase-rutile phase transition in nano TiO(2)

Nanopowders of TiO(2) has been prepared using a microwave irradiation-assisted route, starting from a metalorganic precursor, bis(ethyl-3-oxo-butanoato)oxotitanium (IV), [TiO(etob)(2)](2). Polyvinylpyrrolidone (PVP) was used as a capping agent. The as-prepared amorphous powders crystallize into anatase phase, when calcined. At higher calcination temperature, the rutile phase is observed to form in increasing quantities as the calcination temperature is raised. The structural and physicochemical properties were measured using XRD, FT-IR, SEM, TEM and thermal analyses. The mechanisms of formation of nano-TiO(2) from the metal-organic precursor and the irreversible phase transformation of nano TiO(2) from anatase to rutile structure at higher temperatures have been discussed. It is suggested that a unique step of initiation of transformation takes place in Ti(1/2)O layers in anatase which propagates. This mechanism rationalizes several key observations associated with the anatase rutile transformation.

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.

Segmental relaxations and crystallization-induced phase separation in PVDF/PMMA blends in the presence of surface-functionalized multiwall carbon nanotubes

Crystallization-induced phase separation and segmental relaxations in poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blends was systematically investigated by melt-rheology and broadband dielectric spectroscopy in the presence of multiwall carbon nanotubes (MWNTs). Different functionalized MWNTs (amine, -NH2; acid, -COOH) were incorporated in the blends by melt-mixing above the melting temperature of PVDF, where the blends are miscible, and the crystallization induced phase separation was probed in situ by shear rheology. Interestingly, only -NH2 functionalized MWNTs (a-MWNTs) aided in the formation of beta-phase (trans-trans) crystals in PVDF, whereas both the neat blends and the blends with -COOH functionalized MWNTs (c-MWNTs) showed only alpha-phase (trans-gauche-trans-gauche') crystals as inferred from wide-angle X-ray diffraction (WXRD) and Fourier transform infrared (FTIR). Furthermore, blends with only a-MWNTs facilitated in heterogeneous nucleation in the blends manifesting in an increase in the calorimetric crystallization temperature and hence, augmented the theologically determined crystallintion induced phase separation temperature. The dielectric relaxations associated with the crystalline phase of PVDF (alpha(c)) was completely absent in the blends with a-MWNTs in contrast to neat blends and the blends with c-MWNTs in the dielectric loss spectra. The relaxations in the blends investigated here appeared to follow Havriliak-Negami (HN) empirical equations, and, more interestingly, the dynamic heterogeneity in the system could be mapped by an extra relaxation at higher frequency at the crystallization-induced phase separation temperature. The mean relaxation time (tau(HN)) was evaluated and observed to be delayed in the presence of MWNTs in the blends, more prominently in the case of blends with a-MWNTs. The latter also showed a significant increase in the dielectric relaxation strength (Delta epsilon). Electron microscopy and selective etching was used to confirm the localization of MWNTs in the amorphous phases of the interspherulitic regions as observed from scanning electron microscopy (SEM). The evolved crystalline morphology, during crystallization-induced phase separation, was observed to have a strong influence on the charge transport processes in the blends. These observations were further supported by the specific interactions (like dipole induced dipole interaction) between a-MWNTs and PVDF, as inferred from FTIR, and the differences in the crystalline morphology as observed from WXRD and polarized optical microscopy (POM).

Phase Field Simulation of Equiaxed Microstructure Formation during Semi-solid Processing of A380 Al Alloy

A phase field modelling approach is implemented in the present study towards simulation of microstructure evolution during cooling slope semi solid slurry generation process of A380 Aluminium alloy. First, experiments are performed to evaluate the number of seeds required within the simulation domain to simulate near spherical microstructure formation, occurs during cooling slope processing of the melt. Subsequently, microstructure evolution is studied employing a phase field method. Simulations are performed to understand the effect of cooling rate on the slurry microstructure. Encouraging results are obtained from the simulation studies which are validated by experimental observations. The results obtained from mesoscopic phase field simulations are grain size, grain density, degree of sphericity of the evolving primary Al phase and the amount of solid fraction present within the slurry at different time frames. Effect of grain refinement also has been studied with an aim of improving the slurry microstructure further. Insight into the process has been obtained from the numerical findings, which are found to be useful for process control.

Effect of processing route on phase stability in equiatomic multicomponent Ti20Fe20Ni20Co20Cu20 high entropy alloy

The evolution of microstructure and phase formation in equiatomic Ti20Fe20Ni20Co20Cu20 high entropy alloy synthesised by conventional arc melting followed with suction casting and ball milling with spark plasma sintering route is distinctly different. The cast microstructure exhibits one body centre cubic and two face centre cubic high entropy phases based on titanium, cobalt and copper respectively along with a eutectic containing Ti2Ni type Laves phase. On the contrary, spinodal decomposed microstructure consisting of cobalt and copper solid solution is obtained in the sintered sample. However, long term annealing of cast sample at 950 degrees C reveals a eutectoid transformation with different phases than the cast sample. The aforementioned observations are discussed using CALPHAD thermodynamical approach and available literature.

Phase Inversion of Agitated Liquid-Liquid Dispersions in the Presence of Micrometer-Sized Particles

We have investigated the impact of partially wetting particles of tens of micrometers on inversion instability of agitated liquid liquid dispersions. Particles of this size can be easily separated from the exit streams to avoid downstream processing-related issues. The results show that the presence of hydrophilic particles in small quantities (volume fraction range of 2 X 10(-4) to 1.25 x 10(-2)) significantly decreases the dispersed phase fraction at which water-in-oil (w/o) dispersions invert but leaves the inversion of oil-in-water (o/w) dispersions nearly unaffected. The addition of the same particles after they are hydrophobized decreases the dispersed phase fraction at which o/w dispersions invert but leaves the inversion of w/o dispersions unaffected. These findings suggest an increased rate of coalescence of drops when particles wet drops preferentially and a marginal decrease when they wet the continuous phase preferentially. High-speed conductivity measurements on w/o dispersion show transient conduction of a few hundred milliseconds duration through voltage pulses. Close to the inversion point, voltage pulses appear at high frequency for even 7 cm separation between the electrodes. The presence of hydrophilic particles produces a nearly identical signal at a significantly lower dispersed phase fraction itself, close to the new lowered inversion point in the presence of particles. We propose formation of elongated domains of the conducting dispersed phase through a rapid coalescence-deformation-breakup process to explain the new observations. The voltage signal appears as a forerunner of inversion instability.

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.

Anomalous reduction in domain wall displacement at the morphotropic phase boundary of the piezoelectric alloy system PbTiO3-BiScO3

A comparative study of field-induced domain switching and lattice strain was carried out by in situ electric-field-dependent high-energy synchrotron x-ray diffraction on a morphotropic phase boundary (MPB) and a near-MPB rhombohedral/pseudomonoclinic composition of a high-performance piezoelectric alloy (1-x) PbTiO3-(x)BiScO3. It is demonstrated that the MPB composition showing large d(33) similar to 425 pC/N exhibits significantly reduced propensity of field-induced domain switching as compared to the non-MPB rhombohedral composition (d(33) similar to 260 pC/N). These experimental observations contradict the basic premise of the martensitic-theory-based explanation which emphasizes on enhanced domain wall motion as the primary factor for the anomalous piezoelectric response in MPB piezoelectrics. Our results favor field-induced structural transformation to be the primary mechanism contributing to the large piezoresponse of the critical MPB composition of this system.

Evolution of multivariant microstructures with anisotropic misfit: A phase field study

We study, in two dimensions, the effect of misfit anisotropy on microstructural evolution during precipitation of an ordered beta phase from a disordered alpha matrix; these phases have, respectively, 2- and 6-fold rotation symmetries. Thus, precipitation produces three orientational variants of beta phase particles, and they have an anisotropic (and crystallographically equivalent) misfit strain with the matrix. The anisotropy in misfit is characterized using a parameter t = epsilon(yy)/epsilon(xx), where epsilon(xx) and epsilon(yy) are the principal components of the misfit strain tensor. Our phase field, simulations show that the morphology of beta phase particles is significantly influenced by 1, the level of misfit anisotropy. Particles are circular in systems with dilatational misfit (t = 1), elongated along the direction of lower principal misfit when 0 < t < 1 and elongated along the invariant direction when - 1 <= t <= 0. In the special case of a pure shear misfit strain (t = - 1), the microstructure exhibits star, wedge and checkerboard patterns; these microstructural features are in agreement with those in Ti-Al-Nb alloys.

Evaluation of CaO-CeO2-partially stabilized zirconia thermal barrier coatings

Plasma sprayable powders were prepared from ZrO2-CaO-CeO2 system using an organic binder and coated onto stainless steel substrates previously coated by a bond coat (Ni 22Cr 20Al 1.0Y) using plasma spraying. The coatings exhibited good thermal barrier characteristics and excellent resistance to thermal shock at 1000 degrees C under simulated laboratory conditions (90 half hour cycles without failure) and at 1200 degrees C under accelerated burner rig test conditions (500 2 min cycles without failure). No destabilization of cubic/tetragonal ZrO2 phase fraction occured either during the long hours (45 h cumulative) or the large number of thermal shock tests. Growth of a distinct SiO2 rich region within the ceramic was observed in the specimens thermal shock cycled at 1000 degrees C apart from mild oxidation of the bond coat. The specimens tested at 1200 degrees C had a glassy appearance on the top surface and exhibited severe oxidation of the bond coat at the ceramic-bond coat interface. The glassy appearance of the surface is due to the formation of a liquid silicate layer attributable to the impurity phase present in commercial grade ZrO2 powder. These observations are supported by SEM analysis and quantitative EDAX data.

The physics of ENSO-monsoon connection

The physical mechanism through which Ei-Nino and Southern Oscillation (ENSO) tends to produce deficient precipitation over Indian continent is investigated using both observations as well as a general circulation model. Both analysis of observations and atmospheric general circulation model (AGCM) study show that the planetary scale response associated with ENSO primarily influences the equatorial Indian Ocean region. Through this interaction it tends to favour the equatorial heat source, enhance precipitation over the equatorial Indian Ocean and indirectly cause a decrease in continental precipitation through induced subsidence. This situation is further complicated by the fact the regional tropospheric quasi biennial oscillation (QBO) has a bimodal structure over this region with large amplitude over the Indian continent. While the ENSO response has a quasi-four year periodicity and tends peak during beginning of the calendar year, the QBO mode tends to peak during northern summer. Thus, the QBO mode exerts a stronger influence on the interannual variability of the monsoon. The strength of the Indian monsoon in a given year depends on the combined effect of the ENSO and the QBO mode. Sines the two oscillations have disparate time scales, exact phase information of the two modes during northern summer is important in determining the Indian summer monsoon. The physical mechanism of the interannual variations of the Indian monsoon precipitation associated with ENSO presented here is similar to the physical process that cause intraseasonal 'active', 'break' oscillations of the monsoon.