First-order structural transition in the magnetically ordered phase of Fe(1.13)Te

Specific heat, resistivity, magnetic susceptibility, linear thermal expansion (LTE), and high-resolution synchrotron x-ray powder diffraction investigations of single crystals Fe(1+y) Te (0.06 <= y <= 0.15) reveal a splitting of a single, first-order transition for y <= 0.11 into two transitions for y >= 0.13. Most strikingly, all measurements on identical samples Fe(1.13)Te consistently indicate that, upon cooling, the magnetic transition at T(N) precedes the first-order structural transition at a lower temperature T(s). The structural transition in turn coincides with a change in the character of the magnetic structure. The LTE measurements along the crystallographic c axis display a small distortion close to T(N) due to a lattice striction as a consequence of magnetic ordering, and a much larger change at T(s). The lattice symmetry changes, however, only below T(s) as indicated by powder x-ray diffraction. This behavior is in stark contrast to the sequence in which the phase transitions occur in Fe pnictides.

Magnetic properties of nanostructured ferrimagnetic zinc ferrite

Nanostructured ZnFe2O4 ferrites with different grain sizes were prepared by high energy ball milling for various milling times. Both the average grain size and the root mean square strain were estimated from the x-ray diffraction line broadening. The lattice parameter initially decreases slightly with milling and it increases with further milling. The magnetization is found to increase as the grain size decreases and its large value is attributed to the cation inversion associated with grain size reduction. The Fe-57 Mossbauer spectra were recorded at 300 K and 77 K for the samples with grain sizes of 22 and 11 nm. There is no evidence for the presence of the Fe2+ charge state. At 77 K the Mossbauer spectra consist of a magnetically ordered component along with a doublet due to the superparamagnetic behaviour of small crystalline grains with the superparamagnetic component decreasing with grain size reduction. At 4.2 K the sample with 11 nm grain size displays a magnetically blocked state as revealed by the Mossbauer spectrum. The Mossbauer spectrum of this sample recorded at 10 K in an external magnetic field of 6 T applied parallel to the direction of gamma rays clearly shows ferrimagnetic ordering of the sample. Also, the sample exhibits spin canting with a large canting angle, maybe due to a spin-glass-like surface layer or grain boundary anisotropies in the material.

Mechanochemical decomposition of Gd3Fe5O12 garnet phase

Gadolinium iron garnet was milled in a high energy ball mill to study its magnetic properties in the nanocrystalline regime. XRD reveals the decomposition of the garnet phase into Gd-orthoferrite and Gd2O3 on milling. The variation of saturation magnetization and coercivity with milling is attributed to a possible shift in the compensation temperature on grain size reduction and an increase in the orthoferrite content. The Mössbauer spectrum at 16 K is characteristic of the magnetically ordered state corresponding to GdIG, GdFeO3 and α-Fe2O3 whereas at room temperature it is a superparamagnetic doublet.

Flower-like porous cobalt(II) monoxide nanostructures as anode material for Li-ion batteries

In the present study, a microwave-assisted, solution-based route has been employed to obtain porous CoO nano structures. Detailed characterization reveals that the flower-like nanostructures comprise petal-like sheets, each of which is made of an ordered, porous arrangement of crystallites of CoO measuring about 6 nm. TEM analysis shows that each ``petal'' is an oriented aggregate of CoO nanocrystals, such aggregation promoted by the hydroxyl moieties derived from the solution. The structure provides a large specific area as well as the porosity desirable in electrodes in Li-ion batteries. Electrochemical measurements carried out on electrodes made of nanostructured CoO show excellent Li ion-storing capability. A specific capacitance of 779 mAh g(-1) has been measured at a specific current of 100 mA g(-1). Measurements show also excellent cyclability and coulombic efficiency. Impedance spectroscopy provides evidence for charge transfer occurring in the porous networks. (C) 2015 Elsevier B.V. All rights reserved.

Electronic Structure of Vacancy Ordered Spinels, $GaMo_{4}S_{8}$ and $GaV_{4}S_{8}$, from ab Initio Calculations

We report ab initio calculations for the band dispersions and total as well as partial densities of states for vacancy ordered, clustered spinels, GaMo4S8 and GaV4S8. Results are presented for the high temperature cubic phase for both compounds. Additionally, we discuss results of similar calculations for GaMo4S8 in an idealized cubic structure, as well as the nonmagnetic and the ferromagnetic states of the low temperature rhombohedral structure. Comparison of these results allows us to discuss the unusual aspects of the electronic structure of this interesting class of compounds, and provide estimates of the crystal-field and exchange splitting strengths.

The nature of the charge-ordered state in Y0.5Ca0.5MnO3 with a very small average radius of the A-site cations

A detailed investigation of Y0.5Ca0.5MnO3 with a very small radius of the A-site cations ([r(A)] approximate to 1.13 Angstrom reveals the occurrence of a charge-ordering transition in the paramagnetic state, at a relatively high temperature of 260 K. The orthorhombic lattice distortion, as measured by the dimensionless index D, is large (similar to 1.75%) over the entire 300-100 K range, but the antiferromagnetic interactions become prominent only at low temperatures (< 160 K). The charge-ordering gap in Y0.5Ca0.5MnO3, measured by low-temperature vacuum tunnelling spectroscopy, is large (similar to 0.5 eV) and the charge-ordered state is unaffected by the application of a magnetic field of 6 T. The study indicates that the nature of charge-ordering in Y0.5Ca0.5MnO3 which is dominated by the cooperative Jahn-Teller effect and the associated lattice distortion is distinctly different from analogous manganates with larger [r(A)].

Synthesis of nanoparticles of the giant dielectric material, CaCu3Ti4O12 from a precursor route

A complex oxalate precursor, CaCu3(TiO)(4)(C2O4)(8)center dot 9H(2)O, (CCT-OX), was synthesized and the precipitate that obtained was confirmed to be monophasic by the wet chemical analyses, X-ray diffraction, FTIR absorption and TG/DTA analyses. The thermal decomposition of this oxalate precursor led to the formation of phase-pure calcium copper titanate, CaCu3Ti4O12, (CCTO) at a parts per thousand yen680A degrees C. The bright-field TEM micrographs revealed that the size of the as synthesized crystallites to be in the 30-80 nm range. The powders so obtained had excellent sinterability resulting in high density ceramics which exhibited giant dielectric constants upto 40000 (1 kHz) at 25A degrees C, accompanied by low dielectric losses.

Remarkable Capacity Retention of Nanostructured Manganese Oxide upon Cycling as an Electrode Material for Supercapacitor

Electrochemical capacity retention of nearly X-ray amorphous nanostructured manganese oxide (nanoMnO2) synthesized by mixing directly KMnO4 with ethylene glycol under ambient conditions for supercapacitor studies is enhanced significantly. Although X-ray diffraction (XRD) pattern of nanoMnO2 shows poor crystallinity, it is found that by Mn K-edge X-ray absorption near edge structure (XANES) measurement that the nanoMnO2 obtained is locally arranged in a δ-MnO2-type layered structure composed of edge-shared network of MnO6 octahedra. Field emission scanning electron microscopy and XANES measurements show that nanoMnO2 contains nearly spherical shaped morphology with δ-MnO2 structure, and 1D nanorods of α-MnO2 type structure (powder XRD) in the annealed (600 °C) sample. Volumetric nitrogen adsorption−desorption isotherms, inductively coupled plasma analysis, and thermal analysis are carried out to obtain physicochemical properties such as surface area (230 m2 g−1), porosity of nanoMnO2 (secondary mesopores of diameter 14.5 nm), water content, composition, etc., which lead to the promising electrochemical properties as an electrode for supercapacitor. The nanoMnO2 shows a very high stability even after 1200 cycles with capacity retention of about 250 F g−1.

Realizing the 'hindered charge ordered phase' in nanoscale charge ordered manganites: magnetization, magneto-transport and EPR investigations

We report three prominent observations made on the nanoscale charge ordered ( CO) manganites RE(1-x)AE(x)MnO(3) (RE = Nd, Pr; AE = Ca; x = 0.5) probed by temperature dependent magnetization and magneto-transport, coupled with electron magnetic/paramagnetic resonance spectroscopy (EMR/EPR). First, evidence is presented to show that the predominant ground state magnetic phase in nanoscale CO manganites is ferromagnetic and it coexists with a residual anti-ferromagnetic phase. Secondly, the shallow minimum in the temperature dependence of the EPR linewidth shows the presence of a charge ordered phase in nanoscale manganites which was shown to be absent from the DC static magnetization and transport measurements. Thirdly, the EPR linewidth, reflective of spin dynamics, increases significantly with a decrease of particle size in CO manganites. We discuss the interesting observations made on various samples of different particle sizes and give possible explanations. We have shown that EMR spectroscopy is a highly useful technique to probe the 'hindered charge ordered phase' in nanoscale CO manganites, which is not possible by static DC magnetization and transport measurements.

Role of Melt Convection on the Thermal Performance of Heat Sinks with Phase Change Material

The role of melt convection oil the performance of beat sinks with Phase Change Material (PCM) is presented in this paper. The beat sink consists of aluminum plate fins embedded in PCM and heat flux is supplied from the bottom. The design of such a heat sink requires optimization with respect to its geometrical parameters. The objective of the optimization is to maximize the heat sink operation time for the prescribed heat flux and the critical chip temperature. The parameters considered for optimization are fin number and fill thickness. The height and base plate thickness of heat sink are kept constant in the present analysis. An enthalpy based CFD model is developed, which is capable Of Simulating phase change and associated melt convection. The CFD model is Coupled with Genetic Algorithm (GA) for carrying out the optimization. Two cases are considered, one without melt convection (conduction regime) and the other with convection. It is found that the geometrical optimizations of heat sinks are different for the two cases, indicating the importance of inch convection in the design of heat sinks with PCMs.

Modeling of dynamic material behavior in hot deformation: Forging of Ti-6242

A new method of modeling material behavior which accounts for the dynamic metallurgical processes occurring during hot deformation is presented. The approach in this method is to consider the workpiece as a dissipator of power in the total processing system and to evaluate the dissipated power co-contentJ = ∫o σ ε ⋅dσ from the constitutive equation relating the strain rate (ε) to the flow stress (σ). The optimum processing conditions of temperature and strain rate are those corresponding to the maximum or peak inJ. It is shown thatJ is related to the strain-rate sensitivity (m) of the material and reaches a maximum value(J max) whenm = 1. The efficiency of the power dissipation(J/J max) through metallurgical processes is shown to be an index of the dynamic behavior of the material and is useful in obtaining a unique combination of temperature and strain rate for processing and also in delineating the regions of internal fracture. In this method of modeling, noa priori knowledge or evaluation of the atomistic mechanisms is required, and the method is effective even when more than one dissipation process occurs, which is particularly advantageous in the hot processing of commercial alloys having complex microstructures. This method has been applied to modeling of the behavior of Ti-6242 during hot forging. The behavior of α+ β andβ preform microstructures has been exam-ined, and the results show that the optimum condition for hot forging of these preforms is obtained at 927 °C (1200 K) and a strain rate of 1CT•3 s•1. Variations in the efficiency of dissipation with temperature and strain rate are correlated with the dynamic microstructural changes occurring in the material.

Vacancy ordered phases and one-dimensional quasiperiodicity

The metastable vacancy ordered phases observed in aluminium transition metal alloys on rapid solidification or vapour deposition can be considered as a periodic arrangement of a truncated quasiperiodic string based on the Fibonacci sequence along the left angle bracket111right-pointing angle bracket stacking direction of the original CsCl cell. Using the projection formalism developed in the context of quasicrystals, the diffraction patterns of the vacancy ordered phases are calculated for both commensurate and incommensurate projection from a periodic cubic cell in four dimensions. These are compared with experimentally observed patterns. It is shown that at increasingly longer periodicity the patterns from commensurate crystals become indistinguishable from the truly quasiperiodic one. It is suggested that there is a strong link between vacancy ordered phases and quasicrystals.

Estimation of Cavitation Erosion with Incubation Periods and Material Properties

A detailed study of the normalized correlations between the incubation period tc and the properties of various materials tested in a rotating disk device indicates that, at very high intensities, the strength properties influence the duration of tc. The analysis of extensive data from other laboratories for cavitation and liquid impingement erosion also indicates that, while both energy and strength properties influence the duration of tc, the latter ones predominate for a majority of cases. A fatigue-type failure occurs during tc. For estimating the time required to pierce a metallic specimen in a rotating device a relationship tp = 160 tc0.44 is proposed. A detailed study of normalized correlations between erosion resistance (inverse of erosion rate) and tc values of different materials tested in the rotating disk shows that correlations are good. Analysis of data from eight other investigators clearly points out the validity and the usefulness of this type of prediction.

An Electron-Microscopic Investigation Of Oxides Related To Beta-Alumina

High resolution electron microscopic (HREM) investigation of potassiumbeta-alumina and the related gallate and ferrite has revealed that whereas the aluminate and gallate are highly disordered, consisting of random sequence ofbeta andbetaPrime units, the ferrite is more ordered. The aluminate and gallate are sensitive to electron beam irradiation exhibiting beam-induced damage similar to sodiumbetaPrime-alumina. Significantly, the ferrite is beamstable, the difference in behaviour amongst these related oxides arising from the different mechanisms by which alkali metal nonstoichiometry is accommodated. Barium hexaaluminate and hexaferrite are both highly ordered; specimens prepared by the barium borate flux method exhibit a new radic3a×radic3a superstructure of the hexagonal magnetoplumbite cell.

Ce1-xRuxO2-delta (x=0.05, 0.10): A New High Oxygen Storage Material and Pt, Pd-Free Three-Way Catalyst

Nanocrystalline Ce1-xRuxO2-delta (x = 0.05 and 0.10) of 8-10 nm sizes have been synthesized by hydrothermal method using melamine as complexing agent. Compounds have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray analysis (EDX) and their structures have been refined by the Rietveld method.The compounds crystallize in fluorite structure and the composition is Ce1-xRuxO2-x/2 where Ru is in +4 state and Ce is in mixed-valence (+3, +4) state. Substitution of Ru4+ ion in CeO2 activated the lattice oxygen. Ce1-xRuxO2-x/2 reversibly releases 0.22[O] and 0.42[O] for x = 0.05 and 0.10, respectively, which is higher than the maximumpossible OSC of 0.22 [O] observed for Ce0.50Zr0.50O2. Utilization of Higher OSC of Ce1-xRuxO2-delta (x = 0.05 and 0.10) is also reflected in terms of low-temperature CO oxidation with these catalysts, both in the presence and absence of feed oxygen. The Ru4+ ion acts as an active center for reducing molecules (CO, hydrocarbon ``HC'') and oxide ion vacancy acts as an active center for O-2 and NO, leading to low-temperature NO conversion to N-2. Thus due to Ru4+ ion, Ce1-xRuxO2-delta is not just a high oxygen storage material but also shows high activity toward CO, hydrocarbon ``HC'' oxidation, and NO reduction by CO at low temperature with high N-2 selectivity for three-way catalysis.