Complete 'melting' of charge order in hydrothermally grown Pr0.57Ca0.41Ba0.02MnO3 nanowires

Nanowires of Pr0.57Ca0.41Ba0.02MnO3 (PCBM) (diameter similar to 80-90 nm and length similar to 3.5 mu m) were synthesized by a low reaction temperature hydrothermal method. Single-phase nature of the sample was confirmed by XRD experiments. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the morphology and microstructures of the nanowires. While the bulk PCBM is known to exhibit charge order (CO) below 230 K along with a ferromagnetic transition at 110 K, SQUID measurements on the nanowires of PCBM show that the charge order is completely absent and a ferromagnetic transition occurs at 115 K. However, the magnetization in the nanowires is observed to be less compared to that in the bulk. This observation of the complete 'melting' of the charge order in the PCBM nanowires is particularly significant in view of the observation of only a weakening of the CO in the nanowires of Pr0.5Ca0.5MnO3. Electron paramagnetic resonance experiments were also carried out on the PCBM nanowires using an X-band EPR spectrometer. Characteristic differences were observed in the line width of nanowires when compared with that of the bulk.

The oxygen potential of the systems Fe+FeCr2O4+ Cr2O3 and Fe+FeV2O4+ V2O3 in the temperature range 750 1600o C

From electromotive force (emf) measurements using solid oxide galvanic cells incorporating ZrOz-CaO and ThOz-YO~.s electrolytes, the chemical potentials of oxygen over the systems Fe + FeCrzO 4 + Cr20 ~ and Fe + FeV204 + V203 were calculated. The values may be represented by the equations: 2Fe(s, I) + Oz(g) + 2Cr2Oa(s) -- 2FeCr204 (s)Akto2 = - 151,400 + 34.7T (• cal= -633,400 + 145.5T(• J (750 to 1536~ A~tO2 = -158,000 + 38.4T(• cal= -661,000 + 160.5T(*1250) J (1536 to 1700~2Fe (s, I) + O2 (g) + 2V203 (s) -- 2FeV204 (s) A/~Oz = - 138,000 + 29.8T(+300) cal= - 577,500 + 124.7T (• J (750 to 1536~A/IO2 = -144,600 + 33.45T(-300) cal = -605,100 + 140.0T(~-1250) J (1536 to 1700~At the oxygen potentials corresponding to Fe + FeCrzO a + Cr203 equilibria, the electronic contribution to the conductivity of ZrO2-CaO electrolyte was found to affect the measured emf. Application of a small 60 cycle A.C. voltage with an amplitude of 50 mv across the cell terminals reduced the time required to attain equilibrium at temperatures between 750 to 9500C by approximately a factor of two. The second law entropy of iron chromite obtained in this study is in good agreement with that calculated from thermal data. The entropies of formation of these spinel phases from the component oxides can be correlated to cation distribution and crystal field theory.

Revision of thermodynamic data on MnO Al2O3 melts

The high temperature region of the MnO-A1203 phase diagram has been redetermined to resolve some discrepancies reported in the literature regarding the melting behaviour of MnA1,04. This spinel was found to melt congruently at 2108 (+ 15) K. Theactivity of MnOin MnO-Al,03 meltsand in the two phase regions, melt + MnAI,04 and MnAI2O4 + A1203, has been determined by measuring the manganese concentration in platinum foils in equilibrium under controlled oxygen potentials. The activity of MnO obtained in this study for M ~ O - A I ,m~el~ts is in fair agreement with the results of Sharma and Richardson.However. the alumina-rich melt is found to be in equilibrium with MnAl,04 rather than AI2O3. as suggested by ~ha rmaan d Richardson. The value for the acthity of MnO in the M~AI ,O,+ A1,03 two phaseregion permits a rigorous application of the Gibbs-Duhem equation for calculating the activity of A1203 and the integral Gibbs' energy of mixing of MnO-A1203 melts, which are significantly different from those reported in the literature.

Thermodynamic study of Fe2O3 Fe2(SO4)3 equilibrium using an oxyanionic electrolyte (Na2SO4 I)

The emf of the cell, Pt, Ar + O2 + SO2 + SO3/Na2SO4-I/Fe2O2 + Fe2(SO4)3, Pt, has been measured in the temperature range 800 to 1000 K, using a gas mixture of known input composition as the reference electrode. The equilibrium composition of the reference gas at the measuring temperatures was computed using the thermodynamic data on the gaseous species reported in the literature. A mixture of ferric oxide and sulfate was kept in a closed system to ensure establishment of equilibrium partial pressure at the electrode. The cell was designed to avoid physical contact between Fe2(SO4)3 and Na2SO4 electrolyte. Uncertainties arising from the formation of sulfate solid solution were thus eliminated. The Gibbs’ energy of formation of ferric sulfate calculated from the emf is discussed in comparison with data reported in the literature. There is no evidence for the formation of oxysulfates in the Fe-S-0 system. Based on the results obtained in the present study for Fe2(SO4)3 and literature data for other phases, chemical potential diagrams have been constructed for the Fe-S-O system at 900 and 1100 K.

Oxygen content of liquid cobalt in equilibrium with CoO.(1+x)Al2O3 and -Al2O3

The oxygen concentration of liquid cobalt in equilibrium with cobalt aluminate and a-alumina has been measured by suction sampling and crucible quenching techniques at temperatures between 1770 and 1975 K. Experiments were made with cobalt of high and low initial oxygen contents, and with and without the addition of cobalt aluminate. The effect of temperature on the equilibrium oxygen content is represented by the equation, log (at.% 0) = -10,4001T(K) + 4.64 (±0.008). The composition of the spinel phase, CoO.(1+x)AI20 3, saturated with alumina, has been determined by electron probe microanalysis. The values of x are 0.22 at 1770 Kand 0.28 at 1975 K. The oxygen potential corresponding to the three-phase equilibrium between cobalt, aluminate and alumina, and the standard Gibbs' energy of formation of nonstoichiometric cobalt aluminate are evaluated by combining the results of this study with recently published data on the activity of oxygen in liquid cobalt. Implications of the present results to aluminium deoxidation of liquid cobalt are discussed.

Solubility and activity of oxygen in liquid nickel in equilibrium with -Al2O3 and NiO.(1+x)Al2O3

The limiting solubility of oxygen in liquid nickel in equilibrium withα-alumina and nickel aluminate has been measured by inert gas fusion analysis of suction samples in the temperature range 1730 to 1975 K. The corresponding oxygen potential has been monitored by a solid electrolyte cell consisting of calcia stabilized zirconia as the electrolyte and Mo + MoO2 as the reference electrode. The results can be summarized by the following equations: log(at. pct O) = \frac - 10,005T + 4.944 ( ±0.015)log(atpctO)=T−10005+4944(0015) % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn DmO2 /4.606RT = log P O2 1/2 = \frac - 13,550T + 4.411 ( ±0.009)O24606RT=logPO212=T−13550+4411(0009) From simultaneous measurements of the potential and concentration of oxygen in melts, not in thermodynamic equilibrium with alumina and aluminate phases, information on the composition dependence of the activity coefficient and the standard free energy of solution of oxygen is obtained. For the reaction, $\frac{1}{2} O_2 \to \underset{\raise0.3em\hbox{$Missing close brace ΔG o = -72,930 - 7.11T (±840) J gr.at.–1 = + 0.216 at. pct OlogfO=T−500+0216atpctO where the standard state for dissolved oxygen is that which makes the value of activity equal to the concentration (in at. pct) in the limit as concentration approaches zero. The oxygen solubility in liquid nickel in equilibrium with solid NiO, evaluated from thermodynamic data, is compared with information reported in the literature. Implications of the results to the deoxidation equilibria of aluminum in nickel are discussed.

Crystal packing and melting temperatures of small oxalate esters: the role of C-H center dot center dot center dot O hydrogen bonding

The simple dialkyl oxalates are generally liquids at room temperature except for dimethyl and di-tert-butyl oxalate which melt at 327 and 343 K. The crystal structures of diethyl, di-iso-propyl, di-n-butyl, di-tert-butyl and methyl ethyl oxalates were determined. The liquid esters were crystallized using the cryocrystallization technique. A comparison of the intermolecular interactions and packing features in these crystal structures was carried out. The crystal structure of dimethyl oxalate was redetermined at various temperatures. The other compounds were also studied at several temperatures in order to assess the attractive nature of the hydrogen bonds therein. A number of moderate to well defined C-H center dot center dot center dot O interactions account for the higher melting points of the two solid esters. Additionally, a diminished entropic contribution Delta S(m) in di-tert-butyl oxalate possibly increases the melting point of this compound further.

Structure and temperature dependence of conductivity of Ag2.5Se‐Se composite

Rapid solidification of Ag‐53 at. % Se alloy resulted in the formation of a composite mixture of Ag2.5Se and Se. The microstructure consists of spherical Se grains of 2–20 μm size, randomly distributed in a matrix of Ag2.5 Se. The Se grains were found to be layered hexagonal while the Ag2.5 Se had an orthorhombic crystal structure. The unit cell size of this phase, however, was twice that reported for the equilibrium orthorhombic Ag2 Se compound. The conductivity σ variation with temperature in the range 80–320 K was found to be similar to that observed in degenerate semiconductors. The σ decreased from 295 Ω−1 cm−1 at room temperature to a saturation value of 70 Ω−1 cm−1 for temperatures <80 K. The results are discussed in terms of percolation conduction in the Ag2.5 Se phase.

Microstructure, shape, stability and melting inembeddednanoparticles

The present article reviews some of the current work on a new class of materials which are nanoscale granular materials. We shall discuss in this paper two phase granular materials where one of the phases having nanometric dimension is embedded in a matrix of larger dimension. Known as nanoembedded materials, nanocomposites or ultrafine granular materials, this class of materials has attracted attention because of the opportunity of basic studies on the effect of size and embedding matrix on transformation behaviors as well as some novel properties, which include structural, magnetic and transport properties. These are in addition to the tremendous interests in what is known as quantum structures(embedded particles size less than 5 nm) for the case of semiconductors, which will not be discussed here. We shall primarily review the work done on metallic systems where the dispersed phases have low melting points and borrow extensively from the work done in our group. The phase transformations of the embedded particles show distinctive behavior and yield new insights. We shall first highlight briefly the strategy of synthesis of these materials by non-equilibrium processing techniques, which will be followed by examples where the effect of length scales on phase transformation behaviors like melting and solidification are discussed.

Non-resonant rf absorption evidence for reentrant melting of vortex lattice in Bi2Sr2CaCu2O8 single crystals

We have studied the magnetic field dependent rf (20 MHz) losses in Bi2Sr2CaCu2O8 single crystals in the low field and high temperature regime. Above HCl the dissipation begins to decrease as the field is increased and exhibits a minimum at HM>HCl. For H>HM the loss increases monotonically. We attribute the decrease in loss above HCl to the stiffening of the vortex lines due to the attractive electromagnetic interaction between the 2D vortices (that comprise the vortex line at low fields) in adjacent CuO bilayers. The minimum at HM implies that the vortex lines are stiffest and hence represents a transition into vortex solid state from the narrow vortex liquid in the vicinity of HCl. The increase in loss for H>HM marks the melting of the vortex lattice and hence a second transition into vortex liquid regime. We discuss our results in the light of recent theory of reentrant melting of the vortex lattice by G. Blatter et al. (Phys. Rev. B 54, 72 (1996)).

Ultrahigh-temperature metamorphism from an unusual corundum plus orthopyroxene intergrowth bearing Al-Mg granulite from the Southern Marginal Zone, Limpopo Complex, South Africa

The Southern Marginal Zone of the Limpopo Complex is composed of granite-greenstone cratonic rocks reworked by a Neoarchean high-grade tectono-metamorphic event. Petrographic and mineral chemical characterization of an Al-Mg granulite from this zone is presented here. The granulite has a gneissic fabric with distinct Al-rich and Si-rich layers, with the former preserving the unusual lamellar (random and regular subparallel) intergrowths of corundum and symplectic intergrowth of spinel with orthopyroxene. The Al-rich layer preserves mineral assemblages such as rutile with orthopyroxene + sillimanite +/- A quartz, Al-rich orthopyroxene (similar to 11 wt%), spinel + quartz, and corundum in possible equilibrium with quartz, while the Si-rich layer preserves antiperthites and orthopyroxene + sillimanite +/- A quartz, all considered diagnostic of ultrahigh-temperature metamorphism. Application of Al-in-opx thermometry, ternary feldspar thermometry and construction of suitable pressure-temperature phase diagrams, compositional and model proportion isopleth results indicate P-T conditions as high as similar to 1,050-1,100 A degrees C, and similar to 10-12 kbars for the Al-Mg granulite. Our report of ultrahigh-temperature conditions is significant considering that the very high temperature was reached during decompression of an otherwise high-pressure granulite complex (clockwise P-T path), whereas most other ultrahigh-temperature granulites are linked to magma underplating at the base of the crust (counterclockwise P-T path).

Simulation of Influence of Bilayer Melting on Dynamics and Thermodynamics of Interfacial Water

We investigate the effect of bilayer melting transition on thermodynamics and dynamics of interfacial water using molecular dynamics simulation with the two-phase thermodynamic model. We show that the diffusivity of interface water depicts a dynamic crossover at the chain melting transition following an Arrhenius behavior until the transition temperature. The corresponding change in the diffusion coefficient from the bulk to the interface water is comparable with experimental observations found recently for water near 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) vesicles Phys. Chem. Chem. Phys. 13, 7732 (2011)]. The entropy and potential energy of interfacial water show distinct changes at the bilayer melting transition, indicating a strong correlation in the thermodynamic state of water and the accompanying first-order phase transition of the bilayer membrane. DOI: 10.1103/PhysRevLett.110.018303

Two-Dimensional Correlation Analysis of Temperature-Dependent FT-IR Spectra of Oleic Acid

In the present study, variable temperature FT-IR spectroscopic investigations were used to characterize the spectral changes in oleic acid during heating oleic acid in the temperature range from -30 degrees;C to 22 degrees C. In order to extract more information about the spectral variations taking place during the phase transition process, 2D correlation spectroscopy (2DCOS) was employed for the stretching (C?O) and rocking (CH2) band of oleic acid. However, the interpretation of these spectral variations in the FT-IR spectra is not straightforward, because the absorption bands are heavily overlapped and change due to two processes: recrystallization of the ?-phase and melting of the oleic acid. Furthermore, the solid phase transition from the ?- to the a-phase was also observed between -4 degrees C and -2 degrees C. Thus, for a more detailed 2DCOS analysis, we have split up the spectral data set in the subsets recorded between -30 degrees C to -16 degrees C, -16 degrees C to 10 degrees C, and 10 degrees C to 22 degrees C. In the corresponding synchronous and asynchronous 2D correlation plots, absorption bands that are characteristic of the crystalline and amorphous regions of oleic acid were separated.

An estimate of equilibrium sensitivity of global terrestrial carbon cycle using NCAR CCSM4

Increasing concentrations of atmospheric CO2 influence climate, terrestrial biosphere productivity and ecosystem carbon storage through its radiative, physiological and fertilization effects. In this paper, we quantify these effects for a doubling of CO2 using a low resolution configuration of the coupled model NCAR CCSM4. In contrast to previous coupled climate-carbon modeling studies, we focus on the near-equilibrium response of the terrestrial carbon cycle. For a doubling of CO2, the radiative effect on the physical climate system causes global mean surface air temperature to increase by 2.14 K, whereas the physiological and fertilization on the land biosphere effects cause a warming of 0.22 K, suggesting that these later effects increase global warming by about 10 % as found in many recent studies. The CO2-fertilization leads to total ecosystem carbon gain of 371 Gt-C (28 %) while the radiative effect causes a loss of 131 Gt-C (10 %) indicating that climate warming damps the fertilization-induced carbon uptake over land. Our model-based estimate for the maximum potential terrestrial carbon uptake resulting from a doubling of atmospheric CO2 concentration (285-570 ppm) is only 242 Gt-C. This highlights the limited storage capacity of the terrestrial carbon reservoir. We also find that the terrestrial carbon storage sensitivity to changes in CO2 and temperature have been estimated to be lower in previous transient simulations because of lags in the climate-carbon system. Our model simulations indicate that the time scale of terrestrial carbon cycle response is greater than 500 years for CO2-fertilization and about 200 years for temperature perturbations. We also find that dynamic changes in vegetation amplify the terrestrial carbon storage sensitivity relative to a static vegetation case: because of changes in tree cover, changes in total ecosystem carbon for CO2-direct and climate effects are amplified by 88 and 72 %, respectively, in simulations with dynamic vegetation when compared to static vegetation simulations.

Out of equilibrium plasticity dynamics and the annealing of supersolidity in solid He-4

We present a numerical study of a continuum plasticity field coupled to a Ginzburg-Landau model for superfluidity. The results suggest that a supersolid fraction may appear as a long-lived transient during the time evolution of the plasticity field at higher temperatures where both dislocation climb and glide are allowed. Supersolidity, however, vanishes with annealing. As the temperature is decreased, dislocation climb is arrested and any residual supersolidity due to incomplete annealing remains frozen. Our results may provide a resolution of many perplexing issues concerning a variety of experiments on bulk solid He-4.