High-Resolution Thermochemical Study of Phase Stability and Rapid Oxygen Incorporation in YBaCo4- xZn xO7+δ 114-Cobaltites.

The formation thermodynamics of YBaCo4- xZn xO7+δ ( x = 0, 1, and 3) oxides was determined by high-temperature oxide melt solution calorimetry. All of the studied oxides are thermodynamically metastable due to the tendency of cobalt to increase the oxidation state under oxidizing conditions as well as to significant bond valence sum mismatch for Ba and Y in 114-oxides. Complex phase evolution in YBaCo4O7+δ at 350-400 °C upon oxygen absorption was revealed using incremental precise oxygen dosing. The calorimetric results support phase changes seen during in situ X-ray diffraction structural studies and provide high-resolution measurement of the amount and energetics of oxygen absorbed by YBaCo4- xZn xO7+δ under equilibrium conditions.

[Diagnostic possibilities of methods for the evaluation of liver fibrosis in chronic viral hepatitis]. / Diagnosticheskie vozmozhnosti metodov otsenki fibroza pecheni pri khronicheskikh virusnykh gepatitakh.

The paper reviews the diagnostic possibilities of different methods for the evaluation of liver fibrosis in chronic viral hepatitis from the point of view of their clinical application. Histological examination retains its value as the gold standard method in evaluating the liver. Transient elastography is a rather effective tool for identifying severe liver fibrosis.

Energetics of sodium-calcium exchanged zeolite A.

A series of calcium-exchanged zeolite A samples with different degrees of exchange were prepared. They were characterized by powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC). High temperature oxide melt drop solution calorimetry measured the formation enthalpies of hydrated zeolites CaNa-A from constituent oxides. The water content is a linear function of the degree of exchange, ranging from 20.54% for Na-A to 23.77% for 97.9% CaNa-A. The enthalpies of formation (from oxides) at 25 °C are -74.50 ± 1.21 kJ mol(-1) TO2 for hydrated zeolite Na-A and -30.79 ± 1.64 kJ mol(-1) TO2 for hydrated zeolite 97.9% CaNa-A. Dehydration enthalpies obtained from differential scanning calorimetry are 32.0 kJ mol(-1) H2O for hydrated zeolite Na-A and 20.5 kJ mol(-1) H2O for hydrated zeolite 97.9% CaNa-A. Enthalpies of formation of Ca-exchanged zeolites A are less exothermic than for zeolite Na-A. A linear relationship between the formation enthalpy and the extent of calcium substitution was observed. The energetic effect of Ca-exchange on zeolite A is discussed with an emphasis on the complex interactions between the zeolite framework, cations, and water.

Energetics and structural evolution of Na-Ca exchanged zeolite A during heating.

The properties of zeolite A change significantly upon sodium-calcium exchange. The impact of cation composition on the temperature-induced phase transformations and energetics of Na-Ca exchanged zeolite A was studied systematically using powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and high-temperature oxide melt solution calorimetry. As the temperature increases, the structural evolution of each Na-Ca exchanged zeolite A sample undergoes three distinct stages - dehydration, amorphization, and densification/recrystallization. Initially complete dehydration does not result in framework degradation, but further heating leads to zeolite phase degradation into other aluminosilicate phases. Both amorphization and recrystallization shift to higher temperatures as the calcium content increases. On the other hand, the enthalpies of formation for the high temperature aluminosilicate phases, the amorphous phase (AP) and the dense phase (DP), appear to be a linear function of calcium content (average ionic potential) with diminishing of energetic stability upon increasing the Ca content. 100% Na-A heated at 1200 °C has the most exothermic enthalpy of formation from oxides (-65.87 ± 0.87 kJ mol(-1)- TO2), while 97.9% CaNa-A heated at 945 °C has the least exothermic value (-5.26 ± 0.62 kJ mol(-1)- TO2). For different aluminosilicates with the same chemical composition, the dense phase (DP) assemblage is more stable than the amorphous phase (AP).

[A case of acute opisthorchiasis concurrent with chronic hereditary hemolytic anemia].

The paper analyzes the clinical and laboratory manifestations of acute Opisthorchis invasion concurrent with chronic hereditary hemolytic anemia before and after antihelminthic therapy. It gives the results of direct clinical observation of a patient in the acute phase of opisthorchiasis in the presence of Minkowsky-Shauffard disease. His examination encompassed conventional laboratory and instrumental studies used in hepatology, such as physical, biochemical, and immunological examinations (tests for viral hepatitismarkers and autoimmune liver diseases), and abdominal ultrasound scanning and magnetic resonance imaging. The patient with acute opisthorchiasis concurrent with hemolytic anemia was found to have a preponderance of clinical and laboratory manifestations of hepatocholangitis in the early stages of the disease and a prevalence of subfebrility with progressive eosinophilia in the presence of regressive symptoms. The clinical and laboratory signs of hereditary microspherocytosis suggest that the process is decompensated. The found clinical and laboratory changes correspond to the natural course of the diseases. The magnitude of changes in laboratory parameters suggests that there is an intercurrent interaction of infectious and somatic diseases, but does not hinder dehelminthization.

Heat capacity of microgram oxide samples by fast scanning calorimetry.

Quantitative scanning calorimetry on microgram-sized samples opens a broad, new range of opportunities for studying the thermodynamic properties of quantity-limited materials, including those produced under extreme conditions or found as rare accessory minerals in nature. We calibrated the Mettler Toledo Flash DSC 2+ calorimeter to obtain quantitative heat capacities in the range 200-350 °C, using samples weighing between 2 and 11.5 µg. Our technique is applied to a new set of oxide materials to which it has never been used before, without the need for melting, glass transitions, or phase transformations. Heat capacity data were obtained for silica in the high pressure stishovite (rutile) structure, dense post-stishovite glass, standard fused quartz, and for TiO2 rutile. These heat capacities agree within 5%-15% with the literature values reported for rutile, stishovite, and fused SiO2 glass. The heat capacity of post-stishovite glass, made by heating stishovite to 1000 °C, is a newly reported value. After accurate calibrations, measured heat capacities were then used to calculate masses for samples in the microgram range, a substantial improvement over measurement in conventional microbalances, which have uncertainties approaching 50%-100% for such small samples. Since the typical uncertainty of heat capacities measured on 10-100 mg samples in conventional differential scanning calorimetry is typically 7% (1%-5% with careful work), flash differential scanning calorimetry, using samples a factor of 1000 smaller, increases the uncertainty of heat capacity measurements by a factor of <3, opening the door for meaningful measurements on ultra-small, high-pressure samples and other quantity-limited materials.

A Comparison of Order-Disorder in Several Families of Cubic Oxides.

Order-disorder on both cation and oxygen sites is a hallmark of fluorite-derived structures, including pyrochlores. Ordering can occur on long- and short-range scales and can result in persistent metastable states. In various cubic oxide systems, different types of disorder are seen. The purpose of this paper is to review and compare the types and energetics of order-disorder phenomena in several families of cubic oxides having pyrochlore, weberite, defect fluorite, perovskite, rocksalt, and spinel structures. The goal is to better understand how structure, composition, and thermodynamic parameters (enthalpy and entropy) determine the feasibility of different competing ordering processes and structures in these diverse systems.

Enthalpy of transformation of a high-pressure polymorph of titanium dioxide to the rutile modification.

The enthalpy of transformation of a high-pressure form of titanium dioxide, which has the alpha lead dioxide structure, to the rutile modification was measured by the method of "transposed temperature-drop calorimetry." For the reaction, titanium dioxide (alpha lead dioxide form) transforming to rutile, the change in the heat content is -0.76 +/- 0.17 kilocalorie per mole. From this value and the volume change (+ 2.8 percent) associated with the transformation, we estimate the equilibrium pressure at 294 degrees K to be 60 +/- 20 kilobars.

Negative Pressure-Temperature Slopes for Reactions Formign MgSiO3 Perovskite from Calorimetry.

A new and sensitive differential drop solution calorimetric technique was developed for very small samples. A single experiment using one 5.18-milligram sample of perovskite, synthesized at 25 gigapascals and 1873 Kelvin, gave 110.1 +/- 4.1 kilojoules per mole for the enthalpy of the ilmenite-pervoskite transition in MgSiO(3). The thermodynamics of the reaction of MgSiO(3) (ilmenite) to MgSiO(3) (perovskite) and of Mg(2)SiO(4) (spinel) to MgSiO(3) (pervoskite) and MgO (periclase) were assessed. Despite uncertainties in heat capacity and molar volume at high pressure and temperature, both reactions clearly have negative pressure-temperature slopes, -0.005 +/- 0.002 and -0.004 +/- 0.002 gigapascals per Kelvin, respectively. The latter may be insufficiently negative to preclude whole-mantle convection.

Effect of structure and thermodynamic stability on the response of lanthanide stannate pyrochlores to ion beam irradiation.

The lanthanide stannates, Ln2Sn2O7, Ln=La-Lu and Y, have the isometric pyrochlore structure, A2B2O7, and their structural properties have been refined by Rietveld analysis of powder neutron and synchrotron X-ray diffraction data. In this study, the enthalpies of formation of selected stannate pyrochlores, Ln=La, Nd, Sm, Eu, Dy, and Yb, were measured by high-temperature oxide melt solution calorimetry. Their radiation response was determined by 1 MeV Kr2+ ion irradiation combined with in situ TEM observation over the temperature range of 25 to 1000 K. The enthalpy of formation from binary oxides of stannate pyrochlores became more endothermic (from -145 to -40 kJ/mol) as the size of the lanthanide in the A-site decreases. A more exothermic trend of the enthalpy of formation was observed in stannate pyrochlores with larger lanthanide ions, particularly La, possibly as a result of increased covalency in the Sn-O bond. In contrast to lanthanide titanate pyrochlores, Ln2Ti2O7, that are generally susceptible to radiation-induced amorphization and zirconate pyrochlores, Ln2Zr2O7, that are generally resistant to radiation-induced amorphization, the lanthanide stannate pyrochlores show a much greater variation in their response to ion irradiation. La, Nd, and Gd stannates experience the radiation-induced transformation to the aperiodic state, and the critical amorphization temperatures are approximately 960, 700, and 350 K, respectively. Y and Er stannate pyrochlores cannot be amorphized by ion beam irradiation, even at 25 K, and instead disorder to a defect fluorite structure. Comparison of the calorimetric and ion irradiation data for titanate, zirconate, and stannate pyrochlores reveals a strong correlation among subtle changes in crystal structure with changing composition, the energetics of the disordering process, and the temperature above which the material can no longer be amorphized. In summary, as the structure approaches the ideal, ordered pyrochlore structure, radiation-induced amorphization is more easily attained. This is consistent with an increasingly exothermic trend in the enthalpies of formation of pyrochlores from the oxides, that is, the greater the thermochemical stability of the pyrochlore structure, the more likely it will be amorphized upon radiation damage rather than recover to a disordered fluorite structure.

Phase transformations and indications for acoustic mode softening in Tb-Gd orthophosphate.

At ambient conditions the anhydrous rare earth orthophosphates assume either the xenotime (zircon) or the monazite structure, with the latter favored for the heavier rare earths and by increasing pressure. Tb0.5Gd0.5PO4 assumes the xenotime structure at ambient conditions but is at the border between the xenotime and monazite structures. Here we show that, at high pressure, Tb0.5Gd0.5PO4 does not transform directly to monazite but through an intermediate anhydrite-type structure. Axial deformation of the unit cell near the anhydrite- to monazite-type transition indicates softening of the (c1133 + c1313) combined elastic moduli. Stress response of rare-earth orthophosphate ceramics can be affected by both formation of the anhydrite-type phase and the elastic softening in the vicinity of the monazite-phase. We report the first structural data for an anhydrite-type rare earth orthophosphate.

Determination of the magnetic contribution to the heat capacity of cobalt oxide nanoparticles and the thermodynamic properties of the hydration layers.

We present low temperature (11 K) inelastic neutron scattering (INS) data on four hydrated nanoparticle systems: 10 nm CoO·0.10H(2)O (1), 16 nm Co(3)O(4)·0.40H(2)O (2), 25 nm Co(3)O(4)·0.30H(2)O (3) and 40 nm Co(3)O(4)·0.026H(2)O (4). The vibrational densities of states were obtained for all samples and from these the isochoric heat capacity and vibrational energy for the hydration layers confined to the surfaces of these nanoparticle systems have been elucidated. The results show that water on the surface of CoO nanoparticles is more tightly bound than water confined to the surface of Co(3)O(4), and this is reflected in the reduced heat capacity and vibrational entropy for water on CoO relative to water on Co(3)O(4) nanoparticles. This supports the trend, seen previously, for water to be more tightly bound in materials with higher surface energies. The INS spectra for the antiferromagnetic Co(3)O(4) particles (2-4) also show sharp and intense magnetic excitation peaks at 5 meV, and from this the magnetic contribution to the heat capacity of Co(3)O(4) nanoparticles has been calculated; this represents the first example of use of INS data for determining the magnetic contribution to the heat capacity of any magnetic nanoparticle system.

Possible presence of high-pressure ice in cold subducting slabs.

During the subduction of oceanic lithosphere, water is liberated from minerals by progressive dehydration reactions and is thought to be critical to several geologically important processes such as island-arc volcanism, intermediate-depth seismicity and chemical exchange between the subducting lithosphere and mantle. Although dehydration reactions would yield supercritical fluid water in most slabs, we report here that the stable phase of H2O should be solid ice VII in portions of the coldest slabs. The formation of ice VII as a dehydration product would affect the generation, storage, transport and release of water in cold subduction zones and equilibrium conditions of dehydration would shift, potentially affecting the depths of seismogenesis and magmagenesis. Large amounts of pure ice VII might accumulate during subduction and, as a sinking slab warms, eventual melting of the ice would release large amounts of water in a small region over a short period of time, with a significant positive volume change. Moreover, the decreasing availability of fluid water, owing to the accumulation of ice VII and its subsequent reaction products in a cooling planetary interior (for example, in Mars or the future Earth), might eventually lead to a decline in tectonic activity or its complete cessation.

Energetics of nanocrystalline TiO2.

The energetics of the TiO(2) polymorphs (rutile, anatase, and brookite) were studied by high temperature oxide melt drop solution calorimetry. Relative to bulk rutile, bulk brookite is 0.71 +/- 0.38 kJ/mol (6) and bulk anatase is 2.61 +/- 0.41 kJ/mol higher in enthalpy. The surface enthalpies of rutile, brookite, and anatase are 2.2 +/- 0.2 J/m(2), 1.0 +/- 0.2 J/m(2), and 0.4 +/- 0.1 J/m(2), respectively. The closely balanced energetics directly confirm the crossover in stability of nanophase polymorphs inferred by Zhang and Banfield (7). An amorphous sample with surface area of 34,600 m(2)/mol is 24.25 +/- 0.88 kJ/mol higher in enthalpy than bulk rutile.