Dielectric properties and I-V characteristics of (Pb<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>)TiO<Subscript>3</Subscript> thin films improved by TiO<Subscript>2</Subscript> buffer layers

A TiO₂ thin buffer layer was introduced between the (Pb_0.4Sr_0.6)TiO₃ (PST) film and the Pt/Ti/SiO₂/Si substrate in an attempt to improve their electrical properties. Both TiO₂ and PST layers were prepared by a chemical solution deposition method. It was found that the TiO₂ buffer layer increased the (100)/(001) preferred orientation of PST and decreased the surface roughness of the films, leading to an enhancement in electrical properties including an increase in dielectric constant and in its tunability by DC voltage, as well as a decrease in dielectric loss and leakage current density. At an optimized thickness of the TiO₂ buffer layer deposited using 0.02 mol/l TiO₂ sol, the 330-nm-thick PST films had a dielectric constant, loss and tunability of 1126, 0.044 and 60.7% at 10 kHz, respectively, while the leakage current density was 1.95 × 10⁻⁶ A/cm² at 100 kV/cm.     

Thermodynamic properties of alkali halides. II. Enthalpies of dilution and heat capacities in water at 25°C

The enthalpies of dilution and volumetric specific heats of most alkali halides were measured in water at 25°C with flow microcalorimeters in the concentration range 0.01 to 1m. Apparent molal relative enthalpies _L, derived from the enthalpies of dilution, can be represented by a parametric equation in molality. Combining _L with osmotic data, excess entropies can be calculated. Excess free energies, enthalpies, and entropies are compared at 0.5m, and the observed trends are consistent with a model of structural interactions in aqueous alkali halide solutions. The apparent molal heat capacities _C were fitted with the equation _C= _C ^° +A_C(d₀m)^1/2+B _C m. The _C ^° are, in general, additive to better than 1 J-K^–1-mole^–1 and reflect mostly the structural part of ion-solvent interactions. Taking _C ^° (H⁺)=0, conventional ionic _C ^° are obtained. The parameterB _C for different pairs of ions follows approximately the same trends as the corresponding parameterB _V for apparent molal volumes and seems to reflect structural interactions between the ions.     

Thermodynamic investigation of room temperature ionic liquid

The molar heat capacities of the room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF₄) were measured by an adiabatic calorimeter in temperature range from 80 to 390 K. The dependence of the molar heat capacity on temperature is given as a function of the reduced temperature X by polynomial equations, C _P,m (J K^–1 mol^–1)= 195.55+47.230 X–3.1533 X ²+4.0733 X ³+3.9126 X ⁴ [X=(T–125.5)/45.5] for the solid phase (80~171 K), and C _P,m (J K^–1 mol^–1)= 378.62+43.929 X+16.456 X ²–4.6684 X ³–5.5876 X ⁴ [X=(T–285.5)/104.5] for the liquid phase (181~390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BMIBF₄ relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass translation of BMIBF₄ was observed at 176.24 K. Using oxygen-bomb combustion calorimeter, the molar enthalpy of combustion of BMIBF₄ was determined to be Δ_c H _m ^o= – 5335±17 kJ mol^–1. The standard molar enthalpy of formation of BMIBF₄ was evaluated to be Δ_f H _m ^o= –1221.8±4.0 kJ mol^–1 at T=298.150±0.001 K.     

Water Accessibilities of Man-made Cellulosic Fibers – Effects of Fiber Characteristics

The dynamic vapor water sorption and desorption experiments were performed on cellulosic fibers with different characteristics. The hysteresis between moisture sorption and desorption cycle at 10% relative humidity (RH) was independent on the total moisture regain and approximately 45% for all materials except for viscose fibers. Brunauer–Emmett–Teller surface volume (V_m) for moisture sorption and retention capacity of liquid water (WRV) were also measured. The V_m and WRV increase in proportion to the total amount of moisture sorption (M_inf(total)) in all specimen except in poplar fiber. The coefficients of parallel exponential kinetics (PEK) were estimated by the curve-fitting of experimental data of the moisture regain, and the influences of the fiber characteristics on the PEK coefficients, the moisture regain, the hysteresis, V_m and WRV are discussed. The total equilibrium moisture content in the viscose fibers was higher but the moisture uptake and release rate was slower than the lyocell and poplar fibers. The cationization and the modification of shape of cross section accelerated the total equilibrium moisture content in the viscose fiber. A drying process at low temperature enhanced both the equilibrium moisture content and the moisture uptake and release rate in lyocell fibers while a spin finish retarded them. The total equilibrium moisture content was heightened by the crosslinking of the fiber, however, no obvious effect of the crosslinking on the moisture uptake and release rate was found. Effects of the type of the specimen and linear density on the moisture accessibilities are also discussed.     

Specific heat capacity and Debye temperature of zirconia and its solid solution

Specific heat C_P of zirconia and yttria stabilized zirconia doped or not with erbia and ceria was measured from 128 to 823 K and of yttria stabilized zirconia doped with erbia and plutonia from 443 to 1573 K. The new determined data were modelled using Debye theory. Data for the tetravalent oxide and for the studied solid solutions show that the extended Dulong and Petit law in Neumann-Kopp rule is verified for zirconia and the quaternary compounds. The Debye temperature of zirconia (590 K) and its yttria, erbia and ceria doped solid solutions (575-625 K) derived from these C_P measurements between 150 and 823 K is discussed and compared with that reported for other tetravalent metal oxides.     

Pitzer-Debye-Hückel limiting slopes for water from 0 to 350°C and from saturation to 1 kbar

Using internationally recognized critical evaluations for the dielectric constant of water by Uematsu and Franck and the thermodynamic surface of water by Haar, Gallagher, and Kell, the Bureau of Mines presents values for the Pitzer-Debye-Hückel limiting slopes for osmotic coefficients, apparent molal enthalpies, apparent molal heat capacities, apparent molal volumes, molal compressibilities, and apparent molal expansivities from 0 to 350°C and from saturation to 1 kbar.     

水与正丁醇二元体系最低共沸混合物的热容

Molar heat capacities of n-butanol and the azeotropic mixture in the binary system [water （x=0.716） plus n-butanol （x=0.284）] were measured with an adiabatic calorimeter in a temperature range from 78 to 320 K. The functions of the heat capacity with respect to thermodynamic temperature were estabhshed for the azeotropic mixture. A glass transition was observed at （111.9±1.2） K. The phase transitions took place at （179.26±0.77） and （269.69±0.14） K corresponding to the solid-hquid phase transitions of n-butanol and water, respectively. The phase-transition enthalpy and entropy of water were calculated. A thermodynamic function of excess molar heat capacity with respect to temperature was estabhshed, which took account of physical mixing, destructions of self-association and cross-association for n-butanol and water, respectively. The thermodynamic functions and the excess thermodynamic ones of the binary systems relative to 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity and the calculated excess heat capacity with respect to temperature.     

Nanosized CeO2–SiO2, CeO2–TiO2, and CeO2–ZrO2 Mixed Oxides: Influence of Supporting Oxide on Thermal Stability and Oxygen Storage Properties of Ceria

The influence of SiO₂, TiO₂, and ZrO₂ on the structural and redox properties of CeO₂ were systematically investigated by various techniques namely, X-ray diffraction (XRD), Raman spectroscopy (RS), UV–Vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HREM), BET surface area, and thermogravimetry methods. The effect of supporting oxides on the crystal modification of ceria was also mainly focused. The investigated oxides were obtained by soft chemical routes with ultrahigh dilute solutions and were subjected to thermal treatments from 773 to 1073 K. The XRD results suggest that the CeO₂–SiO₂ sample primarily consists of nanocrystalline CeO₂ on the amorphous SiO₂ surface. Both crystalline CeO₂ and TiO₂-anatase phases were noted in the case of CeO₂–TiO₂ sample. Formation of cubic Ce_0.75Zr_0.25O₂ and Ce_0.6Zr_0.4O₂ (at 1073 K) were observed in the case of CeO₂–ZrO₂ sample. The cell ‘a’ parameter estimations revealed an expansion of the ceria lattice in the case of CeO₂–TiO₂, while a contraction is noted in the case of CeO₂–ZrO₂. The DRS studies suggest that the supporting oxides significantly influence the band gap energy of CeO₂. Raman measurements disclose the presence of oxygen vacancies, lattice defects, and displacement of oxide ions from their normal lattice positions in the case of CeO₂–TiO₂ and CeO₂–ZrO₂ samples. The XPS studies revealed the presence of silica, titania, and zirconia in their highest oxidation states, Si(IV), Ti(IV), and Zr(IV) at the surface of the materials. Cerium is present in both Ce⁴⁺ and Ce³⁺ oxidation states. The HREM results reveal well-dispersed CeO₂ nanocrystals over the amorphous SiO₂ matrix in the case of CeO₂–SiO₂, isolated CeO₂ and TiO₂ (A) nanocrystals and some overlapping regions in the case of CeO₂–TiO₂, and nanosized CeO₂ and Ce–Zr oxides in the case of CeO₂–ZrO₂ sample. The exact structural features of these crystals as determined by digital diffraction analysis of HREM experimental images reveal that the CeO₂ is mainly in cubic fluorite geometry. The oxygen storage capacity (OSC) as determined by thermogravimetry reveals that the OSC of mixed oxides is more than that of pure CeO₂ and the CeO₂–ZrO₂ exhibits highest OSC.     

Standard pH values for phosphate buffer reference solutions in acetonitrile-water mixtures up to 50% (m/m)

Reference pH_ps values for 0.025 mol/kg potassium dihydrogen phosphate + 0.025 mol/kg disodium hydrogen phosphate primary standard buffer solutions in 10, 30, 40 and 50% (m/m) acetonitrile-water mixtures at 298.15 K have been determined from reversible e.m.f. measurements of the cell Pt/Ag/AgCl/primary standard buffer + KCl in acetonitrile-water/glass electrode. The consistency of the results is confirmed by multilinear regression analysis of the pH_ps values obtained for each solution composition. Considering the high number of possible acetonitrile-water mixtures, the methodology of linear solvation energy relationships (LSER) was applied and pH_ps data have been correlated with the Kamlet-Taft solvatochromic parameters of the acetonitrile-water mixtures over the whole of the experimental range.     

Heat capacity and thermodynamic properties of crystalline ornidazole (C7H10ClN3O3)

The molar heat capacities of 1-(2-hydroxy-3-chloropropyl)-2-methyl-5-nitroimidazole (Ornidazole) (C₇H₁₀ClN₃O₃) with purity of 99.72 mol% were measured with an adiabatic calorimeter in the temperature range between 79 and 380 K. The melting-point temperature, molar enthalpy, Δ_fusH_m, and entropy, Δ_fusS_m, of fusion of this compound were determined to be 358.59±0.04 K, 21.38±0.02 kJ mol⁻¹ and 59.61±0.05 J K⁻¹ mol⁻¹, respectively, from fractional melting experiments. The thermodynamic function data relative to the reference temperature (298.15 K) were calculated based on the heat capacities measurements in the temperature range from 80 to 380 K. The thermal stability of the compound was further investigated by DSC and TG. From the DSC curve an intensive exothermic peak assigned to the thermal decomposition of the compound was observed in the range of 445-590 K with the peak temperature of 505 K. Subsequently, a slow exothermic effect appears when the temperature is higher than 590 K, which is probably due to the further decomposition of the compound. The TG curve indicates the mass loss of the sample starts at about 440 K, which corresponds to the decomposition of the sample.