Determination of the enthalpy of fusion of K3TaF8 and K3TaOF6

The areas of the fusion and crystallization peaks of K₃TaF₈ and K₃TaOF₆ have been measured using the DSC mode of the high-temperature calorimeter (SETARAM 1800 K). On the basis of these quantities and the temperature dependence of the used calorimetric method sensitivity, the values of the enthalpy of fusion of K₃TaF₈ at temperature of fusion 1039 K: Δ_fusH_m(K₃TaF₈; 1039 K) = (52 ± 2) kJ mol⁻¹ and of K₃TaOF₆ at temperature of fusion 1055 K: Δ_fusH_m(K₃TaOF₆; 1055 K) = (62 ± 3) kJ mol⁻¹ have been determined.     

Structure and high-temperature thermoelectric properties of SrAl2Si2

Single crystals of SrAl₂Si₂ were synthesized by reaction of the elements in an aluminum flux at 1000 °C. SrAl₂Si₂ is isostructural to CaAl₂Si₂ and crystallizes in the hexagonal space group P-3m1 (90 K, a=4.1834 (2), c=7.4104 (2) Å, Z=1, R1=0.0156, wR2=0.0308). Thermal analysis shows that the compound melts at ∼1020 °C. Low-temperature resistivity on single crystals along the c-axis shows metallic behavior with room temperature resistivity value of ∼7.5 mΩ cm. High-temperature Seebeck, resistivity, and thermal conductivity measurements were made on hot-pressed pellets. The Seebeck coefficient shows negative values in entire temperature range decreasing from ∼−78 μV K⁻¹ at room temperature to −34 μV K⁻¹ at 1173 K. Seebeck coefficients are negative indicating n-type behavior; however, the temperature dependence is consistent with contribution from minority p-type carriers as well. The lattice contribution to the thermal conductivity is higher than for clathrate structures containing Al and Si, approximately 50 mW cm⁻¹ K, and contributes to the overall low zT for this compound.     

Thermoelectric properties of polycrystalline La1−xSrxCoO3

Thermoelectric properties of polycrystalline La_1−xSr_xCoO₃, where Sr²⁺ is substituted in La³⁺ site in perovskite-type LaCoO₃, have been investigated. Sr-doping increases the electrical conductivity (σ) of La_1−xSr_xCoO₃, and also decreases the Seebeck coefficient (S) for 0.01?x?0.40. A Hall coefficient measurement reveals that the increase in electrical conductivity arises from increases in both carrier concentration and the Hall mobility. The decrease in the Seebeck coefficient is caused by a decrease in carrier effective mass as well as increase in carrier concentration. The highest power factor (σS²) is 3.7×10⁻⁴ W m⁻¹ K⁻² at 250 K for x=0.10. The thermal conductivity (κ) is about 2 W m⁻¹ K⁻¹ at 300 K for 0?x?0.04, and increases for x?0.05 because of an increase in heat transport by conductive carrier. The thermoelectric properties of La_1−xSr_xCoO₃ are improved by Sr-doping, and the figure of merit (Z=σS² κ⁻¹) reaches 1.6×10⁻⁴ K⁻¹ for x=0.06 at 300 K (ZT=0.048). For heavily Sr-doped samples, the thermoelectric properties diminish mainly because of the decrease in the Seebeck coefficient and the increase in thermal conductivity.     

Investigation of the quasi-ternary system LaMnO3-LaCoO3-“LaCuO3”—I: the series La(Mn0.5Co0.5)1−xCuxO3−δ

The La(Mn_0.5Co_0.5)_1−xCu_xO_3−δ series with x=0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8 and 1 was synthesized by the Pechini method to obtain insight into the phase formation in the quasi-ternary LaMnO₃-LaCoO₃-“LaCuO₃” system caused by the instability of LaCuO₃ under ambient conditions. After sintering at 1100°C some remarkable results were obtained: LaMn_0.3Co_0.3Cu_0.4O_3−δ crystallized as a single phase in the orthorhombic perovskite structure typical of LaCuO₃. Among the synthesized compositions this compound showed the highest electrical conductivity in air at 800°C (155 S cm⁻¹) and also the highest thermal expansion coefficient (α_30−800°C=15.4×10⁻⁶ K⁻¹). The LaCuO_3−δ composition also crystallized as a single phase but in a monoclinic structure although previous investigations have shown that other phases are preferably formed after sintering at 1100°C. The electrical conductivity and thermal expansion coefficient were the lowest within the series of compositions, i.e. 9.4 S cm⁻¹ and 11.9×10⁻⁶ K⁻¹, respectively.     

Structural evolution of Na0.5K0.5NbO3 at high temperatures

Changes in structure and dielectric properties at elevated temperatures have been investigated on single-crystals of sodium potassium niobate, Na_0.5K_0.5NbO₃, grown by the flux method. Single-crystal X-ray diffraction studies revealed that the crystals underwent orthorhombic-tetragonal and tetragonal-cubic phase transitions at 465 and 671 K during heating and 446 and 666 K during cooling, respectively. Both transitions were accompanied by volumetric discontinuities of collapse upon heating and expansion upon cooling, suggesting that the transitions were of the first order. The coordination numbers of an Nb showed a decreasing tendency with decreasing temperature, i.e., 6 in cubic, 5+1 in tetragonal and 4+2 in orthorhombic. An Na atom occupied a slightly different position from the K atom in 12-fold coordination, resulting in fewer coordination numbers of 8+4 in cubic and tetragonal and 7+5 in orthorhombic. The spontaneous polarisation (P_s) estimated from the atom positions and formal charges were approximately 0.29 C m⁻² in orthorhombic and 0.18 C m⁻² in tetragonal. The contribution of the alkaline oxide components to P_s was estimated to be approximately 15% in both ferroelectric forms. The temperature-induced transitions were also confirmed through the dielectric constant and dielectric loss at various frequencies and the differential scanning calorimetry.     

Temperature behavior of the protonic conductor K4LiH3(SO4)4

The results of the X-ray structural study for the K₄LiH₃(SO₄)₄ single crystal are presented at a wide temperature range. The thermal expansion of the crystal using the X-ray dilatometry and the capacitance dilatometry from 8 to 500 K was carried out. The crystal structures data collection, solution and refinement at 125, 295, 443 and 480 K were performed. The K₄LiH₃(SO₄)₄ crystal has tetragonal symmetry with the P4₁ space group (Z=4) at room temperature as well as at the considered temperature range. The existence of a low-temperature, para-ferroelastic phase transition at about 120 K is excluded. The layered structure of the crystal reflects a cleavage plane parallel to (001) and an anisotropy of the protonic conductivity. The superionic high-temperature phase transition at T_S=425 K is isostructural. Nevertheless, taking into account an increase of the SO₄ tetrahedra libration above T_S, a mechanism of the Grotthus type could be applied for the proton transport explanation.     

Synthesis, heat capacity and enthalpy of formation of [Ho2(l-Glu)2(H2O)8](ClO4)4·H2O

A complex of holmium perchlorate coordinated with l-glutamic acid, [Ho₂(l-Glu)₂(H₂O)₈](ClO₄)₄·H₂O, was prepared with a purity of 98.96%. The compound was characterized by chemical, elemental and thermal analysis. Heat capacities of the compound were determined by automated adiabatic calorimetry from 78 to 370 K. The dehydration temperature is 350 K. The dehydration enthalpy and entropy are 16.34 kJ mol⁻¹ and 16.67 J K⁻¹ mol⁻¹, respectively. The standard enthalpy of formation is −6474.6 kJ mol⁻¹ from reaction calorimetry at 298.15 K.     

Calorimetric study and thermal analysis of [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O (Gly: glycin)

Two solid-state coordination compounds of rare earth metals with glycin, [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O and [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 342.90 K, while [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol⁻¹ and 53.9 J K⁻¹ mol⁻¹ for [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, 1.82 kJ mol⁻¹ and 5.5 J K⁻¹ mol⁻¹ for [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed.     

A new room temperature ionic liquid of oxyfluorometallate anion: 1-Ethyl-3-methylimidazolium oxypentafluorotungstate (EMImWOF5)

The first room temperature ionic liquid (room temperature molten salt) containing oxyfluorometallate anion, 1-ethyl-3-methylimidazolium oxypentafluorotungstate (EMImWOF₅), has been synthesized and characterized compared to other known EMIm fluorocomplex salts. EMImWOF₅ is synthesized by two routes: one is the hydrolysis of EMImWF₇ and the other is the fluoroacid-base reaction of EMIm(HF)_2.3F and WOF₄. EMImWOF₅ is a hydrophilic room temperature ionic liquid but is stable in aqueous solution. From the result of DSC analysis, EMImWOF₅ exhibits a glass transition at 182 K and melts at 253 K. The density, conductivity and viscosity at 298 K are 2.25 g cm⁻³, 3.0 mS cm⁻¹ and 105.1 cP, respectively.     

Transport coefficients of titanium-doped Sb2Te3 single crystals

Titanium-doped single crystals (c_Ti=0-2×10²⁰ atoms cm⁻³) were prepared from the elements Sb, Ti, and Te of 5 N purity by a modified Bridgman method. The obtained crystals were characterized by measurements of the temperature dependence of the electrical resistivity, Hall coefficient, Seebeck coefficient and thermal conductivity in the temperature range of 3-300 K. It was observed that with an increasing Ti content in the samples the electrical resistivity, the Hall coefficient and the Seebeck coefficient increase. This means that the incorporation of Ti atoms into the Sb₂Te₃ crystal structure results in a decrease in the concentration of holes in the doped crystals. For the explanation of the observed effect a model of defects in the crystals is proposed. The data of the lattice thermal conductivity were fitted well assuming that phonons scatter on boundaries, point defects, charge carriers, and other phonons.     

Thermodynamic properties of BaCeO3 and BaZrO3 at low temperatures

Specific heat capacities (C_p) of polycrystalline samples of BaCeO₃ and BaZrO₃ have been measured from about 1.6 K up to room temperature by means of adiabatic calorimetry. We provide corrected experimental data for the heat capacity of BaCeO₃ in the range T < 10 K and, for the first time, contribute experimental data below 53 K for BaZrO₃. Applying Debye's T³-law for T → 0 K, thermodynamic functions as molar entropy and enthalpy are derived by integration. We obtain C_p = 114.8 (±1.0) J mol⁻¹ K⁻¹, S° = 145.8 (±0.7) J mol⁻¹ K⁻¹ for BaCeO₃ and C_p = 107.0 (±1.0) J mol⁻¹ K⁻¹, S° = 125.5 (±0.6) J mol⁻¹ K⁻¹ for BaZrO₃ at 298.15 K. These results are in overall agreement with previously reported studies but slightly deviating, in both cases. Evaluations of C_p(T) yield Debye temperatures and identify deviations from the simple Debye-theory due to extra vibrational modes as well as anharmonicity. The anharmonicity turns out to be more pronounced at elevated temperatures for BaCeO₃. The characteristic Debye temperatures determined at T = 0 K are Θ₀ = 365 (±6) K for BaCeO₃ and Θ₀ = 402 (±9) K for BaZrO₃.     

Thermoelectric properties of p-type pseudo-binary (Ag0.365Sb0.558Te)x-(Bi0.5Sb1.5Te3)1−x (x=0-1.0) alloys prepared by spark plasma sintering

In this paper, pseudo-binary (Ag_0.365Sb_0.558Te)_x-(Bi_0.5Sb_1.5Te₃)_1−x (x=0-1.0) alloys were prepared using spark plasma sintering technique, and the composition-dependent thermoelectric properties were evaluated. Electrical conductivities range from 7.9×10⁴ to 15.6×10⁴ Ω⁻¹ m⁻¹ at temperatures of 507 and 318 K, respectively, being about 3.0 and 8.5 times those of Bi_0.5Sb_1.5Te₃ alloy at the corresponding temperatures. The optimal dimensionless figure of merit (ZT) of the sample with molar fraction x=0.025 reaches 1.1 at 478 K, whereas that of the ternary Bi_0.5Sb_1.5Te₃ alloy is 0.58 near room temperature. The results also reveal that a direct introduction of Ag_0.365Sb_0.558Te in the Bi-Sb-Te system is much more effective to the property improvement than naturally precipitated Ag_0.365Sb_0.558Te in the Ag-doped Ag-Bi-Sb-Te system.     

The ionic conductivity and local environment of cations in Bi9ReO17

The influence of temperature on the structure of Bi₉ReO₁₇ has been investigated using differential thermal analysis, variable temperature X-ray diffraction and neutron powder diffraction. The material undergoes an order-disorder transition at ∼1000 K on heating, to form a fluorite-related phase. The local environments of the cations in fully ordered Bi₉ReO₁₇ have been investigated by Bi L_III- and Re L_III-edge extended X-ray absorption fine structure (EXAFS) measurements to complement the neutron powder diffraction information. Whereas rhenium displays regular tetrahedral coordination, all bismuth sites show coordination geometries which reflect the importance of a stereochemically active lone pair of electrons. Because of the wide range of Bi-O distances, EXAFS data are similar to those observed for disordered structures, and are dominated by the shorter Bi-O bonds. Ionic conductivity measurements indicate that ordered Bi₉ReO₁₇ exhibits reasonably high oxide ion conductivity, corresponding to 2.9×10⁻⁵ Ω⁻¹ cm^-1 at 673 K, whereas the disordered form shows higher oxide ion conductivity (9.1×10⁻⁴ Ω⁻¹ cm⁻¹ at 673 K).     

Thermodynamic properties of hydrated sodium l-threonate Na(C4H7O5)·H2O(s)

Low-temperature heat capacities of the compound Na(C₄H₇O₅)·H₂O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are Δ_transH_m = (5.75 ± 0.01) kJ mol⁻¹ and Δ_transS_m = (18.47 ± 0.02) J K⁻¹ mol⁻¹. The enthalpy and entropy of the dehydration are Δ_dH_m = (15.35 ± 0.03) kJ mol⁻¹ and Δ_dS_m = (41.35 ± 0.08) J K⁻¹ mol⁻¹. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations.     

Preparation of COF2 using CO2 and F2 in the electrochemical cell with PbSnF4 as a solid electrolyte

Tetragonal PbSnF₄ was prepared by precipitation method with Pb(NO₃)₂ and SnF₂ aqueous solutions. The product was characterized using X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XFS), and the other chemical analyses. Tetragonal PbSnF₄ exhibited the highest electric conductivity of 3.2 Sm⁻¹ at 473 K in air as a fluoride ion conductor. We have investigated the possibility of COF₂ formation using CO₂ and F₂ in an electrochemical cell with PbSnF₄ as a solid electrolyte. At same time, we tried to produce an electric power from an electrochemical cell. This CO₂/F₂ electrochemical cell was constructed with a tetragonal PbSnF₄ disk having Au electrodes. The electromotive force was about 0.9 V at room temperature for 0.1 MPa CO₂/(0.01 MPa F₂ + 0.09 MPa Ar). However, the short circuit current density was 0.24 A m⁻², which was quite small. This current density was so small that no fluorocarbon compound was detected after 3 h discharge using FT-IR.     

Vaporization of DyI3(s) and thermochemistry of the homocomplexes (DyI3)2(g) and (DyI3)3(g)

The vaporization of DyI₃(s) was investigated in the temperature range between 833 and 1053 K by the use of Knudsen effusion mass spectrometry. The ions DyI₂⁺, DyI₃⁺, Dy₂I₄⁺, Dy₂I₅⁺, Dy₃I₇⁺, and Dy₃I₈⁺ were detected in the mass spectrum of the equilibrium vapor. The gaseous species DyI₃, (DyI₃)₂, and (DyI₃)₃ were identified and their partial pressures determined. Enthalpies and entropies of sublimation resulted according to the second- and third-law methods. The following sublimation enthalpies at 298 K were determined for the gaseous species given in brackets: 274.8±8.2 kJ mol⁻¹ [DyI₃], 356.0±11.3 kJ mol⁻¹ [(DyI₃)₂], and 436.6±14.6 kJ mol⁻¹ [(DyI₃)₃]. The enthalpy changes of the dissociation reactions (DyI₃)₂=2 DyI₃ and (DyI₃)₃=3 DyI₃ were obtained as Δ_dH°(298)=193.3±5.6 and 390.3±13.0 kJ mol⁻¹, respectively.     

Ion-beam irradiation of lanthanum compounds in the systems La2O3-Al2O3 and La2O3-TiO2

Thin crystals of La₂O₃, LaAlO₃, La_2/3TiO₃, La₂TiO₅, and La₂Ti₂O₇ have been irradiated in situ using 1 MeV Kr²⁺ ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La₂O₃ remained crystalline to a fluence greater than 3.1×10¹⁶ ions cm⁻² at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (T_c) of 647 K for LaAlO₃, 840 K for La₂Ti₂O₇, 865 K for La_2/3TiO₃, and 1027 K for La₂TiO₅. The T_c values observed in this study, together with previous data for Al₂O₃ and TiO₂, are discussed with reference to the melting points for the La₂O₃-Al₂O₃ and La₂O₃-TiO₂ systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between T_c and melting temperature (T_m) in the two systems. More complex relationships exist between T_c and crystal structure, with the stoichiometric perovskite LaAlO₃ being the most resistant to amorphisation.     

Kinetic analysis of the thermal stability of lithium silicates (Li4SiO4 and Li2SiO3)

The kinetics describing the thermal decomposition of Li₄SiO₄ and Li₂SiO₃ have been analysed. While Li₄SiO₄ decomposed on Li₂SiO₃ by lithium sublimation, Li₂SiO₃ was highly stable at the temperatures studied. Li₄SiO₄ began to decompose between 900 and 1000 °C. However, at 1100 °C or higher temperatures, Li₄SiO₄ melted, and the kinetic data of its decomposition varied. The activation energy of both processes was estimated according to the Arrhenius kinetic theory. The energy values obtained were −408 and −250 kJ mol⁻¹ for the solid and liquid phases, respectively. At the same time, the Li₄SiO₄ decomposition process was described mathematically as a function of a diffusion-controlled reaction into a spherical system. The activation energy for this process was estimated to be −331 kJ mol⁻¹. On the other hand, Li₂SiO₃ was not decomposed at high temperatures, but it presented a very high preferential orientation after the heat treatments.     

Thermodynamic properties of the gaseous barium silicates BaSiO2 and BaSiO3

In the present study, the stability of gaseous barium silicates was confirmed by the high temperature mass spectrometry. On the basis of equilibrium constants measured for gas-phase reactions, the standard formation enthalpies were determined for gaseous barium silicates as (−510 ± 15) kJ · mol⁻¹ and (−884 ± 18) kJ · mol⁻¹ at 298 K; standard atomization enthalpies as (1637 ± 17) kJ · mol⁻¹ and (2318 ± 20) kJ · mol⁻¹ at 298 K for BaSiO₂ and BaSiO₃, respectively. Based on the results obtained the critical analysis of the literature data was carried out.