High-temperature heat capacity and thermodynamic properties of Tb<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Tb₂Sn₂O₇ has been prepared by solid-state reaction in air at 1473 K over a period of 200 h and its isobaric heat capacity has been studied experimentally in the range 350–1073 K. The C _p(T) data for this compound have no extrema and are well represented by the classic Maier–Kelley equation. The experimental C _p(T) data have been used to evaluate the thermodynamic properties of terbium stannate (pyrochlore structure): enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(Т).     

Heat capacity of the MVO<Subscript>4</Subscript> (M = Al,Ga, In,Tl) orthovanadates

The heat capacity of InVO₄ has been determined by differential scanning calorimetry in the temperature range 339–1089 K. The experimental C_p(T) data have been used to evaluate the thermodynamic functions of indium orthovanadate: enthalpy increment H°(T)–H°(339 K), entropy change S°(T)–S°(339 K), and reduced Gibbs energy Ф°(Т). The specific heats of GaVO₄ and TlVO₄ have been evaluated.     

Synthesis and High-Temperature Heat Capacity of Dy<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Ho<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates have been prepared by solid-state reactions in several sequential firing steps in the temperature range 1237–1473 K using stoichiometric mixtures of Dy₂O₃ (or Ho₂O₃) and GeO₂. The heat capacity of the synthesized germanates has been determined as a function of temperature by differential scanning calorimetry in the range 350–1000 K. The experimentally determined C _p (T) curves of the dysprosium and holmium germanates have no anomalies and are well represented by the Maier–Kelley equation. The experimental C _p (T) data have been used to evaluate the thermodynamic functions of the Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates: enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(T).     

High-temperature heat capacity and vibrational spectra of Eu<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Eu₂Sn₂O₇ compound has been prepared by solid-state reaction (by sequentially firing a stoichiometric mixture of Eu₂O₃ and SnO₂ in air at 1273 and 1473 K) and its heat capacity has been determined by differential scanning calorimetry in the temperature range 370–1000 K. The heat capacity data have been used to evaluate the thermodynamic properties of europium stannate: enthalpy increment H°(T)–H°(370 K), entropy change S°(T)–S°(370 K), and reduced Gibbs energy Ф°(T). Raman spectra of Eu₂Sn₂O₇ polycrystals with the pyrochlore structure have been measured in the range 200–1200 cm^–1.     

The calorimetry and thermodynamic functions of Nd Mg<Stack><Subscript>3</Subscript><Superscript>I</Superscript></Stack>Mn<Subscript>4</Subscript>O<Subscript>12</Subscript> (Me<Superscript>I</Superscript>-Li,Na, K) manganites in the range from 298.15 to 673 K

The ceramic technology is employed for synthesizing manganites of composition Nd Mg ₃ ^I Mg₃Mn₄O₁₂(Me^I-Li, Na, K). The X-ray technique is used to find that the compounds crystallize in tetragonal syngony. The parameters of their crystal lattices are determined. Their heat capacities are experimentally determined in the range from 298.15 to 673 K, which enables one to reveal second-order phase transitions. In view of these transitions, equations describing the C _p ^° ～ f(T) dependence are derived, and the thermodynamic functions C _p ^° (T), H°(T)-H°(298.15), S°(T), and Φ ^xx (T) are calculated.     

Vapor pressure determination for solid and liquid La<Subscript>2</Subscript>S<Subscript>3</Subscript> using boiling points

A high-temperature technique was developed for vapor pressure determination of solid and liquid γ-La₂S₃ (we called it the boiling point technique). Melting temperatures and total vapor pressures were measured for incongruently vaporizing γ-La₂S₃ at 1853–2210 K and 0.3–3.0 atm pressures. Having compared the slopes of the log p(S₂) versus 1/T plots measured by various techniques, we recommend the equation log p(S₂) [atm] = (6.31 ± 0.15) ? (12720±310)T ^?1 for T = 1021–2013 K as the most reliable for practical use.     

Dissociation energy of a Sc<Subscript>2</Subscript> molecule

The–(G°(T)–H°(0))/T Gibbs energy functions have been calculated for Sc₂ at Т = 2000 K in the context of recent data on the low-lying electron states for this kind of molecules. In particular, some recent experimental results on the vapor composition over scandium are presented in this study. The data on the measured scandium vapor composition have been processed using the evaluated Gibbs energy function values. The advised dissociation energy value for Sc₂ is found to be D°₀(Sc₂) = 7750 ± 1750 cm^–1.     

Heat Capacity and thermodynamic functions of DyMe<Superscript>II</Superscript>Cr<Subscript>2</Subscript>O<Subscript>5.5</Subscript>(Me<Superscript>II</Superscript>-Mg,Ca) in the range from 298.15 to 673 K

The calorimetric method is used to investigate the heat capacity of DyMe^IICr₂O_5.5(Me^II-Mg, Ca) chromites in the range from 298.15 to 673 K. The C _p ⁰ ～ f(T) curves exhibit λ-like effects at 348 and 548 K for DyMgCr₂O_5.5 and at 473 K for DyCaCr₂O_5.5, which apparently relate to second-order phase transitions. The temperature dependences are calculated for thermodynamic functions C _p ⁰ (T), H ⁰(T)-H ⁰(298.15), S ⁰(T), and Φ**(T).     

Interaction of hydrogen with the intermetallic compound Nd<Subscript>2</Subscript>Fe<Subscript>17</Subscript> studied by calorimetry

Interaction of hydrogen with the intermetallic compound Nd₂Fe₁₇ has been studied for the first time by calorimetry using a differential heat conduction calorimeter coupled to a Sieverts apparatus. Hydrogen absorption and desorption reactions were run at 200°C, and two types of data were obtained: p–C–T and ΔH–C–T (where p is the equilibrium hydrogen pressure, C = H/Nd₂Fe₁₇, ΔH is the reaction enthalpy, and T is the measurement temperature). The p–C–T curves obtained for the hydrogen absorption and desorption processes have no plateau or two-phase region, in contrast to what is characteristic of the formation of a hydride phase. At the same time, the ΔH(C) curves have a few portions where the enthalpy of reaction between hydrogen and the intermetallic compound remains constant: 0 < C < 2.0, with ΔH _abs =–85.05 ± 0.65 kJ/mol H ₂; 2.0 < C < 2.7, with ΔH _abs =–80.64 ± 1.00 kJ/mol H₂; and 1.9 < C < 2.7, with ΔH _des = 76.48 ± 0.85 kJ/mol H₂. The data obtained in this study suggest that positions 9e and 18g in the intermetallic compound are occupied by hydrogen in a particular order.     

Critical Behavior of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.95</Subscript>Fe<Subscript>0.05</Subscript>O<Subscript>3</Subscript> Manganite

The critical behavior of perovskite manganite La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ at the ferromagnetic–paramagnetic has been analyzed. The results show that the sample exhibited the second-order magnetic phase transition. The estimated critical exponents derived from the magnetic data using various such as modified d’Arrott plot Kouvel–Fisher method and critical magnetization M(T _C, H). The critical exponents values for the La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ are close to those expected from the mean field model β = 0.504 ± 0.01 with T _C = 275661 ± 0.447 (from the temperature dependence of the spontaneous magnetization below T _C ), γ = 1.013 ± 0.017 with T _C = 276132 ± 0.452 (from the temperature dependence of the inverse initial susceptibility above T _C ), and δ = 3.0403 ± 0.0003. Moreover, the critical exponents also obey the single scaling equation of M(H, ε) = |ε| ^β f _±(H/|ε| ^β+γ ).     

Magnetic,magnetocaloric properties,and critical behavior in a layered perovskite La<Subscript>1.4</Subscript>(Sr<Subscript>0.95</Subscript>Ca<Subscript>0.05</Subscript>)<Subscript>1.6</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript>

We report the results of magnetic, magnetocaloric properties, and critical behavior investigation of the double-layered perovskite manganite La_1.4(Sr_0.95Ca_0.05)_1.6Mn₂O₇. The compounds exhibits a paramagnetic (PM) to ferromagnetic (FM) transition at the Curie temperature T _C = 248 K, a Neel transition at T _N = 180 K, and a spin glass behavior below 150 K. To probe the magnetic interactions responsible for the magnetic transitions, we performed a critical exponent analysis in the vicinity of the FM–PM transition range. Magnetic entropy change (??S _M) was estimated from isothermal magnetization data. The critical exponents β and γ, determined by analyzing the Arrott plots, are found to be T _C = 248 K, β = 0.594, γ = 1.048, and δ = 2.764. These values for the critical exponents are close to the mean-field values. In order to estimate the spontaneous magnetization M _S(T) at a given temperature, we use a process based on the analysis, in the mean-field theory, of the magnetic entropy change (??S _M) versus the magnetization data. An excellent agreement is found between the spontaneous magnetization determined from the entropy change [(??S _M) vs. M ²] and the classical extrapolation from the Arrott curves (µ₀H/M vs. M ²), thus confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in this system and in other compounds as well.     

The H-T and P-T Phase Diagram of the Superconducting Phase in Pd:Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>

We study the magnetic field vs. temperature (H – T) and pressure vs. temperature (P – T) phase diagrams of the T _c ≈ 5.5 K superconducting phase in Pd _x Bi₂Te₃ (x ≈ 1) using electrical resistivity versus temperature measurements at various applied magnetic fields (H) and magnetic susceptibility versus temperature measurements at various applied magnetic fields (H) and pressure (P). The H – T phase diagram has an initial upward curvature as observed in some unconventional superconductors. The critical field extrapolated to T = 0 K is H _c (0) ≈ 6–10 kOe. The T _c is suppressed approximately linearly with pressure at a rate d T _c /d P ≈ ?0.28 K/GPa.     

Influence of coronene addition on some superconducting properties of bulk MgB<Subscript>2</Subscript>

This study reports the effect of coronene (C₂₄H₁₂) addition on some superconducting properties such as critical temperature (T_c), critical current density (J_c), flux pinning force density (F_p), irreversibility field (H_irr), upper critical magnetic field (H_c2), and activation energy (U₀), of bulk MgB₂ superconductor by means of magnetisation and magnetoresistivity measurements. Disk-shaped polycrystalline MgB₂ samples with varying C₂₄H₁₂ contents of 0, 2, 4, 6, 8, 10 wt%, were produced at 850 °C in Ar atmosphere. The obtained results show an increase in field-J_c values at 10 and 20 K resulting from the strengthened flux pinning, and a decrease in critical temperature (T_c) because of C substitution into MgB₂ lattice, with increasing amount of C₂₄H₁₂ powder. The H_c2(0) and H_irr(0) values are respectively found as 144, 181, 172 kOe, and 128, 161, 145 kOe for pure, 4 wt% and 10 wt% C₂₄H₁₂ added samples. The U₀ depending on the magnetic field curves were plotted using thermally activated flux flow model. The maximum U₀ values are respectively obtained as 0.20, 0.23 and 0.12 eV at 30 kOe for pure, 4 wt% and 10 wt% C₂₄H₁₂ added samples. As a result, the superconducting properties of bulk MgB₂ at high fields was improved using C₂₄H₁₂, active carbon source addition, because of the presence of uniformly dispersed C particles with nanometer order of magnitude, and acting as effective pinning centres in MgB₂ structure.     

Comparative Experimental and Density Functional Theory (<Emphasis Type="Italic">DFT</Emphasis>) Study of the Physical Properties of MgB<Subscript>2</Subscript> and AlB<Subscript>2</Subscript>

In the present study, we report an intercomparison of various physical and electronic properties of MgB₂ and AlB₂. In particular, the results of phase formation, resistivity ρ(T), thermoelectric power S(T), magnetization M(T), heat capacity (C _P ), and electronic band structure are reported. The original stretched hexagonal lattice with a=3.083 Å, and c=3.524 Å of MgB₂ shrinks in c-direction for AlB₂ with a=3.006 Å, and c=3.254 Å. The resistivity ρ(T), thermoelectric power S(T) and magnetization M(T) measurements exhibited superconductivity at 39 K for MgB₂. Superconductivity is not observed for AlB₂. Interestingly, the sign of S(T) is +ve for MgB₂ the same is ?ve for AlB₂. This is consistent with our band structure plots. We fitted the experimental specific heat of MgB₂ to Debye–Einstein model and estimated the value of Debye temperature (Θ _D) and Sommerfeld constant (γ) for electronic specific heat. Further, from γ, the electronic density of states (DOS) at Fermi level N(E _F) is calculated. From the ratio of experimental N(E _F) and the one being calculated from DFT, we obtained value of λ to be 1.84, thus placing MgB₂ in the strong coupling BCS category. The electronic specific heat of MgB₂ is also fitted below T _c using α-model and found that it is a two gap superconductor. The calculated values of two gaps are in good agreement with earlier reports. Our results clearly demonstrate that the superconductivity of MgB₂ is due to very large phonon contribution from its stretched lattice. The same two effects are obviously missing in AlB₂, and hence it is not superconducting. DFT calculations demonstrated that for MgB₂, the majority of states come from σ and π 2p states of boron on the other hand σ band at Fermi level for AlB₂ is absent. This leads to a weak electron phonon coupling and also to hole deficiency as π bands are known to be of electron type, and hence obviously the AlB₂ is not superconducting. The DFT calculations are consistent with the measured physical properties of the studied borides, i.e., MgB₂ and AlB₂.     

Temperature effect on the photoluminescence intensity and Eu<Superscript>2+</Superscript> excited state lifetime in EuGa<Subscript>2</Subscript>S<Subscript>4</Subscript> and EuGa<Subscript>2</Subscript>S<Subscript>4</Subscript>:Er<Superscript>3+</Superscript>

The photoluminescence (PL) spectra and Eu²⁺ excited state lifetime of EuGa₂S₄ and EuGa₂S₄:Er³⁺ have been studied in the range 78–500 K. The spectra show a band at 545 nm, due to the 4f ⁶5d → 4f ⁷(⁸ S _7/2) transition. With increasing temperature, the full width at half maximum Γ(T) of the PL band of EuGa₂S₄ and EuGa₂S₄:Er³⁺ crystals increases from 0.15 to 0.22 and from 0.13 to 0.19 eV, respectively. Over the entire temperature range studied, Γ(T) is a linear function of T ^1/2. The 545-nm emission intensity and Eu²⁺ excited state lifetime in EuGa₂S₄ and EuGa₂S₄:Er³⁺ vary exponentially with temperature. The luminescence quenching energies evaluated from the Arrhenius plots of I(10³/T) and τ(10³/T) coincide (0.10 eV) within the error of determination.     

Thermal Dissociation of RMnO<Subscript>3</Subscript> (R = Dy,Yb, Lu)

The phase equilibria involved in the thermal dissociation of RMnO₃ (R = Dy, Yb, Lu) were studied in the range 973–1173 K by a static method in a vacuum circulation unit and by x-ray diffraction analysis of quenched solid phases. The RMnO₃ manganites were shown to dissociate by the reaction RMnO₃ = 1/2R₂O₃ + MnO + 1/4O₂. The temperature dependences of the equilibrium oxygen pressure and Gibbs energy change in this reaction were determined for the three compounds. The experimental data were used to evaluate the standard thermodynamic functions of formation of RMnO₃ from R₂O₃ and Mn₂O₃: ΔH⁰(T) = ?88.93 kJ/mol, Δ S⁰(T) = 46.56 J/(mol K) for DyMnO₃; ΔH⁰(T) = ?130.95 kJ/mol, Δ S⁰(T) = 86.25 J/(mol K) for YbMnO₃; ΔH⁰(T) = ?142.94 kJ/mol, Δ S⁰(T) = 102.87 J/(mol K) for LuMnO₃.     

Synthesis and High-Temperature Heat Capacity of Neodymium Titanate

Neodymium dititanate, Nd₂Ti2O₇ (monoclinic structure, sp. gr. P2₁), has been prepared by solid-state reaction in air at temperatures from 1673 to 1773 K using the Nd₂O₃ and TiO₂ oxides as starting materials. The high-temperature heat capacity of the resultant polycrystalline Nd₂Ti₂O₇ samples has been determined by differential scanning calorimetry. The experimental C_p(T) data have been used to evaluate the thermodynamic functions of neodymium dititanate (enthalpy increment H°(T)–H°(320 K), entropy change S°(T)–S°(320 K), and reduced Gibbs energy Ф°(T)) in the temperature range 320–1053 K.     

Heat Capacity and Thermodynamic Functions of Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript> from 14 to 320 K

The heat capacity of Ga₂Se₃ is measured from 14 to 320 K by adiabatic calorimetry. The smoothed heat capacity data are used to evaluate temperature-dependent thermodynamic functions (entropy, enthalpy increment, and reduced Gibbs energy) of gallium selenide. Under standard conditions, the thermodynamic properties of Ga₂Se₃ are C _p ⁰ (298.15 K) = 120.8 ± 0.2 J/(K mol), S⁰(298.15 K) = 180.4 ± 0.4 J/(K mol), H⁰(298.15 K) - H⁰(0) = 25.32 ± 0.05 kJ/mol, and Φ⁰(298.15 K) = 95.52 ± 0.19 J/(K mol). The Debye characteristic temperature of Ga₂Se₃ evaluated from heat capacity data is 340 ± 10 K.     

Investigation of Magnetic,Magnetocaloric, and Critical Properties of La<Subscript>0.5</Subscript>Ba<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> Manganite

We present an extensive study of the magnetic properties of a novel La_0.5Ba_0.5MnO₃ perovskite material prepared by the hydrothermal method. The explored sample was structurally studied by the x-ray diffraction (XRD) method which confirms the formation of a pure cubic phase of a perovskite structure with Pm3m space group. The magnetic properties were probed by employing temperature M (T) and external magnetic field M (μ_oH) dependence of magnetization measurements. A magnetic phase transition from ferromagnetic to paramagnetic phase occurs at 339 K in this sample. The maximum magnetic entropy change (\(\left | {{\Delta } S}_{M}^{\max } \right |\)) took a value of 1.4 J kg^??1 K^??1 at the applied magnetic field of 4.0 T for the explored sample and has also been found to occur at Curie temperature (T_C). This large entropy change might be instigated from the abrupt reduction of magnetization at T_C. The magnetocaloric effect (MCE) is maximum at T_C as represented by M (μ_oH) isotherms. The relative cooling power (RCP) is 243.2 J kg^??1 at μ_oH =?4.0 T. Moreover, the critical properties near T_C have been probed from magnetic data. The critical exponents δ, β, and γ with values 3.82, 0.42, and 1.2 are close to the values predicted by the 3D Ising model. Additionally, the authenticity of the critical exponents has been confirmed by the scaling equation of state and all data fall on two separate branches, one for T < T_C and the other for T > T_C, signifying that the critical exponents obtained in this work are accurate.     

Synthesis and High-Temperature Heat Capacity of Sm<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Eu<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Sm₂Ge₂O₇ and Eu₂Ge₂O₇ germanates have been prepared by solid-state reactions via multistep firing of stoichiometric mixtures of Sm₂O₃ (Eu₂O₃) and GeO₂ in air at temperatures from 1273 to 1473 K. The molar heat capacity of the samarium and europium germanates has been determined by differential scanning calorimetry in the range 350–1000 K and the C _p (T) data have been used to evaluate their thermodynamic properties.