Thermodynamic properties of NaZr<Subscript>2</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The heat capacity C _p ⁰ of crystalline NaZr₂(AsO₄)₃ has been measured in the range 7–650 K using precision adiabatic calorimetry and differential scanning calorimetry. The experimental data have been used to calculate the standard thermodynamic functions of the arsenate: C _p ⁰, enthalpy H ⁰(T) − H ⁰(0), entropy S ⁰(T), and Gibbs function G ⁰(T) − H ⁰(0) from T → 0 to 650 K. The standard entropy of its formation from elements is Δ_f S ⁰(NaZr₂(AsO₄)₃, cr, 298.15 K) = −1087 ± 1 J/(mol K).     

Thermodynamic properties of Cu<Subscript>5</Subscript>SmSe<Subscript>4</Subscript>

The heat capacity of Cu₅SmSe₄ has been measured from 80 to 300 K. The results have been used to assess the main thermodynamic functions of Cu₅SmSe₄: entropy (S ⁰(T) − S ⁰(0)), enthalpy increment (H ⁰(T) − H ⁰(0)), and reduced Gibbs energy (Φ⁰(T)).     

Revised heat capacity and thermodynamic functions of GdVO<Subscript>4</Subscript>

The heat capacity of GdVO₄ has been determined by adiabatic calorimetry in the range 5–345 K. The present experimental data and earlier results have been used to evaluate the thermodynamic functions of gadolinium orthovanadate (C _p ⁰(T), S ⁰(T), H ⁰(T) − H ⁰(0), and Φ⁰(T)) as functions of temperature (5–350 K). Its Gibbs energy of formation is determined to be Δ_f G ⁰(GdVO₄, 298.15 K) = −1684.5 ± 1.6 kJ/mol.     

Thermodynamic functions of ScVO<Subscript>4</Subscript> at temperatures from 0 to 350 K

The heat capacity of ScVO₄ has been determined by adiabatic calorimetry at temperatures from 14.52 to 347.13 K, and smoothed heat capacity data have been used to evaluate its thermodynamic functions (entropy, enthalpy increment, and reduced Gibbs energy). At 298.15 K, the thermodynamic functions of scandium orthovanadate are C _p ⁰(298.15 K) = 110.5 ± 0.1 J/(mol K), S ⁰(298.15 K) = 110.9 ± 0.1 J/(mol K), H ⁰(298.15 K) − H ⁰(0) = 18.53 ± 0.01 kJ/mol, and Φ⁰(298.15 K) = −[G ⁰(298.15 K)/298.15] = 48.75 ± 0.12 J/(mol K). The calculated Gibbs energy of formation of scandium orthovanadate from its constituent elements is Δ_f G ⁰(ScVO₄, 298.15 K) = −1644.0 ± 2.2 kJ/mol.     

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.     

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).     

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.     

Scaling of the Temperature Dependent Resistivity and Hall Effect in Ba(Fe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Co<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)As<Subscript>2</Subscript>

We show that the temperature-dependent resistivity ρ(T), Hall number n _H(T) and the cotangent of the Hall angle cot θ _H(T) of Ba(Fe_1−x Co _x )As₂ (x=0.0–0.2) can be scaled using a recently proposed model-independent scaling method (Luo et al. in Phys. Rev. B 77:014529, 2008). The zero field normal-state resistivity above T _c can be reproduced by the expresion r(T) = r₀ +cTexp(- \frac2\varDelta T )\rho(T) = \rho_{0} +cT\exp(- \frac{2\varDelta }{T} ) and scaled using the energy scale Δ, c and the residual resistivity ρ ₀ as scaling parameters. The scaling parameters have been calculated and the compositional variation of 2Δ and ρ ₀ has been determined. The 2Δ(x) dependence show almost linear decreasing in underdoped regime, minimum corresponding to the T _c maximum and increasing in overdoped regime. The latter is different from that reported for cuprates. The existence of a universal metallic ρ(T) curve which, however, is restricted for the underdoped compounds to temperatures above a structural and antiferromagnetic transition is interpreted as an indication of a single mechanism which dominates the scattering of the charge carriers in Ba(Fe_1−x Co _x )As₂ (x=0.0–0.2).     

Low-field Magnetoresistance,Specific Heat and Magnetocaloric Effect in Sr Substituted Pr<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>

We investigate the effect of ionic size variation on the electrical and thermodynamic properties in a series of Pr_0.7Ca_0.3−x Sr _x MnO₃ (PCSMO) samples. The increase in Sr content results in an increase of the unit cell volume, as a bigger Sr²⁺ ion replaces the smaller Ca²⁺ ions. Resistivity measurements show that the increase in the Sr content also results in the induction of a metal–insulator transition (T _MI), which increases with increasing Sr content. The activation energy (E _a), calculated from the resistivity data, decreases with increasing Sr content confirming the metallic character. The effect of the magnetic field on resistivity and specific heat has also been studied.     

Ac and dc magnetotransport properties of the phase-separated La<Subscript>0.6</Subscript>Y<Subscript>0.1</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> manganite

The physical properties of the La_0.6Y_0.1Ca_0.3MnO₃ compound have been investigated, focusing on the magnetoresistance phenomenon studied by both dc and ac electrical transport measurements. X-ray diffraction and scanning electron microscopy analysis of ceramic samples prepared by the sol–gel method revealed that specimens are single phase and have average grain size of ∼0.5 μm. Magnetization and 4-probe dc electrical resistivity ρ(T,H) experiments showed that a ferromagnetic transition at T _C ∼ 170 K is closely related to a metal-insulator (MI) transition occurring at essentially the same temperature T _MI . The magnetoresistance effect was found to be more pronounced at low applied fields (H ≤ 2.5 T) and temperatures close to the MI transition. The ac electrical transport was investigated by impedance spectroscopy Z(f,T,H) under applied magnetic field H up to 1 T. The Z(f,T,H) data exhibited two well-defined relaxation processes that exhibit different behaviors depending on the temperature and applied magnetic field. Pronounced effects were observed close to T _C and were associated with the coexistence of clusters with different electronic and magnetic properties. In addition, the appreciable decrease of the electrical permittivity ε′(T,H) is consistent with changes in the concentration of e _g mobile holes, a feature much more pronounced close to T _C .     

Controlled magnetoresistance in Y<Subscript>3/4</Subscript>Lu<Subscript>1/4</Subscript>Ba<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7</Subscript>-CuO composites at 77 K

We have studied the low-temperature magnetoresistance of Y_3/4Lu_1/4Ba₂Cu₃O₇-CuO composites obtained by fast sintering technique and established a relation between the probing to critical current density ratio j/j _c and the shape of the magnetoresistance curve ρ(H). For j/j _c<1, the electric resistance arises at a threshold value of the magnetic field strength H _c. For j/j _c≥1, a linear variation of ρ(H) at 77 K in the range from 0 to 14 Oe can be provided by selecting the CuO content (in the 15–30 vol % interval) and the j value (in the 0.003–0.2 A/cm² range). In the latter case, the slope dρ/dH (i.e., the sensitivity of the electric resistivity with respect to the magnetic field) is 1–20 mΩ cm/Oe and the relative field-induced increase in the resistivity ρ₀=(ρ(H)−ρ(H=0))/ρ(H=0) amounts to 1320 and 685% at H=200 and 35 Oe, respectively. Composites possessing controlled magnetoresistance are promising materials for the active elements of magnetic field sensors capable of operating at a practically convenient liquid nitrogen temperature.     

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).     

Synthesis and high-temperature heat capacity of Gd<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Gd₂Sn₂O₇ gadolinium stannate with the pyrochlore structure has been prepared by solid-state reaction and its high-temperature heat capacity has been determined by differential scanning calorimetry in the temperature range 350–1020 K. The C_p(T) data are shown to be well represented by the classic Maier–Kelley equation. The experimental C_p(T) data have been used to evaluate the thermodynamic functions of gadolinium stannate: enthalpy increment H°(T)–H°(339 K), entropy change S°(T)–S°(339 K), and reduced Gibbs energy Ф°(Т).     

Interplay of Superconductivity and Ferromagnetism in UGe<Subscript>2</Subscript>

The emergence of pressure induced superconductivity (SC) under the background of ferromagnetic state in 5f-electron based itinerant ferromagnetic superconductor UGe₂ is studied in the single band model by using a mean-field approximation. The solutions to the coupled equations of superconducting gap (Δ) and magnetization (m) are obtained using Green’s function technique and equation of motion method. It is shown that there generally exists a coexistent (Δ≠0, m≠0) solution to the coupled equations of the order parameters in the temperature range 0<T<min (T _C,T _FM), where T _C and T _FM are respectively the superconducting and ferromagnetic transition temperatures. The study of electronic specific heat (C/T), density of states, free energy, etc. are also presented. The specific heat capacity at low temperature shows linear temperature dependence as opposed to the activated behavior. Density of states increases as opposed to the case of a standard ferromagnetic metal. Free energy study reveals that the superconducting ferromagnetic state has lower energy than the normal ferromagnetic state and, therefore, realized at low enough temperature. The agreement between theory and experimental results for UGe₂ is quite satisfactory.      

Impact of Tuning Molar Ratio in the Starting Materials: <Emphasis Type="Italic">Magneto</Emphasis>-Transport Features of Hybrid YSr<Subscript>2</Subscript>Ru<Subscript>0.9</Subscript>Cu<Subscript>2.1</Subscript>O<Subscript>7.9</Subscript>

The impact of slightly tuning molar ratio in the starting materials on the physical properties of 1212-type rutheno-cuprate, YSr₂Ru_0.9Cu_2.1O_7.9 (nominal) samples prepared under four synthesis approaches are reported. Interestingly, all samples clearly show the differences in the physical properties of the samples prepared under different synthetic protocols. However, neither XRD nor EDX reveal any notable differences in the crystal structure or sample composition. All the samples exhibit magneto-superconducting properties (H _ext=5 Oe) which are slightly varied with synthetic approaches. The high field (H _ext=10 kOe) temperature dependence of magnetization data shows a sharp ferromagnetic transition around 150 K and all the samples obey Curie–Weiss linear behavior above 180 K. The experimental effective paramagnetic moment for the various samples is in the range of 2.5 and 2.7μ _B/Ru which are in line with the literature report. The magnetization, M(H) isotherm curves measured at 5 K and −10 kOe≤H≤10 kOe conditions reveal weak ferromagnetic-like hysteresis loops for all samples with returning moment (M _r) and coercive field (H _c), whereas the high field M(H) loops indicate soft ferromagnetic behaviors with magnetic saturation. The saturation moment of the samples is slightly varied with the synthesis approaches. None of the samples showed bulk superconductivity (T_c^{R = 0})T_{\mathrm{c}}^{R = 0}) down to 2 K, while all samples show onset transitions (T_c^onsetT_{\mathrm{c}}^{\mathrm{onset}}) except the sample prepared by approach-3. The latter approach sample shows semiconducting behavior down to 2 K. The T_c^onsetT_{\mathrm{c}}^{\mathrm{onset}} noticed at 34 K, 12 K, and 6 K for the sample prepared by approach-1, 2, and 4, respectively. The nearly linear dependence suggests that hopping conduction is dominant in certain temperature range for all samples. The magneto-transport features of these samples exhibit maximum magnetoresistance (MR) at low temperatures. Remarkably, the sample prepared by approach-1 shows largest −MR about 77% at low temperature 2 K and H=90 kOe which stimulates for further investigations. Among the four synthesis approaches employed in the present study, we can probably suggest that the approach-1 (0.5Y₂O₃+0.5SrO₂+1.5SrCuO₂+0.9RuO₂+0.6CuO) is the preferable method to achieve the best sample (in terms of magneto-transport features).     

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).     

Composition range and thermodynamic properties of Tl<Subscript>5</Subscript>Se<Subscript>2</Subscript>Br-based solid solutions

The equilibrium subsolidus phase diagram of the TlBr-Tl₂Se-TlSe system has been mapped out using X-ray diffraction analysis and emf measurements on thallium concentration cells. Tl₅Se₂Br has been shown to have a broad homogeneity region. The emf results are used to evaluate the relative partial thermodynamic functions of the thallium in the alloys studied and the standard integral thermodynamic functions (ΔG ⁰(298 K), ΔH ⁰(298 K), S ⁰(298 K)) of the Tl₅Se₂Br-based solid solutions.     

The Activation Energy <Emphasis Type="Italic">U</Emphasis>(<Emphasis Type="Italic">T</Emphasis>,<Emphasis Type="Italic">H</Emphasis>) in Y-based Superconductors

Based on the Arrhenius equation, a method to calculate the activation energy from the resistance transition is proposed for high temperature superconductors. This method is applied to the Y-based superconductors. The activation energy is found to be U(T,H)∼(1−T/T _c )^4.8(H/H ₀)^−3.8 of YBCO crystal, and U(T,H)∼(1−T/T _c )^3.3(H/H ₀)^−2.2 of Er doped MTG YBCO crystal, respectively. With the obtained activation energy U(T,H), the lower part of the experimental curve ρ(T,H) and its derivative can be reproduced.      

Fabrication and magnetoresistivit of ex-situ processed MgB<Subscript>2</Subscript>/Fe monofilament tapes without any intermediate annealing

We have fabricated MgB₂/Fe monofilament wires and tapes by a powder-in tube (PIT) technique, using an ex-situ process without any intermediate annealing. MgB₂/Fe monofilament tapes were annealed at 650–1,050°C for 60 min and 950°C for 30–240 min. We have investigated the effect of annealing temperatures and times on the formation of MgB₂ phase, activation energy, temperature dependence of irreversibility field H _irr(T) and upper critical field H _c2(T), transition temperature (T _c), lattice parameters (a and c), full width at half maximum, crystallinity, resistivity, residual resistivity ratio, active cross-sectional area fraction and critical current densities. We observed that the activation energies of the MgB₂/Fe monofilament samples increased with increasing annealing temperature up to 950°C and with increasing annealing time up to 60 min while it decreased with increasing magnetic field. For the MgB₂/Fe monofilament tape, the slope of the H _c2–T and H _irr–T curves decreased with increasing annealing temperature from 850 to 950°C as well as with increasing annealing time from 30 to 60 min. The transport and microstructure investigations show that T _c, J _c and microstructure properties are remarkably enhanced with increasing annealing temperature. The highest value of critical current density is obtained for the sample annealed at 950°C for 60 min. The J _c and T _c^offset values of the sample annealed at 950°C for 60 min were found to be 260.43 A/cm² at 20 and 38.1 K, respectively.     

Thermodynamic properties of LaF<Subscript>3</Subscript> superionic crystals near their phase transition

We examine the behavior of the entropy (S _d), enthalpy (H), and concentration of disordered fluoride ions (n) in LaF₃ in a broad temperature range around its critical temperature using a model for structural lattice disordering. We analyze the relationship between the free energy of a crystal and LaF₃ lattice disordering parameters: entropy, S _d; anion sublattice disordering energy, E _a; and the concentration of vacancy-interstitial defect complexes, n. H(T), n(T), and S _d(T) data are obtained for the phase transition region.