A calorimetric study of the dimerized phase of C60 fullerene

The temperature dependence of the heat capacity at a constant pressure C _p ⁰ = f(T) for the dimerized phase of the C₆₀ fullerene in the temperature range 300–575 K and the thermodynamic characteristics for depolymerization of this phase under normal pressure are investigated using precision differential scanning calorimetry. It is established that thermal depolymerization is a kinetically hindered process. The final products of thermal depolymerization are identified as a partially crystalline monomer face-centered cubic phase of C₆₀ with a degree of crystallinity α = 67 mol %. The results obtained in this study and our previous experimental data on the low-temperature heat capacity are used in the calculations of standard thermodynamic functions for the (C₆₀)₂ crystalline dimer, namely, the heat capacity C _p ⁰ (T), the enthalpy H ⁰(T) ? H ⁰(0), the entropy S ⁰(T), and the Gibbs function G ⁰(T) ? H ⁰(0) in the temperature range from T → 0 to 394 K.     

Thermal and magnetic properties of DyB62 at low temperatures

Temperature dependences of heat capacity C_P(T) and magnetization M(T) of an icosahedral dysprosium boride (DyB₆₂) single crystal have been experimentally investigated in the temperature range of 2-300 K. The magnetic susceptibility χ(T) of DyB₆₂ follows Curie-Weiss law with a paramagnetic Curie temperature of −3.7 K, which implies that the antiferromagnetic interactions are dominant in this material and suggests the possibility of magnetic ordering at low temperatures. This conjecture is supported by the temperature dependence of heat capacity C_P(T), which decreases upon heating from 2 to 7 K. The heat capacity of DyB₆₂ at 2 K is analyzed as a sum of magnetic, Debye, two-level system and soft atomic potential components.     

Dielectric properties of C60 molecular complexes

The permittivity ? of the molecular complexes (BTX)C₆₀CS₂, (DAN)C₆₀(C₆H₆)₃, and (S₄N₄)_1.2C₆₀(C₆H₆)_0.8 has been studied at 100 MHz. A maximum has been observed to appear in the temperature dependence ?(T) at T≈90 K, which can be assigned to freezing of the orientational disorder. A region of anomalous growth of ? with decreasing temperature has been found in the low-temperature range T≤25 K, this feature being apparently sensitive to the actual packing pattern of C₆₀ spheres in the molecular complex.     

Features of the low-temperature specific heat in underdoped YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + <Emphasis Type="Italic">x</Emphasis></Subscript> single crystals

The behavior of the low-temperature specific heat C(T) for YBa₂Cu₃O_{6 + x} single crystals with the doping level corresponding to the normal phase has been studied by the relaxation technique at different values of the applied magnetic field. It has been found that the C(T)/T plot exhibits such an anomaly as a steep increase with decreasing temperature from T about 4 K down to T ≤ 2 K (the minimum temperature value accessible in the experiment). The applied magnetic field as high as 9 T inverts this anomaly and leads to a sharp drop in C(T)/T during cooling within the same temperature range. A model involving the Schottky-type centers formulated in this work and the data on spin correlation functions has allowed us to calculate the temperature dependence of the specific heat, which fits the experimental curves quite well.     

High-temperature heat capacity of YFe3(BO3)4

The molar heat capacity of YFe₃(BO₃)₄ has been measured using differential scanning calorimetry in the temperature range 339–1086 K. It has been found that the dependence C _p = f(T) exhibits an extremum at a temperature of 401 K due to the structural transition.     

Influence of Pr-doping on structural, electronic transport, magnetic properties of perovskite molybdates Sr1−xPrxMoO3 (0≤x≤0.15)

The effect of Pr-doping on structural, electronic transport, magnetic properties in perovskite molybdates Sr_1−xPr_xMoO₃ (0≤x≤0.15) has been investigated. The Pr-doping at Sr-site does not change the space group of the samples, but decreases the lattice parameter a. The magnitude of resistivity ρ increases initially (x≤0.08) and then decreases with further increasing Pr-doping level x and ρ(T) behaves as T² and T dependence in the low-temperature range blow T* and high-temperature range of 150 K<T<350 K, related to the electron-electron (e-e) and electron-phonon (e-ph) scattering, respectively. The magnetic susceptibility χ value of the sample increases with increasing x and the χ(T) curve for all samples can be well described by the model of exchange-enhanced paramagnetism. The specific heat magnitude in the low-temperature region increases with increasing Pr-doping level. The specific heat value agrees with the classical Dulong-Petit phonon specific heat, C_cl=3k_BrN_A=124.7 J/mol K in the high-temperature region and the temperature dependence of the specific heat can be well described by the formula C_p(T)/T=γ_e+β_pT² in the low-temperature range. These behaviors can be explained by the competition between the increase in the density of state (DOS) at Fermi energy level and the disorder effect due to Pr-doping.     

Components of the low-temperature heat capacity of rare-earth hexaborides

The temperature dependence of heat capacity C _p(T) was studied for nine rare-earth hexaborides MB₆(M=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) at temperatures of 5–300 K. Using the correspondence principle for lattice heat capacities of isostructural compounds, the lattice contribution C ₁(T) and the excess contribution ΔC(T) to the heat capacity of the hexaborides were determined. The lattice heat capacity C ₁(T) is represented as the sum of the Debye contributions of the metal and boron sublattices: C ₁(T)=C _M (T)+6C _B(T). The Debye temperatures π_M and π_B of the metal and boron sublattices were determined. The anomalies in the excess heat capacity ΔC(T)=C _p (T)?C ₁(T) are related to the magnetic ordering effects, the Schottky contribution, and the Jahn-Teller effect.     

Specific heat of La(Fe<Subscript>0.873</Subscript>Co<Subscript>0.007</Subscript>Al<Subscript>0.12</Subscript>)<Subscript>13</Subscript> compound in antiferromagnetic and ferromagnetic states

The low-temperature specific heat C _p of La(Fe_0.873Co_0.007Al_0.12)₁₃ compound has been measured in two states: (i) antiferromagnetic (AFM) with a Néel temperature of T _N = 192 K and (ii) ferromagnetic (FM). The FM order appears at T = 4.2 K in a sample exposed to an external magnetic field with induction B _C ≥ 2.5 T and is retained for a long time in a zero field at temperatures up to T*_C = 23 K. The coefficient γ_FM in the low-temperature specific heat C = γT + βT ³ in the FM state differs quite insignificantly from that (γ_AFM) in the AFM state. Contributions to the low-temperature specific heat, which are related to a change in the elastic and magnetoelastic energy caused by magnetostrictive deformations, are considered.     

Heat capacity of the [N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CdBr<Subscript>4</Subscript> crystal in the temperature range 80–300 K

The heat capacity of the [[N(C₂H₅)₄]₂CdBr₄ crystal is measured by the calorimetric method in the temperature range from 80 to 300 K. It is revealed for the first time that the temperature dependence of the heat capacity C _p (T) exhibits an anomaly associated with the first-order phase transition occurring at the temperature T ₁ = 226.5 K. A long relaxation of the temperature of the crystal is observed in the temperature range 150–165 K.     

Specific Heat of the Spin-1/2 Dimerized Antiferromagnetic Chains at Low Temperatures

A spin linear chain with antiferromagnetic nearest-neighbor interaction is considered. The coupling constants of each spin with the right and left neighbors are different. Within the Bulaevskii model, the magnetic specific heat is calculated as a function of temperature for different alternation parameters. It is shown that the temperature dependence of the specific heat has two regimes. In the first one, the temperature is lower than half the band gap; in this case, in the low-temperature limit, C ∝ T^-1 exp(?Δ/k_BT). In the second regime, the temperature exceeds half the band gap; in this case, we approximately have C ∝ T.     

Elastic and thermal properties of Zr z Nb1 − z C x N y solid solutions

The temperature and concentration dependences of the elastic moduli and the thermal linear expansion coefficient of Zr _z Nb_{1 ? z} C _x N _y solid solutions containing from 3 to 8 at % of structural vacancies in a nonmetallic sublattice have been found. The temperature dependences of the Debye temperature Θ_D(T) have been calculated using the elastic data and the data on the heat capacity. It has been shown, using carbide NbC_0.97 as an example, that the Θ_D(T) dependences found from the elastic properties and the heat capacity coincide in the temperature range ～220–300 K. By analogy with the niobium carbide, the heat capacity C _p (300) of Zr _z Nb_{1 ? z} C _x N _y solid solutions of various compositions is calculated based on the values of Θ_D(300) determined from the elastic properties.     

Heat capacity of the 0.7PbNi1/3Nb2/3O3-0.3PbTiO3 ferroelectric ceramics

The temperature dependence of the heat capacity of the 0.7PbNi_1/3Nb_2/3O₃-0.3PbTiO₃ compound has been studied in the temperature range 120?C800 K. The temperature dependence of the heat capacity C _p has two diffuse anomalies in the temperature ranges 250?C450 K and 450?C650 K and a ?? anomaly at temperatures T ?? 225 K. The results are discussed with inclusion of the dielectric and structural data.     

Heat capacity of Tb2Cu2O5 in the temperature range 379–924 K

The heat capacity of Tb₂Cu₂O₅ in the temperature range 379–924 K has been measured using differential scanning calorimetry. It has been shown that the obtained dependence C _p = f(T) can be described by a combination of the Debye and Einstein functions.     

Adiabatic calorimetric study of the intense magnetocaloric effect and the heat capacity of (La<Subscript>0.4</Subscript>Eu<Subscript>0.6</Subscript>)<Subscript>0.7</Subscript>Pb<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript>

The temperature dependences of the intense magnetocaloric effect ΔT _AD(T, H) and the heat capacity C _p (T) of the (La_0.4Eu_0.6)_0.7Pb_0.3MnO₃ manganite are directly measured using adiabatic calorimetry. The experimental dependences ΔT _AD(T) are in satisfactory agreement with those calculated from the data on the behavior of the magnetization. The factors responsible for the absence of an anomaly in the experimental temperature dependence of the heat capacity C _p (T) in the range of the magnetic phase transition are discussed.     

Heat capacity and thermodynamic properties of HoMnO<Subscript>3</Subscript> in the range of 364–1046 K

The temperature dependence of the molar heat capacity of HoMnO₃ has been measured by differential scanning calorimetry. The experimental data have been used to calculate the thermodynamic properties of the oxide compound (changes in the enthalpy H°(T)–H°(364 K), entropy S°(T)–S°(364 K), and reduced Gibbs energy Φ°(T)). The data on the heat capacity of HoMnO₃ have been generalized in the range of 40–1000 K.     

Effect of γ irradiation on the heat capacity of (CH3)2NH2Al(SO4)2 · 6H2O crystals near the ferroelectric phase transition

The heat capacity of dimethyl ammonium-aluminum sulfate crystals (DMAAS), both nonirradiated and γ-irradiated to fluences of 10⁷, 5×10⁷, and 10⁸ R, has been measured by the adiabatic method near the ferroelectric phase transition (PT) within the 80–300 K temperature range. The C _p =f(T) curve exhibits a λ-shaped anomaly near the phase-transition point T _C =152 K. The PT temperature and the magnitude of the anomaly are shown to decrease with increasing γ-irradiation fluence. It has been established that the ferroelectric PT at T _C =152 K, which lies close to the tricritical point, shifts progressively more under γ irradiation toward the second-order PT, and that the behavior of the anomalous part of the heat capacity in the ferroelectric phase is described by the thermodynamic theory of Landau. The experimental heat-capacity data have been used to calculate the variation of the thermodynamic functions of the DMAAS crystal.     

Thermodynamic and dilatometric properties of the dimerized phase of a C<Subscript>60</Subscript> fullerene

This paper reports on the results of complex investigations into the structural, thermodynamic, and dilatometric properties of the C₆₀ dimerized phase prepared under compression of a C₆₀ fullerite at a pressure up to 8 GPa and a temperature of 290 K. It is demonstrated that the dimerized phase has a face-centered cubic structure with a lattice parameter a=14.02±0.05 Å. The dimeric structure of the studied sample is confirmed by x-ray diffraction analysis. According to the dilatometric data, the volume jump observed in the vicinity of the orientational transition for the dimerized phase is estimated to be approximately 30 times less than that for the C₆₀ fullerite. The temperature dependence of the heat capacity of the (C₆₀)₂ crystalline dimer is examined using precision adiabatic vacuum calorimetry under normal pressure in the temperature range from T → 0 K to 340 K. The results obtained are used in the calculations of thermodynamic functions, namely, the heat capacity C _p ⁰ (T), the enthalpy H⁰(T)-H⁰(0), the entropy S⁰(T), and the Gibbs function G⁰(T)-H⁰(0). The fractal dimension D is determined as a function of the heat capacity. The standard entropy of the formation of the (C₆₀)₂ crystalline dimer from a simple compound (graphite) at T=298.15 K and normal pressure is calculated.     

Heat capacity of a white-eucalyptus biocarbon template for SiC/Si ecoceramics

The heat capacity C _p of a biocarbon template based on white eucalyptus wood is measured at a constant pressure in the temperature range T = 3.5–300 K. The phonon mean free path l for a white-eucalyptus biocarbon template is calculated from the measured dependence C _p (T) and data available in the literature on the phonon thermal conductivity and velocity of sound. It is established that, in the range 100–300 K, the phonon mean free path l is nearly constant and equal to ～13 Å. This value is close to the smallest size of graphite-like crystallites (～12 Å), which was derived earlier from x-ray diffraction data for a quasi-amorphous biocarbon template.     

Dielectric constant anomalies of an improper Hg<Subscript>2</Subscript>Cl<Subscript>2</Subscript> ferroelastic near the phase-transition temperature

The temperature dependence of the permittivity of a Hg₂Cl₂ crystal has been investigated within the Landau phenomenological theory. At T < T _C, the linear permittivity has a singularity in the form ～(T _C?T)^1/2; however, this anomaly may disappear in a multidomain sample. The nonlinear permittivity also has an anomaly near T _C but of stronger type: ～(T _C ? T)^?1/2.     

Heat capacity and dielectric properties of multiferroics Bi1 − x Gd x FeO3 (x = 0–0.20)

The heat capacity and the permittivity of multiferroics Bi_{1 ? x} Gd _x FeO₃ (x = 0, 0.05, 0.10, 0.15, 0.20) have been studied in the temperature range 130–800 K. It has been found that insignificant substitution of gadolinium for bismuth markedly shifts the temperature of antiferromagnetic phase transition and increases the heat capacity over a wide temperature range. It has been shown that the temperature dependence of the excess heat capacity is due to the manifestation of three-level states. Additional anomalies characteristic of the phase transitions have been revealed in the temperature dependences of the heat capacity for the compositions with x = 0.1 and 0.15 at T ≈ 680 K and T ≈ 430 K, respectively. The results of studies of the heat capacity have been discussed simultaneously with the data of structural studies.