Thermodynamic study of compounds of the Nd-Ba-Cu-O system

Standard enthalpies of formation for solid solutions of composition Nd_{1 + x} Ba_{2 ? x} Cu₃O _y (x = 0–0.8, y = 6.65–7.24) from oxides were determined by solution calorimetry. The heat capacity of NdBa₂Cu₃O_6.87 phase was measured in the range 5–320 K by low-temperature adiabatic calorimetry. The absolute entropy S ^o(T), the difference of enthalpies H ^o(T)-H ^o(0 K), and the reduced Gibbs energy Φ^o(T) = S ^o(T)–[H ^o(T)–H ^o(0)]/T were calculated on the basis of smoothed dependence C _p (T) in the 0–320 K range. An assessment was made for the heat capacities and the absolute entropies of solid solutions Nd_1+x Ba_2?x Cu₃O _y . The obtained set of thermodynamic parameters can be used for the calculation of phase equilibria in the Nd-Ba-Cu-O system.     

Scaling laws of aquatic locomotion

In recent years studies of aquatic locomotion have provided some remarkable insights into the many features of fish swimming performances. This paper derives a scaling relation of aquatic locomotion CD(Re)~2 =(Sw)~2 and its corresponding log law and power law. For power scaling law,(Sw)~2 = β_nRe~((2-1)/n), which is valid within the full spectrum of the Reynolds number Re=UL/v from low up to high, can simply be expressed as the power law of the Reynolds number Re and the swimming number Sw=ωAL/v as Re ∝ (Sw)~σ,with σ=2 for creeping flows,σ=4/3 for laminar flows, σ=10/9 and σ=14/13 for turbulent flows. For log law this paper has derived the scaling law as Sw ∝ Re=(lnRe+1.287), which is even valid for a much wider range of the Reynolds number Re. Both power and log scaling relationships link the locomotory input variables that describe the swimmer's gait A;ω via the swimming number Sw to the locomotory output velocity U via the longitudinal Reynolds number Re, and reveal the secret input-output relationship of aquatic locomotion at different scales of the Reynolds number.     

Optical and x-ray diffraction studies of the symmetry of distorted phases of the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>ZrF<Subscript>7</Subscript> crystal

(NH₄)₃ZrF₇ single crystals were grown, and polarization-optical and x-ray diffraction studies were performed on powders and crystalline plates of various cuts over a wide temperature range. Phase transitions are revealed at temperatures T _1↑ = 280 K, T _2↑ = 279.6 K, T _3↑ = 260–265 K, and T _4↑ = 238 K on heating and at T _1↓ = 280 K, T _2↓ = 269–270 K, T _3↓ = 246 K, and T _4↓ = 235 K on cooling. The sequence of changes in symmetry is established to be as follows: O _h ⁵ (Z = 4) ? D _2h ²⁵ (Z = 2) ? C _2h ³ (Z = 2) ? C _i ¹ (Z = 108) ? monoclinic²(Z = 216).     

Spectral manifestations of <Emphasis Type="Italic">d</Emphasis>-π exchange and charge transfer interactions in Cu(II) porphyrins

New absorption bands due to spin-forbidden transitions from the ground state to excited triplet states are found at 295 K in the near-IR absorption spectra of a number of Cu(II) complexes of octaethylporphyrin (OEP) that differ in the nature, number, and position of their side substituents. The frequency distribution, number, and nature of these transitions are analyzed using computer decomposition of complex contours into Gaussian components and additional data from the phosphorescence and phosphorescence excitation spectra (295-77 K). The d-π exchange integrals, determining the energy splitting ΔE = E(²T₁)–E(⁴T₁) in the compounds under study, are calculated on the basis of the experimental data obtained. It is shown that, in addition to the formally spin-allowed ²S₀ → ²T₁ transition (λ_max = 833 nm), the absorption spectrum of the nonplanar CuOETPP molecule at 295 K exhibits the low-intensity spin-forbidden ²S₀ → ⁴T₁ transition (λ_max = 937 nm). For this compound at 77 K, phosphorescence from the ⁴T₁ state is observed (λ_max = 955 nm), with a quantum yield equal to ?_Ph = 0.0015 and a decay time amounting to τ_Ph = 190 ns. For the CuOEP-Ph(o-NO₂) molecule, which contains the electron-acceptor nitro group, direct absorption from the ground state S₀ to a charge transfer (CT) state (λ_max = 845 nm) is observed at 295 K. The extinction coefficient of this absorption and the energy of the CT state are determined.     

Superconductor-insulator transition tuned by annealing in Bi-film on top of Co-clusters

We deposited amorphous Bi films with a thickness between 3 and 6.5 nm at 4.2 K on top of previously deposited Co clusters having a mean size of ～4.5 nm. The Co cluster layers thickness was between 2.3 and 5 nm. In-situ electrical transport measurements were performed between 2 and 100 K. Measurements on as-prepared samples having a Bi layer thickness of 3.0 nm show hopping (tunneling) conductivity as σ(T) = σ ₀ exp[?(T ₀/T)^1/2] above the superconducting transition temperature T _C and re-entrance behavior again with hopping (tunneling) conductivity below T _C . Annealing of films having a Bi layer thickness of 5.5 nm results in a decrease of resistivity, with variable-range hopping conduction behavior as σ(T) = σ ₀ exp[?(T ₀/T)^1/3 ]. Quite different are the findings for films having a Bi layer thickness of 6.5 nm: annealing of these films results in a power-law behavior as σ(T) = σ ₀ T ^α with α = 2/3, indicating that these films are close to a quantum critical point separating superconducting and insulating phases. A phase diagram including all experimental observations is proposed.     

Calculation of the diffusion coefficient in acoustic turbulence

The first (Born) approximation commonly used to calculate the diffusion coefficient D_T of a passive scalar in acoustic turbulence is shown to be insufficient. Even for a small main parameter—the Mach number, M?1—the next approximation gives a larger contribution to D_T than does the first approximation, but negative in sign. We present a procedure for correctly calculating D_T based on the solution of a nonlinear DIA (direct interaction approximation) equation for the mean Green’s function of the problem. We include an additional term in the general formula for D_T that directly describes the compressibility of acoustic turbulence. This term has not been known previously and has been disregarded even in the Born approximation. A positive value was obtained for D_T=CM³u₀/p₀. The spectrum E(x) was assumed to be smooth at distances Δ x～M²?1.     

Variable-range hopping conduction in LaMnO<Subscript>3 + δ</Subscript>

The temperature dependence of the electrical resistivity ρ(T) for ceramic samples of LaMnO_{3 + δ} (δ = 0.100–0.154) are studied in the temperature range T = 15–350 K, in magnetic fields of 0–10 T, and under hydrostatic pressures P of up to 11 kbar. It is shown that, above the ferromagnet-paramagnet transition temperature of LaMnO_{3 + δ}, the dependence ρ(T) of this compound obeys the Shklovskii-Efros variable-range hopping conduction: ρ(T) = ρ₀(T)exp[(T ₀/T)^1/2], where ρ₀(T) = AT ^9/2 (A is a constant). The density of localized states g(?) near the Fermi level is found to have a Coulomb gap Δ and a rigid gap γ(T). The Coulomb gap Δ assumes values of 0.43, 0.46, and 0.48 eV, and the rigid gap satisfies the relationship γ(T) ≈ γ(T _v)(T/T _v)^1/2, where T _v is the temperature of the onset of variable-range hopping conduction and γ(T _v) = 0.13, 0.16, and 0.17 eV for δ = 0.100, 0.125, and 0.154, respectively. The carrier localization lengths a = 1.7, 1.4, and 1.2 Å are determined for the same values of δ. The effect of hydrostatic pressure on the variable-range hopping conduction in LaMnO_{3 + δ} with δ = 0.154 is analyzed, and the dependences Δ(P) and γ_v(P) are obtained.     

Surface tension of pure liquid helium isotopes

The effects caused by vapor inhomogeneity over liquid helium are considered. Both pure isotopes have surface levels, whose population increases with temperature T. We separated their contribution to the temperature dependence of surface tension σ₃(T) and σ₄(T) and compared our theoretical results with the results of Japanese experimental works [1–3]. For liquid He³, one has σ₃(T)=σ₃(0)?σ ₃ ^∞ T² at 0.2 K<T<1 K and σ₃(T)=σ₃(0)?α ₃ ⁰ T²exp(?Δ₃/T) at T<0.2 K, with Δ₃≈0.25 K. For liquid He⁴, σ₄(T)=σ₄(0)?AT^7/3? α ₄ ⁰ T²exp(?Δ₄/T) at T<2 K, where A is the Atkins constant and Δ₄≈4 K. The parameters α ₃ ⁰ , α ₃ ^∞ , and α ₄ ⁰ depend on the fluid properties.     

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.     

Antiferromagnetic Resonance in GdB<Subscript>6</Subscript>

The electron spin resonance has been measured for the first time both in the paramagnetic phase of the metallic GdB₆ antiferromagnet (T_N = 15.5K) and in the antiferromagnetic state (T < T_N). In the paramagnetic phase below T* ~ 70 K, the material is found to exhibit a pronounced increase in the resonance linewidth and a shift in the g-factor, which is proportional to the linewidth Δg(T) ~ ΔH(T). Such behavior is not characteristic of antiferromagnetic metals and seems to be due to the effects related to displacements of Gd³⁺ ions from the centrosymmetric positions in the boron cage. The transition to the antiferromagnetic phase is accompanied by an abrupt change in the position of resonance (from μ₀H₀ ≈ 1.9 T to μ₀H₀ ≈ 3.9 T at ν = 60 GHz), after which a smooth evolution of the spectrum occurs, resulting eventually in the formation of the spectrum consisting of four resonance lines. The magnetic field dependence of the frequency of the resonant modes ω₀(H₀) obtained in the range of 28–69 GHz is well interpreted within the model of ESR in an antiferromagnet with the easy anisotropy axis ω/γ = (H ₀ ² +2H_AH_E)^1/2, where H_E is the exchange field and H_A is the anisotropy field. This provides an estimate for the anisotropy field, H_A ≈ 800 Oe. This value can result from the dipole?dipole interaction related to the mutual displacement of Gd³⁺ ions, which occurs at the antiferromagnetic transition.     

Nonergodic state of relaxation ferroelectric Cd<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>7</Subscript> in a constant electric field

The temperature dependence of the residual polarization of the nonergodic relaxation state (NERS) obtained from the measurements of pyroelectric current during zero-field heating (ZFH) in the temperature interval from 10 to 295 K is investigated for the Cd₂Nb₂O₇ relaxation system in two cases: (1) after sample cooling in a constant electric field E (FC) from T = 295 K to a preset temperature, which is much lower than the “freezing” temperature of the relaxation state (T _f ≈ 182 K), field removal, and subsequent cooling in zero field (ZFC) to T = 10 K and (2) after ZFC from T = 295 K to the same temperature below T _f , application of the same field, and FC to T = 10 K. The behavior of the P _r ^FC (T) and P _r ^ZFC (T) dependences is analyzed. In the field E < 2 kV/cm, the P _r ^ZFC curves as functions of 1/T have a broad low-intensity peak in the region T ≈ T _f , which vanishes in stronger fields, when the P _r ^FC (1/T) curves intersect at T ≈ T _f and have no anomalies. The difference in the behavior of P _r ^ZFC (T) and P _r ^FC (T) indicates the difference in the nature of NERS formed during ZFC and FC of the system upon a transition through T _f . In the ZFC mode, NERS exhibits glasslike behavior; in the FC regime, features of the ferroelectric behavior even in the weak field. Analogous variations of P _r ^ZFC (T) and P _r ^FC (T) in a classical ferroelectric KDP are also given for comparison.     

Effect of the Lattice and Spin-Phonon Contributions on the Temperature Behavior of the Ground State Splitting of Gd<Superscript>3+</Superscript> in SrMoO<Subscript>4</Subscript>

The temperature behavior of the EPR spectra of the Gd³⁺ impurity center in single crystals of SrMoO₄ in the temperature range T = 99–375 K is studied. The analysis of the temperature dependences of the spin Hamiltonian b ₂ ⁰ (T) = b₂(F) + b₂(L) and P ₂ ⁰ (T) = P₂(F) + P₂(L) (for Gd¹⁵⁷) describing the EPR spectrum and contributing to the Gd³⁺ ground state splitting ΔE is carried out. In terms of the Newman model, the values of b₂(L) and P₂(L) depending on the thermal expansion of the static lattice are estimated; the b₂(F) and P₂(F) spin-phonon contributions determined by the lattice ion oscillations are separated. The analysis of b ₂ ⁰ (T) and P ₂ ⁰ (T) is evidence of the positive contribution of the spin-phonon interaction; the model of the local oscillations of the impurity cluster with close frequencies ω describes well the temperature behavior of b₂(F) and P₂(F).     

Analytic prediction for planar turbulent boundary layers

Analytic predictions of mean velocity profile(MVP) and streamwise(x) development of related integral quantities are presented for flows in channel and turbulent boundary layer(TBL), based on a symmetry analysis of eddy length and total stress. Specific predictions include the relations for momentum Reynolds number(Reθ) with friction Reτ and streamwise Re_x: Re_θ≈ 3.27Re_τ,and Re_x/Re_θ = 4.94(lnRe_θ + 1.88)~2 + 1; the streamwise development of the friction velocity u_τ: U_e/u_τ≈ 2.22 lnRe_x + 2.86. 3.83ln(lnRe_x), and of the boundary layer thickness δ_e: x/δ_e ≈ 7.27 lnRe_x.5.18.12.52ln(lnRe_x), which are fully validated by recent reliable data.     

On the size dependence of melting parameters for silicon

Using the dependences of melting point T_m and crystallization point T_c on the number of atoms (N) in a spherical silicon crystal that were calculated elsewhere [6] by the method of molecular dynamics, (i) the number of atoms at which the latent heat of the solid–liquid phase transition disappears and (ii) temperature T₀ = T_m(N₀) = _Tc(N₀) below which solidifying nanoclusters remain noncrystalline are estimated. These values are found to be N₀ = 22.8156 and T₀ = 400.851 K. The N dependences for silicon melting parameters, namely, a jump of entropy of melting, latent melting heat, slope of the melting line, and jumps in the surface energy and volume, are derived.     

Frustrated antiferromagnetism in the Sr<Subscript>2</Subscript>YRuO<Subscript>6</Subscript> double perovskite

The spins of Ru⁵⁺ ions in Sr₂YRuO₆ form a face-centered cubic lattice with antiferromagnetic nearest neighbor interaction J≈25 meV. The antiferromagnetic structure of the first type experimentally observed below the Néel temperature T _N =26 K corresponds to four frustrated spins of 12 nearest neighbors. In the Heisenberg model in the spin-wave approximation, the frustrations already cause instability of the antiferromagnetic state at T=0 K. This state is stabilized by weak anisotropy D or exchange interaction I with the next-nearest neighbors. Low D/J～I/J～10^?3 values correspond to the experimental T _N and sublattice magnetic moment values.     

The vibrational spectrum of the OCS molecule based on the data on spectra of liquid and cryosolutions

The IR absorption spectra of liquid OCS (T = 135(1) K) and of the following solutions—OCS + Ar (T = 90 K), OCS + N₂ (T = 90 K), OCS + Kr (T = 130 K), and OCS + Xe (T = 163 K)—are measured in the range 800–7000 cm^?1. From 16 to 40 bands corresponding to transitions to vibrational states up to the third order inclusive are interpreted for basic isotope modification and for the isotopically substituted molecules ¹⁸O¹²C³²S, ¹⁶O¹³C³²S, and ¹⁶O¹²C³⁴S. In the spectra of the liquids, the spectral moments M(1) and M(2) of all the observed bands are determined. The harmonic frequencies ω _i and the anharmonicity constants x _ik are calculated for all the systems, including the liquid. The anharmonicity is found to be constant within the experimental error. A large shift Δω₃ is primarily determined by the dipole-induced dipole interaction.     

Thermal conductivity of partially graphitized biocarbon obtained by carbonization of medium-density fiberboard in the presence of a Ni-based catalyst

The thermal conductivity k and resistivity ρ of biocarbon matrices, prepared by carbonizing medium-density fiberboard at T _carb = 850 and 1500°C in the presence of a Ni-based catalyst (samples MDF-C( Ni)) and without a catalyst (samples MDF-C), have been measured for the first time in the temperature range of 5–300 K. X-ray diffraction analysis has revealed that the bulk graphite phase arises only at T _carb = 1500°C. It has been shown that the temperature dependences of the thermal conductivity of samples MDFC- 850 and MDF-C-850(Ni) in the range of 80–300 K are to each other and follow the law of k(T) ～ T ^1.65, but the use of the Ni-catalyst leads to an increase in the thermal conductivity by a factor of approximately 1.5, due to the formation of a greater fraction of the nanocrystalline phase in the presence of the Ni-catalyst at T _carb = 850°C. In biocarbon MDF-C-1500 prepared without a catalyst, the dependence is k(T) ～ T ^1.65, and it is controlled by the nanocrystalline phase. In MDF-C-1500(Ni), the bulk graphite phase formed increases the thermal conductivity by a factor of 1.5–2 compared to the thermal conductivity of MDF-C-1500 in the entire temperature range of 5–300 K; k(T = 300 K) reaches the values of ～10 W m^–1 K^–1, characteristic of biocarbon obtained without a catalyst only at high temperatures of T _carb = 2400°C. It has been shown that MDF-C-1500(Ni) in the temperature range of 40?300 K is characterized by the dependence, k(T) ～ T ^1.3, which can be described in terms of the model of partially graphitized biocarbon as a composite of an amorphous matrix with spherical inclusions of the graphite phase.     

Peculiarities of magnetic,galvanomagnetic, elastic,and magnetoelastic properties of Eu<Subscript>0.55</Subscript>Sr<Subscript>0.45</Subscript>MnO<Subscript>3</Subscript>

Magnetic, elastic, magnetoelastic, transport, and magnetotransport properties of the Eu_0.55Sr_0.45MnO₃ ceramics have been studied. A break was detected in the temperature dependence of electrical resistivity ρ(T) near the temperature of the magnetic phase transformation (41 K), with the material remaining an insulator down to the lowest measurement temperature reached (ρ=10⁶ Ω cm at 4.2 K). In the interval 4.2≤T≤50 K, the isotherms of the magnetization, volume magnetostriction, and ρ were observed to undergo jumps at the critical field H_C1, which decreases with increasing T. For 50≤T≤120 K, the jumps in the above curves persist, but the pattern of the curves changes and H_C1 grows with increasing T. The magnetoresistance Δρ/ρ = (ρ _H ?ρ_H=0)/ρ _H is positive for H<H_C1 and passes through a maximum at 41 K, where Δρ/ρ = 6%. For H>H_C1, the magnetoresistance is negative, passes through a minimum near 41 K, and reaches a colossal value of 3×10⁵ % at H=45 kOe. The volume magnetostriction is negative and attains a giant value of 4.5×10^?4atH=45 kOe. The observed properties are assigned to the existence of three phases in Eu_0.55Sr_0.45MnO₃, namely, a ferromagnetic (FM) phase, in which carriers are concentrated because of the gain in s-d exchange energy, and two antiferromagnetic (AFM) phases of the A and CE types. Their fractional volumes at low temperatures were estimated to be as follows: ～3% of the sample volume is occupied by the FM phase; ～67%, by the CE-type AFM phase; and ～30%, by the A-type AFM phase.     

Correlation between the giant volume magnetostriction and softening of the crystal lattice in GMR manganites

Giant volume magnetostriction near the Curie temperature T _C has been revealed in single crystals and ceramics of the La_{1 ? x} A _xMnO₃ (A = Sr, Ba, Ca, Ag) and Re _{1 ? x} Sr_xMnO₃ (Re = Sm, Tb_0.25Nd_0.3, Eu_0.4Nd_0.15, Eu) compositions; its values were as high as ～10^?3 in a magnetic field of 8.2 kOe. The giant volume magnetostriction and giant magnetoresistance behave similarly near T _C: the temperature dependences of their moduli pass through a maximum, and their isotherms are similar. This phenomenon is explained by the presence of a magnetic two-phase state in these compositions, which is caused by the strong s-d exchange.