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.     

Thermodynamic properties of (TeO<Subscript>2</Subscript>)<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>(MoO<Subscript>3</Subscript>)<Subscript>1–<Emphasis Type="Italic">n</Emphasis></Subscript> glasses

The thermal behavior of (TeO₂) _n (MoO₃)_1–n (n = 0.75, 0.85, 0.90) tellurite glasses has been studied by differential scanning calorimetry in the range from T = 300 to T = 850 K and heat capacity has been measured in the temperature range. The thermodynamic characteristics of the devitrification process and glassy state have been determined. The experimental data obtained have been used to evaluate the standard thermodynamic functions of the system in glassy and supercooled liquid states: heat capacity C _p °(T), enthalpy H°(T)–H°(320), entropy S°(T)–S°(320), and Gibbs function G°(T)–G°(320) in the temperature range 320–630 K. The composition dependences of the glass transition temperature and thermodynamic functions for the glasses have been obtained. The thermal and thermodynamic properties of the tellurite glasses have been compared to those of previously studied (TeO₂) _n (WO₃)_1–n and (TeO₂) _n (ZnO)_1–n glasses.     

Explanation of Non-linear In-Plane Resistivity and Hall Coefficient in the Normal State of Cuprates: Polaronic Approach

We present a theoretical study of the in-plane resistivity ρ _{a b} (T) and Hall coefficient R _H (T) within the polaronic model and precursor pairing scenario by considering a two-component charge carrier picture in the normal state of high-temperature superconducting cuprates (HTSC). Here, we use a Boltzmann-equation approach and extended BCS-like model to compute ρ _{a b} (T) and R _H (T) in the τ-approximation. The opening of the pseudogap (PG) in the normal state of the cuprates should affect their transport properties. We have found that the transition to the PG regime and the effective conductivity of charge carriers in the normal state are responsible for the pronounced non-linear temperature dependence of ρ _{a b} and R _H . With the two-component model analysis, we conclude that the opening of the BCS-like PG, while the non-linear temperature dependence of ρ _{a b} and R _H could be understood as a consequence of pairing fluctuations in the PG state of cuprate superconductors. The calculated results for ρ _{a b} (T) and R _H (T) were compared with the experimental data obtained for various hole-doped cuprates. For all the considered cases, a good quantitative agreement was found between theory and experimental data. We also show that the energy scales of the binding energies of charge carriers are identified by PG crossover temperature on the cuprate phase diagram.     

Synthesis of M(NpO<Subscript>4</Subscript>)<Subscript>2</Subscript>·<Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O (M = Mg,Ca, Sr,Ba) Using Н<Subscript>3</Subscript>ВО<Subscript>3</Subscript> Solutions and Properties of These Salts

Two procedures for preparing the compounds M(NpO₄)₂·nH₂O (M = Mg, Ca, Sr, Ba) using boric acid were suggested. In the first procedure, samples of freshly prepared salts M₃(NpO₅)₂·nH₂O (M = Ca, Sr, Ba) are treated with excess 0.5 M H₃BO₃ with vigorous stirring. In the process, the initially light green salts rapidly transform into black products of the general composition M(NpO₄)₂·nH₂O. In the second procedure, a measured volume of a Np(VII) solution with a known LiOH concentration was added to excess 0.5 M H3BO3 solution containing a calculated amount of Mg, Ca, Sr, or Ba nitrate. The reaction yields black precipitates of the same compounds as in the previous case. After washing with water and drying in an oxygen stream, the final products contain a small impurity of Np(VI). The IR spectra suggest that the compounds obtained are structurally related to the previously studied salts MNpO₄ (M = K–Cs), i.e., in their lattices there are neptunium–oxygen layers built of NpO₂³⁺ cations and bridging O atoms. New data on the properties of the compounds M₃(NpO₅)₂·nH₂O with M = Ca, Sr, and Ba were also obtained.     

Phase equilibria and crystal structures of phases in the La-Fe-Ni-O system at 1370 K in air

The phase equilibria in the La-Fe-Ni-O system have been studied at 1370 K in air, and the La-Fe-Ni-O phase diagram at constant temperature and pressure has been constructed. Based on x-ray diffraction results for samples prepared by standard solid-state reactions and via citrate and nitrate routes, the following solid solutions have been shown to exist at 1370 K in air: LaFe_{1 ? x} Ni _x O_{3 ? δ} (0 < x ≤ 0.4, sp. gr. Pbnm; 0.6 ≤ x ≤ 0.8, sp. gr. R-3 c), La₄(Ni_{1 ? y} Fe _y )₃O_{10 ? δ} (0 < y ≤ 0.3), La₃(Ni_{1 ? z} Fe _z )₂O_{7 ? δ} (0 < z ≤ 0.05), La₂Ni_{1 ? v} Fe _v O_{4 + δ} (0 < v ≤ 0.05), Ni_kFe_{3 ? k} O₄ (0.81 ≤ k ≤ 1.05), Ni_{1 ? m} Fe _m O (0 < m ≤ 0.05), and Fe_{2 ? p} Ni _p O₃ (0 < p ≤ 0.04). The lattice constants and structural parameters of single-phase samples have been refined by the Rietveld profile analysis method.     

Synthesis of New Crystalline Pu(V) Compounds from Solutions: II. Double Pu(V) Oxalates with Co(NH<Subscript>3</Subscript>)<Subscript>6</Subscript><Superscript>3+</Superscript> Ions in the Outer Sphere

Crystalline compounds of the general composition Co(NH³)⁶PuO₂(C₂O₄)²·nH₂O (n = 2, 3, 5) were isolated from freshly prepared neutral oxalate solutions of Pu(V) by addition of Co(NH₃)₆³⁺ ions. These compounds are fairly stable in storage in air and poorly soluble in water. Previously unknown double Np(V) oxalates Co(NH₃)₆NpO₂(C₂O₄)·nH₂O (n = 2, 5) were also synthesized and studied. All the compounds of Pu(V) and Np(V) of the same composition are mutually isostructural. The behavior of these compounds at heating was studied, and their IR spectra were measured. The optical spectra of new Np(V) compounds were measured.     

Spectral sensitivity of (Si<Subscript>2</Subscript>)<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>(CdS)<Subscript>x</Subscript> solid solutions

Epitaxial layers of n-type solid solutions of the (Si₂)_{1 ? x} (CdS)_x system (0 ≤ x ≤ 0.01) were grown by liquid phase epitaxy from a tin-based solution melt confined between two horizontal p-type single crystal silicon substrates. The photosensitivity spectra of p-Si/n-(Si₂)_{1 ? x} (CdS)_x structures have been measured. A photoresponse peak at E ≈ 2.35 eV (1.25 eV below the top of the valence band of silicon) has been observed, which is probably related to an impurity level due to CdS molecules.     

Synthesis and study of uranosilicates of the uranophane-kasolite group

A series of uranosilicates of alkali (Li, Na, K, Rb, Cs, NH₄), alkaline-earth (Mg, Ca, Sr, Ba), and rare-earth (Y, La, Ln) elements were prepared by precipitation from a solution under hydrothermal conditions. The composition and structure of the compounds were examined by X-ray diffraction analysis, IR spectroscopy, and thermal analysis. It was established that these compounds belong to the uranophane M^k[HSiUO₆] _k ·nH₂O and kasolite M ₂ ^k [SiUO₆] _k ·nH₂O mineral groups.     

Structure and Some Properties of a Double Neptunyl(V) Cesium Molybdate,Cs[NpO<Subscript>2</Subscript>MoO<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)]

A double neptunyl(V) cesium molybdate, Cs[NpO₂MoO₄(H₂O)], was studied by single crystal X-ray diffraction. Crystal data: rhombic system, a = 9.478(2), b = 7.900(1), c = 10.499(2) Å; space group Pnna, Z = 4, d = 5.05 g cm^?3, R = 0.030. The compound has a framework structure; the coordination polyhedron of the Np atom is a distorted pentagonal bipyramid with the equatorial positions occupied by four O atoms of four molybdate groups and an O atom of the coordinated water molecule. The IR and visible absorption spectra of this compound and of Cs₂[(NpO₂)₂Mo₂O₈] whose structure had been determined previously were measured. The NpO ₂ ⁺ stretching vibration frequencies in the IR spectra of these compounds virtually coincide. Incorporation of the O atom of the Mo-O-Mo bridge into the first coordination sphere of the neptunyl(V) ion in Cs₂[(NpO₂)₂Mo₂O₈] exerts the same disturbing effect on the electronic absorption spectrum as does the cation-cation interaction with one of the O atoms acting as a bridge between two Np atoms.     

On VLSI interconnect optimization and linear ordering problem

Some well-known VLSI interconnect optimizations problems for timing, power and cross-coupling noise immunity share a property that enables mapping them into a specialized Linear Ordering Problem (LOP). Unlike the general LOP problem which is NP-complete, this paper proves that the specialized one has a closed-form solution. Let f(x,y):?²→? be symmetric, non-negative, defined for x≥0 and y≥0, and let f(x,y) be twice differentiable, satisfying ? ² f(x,y)/?x?y<0. Let π be a permutation of {1,…,n}. The specialized LOP comprises n objects, each associated with a real value parameter r _i , 1≤i≤n, and a cost f(r _i ,r _j ) associated to any two objects if |π(i)?π(j)|=1,1≤i,j≤n, and f(r _i ,r _j )=0 otherwise. We show that the permutation π which minimizes \(\sum_{i= 1}^{n - 1} f( r_{\pi^{ - 1}( i )},r_{\pi^{ - 1}( i + 1 )} )\), called “symmetric hill”, is determined upfront by the relations between the parameter values r _i .     

A physicochemical study of alkaline-earth metal carbonatouranylates

Optimal procedures were developed for preparing the compounds M ₂ ^II UO₂(CO₃)₃·nH₂O (M^II = Mg, Ca, Sr, Ba; n = 0–18). The structure and thermal decomposition of these compounds were studied by X-ray diffraction, IR spectroscopy, and differential scanning calorimetry. The previously unknown standard enthalpies of formation of the compounds at 298.15 K were determined by reaction calorimetry.     

Kinetics of gas-phase conversion of U<Subscript>3</Subscript>O<Subscript>8</Subscript> into water-soluble compounds in nitrating atmosphere at 25–30°С

The kinetics of the gas-phase conversion of U₃O₈ in NO_x–H₂O (vapor)–air and HNO₃ (vapor)–H₂O (vapor)–air atmospheres was fitted by the Kazeev–Kolmogorov–Erofeev equation. The following parameters n and K were obtained: for experiments in NO_x–H₂O (vapor)–air atmosphere, n = 0.2 ± 0.1 and K = 0.2 ± 0.2 h^–1; for experiments in HNO₃ (vapor)–H₂O (vapor)–air atmosphere, n = 0.3 ± 0.2 and K = 0.03 ± 0.02 h^–1 (confidence probability p = 0.95). For the U₃O₈ conversion in both media, n < 0.5, which suggests the diffusion control of the U₃O₈ conversion under the action of both HNO₃ and NO_x.     

Modification of the properties of tin sulfide films grown by spray pyrolysis

n-Type SnS and SnS₂ sulfide films up to 0.6 μm in thickness, with resistivity in the range 2 ≤ ρ ≤ 17 kΩ cm have been grown by spray pyrolysis of aqueous solutions of the SnCl2 ? 2H₂O, SnCl₄ ? 5H₂O, and (NH₂)₂CS salts at substrate temperatures in the range 523 ≤ T_s ≤ 623 K. At constant thermal conditions of sulfide film growth, varying the chemical composition of the solutions for spray pyrolysis makes it possible to obtain films with substantially different optical properties. Undoped SnS and SnS₂ have high transmittance, T ≈ 40–70%, and a sharp intrinsic absorption edge. The optical band gap of the SnS and SnS₂ sulfide films has been shown to depend on film growth conditions.     

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.     

Coordination of V<Superscript>4+</Superscript> in Vanadium Titanium Oxide Xerogels

V_{2 ? y}Ti _y O_{5 ? δ} · nH₂O (0 < y < 1.33, layered structure) and Ti_{1 ? y}V _y O_{2 + δ} · nH₂O (0 < y < 0.25, anatase structure) solid solutions are synthesized by a sol-gel process. ESR spectra are used to assess the state of tetravalent vanadium in the solid solutions before and after calcination at 350°C and after intercalation with K⁺. Six types of ESR signals arising from paramagnetic ions in different environments are identified. Computer simulation is used to evaluate the ESR parameters of the materials studied.     

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).     

Structure and properties of superhard materials based on aluminum dodecaboride α-AlB<Subscript>12</Subscript>

The structures and mechanical properties of materials based on α-AlB12 without additives and with additions of carbon and titanium carbide sintered under high (2 GPa) pressure and by hot pressing (30 MPa) in the contact with hexagonal BN. The light materials were obtained having high hardness, fracture toughness, ultimate strengths at bending, R _bm , and compression. The addition of 17 wt % C to α-AlB₁₂ and sintering at 30 MPa makes possible to achieve fracture toughness K_Ic (49 N) = 5.9 ± 1.4 MPa·m^0.5, hardness H _V (49 N) = 23.6 ± 2.8 GPa, bending R _bm = 310 MPa and compression R _cs = 423 MPa strengths and specific weight was γ = 2.7 g/cm³. The addition of 20 wt % TiC to α-AlB₁₂ and sintering at 30 MPa resulted in the formation of AlB1₂C₂ and TiB₂, increase of the hardness H _V (49 N) = 28.9 ± 1.9 GPa, R _bm = 633 MPa, R _cs = 640 MPa and γ = 3.2 g/cm³, the K_Ic(49 N) = 5.2 ± 1.5 MPa·m^0.5.     

Structures of gismondine,cymrite, anorthite,and celsian solid solutions

This paper presents a comparative analysis of existing structural models for AAl₂Si₂O₈ · xH₂O (A = alkaline-earth element, 0 ≤ x ≤ 5) solid solutions and highlights their advantages and drawbacks. Water molecules are shown to play an important role in the formation of a zeolite structure, as exemplified by changes in the structural framework of gismondine during its dehydration.     

Monte Carlo Study of Magnetic and Thermal Phase Transitions of a Diluted Magnetic Nanosystem

Monte Carlo (MC) simulation method with the Metropolis algorithm is used to study the magnetic and thermal phase transition properties of a spherical nanoparticle. The system consists of two concentric spheres of rays R _C and R _S, respectively (R _c < R _s). For r < R _c, the spin is σ = ±3 /2 and ±1 /2, and for R _C < r ≤ R _S, the spin is S = ±7 /2, + 5/2, ±3 /2, and ±1 /2 with antiferromagnetic interface coupling. Between R _C and R _S, the sites are populated with the probability (p). We present a detailed discussion on the magnetic and thermal phase transition characteristics of the system under consideration. Our investigations show that this system can be used as a magnetic nanostructure possessing potential applications in magnetism.