Magnetic phase diagram of solid solutions in the CoCr<Subscript>2</Subscript>S<Subscript>4</Subscript>–Cu<Subscript>0.5</Subscript>In<Subscript>0.5</Subscript>Cr<Subscript>2</Subscript>S<Subscript>4</Subscript> system

The magnetic properties of CoCr₂S₄–Cu_0.5In_0.5Cr₂S₄ solid solutions have been studied in the temperature range 5–300 K at different ac magnetic field frequencies (100, 500, and 1000 Hz) and an amplitude of 79.6 A/m. We have determined the temperatures of the magnetic transformations in the system, identified their nature, and constructed the magnetic phase diagram of the solid solutions.     

Crystal growth,X-ray diffraction characterization,and Mössbauer spectroscopy of FeIn<Subscript>2</Subscript>S<Subscript>4</Subscript>-In<Subscript>2</Subscript>S<Subscript>3</Subscript> solid solutions

Crystals of (FeIn₂S₄)_{1 ? x} (In₂S₃) _x solid solutions consisting of large blocks have been grown by directional solidification (horizontal Bridgman process). FeIn₂S₄, In₂S₃, and the solid solutions are shown to crystallize in the spinel structure. The composition dependence of their unit-cell parameter a follows Vegard's law. The local states of the Fe ions in the solid solutions have been studied by Mössbauer spectroscopy in a transmission geometry.     

Growth of bulk β-BaB<Subscript>2</Subscript>O<Subscript>4</Subscript> crystals of high optical quality in the BaB<Subscript>2</Subscript>O<Subscript>4</Subscript>-NaBaBO<Subscript>3</Subscript> system

Phase equilibria along the BaB₂O₄-NaBaBO₃ join of the BaO-B 2 O 3 -Na 2 O system are studied by differential thermal analysis and modified visual thermal analysis. The join is shown to be suitable for growing - BaB₂O₄ crystal of high optical quality.Translated from Neorganicheskie Materialy, Vol. 41, No. 1, 2005, pp. 64–69. Original Russian Text Copyright © 2005 by Kokh, Kononova, Fedorov, Bekker, Kuznetsov.     

Optical and photoelectric properties of α-Dy<Subscript>2</Subscript>S<Subscript>3</Subscript> and α-Dy<Subscript>2</Subscript>S<Subscript>3</Subscript>〈Pb〉 films

A process is described for the growth of thin crystalline α-Dy₂S₃ films by thermal evaporation from separate dysprosium and sulfur sources. The films were doped with Pb, and their reflection and transmission spectra were measured at room temperature and photon energies in the range (0.3−5.2) × 10⁻¹⁹ J. The α-Dy₂S₃ films were shown to have an exponential absorption edge. The photoconductivity of the doped films was measured at photon energies in the range (0.3−5.2) × 10⁻¹⁹ J and temperatures from 115 to 400 K.     

Preparation of β-Ca<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>/Poly(D,L-lactide) and β-Ca<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>/Poly(ε-caprolactone) Biocomposite Implants for Bone Substitution

Highly permeable macroporous implants of various architectures for bone grafting have been fabricated by thermal extrusion 3D printing using highly filled β-Ca₃(PO₄)₂/poly(D,L-lactide) (degree of filling up to 70 wt %) and β-Ca₃(PO₄)₂/poly(ε-caprolactone) (degree of filling up to 70 wt %) composite filaments. To modify the surface of the composite macroporous implants with the aim of improving their wettability by saline solutions, we have proposed exposing them to a cathode discharge plasma (2.5 W, air as plasma gas) in combination with subsequent etching in a 0.5 M citric acid solution. It has been shown that the main contribution to changes in the wettability (contact angle) of the composites is made by the changes produced in their surface morphology by etching in a low-temperature plasma and citric acid. An alternative approach to surface modification of the composites is to produce a carbonate hydroxyapatite layer via precipitation from a simulated body fluid solution a factor of 5 supersaturated relative to its natural analog (5xSBF).     

Formation of Li<Superscript>+</Superscript> superionic crystals from the Li<Subscript>2</Subscript>S–P<Subscript>2</Subscript>S<Subscript>5</Subscript> melt-quenched glasses

The 70Li₂S·30P₂S₅ (mol%) glass was prepared by the melt quenching method and the glass–ceramic electrolytes were obtained by heating the prepared glass over crystallization temperatures. The superionic metastable Li₇P₃S₁₁ crystal was formed by heating the glass in the temperature range from 280 and 360 °C. The conductivity of the glass–ceramics was enhanced by the precipitation and growth of the Li₇P₃S₁₁ crystal, and the highest conductivity of 4.1 × 10⁻³ S cm⁻¹ at room temperature was achieved in the glass–ceramic heated at 360 °C for 1 h. The Li₇P₃S₁₁ crystal changed into the thermodynamically stable phase such as the Li₄P₂S₆ crystal with further increasing heat treatment temperature and holding time, resulting in lowering conductivities of the glass–ceramics.     

Kinetics of Thermal Transformation of Mg<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 8H<Subscript>2</Subscript>O to Mg<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The kinetics of thermal dehydration of Mg₃(PO₄)₂ · 8H₂O was investigated using thermogravimetry at four different heating rates. The activation energies of the dehydration step of Mg₃(PO₄)₂ · 8H₂O were calculated through the isoconversional Ozawa and Kissinger-Akahira-Sunose (KAS) methods and iterative methods, which were found to be consistent and indicate a single mechanism. The possible conversion function of the dehydration reaction for Mg₃(PO₄)₂ · 8H₂O has been estimated through the Coats and Redfern integral equation, and a better kinetic model such as random nucleation of the “Avrami–Erofeev equation (A _3/2 model)” was found. The thermodynamic functions (ΔH*, ΔG*, and ΔS*) of the dehydration reaction are calculated by the activated complex theory and indicate that it is a non-spontaneous process when the introduction of heat is not connected.     

Chemical interaction of InAs,InSb, GaAs,and GaSb with (NH<Subscript>4</Subscript>)<Subscript>2</Subscript>Cr<Subscript>2</Subscript>O<Subscript>7</Subscript>–HBr–C<Subscript>4</Subscript>H<Subscript>6</Subscript>O<Subscript>6</Subscript> etching solutions

This paper presents results on the kinetics and mechanism of the physicochemical interaction of InAs, InSb, GaAs, and GaSb semiconductor surfaces with (NH₄)₂Cr₂O₇–HBr–C₄H₆O₆ etching solutions under reproducible hydrodynamic conditions in the case of laminar etchant flow over a substrate. We have identified regions of polishing and nonpolishing solutions and evaluated the apparent activation energy of the process. The surface morphology of the crystals has been examined by microstructural analysis after chemical etching. The results demonstrate that the presence of C₄H₆O₆ in etchants helps to reduce the overall reaction rate and extend the region of polishing solutions.     

Phase relations in the K<Subscript>2</Subscript>MoO<Subscript>4</Subscript>–Ln<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>–Zr(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> (Ln = La–Lu,Y) systems

We have studied phase relations in the K₂MoO₄–Ln₂(MoO₄)₃–Zr(MoO₄)₂ (Ln = La–Lu, Y) systems by the method of “intersecting cuts,” identified pseudobinary joins in their composition triangles, and constructed their phase compatibility diagrams. The systems have been shown to contain new ternary molybdates with the general formula K₅LnZr(MoO₄)₆ (Ln = Dy–Lu and Y). The thermal characteristics of the synthesized compounds have been studied by differential scanning calorimetry in the temperature range 25–700°C. The new ternary molybdates crystallize in a trigonal structure (sp. gr. R\(\bar 3\)c, Z = 6).     

An Effective Approach to the Synthesis of Nanocrystalline PbMoO<Subscript>4</Subscript> in Na<Subscript>2</Subscript>Mo<Subscript>4</Subscript>O<Subscript>13</Subscript>–PbCO<Subscript>3</Subscript> Melts

This paper presents thermodynamic analysis of reactions of sodium tetramolybdate with Pb₃O₄, PbO₂, PbO, and lead carbonate and describes an effective approach to PbMoO₄ synthesis in melts of the Na₂Mo₄O₁₃–PbCO₃ system, which offers a low synthesis temperature, waste-free character of the process, high rate, and high yield of a reagent-grade synthesis product in a nanocrystalline state. The synthesis product has been identified by chemical analysis, X-ray diffraction, and particle size measurements.     

Effect of the synthesis technique on the physicochemical properties of Ce<Subscript>0.8</Subscript>(Sm<Subscript>0.75</Subscript>Sr<Subscript>0.2</Subscript>Ba<Subscript>0.05</Subscript>)<Subscript>0.2</Subscript>O<Subscript>2 − δ</Subscript>

A multicomponent solid electrolyte of composition Ce_0.8(Sm_0.75Sr_0.2Ba_0.05)_0.2O_{2 − δ} has been synthesized by three different techniques: solid-state reaction, laser evaporation, and the glycine nitrate process. Its microstructure, sintering kinetics, and electrical properties have been studied in relation to the synthesis technique. Ceramics produced using laser evaporation consisted of submicron (0.2 μm) grains and offered the highest electrical conductivity: 27 × 10⁻³ S/cm at 873 K.     

Phase Equilibria in the Cu<Subscript>2</Subscript>Se–Cu<Subscript>3</Subscript>AsSe<Subscript>4</Subscript>–Se System and Thermodynamic Properties of Cu<Subscript>3</Subscript>AsSe<Subscript>4</Subscript>

The Cu₂Se–Cu₃AsSe₄–Se system has been studied using differential thermal analysis, X-ray diffraction, and emf measurements on concentration cells using Cu₄RbCl₃I₂ as a solid electrolyte. We have constructed a number of vertical sections through the phase diagram, the room-temperature solid-state phase compatibility diagram, and a projection of the liquidus surface. The primary crystallization fields of the phases present and the types and coordinates of in- and univariant equilibria in the system have been identified. The system has been shown to contain a broad liquid–liquid immiscibility region. Using emf data, we evaluated the standard thermodynamic functions of formation and standard entropy of the Cu₃AsSe₄ compound.     

Crystal structure of a Np(V) sesquioxalate,Na<Subscript>4</Subscript>(NpO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>·2H<Subscript>2</Subscript>O

The crystal structure of a previously unknown Np(V) sesquioxalate, Na₄(NpO₂)₂(C₂O₄)₃·2H₂O was studied. The crystal structure consists of neptunyl(V) cations, sodium cations, oxalate anions, and water molecules of crystallization. Neptunyl(V) cations and oxalate ions form anionic chains [(NpO₂)₂(C₂O₄)₃] _n ^4n? . The coordination polyhedron (CP) of Np (pentagonal bipyramid) contains two apical “yl” oxygen atoms and five equatorial O atoms of three oxalate ions. The CP of Na(1) and Na(2) cations are combined through the common edges into zigzag chains in the [010] direction. Two independent oxalate ions are tridentate and tetradentate ligands.     

Synthesis and study of structural,dielectric, magnetic and magnetoelectric properties of K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>NbO<Subscript>3</Subscript>–CoMn<Subscript>0.2</Subscript>Fe<Subscript>1.8</Subscript>O<Subscript>4</Subscript> composites

Magnetoelectric (ME) composites consisting of K_0.5Na_0.5NbO₃ (KNN) as ferroelectric phase and CoMn_0.2Fe_1.8O₄ (CMFO) as ferrite phase with general formula (x) CoMn_0.2Fe_1.8O₄–(1???x) K_0.5Na_0.5NbO₃ (x?=?10, 20, 30, 40 and 50 wt%) were synthesized using solid state reaction method. X-ray diffraction analysis asserts the existence of component phases including spinel phase of CMFO and orthorhombic phase of KNN. Field emission scanning electron microscopy has been used for studying the morphology and calculation of average grain size. The temperature dependent dielectric properties including dielectric constant (\(\varepsilon ^{\prime}\)) and dielectric loss (tan δ) at different frequencies has been studied and both are found to increase with incorporation of CMFO. Magnetic hysteresis loops have been measured at temperatures of 300 and 5 K. Variation of magnetization versus temperature has been studied in field cooled and zero field cooled modes. Polarization versus electric field (P–E) hysteresis loops are obtained at room temperature indicating presence of ferroelectric ordering in the composites at room temperature. The remnant polarization (2P_r) and coercive field (2E_c) are found to decrease linearly with incorporation of CMFO. ME voltage coefficient (α_ME) has been measured. The maximum value of α_ME is found to be 5.941 mV/cm-Oe for 10% CMFO–90% KNN bulk composite.     

High- and low-temperature X-ray diffraction studies of aluminate spinels in the CoAl<Subscript>2</Subscript>O<Subscript>4</Subscript>–NiAl<Subscript>2</Subscript>O<Subscript>4</Subscript> system

Co _x Ni_1–x Al₂O₄ (x = 0, 0.25, 0.5, 0.75, 1) aluminate spinels have been prepared by solid-state reactions and their crystal structures have been refined by the Rietveld method. We have analyzed whether the results are consistent with theoretical relationships stemming from the hard sphere model. Using high- and low-temperature X-ray diffraction measurements, we have obtained the temperature dependences of the unit-cell parameters for the synthesized compounds and determined their thermal expansion coefficients. The rate of cation exchange reactions has been shown to be very slow at temperatures below 200°C.     

Stability of the LaCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> and LuCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> Ions Studied by Mass Spectrometry

The enthalpy stability of the LaCl ₄ ^? and LuCl ₄ ^? ions is assessed using high-temperature mass spectrometry. The enthalpy of Cl^? detachment is determined to be Δ_rH⁰(298.15 K) = 332 ± 10 kJ/mol for LaCl ₄ ^? and 359 ± 10 kJ/mol for LuCl ₄ ^? .     

BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript> films produced from BaFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> heterostructures

BaFe₁₂O₁₉ hexaferrite films have been produced on thermally oxidized single-crystal silicon (SiO₂/Si) substrates by sequential ion-beam sputtering of BaFe₂O₄ and α-Fe₂O₃ targets in an argon-oxygen atmosphere. Their crystal structure has been studied, and the origin of the impurity phases forming during heat treatment has been identified. The results show that heat treatment may lead to the formation of eutectic melts. As a result, the hexaferrite films may contain spherulites.     

Effect of refractory nitride nanoadditives on the properties of (Bi,Pb)<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+δ</Subscript>

We have investigated the interaction between (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+δ (Bi-2223) and small additions (0.05–0.3 wt %) of nitride powders (TaN, AlN, HfN, NbN, Si₃N₄, TiN, and ZrN) with a particle size from 0.02 to above 0.5 μm and the effect of these nitrides on the microstructure, phase composition, distribution, and morphology of the resulting second-phase inclusions. The concentration and particle size of the nitrides and sintering conditions are shown to influence the superconducting transition temperature T _c, critical current density j _c, irreversible remanent magnetization, bulk density, and mechanical properties of the Bi-2223/nitride composites.     

Enhanced microwave dielectric properties of Ba<Subscript>0.40</Subscript>Sr<Subscript>0.60</Subscript>TiO<Subscript>3</Subscript>–Zr<Subscript>0.80</Subscript>Sn<Subscript>0.20</Subscript>TiO<Subscript>4</Subscript> composite ceramics

The (1−x) Ba_0.40Sr_0.60TiO₃ (BST)−xZr_0.80Sn_0.20TiO₄ (ZST) composite ceramics with x = 10, 20, 30, and 40 wt% were fabricated by conventional solid-state reaction method. With increasing of ZST content, the dielectric constant of composite ceramics was decreased and dielectric loss increases. The effect of ZnO addition to 70 wt% BST–30 wt% ZST composition on the microstructure and dielectric properties was investigated. The improvements in dielectric constant, dielectric loss, and microwave dielectric properties of composite ceramics can be achieved by ZnO addition. The sample with 98 wt% (70 wt% BST–30 wt% ZST)–2 wt%ZnO composition exhibits promising dielectric properties, with dielectric constant, loss tangent and tunability at 4 kV/mm, of 125, 0.0016 and 12%, at 10 kHz and room temperature. At ~2 GHz, it possesses a dielectric constant of 101 and a Q factor of 187, which makes it a good candidate for tunable microwave device applications.