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.     

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).     

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).     

Sol–gel preparation and high-energy XRD study of (CaO)<Subscript>x</Subscript>(TiO<Subscript>2</Subscript>)<Subscript>0.5−x</Subscript>(P<Subscript>2</Subscript>O<Subscript>5</Subscript>)<Subscript>0.5</Subscript> glasses (x = 0 and 0.25)

Glasses from the CaO–TiO₂–P₂O₅ system have potential use in biomedical applications. Here a method for the sol–gel synthesis of the ternary glass (CaO)_0.25(TiO₂)_0.25(P₂O₅)_0.5 has been developed. The structures of the dried gel and heat-treated glass were studied using high-energy X-ray diffraction. The structure of the binary (TiO₂)_0.5(P₂O₅)_0.5 sol–gel was studied for comparison. The results reveal that the heat-treated (CaO)_0.25(TiO₂)_0.25(P₂O₅)_0.5 glass has a structure based on chains and rings of PO₄ tetrahedra, held together by a combination of electrostatic interaction with Ca²⁺ ions and by corner-sharing oxygen atoms with TiO₆ octahedra. In contrast, the (TiO₂)_0.5(P₂O₅)_0.5 glass has a structure based on isolated P₂O₇ units linked together by corner-sharing with TiO₆ groups. The results suggest that both the dried gels possess open porous structures. For the (CaO)_0.25(TiO₂)_0.25(P₂O₅)_0.5 sample there is a significant increase in Ca–O coordination number with heat treatment.     

Crystal Structure of Uranyl Malonate Trihydrate [UO<Subscript>2</Subscript>(OOC)<Subscript>2</Subscript>CH<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)]·2H<Subscript>2</Subscript>O

Single crystals of [UO₂(OOC)₂CH₂(H₂O)]·2H₂O (I) were prepared by recrystallization of finely crystalline uranyl malonate trihydrate under hydrothermal conditions. The crystal structure of I consists of electroneutral [UO₂(OOC)₂CH₂(H₂O)]_n layers and water molecules located between them. The uranium coordination number is 7. The uranium coordination polyhedron is a distorted pentagonal bipyramid with the oxygen atoms of the uranyl group in the apices. The equatorial plane is occupied by four O atoms of three malonate ligands and the water molecule. The malonate anion is coordinated in the bidentate fashion to one uranyl ion to form a six-membered ring and in the monodentate fashion to two other uranyl ions.     

Mechanism of UO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>·6H<Subscript>2</Subscript>O decomposition under the action of microwave radiation

The effect of microwave radiation (MWR) on the decomposition of UO₂(NO₃)₂·6H₂O was studied. Determination of [UO ₂ ²⁺ ] and [NO ₃ ^? ], and also of the molar ratio NO ₃ ^? : UO ₂ ²⁺ in various fractions of the decomposition product showed that the mechanism of the UO₂(NO₃)₂·6H₂O decomposition under the action of MWR differs from the mechanism of its decomposition under common convection heating. The main precursor of UO₃ as product of UO₂(NO₃)₂·6H₂O decomposition under the action of MWR is uranyl hydroxonitrate UO₂(OH)NO₃ formed already in the first minutes of the irradiation. In contrast to the thermolysis under convection heating, UO₂(NO₃)₂ or its hydrates were not detected as intermediates. The mechanism of the UO₂(NO₃)₂·6H₂O decomposition under the action of MWR can be presented by the reactions UO₂(NO₃)₂·6H₂O → UO₂(OH)NO₃ + 5H₂O + HNO₃ and UO₂(OH)NO₃ → UO₃ + HNO₃. The solubility of UO₂(OH)NO₃ in H₂O at 20°C was estimated experimentally at 6.83 × 10^?2 M.     

Mechanism of UO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>·6H<Subscript>2</Subscript>O decomposition under the action of microwave radiation: Part 2

Products of UO₂(NO₃)₂·6H₂O decomposition under the action of microwave radiation (MWR) were studied by thermal gravimetric analysis, X-ray phase analysis, IR spectroscopy, and electron microscopy. The results of physicochemical studies of these decomposition products were compared to the published data for various uranium compounds, including UO₂(NO₃)₂·6H₂O. Apart from gaseous products, the final products of decomposition of 2–10 g of UO₂(NO₃)₂·6H₂O under the action of MWR for 35 min (the maximal process temperature, 170–320°C, is attained in the first 2–5 min of irradiation) are uranyl hydroxonitrate UO₂(OH)NO₃ and uranium trioxide UO₃ or their hydrates. The results obtained are consistent with the mechanism suggested in our previous paper and involving the reactions (1) UO₂(NO₃)₂·6H₂O → UO₂(OH)NO₃ + 5H₂O + HNO₃ and (2) UO₂(OH)NO₃ → UO₃ + HNO_3. The physicochemical study confirms the conclusions on the composition of products of UO₂(NO₃)₂·6H₂O decomposition under the action of MWR, made previously on the basis of chemical studies. The only precursor of UO₃ in microwave treatment of UO₂(NO₃)₂·6H₂O is UO₂(OH)NO₃ (or its hydrates). This is the main difference between the courses of uranyl nitrate decomposition under the conditions of microwave and convection heating. In the latter case, uranyl nitrate and its hydrates also participate in the formation of UO₃.     

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.     

Synthesis and properties of actinide dimolybdate complexes M<Subscript>2</Subscript>[AnO<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>]·H<Subscript>2</Subscript>O (M = Rb,Cs; An = Np,Pu)

New Np(VI) and Pu(VI) dimolybdates Rb₂NpO₂(MoO₄)₂·H₂O (I), Cs₂NpO₂(MoO₄)₂·H₂O (II), Cs₂PuO₂(MoO₄)₂·H₂O (III), and Rb₂PuO₂(MoO₄)₂·H₂O (IV) were synthesized under hydrothermal conditions. The crystal structures of the compounds were determined, and their absorption spectra in the UV, visible, and IR ranges were measured. The compounds crystallize in the monoclinic system. Their crystal structure is based on [AnO₂(MoO₄)₂]_n^2n– anionic layers (An = Np, Pu) formed by (AnO₂)O₅ pentagonal bipyramids and MoO₄ tetrahedra, sharing common vertices. Each An atom in the layer is bonded to other five An atoms via MoO₄ tetrahedra with the formation of a 4343² network. The effect of the ionic radius of the outer-sphere cation on the parameters of the crystal structure and features of the absorption spectra is discussed.     

Crystal Structure of a Double Neptunium(V) Lanthanum Nitrate,La(NpO<Subscript>2</Subscript>)<Subscript>3</Subscript>(NO<Subscript>3</Subscript>)<Subscript>6</Subscript>·<Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O

The structure of a double neptunium(V) lanthanum nitrate, La(NpO₂)₃(NO₃)₆·nH₂O, was studied by single crystal X-ray diffraction. Each neptunyl(V) ion in the structure of the compound is bonded to four other neptunyl(V) ions, acting simultaneously as a bidentate ligand and as a coordination center for two other dioxocations. The cation-cation interaction of the neptunyl(V) ions results in formation of trigonal-hexagonal cationic networks. The surrounding of each Np atom also includes two bidentate nitrate ions. The CN of the Np atom is 8, and the coordination polyhedron is a distorted hexagonal bipyramid. The La³⁺ cations are surrounded only by water molecules.     

Synthesis and Structure of the Np(VII) Complex with Guanidinium,Li[C(NH<Subscript>2</Subscript>)<Subscript>3</Subscript>]<Subscript>2</Subscript>[NpO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>]·6H<Subscript>2</Subscript>O

The previously unknown Np(VII) compound Li[C(NH₂)₃]₂[NpO₄(OH)₂]·6H₂O (I), containing organic cations, was synthesized and studied by single crystal X-ray diffraction. In contrast to the relatively numerous structurally characterized salts of [NpO₄(OH)₂]^3– anions with Na⁺, K⁺, Rb⁺, and Cs⁺ cations, which were prepared only from strongly alkaline media, crystals of I were isolated from solutions with a very low concentration of OH^– ions (about 0.1 M). The compound is relatively stable in storage in the dry form, but is strongly hygroscopic. In the structure of I, there are two independent Np(VII) atoms with the oxygen surrounding in the form of tetragonal bipyramids. In contrast to the other salts of the [NpO₄(OH)₂]^3– anions with singlecharged alkali metal cations, the C(NH₂) ₃ ⁺ ions and hydrated Li⁺ ions in I interact with the oxygen surrounding of Np(VII) only via hydrogen bonds of types O_w–H···O and N–H···O with the formation of a three-dimensional H-bond network.     

Growth and structure of Mg(Fe<Subscript>0.8</Subscript>Ga<Subscript>0.2</Subscript>)<Subscript>2</Subscript>O<Subscript>4 − δ</Subscript> films

Films 150–200 nm in thickness, with the nominal composition Mg(Fe_0.8Ga_0.2)₂O_{4 − δ} have been grown on (100) single-crystal silicon substrates by ion-beam sputtering in vacuum. The effect of growth and annealing conditions on the crystal structure and morphology of the films has been studied, and the thermal conditions for the growth of spinel-structure films have been optimized.     

Effect of gamma radiation on electrical and optical properties of (TeO<Subscript>2</Subscript>)<Subscript>0·9</Subscript> (In<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0·1</Subscript> thin films

We have studied in detail the gamma radiation induced changes in the electrical properties of the (TeO₂)_0·9 (In₂O₃)_0·1 thin films of different thicknesses, prepared by thermal evaporation in vacuum. The current–voltage characteristics for the as-deposited and exposed thin films were analysed to obtain current versus dose plots at different applied voltages. These plots clearly show that the current increases quite linearly with the radiation dose over a wide range and that the range of doses is higher for the thicker films. Beyond certain dose (a quantity dependent on the film thickness), however, the current has been observed to decrease. In order to understand the dose dependence of the current, we analysed the optical absorption spectra for the as-deposited and exposed thin films to obtain the dose dependences of the optical bandgap and energy width of band tails of the localized states. The increase of the current with the gamma radiation dose may be attributed partly to the healing effect and partly to the lowering of the optical bandgap. Attempts are on to understand the decrease in the current at higher doses. Employing dose dependence of the current, some real-time gamma radiation dosimeters have been prepared, which have been found to possess sensitivity in the range 5–55 μGy/μA/cm². These values are far superior to any presently available real-time gamma radiation dosimeter.     

Microwave dielectric properties of temperature-stable (Mg<Subscript>0.95</Subscript>Co<Subscript>0.05</Subscript>)<Subscript>2</Subscript>TiO<Subscript>4</Subscript>–Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> composite ceramics for LTCC applications

In this paper, the effects of Li₂O–B₂O₃–Bi₂O₃–SiO₂ (LBBS) glass on the phase formation, sintering characteristic, the microstructure and microwave dielectric properties of temperature-stable (Mg_0.95Co_0.05)₂TiO₄–Li₂TiO₃ ceramics were investigated. (Mg_0.95Co_0.05)₂TiO₄–Li₂TiO₃ powders were obtained by using the traditional solid-state process. A small amount of LBBS doping can effectively reduce sintering temperature and promote the densification of the ceramics. X-ray diffraction analysis revealed not only the primary phase (Mg·Co)₂TiO₄ associated with Li₂TiO₃ minor phase but also a third phase (Mg·Co)TiO₃. The dielectric constant and Qf values vary with the doping amount of LBBS and sintering temperatures. With the compensation of the positive temperature coefficient (τ _f ) of Li₂TiO₃ and the negative τ _f of (Mg_0.95Co_0.05)₂TiO₄, the τ _f of the specimens fluctuates around zero. The (Mg_0.95Co_0.05)₂TiO₄ ceramic with 2.5 wt% LBBS addition and sintering at 900?°C for 4 h exhibited excellent microwave dielectric properties: ? _r ?=?19.076, Qf?=?126100 GHz, and τ _f ?=?0.98 ppm/°C.     

Crystal structure of U(VI) phthalate dihydrate [UO<Subscript>2</Subscript>(OOC)<Subscript>2</Subscript>C<Subscript>6</Subscript>H<Subscript>4</Subscript>•H<Subscript>2</Subscript>O]•H<Subscript>2</Subscript>O

Crystalline uranyl phthalate dihydrate was prepared by hydrothermal method, and its crystal structure was determined. The crystal structure consists of infinite chains [UO₂LH₂O]_n coupled in bands [(UO₂)₂L₂(H₂O)₂]_n [L = C₆H₄(COO)₂], between which water molecules of crystallization are located. The coordination polyhedron of uranium atoms is a pentagonal bipyramid with the equatorial plane formed by oxygen atoms of three phthalate ions and coordinated water molecule. The U-O bond length in the UO ₂ ²⁺ cations is 1.766 . The coordination capacity of the ligands is 4. Anions are bidentately coordinated to uranium atoms to form seven-membered rings. Being bridging ligands, phthalate ions combine the neighboring uranium atoms into chains through one carboxy group, and the chains into bands, through the other carboxy group.Translated from Radiokhimiya, Vol. 46, No. 6, 2004, pp. 513–515.Original Russian Text Copyright © 2004 by Charushnikova, Krot, Starikova.     

New NTC thermistors based on LaCrO<Subscript>3</Subscript>–Mg(Al<Subscript>0.7</Subscript>Cr<Subscript>0.3</Subscript>)<Subscript>2</Subscript>O<Subscript>4</Subscript> composite ceramics

In this study, the xLaCrO₃–(1?x)Mg(Al_0.7Cr_0.3)₂O₄ (x?=?0.1, 0.2, 0.3, 0.4) negative temperature coefficient composite ceramics were fabricated through conventional solid state reaction at 1650?°C. X-ray diffraction analysis has revealed that the sintered ceramics are consisted of cubic spinel Mg(Al_0.7Cr_0.3)₂O₄ phase and orthorhombic perovskite LaCrO₃ phase. The obtained values of \({{\rho }_{\text{300}}}\) and \({{B}_{400/800}}\) and \({{E}_{\text{a}}}\) are in the range of 1.55?×?10²–1.41?×?10⁸ Ωcm, 756–11317 K, 0.065–0.976 eV, respectively. The electrical properties of these ceramics can be adjusted by the LaCrO₃ contents. Such ceramics could be suitable for high temperature NTC thermistor application.     

Theoretical Studies of Electronic Paramagnetic Resonance <Emphasis Type="Italic">g</Emphasis> Factors for La<Subscript>2</Subscript>Mg<Subscript>3</Subscript>(NO<Subscript>3</Subscript>)<Subscript>12</Subscript>⋅24H<Subscript>2</Subscript>O

Lanthanum magnesium double nitrate (LMN) crystals can be used as material for adiabatic demagnetization, magnetic thermometers and a proton spin-polarized target in both physics and polarized neutron diffraction. In the past years, the double nitrates doped with transition metal or rare earth ions have been studied by experimental and theoretical methods. For instance, the electronic paramagnetic resonance (EPR) g factors of the Ce³⁺ ions in La₂Mg₃(NO₃)₁₂⋅24H₂O crystal were measured decades ago. But until now, these useful experimental results have not been theoretically explained. In this work, The EPR g factors of the trigonal Ce³⁺ centers in La₂Mg₃(NO₃)₁₂⋅24H₂O are theoretically studied from the perturbation formulae of the EPR parameters for a 4f¹ ion under the trigonal symmetry crystal field. The used crystal parameters are obtained from the superposition model and the local structure of the studied crystal. The calculated results are reasonably constant to the observed values. The results are discussed.     

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.     

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.     

Crystal structure of a Pu(VII) potassium salt,K<Subscript>3</Subscript>PuO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O

A new Pu(VII) compound, K₃PuO₄(OH)₂·2H₂O, was synthesized, and its structure was studied by single crystal X-ray diffraction. This compound is isostructural to the previously described K₃NpO₄(OH)₂·2H₂O. The structure of the latter compound was redetermined to obtain more precise interatomic distances in the NpO₂(OH) ₂ ^3? anion. Changes in An-O bond lengths in the tetragon-bipyramidal coordination polyhedron of the compounds K₃AnO₄(OH)₂·2H₂O in going from Np(VII) to Pu(VII) were considered.