XAFS investigation of [Pd(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>][AuCl<Subscript>4</Subscript>]<Subscript>2</Subscript> and its thermolysis products

Thermolysis of double complex salt [Pd(NH₃)₄][AuCl₄]₂ has been studied in helium atmosphere from ambient to 350 °C. The XAFS of Pd K and Au L₃ edges and thermogravimetry measurements have been carried out to characterize the intermediates and the final product. In the temperature range 115–160 °C the complex is decomposed to form Pd(NH₃)₂Cl₂ and AuCl_4−x N _x species with x ranging from 2 to 3. Subsequent heating of the intermediate up to 300 °C leads to the total loss of NH₃. The Au–Cl and Au–Au bonds form the local environment of Au at the stage of decomposition while only four chlorine atoms are around Pd. At the temperature of 330 °C the Au and Pd nanoparticles as well as residues of palladium chloride are detected. The final product consists of separated Au and Pd nanoparticles.     

Thermal study of the Ce<Subscript>0.9</Subscript>Tb<Subscript>0.1</Subscript>O<Subscript>2</Subscript> pigment prepared by different synthesis

The inorganic ceramic compounds based on the CeO₂ belong into the group of high-temperature pigments. The pigments have been prepared by the classical dry process (i.e. solid-state reaction) in the temperature range from 1,300 to 1,600 °C and by the coprecipitation at the three different temperatures: 400, 600 and 1,100 °C. The principal of these pigments makes the host lattice of the CeO₂, which is doped by terbium ions. This incorporation of the doped ions leads to obtaining of the interesting dark orange colour after application into ceramic glaze. The aim of our research was to improve and optimize the synthesis conditions of these pigments. The samples were submitted to thermal analysis (TG–DTA) for determination of the temperature interval of the pigment formation and the thermal stability of pigments. The compounds were also measured from the point of view of their colouring, structure and particle size distribution.     

Electrical conductivity studies in the system Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript>-Li<Subscript>1.33</Subscript>Ti<Subscript>1.67</Subscript>O<Subscript>4</Subscript>

Electrical conductivity in the monoclinic Li₂TiO₃, cubic Li_1.33Ti_1.67O₄, and in their mixture has been studied by impedance spectroscopy in the temperature range 20–730 °C. Li₂TiO₃ shows low lithium ion conductivity, σ₃₀₀≈10^–6 S/cm at 300 °C, whereas Li_1.33Ti_1.67O₄ has 3×10^–8 at 20 °C and 3×10^–4 S/cm at 300 °C. Structural properties are used to discuss the observed conductivity features. The conductivity dependences on temperature in the coordinates of 1000/T versus log_e(σT) are not linear, as the conductivity mechanism changes. Extrinsic and intrinsic conductivity regions are observed. The change in the conductivity mechanism in Li₂TiO₃ at around 500–600 °C is observed and considered as an effect of the first-order phase transition, not reported before. Formation of solid solutions of Li_{2– x} Ti_{1+ x} O₃ above 900 °C significantly increases the conductivity. Irradiation by high-energy (5 MeV) electrons causes defects and the conductivity in Li₂TiO₃ increases exponentially. A dose of 144 MGy yields an increase in conductivity of about 100 times at room temperature. Electronic Publication     

Synthesis of electrospun BaSrTiO<Subscript>3</Subscript>/PVP nanofibers

Ba_1−x Sr _x TiO₃(x = 0–0.5, BST) nanofibers with diameters of 150–210 nm were prepared by using electrospun BST/polyvinylpyrrolidone (PVP) composite fibers by calcination for 2 h at temperatures in the range of 650–800 °C in air. The morphology and crystal structure of calcined BST/PVP nanofibers were characterized as functions of calcination temperature and Sr content with an aid of XRD, FT-IR, and TEM. Although several unknown XRD peaks were detected when the fibers were calcined at temperatures less than 750 °C, they disappeared with increasing the temperature (above 750 °C) due to its thermal decomposition and complete reaction in the formation of BST. In addition, the FT-IR studies of BST/PVP fibers revealed that the intensities of the O–H stretching vibration bands (at 3430 and 1425 cm⁻¹) became weaker with increasing the calcination temperature and a broad band at 540 cm⁻¹, Ti–O vibration, appeared sharper and narrower after calcination above 750 °C due to the formation of metal oxide bonds. However, no effect of Sr content on the crystal structure of the composites was detected.     

Kinetics of formation of barium tungstate in equimolar powder mixture of BaCO<Subscript>3</Subscript> and WO<Subscript>3</Subscript>

The formation of Barium monotungstate (BaWO₄) particles in equimolar powder mixtures of BaCO₃ and WO₃ was examined under isothermal and non-isothermal conditions upon heating in air at 25–1200 °C, using thermogravimetry. Concurrence of the observed mass loss (due to the release of CO₂) to the occurrence of the formation reaction was evidenced. Accordingly, the extent of reaction (x) was determined as a function of time (t) or temperature (T). The x–t and x–T data thus obtained were processed using well established mathematical apparatus and methods, in order to characterize nature of reaction rate-determining step, and derive isothermal and non-isothermal kinetic parameters. Moreover, the reaction mixture quenched at various temperatures (600–1,000 °C) in the reaction course was analyzed by various spectroscopic and microscopic techniques, for material characterization. The results obtained indicated that the reaction rate may be controlled by unidirectional diffusion of WO₃ species across the product layer (BaWO₄), which was implied to form on the barium carbonate particles. The isothermally determined activation energy (118–125 kJ/mol) was found to be more credible than that (245 kJ/mol) determined non-isothermally.     

Nano-composites SnO(VO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>) as anodes for lithium ion batteries

Nano-composites of SnO(V₂O₃) _x (x = 0, 0.25, and 0.5) and SnO(VO)_0.5 are prepared from SnO and V₂O₃/VO by high-energy ball milling (HEB) and are characterized by X-ray diffraction (XRD), scanning electron microscopy, and high-resolution transmission electron microscopy techniques. Interestingly, SnO and SnO(VO)_0.5 are unstable to HEB and disproportionate to Sn and SnO₂, whereas HEB of SnO(V₂O₃) _x gives rise to SnO₂.VO _x . Galvanostatic cycling of the phases is carried out at 60 mA g⁻¹ (0.12 C) in the voltage range 0.005–0.8 V vs. Li. The nano-SnO(V₂O₃)_0.5 showed a first-charge capacity of 435 (±5) mAh g⁻¹ which stabilized to 380 (±5) mAh g⁻¹ with no noticeable fading in the range of 10–60 cycles. Under similar cycling conditions, nano-SnO (x = 0), nano-SnO(V₂O₃)_0.25, and nano-SnO(VO)_0.5 showed initial reversible capacities between 630 and 390 (±5) mAh g⁻¹. Between 10 and 50 cycles, nano-SnO showed a capacity fade as high as 59%, whereas the above two VO _x -containing composites showed capacity fade ranging from 10% to 28%. In all the nano-composites, the average discharge potential is 0.2–0.3 V and average charge potential is 0.5–0.6 V vs. Li, and the coulombic efficiency is 96–98% after 10 cycles. The observed galvanostatic cycling, cyclic voltammetry, and ex situ XRD data are interpreted in terms of the alloying–de-alloying reaction of Sn in the nano-composite “Sn-VO _x -Li₂O” with VO _x acting as an electronically conducting matrix.     

Effect of heat treatment on electrochromic properties of TiO<Subscript>2</Subscript> thin films

Electrochromic titanium oxide (TiO₂) films were deposited on ITO/glass substrates by chemical solution deposition (CSD). The stock solutions were spin-coated onto substrates and then heated at various temperatures (200–500 °C) in various oxygen concentrations (0–80%) for 10 min. The effects of the processing parameters on the electrochromic properties of TiO₂ films were investigated. X-ray diffraction measurements demonstrated that the amorphous TiO₂ films were crystallized to form anatase films above 400 °C. The electrochromic properties and transmittance of TiO₂ films were measured in 1 M LiClO₄–propylene carbonate (PC) non-aqueous electrolyte. An amorphous 350 nm-thick TiO₂ film that was heated at 300°C in 60% ambient oxygen exhibited the maximum transmittance variation (ΔT%), 14.2%, between the bleached state and the colored state, with a ΔOD of 0.087, Q of 10.9 mC/cm², η of 7.98 cm²/C and x in Li _x ClO₄ of 0.076 at a wavelength (λ) of 550 nm.     

Low-temperature NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Selective Reduction by Hydrocarbons on H-Mordenite Catalysts in Dielectric Barrier Discharge Plasma

Toward achieving selective catalytic reduction of NO _x by hydrocarbons at low temperatures (especially lower than 200 °C), C₂H₂ selective reduction of NO _x was explored on H-mordenite (H-MOR) catalysts in dielectric barrier discharge (DBD) plasma. This work reported significant synergistic effects of DBD plasmas and H-MOR catalysts for C₂H₂ selective reduction of NO _x at low temperatures (100–200 °C ) and across a wide range of O₂ content (0–15%). At 100 °C, NO _x conversions were 3.3, 11.6 and 66.7% for the plasma alone, catalyst alone and in-plasma catalysis (IPC) cases (with a reactant gas mixture of 500 ppm NO, 500 ppm C₂H₂, 10% O₂ in N₂, GHSV = 12,000 h⁻¹ and input energy density of 125 J L ⁻¹), respectively. At 200 °C, NO _x conversions were 3.8, 54.0 and 91.4% for the above three cases, respectively. Also, strong signals of hydrogen cyanide (HCN) byproduct were observed in the catalyst alone system by an on-line mass spectrometer. By contrast, almost no HCN was detected in the IPC system.     

Phase relations in the Zn<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>-Cu<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript> system from room temperature to melting

Phase relations in the Zn₂V₂O₇-Cu₂V₂O₇ system were studied by high-temperature X-ray diffraction and differential thermal analysis. The major phase constituents of the system are solid solutions based on Zn₂V₂O₇ and Cu₂V₂O₇ polymorphs and their coexistence regions. The generation of α-Zn_{2 − 2x} Cu_2x V₂O₇ solid solution, where 0 ≤ x ≤ 0.30, leaves almost unchanged the stabilization temperature of the high-temperature zinc pyrovanadate phase. The α-Cu_{2 − 2x} Zn_2x V₂O₇ homogeneity range is 5 mol % Zn₂V₂O₇. In the range 0.050 ≤ x ≤ 0.09 from 20 to ∼ 620°C, there is the two-phase field of α-Cu₂V₂O₇ and β-Cu₂V₂O₇ base solid solutions. At still higher temperatures, β-Zn_{2 − 2x} Cu_2x V₂O₇ and α-Cu_{2 − 2x} Zn_2x V₂O₇ coexist in the mixed-phase region. β-Zn_{2 − 2x} Cu_2x V₂O₇ solid solution, where 0 ≤ x ≤ 0.30, exists above 610 ± 5°C. The extent of the β′-Cu₂V₂O₇-base solid solution is 9 to 65 mol % Zn₂V₂O₇ at 615 ± 5°C, expanding to 0 mol % Zn₂V₂O₇ with rising temperature. Original Russian Text ￠ T.I. Krasnenko, M.V. Rotermel’, S.A. Petrova, R.G. Zakharov, O.V. Sivtsova, A.N. Chvanova, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 10, pp. 1755–1762.     

Thermal analysis of CsH<Subscript>2</Subscript>PO<Subscript>4</Subscript> nanoparticles using surfactants CTAB and F-68

A study concerned to thermogravimetric analysis is performed in cesium dihydrogen phosphate (CsH₂PO₄) that was synthesized, using cetyltrimethylammonium-bromide (CTAB), polyoxyethylene-polyoxypropylene (F-68) and mixture of (F-68:CTAB) with two mole ratio 0.06 and 0.12 as surfactant. The dehydration behavior of particles was studied using thermal gravimetric analysis and differential scanning calorimetric. Subsequently, the experimental results indicated that the first dehydration temperature in the range of 237–239 °C upon heating, the second peaks occur at temperature range 290–295 °C and overlapping in the thermogravimetric events is observed. The mass loss values are obtained in the range of 6.62–6.97 wt% that is less than reported theoretical value 7.8 wt%. These values show well compatibility of reaction CsH₂PO₄ to Cs₂H₂P₂O₇ with 3.92 wt% whereas mass loss value of CsH₂PO₄ to CsPO₃ is less than theoretical value 7.8 wt%. The activation energy of two steps dehydration are calculated using Kissinger equation for the samples synthesized via CTAB and (F-68) with minimum value mass loss 6.62% and maximum value mass loss 6.97%, respectively. The calculation results reveal that the reaction rate in the first step (CsH₂PO₄ → Cs₂H₂P₂O₇) is faster than the second step (CsH₂PO₄ → CsPO₃). The weight loss values of the samples demonstrate that existence of CTAB can be considered as effective factor which prevents more weight loss during the dehydration process.     

The microstructure and magnetic properties of Ni<Subscript>0.4</Subscript>Zn<Subscript>0.6</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> films prepared by spin-coating method

Nickel zinc ferrite (Ni_0.4Zn_0.6Fe₂O₄) films on Si (100) substrate were synthesized using a spin-coating method. The crystallinity of the Ni_0.4Zn_0.6Fe₂O₄ films with the thickness of about 386 nm became better as the annealing temperature increased. The films have smooth surface, relatively good packing density and uniform thickness. The volatilization of Zn is serious at 900 °C. With the increase of annealing temperature, the saturation magnetization M _s increases in the temperature ranging from 400 to 700 °C, however, decreases above 700 °C, and the coercivity H _c increases in the temperature range 400–800 °C, decreases above 800 °C. After annealed at 700 °C for 2 h in air with the heating rate 2 °C/min, the film shows a maximum saturation magnetization M _s of 349 emu/cc and low coercivity H _c of 66 Oe. The M _s is higher than others which prepared by this method, however, the H _c is lower. The M _s of Ni_0.4Zn_0.6Fe₂O₄ films annealed at 700 °C increases with increasing annealing time and the H _c changes slightly.     

Surface Modification of Silicone Rubber by CF<Subscript>4</Subscript> Radio Frequency Plasma Immersion

Silicone rubber samples were treated by CF₄ capacitively coupled plasma at radio frequency (RF) power of 60, 100 and 200 W for a treatment time up to 20 min under CF₄ flow rate of 20 sccm, respectively. Static contact angle, ATR-FTIR and XPS, and AFM were employed to characterize the changes of surface on hydrophobicity, functional groups, and topography. The results indicate the static contact angle is improved from 100.7 to 150.2°, and the super-hydrophobic surface, which corresponds to a static contact angle of 150.2°, appears at RF power of 200 W for a 5 min treatment time. It is suggested that the formation of super-hydrophobic surface is ascribed to the co-action of the increase of surface roughness created by the ablation reaction of CF₄ plasma and the formation of [–SiF _x (CH₃)_2−x –O–] _n (x = 1, 2) structure produced by the direct attachment of F atoms to Si.     

Phase diagrams of the KF-K<Subscript>2</Subscript>TaF<Subscript>7</Subscript> and KF-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> systems

The phase diagrams of the systems KF-K₂TaF₇ and KF-Ta₂O₅ were determined using the thermal analysis method. The phase diagrams were described by suitable thermodynamic model. In the system KF-K₂TaF₇ eutectic points at x _KF=0.716 and t=725.4°C and at x _KF=0.214 and t=712.2°C has been calculated. It was suggested that K₂TaF₇ melts incongruently at around 743°C forming two immiscible liquids. The system KF-Ta₂O₅ have been measured up to 8 mol% of Ta₂O₅. The eutectic point was estimated to be at x _KF∼0.9 and t∼816°C. The formation of KTaO₃ and K₃TaO₂F₄ compounds has been observed in the solidified samples.     

Electrochemical performance of rare-earth doped LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel cathode materials for Li-ion rechargeable battery

Spinel powders of LiMn_2−x RE _x O₄ (RE = La, Ce, Nd, Sm; 0 ≤ x ≤ 0.1) have been synthesized by solid-phase reaction. The structure and electrochemical properties of these electrode materials were characterized by X-ray diffraction (XRD), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and charge–discharge experiment. The part substitution of rare-earth element RE for Mn in LiMn₂O₄ decreases the lattice parameter, resulting in the improvement of structural stability, and decreases the charge transfer resistance during the electrochemical process of LiMn₂O₄. As a result, the cycle ability, 55 °C high-temperature and high-rate performances of LiMn_2−x RE _x O₄ electrode materials are significantly improved with increasing RE addition, compared to the pristine LiMn₂O₄.     

Thermal behaviour and fragility of Sb<Subscript>2</Subscript>O<Subscript>3</Subscript>-containing zinc borophosphate glasses

Thermal behaviour of the glass series (100-x)[50ZnO-10B₂O₃-40P₂O₅]·xSb₂O₃ (x=0-42 mol%) and (100-y)[60ZnO-10B₂O₃-30P₂O₅]·ySb₂O₃ (y=0-28 mol%) was investigated by DSC and TMA. The addition of Sb₂O₃ results in a decrease of the glass transition temperature and crystallization temperature in both compositional series. All glasses crystallize on heating in the temperature range of 522–632°C. Thermal expansion coefficient of the glasses monotonously increases with increasing Sb₂O₃ content in both series and varies within the range of 6.6–11.7 ppm °C⁻¹. From changes of thermal capacity within the glass transition region it was concluded that with increasing Sb₂O₃ content the ‘fragility’ of the studied glasses increases.     

Preparation and electrical properties of Nd and Mn co-doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

Ferroelectric thin films of Nd and Mn co-doped bismuth titanate, Bi_3.15Nd_0.85Ti_3−x Mn _x O₁₂ (BNTM) (x = 0–0.1), were fabricated on Pt/TiO₂/SiO₂/Si(100) substrates by a sol–gel technique. The BNTM films had a polycrystalline perovskite structure and uniform and dense surface morphologies. A lattice distortion was observed in the BNTM films due to Mn ion doping. The ferroelectric measurement of the films indicated that the values of coercive field (E _c ) decreased gradually with the increase of the Mn content (x), however, the remanent polarization (P _r ) increase firstly and then decrease with the increase of x. The sample with x = 0.05 had optimum electrical properties and a maximum 2P _r value. The 2P _r and 2E _c values of the film at a maximum applied electric field of 400 kV/cm were 38.3 μC/cm² and 180 kV/cm, respectively. Moreover, this BNTM capacitors did not show fatigue behaviors after 1.0 × 10¹⁰ switching cycles at a frequency of 1 MHz, suggesting a fatigue-free character. The main reason for the increase of the 2P _r and the decrease of the 2E _c might be attributed to the lattice distortion in BNTM films due to Mn ion doping.     

Phase formation in mixed TiO<Subscript>2</Subscript>-ZrO<Subscript>2</Subscript> oxides prepared by sol-gel method

Pure titania, zirconia, and mixed oxides (3–37 mol.% of ZrO₂) are prepared using the sol-gel method and calcined at different temperatures. The calcined samples are characterized by Raman spectroscopy, X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption porosimetry. Measurements reveal a thermal stability of the titania anatase phase that slightly increases in the presence of 3–13 mol.% of zirconia. Practically, the titania anatase-rutile phase transformation is hindered during the temperature increase above 700°C. The mixed oxide with 37 mol.% of ZrO₂ treated at 550°C shows a new single amorphous phase with a surface area of the nanoparticles double with respect to the other crystalline samples and the formed srilankite structure (at 700°C). The anatase phase is not observed in the sample containing 37 mol.% of ZrO₂. The treatment at 700°C causes the formation of the srilankite (Ti_0.63Zr_0.37O_x) phase.     

Chemisorption of SO<Subscript>2</Subscript> on the Zn-modified In<Subscript>2</Subscript>O<Subscript>3</Subscript> surface

Chemisorption of SO₂ and O₂ on the In₂O₃ surface containing a zinc additive (0.4–2.7 at.%) was studied in a temperature range of 22–200 °C. At least three forms of sorbed SO₂ exist on the modified In₂O₃ surface. The temperature affects the contribution of single forms of SO₂ sorption and, hence, the change in the electric conductivity. The preliminary sorption of O₂ favors the formation of a donor form of chemisorbed SO₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2228–2232, October, 2005.     

Comparing the electrochemical properties of pure phase Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript> and composite Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript>/C

Compound Zn₂SnO₄ was synthesized by a hydrothermal method in which SnCl₄ · 5H₂O, ZnCl₂ and N₂H₄ · H₂O were used as reactants. Composite Zn₂SnO₄/C was then synthesized through a carbothermic reduction process using the as-prepared Zn₂SnO₄ and glucose as reactants. Comparing to the pure Zn₂SnO₄, some improved electrochemical properties were obtained for composite Zn₂SnO₄/C. When doped with 15% glucose, the composite Zn₂SnO₄/C showed the best electrochemical performance. Its first discharge capacity was about 1500 mA h g⁻¹, with a capacity retain of 500 mA h g⁻¹ in the 40th cycle at a constant current density of 100 mA/g in the voltage range of 0.05–3.0 V. There were also some differences displayed in their cyclic voltammogram.     

Thermal analysis of doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>

New environmentally inorganic pigments based on Bi₂O₃ doped by metal ions, such as Zr⁴⁺ and Dy³⁺ have been developed and characterized using the methods thermal analysis, X-ray powder diffraction, and spectral reflectance data. The compounds having formula Bi_2−x Dy _x/2Zr_3x/8O₃ (x = 0.2, 0.6, 1.0, and 1.2) were prepared by the solid state reaction. Methods of thermal analysis were used for determination of the temperature region of the pigment formation and thermal stability of compounds. The incorporation of doped ions in Bi₂O₃ changes the color from yellow to orange and also contributes to a growth of their thermal stability. This property gives a direction for coloring ceramic glazes.