Structural and electrical properties of SrBi2(Ta0.5Nb0.5)2O9 thin films

SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBTN) thin films were obtained by polymeric precursor method on Pt/Ti/SiO₂/Si(1 0 0) substrates. The film is dense and crack-free after annealing at 700 °C for 2 h in static air. Crystallinity and morphological characteristic were examined by X-ray diffraction (XRD), field emission scanning electron microscopy (FEG-SEM) and atomic force microscopy (AFM). The films displayed rounded grains with a superficial roughness of 3.5 nm. The dielectric permittivity was 122 with loss tangent of 0.040. The remanent polarization (P_r) and coercive field (E_c) were 5.1 μC/cm² and 96 kV/cm, respectively.     

Preparation of epitaxial and polycrystalline bismuth titanate thin films on single crystal (100) MgO by chemical solution deposition

Epitaxial and polycrystalline Bi₄Ti₃O₁₂ thin films were prepared on single crystal (100) MgO substrates by a chemical solution deposition process using metal naphthenates as starting materials. Pyrolyzed films (at 500°C) were annealed for 30 min in air at 650, 700, 750 and 800°C, respectively. The effects of annealing temperature on the crystallinity, epitaxy and surface morphology of the films were investigated by X-ray diffraction θ-2θ scans, pole-figure analysis, and atomic force microscopy (AFM). Epitaxially grown films annealed at 700 and 750°C, respectively, showed growth of three-dimensional needle-shaped grains. During annealing at 800°C, grain growth of Bi₄Ti₃O₁₂ may be suppressed by the formation of a titanium-rich phase such as Bi₂Ti₂O₇ owing to Bi volatilization, resulting in lower root mean square roughness than that of film annealed at 750°C.     

Effect of sintering temperature on the structure and properties of cerium-doped 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 piezoelectric ceramics

Phase structure, microstructure, dielectric and piezoelectric properties of 0.4 wt% CeO₂ doped 0.94(Bi_0.5Na_0.5)TiO₃–0.06BaTiO₃ (Ce-BNT6BT) ceramics sintered in the temperature range from 1120 to 1200 °C have been investigated as a candidate for lead-free piezoelectric ceramics. Tetragonal phase played an important role in improvement of electrical properties and the density of the ceramics. Dielectric constant decreased slightly with the increase of sintering temperature in ferroelectric region but a reverse phenomenon occurred in antiferroelectric and paraelectric regions, suggesting that interfacial polarizations were improved with the increase of sintering temperature and domain walls of ferroelectricity became active after depolarization. At room temperature, Ce-BNT6BT ceramics sintered at 1180 °C showed good performances: dielectric constant was 914 at 1 kHz, thick coupling factor k_t was 0.52, and the ratio of k_t/k_p was 2.3. The ceramics were suitable for narrowband filters and ultrasonic transducers in commercial applications.     

Er-doped SiO2–Al2O3 thin films prepared by the sol–gel route

The synthesis of homogeneous and pure silica–alumina binary glasses doped with rare-earth (RE) ions such as Er³⁺ is currently a key challenge for the development of integrated optics devices such as lasers, optical amplifiers or waveguides. In this study Er³⁺-doped SiO₂–Al₂O₃ films were prepared by the sol–gel route. Aluminium sec-butoxide, Al(O-sec-C₄H₉)₃ (ASB), and tetraethoxysilane, Si(OC₂H₅)₄ (TEOS), were used as glass oxide precursors, whereas erbium was introduced as Er(NO₃)₃. The alumina content in the silica matrix was 10 at.%, while erbium doping ranged between 200 and 5000 ppm. The preparation of the starting sol–gel solution and the layer deposition by a dip-coating procedure were performed in dry-box under nitrogen atmosphere. The obtained films were subsequently annealed in air between 300 and 1000 °C. After treatment at 500 °C, layers 200 nm thick were obtained. The composition, microstructure and surface morphology of the films were investigated by X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS), glancing incidence X-ray diffraction (GIXRD) and atomic force microscopy (AFM). Crack-free, transparent, high purity films were obtained, characterised by compositional and microstructural homogeneity.     

MmM5/Mg multi-layer hydrogen storage thin films prepared by dc magnetron sputtering

MmNi_3.5(CoAlMn)_1.5/Mg (here Mm denoted for mischmetal) multi-layer thin films were deposited on (0 0 1) Si substrate by direct current (dc) magnetron sputtering with dual-target. X-ray diffraction (XRD) and scanning electron microscopy analysis revealed that the microstructure of the MmNi_3.5(CoAlMn)_1.5 layer is amorphous and/or nanocrystalline and that the microstructure of the Mg layer is fine grained crystalline with preferential orientation. Phase analysis of hydrogenated and dehydrogenated MmNi_3.5(CoAlMn)_1.5/Mg multi-layer thin films proved that an apparent absorption of hydrogen in the Mg layer occurs at temperatures higher than 200 °C and that the hydrogen absorbed can be fully released at 250 °C.     

Existence, structure and valence properties of the skutterudites CeyFe4−xCoxSb12

We report on sample preparation, annealing effects, electron microprobe analysis in the series Ce_yFe_4−xCo_xSb₁₂ which shows that a phase separation occurs for substituted samples (0<x<4) annealed at 650 and 550 °C. Single phase samples are obtained for either Ce_yFe₄Sb₁₂ or Ce_yCo₄Sb₁₂ samples annealed at 650 °C and for all compositions when annealed at 700 °C. The valence state of Ce in homogeneous samples has been studied using X-ray absorption spectroscopy (XAS). Ce ions are trivalent throughout the series and the XAS spectra does not show effect of the crystal field on the 5d-final state.     

Sm0.5Sr0.5CoO3 cathode material from glycine-nitrate process: Formation, characterization, and application in LaGaO3-based solid oxide fuel cells

Cathode material Sm_0.5Sr_0.5CoO₃ (SSC) with perovskite structure for intermediate temperature solid oxide fuel cell was synthesized using glycine-nitrate process (GNP). The phase evolution and the properties of Sm_0.5Sr_0.5CoO₃ were investigated. The single cell performance was also tested using La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) as electrolyte and SSC as cathode. The results show that the formation of perovskite phase from synthesized precursor obtained by GNP begins at a calcining temperature of 600 °C. The single perovskite phase is formed completely after sintering at a temperature of 1000 °C. The phase formation temperature for SSC with complete single perovskite phase is from 1000 to 1100 °C. The SrSm₂O₄ phase appeared in the sample sintered at 1200 °C. It is also found that the sample sintered at 1200 °C has a higher conductivity. The electrical conductivity of sample is higher than 1000 S/cm at all temperature examined from 250 to 850 °C, and the highest conductivity reaches 2514 S/cm at 250 °C. The thermal expansion coefficient of sample SSC is 22.8 × 10⁻⁶ K⁻¹ from 30 to 1000 °C in air. The maximum output power density of LSGM electrolyte single cell attains 222 and 293 mW/cm² at 800 and 850 °C, respectively.     

Active soldering of ZnS–SiO2 sputtering targets to copper backing plates using an Sn3.5Ag4Ti(Ce, Ga) filler metal

An Sn3.5Ag4Ti(Ce, Ga) active solder is used for joining ZnS–SiO₂ ceramic sputtering targets with copper backing plates at 250 °C in air. Direct soldering using the Sn3.5Ag4Ti(Ce, Ga) metal filler has been found to be a reliable and simple technique for ZnS–SiO₂ ceramic bonding with ZnS–SiO₂ and copper. The shear strengths for ZnS–SiO₂/ZnS–SiO₂ and ZnS–SiO₂/Cu joints are 6.5 and 5.2 MPa, respectively. The bonding mechanism is described, with emphasis placed on the action of a rare earth element (Ce) and the active metal reaction. The interfacial reaction between Sn3.5Ag4Ti(Ce, Ga) filler metal and copper at temperatures ranging from 120 to 200 °C is conducted and discussed.     

Effect of annealing on the morphology evolution and densification of LiMn2O4 film from chitosan-containing solution

Dense LiMn₂O₄ films deposited on a Pt-coated silicon substrate were obtained by annealing the deposited Li–Mn–O-chitosan films under a two-stage heat-treatment procedure. It was demonstrated that the heat-treatment at 300 °C plays an important role in the subsequent densification of LiMn₂O₄ films. This is attributed to the formation and rearrangement of the nano-sized LiMn₂O₄ crystallites. The surface morphology of the calcined Li–Mn–O-chitosan films was highly related to the annealing temperature. Ridge-like bumps formed on the surface of the films after being heated at 200 °C for 1 h. With calcination at 400 °C or higher, the surface morphology turned into a wrinkle-like microstructure. This morphology transformation is ascribed to the flowing characteristics of the Li–Mn–O-chitosan films during heat-treatment and subsequent thermal decomposition of the precursor at higher temperatures. Moreover, the electrochemical tests showed that the 700 °C-annealed LiMn₂O₄ film possesses the highest discharge capacity of 56.3 μA h/(cm² μm) and best capacity retention of 90.7% after 50 charge/discharge cycles of all annealed films.     

Growth kinetics and oxidation behavior of WSi2 coating formed by chemical vapor deposition of Si on W substrate

The growth kinetics of WSi₂ coating formed by chemical vapor deposition (CVD) of Si on a W substrate at temperatures between 1000 and 1200 °C using SiCl₄–H₂ gas mixtures was investigated and its isothermal oxidation resistance in 80% Ar–20% O₂ atmosphere was evaluated at temperatures between 800 and 1300 °C. WSi₂ coating grew with a parabolic rate law after an initial incubation period, indicating the diffusion-controlled growth. The activation energy for growth of WSi₂ coating was about 42.5 kcal/mol. The isothermal oxidation rate of WSi₂ coating increased with increasing oxidation temperature but rapidly decreased at 1300 °C. The oxidation product of WSi₂ coating was composed of the WO₃ particles embedded in the amorphous SiO₂ matrix at below 1200 °C but consisted of only SiO₂ phase at 1300 °C. The fast oxidation behavior of WSi₂ coating at below 1200 °C was attributed to the formation of many cracks and pores, i.e. short-circuit diffusion path of oxygen, within the oxide scale, which resulted from the internal stress generated both by the large volume expansion caused by the oxidation reactions of WSi₂ and by the evaporation of WO₃ phase. The slow oxidation behavior of WSi₂ coating at 1300 °C was due to the exclusive formation of a slow-growing continuous SiO₂ scale by the rapid evaporation of WO₃ phase.     

High temperature oxidation behavior of Ti3SiC2-based material in air

The oxidation behavior of Ti₃SiC₂-based material in air has been studied from 900°C to 1200°C. The present work showed that the growth of the oxide scale on Ti₃SiC₂-based material obeyed a parabolic law from 900°C to 1100°C, while at 1200°C it followed a linear rule. The oxide scale was generally composed of an outer layer of coarse-grained TiO₂ (rutile) and an inner layer of fine-grained TiO₂ and SiO₂ (tridymite) above 1000°C. A discontinuous coarse-grained SiO₂ layer was observed within the outer coarse-grained TiO₂ layer on the samples oxidized at 1100°C and 1200°C. Marker experiments showed that the oxidation process was controlled by the inward diffusion of oxygen, outward diffusion of titanium and CO or SiO, and that internal oxidation predominated. The TiC content in Ti₃SiC₂ was deleterious to the oxidation resistance of Ti₃SiC₂.     

Formation and chemical leaching effects of nonequilibrium Al0.6(Fe25Cu75) alloy powder produced by rod milling

The formation and chemical leaching effects of a nonequilibrium Al_0.6(Fe₂₅Cu₇₅)_0.4 powder produced by rod milling is described. X-ray diffraction, transmission electron microscopy, differential scanning calorimetry and vibrating sample magnetometry were used to characterize both the as-milled and leached specimens. After 400 h of milling, only the bcc AlFe phase with an amorphous phase was detected in the XRD patterns. The crystallite size for the bcc AlFe phase (110) after 400 h of milling was about 5.3 nm. The peak temperature and the crystallization temperature of the as-milled powders were 448.7 and 428.0 °C, respectively. Al atoms leaching from the as-milled bcc AlFe powders in the L1 condition did not alter the diffraction pattern significantly, even though Al atoms had been removed. After the L1 specimen was annealed at 500 °C for 1 h, the bcc AlFe phase transformed to the fcc Cu, Fe, and CuFe₂O₄ phases. The peak widths of L1 and L2 specimens were similar, but became broader than that of the as-milled powder. The saturation magnetization decreased with increasing milling time, and a value of 10.4 emu/g was reached after 400 h of milling. After cooling the specimen from 750 °C, the magnetization slowly increased at approximately 491.4 °C, indicating that the bcc AlFe phase had transformed to the fcc Cu and Fe phases.     

Synthesis of iron（Ⅲ）-doped nanostructure TiO2/SiO2 and their photocatalytic activity

Iron(Ⅲ)-doped nanostructure TiO2-coated SiO2 (TiO2/SiO2) particles were prepared using the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized employing the sol-gel method with TiCl4 as a precursor. The samples were characterized by Fourier transform infrared spectroscopy (FTIR), SEM, EDS, XPS, and XRD. The experimental results show that TiO2 nanopowders on the surface of SiO2 particles are well distributed, the amount of TiO2 is increased with the adding of coating layers, the pure anatase-TiO2 coating layers are synthesized at 500℃, and the photocatalytic activity of Fe3 -doped TiO/SiO2 is higher than tnat of undoped TiO2/SiO2.     

Preparation of neodymium sulphides by the reaction of Nd2(So4)3 with carbon disulphide

The reaction to synthetize neodymium sulphides from neodymium sulphate octahydrate in a stream of carbon disulphide gas was studied. The dehydration of the octahydrate in vacuum was finished at 300 °C. At 1050–1100 °C in air neodymium oxysulphide, Nd₂O₂SO₄, was formed. Neodymium oxysulphide, Nd₂O₂S, was formed upon heating with a reducing agent such as annealed carbon. The reaction of neodymium sulphate with carbon disulphide commenced at 500–600 °C, resulting in formation of the disulphide, NdS₂. The crystal structure of NdS₂ heated at 500 °C was, however, different from that of the sample heated at 600 °C. In the temperature range 800–900 °C -Nd₂S₃ was obtained as a single phase after heating for at least 3 h in high flow rates of gas mixtures of nitrogen and high concentrations of carbon disulphide. The sesquisulphide, γ-Nd₂S₃ (or Nd₃S₄), was formed at temperatures as high as 1100 °C. The reaction conditions for the compounds mentioned above are discussed together with the analysis of their crystal structures by X-ray powder diffractometry.     

Low temperature oxidation of Cr-alloyed MoSi2

Cr-alloyed MoSi2 was compared with monolithic MoSi2 with respect to oxidation at 450℃ for 456 h. Phases formed on Cr-alloygd MoSi2 after exposure are Cr2（MoO4）3, MOO3, and cristobalite （SiO2） according to X-ray diffraction results. Monolithic MoSi2 forms MoO3 and mainly amorphous SiO2. X-ray photoelectron spectroscopy indicates that the main oxidation product on the outermost surface is SiO2 for all studied samples. The samples form a relatively loose oxide but the oxide adherence improves with increasing Cr content. It is indicated that Cr addition can benefit pesting control in MoSi2.     

Solid state reactions in highly dispersed praseodymium oxide–SiO2 system

This paper reports results of studies on the interaction of praseodymium oxide nanocrystals with an amorphous silica. Nano-sized (3–4 nm) amorphous precursor of praseodymium oxide synthesized using a microemulsion technique were supported onto a high surface SiO₂ or occluded into SiO₂ matrix. Solid state reactions occurring in these binary systems upon heat treatment in air, argon or hydrogen at 800–1100 °C were studied by TEM, XRD, FT-IR and UV–vis spectroscopy. It has been found that morphology of the sample as well as annealing atmosphere influence greatly the phase evolution. At temperatures above 900 °C, nanocrystalline praseodymium silicates of various morphology and crystal structure were obtained. In particular, a new polymorph of Pr₂Si₂O₇, isostructural with I-type Ln₂Si₂O₇ (Ln₆[Si₄O₁₃][SiO₄]₂) Ln = Ce, La, has been identified.     

Achieving tensile superplasticity in 8 mol% Y2O3 cubic stabilized ZrO2 through the addition of intergranular silica

The addition of 5 wt.% SiO₂, a viscous second phase, to 8 mol% Y₂O₃ cubic stabilized ZrO₂ (8Y-CSZ) made superplastic 8Y-CSZ. This material had a fine grain size of 0.4 μm and exhibited deformations in tension as large as 520% at 1430 °C with a strain rate of 1.0 × 10⁻⁴ s⁻¹.     

Preparation and luminescent properties of europium-activated YInGe2O7 phosphors

Effects of precursor milling on phase evolution and morphology of mullite (3Al₂O₃·2SiO₂) processed by solid-state reaction have been investigated. Alumina and silica powders were used as starting materials and milling was taken place in a medium energy conventional ball mill and a high-energy planetary ball mill. Milling in a conventional ball mill although decreases mullite formation temperature by 200 °C, but does not considerably change mullite phase morphology. Use of a planetary ball mill after 40 h of milling showed to be much more effective in activating the oxide precursors, and mullitization temperature was reduced to below 900 °C. Whisker like mullite was formed after sintering at 1450 °C for 2 h and volume fraction of this structure was increased by increasing the milling time. XRD results showed that samples mechanically activated for 20 h in the planetary ball mill were fully transformed to mullite after sintering at 1450 °C, whereas Al₂O₃ and SiO₂ phases were still detected in the samples milled in the conventional ball mill for 20 h and then sintered at the same conditions.     

Characteristics and properties of surface coated nano-TiO2

Nano-TiO₂ was coated with Al₂O₃, SiO₂ and silane coupling agent by chemical liquid deposition. The coating was characterized by Raman spectroscopy, XRD, TEM and FT-IR. The coating content and anti-ultraviolet capacity of nano-TiO₂ were measured by XRF and UV-vis spectrometer. The results show that dense coatings containing 5% Al₂O₃ or SiO₂ can be obtained by mixing slurry at pH 10, adding coating reagent and neutralization reagent into the slurry for 60 min at 85–95 °C, and finally aging for 120 min. Noncrystal SiO₂ was coated on the surface of nano-TiO₂ to form silica gel polymer with a Ti—O—Si bond, while aluminum compound exists in the form of AlOOH and part Al(OH)₃. The integrated dense film can shield photocatalysis effectively. The inorganic coating film can increase the wettability for xylene and stability in water. The surface modification of nano-TiO₂ will not impair its ability for anti-ultraviolet radiation, and more short band ultraviolet radiation can be absorbed. In addition, the optimal coating amount of silane coupling agent should be less than 3% and the best wettability for xylene can be reached when the amount is 1.2%.     

Structure and electrochemical properties of Li(Ni0.5Mn0.5)1-xTixO2 prepared by one-step solid state reaction

The layered compound Li(Ni_0.5Mn_0.5)_1-xTi_xO₂ powders were prepared with Ni(OH)₂, MnCO₃, Li₂CO₃ and TiO₂ by one-step solid state reaction. The effect of doping Ti on the structure and electrochemical properties was studied. The XRD results indicate that the powders with 0≤x≤0.05 have good layered structure and trace of impurity appears in the samples with x≥0.1. The SEM photographs show that the particle size distributes homogeneously and the sample with x=0.15 has larger particle size than other samples. The charge-discharge tests show that Li(Ni_0.5Mn_0.5)_0.95Ti_0.05O₂ synthesized at 800 °C for 36 h exhibits good electrochemical properties. It firstly delivers 173 mA·h/g and maintains 90% of the initial discharge capacity after 30 cycles. The cyclic voltammetry and differential capacity vs voltage curves show that the major oxidation and reduction peaks are around 3.95 V and 3.75 V, respectively, assigned to Ni²⁺/Ni⁴⁺ oxidation-reduction process. A weak peak around 4.5 V is found during the oxidation process in the first cycle, which can be regarded as the main reason of the large drop of discharge capacity in the initial cycle.