Thermoluminescence glow curves analysis of pure and CeO2-doped Li2O-Al2O3-SiO2 glass ceramics

A comparative study of the thermoluminescence (TL) emission between beta-irradiated lithium aluminosilicates, Li₂O-Al₂O₃-SiO₂ (LAS), and beta-irradiated CeO₂-doped lithium aluminosilicates, Li₂O-Al₂O₃-SiO₂-CeO₂ (LAS:Ce), grown by sol-gel technique and preannealed at 1250 °C is presented. It is found that doping reinforces the result of preannealing the sample; the incorporation of CeO₂ at low concentrations shifts the TL curves towards higher temperatures and increases the total intensity with respect to samples without the dopant. This behavior, together with the fact that CeO₂ is a good densification agent, suggests the possibility of using CeO₂ to improve the technological properties of LAS. Deconvolution analysis of the thermoluminescence glow curves of doped materials under general order kinetics shows that the relevant temperatures at which the component signals appear are virtually the same as for pure samples. This suggests that CeO₂ does not introduce new types of traps, but only changes the population and distribution of impurities responsible for the TL in the original matrix of LAS. Finally, the kinetic parameters for the deconvoluted curves are reported. They corroborate that changes in CeO₂ concentration only vary the depth and distribution of the same kind of original traps.     

Synthesis of Au-CeO2/SiO2 catalyst via adsorbed-layer reactor technique combined with alcohol-thermal treatment

Au-CeO₂/SiO₂ was prepared via adsorbed-layer reactor technique combined with alcohol-thermal treatment. The catalytic performance in complete oxidation of benzene was investigated. TEM, Raman characterization showed that Au particles grew up obviously during alcohol-thermal process, while CeO₂ particles maintained 4 nm in diameter. The content of oxygen vacancies and adsorbed oxygen species on catalysts surface increased apparently. Alcohol-thermally treated Au-CeO₂/SiO₂ and CeO₂/SiO₂ showed similar change in catalytic performance, and were much superior to calcined CeO₂/SiO₂. Of alcohol-thermally treated and calcined CeO₂/SiO₂, initial temperatures of the reaction were 80 °C and 150 °C, respectively. The benzene conversions reached 85% and 40% at 300 °C.     

Characterization of Pd-CeOx interaction on α-Al2O3 support

The Pd-Ce interaction was studied over CeO₂ (0.3-2.5 wt.%)-Pd (1 wt.%)/α-Al₂O₃ catalysts used in the reforming reaction of CH₄ with CO₂. The samples were characterized by using high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). The activity and selectivity behavior was in good agreement with that of other supported metal catalysts (Ni and Pd) modified with different promoters. The preliminary results of HRTEM would indicate that the CeO_x forms small crystallites around the Pd particle. The XPS analysis for the regions of Ce 3d and Pd 3d, gives an account of Ce being present mostly as Ce³⁺ and a high binding energy for Pd 3d_5/2 (335.3 eV), an evidence of Pd-Ce chemical interaction. The Pd/Al XPS intensity ratios vs. the Pd average particle size, determined by TEM, show an excellent correlation for fresh and used catalyst. These results indicate that the diminution of the Pd/Al ratios was due to Pd sintering. Consequently, the small amounts of CeO_x species do not cover the Pd particle, in agreement with the HRTEM results. The overall results stand for the promoter action mechanism of the CeO_x for the reforming reaction with CO₂.     

The effect of TiO2 addition on the crystallization and phase formation in lithium aluminum silicate (LAS) glasses nucleated by P2O5

We have prepared lithium aluminum silicate (LAS) glasses of compositions (wt%) 10.6Li₂O-71.7SiO₂-7.1Al₂O₃-4.9K₂O-3.2B₂O₃-2.5P₂O₅(LAS-P) and 10.6Li₂O-71.7SiO₂-7.1Al₂O₃-4.9K₂O-3.2B₂O₃-1.25P₂O₅-1.25TiO₂ (LAS-PT) by the conventional melt quench technique. P₂O₅ and TiO₂ are added as nucleating agents to transform them into glass ceramics. We have studied the interdependence of different phases formed, microstructure, thermal expansion coefficient (TEC), and microhardness (MH) using X-ray diffraction (XRD), scanning electron microscopy (SEM), thermo-mechanical analysis (TMA), and MH (μ-hardness) measurements. The incorporation of TiO₂, in addition to P₂O₅, greatly affects phase evolution and morphology, thereby affecting the thermo-physical properties. Its presence resulted in the formation of only lithium disilicate phase in LAS-PT samples as compared to lithium disilicate and quartz in LAS-P samples on heat treatment at 820 °C. This produced low-aspect-ratio plate-like crystallites in LAS-PT vis-à-vis granular microstructure in LAS-P. Consequently due to the combined effect of both phase formation and morphology a single-phase glass ceramic with overall higher MH, TEC, and glass transition temperature (T_g) is produced.     

Synthesis and fine patterning of organic-inorganic composite SiO2-Al2O3 thick films

Organic-inorganic composite SiO₂-Al₂O₃ films have been prepared by sol-gel using methacryloxypropyl trimethoxysilane and aluminum sec-butoxide as the precursors. By introduction of organic groups into the inorganic backbone, the smooth and crack-free films could be readily achieved by a one-step dip-coating process, with the thickness up to 4.6 μm after being post-baked at 200 °C for 2 h. The films presented in an amorphous phase with an acceptable chemical homogeneity. Owing to the formation of chelate rings, the gel films showed a strong photosensitivity to ultraviolet light at 325 nm. The uniform fine patterns of SiO₂-Al₂O₃ thick films could be well defined by ultraviolet light imprinting simply using a mask. These performances of SiO₂-Al₂O₃ films indicate the potential for integrated optical systems.     

In-situ XAS study on the Cu and Ce local structural changes in a CuO-CeO2/Al2O3 catalyst under propane reduction and re-oxidation

The redox behaviour of a CuO-CeO₂/Al₂O₃ catalyst is studied under propane reduction and re-oxidation. The evolution of the local Cu and Ce structure is studied with in-situ transmission X-ray absorption spectroscopy (XAS) at the Cu K and Ce L₃ absorption edges.CuO and CeO₂ structures are present in the catalyst as such. No structural effect on the local Cu structure is observed upon heating in He up to 873 K or after pre-oxidation at 423 K.Exposure to propane at reaction temperature (600-763 K) fully reduces the Cu²⁺ cations towards metallic Cu⁰. Quick EXAFS spectra taken during reduction show a small amount of intermediate Cu¹⁺ species. Parallel to the CuO reduction, CeO₂ is also reduced in the same temperature range. About 25% of the Ce⁴⁺ reduces rapidly to Ce³⁺ in the 610-640 K temperature interval, while beyond 640 K a further slower reduction of Ce⁴⁺ to Ce³⁺ occurs. At 763 K, Ce reduction is still incomplete with 32% of Ce³⁺.Re-oxidation of Cu and Ce is fast and brings back the original oxides.The propane reduction of the CuO-CeO₂/Al₂O₃ catalyst involves both CuO and CeO₂ reduction at similar temperatures, which is ascribed to an interaction between the two compounds.     

Structural and optical characterization of Ce-doped Gd2SiO5 films by sol-gel technique

Cerium-doped Gd₂SiO₅ (GSO:Ce) films have been prepared on (1 1 1) silicon substrates by the sol-gel technique. Annealing was performed in the temperature range from 400 to 1000 °C. X-ray diffraction (XRD), and atomic force microscopy (AFM) were used to investigate the structure and morphology of GSO:Ce films. Results showed that GSO:Ce film starts to crystallize at about 600 °C, GSO:Ce films have a preferential (0 2 1) orientation, as the annealing temperature increase, the (0 2 1) peak intensity increases, the full width of half maximum (FWHM) decreases, and the grain size of GSO:Ce films increases. Emission spectra of GSO:Ce films were measured, results exhibit the characteristic blue emission peak at 427 nm.     

Characteristics of spherical-shaped Li4Ti5O12 anode powders prepared by spray pyrolysis

Spherical-shaped Li₄Ti₅O₁₂ anode powders with a mean size of 1.5 μm were prepared by spray pyrolysis. The precursor powders obtained by spray pyrolysis had no peaks of crystal structure of Li₄Ti₅O₁₂. The powders post-treated at temperatures of 800 and 900 °C had the single phase of spinel Li₄Ti₅O₁₂. The powders post-treated at a temperature of 1000 °C had main peaks of the Li₄Ti₅O₁₂ phase and small impurity peaks of Li₂Ti₃O₇. The spherical shape of the precursor powders was maintained after post-treatment at temperatures below 800 °C. The Brunauer-Emmett-Teller (BET) surface areas of the Li₄Ti₅O₁₂ anode powders post-treated at temperatures of 700, 800 and 900 °C were 4.9, 1.6 and 1.5 m²/g, respectively. The initial discharge capacities of Li₄Ti₅O₁₂ powders were changed from 108 to 175 mAh/g when the post-treatment temperatures were changed from 700 to 1000 °C. The maximum initial discharge capacity of the Li₄Ti₅O₁₂ powders was obtained at a post-treatment temperature of 800 °C, which had good cycle properties below current densities of 0.7 C.     

The surface properties and the activities in catalytic wet air oxidation over CeO2-TiO2 catalysts

No-noble metal CeO₂-TiO₂ catalysts prepared by sol-gel method were developed and examined for catalytic wet air oxidation (CWAO) of acetic acid. The structure of the catalysts was measured by BET, SEM, XRD, XPS and DTA-TG. We investigated the effect of the interactions of Ce and Ti on the structure of CeO₂-TiO₂ catalysts. The mechanisms of the relationships between the different content of Ti and the activity of CeO₂-TiO₂ catalysts were discussed. The results showed that the average crystal size of CeO₂ decreased and the surface areas increased; the low valence of Ce³⁺ increase, and the chemisorbed oxygen slightly decreased with the increase of Ti content on the surface of CeO₂-TiO₂ catalysts. The order of the activity in CWAO of acetic acid followed: Ce/Ti 1/1 > Ce/Ti 3/1 > Ce/Ti 1/3 > Ce/Ti 5/1 > CeO₂ > TiO₂ > no catalyst. In CWAO of acetic acid, the optimal atomic ratio of Ce and Ti was 1, and the highest COD removal was over 64% at 230 °C, 5 MPa and 180 min reaction time over Ce/Ti 1/1 catalyst. The excellent activity and stability of CeO₂-TiO₂ catalysts was observed in our study.     

Low-temperature sintering and microwave dielectric properties of Ca2Zn4Ti15O36 ceramics

The sintering behavior, microstructures, and microwave dielectric properties of Ca₂Zn₄Ti₁₅O₃₆ ceramics with B₂O₃ addition were investigated. The crystalline phases and microstructures of Ca₂Zn₄Ti₁₅O₃₆ ceramics with 0-10 wt% B₂O₃ addition were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). The sintering temperature of Ca₂Zn₄Ti₁₅O₃₆ ceramic was lowered from 1170 to 930 °C by 10 wt% B₂O₃ addition. Ca₂Zn₄Ti₁₅O₃₆ ceramics with 8 wt% B₂O₃ addition sintered at 990 °C for 2 h exhibited good microwave dielectric properties, i.e., a quality factor (Qf) 11,400 GHz, a relative dielectric constant (ε_r) 41.5, and a temperature coefficient of resonant frequency (τ_f) 94.4 ppm/°C.     

Luminescence properties of Ge implanted SiO2:Ge and GeO2:Ge films

We have investigated cathodeluminescence (CL) of Ge implanted SiO₂:Ge and GeO₂:Ge films. The GeO₂ films were grown by oxidation of Ge substrate at 550 °C for 3 h in O₂ gas flow. The GeO₂ films on Ge substrate and SiO₂ films on Si substrate were implanted with Ge-negative ions. The implanted Ge atom concentrations in the films were ranging from 0.1 to 6.0 at%. To produce Ge nanoparticles the SiO₂:Ge films were thermally annealed at various temperatures of 600-900 °C for 1 h in N₂ gas flow. An XPS analysis has shown that the implanted Ge atoms were partly oxidized. CL was observed at wavelengths around 400 nm from the GeO₂ films before and after Ge⁻-implantation as well as from SiO₂:Ge films. After Ge⁻-implantation of about 0.5 at% the CL intensity has increased by about four times. However, the CL intensity from the GeO₂:Ge films was several orders of magnitude smaller than the intensity from the 800 °C-annealed SiO₂:Ge films with 0.5 at% of Ge atomic concentration. These results suggested that the luminescence was generated due to oxidation of Ge nanoparticles in the SiO₂:Ge films.     

Cluster size dependence of SiO2 thin film formation by O2 gas cluster ion beams

Cluster size effects of SiO₂ thin film formation with size-selected O₂ gas cluster ion beams (GCIBs) irradiation on Si surface were studied. The cluster size varied between 500 and 20,000 molecules/cluster. With acceleration voltage of 5 kV, the SiO₂ thickness was close to the native oxide thickness by irradiation of (O₂)_20,000 (0.25 eV/molecule), or (O₂)_10,000 (0.5 eV/molecule). However, it increased suddenly above 1 eV/molecule (5000 molecules/cluster), and increased monotonically up to 10 eV/molecule (500 molecules/cluster). The SiO₂ thickness with 1 and 10 eV/molecule O₂-GCIB were 2.1 and 5.0 nm, respectively. When the acceleration voltage was 30 kV, the SiO₂ thickness has a peak around 10 eV/molecule (3000 molecules/cluster), and it decreased gradually with increasing the energy/molecule. At high energy/molecule, physical sputtering effect became more dominant process than oxide formation. These results suggest that SiO₂ thin film formation can be controlled by energy per molecule.     

Degradation of Y2SiO5:Ce phosphor powders

The degradation of the cathodoluminescence (CL) intensity of cerium-doped yttrium silicate (Y₂SiO₅:Ce) phosphor powders was investigated for possible application in low voltage field emission displays (FEDs). Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and CL spectroscopy were used to monitor changes in the surface chemical composition and luminous efficiency of commercially available Y₂SiO₅:Ce phosphor powders. The degradation of the CL intensity for the powders is consistent with a well-known electron-stimulated surface chemical reaction (ESSCR) model. It was shown with XPS and CL that the electron stimulated reaction led to the formation of a luminescent silicon dioxide (SiO₂) layer on the surface of the Y₂SiO₅:Ce phosphor powder. XPS also indicated that the Ce concentration in the surface layer increased during the degradation process and the formation of CeO₂ and CeH₃ were also part of the degradation process. The CL intensity first decreased until about 300 C cm⁻² and then increased due to an extra peak arising at a wavelength of 650 nm.     

Electrical behaviour of Li2O-ZnO-SiO2 glass and glass-ceramics system

Sealing quality lithium zinc silicate (LZS) glasses of compositions (wt.%) (a) LZSL- Li₂O: 12.65, ZnO: 1.85, SiO₂: 74.4, Al₂O₃: 3.8, K₂O: 2.95, P₂O₅: 3.15, B₂O₃: 1.2 (low ZnO), and (b) LZSH- Li₂O: 8.9, ZnO: 24.03, SiO₂: 53.7, Na₂O: 5.42, P₂O₅: 2.95, B₂O₃: 5 (high ZnO) were prepared by conventional melt-quench technique and converted to glass-ceramics by controlled crystallization process. The electrical properties of these samples were measured using ac impedance spectroscopy technique over a frequency range of 10 Hz-15 MHz at several temperatures in the range of 323-673 K. The ac conductivity, dc conductivity, dielectric constant and loss factor were obtained from these measurements. The dc conductivity (σ_dc) follows the Arrhenius behaviour with temperature. It is observed that σ_dc in LZSL glass is significantly higher than in the LSZH glass and the activation energies for σ_dc for LZSL and LZSH glasses are 0.59 and 1.08 eV, respectively. It further observed that the conductivity value decreases nearly one order of magnitude on conversion to glass-ceramics. The behaviour is explained on the basis of distributions and nature of alkali ions and network structures in these samples.     

Immobilization of glucose oxidase using CoFe2O4/SiO2 nanoparticles as carrier

Aminated-CoFe₂O₄/SiO₂ magnetic nanoparticles (NPs) were prepared from primary silica particles using modified StÖber method. Glucose oxidase (GOD) was immobilized on CoFe₂O₄/SiO₂ NPs via cross-linking with glutaraldehyde (GA). The optimal immobilization condition was achieved with 1% (v/v) GA, cross-linking time of 3 h, solution pH of 7.0 and 0.4 mg GOD (in 3.0 mg carrier). The immobilized GOD showed maximal catalytic activity at pH 6.5 and 40 °C. After immobilization, the GOD exhibited improved thermal, storage and operation stability. The immobilized GOD still maintained 80% of its initial activity after the incubation at 50 °C for 25 min, whereas free enzyme had only 20% of initial activity after the same incubation. After kept at 4 °C for 28 days, the immobilized and free enzyme retained 87% and 40% of initial activity, respectively. The immobilized GOD maintained approximately 57% of initial activity after reused 7 times. The K_M (Michaelis-Menten constant) values for immobilized GOD and free GOD were 14.6 mM and 27.1 mM, respectively.     

Fabrication of three-dimensional dendrite-like CeO2 crystallites via simple template-free solution route

Highly uniform three-dimensional dendrite-like CeO₂ crystallites were successfully prepared in large quantities with a thermal decomposition of precursor approach applied. The precursor with an average size of 10 μm was prepared in an aqueous solution containing Ce(NO₃)₃·6H₂O, CO(NH₂)₂ and ammonia at 160 °C with no additional phase. The influence of ammonia on the dendrites formation was discussed. The dendritic pattern of precursor almost remained in the as-prepared product. The optical absorption spectrum indicates that CeO₂ dendrites have a direct band gap of 3.52 eV.     

Electrochemical properties of electrosynthesized TiO2 thin films

Titanium dioxide (TiO₂) thin films prepared by cathodic electrodeposition on indium-tin-oxide coated glass substrates from simple aqueous peroxo-titanium complex solutions have been studied as a function of sintering temperature (25-500 °C). The films crystallized in to anatase phase at relatively low temperature (300 °C). Electrochemical properties of amorphous and anatase films were investigated by cyclic voltammogram (CV) in lithium ion containing organic electrolyte. All the films were found to show reversible electrochemical properties upon Li⁺ ion intercalation. The effects of sintering temperature on the crystallinity and consequently on the electrochemical properties of TiO₂ has been discussed.     

The effect of B2O3 addition to the microstructure and magnetic properties of Ni0.4Zn0.6Fe2O4 ferrite

The effects of 0.01 and 0.1 mol B₂O₃ addition to the microstructure and magnetic properties of a Ni–Zn ferrite composition expressed by a molecular formula of Ni_0.4Zn_0.6Fe₂O₄ were investigated. The toroid-shaped samples prepared by pressing the milled raw materials used in the preparation of the composition were sintered in the range of 1000–1300 °C. The addition of 0.01 mol B₂O₃ increased the grain growth and densification giving rise to reduced intergranular and intragranular porosity due to liquid-phase sintering. The sintered toroid sample at 1300 °C gave the optimum magnetic properties of B_r=170 mT, H_c=0.025 kA/m and a high initial permeability value of μ_i=4000. The increment of the B₂O₃ content to 0.1 mol resulted in a pronounced grain growth and also gave rise to large porosity due to the evaporation of B₂O₃ at higher sintering temperatures. Hence, it resulted in an air-gap effect in the hysteresis curves of these samples.     

Intrinsic ultraviolet luminescence from Lu2O3, Lu2SiO5 and Lu2SiO5:Ce

Radioluminescence and thermally stimulated luminescence measurements on Lu₂O₃, Lu₂SiO₅ (LSO) and Lu₂SiO₅:Ce³⁺ (LSO:Ce) reveal the presence of intrinsic ultraviolet luminescence bands. Characteristic emission with maximum at 256 nm occurs in each specimen and is attributed to radiative recombination of self-trapped excitons. Thermal quenching of this band obeys the Mott-Seitz relation yielding quenching energies 24, 38 and 13 meV for Lu₂O₃, LSO and LSO:Ce, respectively. A second intrinsic band appears at 315 nm in LSO and LSO:Ce, and at 368 nm in Lu₂O₃. Quenching curves for these bands show an initial increase in peak intensity followed by a decrease. Similarity in spectral peak position and quenching behavior indicate that this band has a common origin in each of the samples and is attributed to radiative recombination of self-trapped holes, in agreement with previous work on similar specimens. Comparison of glow curves and emission spectra show that the lowest temperature glow peaks in each specimen are associated with thermal decay of self-trapped excitons and self-trapped holes. Interplay between the intrinsic defects and extrinsic Ce³⁺ emission in LSO:Ce is strongly indicated.     

Dielectric properties of barium titanate ceramics modified by SiO2 and by BaO-SiO2

The influence of SiO₂ on the dielectric properties of barium titanate ceramics was investigated. SiO₂ had been doped solely and together with BaO into barium titanate before calcination. X-ray diffraction showed that all the ceramics were of a pure perovskite phase after sintering at 1275 °C for 2 h. For SiO₂-doping, there was about 2.5 °C increase in Curie temperature per molar percentage of doping and the leakage current was obviously increased, especially at low voltages for relatively high doping levels. While for the co-doping of SiO₂ and BaO, there was little change in Curie temperature. The point defects formed through the dopings were proposed responsible for the effects. It was suggested that SiO₂ is important to barium titanate ceramics not only for sintering but also for modifying their properties.