The role of water vapour on the oxidation of two Ln-Si-Al-O-N glasses (Ln=Y, La)

The oxidation behaviour of LnSiAlON (Ln=Y, La) glasses was studied at different temperatures (990-1150 °C) and under different water vapour pressures (360-2690 Pa). These results were also compared with those obtained under O₂, N₂/H₂O or O₂/H₂O mixtures. When glasses are treated under a N₂/H₂O mixture, optical and SEM observations show porous scales. Transformations of the reaction rate data and a kinetic model show that there is only one limiting process occurring during oxidation. This rate limiting step is the progress of the chemical reaction at the internal interface. Determination of the pressure law dependence and thermodynamics calculations of water vapour molecules dissociation at the investigated temperatures allow us to suggest that the mechanism of oxidation corresponds to decomposition of water molecules on the oxynitride glass surface.     

The fatigue of high-strength fused silica optical fibers in low humidity

The strength and dynamic fatigue of UV-acrylate coated silica optical fibers were measured as a function of relative humidity in the range ∼0.025-13% at 25 °C. The degradation kinetics of silica in low humidities was investigated and it was found that the reaction order was approximately first-order with respect to humidity. In our previous work, a second-order reaction was found in the humidity range 20-95% RH at 25 °C and the process for obtaining this reaction order was found to be independent of the mathematical form of the kinetic models used. The change in reaction order observed here verifies some earlier results based on the power law which implied a change in the reaction order from ∼2 (15-100% RH) to ∼1 at low humidity (<0.01%).     

Proton conduction in glass - an impedance and infrared spectroscopic study on hydrous BaSi2O5 glass

Hydrous barium disilicate glasses (BaSi₂O₅) containing 2.75 and 3.54 wt% dissolved water (corresponding to a molar concentration of hydrogen atoms of 11.1 and 14.2 mol/l, respectively) were synthesized by high temperature fusion in an internally heated gas pressure vessel. Near-infrared spectroscopy gives evidence that both OH groups and H₂O molecules are present in the glasses. The maximum intensity in the range of OH stretching vibrations is at 2800 cm⁻¹ indicating strong hydrogen bonding in the glasses. Electric conductivity measurements were carried out at temperatures up to 523 K without significant alteration of the sample. At higher temperatures, OH groups are converted to molecular H₂O and water diffuses out of the sample resulting in a continuous decrease of the conductivity. An activation energy of 87 kJ/mol was derived for the dc conductivity in the unaltered glasses similar to the activation energy for bulk water diffusion in other silicate glasses. Because the dry barium disilicate glass is an electrical insulator at experimental conditions, we infer that the dc conductivity of the hydrous glasses is due to proton conduction.     

Crystallisation and performance characteristics of high‐temperature annealed electroless Ni‐W‐P coatings

Electroless deposition of Ni–P based alloys is a well‐known commercial process that has numerous applications because of their excellent anticorrosive and wear properties. However, for some special occasions, like the components for gas making furnaces in chemical fertiliser industry, the coatings must be reinforced to withstand short‐term high temperatures between 600 °C and 700 °C as well as light erosive wear. Therefore, co‐deposition of high melting point metallic element, W, has been considered as a preferred choice. In the present study, two Ni–W–P alloy coatings were deposited on mild steel panels from different alkaline baths. The microstructures of the annealed coatings were characterised by quantitative XRD, XPS and SEM/EDS analysis techniques and their microhardness, friction and wear behaviour, corrosion mechanism as well as microstrain and residual stress are discussed in comparison with the as‐plated state. The results indicate that the hardness mainly depends on the volume fraction and crystallite size of Ni₃P phase; the uniform corrosion in sulfuric acid solution is closely related to the ratio of I_Ni/I_Ni3P as well as grain size. The wear mechanism of the high‐temperature annealed coating is dominated by abrasive wear, but the wear in the early stages started from mild adhesive wear caused by adhesion between the friction couples. Electroless deposited Ni‐W‐P alloys with high phosphorus present relatively good properties, including hardness, wear and corrosion resistance when 700 °C is applied for annealing process.     

Water diffusion into a silica glass optical fiber

The diffusion coefficient and solubility of water in silica glass optical fiber cladding were measured in the temperature range of 600-800 °C and were compared with the corresponding values of bulk silica glasses. It was found that the diffusion coefficient was slightly lower and the solubility was appreciably higher in optical fiber, especially at low temperatures, compared with those in bulk silica glasses. The observed trend was consistent with the expected effect of fictive temperature.     

Structural implications of water and boron dissolution in albite glass

A combined nuclear magnetic resonance, infrared and Raman spectroscopic study on the effect of water dissolution on the structure of B-bearing aluminosilicate glasses is presented. The base composition was albite (NaAlSi₃O₈) to which different amounts of B₂O₃ (4.8, 9.1, 16.7 wt%) were added. Hydrous glasses containing 4.4 ± 0.1 wt% water were synthesized at pressures of 2000 bar. The results show that B dissolves in both dry and hydrous glasses by forming predominantly trigonal BO₃ groups although some tetrahedral BO₄ is also present. In anhydrous glasses prepared at high pressures (above 10 kbar) the fraction of BO₄ increased. The hydrous glasses contain more BO₄ groups compared to the dry counterparts, suggesting that this species is stabilized by water. The Raman and NMR (¹⁷O, ²⁷Al, ²⁹Si) spectra show that B interacts with the aluminosilicate network by formation of Si-O-B and probably Al-O-B units. In the hydrous glasses the water speciation changes significantly towards higher hydroxyl concentrations with increasing B-content. The NIR peaks, which are related to OH groups and molecular H₂O, develop additional shoulders, suggesting that possibly B-OH complexes are formed.     

水蒸汽辅助转化法合成W分子筛

以硅酸钠和硫酸铝反应物硅铝干凝胶为硅铝源,氢氧化钾为碱源,采用水蒸汽辅助转化法合成W分子筛,考察了反应体系组成、晶化温度和晶化时间对W分子筛结构、形貌和性能的影响.得到最佳合成条件为:K2O/SiO2=0.386,H3O/SiO2=11.2,添加于固体反应原料中的水量与釜底水量的比值为2.85,晶化温度为160 ℃,晶化时间为48 h.所得样品经XRD和SEM表征确认得到了形貌均一、结晶良好的W分子筛,其在人工模拟海水中的钾离子交换容量为52.4 mg/g.     

Cystamine-incorporated gelatin microsphere and its redox-responsive release property

Reduction-responsive cystamine-incorporated gelatin microspheres were prepared by an emulsification method. On SEM micrograph, the microsphere, prepared at pH 9.0 and at the carboxyl/amino group molar ratio of 1:1, was sphere-like and its diameter was a few to 100 µm. The gelatin to cystamine ratio of the microsphere was about 1:0.2 (w/w), determined by energy dispersive X-ray spectroscopy. Two endothermic peaks were observed around 92°C and 126°C, which were thought to be the melting point of gelatin-rich phase and that of cystamine-rich phase, respectively. The microsphere released its payload (FITC-dextran) in dithiothreitol (a reducing agent) concentration-dependent manner.     

Determination of the supersaturation in the LiIO3–HIO3–H2O system using a refractive index value at near saturation concentration

The exact determination of supersaturation is essential for the studies of crystal growth processes in solutions. Due to peculiarities in the solubility of LiIO₃, the refractive index of the solution is chosen as a measure of the supersaturation instead of undercooling. The experimental setup is based on a refractometer and a special setup to create supersaturation in the cuvette by means of successive evaporation of small amounts of solvent. The refractive index is measured at different solution concentrations and pH and the data are correlated as dependences of concentration and pH on the refractive index. The accuracy of the method and the adequacy of the model are discussed.     

Surface removal of a weathered organic glass

A tubular, stratified glass–epoxy material composite has been subjected to either natural or artificial aging. After aging, the degradation of this material is characterised by the ablation of the organic matrix. For the first time, we have measured the ablation using a three-dimensional surface microanalysis system equipped with a sensitive topographical probe. In a previous study involving the measurement of the ablation during artificial photo-aging, an innovative hypothesis concerning the creation of a thin photo-oxidation layer in close proximity to the irradiated surface of the organic matrix was proposed. During weathering, from time to time, rain leaches the thin photo-oxidation layer and causes a significant ablation via a complementary mechanism. Given that the material surface always presents hemi-cylindrical concavity imprints, we studied the surface changes, due to the ablation, by measuring the cross-section half-circle radii of the concavities after different photo-aging times. The surface erosion is characterized by growth of the circle radii, whose changes progressively lead towards surface flatness. A 2-D model of the concavities’ growth has been validated: the simulation results lead to calculated circle radii growth values near the measured ones. Comparison between photo-aged organic matrix removal and erosion of a leached mineral glass shows that the morphological removal of this isotropic organic matrix evolves in a manner analogous to that of an amorphous inorganic material.     

Irrational orientation relationship derived from rational orientation relationships using EBSD data

The determination of the orientation relationship (OR) between α ‐Fe matrix (bcc) and γ ‐Fe precipitates (fcc) is discussed using orientation data collected by electron backscatter diffraction (EBSD). The comparatively low accuracy of EBSD is compensated by the high number of measurements what allows a general statement regarding to the mean OR existing in a sample. The representation and discussion is realized on a part of the Bain zone in a {001} pole figure. A discussion of some selected rational OR which are commonly used for the phase boundary characterization between α and γ shows that the pole figures describing a transformation from γ → α are different to those for α → γ. A technique is proposed based on at least three misorientation angles between the experimental OR to the rational OR's as reference. For the misorientation angle distribution a refinement is applied to extract the mean values. They are used to detect the mean OR, what is also possible for only a few or even a single precipitate if the number of measurements describing the phase boundary is sufficiently high. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of laser‐induced nanocrystallisation on the properties of electroless Ni‐P/Ni‐W‐P duplex coatings

This paper presents a comparative study of nanocrystallisation and the wear resistance of electroless plated Ni‐P/Ni‐W‐P duplex coatings with a single Ni‐W‐P coating before and after high‐ power diode laser treatment. Effects of the laser operating parameters on microstructures, in terms of crystallisation, porosity formation, phase transformation and grain growth, were investigated using scanning electron microscopy (SEM) with energy dispersive X‐ray spectroscopy (EDX) and quantitatively X‐ray Diffraction (XRD). Microhardness and wear behaviour of the coatings before and after laser treatment were evaluated by measurement of coating surface and cross‐section hardness as well as un‐lubricated friction and wear tests. The results revealed that in the case of laser treatment, the Ni‐P/Ni‐W‐P duplex coatings offered better wear resistance than the single Ni‐W‐P coating, while the as‐plated, single Ni‐W‐P coating showed better wear resistance than the Ni‐P/Ni‐W‐P duplex coatings. Adhesive wear mechanism prevails in the laser‐treated coatings when subjected to wear test against hardened steel material. The effects of microstructural characteristics in the coatings, in particularly the grain size of Ni₃P phase and the degree of crystallisation, on the adhesive wear behaviour have been investigated and found to be dominant besides the effect of hardness.     

Er3+:NaY(Wo.9Moo.1O4)2晶体的生长及光谱性能

采用提拉法(CZ法),生长出质量良好的Er3+:NaY(W0.9Mo0.1O4)2晶体.通过X射线粉末衍射,红外光谱分析,并与NaY(WO4)2相比较,得到Er3+:NaY(W0.9Mo0.1O4)2晶体的结构与NYW类似,仍为四方晶系的白钨矿结构,I4(1)/α空间群.测定了晶体的实际组成,得到晶体中各元素均按理论值进行掺杂,计算了掺杂离子的分凝系数约为1.15.在光谱性质上,测试了晶体的吸收光谱,及晶体在50～1000cm-1波数范围内的拉曼光谱,并计算了各吸收峰的半峰宽及吸收系数A.     

Non-isothermal approach to crystallization process of a Co-rich alloy

In this work we have investigated the crystallization of a Co-rich alloy obtained by melt-spinning. The same process was repeated by applying a magnetic field at the moment of the solidification process. Furthermore, the melt-spun amorphous ribbons were subjected to mechanical alloying in a planetary ball-milling. The milling conditions were chosen to develop a material in a like-powdered form. The samples are amorphous as determined by X-ray diffraction patterns. Non-isothermal experiments were carried out by differential scanning calorimetry. An isoconversional method is applied to perform the kinetic analysis in order to obtain the activation energy and de Jhonson–Mehl–Avrami parameter. It was found a decrease of 15–25% in the activation energy of the main crystallization process in mechanically alloyed samples.     

Synthesis of dense polycrystalline GaN of high purity by the chemical vapor reaction process

A process for producing high-purity, dense polycrystalline gallium nitride is proposed. Dense polycrystalline gallium nitride was produced by the reaction of ammonia, gallium metal, and a halide source in a quartz boat containing metallic gallium. The process is called the chemical vapor reaction process. The hard crust-like pieces of polycrystalline GaN obtained are of high purity, can be used as source material for single-crystal growth by the ammonothermal technique, sublimation, sputtering, and pulse laser deposition.     

Berechnung der Übersättigung bei der Kristallisation von InAs aus der Gasphase

It is proved that under experimental conditions for the growing of InAs crystals from the vapour phase the partial supersaturation of indium monoiodide corresponding to the difference of partial pressure of InJ_(g) in the source and in the crystallisation zones, can serve as a quantitative process parameter granting predictions on process development and results in a wide range of ruling conditions. Experiments confirmed the conclusions postulated on the base of quantitative analysis of the transport process. The analysis enables to controll the process parameters of crystal growth by chemical transport.     

Thermosoftening phenyl siloxane glasses prepared via sol concentration

Thermosoftening phenyl polysiloxane glasses have been prepared by concentration of the corresponding sol above the melting temperature of the resultant materials, which we call the ‘sol concentration method’ (SCM). Because the glass melt is directly obtained without a gelation process, a remarkable shortening of the process time and suppression of crack formation in the sol–gel transition region have been realized. That is the whole process time of the SCM (about 24 h) is much shorter than that of the conventional sol–gel process (about 10 days). Thermosoftening phenyl polysiloxane glasses with high transparency in the UV region were obtained by the SCM.     

壳熔法生长技术及其应用

壳熔法是利用高频感应电源加热使原料内部熔化并由水冷系统在其外围形成硬壳作为坩埚的一种晶体生长技术,特别适合于高温和难熔晶体的生长.本文介绍了壳熔法晶体生长原理和特点,综述了壳熔法生长立方氧化锆晶体的研究进展,探讨了壳熔法的其它工业应用,包括高温合金的铸造、核废料的处理、多晶硅的制备等.     

铜锌锡硫正极全固态薄膜锂离子电池的研究

采用铜锌锡硫(CZTS)四元硫化物材料作为全固态薄膜锂离子电池(TFLB)的正极功能层.通过磁控溅射及硫化工艺制备了CZTS多晶薄膜,并经过组分调控及硫化工艺控制等方案,提高了CZTS正极薄膜的电子导电性.此外,通过引入疏松的微观结构,抑制了由充放电过程中的体积膨胀所导致的容量衰减,提升了TFLB循环性能.所制得的TFLB结构为玻璃/Mo/CZTS/LiPON/Li,首圈放电容量高达200μAh·cm-2 ·μm-1(482 mAh ·g-1),放电平台约为1.1V.     

Silica Λ-shape wedge arrays fabrication and interspace tuning via hot embossing and sol–gel replication

New-type silica Λ-shape wedge arrays (SWAs) were fabricated by a combined process of template fabrication, hot embossing and sol–gel replication. Using silica needle arrays (SNAs) as template, the configuration of Λ-shape was transferred from SNAs to PMMA/PC molds by hot-pressing process. Then they were casted to form silica Λ-shape wedge arrays by sol–gel process. Using this procedure, high quality silica Λ-shape wedge arrays can be obtained with designed sizes and shapes over a large area. The taper height and interspace of SWAs can be tuned by the imprint depth during the hot-embossing process. This technology provides a cost-effective method to fabricate Λ-shape silica wedges. By changing the primal template, other patterned silica substrate can also be fabricated, such as grating, pillar and spherical structures. These silica based microstructure can find many applications in semiconductor devices, solar cells and optics etc.