Effect of Polyethylenimine on Hydrolysis and Dispersion Properties of Aqueous Si3N4 Suspensions

The roles of polyethylenimine (PEI) in the hydrolysis and dispersion properties of aqueous Si₃N₄ suspensions were studied in terms of the hydrolysis, adsorption, electrokinetic, and rheological measurements. It was found that the pH change of the suspensions in the acidic environment could be minimized in the presence of ≥0.5 dwb% PEI. The ammonia and oxygen measurements suggest that this phenomenon is primarily attributed to the buffer mechanism generated by the ionized PEI, instead of the protection mechanism. The constant pH enables the suspensions to retain a better stability with time at acidic pH. The adsorption of PEI on Si₃N₄ is a high-affinity type at highly basic pH, but is a low-affinity type at acidic pH. As the PEI amount increases, the adsorption shifts the isoelectric point (IEP) of Si₃N₄ from pH 5.9 to pH ∼11 until complete coverage is attained. The stability of Si₃N₄ suspensions is found to depend strongly on the saturated adsorption of PEI, which is as a function of the pH and PEI amount. Once the saturated adsorption limit is reached, the excess free PEI molecules become more detrimental to the stability with increased solid loading. The stabilization mechanisms of Si₃N₄ suspensions by PEI were discussed in detail.     

Copper ⇌ Alkali Ion Exchange of Alkali Aluminosillcate Glasses in Copper-Containing Molten Salt: I, Monovalent Copper Salt, CuCl

Cu⁺⇌ R⁺ (R = Li, Na, and K) ion exchange experiments were conducted for 20R₂O·10Al₂O₃·70SiO₂ glasses in molten CuCl at 550°C in air and nitrogen atmospheres. The depth profiles of the copper incorporated into glasses were determined with an electron microprobe X-ray analyzer. The total amount of diffusing copper, M _t, strongly depended on the type of alkali ion in the glass and the ion-exchange atmosphere; i.e., M _t increased with increasing cationic size in the order Li < Na < K and M _t was greater in air than in nitrogen. The Cu ⇌ R⁺ ion exchange kinetics are discussed in detail.     

Variational Bayes solution of linear neural networks and its generalization performance

It is well known that in unidentifiable models, the Bayes estimation provides much better generalization performance than the maximum likelihood (ML) estimation. However, its accurate approximation by Markov chain Monte Carlo methods requires huge computational costs. As an alternative, a tractable approximation method, called the variational Bayes (VB) approach, has recently been proposed and has been attracting attention. Its advantage over the expectation maximization (EM) algorithm, often used for realizing the ML estimation, has been experimentally shown in many applications; nevertheless, it has not yet been theoretically shown. In this letter, through analysis of the simplest unidentifiable models, we theoretically show some properties of the VB approach. We first prove that in three-layer linear neural networks, the VB approach is asymptotically equivalent to a positive-part James-Stein type shrinkage estimation. Then we theoretically clarify its free energy, generalization error, and training error. Comparing them with those of the ML estimation and the Bayes estimation, we discuss the advantage of the VB approach. We also show that unlike in the Bayes estimation, the free energy and the generalization error are less simply related with each other and that in typical cases, the VB free energy well approximates the Bayes one, while the VB generalization error significantly differs from the Bayes one.     

Studies on Si-O bonding in silicate and aluminosilicate glasses based on SiKβ emission X-rays

The SiK X-ray emission spectra of silicate and aluminosilicate glasses and crystals have been measured with an X-ray fluorescence spectrometer and the chemical shifts of the SiK peak relative to that of SiO₂ glass have been determined. Trends in the chemical shift of the SiK peak for Na₂O-SiO₂, Li₂O-SiO₂ and Li₂O-Al₂O₃-SiO₂ glasses were similar to those of their crystalline counterparts, indicating that the strength of the Si-O bond varies in the same way with composition in both glass and crystal. The chemical shift in alkali aluminosilicate glasses containing equal molar proportions of aluminium oxide and alkali oxide increased with decreasing SiO₂ content, indicating that the Si-O bond also weakened in aluminosilicate glasses. The same effect was also observed when zirconia was added. The SiK bandwidths for Na₂O-Al₂O₃-SiO₂ and Li₂O-Al₂O₃-SiO₂ glasses with the Al₂O₃: M₂O ratio equal to one, remained almost the same as for SiO₂ glass, indicating that the addition of alkali does not result in the formation of non-bridging oxygens in the framework if accompanied by Al₂O₃.     

A pilot survey of 39 Victorian WWTP effluents using a high speed luminescent umu test in conjunction with a novel GC-MS-database technique for automatic identification of micropollutants

In 2007, samples of treated effluent were collected at point of discharge to the environment from 39 wastewater treatment plants (WWTPs) located across Victoria, Australia grouped by treatment type. Sample genotoxicity was assessed with a high-throughput luminescent umu test method using Salmonella typhimurium TL210 strain, with and without addition of a commercially available metabolic activation system. Samples were also screened using a gas chromatographic-mass spectrometric mass-structure database recognition method. A genotoxic response was observed in half of the samples tested without metabolic activation system (相似文献   

Zr-Hf interdiffusion in polycrystalline Y2O3-(Zr+Hf)O2

Lattice and grain-boundary interdiffusion coefficients were calculated from the concentration distributions determined for Zr-Hf interdiffusion in polycrystalline 16Y₂O₃·84(Zr_1–x Hf _x )O₂ withx=0.020 and 0.100. The lattice interdiffusion coefficients were described byD=0.031 exp [–391 (kJ mol^–1)/RT] cm² sec^–1 and the grain-boundary diffusion parameters byD=1.5×10^–6exp [–309(kJ mol^–1)/RT] cm³ sec^–1 in the temperature range 1584–2116° C. Comparison of the results with those for the systems CaO-(Zr+Hf)O₂ and MgO-(Zr+Hf)O₂ indicated that the Zr self-diffusion coefficient was insensitive to the dopants in the fluorite-cubic ZrO₂ solid solutions.     

复杂结构ADC12铝合金汽车支架挤压铸造工艺参数优化

目的 解决ADC12铝合金汽车发动机支架在挤压铸造成形工艺下的缺陷问题。方法 利用ProCAST模拟软件对该汽车发动机支架的挤压铸造充型和凝固过程进行模拟,对挤压铸造工艺参数进行正交试验设计并模拟得到最佳工艺参数,对铸件浇注远端厚壁部位采取局部加压优化措施,并对厚壁部位进行X-Ray探伤,观察铸件的缺陷情况。结果 对挤压铸造的工艺参数进行正交试验极差分析后,发现各工艺参数按对铸件凝固后质量的影响程度从大到小的顺序依次为挤压比压、浇注温度、模具温度。通过正交试验得到优化后的工艺参数为浇注温度730 ℃、模具温度300 ℃、挤压比压150 MPa。局部加压时挤压销的最佳激活时间为4 s,此时可以完全消除铸件内部的缩孔缩松缺陷。选择优化后的工艺参数生产该汽车发动机支架,产品外观完整,没有出现表面裂纹等缺陷。在X-Ray探伤下无明显缺陷,内部质量良好。结论 选择合理的浇注温度、模具温度和挤压比压可以有效减少铸件内部的缩孔缩松缺陷,采用局部加压并合理控制挤压销的激活时间可以完全消除缩孔缩松缺陷。     

Computational cavitation flows at inception and light stages on an axial-flow pump blade and in a cage-guided control valve

Cavitation flows induced around an axial-flow pump blade and inside a high pressure cage-type valve are simu-lated by a two-dimensional unsteady Navier-Stokes analysis with the simplest treatment of bubble dynamics.Thefluid is assumed as a continuum of homogeneous dispersed mixture of water and vapor nuclei.The analysis isaimed to capture transient stages with high amplitude pressure change during the birth and collapse of the bubbleespecially at the stage of cavitation inception.By the pump blade analysis,in which the field pressure is moderate,cavitation number of the inception and locations of developed cavitation are found to agree with experimental re-suits in a wide flow range between high incidence and negative incidence.In the valve flow analysis,in which thewater pressure of 5MPa is reduced to 2MPa,pressure change responding to the bubble collapse between the vaporpressure lower than 1 KPa and the extreme pressure of higher than 10~4 KPa is captured through a stable computa-tion.Location of the inception bubble and pressure force to the valve plug is found agree well with the respectiveexperimental features.     

One-step route to a hybrid TiO2/TixW1?xN nanocomposite by in situ selective carbothermal nitridation

Metal oxide/nitride nanocomposites have many existing and potential applications, e.g. in energy conversion or ammonia synthesis. Here, a hybrid oxide/nitride nanocomposite (anatase/Ti_xW_1−xN) was synthesized by an ammonia-free sol–gel route. Synchrotron x-ray diffraction, complemented with electron microscopy and thermogravimetric analysis, was used to study the structure, composition and mechanism of formation of the nanocomposite. The nanocomposite contained nanoparticles (<5 nm diameter) of two highly intermixed phases. This was found to arise from controlled nucleation and growth of a single oxide intermediate from the gel precursor, followed by phase separation and in situ selective carbothermal nitridation. Depending on the preparation conditions, the composition varied from anatase/Ti_xW_1−xN at low W content to an isostructural mixture of Ti-rich and W-rich Ti_xW_1−xN at high W content. In situ selective carbothermal nitridation offers a facile route to the synthesis of nitride-oxide nanocomposites. This conceptually new approach is a significant advance from previous methods, which generally require ammonolysis of a pre-synthesized oxide.     

Effects of Gd Substitution on Sintering and Optical Properties of Highly Transparent (Y0.95−xGdxEu0.05)2O3 Ceramics

Highly transparent (Y_0.95?xGd_xEu_0.05)₂O₃ (x = 0.15–0.55) ceramics have been fabricated by vacuum sintering at the relatively low temperature of 1700°C for 4 h with the in‐line transmittances of 73.6%–79.5% at the Eu³⁺ emission wavelength of 613 nm (~91.9%–99.3% of the theoretical transmittance of Y_1.34Gd_0.6Eu_0.06O₃ single crystal), whereas the x = 0.65 ceramic undergoes a phase transformation at 1650°C and has a transparency of 53.4% at the lower sintering temperature of 1625°C. The effects of Gd³⁺ substitution for Y³⁺ on the particle characteristics, sintering kinetics, and optical performances of the materials were systematically studied. The results show that (1) calcining the layered rare‐earth hydroxide precursors of the ternary Y–Gd–Eu system yielded rounded oxide particles with greatly reduced hard agglomeration and the particle/crystallite size slightly decreases along with increasing Gd³⁺ incorporation; (2) in the temperature range 1100°C–1480°C, the sintering kinetics of (Y_0.95?xGd_xEu_0.05)₂O₃ is mainly controlled by grain‐boundary diffusion with similar activation energies of ~230 kJ/mol; (3) Gd³⁺ addition promotes grain growth and densification in the temperature range 1100°C–1400°C; (4) the bandgap energies of the (Y_0.95?xGd_xEu_0.05)₂O₃ ceramics generally decrease with increasing x; however, they are much lower than those of the oxide powders; (5) both the oxide powders and the transparent ceramics exhibit the typical red emission of Eu³⁺ at ~613 nm (the ⁵D₀→⁷F₂ transition) under charge transfer (CT) excitation. Gd³⁺ incorporation enhances the photoluminescence and shortens the fluorescence lifetime of Eu³⁺.