氮化镓纳米固体的合成及其激光拉曼光谱

利用氨热法合成了一种新型致密材料—氮化镓纳米固体。该纳米固体呈淡黄色,半透明,其组成颗粒的平均粒径为12nm,为六方纤锌矿型结构。与氮化镓单晶相比,在该纳米固体的激光拉曼光谱上观察到了由于纳米尺寸效应而引起的E2(high)声子带的红移、带的宽化和新的声子带(656cm-1和714cm-1)的出现     

固-固结构声子晶体中弹性波的禁带及其转型

引入四维波矢的概念,推导出弹性波斜入射固-固结构声子晶体的转移矩阵以及透射系数公式.利用这些公式计算了纵波和横波斜入射固-固结构声子晶体时纵波和横波的透射系数.结果表明:当纵波斜入射时,在透射波中纵波会出现禁带,并且也出现了纵波向横波的转型,随着入射角的增大转型越明显.当横波斜入射时也会出现类似于纵波斜入射时的现象.这些公式成功地解决了弹性波斜入射固-固结构声子晶体的传输问题和转型问题.     

The coprecipitation of Magnesium Nickel Oxalate Dihydrate Powders (solid solutions) from aqueous solution: Precipitate compositions and Cporecipitate Mechanisms

The coprecipitation of magnesium nickel oxalate dihydrates from mixed metal cation solutions was monitored by conductivity measurements. A series of coprecipitates was then prepared from 0.2 M solutions with Mg contents varying from 0.2 to 0.9 total metal cation and their compositions and structures studied by chemical analysis, infra-red spectrophotometry, thermogravimetric analysis and detailed differential calorimetry. The coprecipitates with upto 20 percent Mg content were solid solutions with structures similar to nickel oxalate dihydrate, the coprecipitates with 20 to 80 percent Mg content were probably mixed solid solutions while the coprecipitates with over 80 percent Mg content were solid solutions with structures similar to magnesium oxalate dihydrate. The ionic equilibria in supersaturated magnesium nickel oxalate solutions were analysed and mechanisms are proposed for coprecipitations from solutions of different Mg/(Mg + Ni) ratios.     

Calculation of the Suspension Volume of Crystallizers with Non-ideally Mixed Suspension

For the calculation of the suspension volume of crystallizers with non-ideally mixed suspension the material balance was derived. The model of complete segregation and the cell modell were used to describe the micro-mixing of solid phase. Testing was carried out in a laboratory crystallizer. The residence time distribution and the weight increase of the crystals were measured. The results showed that the model of complete segregation is suitable for describing the flow behaviour of the solid phase in crystallizers.     

Bubbles engulfment and entrapment by cellular and dendritic interfaces during directional solidification

The purpose of this work was to investigate bubbles engulfment and entrapment by cellular and dendritic interfaces during directional solidification. The experiments were performed in succinonitrile-based transparent alloys (SCN-1.5 wt%ACE). While the solid–liquid interface is cellular, the solid–liquid interface is separated into two layers by the bubble. Experimental results show that a cellular–planar–cellular transition for solid–liquid interface occurs on the lower layer and the stability of the tubular bubble is determined by local microstructure on the upper layer. When the interface is dendritic, morphological instability occurs on the solid thin film attached to the bubble after the solid–liquid interface hits the bubble. We analyzed the evolution of such cells (some cells become dendrites with time) as a function of the angle between the opposite growth direction of dendritic array and the small cell growth direction. It is demonstrated that the relative position between the existing bubble and the dendritic tip influences on the local growth pattern of dendritic array.     

高性能氮化硅陶瓷凝胶注模成型的研究

凝胶注模成型工艺的关键在于制备低粘度高固相体积含量的陶瓷浆料.本文以四甲基氢氧化铵(TMAH)溶液为分散剂制备氮化硅陶瓷浆料,研究了pH值、分散剂含量、助烧剂含量以及固相体积含量对氮化硅浆料流变性的影响;测定了凝胶注模成型素坯以及烧结体的力学性能.研究结果表明:当pH＝10.5,分散剂加入量为6;(相对于氮化硅固相体积比),助烧剂加入量为10;(质量分数)时,浆料具有最好的流变性.根据以上制备的工艺参数,制备得到固相体积含量大于50;,具有良好流变性的浆料.铸模成型干燥后,素坯的抗弯强度达27MPa;常压烧结后氮化硅陶瓷具有优异的力学性能,其抗弯强度为730 MPa,断裂韧性高达8.8 MPa·m1/2.     

Crystallization of phosphogypsum in continuous phosphoric acid industrial plant

Understanding crystallization of phosphogypsum is generally of basic importance for industrial wet‐process phosphoric acid production. In this paper, measuring the phosphogypsum crystal size distribution during primary and secondary nucleation is reported. The results show that, secondary nucleation was occurred at 5 hr run time (12.5% solid content). Crystal growth rates were about 18.4 μm/hr at 2.5% solid content and about 4.5 μm at 30% solid content. At steady state (16 hr run time and 30% solid content), the mean diameter of the crystals and the average specific surface area are about 25 μm and 0.69 m²/g, respectively. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X-ray powder diffraction investigations of solid solutions in the KCl?KBr?H2O system at 298 K

The measurements of crystal lattice parameters (a) of solid solutions being formed in the system KCl KBr H₂O at 298 K were conducted. The volumes (v) of unit cells and the densities (ϱ) of mixed crystals K(Cl, Br) were calculated. It was confirmed that in the investigated system continuous solid solutions were formed. The lattice parameters of these crystals formed from aqueous solutions of salts as well as from molten salts and also calculated by Durham-Hawkins method were nearly identic.     

Phosphate Composition of Precipitates from Urine-like Liquors

The composition of the solid phases precipitating from urine-like liquors has been determined at 37°C over the pH range between 6 and 8 for solutions with varying amounts of magnesium, citrate, oxalate and ammonium ions. At pH ⩽7 hydroxyapatite appeared, either alone or, depending on the magnesium ion concentration, in a mixture with brushite. Stravite and calcium phosphates precipitated at pH ⩾ 7.5. No other phosphate solids were observed to precipitate from these urine-like liquors under physiological conditions. No influence on the nature of the solid phase was exerted by citrate, oxalate or ammonium ions. The variation of solid phase composition caused by changing solution composition is ascribed to kinetic rather than thermodynamic factors.     

Melting and Crystallization Processes of EBBA I. Thermal Analysis

Melting and crystallization processes of EBBA (N-p-Ethoxybenzylidene-p'-butylaniline) have been studied by the method of thermal analysis and measurement of light transmittance. When the sample is cooled down from the nematic phase at a rapid cooling rate, solid phase (solid S) is formed directly. Solid S contains two solid modifications (solid S₁ and solid S₂. By heating the solid S, some amount of Solid S₁ is transformed into the nematic phase through the process of (melting of solid S₁ → crystallization to solid S₂ → melting of solid S₂). After the melting of solid S₁, some liquid crystalline state appears transiently. Solid S₁ is stabilized by the heat treatment at low temperature. The quantity of solid S₁ in solid S increases with the heat treatment time and/or with cooling at a low temperature.     

TiO2烧结助剂对纳米η-Al2 O3制备Al2 O3-Cr2 O3固溶体的影响研究

以纳米η-Al₂O₃粉和工业铬绿为原料,以摩尔比1:1配比制备Al₂O₃-Cr₂O₃固溶体,以TiO₂为烧结助剂,在还原气氛下经1400 ℃、1500 ℃和1600 ℃固相烧结.研究了TiO₂的加入对纳米η-Al₂O₃制备Al₂O₃-Cr₂O₃固溶体的致密度、线收缩率、相组成、晶胞参数、互扩散程度和微观结构的影响.结果表明:TiO₂的加入能促进Al₂O₃-Cr₂O₃固溶体的致密化;当温度为1600 ℃,TiO₂的添加量为2wt;时,试样的体积密度最大为4.57 g·cm^-3,线收缩率为19.8;;TiO₂的加入能使Al₂O₃-Cr₂O₃固溶体中Al³⁺和Cr³⁺的互扩散程度增加;微观结构表明,TiO₂的加入能使Al₂O₃-Cr₂O₃固溶体晶粒之间结合更紧密,实验温度范围内,随着TiO₂添加量的增加晶粒从沿晶断裂向穿晶断裂转变,只在晶间和晶内存在极少量气孔,当温度为1600 ℃,TiO₂的添加量为2wt;时,晶粒大小较均匀,平均晶粒尺寸约10μm.     

Study of the temperature dependence of the electrical conductivity in strontium-barium niobate crystals with different dopants

The electrical characteristics of single crystals of strontium-barium niobate solid solutions have been studied. The temperature dependences of the electrical conductivity were obtained for different SBN compositions, nominally pure SBN:61 and SBN:75 and SBN doped with rare earth and transition-metal impurities. The influence of the chemical composition of a solid solution, thermal treatment conditions, dopant concentration, and electrode type on the specific features of the electrical conductivity of single crystals in the temperature range 20–450°C is shown.     

Growth of equiaxed dendritic crystals settling in an undercooled melt,Part 2: Internal solid fraction

Experiments are conducted to measure the internal solid fraction evolution of equiaxed dendritic crystals that are freely growing and settling in an undercooled melt using the transparent model alloy succinonitrile–acetone. The internal solid fraction is determined from the measured settling speed and crystal envelope shape and size. Depending on the melt undercooling and acetone concentration, the internal solid fraction is found to vary between 0.55 and 0.1. In all experiments, the internal solid fraction decreases continually during settling. Based on heat and solute balances, a model is developed for predicting the internal solid fraction evolution under convective conditions. Nusselt and Sherwood number correlations are obtained that allow for the calculation of the thermal and solutal boundary layer thicknesses at the crystal envelope. The measured and predicted internal solid fraction evolutions are found to be in good agreement.     

Viscosity of Ba-B-Si-Al-O glass measured by indentation creep test at operating temperature of IT-SOFC

Viscosity of a specific Ba-B-Si-Al-O glass used for intermediate-temperature solid oxide fuel cell was measured using indentation creep tests. Responses of shear strain to corresponding shear stress at the operating temperature of solid oxide fuel cell were analyzed, and the results revealed that the glass system possesses Newtonian flow behavior at 600-630 °C. In addition, the stress exponent and the activation energy for viscous flow at different temperatures and stresses were also determined. Finally, the absolute-rate theory was adopted to describe the viscous flow for the glass. The results were compared with other glass systems.     

Morphology analysis of magnesium hydroxide prepared by magnesium oxide hydration within seawater

In order to investigate the microstructure of magnesium oxide hydration product within seawater, two reaction conditions (liquid‐solid and gas‐liquid‐solid) and two solutions (seawater and deionized water) were adopted for magnesium oxide hydration. The characterization of the hydration product using X‐Ray diffraction and scanning electron microscope was performed. Experimental results indicate that cations and anions in seawater promote the hydration. Most of the hydration products within seawater system display flower‐like morphology, but the agglomeration phenomenon is not obvious within deionized water system, especially for the supernatant layer products within deionized water system under gas‐liquid‐solid reaction condition. There was no stratification phenomenon occurred when MgO hydrated with seawater under three‐phase reaction condition.     

X-ray powder diffraction investigations of solid solutions with limited miscibility in the KNO3?NH4NO3?H2O system at 298 K

The measurements of crystal lattice parameters (a, b, c) were conducted and the volumes (v) of unit cells of solid solutions forming in the system KNO₃ NH₄NO₃ H₂O at 298 K were calculated. It was established that in this system at 298 K two series of solid solutions were formed: the mNH₄NO₃ · n(KNO₃ · 2 NH₄NO₃) solid solution with the gap of miscibility and the kKNO₃ · l(KNO₃ · 2 NH₄NO₃) solid solution with one-sided limited miscibility.     

锶铁氧体凝胶注模成形技术研究

锶铁氧体是重要的永磁材料,但锶铁氧体粉体很难制备高固相含量、低粘度的浆料.本实验通过对锶铁氧体粉进行预还原处理,制备出适用于凝胶注模成形的浆料,并进行了在磁场中及不在磁场中的凝胶注模成形.分析了还原处理工艺对锶铁氧体组成的影响,研究了预还原锶铁氧体浆料的流变特性及其磁场凝胶注模成形对材料性能的影响.结果显示:通过预还原处理,可以制备出固相体积分数达46vo1;的预还原锶铁氧体低粘度浆料;预还原锶铁氧体浆料的磁场凝胶注模成型,不能使锶铁氧体材料的晶粒一致取向.     

The co-existence of multi-component liquid and solid intermediate phases before the hetero-LPE of III–V solid solutions

Liquid phase epitaxial growth of III–V solid solutions invariably involves contact between the multi-component saturated or undersaturated liquid and solid phases which are not in thermodynamic equilibrium because either the number of components is different or the composition of the layer to be grown differs from the composition of the underlying layer. The non-equilibrium system must relax to the final equilibrium state through some intermediate ones.The main point of the present review is to show that all non-equilibrium systems encounted in hetero-LPE come through the following stages of relaxation:

• 1.1. Partial dissolution of the solid with simultaneous formation of a thin diffusive dividing layer (0.5–3 nm thick) (DDL) at the solid/liquid interface (in the subsurface region of the solid). The layer contains all the components of the given system and in some cases the quasi-equilibrium between the saturaed multi-component liquid and the solid diffusive dividing layer can be observed experimentally. If the DDL is mismatched to the substrate the former must be strained. So, the Gibbs potential of the solid increased additionally and the liquid must become supersaturated by additionally dissolving the substrate.
• 2.2. The nucleation and the growth of centres of a new phase at some points on the solid/liquid interface with the simultaneous dissolution of the solid at other areas of the same interface (mechanism of “etch-back and regrowth”).
• 3.3. The formation of a continuous epitaxial dividing layer (EDL), separating a bulk solid from a multi-component liquid. At this stage the system stratifies into a three-layer configuration: multi-component liquid/EDL/substrate, further relaxation is limited by a solid state diffusion.

It is only during dedicated experiments on selected systems that stages 1 to 3 can be observed separately in their more or less pure form. Usually, the first and the second stages almost escape experimental detection due to an enormous variability in time scales and an inherent randomness of events during the “fast” stage 2. So, in practice the varied combination of relaxation modes is observed. It is, however, true that, among many parameters which influence the mode of non-equilibrium solid/liquid interface relaxation, the most critical are the temperature of isothermal contact between liquid and solid phases and the lattice mismatch between a substrate and a new solid phase. This concerns not only the magnitude of the mismatch but its sign as well.