Dissolution retardation of solid silica during glass-batch melting

During glass-batch melting, solid silica (quartz) usually dissolves last. The measured rate of dissolution, while the temperature was increasing at a constant rate, was compared with the hypothetical diffusion-controlled volume flux from regularly distributed particles through concentration layers of a uniform thickness. The actual rate was up to two orders of magnitude lower than that of the “ideal” case, revealing a progressive inhibition of silica dissolution. As a measure of this retarded dissolution, we introduced a retardation factor defined as a ratio of the actual and “ideal” dissolution rates measured as the volume flux at the melt-particle interface. The severe inhibition of silica dissolution has been attributed to the irregular spatial distribution of silica particles that is associated with the formation of nearly saturated melt on a portion of their surfaces. Irregular shapes and unequal sizes of particles also contribute to their extended lifetime.     

Formation of crystalline phases by means of solid state reactions at the base of vitreous industrial slags

In comparison with the solid state synthesis from the oxide components melilites are formed from vitreous materials with added oxides at lower temperatures and with higher velocity of reaction resulting in larger and more idiomorphic crystals. The crystallization mechanism of the applied vitreous materials is important for the course of the formation of the texture during sintering depending on their chemical composition. In copper slag with polyphase composition the melilite forming reaction starts during the crystallization of pyroxene using the newly relased relictic glass phase in statu nascendi. Lateron, at higher temperatures the pyroxene also reacts with other components to form melilite. In phosphor furnace slag with stoichiometric composition the polymorphic transformation of calcium silicate (CS) is important for the formation of melilite. The change of the glass structure during the nucleation of wollastonite is the process initiating the reaction. Later at higher temperatures the polymorphic transformation of metastable pseudowollastonite accelerates the formation of melilite. It could be proved that the excess of free energy in glasses speeds up crystal forming reactions with admixture components in sintering processes. The mechanism of structural and phase change processes is reflected in the temperature dependence of reaction velocity.     

Conversion of batch to molten glass, II: Dissolution of quartz particles

Quartz dissolution during the batch-to-glass conversion influences the melt viscosity and ultimately the temperature at which the glass forms. Batches to make a high-alumina borosilicate glass (formulated for the vitrification of nuclear waste) were heated at 5 K min^− 1 and quenched from temperatures of 400 to 1200 °C at 100 K intervals. The batches contained quartz as a silica source, with particles ranging from 5 to 195 μm in diameter. The content of unreacted quartz in the samples was determined with X-ray diffraction. Most of the fine quartz dissolved during the early batch reactions (at temperatures < 800 °C), whereas coarser quartz dissolved mostly in a continuous glass phase via diffusion. The mass-transfer coefficients were assessed from the data as functions of the initial particle sizes and the temperature. A series of batches were also tested that contained nitrated components and additions of sucrose, known to accelerate melting. While sucrose addition had no discernible impact on quartz dissolution, nitrate batches melted somewhat more slowly than batches containing carbonates and hydroxides in addition to nitrates.     

Particle pushing: the concentration of particles near a solid interface during downward flow

We have measured the distribution of insoluble particles within a few millimeters of the tube wall in a downward flowing liquid in order to verify that the velocity gradient mechanism for particle pushing works for particles less than a few hundred microns in diameter. The experimental results show that particles that are denser than the liquid concentrate near the tube wall whereas particles less dense than the liquid migrate away from the wall, leaving a particle deficient layer near the surface, confirming the velocity gradient mechanism. The experimental results have been modelled using the velocity gradient mechanism and the model is in good agreement with experimental results. Calculation shows that the concentration of particles near a solid surface depends on the density and size of the particles, the flow speed and the distance from the inlet of the flow.     

Carbon-limited Dissolution of Oxygen in Niobium

This article deals with results of the invsetigations connected with limitation of oxygen dissolution in niobium by means of creating of the carbide protective coating on the niobium surface or forming of the solid solution of carbon in niobium. It is shown that the carbide coating increases essentially the life time of the niobium parts for vacuum equipment and is consumed as a result of interaction with oxygen. The carbon dissolution in niobium does not hinder redox reaction at the Nb(C)/Nb₂O₅ boundary and causes the conductivity increase of the dielectric film Nb₂O₅.     

Dependence of positron capture rate on dislocation density in solid solutions of KCl—KBr

Generally well-annealed alkali halide crystals exhibit three lifetime components. τ₁ arises due to annihilation with anion and τ₂ due to Bloch Ps. The origin of τ₃ is not well understood. Positron lifetime and etching techniques have been performed on solid solutions of KCl_100−xBr_x with mole % of x = 0.0, 15, 30, 37, 50, 70, and 100. The positron lifetime spectra have been analysed to resolve into three components. The positron capture rate K₃ for the longest lived component and the dislocation density shows a non-linear variation with composition. The positron capture rate varies linearly with the dislocation density of the samples. The origin of τ₃ is identified as due to positronium formation in the dislocations present in the samples. The trapping probability per dislocation has been estimated to be 2.2 × 10⁻¹²/s.     

Etching and Polishing Studies on MgO Crystals in Acids

The effect of temperature and concentration of a variety of inorganic and organic acids, on etch rates is investigated. It is observed that in HCl, CH₃COOH and C₂H₅COOH the value of activation energy of dissolution and that of the corresponding pre-exponential factor are sensitive to acid concentration. In H₃PO₄ and HCOOH, while the value of activation energy remains unchanged, only the pre-exponential factor changes. The concentration dependence of etch rates in HCl, CH₃COOH and C₂H₅COOH is different from that of H₃PO₄ and HCOOH. In the former acids maximum and minimum values are obtained on the etch rate versus concentration curves, but in the letter ones etch rate slowly increases with concentration. The influence of temperature on the maximum value of etch rate on the etch rate-concentration plots of HCl, and that of the degree of dissociation of the acids on etch rate are also studied. The observations are discussed, and important conclusions are enumerated.     

Influence of crystallization conditions on the mechanism and rate of crystal growth of potassium sulphate

Growth rate of potassium sulfate crystals was studied in a fluidized bed crystallizer. Higher growth rates were observed at larger bed heights. Larger crystals grow faster than smaller size crystals due to the changed fluid dynamics. The growth rate was found to be very sensitive to the pH value of the solution. The growth rate increases with increasing the pH value and the increase of growth in the acidic medium is faster than in the basic medium. The presence of small amounts of Cr³⁺ ions reduces the growth rate of potassium sulfate dramatically. The presence of Cr³⁺ ions lowers the saturation temperature and increases the width of the metastable zone, i.e. shifts the metastability of the solution to be at lower level of supersaturation.     

中子辐照MgO晶体的损伤和恢复

用剂量为5.74×1018cm-2的中子对MgO晶体进行了辐照,利用吸收光谱、荧光光谱等手段观测了中子辐照引起的损伤及其恢复.中子辐照产生了大量的阴离子单空位(F+)、阴离子双空位(F2)及其它更高阶的缺陷.通过等时退火,这些缺陷发生了一系列消长和转型的变化过程,并最终在900℃左右全部消失.实验结果表明,吸收峰位于573nm的色心是与位于424nm、451nm的色心类型不同的更高阶的阴离子空位聚集态.     

MgO晶须的物相组成和微观形貌多样性

采用适当MgO-Al比例物料,压制成型后放入气氛炉中于1500℃烧制6h,最终在样块表面得到 MgO晶须.晶须的物相组成为方镁石,显微结构研究表明多数呈细长的柱状,顶端尖锐,长约600～800μm ,长径比100～200;晶须发育的纹理特征有多种,晶须的横截面有扁六边形、正六边形、菱形和正四边形以及不规则形状等多种,能谱分析表明晶须的形貌与化学组成有关.     

氧化镁晶体电注入着色及光谱特性

用自行研制的电注入装置,在不同条件下对氧化镁晶体进行电注入并使之有效着色.在着色晶体中有效地产生大量F、F2和一些未知色心,并探讨了色心形成机理.对着色氧化镁晶体进行了系统光谱测量,确定这些色心的吸收光谱带光谱参数,并对色心形成过程进行分析.结果表明,随着电压的升高,通电时间增长,色心的浓度增大,电注入仅经单步过程,便可获得以往采用其他着色方法多步处理才能产生的多种类色心,更具实用性.     

Dissolution and growth of spinel crystals in a borosilicate glass

The rate of dissolution and growth of settling crystals of spinel was measured optically in a borosilicate melt that was pre-heated at a temperature above liquidus to erase the effects of previous history. The Hixson-Crowell equation, which is based on Fick's first law, was used to determine mass-transfer coefficients (k_H) for dissolution and growth; both were found to fit the same Arrhenius function of temperature (T). An attempt was made to estimate the diffusion coefficient (D) and the concentration-boundary-layer thickness (δ). The calculated values of δ compared well with experimental results and observations. The D vs. T function was similar to a literature function obtained for the dissolution of magnetite in sodium disilicate glass.     

单晶MgO基片超精密加工技术研究

单晶MgO具有良好的物理化学性能及光学性能,是性能优异的薄膜基片及光学零件材料,广泛应用于高温超导、航空航天、光电技术等领域.用作薄膜生长的基片必须具有高精度超光滑无损伤的表面,而单晶MgO是典型的硬脆难加工材料,这对MgO晶体的超精密加工技术提出了很高的要求.本文介绍了单晶MgO的特性及其应用领域,针对高温超导薄膜制备对MgO基片的要求,讨论了现有的MgO基片加工工艺存在的问题,分析了几种可用于MgO基片超精密加工的先进工艺技术的特点和应用研究现状.     

Combustion synthesis and luminescence properties of Dy-doped MgO nanocrystals

MgO nanocrystals doped with Dy³⁺ have been synthesized by a combustion method. The synthesized sample is characterized by X-ray diffraction, transmission electron micrograph, Fourier transform infrared, and photoluminescence spectroscopy. The as-prepared MgO nanocrystals appear to be single cubic crystalline phase and the diameter is in the range of 20–25 nm. The hypersensitive transition (⁴F_9/2→⁶H_13/2 of Dy³⁺) emission is prominent in the emission spectra resulting from the low-symmetry local site at which Dy³⁺ ions locate. In addition, the dependence of the luminescence intensity on Dy³⁺ concentration is also discussed.     

Etching and Dissolution Mechanism of Cadmium Oxalate Trihydrate Crystals

Dislocation etching and dissolution of gel-grown cadmium oxalate trihydrate crystals are carried out using different etchants. The study revealed the existence of dislocation network in the body of the crystal and shallow dislocation loops in the substructure. Faster dissolution of the crystal at elevated temperatures revealed that the rate of dissolution in the initial part of the dissolution time is much lesser, which increases fast to attain a steady value. This observation is related to the available specific surface area of the crystal.     

Morphology of MgO smoke crystallites upon etching in wet environment

The etching of MgO smoke in wet conditions – an archetype for aqueous dissolution of oxide crystals – is explored on the basis of transmission electron microscope (TEM) analyses. In pure water with neutral pH, in acid solutions and in moist air, the MgO cubic crystallites show first (1 1 0) truncations of the 〈1 1 0〉 edges and then (1 1 1) cuts at the corners. Criteria are given to characterize (1 1 0) and (1 1 1) cuts on the TEM images. It is shown that (1 1 0) truncations appear independently of the formation of the (1 1 1) cuts and are associated with a stationary state. The picture is fully consistent with the previous suggestion of a “constrained Wulff profile” [9] which explains the formation of (1 1 0) cuts by excluding (1 1 1) facets.     

Stability of dislocations in MgO single crystals at high temperatures

The dislocation structures of MgO single crystals annealed at 1900 °C for 3 hrs and at 2000°C for 1 hr were observed electron microscopically, and it was found that the following reactions took place at high temperatures: a/2 〈11 0〉 + a/2 [110], = a [100], a/2 [110] + a/2 〈11 01〉 = a/2 [011]. The resultant dislocations were sessile. Their interaction with impurities would make the subgrain boundaries stable.     

四方体MgO的制备及对有机染料的吸附

以六水氯化镁和六次甲基四胺为原料,采用水热法合成四方体MgO,考察其对有机染料甲基橙和亚甲基蓝的吸附行为.通过TGA-DTA、SEM、XRD、N2-sorption和FT-IR等手段表征样品.结果表明,原料浓度、温度和表面活性剂对四方体MgO结构的形成影响较小,而反应时间的延长有助于有序结构的组装.温度170℃、时间24h、MgCl2·6H2O与C6H12N4浓度比为1∶2和表面活性剂PVP是制备四方体MgO的最佳条件.在溶液浓度10mg · L-1的单一吸附实验过程中,四方体MgO对甲基橙和亚甲基蓝的去除率分别为91.3;和22.3;,吸附过程均为单层吸附且符合Langmuir等温吸附模型和伪二级吸附动力学方程.在溶液浓度40 mg·L-1、甲基橙和亚甲基蓝浓度比3∶1的混合溶液吸附过程中,四方体MgO对甲基橙和亚甲基蓝的去除率分别为80.1;和97.9;.