Microwave-specific heating of crystalline species in nuclear waste glass

The microwave heating of a crystal-free and a partially trevorite-crystallized nuclear waste glass simulant was evaluated. Our results show that a 500-mg monolith of partially crystallized waste glass can be heated from room temperature to above 1600°C within 2 minutes using a single-mode, highly focused, 2.45-GHz microwave, operating at 300 W. Using X-ray diffraction measurements, we show that trevorite is no longer detectable after irradiation and thermal quenching. When a crystal-free analog of the same waste glass simulant composition was exposed to the same microwave radiation, it could not be heated above 450°C regardless of the heating time. The reduction in crystalline content achieved by selectively heating spinels in the presence of glass suggests that microwave-specific heating should be further explored as a technique for remediating crystal accumulation in a glass melt.     

X‐ray tomography of feed‐to‐glass transition of simulated borosilicate waste glasses

High‐level waste feed composition affects the overall melting rate by influencing the chemical, thermophysical, and morphological properties of a cold cap layer that floats on the molten glass where most feed‐to‐glass reactions occur. Data from X‐ray computed tomography imaging of melting pellets comprised of a simulated high‐aluminum feed reveal the morphology of bubbles, known as the primary foam, for various feed compositions at temperatures between 600°C and 1040°C. These feeds were formulated to make glasses with viscosities ranging from 0.5 to 9.5 Pa s at 1150°C, which was accomplished by changing the SiO₂/(B₂O₃+Na₂O+Li₂O) ratio in the final glass. Pellet dimensions and profile area, average and maximum bubble areas, bubble diameter, and void fraction were evaluated. The feed viscosity strongly affects the onset of the primary foaming and the foam collapse temperature. Despite the decreasing amount of gas‐evolving components (Li₂CO₃, H₃BO₃, and Na₂CO₃), as the feed viscosity increases, the measured foam expansion rate does not decrease. This suggests that the primary foaming is not only affected by changes in the primary melt viscosity but also by the compositional reaction kinetic effects. The temperature‐dependent foam morphological data will be used to inform cold cap model development for a high‐level radioactive waste glass melter.     

Formation of the bubble structure in the 26Li<Subscript>2</Subscript>O · 74SiO<Subscript>2</Subscript> glass

The formation of a bubble structure in the glass of composition 26Li₂O · 74SiO₂ is investigated. The stable reproducible characteristics of the bubble structure are obtained, namely, dependences of the number of bubbles on the conditions of glass synthesis, i.e., the synthesis temperature, the synthesis time, and the type of initial reagents. It is shown that the number of bubbles decreases with an increase in the height of the sample (glass melt in the crucible), as well as with an increase in the synthesis temperature at a fixed synthesis time or with an increase in the synthesis time for each specific temperature. The bubble size distribution curves are obtained for all synthesis conditions. The reproducible bubble structure is determined for each layer of the glass sample, which is subsequently used in studying the kinetics of heterogeneous nucleation.     

Effects of Al:Si and (Al + Na):Si ratios on the properties of the international simple glass,part I: Physical properties

Understanding composition-structure-property relationships of high-alumina nuclear waste glasses are important for vitrification of nuclear waste at the Hanford Site. Two series of glasses were designed, one with varying Al:Si ratios and the other with (Al + Na):Si ratios based on the international simple glass (ISG, a simplified nuclear waste model glass), with Al₂O₃ ranging from 0 to 23 mol% (0 to 32 wt%). The glasses were synthesized and characterized using electron probe microanalysis, X-ray photoelectron spectroscopy, small angle X-ray scattering, high-temperature oxide melt solution calorimetry, and infrared spectroscopy. Glasses were crystal free, and the lowest Na₂O and Al₂O₃ glass formed an immiscible glass phase. Evolution of various properties—glass-transition temperature, percentage of 4-coordinated B, enthalpy of glass formation—and infrared spectroscopy results indicate that structural effects differ based on the glass series.     

Spontaneous Bubble Formation in Silicate Melts at High Temperatures

Heating previously melted glasses usually produces gas bubbles in the melt at constant pressure. Bubble formation generally occurs in a narrow temperature range; if experimental conditions are carefully controlled the temperature at which gas bubbles form and the characteristics of the bubbles can be reproduced with reasonable accuracy. Extensive measurements were made with binary silicates of lithia, soda, and potash. Significant bubble evolution occurred only when there was sulfur in the glass. Bubbles formed at quite high temperatures (1400° to 1500°C) in dry oxygen but did not form in reducing atmospheres and quite stable foams resulted. In dry reducing atmospheres some bubble formation was observed at lower temperatures (1200° to 1300°C). The behavior was considerably altered in atmospheres containing water vapor and by changes in base glass composition or sulfur content.     

Effect of the process atmosphere on glass foam synthesis: A high-temperature environmental scanning electron microscopy (HT-ESEM) study

The effect of the process atmosphere composition on the foam formation of cathode-ray tube (CRT) glass containing graphite and MnO₂ was studied using in situ environmental scanning electron microscopy at high temperature (HT-ESEM). When compared to He+4% H₂, O₂ or air, water steam facilitates glass grain sintering. This is probably due to the formation of hydroxyl groups at the glass grain surface that locally decrease the glass viscosity. We have shown that increasing the steam pressure from 50 Pa to 750 Pa decreases both sintering and foaming onset temperatures by approximately 100 °C, favouring the formation of closed pores in viscous glass. At high temperature, the presence of water steam or oxygen promotes foam formation, while the presence of a reducing atmosphere (He+4%H₂) limits glass melt foaming. A synergetic effect of O₂ and H₂O on the onset temperature of glass sintering and foam formation is evidenced.     

Conversion of Nuclear Waste to Molten Glass: Cold‐Cap Reactions in Crucible Tests

The feed‐to‐glass conversion, which comprises complex chemical reactions and phase transitions, occurs in the cold cap during nuclear waste vitrification. To investigate the conversion process, we analyzed heat‐treated samples of a simulated high‐level waste feed using X‐ray diffraction, electron probe microanalysis, leaching tests, and residual anion analysis. Feed dehydration, gas evolution, and borate phase formation occurred at temperatures below 700°C before the emerging glass‐forming melt was completely connected. Above 700°C, intermediate aluminosilicate phases and quartz particles gradually dissolved in the continuous borosilicate melt, which expanded with transient foam. Knowledge of the chemistry and physics of feed‐to‐glass conversion will help us control the conversion path by changing the melter feed makeup to maximize the glass production rate.     

Experimental and numerical investigations of an oxygen single-bubble shrinkage in a borosilicate glass-forming liquid doped with cerium oxide

The shrinkage of an oxygen single-bubble is investigated in a cerium-doped borosilicate glass melt at 1150°C. Nine glass samples are synthesized and investigated, utilizing three different amounts of Ce₂O₃ and three different redox ratios (Ce-(III)/Ce_total). Employing in-situ observation, the single-bubble behavior is recorded with a camera. For each glass melt, five experiments are performed with different initial bubble radii. The shrinkage rate () depends strongly on the cerium content as well as the redox ratio. Numerical calculations are also conducted to support the understanding of the bubble shrinkage mechanism in the given cases. The model adequately estimates the experimental data for several cases, and an explanation is proposed for the cases, in which it does not. Moreover, we demonstrate, physically and mathematically, the influence of the initial radius of the bubble on the mass transfer between the rising bubble and the melt. We confirm the utilization of the “modified Péclet number,” which is a dimensionless number that takes into consideration the influence of multivalent elements on mass transfer. Finally, we master the bubble shrinkage behavior by normalizing the experimental data employing a characteristic time for the mass transfer (τ).     

Corrosion behavior of Monofrax K-3 refractory in borosilicate-based model low activity waste glass melts

Owing to its good chemical and thermal durabilities at high temperatures, Monofrax K-3 refractory is widely used in nuclear waste vitrification as a lining material in melting vessels. However, the corrosion of K-3 refractory during the vitrification of nuclear waste is a serious problem because it affects the melter's safety, performance, and lifetime. Therefore, in the present study, we have focused on unearthing the impact of glass network formers, such as SiO₂, B₂O₃, and Al₂O₃, in a model nuclear waste glass composition on the corrosion of Monofrax K-3 refractory. The corrosion tests have been performed per ASTM C621 at 1150°C for 5 days. The dimensional measurements on corroded K-3 refractory suggest that Al₂O₃ and SiO₂ tend to reduce the refractory corrosion (neck loss), with the effect of Al₂O₃ being significant. A corroded region on the K-3 refractory at the melt–refractory interface is observed. The corrosion occurs via a coupling of the melt infiltration induced by a capillary effect and the dissolution of Al, Mg, and Fe components from K-3 into the melt through chemical reactions. A Cr-rich layer is retained on the glass contact surface of the corroded K-3 refractory.     

Production of alumino-borosilicate foamed glass body from waste LCD glass

A foaming process for waste LCD glass is presented, in which waste LCD glass is recycled to produce alumino-borosilicate foamed glass, which can eventually be used as a heat-insulating material, a light-weight aggregate for civil engineering applications, or a carrier for sewage treatment. The effects on waste LCD glass foaming of a variety of carbon foaming agents, metal salt foaming agents, and bonding agents are examined, as well as other factors such as chemical composition, foaming temperature, and grain size of the raw materials from the waste LCD glass. After examining all the variables that influence the foaming process, it was confirmed that the waste LCD glass is suitable as a raw material for producing alumino-borosilicate foamed glass. The alumino-borosilicate foamed glass has excellent physical properties, with density less than 0.14 g/cm³, heat conductivity less than 0.054 W/(mK) @20 °C, bending strength more than 35 N/cm², compressive strength more than 39 N/cm² and a coefficient of linear thermal expansion less than 4.5 × 10^?6 m/m °C. This clearly shows that the lightweight alumino-borosilicate foamed glass could be useful for various applications.     

Visualisation research on characteristics of the cryogenic slug flow in vertical and inclined tubes

The statistical parameters of Taylor bubbles in cryogenic slug flow along glass tube were studied experimentally for various inclination angles θ (0°–60° from the vertical direction) and four tube inner diameters D (14, 18, 25 and 32 mm) by using high speed digital camera. The distributions and mean values of initial formation position, and the length and velocity of Taylor bubbles along the tube at various inclination angles were obtained. Initial position of Taylor bubbles increases as tube inner diameter increases and the effect of tube diameter on Taylor bubble initial position becomes more obvious at θ ≥ 30°. Taylor bubble length shows an allometric decreasing trend with the increasing of tube inner diameter. The influence of inclination angle and axial position on the length and velocity of Taylor bubble in cryogenic slug flow agrees qualitatively with conventional air–water system. The maximum mean velocity of Taylor bubble occurs at 30° ≤ θ ≤ 45° and the minimum mean length of Taylor bubble occurs at 0° ≤ θ ≤ 20°. The Mean length of Taylor bubble increases along the tube for x/D ≤ 60. © 2011 Canadian Society for Chemical Engineering     

浮法玻璃下开口泡形成机理研究

通过对某锡槽槽底温度升高时,玻璃板下开口泡的气体分析,发现该气泡组分主要是氢气;根据气泡形成相关理论计算结合生产实际情况,研究分析表明,浮法玻璃下开口氢气泡形成的主要机理是锡槽槽底温度升高,槽底气体空间中氢气通过耐火砖贯通孔扩散溶入锡液中,形成氢的过饱和溶液,过饱和的氢再向耐火砖表面易于形成气泡的开口孔处聚集、形成气泡并长大、上浮,最终导致玻璃板下开口泡缺陷.     

The influence of iodide on glass transition temperature of high-pressure nuclear waste glasses

The glass transition temperature (T_g) is a key parameter to investigate for application in nuclear waste immobilization in borosilicate glasses. T_g for several glasses containing iodine (I) has been measured in order to determine the I effect on T_g. Two series of glass composition (ISG and NH) containing up to 2.5 mol% I and synthesized under high pressure (0.5 to 1.5 GPa) have been investigated using differential scanning calorimetry (DSC). The I local environment in glasses has been determined using X-ray photoelectron spectroscopy and revealed that I is dissolved under its iodide form (I⁻). Results show that T_g is decreased with the I addition in the glass in agreement with previous results. We also observed that this T_g decrease is a strong function of glass composition. For NH, 2.5 mol% I induces a decrease of 24°C in T_g, whereas for ISG, 1.2 mol% decreases the T_g by 64°C. We interpret this difference as the result of the I dissolution mechanism and its effect on the polymerization of the boron network. The I dissolution in ISG is accompanied by a depolymerization of the boron network, whereas it is the opposite in NH. Although ISG corresponds to a standardized glass, for the particular case of I immobilization it appears less adequate than NH considering that the decrease in T_g for NH is small in comparison to ISG.     

Behavior of Multicomponent Gas Bubbles in Glass Melts

A mathematical model is proposed to study the behavior of multicomponent gas bubbles in glass melts. The effects of the melt temperature on bubble radius, trajectory, and composition were studied as a function of time, both accounting for and disregarding bubble boundary motion. It is shown that accounting for the boundary motion results in shorter refining times, smaller bubbles, and larger concentrations of the gaseous species than if this motion is disregarded. It is also shown that the bubble trajectory is almost a linear function of time and that mass transfer has a very small effect on bubble trajectory and refining times; however, it has a strong influence on the bubble radius, which, in the absence of mass transfeir, increases linearly with the temperature.     

泡沫玻璃气泡缺陷与解决方案

泡沫玻璃是一种具有均匀气泡结构的玻璃制品,具有隔热、吸声、防潮、防火等特点的轻质高强建筑材料和装饰材料。泡沫玻璃的生产过程中,经常会遇到气泡结构不均或大气泡等气泡缺陷。本文从气泡的产生机理分析入手,针对具体的气泡缺陷种类,分析产生原因,提出解决方案,更好地实现泡沫玻璃的内在和外观质量。     

Synthesis of yttrium titanate stannate (Y2Ti2−xSnxO7, x = 0–2) pyrochlore glass–ceramics as potential nuclear waste form

Y₂Ti_2−xSn_xO₇ (x = 0–2) pyrochlore sodium aluminoborosilicate glass–ceramics (GCs) are produced by calcining the pelletized Y–Ti–Sn oxide mixture and glass precursor at 1200 or 1300°C for 4 h. The metal oxide mixture is prepared by a soft chemistry route. X-ray diffraction, Raman spectroscopy, and electron microscopy are employed to investigate the formation of pyrochlore GCs and local crystal structures. Near phase pure Ti-rich pyrochlores are produced with minor phase SnO₂ observed for Sn-rich materials. The cell parameters of the pyrochlore structures refined by Le Bail fitting are in good agreement with the published data and increase linearly with the gradual increment of Sn substitution. With progressively increasing Sn proportion on pyrochlore B-site, Raman characteristic bands of the pyrochlore structure become sharper and well defined. The Raman A_1g peak position and its full width at half-maximum are linearly progressed with increasing x (Sn). The presence of the melting glass facilitates the pyrochlore formation, with ceramic grain sizes ranging from submicron to microns. Transmission electron microscopy and selected area electron diffraction observations indicate the sample possesses a relatively high crystallographic perfection at the atomic level. This new series of pyrochlore GCs and the method disclosed herein may pave the way for further materials development as potential nuclear waste forms.     

Bubble growth model and its influencing factors in a polymer melt under nonisothermal conditions

Traditionally, in order to simplify the bubble growth process in a polymer melt, an isothermal model is typically used. In fact, the temperature of the polymer melt is changing during the foaming process. In order to accurately study the growth mechanism of bubbles in polymer melts, we build a physical and mathematical model of bubble growth in a polymer melt under nonisothermal conditions. The parameters of pressure, zero-shear viscosity, relaxation time, Henry's constant, diffusion coefficient, and surface tension were determined. The fourth-order Runge–Kutta method was used to solve the nonisothermal bubble model in the polymer melt. A computational program is developed to find the dimensional change during the bubble growth process, and the correctness of the model is verified. The nonisothermal growth mechanism of and factors influencing bubbles in the polymer melt are analyzed. Combined with the design of experiment (DOE) analysis method, the transfer function of the bubble radius and the maximum growth rate of bubbles with the process parameters were obtained, such as cooling rate, system pressure, and gas concentration. The results show that system pressure has the most significant effect on bubble growth. At the same time, a bubble growth prediction model is built, which can be used to predict the growth of bubbles. Through optimization analysis, it can be used to control the growth of bubbles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47210.     

浅议浮法玻璃气泡问题的分析与解决

在生产实践中,玻璃产品中的气泡问题一直是困扰玻璃生产厂家的一大难题。本文介绍了某玻璃企业玻璃产品出现气泡以后的观察、分析和解决过程,提出气泡的形成、变化、消失、再出现的过程,是气体在玻璃熔体中溶解和扩散的结果,了解各种气体在玻璃熔体中的特性和行为方式,有针对性地确定好玻璃熔化的温度曲线和燃料分配,这对减少玻璃中气泡是很重要的。     

Radiation Characteristics of Glass Containing Gas Bubbles

In many materials processing and manufacturing situations such as steel, aluminum, ceramics, and glass, gas bubbles can form in liquid and solid phases. The presence of such bubbles affects the thermophysical properties and radiation characteristics of the two-phase system and hence the transport phenomena. This paper presents a general formulation of the radiation characteristics of semitransparent media containing large gas bubbles (bubble radius is much larger than the wavelength of radiation). Sample calculations for the spectral absorption and extinction coefficients and single scattering albedo of soda–lime silicate glass containing bubbles are discussed. Particular attention is paid to the effect of the volumetric void fraction and the bubble size distribution. Results clearly show that the presence of bubbles strongly affects the radiation characteristics of the semitransparent media containing entrapped gas bubbles, particularly if bubbles, void fractions, and the spectral absorption coefficient of the continuous phase are small.     

通过气泡成分分析解决超白浮法玻璃生产中的气泡缺陷

气泡是玻璃生产中最常见的玻璃缺陷之一,由于它的大小、密度、位置的不确定性,增加了对气泡缺陷来源诊断的难度。超白浮法玻璃生产中气泡更是影响玻璃质量的主要缺陷,通过测定气泡中气体的组成含量,可以较准确、快速地判断该缺陷产生的根源,从而采取有效措施消除缺陷。