Rheology evolution of a geopolymer precursor aqueous suspension during aging

Geopolymer-based glass-ceramic matrix composites can be processed at room temperature and a heat treatment below 100°C leads to matrix hardening thanks to the geopolymerization mechanisms. The stabilization of the matrix into glass-ceramics is achieved via a post-curing at high temperature. This paves the way of the utilization of cost-effective liquid composite molding processes, for which all the necessary equipment is already available for processing temperature ranges related to polymer matrix composites, provided that the rheological behavior of the precursor is suitable to conveniently permeate the fibrous preform. The paper describes the thixotropic rheological behavior of a reference suspension at processing temperature (10°C-20°C) and its evolution along aging at −18°C. The changes are interpreted in terms of geopolymerization mechanisms (dissolution and polycondensation) and suspension rheology (predominance of hydrodynamic effects at high shear rate). On this basis, a phenomenological modeling framework, combining two Krieger-Dougherty equations, is proposed to build a relationship between the effective viscosity of the suspension and the phenomena involved during aging (dissolution of aluminosilicate particles) and shearing (microstructure scalar variable).     

Glass production rate in electric furnaces for radioactive waste vitrification

Correlating the melting rates of feeds in electric melters with results of simple laboratory experiments can help evaluate melter feed additives and their effects on melting rate, and support the feed scheduling and plant operation. A recently proposed melting rate correlation (MRC) equation, relating the melting rate to melt viscosity, feed-to-glass conversion heat, and cold-cap bottom temperature, was tested using data from experiments covering various feed compositions and melter operating parameters. The MRC equation is shown to reasonably represent the measured data and thus can be used to quantify how individual variables (melt viscosity, cold-cap bottom temperature, conversion heat, melter operating temperature, and bubbling flux) affect the glass production rate.     

Dynamic Rheology of Agar Gel Based Aqueous Binders

Dynamic rheology was used to study the gelation behavior of agar gel based aqueous binders (1–3 wt%) for powder injection molding. Typical gelation temperatures, T _gel, and liquefaction temperatures, T _liq, were 36° and 78°C, respectively. The thermal history of the gels was found to influence T _gel and the asymptotic storage modulus, G '. A higher degree of undercooling (Δ T = T _gel− T _hold) enhanced the driving force for gelation. G ' master curves were created and revealed a relatively weak frequency dependence. G ' increased significantly with agar content. The shape of the gel's relaxation spectrum was found to be independent of agar content, indicating that the nature of the relaxation processes does not change significantly.     

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.     

玻璃固化体抗浸蚀性能实验研究进展

玻璃固化是高放废物固化中较成熟、应用较广的一种技术。本文综述了玻璃固化体的浸出机理、浸出模型及浸蚀实验方法的研究进展。针对目前对温度和pH这两种因素在静态条件下的影响情况研究较多,对气体环境、压强和辐射等因素对玻璃固化体浸出行为的影响研究较少的现状,建议今后应重点进行玻璃固化体受浸泡剂-温度-辐射-压力-气流等多种因素耦合作用影响的抗侵蚀实验研究。     

Direct-Write Fabrication of Pb(Nb,Zr,Ti)O3 Devices: Influence of Paste Rheology on Print Morphology and Component Properties

Lead niobium zirconate titanate (PNZT) pastes with tailored rheological properties have been developed for direct-write fabrication of thick-film capacitor elements in highly integrated, multifunctional electroceramic devices. Such pastes exhibited pseudoplastic behavior with a low shear apparent viscosity of roughly 1 × 10⁶ cP. On aging, the degree of shear thinning and the low shear apparent viscosity decreased. Pastes prepared from as-received powders attained printable, steady-state viscosities of ∼2 × 10⁵ cP after 50 days of aging. In contrast, pastes prepared from dispersant-coated powders showed no measurable rheological changes after 1 day of aging. Square elements were patterned on dense alumina substrates or Teflon sheets. Leveling behavior as a function of time for single line prints, and the resulting surface topographies of dried PNZT films were measured by laser profilometry. PNZT layers sintered at varying temperatures between 950° and 1050°C for 5 h in either air or a lead-rich atmosphere yielded porous microstructures as revealed by scanning electron microscopy (SEM). Such layers exhibited dielectric constants ( K ) of 1400–1570 at 1 kHz with dissipation factors ( D ) of less than 4.1%.     

Isolating the effects of thixotropy in geopolymer pastes

The rheological properties of potassium-based geopolymers were investigated through a series of experiments intended to isolate the influence of shear rate, recovery time, and shear ramping on thixotropy for a greater understanding of geopolymer thixotropic properties within the context of the geopolymer setting reaction. It is shown that for thixotropic disruption to occur a critical shear rate of 100 s⁻¹ must be reached or surpassed, full thixotropic restructuring occurs at around 90–100 min of total undisturbed rest time, and that reaching a state of full thixotropic disturbance heavily depends on subjected processing parameters. In addition, a consistent crossover between the storage and loss modulus within 1–3 min of oscillation during cyclical oscillatory measurements greatly indicates the repeatability and reversibility of thixotropy in geopolymers and the potential for tailorable viscosity. Overall, it is found that geopolymer pastes exhibit strong evidence of thixotropy, which is favorable for additive manufacturing, and that allotted rest time before shear and shear rate greatly influence the overall rheological properties.     

Thermodynamic assessment of the hollandite high-level radioactive waste form

Hollandite has been studied as a candidate ceramic waste form for the disposal of high-level radioactive waste due to its inherent leach resistance and ability to immobilize alkaline-earth metals such as Cs and Ba at defined lattice sites in the crystallographic structure. The chemical and structural complexity of hollandite-type phases developed for high-level waste immobilization limits the systematic experimental research that is required to understand phase development due to the large number of potential additives and compositional ranges that must be evaluated. Modeling the equilibrium behavior of the complex hollandite-forming oxide waste system would aid in the design and processing of hollandite waste forms by predicting their thermodynamic stability. Thus, a BaO–Cs₂O–TiO₂–Cr₂O₃–Al₂O₃–Fe₂O₃–FeO–Ga₂O₃ thermodynamic database was developed in this work according to the CALPHAD methodology. The compound energy formalism was used to model solid solution phases such as hollandite while the two-sublattice partially ionic liquid model characterized the oxide melt. Results of model optimizations are presented and discussed including a 1473 K isothermal BaO–Cs₂O–TiO₂ pseudo-ternary diagram that extrapolates phase equilibrium behavior to regions not experimentally explored.     

Melter feed viscosity during conversion to glass: Comparison between low‐activity waste and high‐level waste feeds

During nuclear waste vitrification, a melter feed (a slurry mixture of a nuclear waste and various glass forming and modifying additives) is charged into the melter where undissolved refractory constituents are suspended together with evolved gas bubbles from complex reactions. Knowledge of flow properties of various reacting melter feeds is necessary to understand their unique feed‐to‐glass conversion processes occurring within a floating layer of melter feed called a cold cap. The viscosity of two low‐activity waste (LAW) melter feeds were studied during heating and correlated with volume fractions of undissolved solid phase and gas phase. In contrast to the high‐level waste (HLW) melter feed, the effects of undissolved solid and gas phases play comparable roles and are required to represent the viscosity of LAW melter feeds. This study can help bring physical insights to feed viscosity of reacting melter feeds with different compositions and foaming behavior in nuclear waste vitrification.     

Direct ink writing of hierarchical porous alumina-stabilized emulsions: Rheology and printability

Bio-inspired multi-scaled (hierarchical) porous structures have remarkable strength and stiffness-to-density properties. Direct ink writing (DIW) or robocasting, an additive manufacturing (or also commonly known as 3D printing) material extrusion technique is able to create near-net-shaped complex geometries. A new approach of combining DIW, colloidal particle-stabilized emulsion paste inks and partial densification to create tailored architectures of hierarchical porosity on three scales has been demonstrated. The printed and sintered ceramic lattice structures possess relatively high overall porosity of 78.7% (on average), comprising mainly (64.7%) open porosity. The effects of formulation (surfactant and oil concentrations, solids particle size, and mixing speed) on rheology and pore size and morphology have been investigated. The rheological properties (storage modulus, yield stress, and recovery of storage modulus) of the emulsions have been found to delineate the samples with good shape retention from those that slump. Additionally, the internal features of the sintered structures have been analyzed via X-ray tomography and scanning electron microscope. The role of emulsion stability on printability and the internal structure of the prints has been investigated.     

Predicting nepheline precipitation in waste glasses using ternary submixture model and machine learning

Nepheline precipitation in nuclear waste glasses during vitrification can be detrimental due to the negative effect on chemical durability often associated with its formation. Developing models to accurately predict nepheline precipitation from compositions is important for increasing waste loading since existing models can be overly conservative. In this study, an expanded dataset of 955 glasses, including 352 high-level waste glasses, was compiled from literature data. Previously developed submixture models were refitted using the new dataset, where a misclassification rate of 7.8% was achieved. In addition, nine machine learning (ML) algorithms (k-nearest neighbor, Gaussian process regression, artificial neural network, support vector machine, decision tree, etc.) were applied to evaluate their ability to predict nepheline precipitation from glass compositions. Model accuracy, precision, recall/sensitivity, and F1 scores were systemically compared between different ML algorithms and modeling protocols. Model prediction with an accuracy of ~0.9 (misclassification rate of ~10%) was observed for different algorithms under certain protocols. This study evaluated various ML models to predict nepheline precipitation in waste glasses, highlighting the importance of data preparation and modeling protocol, and their effect on model stability and reproducibility. The results provide insights into applying ML to predict glass properties and suggest areas for future research on modeling nepheline precipitation.     

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.     

Investigation of high-level waste glass melting using X-ray computed tomography

A method has been developed to quantitatively assess the melting behavior of simulated nuclear waste glasses in a 5-cm-diameter stainless steel beaker heated from the bottom. The method applies X-ray scanning and computed tomography to build three-dimensional volumetric data of a heat-treated sample and performs an adaptive segmentation analysis of the volumetric data to identify morphologically distinct regions in the sample matrix and quantify the amount of material in each region based on computed tomography density. The method was applied to two different series of simulated high-level waste glass melter feeds, and the results showed that it provides detailed images of samples at various stages of melting, including distribution of gas bubbles of varying sizes within the sample matrix, as well as a quantitative measure of how fast various waste/frit feeds melted relative to each other. The results show that the melting rate is influenced by the rate of calcine gas evolution, melt viscosity, and the presence of modifier ions in the feed.     

Thermal properties of simulated Hanford waste glasses

The Hanford Tank Waste Treatment and Immobilization Plant will vitrify the mixed hazardous wastes generated from 45 years of plutonium production at the Hanford Site in Washington State. The molten glasses will be poured into stainless steel containers or canisters and subsequently cooled for storage and disposal. For appropriate facility design and operations to handle such highly energy‐consuming processes, knowledge of the material properties is required. The thermal properties (heat capacity, thermal diffusivity, and thermal conductivity) of representative high‐level and low‐activity waste glasses were studied as functions of temperature in the range of 200°C‐800°C (relevant to the cooling process). Simultaneous differential scanning calorimetry‐thermal gravimetry (DSC‐TGA), Xe‐flash diffusivity, pycnometry, and dilatometry were implemented. The study showed that simultaneous DSC‐TGA would be a reliable method for obtaining the heat capacity of various glasses in the temperature range of interest. Accurate thermal properties from this study were shown to provide a more realistic guideline for capacity and time constraints of the heat removal process when compared to the original conservative design‐basis engineering estimates. The estimates, though useful for design in the absence of measured physical properties, can now be supplanted and the measured thermal properties can be used in design verification activities.     

Rheological Characterization of Synergistic Mixtures of Carrageenan and Locust Bean Gum for Aqueous Gelcasting of Alumina

Previous works have shown that carrageenan can be successfully used in the aqueous gelforming of powders, because carrageenan forms a firm gel, similar to that formed by agarose, but at a much lower cost. In this work, the synergistic effect of carrageenan with locust bean gum is studied. The rheological behavior of 2 wt% solutions of these polysaccharides and their mixtures are measured under mixing conditions (60°C) and by recording the viscosity and elastic modulus on cooling. The effect of the addition of these solutions to 50 vol% alumina slurries up to a concentration of 0.5 wt% is studied. Although gelling time increases, the resulting gels are stronger than for carrageenan alone. Gelcast alumina bodies with green and sintered densities of 57% and 97.6% of theoretical have been obtained.     

Gelation, Consolidation, and Rheological Properties of Boehmite-Coated Silicon Carbide Suspensions

We have studied the gelation, consolidation, and rheological properties of boehmite-coated SiC suspensions. A boehmite-coated SiC suspension consists of SiC particles covered with a boehmite layer of a few nanometers in thickness in the suspension. Similar to boehmite suspensions, the boehmite-coated SiC suspension can gel over time. The gelation, as well as the rheological behavior of the boehmite-coated SiC suspension with respect to pH, is shown to be similar to that of a boehmite suspension. However, because of the particle-size difference, a boehmite-coated SiC suspension gels more slowly than suspensions of smaller boehmite particles. The boehmite coating improves the consolidation density of SiC, increasing the sediment density from 39 to 52 vol% and the centrifuged density from 50 to 60 vol%. It, also, makes the consolidation behavior of a boehmite-coated SiC suspension with respect to pH more consistent with the rheological behavior; i.e., lower suspension viscosity and storage modulus correlate with a higher consolidated density. In contrast, suspensions containing SiC particles partially covered with boehmite and individual boehmite particles in the suspensions show no improvement in the sediment density and no systematic correlation between the consolidation density and the rheological properties. This indicates that the complete coating of boehmite on the SiC particles is critical to the improvement in consolidation density.     

Influence of Acidity on the Stability and Rheological Properties of Ionically Stabilized Alumina Suspensions in Ethanol

The ionic stability of alumina particles in moderately concentrated ethanol suspensions is studied. Surface chemistry and interparticle forces are manipulated by controlling the acidity of the suspensions without dispersants. The acidity of ethanol solution is determined using ion transfer functions, wherein the relationships between acidity, alumina particle surface charge, zeta-potential, stability, and suspension rheological behavior are established. Positive isoelectric point (IEP) shift is observed for alumina in ethanol on increasing the solids concentration. However, dilute and concentrated aqueous suspensions of alumina give the same IEP. The viscosity and flow curves for alumina/ethanol suspensions are acidity dependent. The flow curves of the suspensions follow the Casson model, and the Casson yield value is used to evaluate suspension stability.     

Accelerated Leach Testing of GLASS (ALTGLASS): I. Informatics approach to high level waste glass gel formation and aging

Glass corrosion data from the ALTGLASS^™ database were used to determine if gel compositions, which evolve as glass systems corrode, are correlated with the generation of zeolites and subsequent increase in the glass dissolution rate at long times. The gel compositions were estimated based on the difference between the elemental glass starting compositions and the measured elemental leachate concentrations from the long-term product consistency tests (ASTM C1285) at various stages of dissolution, ie, reaction progress. A well-characterized subset of high level waste glasses from the database was selected: these glasses had been leached for 15-20 years at reaction progresses up to ~80%. The gel composition data, at various reaction progresses, were subjected to a step-wise regression, which demonstrated that hydrogel compositions with Si^*/Al^* ratios of <1.0 did not generate zeolites and maintained low dissolution rates for the duration of the experiments. Glasses that formed hydrogel compositions with Si^*/Al^* ratios ≥1, generated zeolites accompanied by a resumption in the glass dissolution rate. The role of the gel Si/Al ratio, and the interactions with the leachate, provides the fundamental understanding needed to predict if and when the glass dissolution rate will increase due to zeolitization.     

Effects of Boehmite-Coating Thickness on the Consolidation and Rheological Properties of Boehmite-Coated SiC Suspensions

We examined the effect of the boehmite coating thickness on the rheology and consolidation of boehmite-coated SiC suspensions. The thickness of the boehmite coating on SiC was varied by adjusting the boehmite concentration relative to SiC. For boehmite concentrations less than 10 wt%, the coating thickness increased with increasing boehmite concentration. For boehmite concentrations higher than 10 wt%, the coating thickness saturated. Further increase in the boehmite concentration led to the presence of small boehmite particles in the suspensions. All boehmite-coated suspensions gelled near their isoelectric points and the storage moduli of the gels with respect to pH exhibited a maximum near the isoelectric points. Below 10 wt% boehmite, the suspensions had very few small boehmite particles. The maximum storage modulus, G ^'_0,max, of the boehmite-coated SiC gel decreased with increasing coating thickness, t , as G ^'_0,max∝ t ⁻², in good agreement with our earlier theoretical prediction. Meanwhile, the maximum sedimentation densities, φ_max, of the coated suspensions occurred at around pH ∼ 4.0 and increased with increasing coating thickness from under φ_max= 25 vol% with 1 wt% boehmite to above φ_max= 65 vol% with 10 wt% boehmite due to increased zeta potential with increasing coating thickness. Above 10 wt% boehmite, the excess boehmite particles in the suspension increased the maximum suspension storage modulus, G ^'_0,max, and decreased the maximum sedimentation density, φ_max.