Glass Dissolution Kinetics Research Articles

Aqueous dissolution rate of nuclear waste glasses as a function of aqueous Si concentration and pH

The aqueous dissolution rate was measured precisely for two kinds of reference nuclear waste glasses, ISG and P0798, as a function of aqueous Si concentration and pH of a solution by using the micro-channel flow-through test method with Si isotopes. The glass dissolution rate determined from the Si dissolution rate decreased with increasing aqueous Si concentration at pH 9. In contrast, the dissolution rate at pH 4 was not affected by the Si concentration or increased slightly with an increase in the Si concentration. Therefore, the glass dissolution mechanism with the altered surface properties depended sensitively on pH, causing large changes in the glass dissolution kinetics.

Dissolution of simulated nuclear waste glass at high surface area to solution volume, high pH and 70 °C: comparison of international simple glass and SON68 glass.

Long-term static dissolution experiments, lasting up to ∼1500 days, were conducted on International Simple Glass (ISG) and SON68 glass under hyperalkaline pH, at 70 °C, and at a very high glass surface area to solution volume ratio. The study compared (1) glass dissolution kinetics, (2) secondary phase formation, and (3) the microstructure of the altered glass and secondary phase interface. Boron release indicated rapid initial dissolution followed by a slowdown mainly due to a significant pH drop. ISG reached a residual rate regime, while SON68 approached this regime near the experiment's end, with both glasses having similar final dissolution rates. Electron microscopy (SEM, TEM, EDS) of the reacted glass surfaces and the alteration products revealed nontronite formation on SON68, while C(A)SH phases and later rhodesite appeared on ISG, in addition to phillipsite-type zeolite formation observed in both experimental series. TEM observations revealed a porous, foam-like surface altered layer (SAL) near the pristine glass. SON68's SAL nanostructure, more complex than ISG's, had two porous zones, hindering water transfer and glass constituent release, in addition to a pH drop reducing silica network hydrolysis. TEM-EDS showed cation exchange and iron depletion in SON68's SAL, leading to nontronite formation. Secondary phases at the SAL-solution interface did not destabilize the SAL, and no alteration resumption was observed due to the pH drop below the threshold necessary for an alteration resumption due to zeolite formation. In conclusion, the combination of alkaline conditions and very high reaction progress does not lead to the dissolution of the glass by a dissolution-reprecipitation mechanism, as typically observed at much lower SA/V ratios. At the relatively mildly alkaline pH reached within the first year of the experiments, the diffusion of cations through the SAL becomes rate-controlling.

Aqueous dissolution of Li-Na borosilicates: Insights from machine learning and experiments

Previously acquired data could be utilised in predicting glass dissolution kinetics at long times, but the application of machine learning methods needs to be assessed. Here, the dissolution processes of two Li-Na borosilicate ‘base glasses’ at 40 and 90 °C were investigated by SEM-EDS, NMR and Raman spectroscopy. Boron and sodium machine learning predictions were excellent when considering other normalised releases as features. However, extrapolating the training feature space yielded poorer performance and the absence of incorporated waste elements resulted in underestimated predicted long-term lithium and silicon releases. Faster dissolution kinetics were observed for MW than MW-½Li but the MW-½Li gel layer at 40 °C trapped more water. Whilst BO3 rings leached preferentially at 90 °C, surface enrichment of BO3 at 40 °C suggested [BO4]− transformed prior to dissolution. Results were consistent with interdiffusion being significant at 40 °C and interface-coupled dissolution precipitation beyond 7 days at 90 °C.

Kinetic Monte Carlo Study on the Role of Heterogeneity in the Dissolution Kinetics of Glasses

Kinetic Monte Carlo Study on the Role of Heterogeneity in the Dissolution Kinetics of Glasses

Bioactive glass/poloxamer 407 hydrogel composite as a drug delivery system: The interplay between glass dissolution and drug release kinetics

Since patients suffer pain in the post-surgery of bone repair interventions, bioactive glass/hydrogel drug delivery systems containing local anesthetics, such as ropivacaine, could improve patient life quality by combining bone regeneration with anesthetics. However, poloxamer-based hydrogel properties are sensitive to ions, temperature, and water contents and could be structurally influenced by the ionic dissolution products from bioactive glasses of different compositions. Therefore, this study evaluated the interplay between bioactive glass dissolution kinetics and poloxamer 407 properties, establishing a correlation between changes in the hydrogel and drug release kinetics. Three glass compositions were produced, yielding Ca-rich, Na-rich, and an intermediate glass composition. The influence of Ca/Na ratios on the glass structure and dissolution was investigated. Further, the glasses and ropivacaine were incorporated in the poloxamer hydrogel, and the self-assembly ability of poloxamer, the degradation rate, and the drug release kinetics of the composites were evaluated. The results suggested that glass connectivity affected the early-stage of glass dissolution, while sodium mobility influenced the long-term. The dissolution products from the glasses interact with the supramolecular structure of the poloxamer, causing structural changes responsible for hydrogel degradation. Consequently, by changing the Ca/Na ratio in the glasses, it is possible to modulate glass dissolution that, in turn, influences the ropivacaine release. Thus, we propose that the Ca/Na ratio in quaternary bioactive glasses can be used to modulate drug-delivery properties from systems based on bioactive glasses and poloxamer 407.

Early-Stage Dissolution Kinetics of Silicate-Based Bioactive Glass under Dynamic Conditions: Critical Evaluation.

This manuscript presents a systematic and detailed study of ion release from 45S5 bioactive glass to develop a methodology to directly monitor dissolved ions in a simulated fluid via inductively coupled plasma optical emission spectrometry (ICP OES). For the kinetic study, two dynamic tests, an inline ICP test and a flow-through test, are performed with the same flow rate, temperature, pH, ionic strength of the solution, and sample surface to leaching solution volume ratio. The flow-through test allows for the measurement of an initial dissolution rate, as well the maximum amount of any species released from the surface of the glass. In addition, the data from the inline ICP test are obtained by immediate and direct monitoring of ions from the first minutes of contact of the glass with aqueous fluids with pH values of 4 and 7.4. The overall dissolution rates of the tested commercial bioactive glass in simulated body fluid (SBF) (pH 7.4) were significantly lower compared to the initial rate acquired. The methodology developed in this study can be applied to monitor the controlled release of ions with additional therapeutic functionalities, where the amount of ions released in the first minutes can be critical for the resulting biological performance.

Dissolution Kinetics of International Simple Glass and Formation of Secondary Phases at Very High Surface Area to Solution Ratio in Young Cement Water.

Static dissolution experiments were carried out with the reference International Simple Glass under hyperalkaline pH at 70 °C and very high SA/V ratio. Three aspects of glass dissolution behavior were investigated, (1) the rate drop regime and the residual rate (stage II), (2) the formation of secondary phases including thermodynamic aspects, and (3) the microstructure of the interface of altered glass and secondary phases. A very low residual rate of 6 × 10−6 g/m2d was determined based on boron release, which was several orders of magnitude lower than the initial rate established between the start of the experiments and the first sampling on day 59. The presence of a porous layer with a thickness varying between 80 nm and 250 nm and a pore size between 10 nm and 50 nm was observed. CSH phases with a low Ca/Si ratio of 0.3–0.4 and zeolites were also visible at the surface of the altered glass grains, but no glass alteration resumption occurred, probably due to an important pH decrease already at day 59. Thermodynamic calculations assuming congruent glass dissolution and precipitation of the dissolved aqueous species confirmed the precipitation of CSH phases and zeolites.

Dissolution kinetics of a sodium borosilicate glass in Tris buffer solutions: impact of Tris concentration and acid (HCl/HNO3) identity.

Understanding the corrosion behavior of glasses in near-neutral environments is crucial for many technologies including glasses for regenerative medicine and nuclear waste immobilization. To maintain consistent pH values throughout experiments in the pH = 7 to 9 regime, buffer solutions containing tris(hydroxymethyl)aminomethane ("Tris", or sometimes called THAM) are recommended in ISO standards 10993-14 and 23317 for evaluating biomaterial degradation and utilized throughout glass dissolution behavior literature-a key advantage being the absence of dissolved alkali/alkaline earth cations (i.e. Na+ or Ca2+) that can convolute experimental results due to solution feedback effects. Although Tris is effective at maintaining the solution pH, it has presented concerns due to the adverse artificial effects it produces while studying glass corrosion, especially in borosilicate glasses. Therefore, many open questions still remain on the topic of borosilicate glass interaction with Tris-based solutions. We have approached this topic by studying the dissolution behavior of a sodium borosilicate glass in a wide range of Tris-based solutions at 65 °C with varied acid identity (Tris-HCl vs. Tris-HNO3), buffer concentration (0.01 M to 0.5 M), and pH (7-9). The results have been discussed in reference to previous studies on this topic and the following conclusions have been made: (i) acid identity in Tris-based solutions does not exhibit a significant impact on the dissolution behavior of borosilicate glasses, (ii) ∼0.1 M Tris-based solutions are ideal for maintaining solution pH in the absence of obvious undesirable solution chemistry effects, and (iii) Tris-boron complexes can form in solution as a result of glass dissolution processes. The complex formation, however, exhibits a distinct temperature-dependence, and requires further study to uncover the precise mechanisms by which Tris-based solutions impact borosilicate glass dissolution behavior.

Zero Stress Aging of Glass and Carbon Fibers in Water and Oil—Strength Reduction Explained by Dissolution Kinetics

Understanding the strength degradation of glass and carbon fibers due to exposure to liquids over time is important for structural applications. A model has been developed for glass fibers that links the strength reduction in water to the increase of the Griffith flaw size of the fibers. The speed of the increase is determined by regular chemical dissolution kinetics of glass in water. Crack growth and strength reduction can be predicted for several water temperatures and pH, based on the corresponding dissolution constants. Agreement with experimental results for the case of water at 60 °C with a pH of 5.8 is reasonably good. Carbon fibers in water and toluene and glass fibers in toluene do not chemically react with the liquid. Subsequently no strength degradation is expected and will be confirmed experimentally. All fiber strength measurements are carried out on bundles. The glass fibers are R-glass.

Coupling Radioactive Waste Glass Dissolution Measurements in Generic Groundwaters With Reactive Transport Modeling of Repository Scenarios

AbstractThe reliable simulation of radionuclide migration away from the near field of a geological repository for safety analyses requires a fundamental understanding of processes in the near field. We focus this study on investigating the behavior of UK MW25 waste glass (a nonradioactive simulant of U.K. Magnox glass) and other near‐field components in a geological repository over long periods of time. The approach used involved a two‐step process: waste glass dissolution measurements and modeling in potential repository groundwaters, and reactive transport simulation of radionuclide release and transport in the near field. The Stage 1 rate of MW25 measured in lower‐strength‐sedimentary‐rock groundwater was found to be slightly higher than that measured in higher‐strength‐rock groundwater. Experimental results show the critical role of groundwater chemistry on waste glass dissolution kinetics. Reactive transport model parameterization was accomplished by coupling direct laboratory measurements and literature data with transport processes. The results revealed that 79Se, 99Tc, and 237Np are the radionuclides that will have the greatest impact on the environment at long times. The performance assessment results show that the improvement afforded by the addition of a copper canister in the waste package, as opposed to having only a steel canister, is marginal and higher strength rock would be a more effective barrier at long time than lower strength sedimentary rock in terms of restricting the transport of the radionuclides. Our model provides deep insights into the contribution of waste glass durability and other near‐field components in the containment and retardation of radionuclide transport.

Numerical Modeling of Leaching of Aluminophosphate Glass in the Batch Mode in the Presence of Bentonite

A numerical kinetic model of leaching of aluminophosphate glass, an analog of a glass matrix for radioactive waste, in the batch mode in the presence of bentonite, taking into account the sorption processes, was constructed on the basis of the experimental data. The model describes the glass dissolution kinetics within the framework of the concept of approach to the equilibrium, taking into account shielding of the surface with glass corrosion products. The sorption is described within the framework of the ion exchange model. Modeling was performed using PhreeqC code.

Predicting the dissolution kinetics of silicate glasses by topology-informed machine learning

Machine learning (ML) regression methods are promising tools to develop models predicting the properties of materials by learning from existing databases. However, although ML models are usually good at interpolating data, they often do not offer reliable extrapolations and can violate the laws of physics. Here, to address the limitations of traditional ML, we introduce a “topology-informed ML” paradigm—wherein some features of the network topology (rather than traditional descriptors) are used as fingerprint for ML models—and apply this method to predict the forward (stage I) dissolution rate of a series of silicate glasses. We demonstrate that relying on a topological description of the atomic network (i) increases the accuracy of the predictions, (ii) enhances the simplicity and interpretability of the predictive models, (iii) reduces the need for large training sets, and (iv) improves the ability of the models to extrapolate predictions far from their training sets. As such, topology-informed ML can overcome the limitations facing traditional ML (e.g., accuracy vs. simplicity tradeoff) and offers a promising route to predict the properties of materials in a robust fashion.

Corrosion of the International Simple Glass under acidic to hyperalkaline conditions

Assessment of glass dissolution kinetics, under disposal relevant temperature and pH environments, is required to credibly estimate radionuclide release rates from vitrified radioactive waste. Leaching of the International Simple Glass (ISG) under acidic to hyperalkaline conditions was examined. Forward rate measurements have been obtained using the dynamic leaching SPFT protocol and rate parameters for B, Na and Si in the basic regime; errors in rates predicted using these parameters at high pH and temperature are significant because the fitting uses logarithmic data. Longer term behaviour under hyperalkaline conditions, representative of some disposal environments, was investigated using the PCT and MCC-1 static leaching protocols with Ca(OH)2 solutions for up to 120 days (PCT) and 720 days (MCC-1). In hyperalkaline conditions dissolution was incongruent for all elements and the presence of alternating zirconia-rich and zirconia-poor alteration layers was observed on all leached monoliths, indicating the occurrence of a self-organisation phenomenon during leaching.

Application of GRAAL model to the resumption of International Simple Glass alteration

The methodology developed for predicting nuclear waste behavior under disposal conditions combines experimental approaches and modeling. A waste glass canister placed in contact with water undergoes irreversible chemical processes leading to its degradation into more stable phases. This transformation occurs in three kinetic stages: the initial alteration rate (stage I), the residual rate (stage II), and, in some cases, a resumption of alteration (stage III) related to zeolites precipitation. Affinity effects based on the transition state theory are used to account for the rate drop from stage I to stage II. However, modeling of stage III has not been extensively studied. This study investigates the ability of the "glass reactivity with allowance for the alteration layer" (GRAAL) model to describe the effect of zeolite precipitation on the dissolution kinetics of the international simple glass (ISG). The GRAAL model-based description of the alteration layer was adapted to account for alkaline pH alteration mechanisms. A model describing the nucleation and growth kinetics of zeolites was proposed based on simple formalisms whose parameters can be inferred from previous studies’ results. These improvements give a description of the moment where a resumption of alteration occurs. As the predictive capacity of the GRAAL model is strongly dependent on the appropriateness of the alteration layers’ description, this work shows the need to develop new functions to describe the evolution of their compositions and solubilities with pH changes. Calculations also show the importance of Al and Ca activities and the effect of Al on the silica solubility.

Predicting the dissolution kinetics of silicate glasses using machine learning

Predicting the dissolution rates of silicate glasses in aqueous conditions is a complex task as the underlying mechanism(s) remain poorly understood and the dissolution kinetics can depend on a large number of intrinsic and extrinsic factors. Here, we assess the potential of data-driven models based on machine learning to predict the dissolution rates of various aluminosilicate glasses exposed to a wide range of solution pH values, from acidic to caustic conditions. Four classes of machine learning methods are investigated, namely, linear regression, support vector machine regression, random forest, and artificial neural network. We observe that, although linear methods all fail to describe the dissolution kinetics, the artificial neural network approach offers excellent predictions, even for untrained data, thanks to its inherent ability to handle non-linear data. We further note that the predictive ability of simpler methods, such as linear regression, could be improved using additional physics-based constraints. Such methods, called as physics-informed machine learning can be used to extrapolate the behavior of untrained compositions as well. Overall, we suggest that a more extensive use of machine learning approaches could significantly accelerate the design of novel glasses with tailored properties.

Understanding the structural drivers governing glass-water interactions in borosilicate based model bioactive glasses.

Realizing the goal of designing third generation bioactive glasses requires a thorough understanding of the complex sequence of reactions that control their rate of degradation (in physiological fluids) and the structural drivers that control them. In this article, we have highlighted some major experimental challenges and choices that need to be carefully navigated in order to unearth the mechanisms governing the chemical dissolution behavior of borosilicate based bioactive glasses. The proposed experimental approach allows us to gain a new level of conceptual understanding about the composition-structure-property relationships in these glass systems, which can be applied to attain a significant leap in designing borosilicate based bioactive glasses with controlled dissolution rates tailored for specific patient and disease states.

Dissolution Kinetics of Hot Compressed Oxide Glasses.

The chemical durability of oxide glasses is an important property for a wide range of applications and can in some cases be tuned through composition optimization. However, these possibilities are relatively limited because around 3/5 of the atoms in most oxide glasses are oxygens. An alternative approach involves post-treatment of the glass. In this work, we focus on the effect of hot compression on dissolution kinetics because it is known to improve, for example, elastic moduli and hardness, whereas its effect on chemical durability is poorly understood. Specifically, we study the bulk glass dissolution rate of phosphate, silicophosphate, borophosphate, borosilicate, and aluminoborosilicate glasses, which have been compressed at 0.5, 1.0, and 2.0 GPa at the glass transition temperature (Tg). We perform weight loss and supplementary modifier leaching measurements of bulk samples immersed in acid (pH 2) and neutral (pH 7) solutions. Compression generally improves the chemical durability as measured from weight loss, but the effect is highly composition- and pressure-dependent. As such, we show that the dissolution mechanisms depend on the topological changes induced by permanent densification, which in turn are a function of the changes in the number of nonbridging oxygens and the network cross-linking. We also demonstrate a direct relationship between the chemical durability and the number of chemical topological constraints per atom (nc) acting within the molecular network.

Influence of zeolite precipitation on borosilicate glass alteration under hyperalkaline conditions

This study enables a better understanding of how nucleation-growth of zeolites affects glass dissolution kinetics in hyperalkaline solutions characteristic of cement waters. A 20-oxide borosilicate glass, an inactive surrogate of a typical intermediate level waste glass, was altered in static mode at 50 °C in a hyperalkaline solution rich in Na+, K+ and Ca2+ and at an initial pH50°C of 12.6. Experiments were performed at four glass-surface-area-to-solution-volume (S/V) ratios to investigate various reaction progresses. Two types of glass alteration kinetics were obtained: (i) at low S/V, a sharp alteration resumption occurred after a rate drop regime, (ii) at high S/V, a high dissolution rate was maintained throughout the test duration with a slight progressive slow-down. In all the experiments, zeolites precipitated but the time taken to form stable zeolite nuclei varied dramatically depending on the S/V. Resulting changes in pH affected zeolite composition, morphology, solubility and growth rate. A change in a critical parameter such as S/V affected all the processes controlling glass dissolution.

Numerical simulations of CO2 sequestration in basaltic rock formations: challenges for optimizing mineral-fluid reactions

Abstract Numerical simulations were carried out for determining the chemical reactions relevant for the sequestration of CO2 in basaltic rock formations. The mineralogy of natural geological systems consists of silicate minerals such as the phyllosilicates and zeolites that form complex solid solutions. Using the GEMS code package based on Gibbs energy minimization, combined with the new MINES database, we can now simulate the solubility of these multicomponent and multisite mineral solid solutions in basaltic rocks. This study explores the varying effects of CO2 partial pressures, basaltic glass dissolution kinetics and reaction time on the complex chemistry of the overall CO2-water-basalt reaction path. The simulations indicate four reaction progress stages with the competing reactions between smectites (di- and trioctahedral) and Ca-Fe-Mg-carbonates controlling the amount of CO2 mineralized. A better understanding of these key mineral-fluid reactions and improvement of their thermodynamic models is critical for making more acurate predictive calculations. This comprises the basis for extending the simulations to reactive transport models, and for the assessment of the feasibility of long-term CO2 storage in basaltic rock formations.

Correlating the Network Topology of Oxide Glasses with their Chemical Durability.

Glasses gradually dissolve and corrode when they are exposed to aqueous solutions, and for many applications it is necessary to understand and predict the kinetics of the glass dissolution. Despite the recent progress in understanding the impact of chemical composition on the dissolution rate, a detailed understanding of the structural and topological origin of chemical durability in solutions of different pH is still largely lacking. Such knowledge would enable the tailoring of glass dissolution kinetics as a function of chemical composition. In a recent study focusing on silicate minerals and glasses, a direct relation was demonstrated between the dissolution rate at high pH and the number of chemical topological constraints per atom (nc) acting within the molecular network [Pignatelli, I.; Kumar, A.; Bauchy, M.; Sant, G. Langmuir 2016, 32, 4434-4439]. Here, we extend this work by studying the bulk dissolution rate (Dr) of a wider range of oxide glasses in various acidic, neutral, and basic solutions. The glass compositions have been selected to obtain a wide range of chemistries and values of nc, from flexible phosphate glasses to stressed-rigid aluminosilicate glasses. We show that, in flexible glasses, the internal modes of deformation facilitate the hydration of the network, whereas, in stressed-rigid glasses, the high number of constraints largely inhibits hydration in basic, neutral, and acidic solutions. Our study of chemical dissolution also allows establishing the kinetic mechanisms, which is controlled through an effective activation energy and depends on pH and glass topology. The energy barrier that needs to be overcome to break a unit atomic constraint is approximately constant for pH > 2, but then decreases at lower pH, indicating a change in dissolution mechanism from hydrolysis to ion exchange at low pH. Thus, with this research and existing topological models, the atomistic design of new oxide glasses with a specific chemical durability for a determined pH could become possible.