Incorporation limit of MoO3 in sodium borosilicate glasses

Optimizing the concentration of molybdenum incorporated in a borosilicate glass matrix is essential in the vitrification of high-level radioactive waste. However, the incorporation limit of MoO₃ in fundamental borosilicate systems has been rarely correlated with the local structure of the molybdenum cations. This study investigates the variations in the incorporation limit of MoO₃ in ternary sodium borosilicate glass upon varying the B₂O₃/(SiO₂ + B₂O₃) ratio (i.e., B)_. The incorporation limit of MoO₃ was less than 3 mol% in the low-B region (B < 0.7), where molybdenum cations mainly existed as [MoO₄]²⁻. However, when B was higher than 0.85, the incorporation limit was higher than 6 mol%, and the Raman spectra indicated the presence of octahedrally coordinated molybdenum cations, essential to stabilize the Mo–O–Mo linkage. The variation in the local structure of molybdenum cations can be explained by the available amount of non-framework cations compensating for the negative charge near [MoO₄]²⁻. These results allow the development of glass compositions with a high incorporation limit of MoO₃ simply by controlling the local structure near the molybdenum cations.     

Structural drivers controlling sulfur solubility in alkali aluminoborosilicate glasses

If the direct feed approach to vitrify the Hanford's tank waste is implemented, the low activity waste (LAW) will comprise higher concentrations of alkali/alkaline-earth sulfates than expected under the previously proposed vitrification scheme. To ensure a minimal impact of higher sulfate concentrations on the downstream operations and overall cost of vitrification, advanced glass formulations with enhanced sulfate loadings (solubility) are needed. While, the current sulfate solubility predictive models have been successful in designing LAW glasses with sulfate loadings <2 wt.%, it will be difficult for them to design glass compositions with enhanced loadings due to our limited understanding of the fundamental science governing these processes. In this pursuit, this article unearths the underlying compositional and structural drivers controlling the sulfate solubility in model LAW glasses. It has been shown that the preferentially removes non-framework cations from the modifier sites in the silicate network, thus, leading to the polymerization in the glass network via the formation of ring-structured borosilicate units. Furthermore, though the sulfate solubility slightly decreases with increasing Li⁺/Na⁺ in the glasses, the prefers to be charge compensated by Na⁺, as it is easier for to break Na–O bonds instead of Li–O bonds.     

Effect of irradiation on the atomic structure of borosilicate glasses

Borosilicate glasses incorporating high-level nuclear waste are exposed to high-energy radiations during their storage in the deep geological repositories. However, the effect of radiation on the atomic structure of borosilicate glasses remains poorly understood. Herein, using molecular dynamics simulations, we study the irradiation-induced structural changes of a series of calcium-sodium borosilicate glasses with varying Si/B molar ratios—ranging from pure silicate to pure borate glasses. We observe that irradiation leads to an increase in disorder, both in the short- and medium-range, as evidenced by the enthalpy, coordination number, and ring distribution. In particular, the impact of the change in the atomic structure (due to radiation) on the glass volume is investigated. Interestingly, we observe a composition-dependent transition in the volumetric response of borosilicate glasses under irradiation—wherein borate-rich compositions tend to swell, whereas silica-rich glasses tend to densify. Through a detailed analysis of the structure, we demonstrate two competing mechanisms contributing to the volume change, i.e., a decrease in the coordination number of boron atoms and a reduction in the average silicon inter-polytope angle. We also show that the increase in the disorder in the medium-range order may play a major role in governing the volumetric changes in the irradiated structure in a non-trivial fashion. Altogether, the present study highlights that irradiation has a non-trivial effect on borosilicate glasses, which, in turn, could impact their corrosion kinetics.     

Surface structures of sodium borosilicate glasses from molecular dynamics simulations

Surface plays an important role in the physical and chemical properties of oxide glasses and controls the interactions of these glasses with the environment, thus dominating properties such as the chemical durability and bioactivity. The surface atomic structures of a series of sodium borosilicate glasses were studied using classical molecular dynamics simulations with recently developed compositional dependent partial charge potentials. The surface structural features and defect speciation were characterized and compared with the bulk glasses with the same composition. Our simulation results show that the borosilicate glass surfaces have significantly different chemical compositions and structures as compared to the bulk. The glass surfaces are found to be sodium enriched and behave like borosilicate glasses with higher R (Na₂O/B₂O₃) values. As a result of this composition and associated structure changes, the amount of fourfold boron decreases at the surface and the network connectivity on the surface decreases. In addition to composition variation and local structure environment change, defects such as two‐membered rings and three‐coordinated silicon were also observed on the surface. These unusual surface composition and structure features are expected to significantly impact the chemical and physical properties and the interactions with the environments of sodium borosilicate glasses.     

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.     

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.     

Effects of optical dopants and laser wavelength on atom probe tomography analyses of borosilicate glasses

Atom probe tomography (APT) is a novel analytical microscopy method that provides three dimensional elemental mapping with sub‐nanometer spatial resolution and has only recently been applied to insulating glass and ceramic samples. In this paper, we have studied the influence of the optical absorption in glass samples on APT characterization by introducing different transition metal optical dopants to a model borosilicate nuclear waste glass. A systematic comparison is presented of the glass optical properties and the resulting APT data quality in terms of compositional accuracy and the mass spectra quality for two APT systems: one with a green laser (532 nm, LEAP 3000X HR) and one with a UV laser (355 nm, LEAP 4000X HR). These data were also compared to the study of a more complex borosilicate glass (SON68). The results show that the analysis data quality, particularly the compositional accuracy and sample yield, was clearly linked to optical absorption when using a green laser, while for the UV laser optical doping aided in improving data yield but did not have a significant effect on compositional accuracy. Comparisons of data between the LEAP systems suggest that the smaller laser spot size of the LEAP 4000X HR played a more critical role for optimum performance than the optical dopants themselves. The smaller spot size resulted in more accurate composition measurements due to a reduced background level independent of the material's optical properties.     

Mixed modifier effect in lithium‐calcium borosilicate glasses

The mixed modifier effect (MME) in the lithium‐calcium borosilicate glasses, which have a composition of 0.4[(1?x)Li₂O–xCaO]–0.6[(1?y)B₂O₃–ySiO₂] with x in the range of 0~1 and y in the range of 0.33~0.83, is investigated. The MME manifests itself as a positive deviation from linearity in the activation energy of electrical conductivity (Ea^σ) and as a negative deviation from linearity in the fraction of four‐coordinated boron (N₄), glass transition temperature (T_g), dilatometric softening temperature (T_d), Vickers microhardness (H_v), dielectric constant (ε), and dielectric loss (tanδ). Moreover, the deviation, which exhibits a maximum at [CaO]/([CaO]+[Li₂O])=0.5, is enhanced with increasing [SiO₂]/[B₂O₃] ratio in the glass network. The observed MME in T_g, T_d, and H_v are attributed to the bond weakening in the network; however, the MME in ε, tanδ, and Ea^σ are caused by the obstruction of modifier transport in the glass network.     

Physico-chemical properties of international simple glass (ISG) nuclear waste simulants: Luminescence baseline study

Borosilicate glass has been adopted internationally for the treatment of nuclear waste with the object of long-term stabilization through vitrification. Aiming to facilitate experimental comparisons across laboratories, the six-component international simple glass (ISG) was developed as benchmark. The original ISG produced by Mo-SCI Corporation (Rolla, MO) was distributed and characterized for different physical properties thus serving as reference for further studies. Still, photoluminescence (PL) properties, which may be useful for scrutinizing radiation-induced damage, have not been reported. Further, the original ISG contained significant iron impurities, which may present interference in various studies (e.g., optical). Consequently, two new ISG analogs lacking iron impurities (labeled ISG-1 [closest composition to original ISG] and ISG-2 [some MgO added at expense of CaO]) were synthesized by Corning Inc. (Corning, NY) (also doped with lanthanum for subsequent corrosion tests involving atom probe tomography), which remain to be fully characterized. Accordingly, this work was undertaken to perform a comprehensive study comparing the three ISG specimens. Various characterizations were then performed on the pristine glasses: X-ray diffraction and vibrational spectroscopy (structural properties); static-leach product consistency test (PCT, dissolution behavior); dilatometry and calorimetry measurements (thermal properties); and optical absorption with Tauc and Urbach plots analysis, followed by PL spectroscopy with decay kinetics assessment (optical properties). While the general structural features appeared similar among the glasses, the deconvolution of Raman spectra suggested a lower degree of connectivity in the silica network for ISG-2. In addition, some differences were indicated from the PCT results and thermal properties assessed, which were discussed based on compositional variations. Further on, the optical properties were shown to be the most distinct. The optical absorption of the original ISG was characterized by Fe²⁺/Fe³⁺ impurities not detected for ISG-1 and ISG-2. The glasses all exhibited two main PL features (∼1.8 and 2.5 eV) with multiexponential decay behavior apparently of intrinsic origin. In addition, ISG-1 and ISG-2 showed a third high-energy (∼3.4 eV) fast-decaying contribution tentatively credited to tin impurities, which appeared most significantly for ISG-1. The results are expected to serve as baseline for future studies simulating the effects of radioactive element decay.     

Pressure effects on shear deformation of borosilicate glasses

The shear behaviors of two multicomponent borosilicate glasses, Borofloat®33 (Boro33) and N-BK7® (N-BK7), under different pressures are investigated using molecular dynamics simulations. The addition of alkali ions lowers the yield stress and changes the pressure dependence of shear modulus. Shear-induced densification is observed in both glasses. It is found that the decreases of the oxygen-centered bond angle and the coordination number change of B are responsible for the density changes at low pressures, and the increase of 5-coordinated Si is the dominant mechanism for densification at high pressures. The average shear stresses experienced by Si and B decrease with pressure except that the flow stress of Si at the end of shear deformation in N-BK7. Moreover, the average shear stress of B is more sensitive to the applied pressures compared to Si, suggesting that B is able to relax mechanical stress more easily under pressurized-shear. By analyzing the nonaffine displacement of atoms, it is found that N-BK7 exhibits more localized plastic deformation compared to Boro33 at low pressures and the local rearrangements in both glasses become more homogeneous with increasing pressure. The mean squared nonaffine displacement curves show that alkali ions have the highest mobility induced by shear compared to the network formers and B is more mobile than Si for both glasses. We also observed that plastic deformation tends to take place around boron atoms for Boro33, whereas it occurs in the alkali-rich regions for N-BK7, indicating that these two glasses have different atomic-scale deformation mechanisms.     

Effect of pressurization on the fracture toughness of borosilicate glasses

In this study, hot-compression is applied to two multicomponent borosilicate glasses, Borofloat33 (Boro33) and N-BK7, using molecular dynamics simulations. The effects of pressure on elastic properties, surface energy, and fracture toughness ( are investigated. It is found that the impact on is mainly dominated by the change of Young's modulus under pressure, which is proportional to the relative change in density. Between the two glasses under investigation, can be improved more effectively by the hot-compression process for Boro33, due to its higher concentration of 3-coordinated boron (B³), which facilitates densification via B³ to B⁴ conversion under compression.     

硼硅酸盐玻璃鳞片研制开发概况

叙述了我国玻璃鳞片的研究和开发历程，提出了厚度和表面处理的重要性。     

Biocompatibility of borosilicate glass-ceramics based LTCC materials for microfluidic biosensor application

Three kinds of borosilicate glass-ceramics Low temperature co-fired ceramics (LTCC) substrate materials, Ca-B-Si-O (CBS), Ca-Al-B-Si-O (CABS), and Ca-Mg-B-Si-O (CMBS), have been prepared, and the biocompatibility of these materials was evaluated. Compared with CBS and CMBS samples, the CABS sample presented the lowest crystallinity and dissolution in the bioleaching experiments. The direct and indirect cell culturing results showed that the CABS sample also possessed the best biocompatibility to the bone mesenchymal stem cells (BMSCs) due to its good bio-stability and surface micro-pore structure. The effects of surface topography and released ions on cytocompatibility were analyzed. These results were expected to offer some guideline information for developing LTCC substrate materials used in the microfluidic biosensors for the future biological and medical application.     

Corrosion of Borosilicate Glasses Subjected to Aggressive Test Conditions: Structural Investigations

Sodium borosilicate (NBS) and barium sodium borosilicate (BBS) glasses, used for immobilization of high‐level nuclear waste with compositions (SiO₂)_0.477(B₂O₃)_0.239(Na₂O)_0.170(TiO₂)_0.023(CaO)_0.068(Al₂O₃)_0.023 and (SiO₂)_0.482(B₂O₃)_0.244(Na₂O)_0.220(BaO)_0.054 were subjected leaching experiments under hydrothermal conditions in an autoclave at 200°C for different time durations. Morphological and structural transformations associated with leaching, have been monitored with techniques like XRD, SEM, solid‐state nuclear magnetic resonance. XRD and SEM along with NMR studies have confirmed that, upon leaching, formation of an aluminosilicate phase, Zeolite‐P (Na₆Al₆Si₁₀O₃₂·12H₂O), occurs with NBS glass. BBS glass upon subjecting to the same conditions leads to formation of multiple amorphous phases having Q⁴ (silica rich phase) and Q³ structural units of Silicon along with structurally modified residual glass. Upon leaching BO₃ structural units preferentially get released from BBS glass. Comparison of results with international simple glass confirmed that, for the latter, mass loss rates are one order of magnitude lower.     

Structural changes on the surfaces of borosilicate glasses induced by gamma-ray irradiation

Vitrification is a kind of glass that can solidify high-level radioactive waste (HLW). As the basic material of vitrification, borosilicate glass was studied extensively. To keep HLW away from the biosphere, the tolerance of borosilicate glass to irradiation is important. In this work, various samples of borosilicate glass with different compositions were irradiated with gamma rays at ambient temperature to study their stability. The hardness, moduli, and microscopic changes on surfaces of the borosilicate glasses were measured at specific absorbed doses. Upon the gamma irradiation, the structural changes on surfaces of borosilicate glasses were identified, which were strongly influenced by the composition of borosilicate glasses. The results demonstrate that gamma irradiation, as well as beta irradiation, might strongly influence the properties of vitrification. The irradiation effects on vitrification induced by gamma irradiation should be paid more attention to than before.     

Structural dependence of crystallization in phosphorus-containing sodium aluminoborosilicate glasses

The article reports on the structural dependence of crystallization in Na₂O–Al₂O₃–B₂O₃–P₂O₅–SiO₂-based glasses over a broad compositional space. The structure of melt-quenched glasses has been investigated using ¹¹B, ²⁷Al, ²⁹Si, and ³¹P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, while the crystallization behavior has been followed using X-ray diffraction and scanning electron microscopy combined with energy dispersive spectroscopy. In general, the integration of phosphate into the sodium aluminoborosilicate network is mainly accomplished via the formation of Al–O–P and B–O–P linkages with the possibility of formation of Si–O–P linkages playing only a minor role. In terms of crystallization, at low concentrations (≤5 mol.%), P₂O₅ promotes the crystallization of nepheline (NaAlSiO₄), while at higher concentrations (≥10 mol.%), it tends to suppress (completely or incompletely depending on the glass chemistry) the crystallization in glasses. When correlating the structure of glasses with their crystallization behavior, the MAS NMR results highlight the importance of the substitution/replacement of Si–O–Al linkages by Al–O–P, Si–O–B, and B–O–P linkages in the suppression of nepheline crystallization in glasses. The results have been discussed in the context of (1) the problem of nepheline crystallization in Hanford high-level waste glasses and (2) designing vitreous waste forms for the immobilization of phosphate-rich dehalogenated Echem salt waste.     

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.     

Chemical durability of borosilicate pharmaceutical glasses: Mixed alkaline earth effect with varying [MgO]/[CaO] ratio

Glass for pharmaceutical packaging requires high chemical durability for the safe storage and distribution of newly developed medicines. In borosilicate pharmaceutical glasses which typically contain a mixture of different modifier ions (alkali or alkaline earth), the dependence of the chemical durability on alkaline earth oxide concentrations is not well understood. Here, we have designed a series of borosilicate glasses with systematic substitutions of CaO with MgO while keeping their total concentrations at 13 mol% and a fixed Na₂O concentration of 12.7 mol%. We used these glasses to investigate the influence of R = [MgO]/([MgO] + [CaO]) on the resistance to aqueous corrosion at 80°C for 40 days. It was found that this type of borosilicate glass undergoes both leaching of modifier ions through an ion exchange process and etching of the glass network, leading to dissolution of the glass surface. Based on the concentration analysis of the Si and B species dissolved into the solution phase, the dissolved layer thickness was found to increase from ~100 to ~170 nm as R increases from 0 to 1. The depth profiling analysis of the glasses retrieved from the solution showed that the concentration of modifier ions (Na⁺, Ca²⁺, and Mg²⁺) at the interface between the solution and the corroded glass surface decreased to around 40%–60% of the corresponding bulk concentrations, regardless of R and the leaching of modifier cations resulted in a silica-rich layer in the surface. The leaching of Ca²⁺ and Mg²⁺ ions occurred within ~50 and <25 nm, respectively, from the glass surface and this thickness was not a strong function of R. The leaching of Na⁺ ions varied monotonically; the thickness of the Na⁺ depletion layer increased from ~100 nm at R = 0 to ~200 nm at R = 1. Vibrational spectroscopy analysis suggested that the partial depletion of the ions may have caused some degree of the network re-arrangement or re-polymerization in the corroded layer. Overall, these results suggested that for the borosilicate glass, replacing [CaO] with [MgO] deteriorates the chemical durability in aqueous solution.