An official website of the United States government
Abstract 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 ofR = [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 asRincreases 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 ofRand 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 ofR. The leaching of Na+ions varied monotonically; the thickness of the Na+depletion layer increased from ~100 nm atR = 0 to ~200 nm atR = 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.
more »
« less
Synergy between Ca 2+ and high ionic field‐strength cations during the corrosion of alkali aluminoborosilicate glasses in hyper‐alkaline media
Abstract One major factor impeding the design of nuclear waste glasses with enhanced waste loadings is our insufficient understanding of their composition–structure–durability relationships, specifically in the environments the waste form is expected to encounter in a geological repository. In particular, the high field‐strength cations (HFSCs) are an integral component of most waste streams. However, their impact on the long‐term performance of the glassy waste form remains mostly undeciphered. In this context, the present study aims to understand the impact of some HFSCs (i.e., Nb5+, Zr4+, Ti4+, and La3+) on the dissolution behavior of alkali/alkaline‐earth aluminoborosilicate‐based model nuclear waste glasses in hyper‐alkaline media. At pH = 13, the studied glasses dissolve through the dissolution–reprecipitation mechanism, with Ca precipitation being the most vital step to passivation. In Ca‐free glasses, although the HFSCs slow down the forward rate, they do not seem to impact the residual rate behavior of glasses. The presence of Ca2+, however, initiates the rapid precipitation of network polymerizing HFSCs (i.e., Nb5+, Zr4+, and Ti4+) into a Ca2+/HFSCs‐based passivating layer, thus suggesting a synergy between Ca2+and HFSCs that contributes to the enhanced long‐term durability of the glasses. Such synergy is not strongly evident for La3+, but instead, a potential La/Si affinity is observed upon the formation of the alteration layer.
more »
« less
- Award ID(s):
- 2034871
- PAR ID:
- 10499123
- Publisher / Repository:
- Wiley-Blackwell
- Date Published:
- Journal Name:
- Journal of the American Ceramic Society
- ISSN:
- 0002-7820
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
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 Ca 2+ ) 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–HNO 3 ), 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.more » « less
-
Abstract Magnesium silicate hydrate (M‐S‐H) represents a promising alternative to traditional cement, particularly for low‐pH construction applications such as nuclear waste encapsulation and carbon dioxide injection. The durability of construction materials, a critical aspect of their suitability for various purposes, is primarily governed by the kinetics of dissolution of the binder phase under service conditions. In this study, we employed in situ atomic force microscopy to assess the dissolution rates of M‐S‐H in water equilibrated with air. Quantitative analysis based on changes in volume and height revealed dissolution rates ranging from 0.18 to 3.09 × 10−12 mol/cm2/s depending on the precipitate Mg/Si ratio and morphology. This rate surpasses its crystalline analogs, talc (Mg3Si4O10(OH)2) and serpentine (Mg3(Si2O5)(OH)4), by about three to five orders of magnitude. Interestingly, oriented M‐S‐H dissolved faster than non‐oriented M‐S‐H. Spatially resolved assessments of dissolution rates facilitated a direct correlation between rates and morphology, showing that edges and smaller crystallites dissolve at a faster pace compared to facets and larger crystallites. The outcomes of this study provide insights into the mechanisms governing the dissolution of M‐S‐H and the factors dictating its durability. These findings hold implications for the strategic design and optimization of M‐S‐H for various applications.more » « less
-
The sorption properties of [Zr 6 O 4 (OH) 4 (NH 3 + -BDC) 6 ]Cl 6 · x H 2 O ( MOR-1 ) and H 16 [Zr 6 O 16 (H 2 PATP) 4 ]Cl 8 · x H 2 O ( MOR-2 ) towards ReO 4 − and TcO 4 − were studied in detail. Both MOR-1 and MOR-2 are very effective sorbents for ReO 4 − and TcO 4 − anions, with MOR-2 showing the highest sorption capacity (up to 4.1 ± 0.4 mmol g −1 ) among the known metal organic materials. Importantly, the exceptional sorption capacity of MOR-2 is retained even under conditions simulating acidic nuclear waste. In addition, MOR-1 and MOR-2 exhibit selective luminescence ReO 4 − sensing properties, demonstrated for the first time for MOF materials.more » « less
-
Abstract All‐solid‐state batteries have the potential for enhanced safety and capacity over conventional lithium ion batteries, and are anticipated to dominate the energy storage industry. As such, strategies to enable recycling of the individual components are crucial to minimize waste and prevent health and environmental harm. Here, we use cold sintering to reprocess solid‐state composite electrolytes, specifically Mg and Sr doped Li7La3Zr2O12with polypropylene carbonate (PPC) and lithium perchlorate (LLZO−PPC−LiClO4). The low sintering temperature allows co‐sintering of ceramics, polymers and lithium salts, leading to re‐densification of the composite structures with reprocessing. Reprocessed LLZO−PPC−LiClO4exhibits densified microstructures with ionic conductivities exceeding 10−4 S/cm at room temperature after 5 recycling cycles. All‐solid‐state lithium batteries fabricated with reprocessed electrolytes exhibit a high discharge capacity of 168 mA h g−1at 0.1 C, and retention of performance at 0.2 C for over 100 cycles. Life cycle assessment (LCA) suggests that recycled electrolytes outperforms the pristine electrolyte process in all environmental impact categories, highlighting cold sintering as a promising technology for recycling electrolytes.more » « less
