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Puck Loop Seal (Final Project Technical Report)

Smartt, Heidi A.; Corbin, William; Wade, James R.; Curtis, Clayton; Cox, Sagan B.; Parada, Corey M.; White, Stephanie L.

Sandia National Laboratories (SNL) is advancing technical capabilities used in passive loop seals. The “Puck” seal used a set of International Atomic Energy Agency (IAEA) requirements for new passive loop seals published in 2020 as a design guide. The seal is based on an oxygen-sensitive inner mixture encased in an oxygen-impermeable shell, is monolithic rather than two-part, incorporates self-capturing wire features, contains colored water beads and bubbles formed during processing as unique identifiers (UIDs), and visually indicates tamper (whether from seal body penetration or from seal wire removal) by irreversibly changing the seal body from multi-colored to black. This paper will provide details on the design, development, and testing of Puck seal prototypes.

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Organoboron Based Antioxidants

Parada, Corey M.; Corbin, William; Groves, Catherine; Redline, Erica M.

Earth’s environment can be considered especially harsh due to the cyclic exposure of heat, moisture, oxygen, and ultraviolet (UV) and visible light. Polymer-derived materials subjected to these conditions over time often exhibit symptoms of degradation and deterioration, ultimately leading to accelerated material failure. To combat this, chemical additives known as antioxidants are often used to delay the onset of weathering and oxidative degradation. Phenol-derived antioxidants have been used for decades due to their excellent performance and stability; unfortunately, concerns regarding their toxicity and leaching susceptibility have driven researchers to identify novel solutions to replace phenolic antioxidants. Herein, we report on the antioxidant efficacy of organoborons, which have been known to exhibit antioxidant activity in plants and animals. Four different organoboron molecules were formulated into epoxy materials at various concentrations and subsequently cured into thermoset composites. Their antioxidant performance was subsequently analyzed via thermal, colorimetric, and spectroscopic techniques. Generally, thermal degradation and oxidation studies proved inconclusive and ambiguous. However, aging studies performed under thermal and UV-intensive conditions showed moderate to extreme color changes, suggesting poor antioxidant performance of all organoboron additives. Infrared spectroscopic analysis of the UV aged samples showed evidence of severe material oxidation, while the thermally aged samples showed only slight material oxidation. Solvent extraction experiments showed that even moderately high organoboron concentrations show negligible leaching susceptibility, confirming previously reported results. This finding may have benefits in applications where additive leaching may cause degradation to sensitive materials, such as microelectronics and other materials science related areas.

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Sustainable Functional Epoxies through Boric Acid Templating

Parada, Corey M.; Redline, Erica M.; Juba, Benjamin W.; Benally, Brynal; Sawyer, Patricia S.; Mowry, Curtis D.; Corbin, William

Thermoset polymers (e.g. epoxies, vulcanizable rubbers, polyurethanes, etc.) are crosslinked materials with excellent thermal, chemical, and mechanical stability; these properties make thermoset materials attractive for use in harsh applications and environments. Unfortunately, material robustness means that these materials persist in the environment with very slow degradation over long periods of time. Balancing the benefits of material performance with sustainability is a challenge in need of novel solutions. Here, we aimed to address this challenge by incorporating boronic acid-amine complexes into epoxy thermoset chemistries, facilitating degradation of the material under pH neutral to alkaline conditions; in this scenario, water acts as an initiator to remove boron species, creating a porous structure with an enhanced surface area that makes the material more amenable to environmental degradation. Furthermore, the expulsion of the boron leaves the residual pores rich in amines which can be exploited for CO2 absorption or other functionalization. We demonstrated the formation of novel boron species from neat mixing of amine compounds with boric acid, including one complex that appears highly stable under nitrogen atmosphere up to 600 °C. While degradation of the materials under static, alkaline conditions (our “trigger”) was inconclusive at the time of this writing, dynamic conditions appeared more promising. Additionally, we showed that increasing boronic acid content created materials more resistant to thermal degradation, thus improving performance under typical high temperature use conditions.

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