Although mass spectrometry is a widely used analytical tool, age-appropriate, interactive outreach activities for laboratory visitors, especially children, are lacking. The presented interactive demonstration, "Did you eat a MOLEcule today?", introduces all ages to molecular weight concepts and mass spectrometry in a research laboratory, while connecting the concepts to real-world applications. Through real-time breath analysis, participants explore the concepts of molecular weight, electrostatic field manipulation of charged molecules, and analyte identification by mass analysis. This module is rapid and highly adaptable for outreach activities but also includes age- or classroom-appropriate variations to decrease or increase difficulty levels. The presented interactive demonstration has repeatedly been implemented, with over 2300 participants during six annual "Take Our Daughters & Sons to Work Day" and two corporate "Family Day" outreach activities, successfully engaging, exciting, and educating both kids and parents.
The development of chemistry is reported to implement selective dual-wavelength olefin metathesis polymerization for continuous additive manufacturing (AM). A resin formulation based on dicyclopentadiene is produced using a latent olefin metathesis catalyst, various photosensitizers (PSs) and photobase generators (PBGs) to achieve efficient initiation at one wavelength (e.g., blue light) and fast catalyst decomposition and polymerization deactivation at a second (e.g., UV-light). This process enables 2D stereolithographic (SLA) printing, either using photomasks or patterned, collimated light. Importantly, the same process is readily adapted for 3D continuous AM, with printing rates of 36 mm h–1 for patterned light and up to 180 mm h–1 using un-patterned, high intensity light.
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.
Fine control over the thermal expansion and contraction behavior of polymer materials is challenging. Most polymers have large coefficients of thermal expansion (CTEs), which preclude long performance lifetimes of composite materials. Herein, we report the design and synthesis of epoxy thermosets with low CTE values below their Tg and large contraction behavior above Tg by incorporating thermally contractile dibenzocyclooctane (DBCO) motifs within the thermoset network. This atypical thermomechanical behavior was rationalized in terms of a twist-boat to chair conformational equilibrium of the DBCO linkages. We anticipate these findings to be generally useful in the preparation of materials with designed CTE values.
This report describes the 2015-2017 fiscal year research efforts to evaluate high temperature plastics as replacement materials for ceramics in electrical contact assemblies. The main objective of this work was to assess the feasibility of replacing existing high-price ceramic inserts with a polymeric material. Current ceramic parts are expensive due to machining costs and can suffer brittle failure. Therefore, replacing the ceramic with a more cost-effective material -- in this case a plastic -- is highly desirable. Not only are plastics easier to process, but they can also eliminate final tooling and are less brittle than ceramics. This effort used a three-phase approach: selection of appropriate materials determined by a comprehensive literature review, performance of an initial thermal stability screening, understanding of aging behavior under normal and off-normal conditions, and evaluation of performance at elevated temperatures. Two polymers were determined to meet the desired criteria: polybenzimidazole, and Vespel(r) SP-1 polyimide. Polymer derived ceramics may also be useful but will require further development of molding capabilities that were beyond the scope of this program. This page intentionally left blank.
The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. The methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for the UDMA system, with parameters calibrated based on fully atomistic simulations of the UDMA monomer in the liquid state. Detailed metrics based on network graph theoretical approaches were implemented to quantify the bond network topology resulting from simulations. For a broad range of polymerization parameters, no discernible differences were seen between TRP and CRP UDMA simulations at equal conversions, although clear differences exist as a function of conversion. Both findings are consistent with experiments. Despite a number of shortcomings, these models have demonstrated the potential of molecular simulations for studying network topology in these systems.
This study evaluates the degradation of six different elastomeric polymers used for O-rings: EPDM, FEPM, type I- and II-FKM, FFKM, and FSR, in five different simulated geothermal environments at 300°C: 1) non-aerated steam/cooling cycles, 2) aerated steam/cooling cycles, 3) water-based drilling fluid, 4) CO2-rich geo-brine fluid, and, 5) heat-cool water quenching cycles. The factors assessed included the extent of oxidation, changes in thermal behavior, micro-defects, permeation of ionic species from the test environments into the O-rings, silicate-related scale-deposition, and changes in the O-rings' elastic modulus. The reliability of the O-rings to maintain their integrity depended on the elastomeric polymer composition and the exposure environment. FSR disintegrated while EPDM was oxidized only to some degree in all the environments, FKM withstood heat-water quenching but underwent chemical degradation, FEPM survived in all the environments with the exception of heat-water quenching where it underwent severe oxidation-induced degradation, and FFKM displayed outstanding compatibility with all the tested environments. This paper discusses the degradation mechanisms of the polymers under the aforementioned conditions.
This paper aims to evaluate the survival of O-rings made with six different elastomeric polymers, EPDM, type I- and II-FKM, FEPM, FFKM, and FSR, in five different simulated geothermal environments at 300°C. It further defines the relative strengths and weaknesses of the materials in each environment. The environments tested were: 1) non-aerated steam-cooling cycles, 2) aerated steam-cooling cycles, 3) water-based drilling fluid, 4) CO2-rich geo-brine fluid, and, 5) heat-cool water quenching cycles. Following exposure, the extent of oxidation, oxidationinduced degradation, thermal behaviors, micro-defects, permeation depths of ionic species present in environments throughout the O-ring, silicate-related scale-deposition, and changes in mechanical properties were assessed.
As part of the Light Water Reactor Sustainability Program, science - based engineering approaches were employed to address cable degradation behavior under a range of exposure environments. Experiments were conducted with the goal to provide best guidance for aged material states, remaining life and expected performance under specific conditions for a range of cable materials. Generic engineering tests , which focus on rapid accelerated aging and tensile elongation , were combined with complementar y methods from polymer degradation science. Sandia's approach, building on previous years' efforts, enabled the generation of some of the necessary data supporting the development of improved lifetime predictions models, which incorporate known material b ehaviors and feedback from field - returned 'aged' cable materials. Oxidation rate measurements have provided access to material behavior under low dose rate thermal conditions, where slow degradation is not apparent in mechanical property changes. Such da ta have shown aging kinetics consistent with established radiati on - thermal degradation models. ACKNOWLEDGEMENTS We gratefully acknowledge ongoing technical support at the LICA facility and extensive sample handling provided by Maryla Wasiolek and Don Hans on. Sam Durbin and Patrick Mattie are recognized for valuable guidance throughout the year and assistance in the preparation of the final report. Doug Brunson is appreciated for sample analysis, compilation and plotting of experimental data.
Nuclear energy is one industry where aging of safety-related materials and components is of great concern. Many U.S. nuclear power plants are approaching, or have already exceeded, 40 years of age. Analysis comparing the cost of new plant construction versus long-term operation under extended plant licensing through 60 years strongly favors the latter option. To ensure the safe, reliable, and cost-effective long-term operation of nuclear power plants, many systems, structures, and components must be evaluated. Furthermore, as new analytical techniques and testing approaches are developed, it is imperative that we also validate, and if necessary, improve upon the previously employed Institute of Electrical and Electronic Engineers (IEEE) qualification standards originally written in 1974. Fortunately, this daunting task has global support, particularly in light of the new social and political climate surrounding nuclear energy in a post-Fukushima era.