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.
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.
Physical stress relaxation in rubbery, thermoset polymers is limited by cross-links, which impede segmental motion and restrict relaxation to network defects, such as chain ends. In parallel, the cure shrinkage associated with thermoset polymerizations leads to the development of internal residual stress that cannot be effectively relaxed. Recent strategies have reduced or eliminated such cure stress in thermoset polymers largely by exploiting chemical relaxation processes, wherein temporary cross-links or otherwise transient bonds are incorporated into the polymer network. Here, we explore an alternative approach, wherein physical relaxation is enhanced by the incorporation of organometallic sandwich moieties into the backbone of the polymer network. A standard epoxy resin is cured with a diamine derivative of ferrocene and compared to conventional diamine curing agents. The ferrocene-based thermoset is clearly distinguished from the conventional materials by reduced cure stress with increasing cure temperature as well as unique stress relaxation behavior above its glass transition in the fully cured state. The relaxation experiments exhibit features characteristic of a physical relaxation process. Furthermore, the cure stress is observed to vanish precipitously upon deliberate introduction of network defects through an increasing imbalance of epoxy and amine functional groups. We postulate that these beneficial properties arise from fluxional motion of the cyclopentadienyl ligands on the polymer backbone.
This report summarizes the results generated in FY13 for cable insulation in support of the Department of Energy's Light Water Reactor Sustainability (LWRS) Program, in collaboration with the US-Argentine Binational Energy Working Group (BEWG). A silicone (SiR) cable, which was stored in benign conditions for %7E30 years, was obtained from Comision Nacional de Energia Atomica (CNEA) in Argentina with the approval of NA-SA (Nucleoelectrica Argentina Sociedad Anonima). Physical property testing was performed on the as-received cable. This cable was artificially aged to assess behavior with additional analysis. SNL observed appreciable tensile elongation values for all cable insulations received, indicative of good mechanical performance. Of particular note, the work presented here provides correlations between measured tensile elongation and other physical properties that may be potentially leveraged as a form of condition monitoring (CM) for actual service cables. It is recognized at this point that the polymer aging community is still lacking the number and types of field returned materials that are desired, but Sandia National Laboratories (SNL) -- along with the help of others -- is continuing to work towards that goal. This work is an initial study that should be complimented with location-mapping of environmental conditions of Argentinean plant conditions (dose and temperature) as well as retrieval, analysis, and comparison with in- service cables.
Parylene C is used in a device because of its conformable deposition and other advantages. Techniques to study Parylene C aging were developed, and "lessons learned" that could be utilized for future studies are the result of this initial study. Differential Scanning Calorimetry yielded temperature ranges for Parylene C aging as well as post-deposition treatment. Post-deposition techniques are suggested to improve Parylene C performance. Sample preparation was critical to aging regimen. Short-term (%7E40 days) aging experiments with free standing and ceramic-supported Parylene C films highlighted "lessons learned" which stressed further investigations in order to refine sample preparation (film thickness, single sided uniform coating, machine versus laser cutting, annealing time, temperature) and testing issues ("necking") for robust accelerated aging of Parylene C.
This paper presents the development of a sensor to detect the oxidative and radiation induced degradation of polypropylene. Recently we have examined the use of crosslinked assemblies of nanoparticles as a chemiresistor-type sensor for the degradation products. We have developed a simple method that uses a siloxane matrix to fabricate a chemiresistor-type sensor that minimizes the swelling transduction mechanism while optimizing the change in dielectric response. These sensors were exposed with the use of a gas chromatography system to three previously identified polypropylene degradation products including 4-methyl-2-pentanone, acetone, and 2-pentanone. The limits of detection 210 ppb for 4-methy-2-pentanone, 575 ppb for 2-pentanone, and the LoD was unable to be determined for acetone due to incomplete separation from the carbon disulfide carrier.
Both conventional and combinatorial approaches were used to study the pore formation process in epoxy based polymer systems. Sandia National Laboratories conducted the initial work and collaborated with North Dakota State University (NDSU) using a combinatorial research approach to produce a library of novel monomers and crosslinkers capable of forming porous polymers. The library was screened to determine the physical factors that control porosity, such as porogen loading, polymer-porogen interactions, and polymer crosslink density. We have identified the physical and chemical factors that control the average porosity, pore size, and pore size distribution within epoxy based systems.