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.

Predicting the residual stress which develops during fabrication of a glass-to-metal compression seal requires material models that can accurately predict the effects of processing on the sealing glass. Validation of the predictions requires measurements on representative test geometries to accurately capture the interaction between the seal materials during a processing cycle required to form the seal, which consists of a temperature excursion through the glass transition temperature of the sealing glass. To this end, a concentric seal test geometry, referred to as a short cylinder seal, consisting of a stainless steel shell enveloping a commercial sealing glass disk has been designed, fabricated, and characterized as a model validation test geometry. To obtain data to test/validate finite element (FE) stress model predictions of this geometry, spatially-resolved residual stress was calculated from the measured lengths of the cracks emanating from radially positioned Vickers indents in the glass disk portion of the seal. The indentation crack length method is described, and the spatially-resolved residual stress determined experimentally are compared to FE stress predictions made using a nonlinear viscoelastic material model adapted to inorganic sealing glasses and an updated rate dependent material model for 304L stainless steel. The measurement method is a first to achieve a degree of success for measuring spatially resolved residual stress in a glass-bearing geometry and a favorable comparison between measurements and simulation was observed.

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.

Glass forming materials like polymers exhibit a variety of complex, nonlinear, time-dependent relaxations in volume, enthalpy and stress, all of which affect material performance and aging. Durable product designs rely on the capability to predict accurately how these materials will respond to mechanical loading and temperature regimes over prolonged exposures to operating environments. This cannot be achieved by developing a constitutive framework to fit only one or two types of experiments. Rather, it requires a constitutive formalism that is quantitatively predictive to engineering accuracy for the broad range of observed relaxation behaviors. Moreover, all engineering analyses must be performed from a single set of material model parameters. The rigorous nonlinear viscoelastic Potential Energy Clock (PEC) model and its engineering phenomenological equivalent, the Simplified Potential Energy Clock (SPEC) model, were developed to fulfill such roles and have been applied successfully to thermoplastics and filled and unfilled thermosets. Recent work has provided an opportunity to assess the performance of the SPEC model in predicting the viscoelastic behavior of an inorganic sealing glass. This presentation will overview the history of PEC and SPEC and describe the material characterization, model calibration and validation associated with the high Tg (similar to 460 degrees C) sealing glass.

To analyze the stresses and strains generated during the solidification of glass-forming materials, stress and volume relaxation must be predicted accurately. Although the modeling attributes required to depict physical aging in organic glassy thermosets strongly resemble the structural relaxation in inorganic glasses, the historical modeling approaches have been distinctly different. To determine whether a common constitutive framework can be applied to both classes of materials, the nonlinear viscoelastic simplified potential energy clock (SPEC) model, developed originally for glassy thermosets, was calibrated for the Schott 8061 inorganic glass and used to analyze a number of tests. A practical methodology for material characterization and model calibration is discussed, and the structural relaxation mechanism is interpreted in the context of SPEC model constitutive equations. SPEC predictions compared to inorganic glass data collected from thermal strain measurements and creep tests demonstrate the ability to achieve engineering accuracy and make the SPEC model feasible for engineering applications involving a much broader class of glassy materials.

Internal residual stresses and overall mechanical properties of thermoset resins are largely dictated by the curing process. It is well understood that fiber Bragg grating (FBG) sensors can be used to evaluate temperature and cure induced strain while embedded during curing. Herein, is an extension of this work whereby we use FBGs as a probe for minimizing the internal residual stress of an unfilled and filled Epon 828/DEA resin. Variables affecting stress including cure cycle, mold (release), and adhesion promoting additives will be discussed and stress measurements from a strain gauge pop-off test will be used as comparison.Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.