Publications

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We are studying PMDI polyurethane with a fast catalyst, such that filling and polymerization occur simultaneously. The foam is over-packed to tw ice or more of its free rise density to reach the density of interest. Our approach is to co mbine model development closely with experiments to discover new physics, to parameterize models and to validate the models once they have been developed. The model must be able to repres ent the expansion, filling, curing, and final foam properties. PMDI is chemically blown foam, wh ere carbon dioxide is pr oduced via the reaction of water and isocyanate. The isocyanate also re acts with polyol in a competing reaction, which produces the polymer. A new kinetic model is developed and implemented, which follows a simplified mathematical formalism that decouple s these two reactions. The model predicts the polymerization reaction via condensation chemis try, where vitrification and glass transition temperature evolution must be included to correctly predict this quantity. The foam gas generation kinetics are determined by tracking the molar concentration of both water and carbon dioxide. Understanding the therma l history and loads on the foam due to exothermicity and oven heating is very important to the results, since the kinetics and ma terial properties are all very sensitive to temperature. The conservation eq uations, including the e quations of motion, an energy balance, and thr ee rate equations are solved via a stabilized finite element method. We assume generalized-Newtonian rheology that is dependent on the cure, gas fraction, and temperature. The conservation equations are comb ined with a level set method to determine the location of the free surface over time. Results from the model are compared to experimental flow visualization data and post-te st CT data for the density. Seve ral geometries are investigated including a mock encapsulation part, two configur ations of a mock stru ctural part, and a bar geometry to specifically test the density model. We have found that the model predicts both average density and filling profiles well. However, it under predicts density gradients, especially in the gravity direction. Thoughts on m odel improvements are also discussed.

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The accelerated aging behavior and aging state of a 30 year old field retrieved polysulfide elastomer was examined. The material is used as an environmental thread sealant for a stainless steel bolt in a steel threaded insert in an aluminum assembly. It is a two component curable polysulfide elastomer that is commercially available in a similar formulation as was applied 30 years ago. The primary goal of this study was to establish if aging over 30 years under moderate aging conditions (mostly ambient temperature and humidity) resulted in significant property changes, or if accelerated aging could identify developing aging pathways which would prevent the extended use of this material. The aging behavior of this material was examined in three ways: A traditional accelerated thermo-oxidative aging study between 95 to 140°C which focused on physical and chemical properties changes, an evaluation of the underlying oxidation rates between RT and 125°C, and an assessment of the aging state of a small 30 year old sample. All three data sets were used to establish aging characteristics, their time evolution, and to extrapolate the observed behavior to predict performance limits at RT. The accelerated aging study revealed a relatively high average activation energy of ~130 kJ/mol which gives overconfident performance predictions. Oxidation rates showed a decreasing behavior with aging time and a lower E a of ~84 kJ/mol from time - temperature superposition , but also predicted sufficient additional performance at RT. Consistent with these projections for extended RT performance, only small changes were observed for the 30 year old material. Extrapolations using this partially aged material also predict ongoing use as a viable option. Unexpected RT degradation could only develop into a concern should the oxidation rate not trend lower over time as was observed at elevated temperature. Considering all data acquired in this limited aging study , there are no immediately apparent concerns with this material for ongoing use. ACKNOWLEDGEMENTS We thank Lisa Deibler for providing us with a small sample of field aged and new commercial material.

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Elastomers are often degraded when exposed to air or high humidity for extended times (years to decades). Lifetime estimates normally involve extrapolating accelerated aging results made at higher than ambient environments. Several potential problems associated with such studies are reviewed, and experimental and theoretical methods to address them are provided. The importance of verifying time-temperature superposition of degradation data is emphasized as evidence that the overall nature of the degradation process remains unchanged versus acceleration temperature. The confounding effects that occur when diffusion-limited oxidation (DLO) contributes under accelerated conditions are described, and it is shown that the DLO magnitude can be modeled by measurements or estimates of the oxygen permeability coefficient (POx) and oxygen consumption rate (Φ). POx and Φ measurements can be influenced by DLO, and it is demonstrated how confident values can be derived. In addition, several experimental profiling techniques that screen for DLO effects are discussed. Values of Φ taken from high temperature to temperatures approaching ambient can be used to more confidently extrapolate accelerated aging results for air-aged materials, and many studies now show that Arrhenius extrapolations bend to lower activation energies as aging temperatures are lowered. Best approaches for accelerated aging extrapolations of humidity-exposed materials are also offered.

The degradation in electrical contact resistance of a contact pair sliding while submerged in silicone fluid has been investigated. While the contamination of electrical contacts by silicone vapors or migrating species at elevated temperature due to decomposition in electric arcs is well known, the present degradation mechanism appears to arise from chemical reactions in the silicone fluid at room temperature, catalyzed by the presence of the freshly-abraded metal surface. As a result of these reactions, a deposit containing Si, C and O forms in the vicinity of mechanical contact. The specific contact metals present and the availability of dissolved oxygen in the fluid have a dramatic influence on the quantity of reaction product formed. The chemistry of the deposit, proposed formation mechanisms, the impact on electrical contact resistance and mitigation strategies are discussed.

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We are developing computational models to help understand manufacturing processes, final properties and aging of structural foam, polyurethane PMDI. Th e resulting model predictions of density and cure gradients from the manufacturing process will be used as input to foam heat transfer and mechanical models. BKC 44306 PMDI-10 and BKC 44307 PMDI-18 are the most prevalent foams used in structural parts. Experiments needed to parameterize models of the reaction kinetics and the equations of motion during the foam blowing stages were described for BKC 44306 PMDI-10 in the first of this report series (Mondy et al. 2014). BKC 44307 PMDI-18 is a new foam that will be used to make relatively dense structural supports via over packing. It uses a different catalyst than those in the BKC 44306 family of foams; hence, we expect that the reaction kineti cs models must be modified. Here we detail the experiments needed to characteriz e the reaction kinetics of BKC 44307 PMDI-18 and suggest parameters for the model based on these experiments. In additi on, the second part of this report describes data taken to provide input to the preliminary nonlinear visco elastic structural response model developed for BKC 44306 PMDI-10 foam. We show that the standard cu re schedule used by KCP does not fully cure the material, and, upon temperature elevation above 150°C, oxidation or decomposition reactions occur that alter the composition of the foam. These findings suggest that achieving a fully cured foam part with this formulation may be not be possible through therma l curing. As such, visco elastic characterization procedures developed for curing thermosets can provide only approximate material properties, since the state of the material continuously evolves during tests.

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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.

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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.

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We are developing computational models to elucidate the expansion and dynamic filling process of a polyurethane foam, PMDI. The polyurethane of interest is chemically blown, where carbon dioxide is produced via the reaction of water, the blowing agent, and isocyanate. The isocyanate also reacts with polyol in a competing reaction, which produces the polymer. Here we detail the experiments needed to populate a processing model and provide parameters for the model based on these experiments. The model entails solving the conservation equations, including the equations of motion, an energy balance, and two rate equations for the polymerization and foaming reactions, following a simplified mathematical formalism that decouples these two reactions. Parameters for the polymerization kinetics model are reported based on infrared spectrophotometry. Parameters describing the gas generating reaction are reported based on measurements of volume, temperature and pressure evolution with time. A foam rheology model is proposed and parameters determined through steady-shear and oscillatory tests. Heat of reaction and heat capacity are determined through differential scanning calorimetry. Thermal conductivity of the foam as a function of density is measured using a transient method based on the theory of the transient plane source technique. Finally, density variations of the resulting solid foam in several simple geometries are directly measured by sectioning and sampling mass, as well as through x-ray computed tomography. These density measurements will be useful for model validation once the complete model is implemented in an engineering code.

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All polymers are intrinsically susceptible to oxidation, which is the underlying process for thermally driven materials degradation and of concern in various applications. There are many approaches for predicting oxidative polymer degradation. Aging studies usually are meant to accelerate oxidation chemistry for predictive purposes. Kinetic models attempt to describe reaction mechanisms and derive rate constants, whereas rapid qualification tests should provide confidence for extended performance during application, and similarly TGA tests are meant to provide rapid guidance for thermal degradation features. What are the underlying commonalities or diverging trends and complications when we approach thermo-oxidative aging of polymers in such different ways? This review presents a brief status report on the important aspects of polymer oxidation and focuses on the complexity of thermally accelerated polymer aging phenomena. Thermal aging and lifetime prediction, the importance of DLO, property correlations, kinetic models, TGA approaches, and a framework for predictive aging models are briefly discussed. An overall perspective is provided showing the challenges associated with our understanding of polymer oxidation as it relates to lifetime prediction requirements.

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A selective literature review was conducted to assess whether currently available accelerated aging and original qualification data could be used to establish operational margins for the continued use of cable insulation and jacketing materials in nuclear power plant environments. The materials are subject to chemical and physical degradation under extended radiationthermal- oxidative conditions. Of particular interest were the circumstances under which existing aging data could be used to predict whether aged materials should pass loss of coolant accident (LOCA) performance requirements. Original LOCA qualification testing usually involved accelerated aging simulations of the 40-year expected ambient aging conditions followed by a LOCA simulation. The accelerated aging simulations were conducted under rapid accelerated aging conditions that did not account for many of the known limitations in accelerated polymer aging and therefore did not correctly simulate actual aging conditions. These highly accelerated aging conditions resulted in insulation materials with mostly inert aging processes as well as jacket materials where oxidative damage dropped quickly away from the air-exposed outside jacket surface. Therefore, for most LOCA performance predictions, testing appears to have relied upon heterogeneous aging behavior with oxidation often limited to the exterior of the cable cross-section a situation which is not comparable with the nearly homogenous oxidative aging that will occur over decades under low dose rate and low temperature plant conditions. The historical aging conditions are therefore insufficient to determine with reasonable confidence the remaining operational margins for these materials. This does not necessarily imply that the existing 40-year-old materials would fail if LOCA conditions occurred, but rather that unambiguous statements about the current aging state and anticipated LOCA performance cannot be provided based on original qualification testing data alone. The non-availability of conclusive predictions for the aging conditions of 40-year-old cables implies that the same levels of uncertainty will remain for any re-qualification or extended operation of these cables. The highly variable aging behavior of the range of materials employed also implies that simple, standardized aging tests are not sufficient to provide the required aging data and performance predictions for all materials. It is recommended that focused studies be conducted that would yield the material aging parameters needed to predict aging behaviors under low dose, low temperature plant equivalent conditions and that appropriately aged specimens be prepared that would mimic oxidatively-aged 40- to 60- year-old materials for confirmatory LOCA performance testing. This study concludes that it is not sufficient to expose materials to rapid, high radiation and high temperature levels with subsequent LOCA qualification testing in order to predictively quantify safety margins of existing infrastructure with regard to LOCA performance. We need to better understand how cable jacketing and insulation materials have degraded over decades of power plant operation and how this aging history relates to service life prediction and the performance of existing equipment to withstand a LOCA situation.

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