Robert Bernstein

Review of nuclear power plant safety cable aging studies with recommendations for improved approaches and for future work.

Many U. S. nuclear power plants are approaching 40 years of age and there is a desire to extend their life for up to 100 total years. Safety-related cables were originally qualified for nuclear power plant applications based on IEEE Standards that were published in 1974. The qualifications involved procedures to simulate 40 years of life under ambient power plant aging conditions followed by simulated loss of coolant accident (LOCA). Over the past 35 years or so, substantial efforts were devoted to determining whether the aging assumptions allowed by the original IEEE Standards could be improved upon. These studies led to better accelerated aging methods so that more confident 40-year lifetime predictions became available. Since there is now a desire to potentially extend the life of nuclear power plants way beyond the original 40 year life, there is an interest in reviewing and critiquing the current state-of-the-art in simulating cable aging. These are two of the goals of this report where the discussion is concentrated on the progress made over the past 15 years or so and highlights the most thorough and careful published studies. An additional goal of the report is to suggest work that might prove helpful in answering some of the questions and dealing with some of the issues that still remain with respect to simulating the aging and predicting the lifetimes of safety-related cable materials.

Thermal degradation of β‐carotene studied by ion mobility atmospheric solid analysis probe mass spectrometry: full product pattern and selective ionization enhancement

Atmospheric solid analysis probe mass spectrometry has the capability of capturing full product patterns simultaneously including both volatile and semi-volatile compounds produced at elevated temperatures. Real-time low-energy collision-induced fragmentation combined with ion mobility separations enables rapid identification of the chemical structures of products. We present here for the first time the recognition of full product patterns resulting from the thermal degradation of β-carotene at temperatures up to 600 °C. Solvent vapor-induced ionization enhancement is observed, which reveals parallel thermal dissociation processes that lead to even- and odd-numbered mass products. The drift-time distributions of high mass products, along with β-carotene, were monitored with temperature, showing multiple conformations that are associated with the presence of two β-rings. Products of masses 346/347, however, show a single conformation distribution, which indicates the separation of two β-rings resulting from the direct bond scission at the polyene hydrocarbon chain. The thermal degradation pathways are evaluated and discussed.

Parylene C Aging Studies

Parylene C is used in a device because of its conformable deposition and other advantages. Techniques to study Parylene C aging were developed, and %22lessons learned%22 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 (~40 days) aging experiments with free standing and ceramic-supported Parylene C films highlighted %22lessons learned%22 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 (%22necking%22) for robust accelerated aging of Parylene C.

Fluorosilicone and silicone o-ring aging study.

Fluorosilicone o-ring aging studies were performed. These studies examined the compressive force loss of fluorosilicone o-rings at accelerated (elevated) temperatures and were then used to make predictions about force loss at room temperature. The results were non-Arrhenius with evidence for a lowering in Arrhenius activation energies as the aging temperature was reduced. The compression set of these fluorosilicone o-rings was found to have a reasonably linear correlation with the force loss. The aging predictions based on using the observed curvature of the Arrhenius aging plots were validated by field aged o-rings that yielded degradation values reasonably close to the predictions. Compression set studies of silicone o-rings from a previous study resulted in good correlation to the force loss predictions for the fluorosilicone o-rings from this study. This resulted in a preliminary conclusion that an approximately linear correlation exists between compression set and force decay values for typical fluorosilicone and silicone materials, and that the two materials age at similar rates at low temperatures. Interestingly, because of the observed curvature of the Arrhenius plots available from longer-term, lower temperature accelerated exposures, both materials had faster force decay curves (and correspondingly faster buildup of compression set) at room temperature than anticipated from typical high-temperature exposures. A brief study on heavily filled conducting silicone o-rings resulted in data that deviated from the linear relationship, implying that a degree of caution must be exercised about any general statement relating force decay and compression set.

Multi-Method Characterization of Compression Set in Fluorosilicone O-Rings

Fluorosilicone o-rings with varying levels of compression set were investigated with a variety of methods. Low field NMR experiments were able to elucidate if the sample had taken a compression set; however, this technique did not have the sensitivity to quantify the relative level of compression set of the o-ring. Water sorption isotherms probe the interior void structure through void space occupation and while complex, the sorption isotherms indicate a systematic loss of void volume with increasing compression set. Similarly, variable temperature 129Xe NMR experiments indicate an elimination of macroscopic void space with increasing compression. The NMR techniques, being noninvasive, have a unique ability to assess the service status of an o-ring in real time.

Identification of volatile butyl rubber thermal-oxidative degradation products by cryofocusing gas chromatography/mass spectrometry (cryo-GC/MS).

Chemical structure and physical properties of materials, such as polymers, can be altered as aging progresses, which may result in a material that is ineffective for its envisioned intent. Butyl rubber formulations, starting material, and additives were aged under thermal-oxidative conditions for up to 413 total days at up to 124 °C. Samples included: two formulations developed at Kansas City Plant (KCP) (#6 and #10), one commercially available formulation (#21), Laxness bromobutyl 2030 starting material, and two additives (polyethylene AC-617 and Vanax MBM). The low-molecular weight volatile thermal-oxidative degradation products that collected in the headspace over the samples were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). The majority of identified degradation species were alkanes, alkenes, alcohols, ketones, and aldehydes. Observations for Butyl #10 aged in an oxygen-18 enriched atmosphere ( 18 O2) were used to verify when the source of oxygen in the applicable degradation products was from the gaseous environment rather than the polymeric mixture. For comparison purposes, Butyl #10 was also aged under non-oxidative thermal conditions using an argon atmosphere. UNCLASSIFIED UNLIMITED RELEASE (UUR) UNCLASSIFIED UNLIMITED RELEASE (UUR) 4 ACKNOWLEDGMENTS The authors gratefully acknowledge the contributions of Donald R. Bradley for his assistance in sample preparation and aging. We would also like to thank Mark Wilson for providing the butyl rubber samples as developed by him at Kansas City Plant. Funding was provided by the Enhanced Surveillance Campaign (ESC). 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 DEAC0494AL85000. UNCLASSIFIED UNLIMITED RELEASE (UUR) UNCLASSIFIED UNLIMITED RELEASE (UUR) 5 CONTENTS

Neutron and gamma irradiation damage to organic materials.

This document discusses open literature reports which investigate the damage effects of neutron and gamma irradiation on polymers and/or epoxies - damage refers to reduced physical chemical, and electrical properties. Based on the literature, correlations are made for an SNL developed epoxy (Epon 828-1031/DDS) with an expected total fast-neutron fluence of {approx}10{sup 12} n/cm{sup 2} and a {gamma} dosage of {approx}500 Gy received over {approx}30 years at < 200 C. In short, there are no gamma and neutron irradiation concerns for Epon 828-1031/DDS. To enhance the fidelity of our hypotheses, in regards to radiation damage, we propose future work consisting of simultaneous thermal/irradiation (neutron and gamma) experiments that will help elucidate any damage concerns at these specified environmental conditions.

Development of a Chemiresistor Sensor for Polypropylene Degradation Products

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.