Radiation-induced degradation of polymeric materials occurs through numerous, simultaneous, competing chemical reactions. Although degradation is typically found to be linear in adsorbed dose, some silicone materials exhibit nonlinear dose dependence due to dose-dependent dominant degradation pathways. We have characterized the effects of radiative and thermal degradation on a model filled-PDMS system, Sylgard 184 (commonly used in electronic encapsulation and in biomedical applications), using traditional mechanical testing, NMR spectroscopy, and sample headspace analysis using solid-phase microextraction (SPME) followed by gas chromatography/mass spectrometry (GC/MS). The mechanical data and 1H spin−echo NMR spectra indicated that radiation exposure leads to predominantly cross-linking over the cumulative dose range studied (0−250 kGy) with a rate roughly linear with dose. 1H multiple-quantum NMR spectroscopy detected a bimodal distribution in the network structure, as expected from the proposed structure of Sylgard 184. The MQ NMR spectra further indicated that the radiation-induced structural changes were not linear in adsorbed dose and that competing chain scission mechanisms made a greater contribution to the overall degradation process in the range of 50−100 kGy (although cross-linking still dominated). The SPME−GC/MS data were analyzed using principal component analysis (PCA), which identified subtle changes in the distributions of degradation products (the cyclic siloxanes and other components of the material) as a function of age that provide insight into the dominant degradation pathways at low and high adsorbed dose.
The silicone elastomer Dow Corning DC 745U is used in two major components in the W80. We have investigated a number of issues concerning this material. Our studies have accomplished a baseline study of the chemical composition of DC745 and LLNL now has a good understanding of the chemical composition of this material. DC745 crystallizes within the system STS. Two potential means identified to mitigate the risk associated with this phenomenon are to 1) change material formulation and 2) predose the parts to ~ 25 MRad γ-radiation. A candidate material identified by Gordon Spellman has been studied for composition and the lack of crystallization within the STS has been verified. A sensitivity study of the effects of relevant aging mechanisms also has been performed. The extent of aging due to radiation exposure or elevated temperatures is minimal over the expected course of the LEP. In addition, since the DC745 parts are expected to be replaced at rebuild, the aging clock is essentially being reset. No significant aging issues seem likely to develop for these parts. DC745 parts are also subject to permanent deformation in service. Our studies have shown that the deformation is likely due to incomplete mixing of the raw gum stock and the curing agent at production. This results in areas of low crosslink density that are subject to a higher degree of compression set in service. We have identified two production diagnostic tools based on Nuclear Magnetic Resonance spectroscopy to prescreen the parts at production at KCP. These studies are concluded with specific recommendation for changes to core surveillance for this part based on the chemical knowledge we have gained from this study.
The aim of the present study is to determine the chemical structure and conformation of DNA adducts formed by incubation of the bioactive form of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), N-acetoxy-PhIP, with a single-stranded 11mer oligodeoxyribonucleotide. Using conditions optimized to give the C8-dG-PhIP adduct as the major product, sufficient material was synthesized for NMR solution structure determination. The NMR data indicate that in duplex DNA this adduct exists in equilibrium between two different conformational states. In the main conformer, the covalently bound PhIP molecule intercalates in the helix, whilst in the minor conformation the PhIP ligand is probably solvent exposed. In addition to the C8-dG-PhIP adduct, at least eight polar adducts are found after reaction of N-acetoxy-PhIP with the oligonucleotide. Three of these were purified for further characterization and shown to exhibit lowest energy UV absorption bands in the range 342-347 nm, confirming the presence of PhIP or PhIP derivative. Accurate mass determination of two of the polar adducts by negative ion MALDI-TOF MS revealed ions consistent with a spirobisguanidino-PhIP derivative and a ring-opened adduct. The third adduct, which has the same mass as the C8-dG-PhIP oligonucleotide adduct, may contain PhIP bound to the N2 position of guanine.
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