Publications

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Thermogravimetric analysis - gas chromatography/mass spectrometry (TGA- GC/MS) experiments were performed on EN-7 and EN-8, analyzed, and reported in [1] . This SAND report derives and describes pyrolytic thermal decomposition models for use in predicting the responses of EN-7 and EN-8 in an abnormal thermal environment.

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Melt state dynamics for a series of strictly linear polyethylenes with precisely spaced associating functional groups were investigated. The periodic pendant acrylic acid groups form hydrogen-bonded acid aggregates within the polyethylene (PE) matrix. The dynamics of these nanoscale heterogeneous morphologies were investigated from picosecond to nanosecond timescales by both quasi-elastic neutron scattering (QENS) measurements and fully atomistic molecular dynamics (MD) simulations. Two dynamic processes were observed. The faster dynamic processes which occur at the picosecond timescales are compositionally insensitive and indicative of spatially restricted local motions. The slower dynamic processes are highly composition dependent and indicate the structural relaxation of the polymer backbone. Higher acid contents, or shorter PE spacers between pendant acid groups, slow the structural relaxation timescale and increase the stretching parameter (β) of the structural relaxation. Additionally, the dynamics of specific hydrogen atom positions along the backbone correlate structural heterogeneity imposed by the associating acid groups with a mobility gradient along the polymer backbone. At time intervals (<2 ns), the mean-squared displacements for the four methylene groups closest to the acid groups are up to 10 times smaller than those of methylene groups further from the acid groups. At longer timescales acid aggregates rearrange and the chain dynamics of the slow, near-aggregate regions and the faster bridge regions converge, implying a characteristic timescale for the passage of chains between aggregates. The characterization of the nanoscale chain dynamics in these associating polymer systems both provides validation of simulation force fields and provides understanding of heterogeneous chain dynamics in associating polymers.

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In this work, we report the synthesis and inclusion of rationally designed organotin compounds in polystyrene matrices as a route towards plastic scintillators capable of gamma-ray spectroscopy. Tin loading ratios of up to 15% w/w have been incorporated, resulting in photopeak energy resolution values as low as 10.9% for 662 keV gamma-rays. Scintillator constituents were selected based upon a previously reported distance-dependent quenching mechanism. Data obtained using UV-Vis and photoluminescence measurements are consistent with this phenomenon and are correlated with the steric and electronic properties of the respective organotin complexes. We also report fast scintillation decay behavior that is comparable to the quenched scintillators 0.5% trans-stilbene doped bibenzyl and the commercial plastic scintillator BC-422Q-1%. These observations are discussed in the context of practical considerations such as optical transparency, ease-of-preparation/scale-up, and total scintillator cost.

Currently we are investigating the inclusion of organotin compounds in polystyrene material to improve plastic scintillators full gamma-ray energy sensitivity with the ultimate goal of achieving spectroscopy. Accurate evaluation of light yield from the newly developed scintillators is crucial to assess merits of compounds and chemical process used in the scintillators development. Full gamma-ray energy peak in measured gammaray spectrum, resulting from total absorption of gamma-ray energy, would be ideal in evaluating the light yield from the new scintillators. However, full energy sensitivity achieved thus far is not statistically viable for fast and accurate light yield energy calibration from the new scintillators. The Compton edge in measured gamma-ray spectrum has been found as an alternate gamma-ray spectrum feature that can be exploited for characterizing the light yield energy from the newly developed plastic scintillators. In this study we present technique implemented for accurate light yield energy calibration using the Compton edge. Results obtained were very encouraging and promise the possibility of using the Compton edge for energy calibration in detectors with poor energy resolution such as plastic and liquid scintillators.

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Two types of water - containing liquid scintillation mixtures were prepared in the present work. In the first, m ixtures of 2 - phenylethanol, water, diphenyl phosphate, sodium phenyl phosphate dibasic dihydrate, and the dye 2,5 - diphenyloxazole (PPO) have been investigated as liquid scintillators. In the second system, nonionic and mixed surfactant systems were investigated in conjunction with water and small amounts of toluene. In both cases, increasing amounts of water led to reductions in the scintillation light yield. Understanding what factors contr ibute to this phenomenon is the focus of this report. Changes in the solution microphase structure, diminishing aromatic content of the cocktail mixtures, and inefficient energy transfer to the dye a ppear to be responsible for the decreased light yield as more water is added . In the 2 - phenylethanol system, the observed experimental results are consistent with the formation of a bicontinuous microemulsion at higher water concentrations, which incorporates PPO and shields it from the quenching effects of the increasing polar matrix. Evidence for this proposed phase change comes from light scattering data, photo - and x - ray luminescence measurements, and optical transparency measurements . In the surfactant - based system, the quenching effect of water was found to be less than both commercially - available dioxane - naphthalene mixtures used for scintillation counting as well as the 2 - phenylethanol mixtures described above. The effect of different surfactant mixtures and concentrations were studied, revealing a benefic ial effect upon the scintillation light yield for mixed surfactant mixtures. These results are interpreted in the context of reactive radical species formation following water ionization , which leads to light - yield quenching in aqueous systems . The presence of surfactant(s) in these mixtures enables the formation of organic - rich regions that are spatially separated from the reactive radicals. This hypothesis is consistent with subsequent experiments that showed reduced light - yield quenching in the presence of radical - trapping additives. A notable result from these surfactant studies was the preparation of an aqueous scintillator that was transparent and showed neutron/gamma pulse - shape discrimination. Section II below provides background information on the significance of this finding. The combined work described herein has implications on other efforts to make water - based solution scintillators -- without aromatic content an efficient mechanism for ionizing radiation to sensitize emission from a dye is limited.

Synthesis of ditopic imidazoliums was achieved using a modular step-wise procedure. The procedure itself is amenable to a wide array of functional groups that can be incorporated into the imidazolium architecture. The resulting compounds range from ditopic zwitterions to highly-soluble dicationic aromatics

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In this report we explore the sensitivities of the insulation resistance between two loops of wire embedded in insulating materials with a simple, approximate model. We discuss limita- tions of the model and ideas for improvements.

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In an attempt to mitigate the hazards associated with storing large quantities of reactive metal hydrides, polymer composite materials were synthesized and tested under simulated usage and accident conditions. The composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride. Composites with vinyl-containing siloxane oligomers were also polymerized with and without added styrene and divinyl benzene. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride reduced the inherent hydrogen storage capacity of the material. The composites were found to be initially effective at reducing the amount of heat released during oxidation. However, upon cycling the composites, the mitigating behavior was lost. While the polymer composites we investigated have mitigating potential and are physically robust, they undergo a chemical change upon cycling that makes them subsequently ineffective at mitigating heat release upon oxidation of the metal hydride. Acknowledgements The authors would like to thank the following people who participated in this project: Ned Stetson (U.S. Department of Energy) for sponsorship and support of the project. Ken Stewart (Sandia) for building the flow-through calorimeter and cycling test stations. Isidro Ruvalcaba, Jr. (Sandia) for qualitative experiments on the interaction of sodium alanate with water. Terry Johnson (Sandia) for sharing his expertise and knowledge of metal hydrides, and sodium alanate in particular. Marcina Moreno (Sandia) for programmatic assistance. John Khalil (United Technologies Research Corp) for insight into the hazards of reactive metal hydrides and real-world accident scenario experiments. Summary In an attempt to mitigate and/or manage hazards associated with storing bulk quantities of reactive metal hydrides, polymer composite materials (a mixture of a mitigating polymer and a metal hydride) were synthesized and tested under simulated usage and accident conditions. Mitigating the hazards associated with reactive metal hydrides during an accident while finding a way to keep the original capability of the active material intact during normal use has been the focus of this work. These composites were made by polymerizing vinyl monomers using free-radical polymerization chemistry, in the presence of the metal hydride, in this case a prepared sodium alanate (chosen as a representative reactive metal hydride). It was found that the polymerization of styrene and divinyl benzene could be initiated using AIBN in toluene at 70°C. The resulting composite materials can be either hard or brittle solids depending on the cross-linking density. Thermal decomposition of these styrene-based composite materials is lower than neat polystyrene indicating that the chemical nature of the polymer is affected by the formation of the composite. The char-forming nature of cross-linked polystyrene is low and therefore, not an ideal polymer for hazard mitigation. To obtain composite materials containing a polymer with higher char-forming potential, siloxane-based monomers were investigated. Four vinyl-containing siloxane oligomers were polymerized with and without added styrene and divinyl benzene. Like the styrene materials, these composite materials exhibited thermal decomposition behavior significantly different than the neat polymers. Specifically, the thermal decomposition temperature was shifted approximately 100 °C lower than the neat polymer signifying a major chemical change to the polymer network. Thermal analysis of the cycled samples was performed on the siloxane-based composite materials. It was found that after 30 cycles the siloxane-containing polymer composite material has similar TGA/DSC-MS traces as the virgin composite material indicating that the polymer is physically intact upon cycling. Hydrogen capacity measurements revealed that addition of the polymer to the metal hydride in the form of a composite material reduced the inherent hydrogen storage capacity of the material. This reduction in capacity was observed to be independent of the amount of charge/discharge cycles except for the composites containing siloxane, which showed less of an impact on hydrogen storage capacity as it was cycled further. While the reason for this is not clear, it may be due to a chemically stabilizing effect of the siloxane on the metal hydride. Flow-through calorimetry was used to characterize the mitigating effectiveness of the different composites relative to the neat (no polymer) material. The composites were found to be initially effective at reducing the amount of heat released during oxidation, and the best performing material was the siloxane-containing composite which reduced the heat release to less than 50% of the value of the neat material. However, upon cycling the composites, all mitigating behavior was lost. The combined results of the flow-through calorimetry, hydrogen capacity, and thermogravimetric analysis tests lead to the proposed conclusion that while the polymer composites have mitigating potential and are physically robust under cycling, they undergo a chemical change upon cycling that makes them ineffective at mitigating heat release upon oxidation of the metal hydride.

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