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At least 253 records · Page 14

Investigation of the structure, filler interaction and degradation of disulfide elastomers made by Reversible Radical Recombination Polymerization (R3P)

In this paper we report the synthesis and analysis of cyclic polydisulfides, their redox depolymerization as well as their interaction with carbon black. Cyclic poly(3,6-dioxa-1,8-octanedithiol)s (pDODT) were synthesized by Reversible Radical Recombination Polymerization (R3P). R3P is a scalable “green” polymerization process using triethylamine (TEA), H 2 O 2 and air for the polymerization of dithiol monomers. pDODTs were synthesized in 5 and 20 g batches. The effect of peroxide concentration (3, 5, 10, 20, 30%) was investigated. It was found that the molecular weights increased exponentially with increasing peroxide concentrations. At 30% peroxide concentration pDODTs with M n up to 400,000 g/mol and polydispersity of 2 were obtained. 700 and 800 MHz NMR were used for investigating the chemical structure of the polymers. The absence of thiol end group signals in polymers made with > 10wt % H 2 O 2 and M n < 100,000 g/mol, including a sample of a fractionated polymer with starting Mn = 600,000 g/mol, verified cyclic structures. Dithiothreitol reduced the polymers to monomer and a small percentage of oligomers. Carbon black was shown to increase the moduli of high molecular weight pDODTs. Swelling tests in chloroform showed that polymers made with 20 and 30w% peroxide swelled 14 and 10 times of their starting weight without dissolving, indicating chemical interaction between the polymers and carbon black. In conclusion, further analysis of these interesting elastomers, available at the 20 g scale, is in progress.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbamoylation as an Effective Tool in the Analysis of the Soman Nerve Agent Marker Pinacolyl Alcohol in Soil Matrices by EI-GC-MS and LC-HRMS

Pinacolyl alcohol (PA) is a Schedule 2 chemical commonly featured in most proficiency tests (PTs) administered by the Organisation for the Prohibition of Chemical Weapons (OPCW) due to its direct as well as forensic link to the nerve agent Soman. Therefore, its detection by Chemical Weapons Convention (CWC) inspection teams during on-site investigations is a strong indicator of the past or latent presence of Soman in the environment. Its small molecular weight (102), early elution time, and poor ionization profile make PA a challenging analyte to detect particularly at low concentrations (∼1–10 μg/g). In this work, 1,1′-carbonyldimidazole (CDI) has been used to effectively modify PA for the first time in two different soil matrices (Virginia type A soil and silt sediment) at two separate concentrations (1 and 10 μg/g) for its subsequent detection by EI-GC-MS and LC-HRMS methods. For the EI-GC-MS analysis, the PA carbamate derivative (PIC) exhibits improved chromatography relative to PA such as improved peak shape, increased molecular weight (196 for PIC and 102 for PA) and increased retention time (16.9 min for PIC and ∼4.1 min for PA). In addition, the derivatization also improves the detection of PA by LC-HRMS as the PIC product possesses protonation sites (i.e., imidazole ring) relative to none exhibited by PA. More importantly, the carbamoylation proceeds under mild conditions (55 °C, no base) and rapidly (3 h), characteristics that make it an appealing protocol for the analysis of PA during OPCW PTs or real case scenarios particularly in instances where it is present at low concentrations. It is anticipated that the protocol can be applied to the forensic analysis of this important Soman marker in various environmental matrices.

Chemistry↗

Solid-State, Single-Ion Conducting, Polymer Blend Electrolytes with Enhanced Li + Conduction, Electrochemical Stability, and Limiting Current Density

The development of solid-state polymer electrolytes with high lithium conductivity is crucial to improve lithium-ion battery performance and ameliorate the safety challenges associated with current solvent-based electrolytes. Unfortunately, sluggish polymer segmental dynamics are known to constrain conductivity enhancements in solid-state polymer electrolyte systems, limiting overall performance. In this work, a glassy single-ion-conducting polymer, poly[lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate] (PLiMTFSI), was blended with a flexible polymer, poly(oligo-oxyethylene methyl ether methacrylate) (POEM), and the impact of PLiMTFSI molecular weight and ion concentration on the thermal and ion-conducting behavior of blend electrolytes was investigated. High ionic conductivities approaching 1 × 10 -2 S/cm at 150 °C were realized in this polymer blend electrolyte system as a result of decoupling Li + transport from polymer segmental dynamics. The decoupled ion transport was attributed to the packing frustration of the glassy PLiMTFSI – sufficient percolating free volume was generated to produce effective ion diffusion pathways. This decoupling was tunable as the ion transport could be altered from being closely coupled to the polymer segmental dynamics (Vogel–Tammann–Fulcher-like) to hopping (Arrhenius-like) by increasing the PLiMTFSI molecular weight and ion concentration. Moreover, the immobilized TFSI anion resulted in high Li + selectivity (Li + transference number = 0.9), high electrochemical stability (up to 4.7 V against Li + / Li), and limiting current density of 1.8 mA/cm 2 (electrolyte thickness = 0.05 cm). These features suggest that this single-ion-conducting, polymer blend electrolyte might be a promising alternative to a benchmark system – salt-doped polyethylene oxide. Moreover, the above characteristics can support the battery operation at higher voltages using energy-dense Li metal anodes, with faster charging rates and enhanced energy/power densities. Altogether, the results suggest that polymer chain packing frustration can be exploited to overcome the constraints of slow polymer segmental relaxations to achieve rapid and highly selective ion transport and enhanced performance in solid-state polymer electrolytes.

36 MATERIALS SCIENCE↗

Renewable low viscosity polyester-polyols for biodegradable thermoplastic polyurethanes

In the transition to renewably sourced, biodegradable polymers, the preparation of low viscosity polyester-polyols has posed a challenge for renewable polyurethane (PU) development. Low viscosity polyols not only reduce the requirement for high process temperatures but also decrease manufacturing time. In our efforts to incorporate increasing ratios of bio-based monomers into renewable PUs, we mixed diacids such as even carbon sebacic acid and odd carbon azelaic acid along with a renewable diol. This provided library of 2000 g/mol molecular weight polyester-polyols, and structures were established by 1 H and 13 C NMR analysis. The prepared polyester-polyols offered lower viscosity and enable lower fabrication temperatures to make TPUs, and their structure and material metrics were evaluated. The formation of TPUs is ascertained from FTIR and NMR analysis. The final TPUs displayed good physical and mechanical properties. Further, these TPUs exhibited T g in the range of -56.5 to -39.7°C, corresponding to TPU soft block structure, and T m between 98.3 and 105.1°C originating from the hard segment. Prepared TPUs exhibit excellent biodegradation under compost environmental conditions. These TPUs showed up to 57% decrease in molecular weight by GPC analysis after 9 weeks of biodegradation, and respirometer analysis displayed up to 97% biodegradation over 120 days.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Correlating processing variables to material properties in recycled polypropylene: A data‐driven approach

Abstract Polypropylene (PP) is one of the most widely used plastics, yet its recycling remains limited, with less than 1% of solid waste PP being reprocessed. Mechanical recycling through extrusion is the most practical method, but inconsistent reprocessing conditions introduce variability in material properties. While temperature, screw speed, and residence time influence the thermomechanical stress applied during reprocessing, there are no standardized guidelines for optimizing these parameters. This study examines how these factors shape the properties of recycled PP, using conditions designed to mimic post‐industrial recycled (PIR) scrap. Residence time was measured using colorimetric tracking and correlated with molecular weight, viscosity, and mechanical properties over multiple extrusion cycles. Data‐driven modeling, including response surface methodology, support vector machines, and artificial neural networks, identified processing temperature as the dominant factor in material degradation, followed by residence time. Mechanical properties remained stable, while viscosity decreased predictably with increasing residence time. By linking reprocessing conditions to property evolution, this study provides a method to optimize processing parameters and reduce variability in recycled PP. These findings help manufacturers improve process control, making recycled PP more predictable for reuse in manufacturing. Highlights Study of PIR‐quality PP without additives or compatibilizers. Residence time analysis shows processing temperature drives PP property changes. Mark‐Houwink enables quick molecular weight checks for quality control. Models predict mechanical and rheological shifts in reprocessing. Optimized processing parameters minimize property degradation in recycling.

Estela‐García, John E. [Polymer Engineering Center↗

Toward sustainable production of N-containing products via nonthermal plasma-enhanced conversion of natural gas resources

Nonthermal plasmas can directly activate and cleave the strong chemical bonds in molecular nitrogen and methane to facilitate the transformation of these inherently stable molecules through the application of electrical energy. Here, we report a low temperature, atmospheric pressure, nonthermal plasma for the “one-pot” synthesis of olefins, alkynes, higher molecular weight hydrocarbons, ammonia, and nitrogen-containing liquids from a representative shale gas feed enriched with nitrogen. Furthermore, we reproducibly observe a wide range of valuable and synthetically challenging gas-phase and liquid-phase products containing C-N, C-C, and N-H bonding by controlling the N 2 concentration in the inlet feed stream. In nitrogen-lean regimes, hydrocarbon products dominate (e.g., ethylene, acetylene, etc.), while nitrogen-rich regimes promote incorporation of nitrogen into the products, leading to the formation of ammonia and liquid products containing a variety of functionalities (e.g., nitriles, amines, heterocycles). High resolution electrospray ionization mass spectrometry was used to measure molecular weights and identify the chemical formulas of the liquid products. Van Krevelen diagrams were created and showed many products with compositions around H/C = 2 and N/C = 0.5, indicating the potential importance of intermediate species with these ratios for liquid formation (e.g., CH 3 CN + H).

03 NATURAL GAS↗

Probing the Morphology and Mobility of Amines in Porous Silica CO 2 Sorbents by 1 H T 1 – T 2 Relaxation Correlation NMR

Molecular and oligomeric amines supported in porous oxide supports are a promising class of CO 2 sorbent materials studied for CO 2 removal from diverse streams such as flue gas and ambient air. Among the various amines investigated, low molecular weight, hyperbranched poly(ethyleneimine) (PEI), and tetraethylenepentamine (TEPA) are among the most extensively studied. While macroscopic structure–performance relationships relating the support structure, amine loading, and other factors affecting CO 2 sorption capacities and kinetics have been developed, structural and dynamic information about the organic amine phase in the porous support is less plentiful. The structure and mobility of amines impregnated in the pores of porous supports directly impact gas sorption, as the accessibility of amine sites in the pores directly relates to amine distribution in the pores and overall pore filling as well as the dynamics of the amine chains. Here, we prepare a family of mesoporous silica SBA-15 materials containing varying loadings of oligomeric (PEI) and molecular (TEPA) amines. 1 H T 1 –T 2 relaxation correlation solid-state NMR experiments are used to characterize the structural and dynamic properties of the confined amines. Both TEPA and PEI are shown to form multiple different domains in the pores, each with distinguishable dynamic properties. TEPA and PEI form more rigid layers around the silica support walls at lower organic loading fractions, characterized by lower mobilities, followed by the formation of more mobile domains less engaged in pore wall interactions at higher loadings. TEPA shows faster mobilities than PEI because of its lower molecular weight. TEPA also appears to more easily transfer between domains within the pores, leading to generally faster CO 2 uptake rates with higher sorption capacities, while PEI located closer to the pore walls remained much less mobile and is thus less engaged in CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vaporization behavior of Ir 4 (CO) 12 and Re 2 (CO) 10 measured by torsion effusion gravimetric method

Metal carbonyls are of great importance in chemical vapor deposition (CVD), composite materials fabrication, and other near-net shape technologies. Carbonyl CVD is used for deposition of high-purity metallic and alloy coatings for which vapor pressure data is essential. In this study, we report vapor pressures of solid Ir 4 (CO) 12 and Re 2 (CO) 10 carbonyls measured by using the Knudsen Cell methodology using a torsion effusion thermogravimetric system. The vapor pressure of the Ir 4 (CO) 12 exhibited incongruent vaporization, as the molecular weight (MW) of the effusing species was determined as 128 g/mol as compared to the theoretical MW of 1105 g/mol. It is proposed that the Ir 4 (CO) 12 (s) partially decomposed (~66%) to Ir 4 (CO) 12 (g), Ir(s), and CO(g). The Re 2 (CO) 10 on the other hand, showed congruent behavior with Re 2 (CO) 10 (s) vaporizing to Re 2 (CO) 10 (g) in the measured temperature range. The raw data for vapor pressures was measured using two sets of Knudsen cells with different orifice sizes, and the equilibrium vapor pressures were calculated using Whitman-Motzfeldt methodology. The equilibrium vapor pressures of these carbonyls, partial pressures of gaseous species in case of decomposition, average molecular weights of the effusing gasses were determined. The vapor pressures and Gibbs energies of vaporization reactions of the two above mentioned carbonyls, as well as comparison of vaporization thermodynamics these two carbonyls with other carbonyls from Group VIB to VIIIB are presented in this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications

Poly(ethylene oxide) (PEO)-based electrolytes have gained increasing attention in both the rechargeable battery industry and fundamental research, but any influence of the ions on the polymer conformation is not fully understood. Small-angle neutron scattering (SANS) is a powerful means to determine single-polymer chain conformations. We conducted SANS experiments on 50:50 blends of perdeuterated PEO (dPEO) and hydrogenous PEO (hPEO) of two different molecular weights (20 and 40 kDa) doped with two different salts (LiTFSI and LiClO 4 ) at various concentrations. An additional measurement with LiI is also reported. The scattering profiles of salt-doped dPEO/hPEO blends were measured, and the incoherent scattering from dPEO and hPEO doped with salt was measured separately. A strong low q upturn was observed in some of the blends and in the pure dPEO homopolymers. The statistical segment lengths of PEO–salt mixtures were derived using a Kratky analysis. The segment length decreases modestly with increasing amounts of LiTFSI but apparently first increases then decreases with added LiClO 4 . At the highest salt concentration examined (r = [Li+]/[EO] = 0.125), a roughly 10% decrease in the statistical segment length was observed in both LiTFSI and LiClO 4 -doped PEOs, for both molecular weights. This work confirms that added salt causes a contraction of the PEO chain dimensions, but the effect appears slightly weaker than reported recently. Certain difficulties in data analysis are also discussed, including the unexplained low q scattering even in pure deuterated polymers, uncertainties in background subtraction, and inappropriate application of the Debye function.

36 MATERIALS SCIENCE↗

Influence of Metal-Alkyls on Early-Stage Ethylene Polymerization over a Cr/SiO 2 Phillips Catalyst: A Bulk Characterization and X-ray Chemical Imaging Study

The Cr/SiO 2 Phillips catalyst has taken a central role in ethylene polymerization since its invention in 1953. The uniqueness of this catalyst is related to its ability to produce broad molecular weight distribution (MWD) PE materials as well as that no co-catalysts are required to attain activity. Nonetheless, co-catalysts in the form of metal-alkyls can be added for scavenging poisons, enhancing catalyst activity, reducing the induction period, and tailoring polymer characteristics. The activation mechanism and related polymerization mechanism remain elusive, despite extensive industrial and academic research. Here, we show that by varying the type and amount of metal-alkyl co-catalyst, we can tailor polymer properties around a single Cr/SiO 2 Phillips catalyst formulation. Furthermore, we show that these different polymer properties exist in the early stages of polymerization. We have used conventional polymer characterization techniques, such as size exclusion chromatography (SEC) and 13 C NMR, for studying the metal-alkyl co-catalyst effect on short-chain branching (SCB), long-chain branching (LCB) and molecular weight distribution (MWD) at the bulk scale. In addition, scanning transmission X-ray microscopy (STXM) was used as a synchrotron technique to study the PE formation in the early stages: allowing us to investigate the produced type of early-stage PE within one particle cross-section with high energy resolution and nanometer scale spatial resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving the performance of PM6 donor polymer by random ternary copolymerization of BDD and DTBT segments

Developing high-performance wide bandgap polymer donors to match the rapidly growing non-fullerene small molecule acceptors (NF-SMAs) is of great importance to further improve the photovoltaic performances of organic solar cells (OSCs). PM6 and D18 are two leading wide bandgap donor polymers, but their performances are highly sensitive to the molecular weights, which have distinct impact on the morphology and thereby the charge generation and recombination processes. Here, in this work, we reported the random ternary copolymerization of PM6 and D18 segments to develop random terpolymers with finely tuned photoelectronic properties and optimized blend morphology for high-performance OSCs. The resulting random terpolymers (PMD-5, PMD-10, PMD-15 and PMD-20) exhibited finely tuned absorptions, energy levels and blend morphology. The optimal morphology of PMD-15:L8-BO contributed to the fast exciton diffusion and dissociation, efficient charge extraction with suppressed recombination. Thus, the power conversion efficiency was improved from 17.22% of the control PM6 devices and 17.47% of the control D18 devices to 18.12% of PMD-15 based devices, which is the top performance of random terpolymers. Moreover, the PMD-15 exhibited much higher batch-to-batch reproducibility at a broad molecular weight range than that of PM6 and D18, showing promising for practical applications.

36 MATERIALS SCIENCE↗

Rheology and engine performance of very low sulfur fuel oil blended with 10% fast pyrolysis and hydrothermal liquefaction oils in a 2-stroke crosshead engine

The performance and emissions for a downscaled single-cylinder 2-stroke crosshead engine were determined for a very low sulfur fuel oil (VLSFO) when blended with 10 wt.% fast pyrolysis (FP) or hydrothermal liquefaction (HTL) bio-intermediates. The FP and HTL oils were derived from biomass and were observed to contain lower molecular weight (MW) hydrocarbons than neat VLSFO (which was evaluated as a baseline comparison). The addition of either biofuel reduced the overall viscosity of the VLSFO. Aging tests at 50, 90, and 120°C showed that the dynamic viscosity of VLSFO increased with exposure time up to two weeks. Similar trends were observed for the FP and HTL blends, but a pronounced spike in viscosity occurred for these fuels during the early period of exposure. None of the viscosity increases exceeded the operational limits of fuel system pumps. Engine performance studies were conducted under low, medium and high load operational settings. The relative performance of the test fuels was highly dependent on operating condition. In general, the engine results for the three test fuels were similar, but modest improvements in brake thermal efficiency and brake specific fuel consumption were observed, which may be attributed to the heightened reactivity of low molecular weight fraction of the FP and HTL oils.

09 BIOMASS FUELS↗

Dramatic Slowdown of Bimolecular Reactions of Criegee Intermediates in Organic Aerosols

Although Criegee intermediates (CIs) play a central role in driving the transformation of organic molecules, their condensed-phase reaction kinetics remains poorly understood. While CIs undergo unimolecular decomposition to produce OH radicals, stabilized CIs participate in a host of other bimolecular reactions forming larger molecular weight products, including secondary ozonides (kSOZ), alkoxyalkyl hydroperoxides (kAlAHP), and acyloxyalkyl hydroperoxides (kAcAHP). Here, we demonstrate, using prior literature and new measurements of heterogeneous organic aerosol reactions using O3 or OH radicals, that these condensed-phase bimolecular reaction rate coefficients kSOZ (10-20 cm3·molecule-1·s-1), kAlAHP, and kAcAHP (10-19 cm3·molecule-1·s-1) are 7-10 orders of magnitude slower than analogous gas-phase reactions (∼ 10-10-10-13 cm3·molecule-1·s-1). This contrasts with current evidence that the rate coefficients for unimolecular steps in the condensed phase are similar in magnitude to those in the gas phase. Kinetic models using gas-phase-like bimolecular coefficients consistently overestimate the importance of bimolecular relative to unimolecular pathways while underpredicting the aerosol reactivity by up to 30-fold. The slowing of bimolecular reactivity in aerosols is likely due to solvation effects and the increased steric hindrance of larger molecular weight CIs and their scavengers in the condensed phase. These results challenge the conventional view that the high reactant density of an organic aerosol should favor bimolecular over unimolecular reactions, underscoring the need for more accurate CI condensed-phase rate constants for reliable modeling of oxidative processes across a diverse set of atmospheric and environmental systems.

Zeng, Meirong↗

Rheo-electric measurements of carbon black suspensions containing polyvinylidene difluoride in N -methyl-2-pyrrolidone

Lithium-ion battery cathode slurries have a microstructure that depends sensitively on how they are processed due to carbon black's (CB) evolving structure when subjected coating flows. While polyvinylidene difluoride (PVDF), one of the main components of the cathode slurry, plays an important role in modifying the structure and rheology of CB, a quantitative understanding is lacking. In this work, we explore the role of PVDF in determining the structural evolution of Super C65 CB in N-methyl-2-pyrrolidinone (NMP) with rheo-electric measurements. We find that PVDF enhances the viscosity of NMP resulting in a more extensive structural erosion of CB agglomerates with increasing polymer concentration and molecular weight. We also show that the relative viscosity of all suspensions can be collapsed by the fluid Mason number (Mnf), which compares the hydrodynamic forces imposed by the medium to cohesive forces holding CB agglomerates together. Using simultaneous rheo-electric measurements, we find at high Mnf, the dielectric strength (Δε) scales with Mnf, and the power-law scaling can be quantitatively predicted by considering the self-similar break up of CB agglomerates. The collapse of the relative viscosity and scaling of Δε both suggest that PVDF increases the hydrodynamic force of the suspending medium without directly changing the CB agglomerate structure. These findings are valuable for optimizing the rheology of lithium ion battery cathode slurries. We also anticipate that these findings can be extended to understand the microstructure of similar systems under flow.

Mechanics↗

Efficient Nighttime Biogenic SOA Formation in a Polluted Residual Layer

Abstract Organic nitrates formed from nighttime reaction between anthropogenic nitrate radicals (NO3) and biogenic volatile organic compounds (BVOCs) are potentially an important but highly uncertain source of secondary organic aerosol (SOA). Here we report on the enhanced nighttime biogenic SOA formation observed in a polluted residual layer over Sacramento, California, the morning of 15 June 2010 during the Carbonaceous Aerosols and Radiative Effects Study (CARES). Trajectory analysis showed that the residual layer air, containing trace amounts of isoprene and monoterpenes left over after nighttime oxidation, was influenced by the San Francisco Bay Area emissions the previous evening. The residual layer aerosol was also enriched in nitrate, with about 64% of it estimated to be in the form of organic nitrates. The nitrate:organic mass ratio of the SOA was about 0.47±0.044, which corresponds to the range typically found in isoprene mononitrates. Assuming the SOA was composed of organic mononitrates, its nominal molecular weight was estimated at 186±11 g mol-1, consistent with the highly functionalized isoprene hydroxynitrates that have been observed in the particle phase in the southeast United States. Overall, our findings show that the efficiency of nighttime biogenic SOA formation, expressed as the change in organic aerosol mass relative to carbon monoxide (?OA/?CO), was about 100 µg m-3 ppmv, which falls in the range 77-157 µg m-3 ppmv previously estimated for enhanced daytime SOA formation from mixed anthropogenic and biogenic emissions during CARES.

Zaveri, Rahul A.↗

Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization

The current scale of plastics production and the accompanying waste disposal problems represent a largely untapped opportunity for chemical upcycling. Tandem catalytic conversion by platinum supported on γ-alumina converts various polyethylene grades in high yields (up to 80 weight percent) to low-molecular-weight liquid/wax products, in the absence of added solvent or molecular hydrogen, with little production of light gases. The major components are valuable long-chain alkylaromatics and alkylnaphthenes (average ~C 30 , dispersity Ð = 1.1). Coupling exothermic hydrogenolysis with endothermic aromatization renders the overall transformation thermodynamically accessible despite the moderate reaction temperature of 280°C. This approach demonstrates how waste polyolefins can be a viable feedstock for the generation of molecular hydrocarbon products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying Properties for a Mechanistic, Predictive Understanding of Aqueous Impact on Aging of Medium and Low Voltage AC and DC Cabling in Nuclear Power Plants

To address the gap in knowledge in understanding degradation in relevant service conditions, this project aimed to develop a mechanistic, predictive model of medium and low voltage cable failure based on the primary environmental degradation parameters of aqueous immersion time, temperature, and the oxidation extent. To do so, we took a two-fold approach toward evaluating degradation as related to the aqueous condition. First, we evaluated the chemical, mechanical, and electrical properties of polymers that comprise the cabling insulation under varied aqueous conditions at different temperatures. Secondly, we evaluated the performance of insulation materials under similar accelerated aging conditions in addition to the dielectric breakdown of the cabling under submersion conditions. Thermal oxidation and immersion of LDPE thin films were done using a Parr vessel and the extent of oxidation was monitored using the carbonyl index from ATR-FTIR spectrum, a ratio quantifying the carbonyl functionality produced on the LDPE film surface. Increasing the temperature, oxidation time, and oxygen pressure increased the water-vapor permeability and the carbonyl content. Thermogravimetric analysis of the films confirmed that there is indeed an initial weight loss of the smaller molecular weight molecules and volatiles. At higher temperatures, there is a secondary mass loss. Up to 70°C, the mass loss curves were similar until 80°C, when the aged films decreased at a much greater rate with respect to increasing temperature. This was seen in the 10, 50, 90% weight loss temperatures. The mechanical properties of sheet PP and HDPE as well as injection molded LDPE, HDPE, HDPP dog bones were plotted with respect to the time spent in the Parr vessel during thermal oxidation. For the sheet PP and HDPE, the UTS and the modulus of elasticity decreased while the elongation increased. The injection-molded LDPE, HDPE, and HDPP dog bones experienced a similar trend where the changes in the properties were within experimental uncertainty. This analysis of LDPE in dry and immersive oxygen-rich environments is an important baseline for future experiments looking at other degradation mechanisms. A predictive aging model for low-density polyethylene insulative cable housings was developed. This model revealed a combination of physical and chemical processes which lead to an increase in permeability and a decrease in strength of the insulator. In creating this predictive model, a gap of knowledge in the literature was revealed in two areas: understanding how the crystallinity of a polymer changes with time and visualizing the predicted pores formed through the insulator which leads to failure. Developing and using an adapted ATR-FTIR method, crystallinity was monitored and compared to bulk crystallinity found via DSC. Inhomogeneity in crystallinity changes were observed but the FTIR method but was found to be less reliable. Pore visualization was found utilizing electrical impedance spectroscopy saturated aged polyethylene films with synthesized citrate-capped gold nanoparticles, and chloroauric acid precursor. results indicate a decreasing impedance of the polyethylene films caused by the transport of ions through the film. SEM imaging was then performed for elemental analysis of the films and counter electrodes for the presence of ions. Chloride and gold ions were detected; however, no nanoparticles were found. This gives an estimated pore size of at least 0.3 nm through the aged film. Cyclic submergence of polyethylene and polypropylene in aqueous solutions of copper sulfate and Harrison’s solution were examined. It was discovered that aging in these mixed conditions and at 90°C did cause a small, yet significant increase to tensile strength for both unaged polyethylene and polypropylene. The PE and PP in cycled and submerged conditions did not have tensile strengths significantly different from dry-aged after 16 weeks. For both solutions, it was determined that capacitance increases with both water tree depth and cable temperature and is relatively independent of changing water tree AR. As for resistance, there is no apparent change between depth percentages of 10 and 80 for both solutions. This is because the water tree has not yet entered the conductor and thus there is no shorting current flowing through the tree yet. Between 80 and 100% water tree depth, it is observed that for both solutions there is a rapid decrease in resistance because the tree is now impacting the conductor shield and allowing shorting current to flow through it. The relationship between resistance and temperature was found to be inversed. As temperature increases, resistance decreases for both water tree solutions with distilled water having the most apparent difference across the range of temperatures simulated. With regards to water tree AR, resistance was found to be relatively independent at depth percentages of 10, 50, and 70, but there was some relationship at 100% depth for both solutions. At this depth, as water tree AR increased, resistance was found to also increase. Through the examination of voltage and electric field distribution plots, it was confirmed for EPR cables that increasing water tree depth leads to increasing distortion. The increase in shorting current at 100% depth for aqueous copper sulfate compared to distilled water was also visualized. Lastly, the relationship between shorting current and temperature for narrow water trees was visualized and validated using the distribution plots. This study has led to a better understanding of the effect of cable temperature, water tree solution, and geometry of the tree region on cable degradation. Furthermore, this study has documented simulation results of water tree degradation in EPR MV cables, which had been previously lacking in information. Future work in this area will add frequency into the mix and examine what effect it has on the rate of cable degradation as a result of water treeing. To compliment the work being carried by UMD on different polymer chemistries, harvested medium voltage (MV) cables were selected for accelerated aging study at ORNL. These medium voltage cables are representative of the vintages and materials that are currently in use at existing nuclear power plants (NPPs). These cables were immersed in water at 90°C and energized for a period of two years at elevated voltage. Partial discharge was measured during this period of time to track potential degradation. Unfortunately, due to the absence of failure, the extent of integration between the UMD techniques and the harvested MV insulation was limited. However, based on the findings and from the UMD research in the previous sections on polyethylene and polypropylene, follow-on characterization for harvested MV cable insulation should focus on sample preparation to take advantage of the UMD techniques to better understand mechanistic degradation in MV cable insulations. This would include: 1.) Utilization of solutions and impedance measurement insulation to track permeability in harvested and accelerated aging insulation samples, 2.) Adaptation of gold nanoparticle synthesis for electrical impedance spectroscopy with supporting SEM characterization to study pore formation in harvested and accelerated aged insulation samples, & 3.) ATR-FTIR crystallinity with multiple temperature dependent harvested MV cable insulation under different air and submerged accelerated aging. In addition, low voltage dielectric spectroscopy and high voltage dissipation factor, tan δ, could be implemented as a condition monitoring tool for harvested MV cable insulation in submerged environments.

24 POWER TRANSMISSION AND DISTRIBUTION↗