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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Upcycling of Polystyrene Waste to Poly(ionic liquid) Materials

The C–H functionalization of commodity polymers could be a promising approach for upcycling plastic waste into advanced materials, which can alter the properties of the original materials through the introduction of different functionalities onto the existing backbone structures. In this study, waste polystyrene (PS) was modified by Friedel–Crafts acylation using 4-chlorobutyryl chloride (4-CBC) followed by reaction with N-alkylimidazoles to form cationic polyelectrolytes. These methods provide access to what are essentially poly(ionic liquid) (poly(IL)) materials with properties that are distinctly different from those of the PS from which they were formed. In one notable example, the glass transition temperature (T g ) of imidazolium-functionalized PS was ∼16 °C, which is a nearly 90 °C reduction from PS. This is also evidenced by macroscopic mechanical properties where the poly(IL) product is highly elastic in stark contrast to brittle PS. Moreover, the resulting ionomers showed self-healing behaviors in the presence of a “free” IL further contributing to the utility of the materials. Here, the methods in this work can open opportunities to utilize waste PS to obtain a vast array of poly(IL) materials with highly tailored structures and properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Upcycling waste polystyrene to adipic acid through a hybrid chemical and biological process

Oxidative catalytic depolymerization of polystyrene (PS) can produce benzoic acid, but the annual consumption of benzoic acid is ~40 times lower than PS. For this catalytic oxidation method to be a viable means to manage PS waste, benzoic acid should be converted to higher-volume chemicals. We demonstrate a hybrid chemical and biological process that uses PS as feedstock for production of adipic acid, a high-volume co-monomer for nylon 6,6 via benzoic acid. Mn/Br co-catalyzed autoxidation of PS to benzoic acid proceeds with a yield of up to 94% in a solvent mixture of benzoic acid and water. The PS-derived benzoic acid undergoes bioconversion at near-quantitative yield to muconic acid, which is readily converted to adipic acid through catalytic hydrogenation. Process modeling, techno-economic analysis, and life cycle assessment estimate an adipic acid minimum selling price of $3.18/kg, with a 61% decrease in greenhouse gas emissions relative to production from fossil fuels.

09 BIOMASS FUELS↗
DOE OSTI2022

Facile synthesis of epoxide-co-propylene sulphide polymers with compositional and architectural control

Here, we present a facile method to produce propylene sulphide (PS) homopolymers up to 100 kg mol -1 and PS-epoxide statistical, block, and ABA copolymers using inexpensive and versatile thio-aluminium (SAl) based initiators. Homopolymerizations of PS with SAl initiators are living and controlled, with number averaged molecular weights ($\bar M$ n ) up to 100 kg mol -1 while maintaining narrow polydispersity (Ð < 1.4). Statistical and block copolymers of PS and epichlorohydrin (ECH) or propylene oxide (PO) are synthesized and characterized by size-exclusion chromatography (SEC), differential scanning calorimetry (DSC), 1 H and 13 C NMR spectroscopy, diffusion ordered spectroscopy (DOSY), and small-angle X-ray scattering (SAXS). This work represents the first statistical copolymerization of PS and epoxides with similar reactivity ratios, allowing fine control over composition. Block-copolymers of PS and epoxides are synthesized by sequential addition, without intermediate preparative steps. Polymer architecture is controlled through modification of the initiator; we synthesized a di-functional (d-H) SAl initiator to produce ABA tri-block-copolymers. Finally, poly(ethylene glycol) (PEG) was used as a macroinitiator to create PEG-b-PPS block copolymers and characterized by 1 H, 13 C NMR spectroscopy, DOSY, DSC, and SEC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

High- χ diblock copolymers containing poly(vinylpyridine- N -oxide) segments

Block copolymers exhibiting an enhanced segregation strength due to an underlying high Flory–Huggins interaction parameter (high χ) have attracted considerable attention because of their potential of forming microphase-separated domains with very small feature sizes (<10 nm) useful for next-generation lithography. Here, we report the synthesis, characterization, and self-assembly of poly(styrene)- block -poly(2-vinylpyridine N -oxide) (PS- b -P2VPNO) and poly(styrene)- block -poly(4-vinylpyridine N -oxide) (PS- b -P4VPNO) block copolymers. These PS- b -PVPNOs were obtained from the oxidation of their precursors, poly(styrene)- block -poly(2-vinylpyridine) (PS- b -P2VP) and poly(styrene)- block -poly(4-vinylpyridine) (PS- b -P4VP), respectively. The PS- b -PVPNOs exhibit an enhanced segregation as revealed by ordered cylindrical and lamellar structures in the sub-10 nm scale from copolymers with relatively low molecular weight. The morphologies and periodicities of the ordered structures were determined by small-angle X-ray scattering, while atomic-force microscopy was used to image the self-assembly in thin films. Estimates of the changes in disorder–order transition temperature and domain spacing are derived from a theory based on the effects of dipolar interactions. All the experimentally observed morphological changes resulting from the oxidation of P2VP and P4VP precursors can be qualitatively explained in terms of an increased dipole moment of vinylpyridine N -oxide segments. Therefore, our results demonstrate that PVPNO based block copolymers are versatile candidates toward nanopatterned structures with small feature sizes critical for the future microelectronics industry and beyond.

36 MATERIALS SCIENCE↗
DOE OSTI2022

How transient effects can change the inferred plasma temperatures when using K-shell sulfur line ratios in a time dependent iron sulfide plasma

This paper describes how the steady state atomic kinetics approximation can underestimate the electron temperature determined from K-shell lines in ps-time-scale transient plasmas. In particular, we model the temperature determination of solid FeS targets used in opacity experiments at the Orion laser facility from the ratio of sulfur He-α to Ly-α lines. Such experiments use short-pulse lasers to heat a thin microdot of FeS buried in a plastic target to temperatures of more than 1 keV and densities of approximately 1–2 g/cm 3 . Using atomic kinetics calculations based on a temperature history from a radiation hydrodynamic simulation of the target evolution, the peak temperature inferred from the sulfur line ratios is 1.29 keV at 3.1 ps as compared with the input peak temperature of 1.41 keV at 2.0 ps. There is a time lag of 1.2 ps at the peak, and an overall 0.5 ps time lag in the temporal history of the temperature as the plasma cools over the next 10 ps.

Rilloraza, Francisco↗
DOE OSTI2023

Towards robust PICOSEC Micromegas precise timing detectors

The PICOSEC Micromegas (MM) detector is a precise timing gaseous detector consisting of a Cherenkov radiator combined with a photocathode and a MM amplifying structure. A 100-channel PICOSEC MM prototype with 10 × 10 cm 2 active area equipped with a Cesium Iodide (CsI) photocathode demonstrated a time resolution below σ = 18 ps. The objective of this work is to improve the PICOSEC MM detector robustness aspects, i.e. integration of resistive MM and carbon-based photocathodes, while maintaining good time resolution. The PICOSEC MM prototypes have been tested in laboratory conditions and successfully characterised with 150 GeV/c muon beams at the CERN SPS H4 beam line. The excellent timing performance below σ = 20 ps for an individual pad obtained with the 10 × 10 cm 2 area resistive PICOSEC MM of 20 MΩ/$\square$ showed no significant time resolution degradation as a result of adding a resistive layer. A single-pad prototype equipped with a 12 nm thick Boron Carbide (B 4 C) photocathode presented a time resolution below σ = 35 ps, opening up new possibilities for detectors with robust photocathodes. The results made the concept more suitable for the experiments in need of robust detectors with good time resolution.

RETHGEM↗
DOE OSTI2024

A Highly Effective Polysulfide-Trapping Approach for the Development of High Energy Density, Scalable Lithium-Sulfur Batteries

Lithium-sulfur (Li-S) batteries are identified as one of the most promising next-generation battery technologies owing to their high theoretical specific energy, sustainability, and affordability. However, the commercialization of Li-S batteries has been hindered by severe technical challenges, including the lithium polysulfide (PS) dissolution/shuttling effect, a major cause of fast capacity degradation over cycling. We demonstrated that, for the first time, nanolayer polymer coated high surface area porous carbons (NPCs) were coated directly on sulfur electrodes (NPC-S), which led to a high specific capacity of ∼1,600 mAh g −1 approaching the theoretical specific capacity limit in the NPC-S based Li-S batteries. The NPC-S based Li-S batteries maintained their large initial specific capacity gain compared with the Baseline-S based Li-S batteries (control) over extended cycles. A follow-on study indicated that the NPC-S approach is a necessary and critical step to boost the near-theoretical specific capacity while being stabilized over long cycles with a synergistic strategy. Our experimental and computational results suggest that NPC coated on sulfur electrodes provides not only an effective and strong PS-trapping power but also an increased redox reaction kinetics for sulfur ↔ PS’s conversions during battery charge and discharge, rendering the realization of near-theoretical discharge specific capacity in the NPC-S based Li-S batteries. The findings presented in this study may inspire a new, simple, low-cost, and commercially scalable approach, without adding any appreciable dead weight or volume to the batteries, in the effort to tackle the technical challenges facing SOA Li-S batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Development of a TSR-based method for understanding structural relationships of cofactors and local environments in photosystem I

All chemical forms of energy and oxygen on Earth are generated via photosynthesis where light energy is converted into redox energy by two photosystems (PS I and PS II). There is an increasing number of PS I 3D structures deposited in the Protein Data Bank (PDB). The Triangular Spatial Relationship (TSR)-based algorithm converts 3D structures into integers (TSR keys). A comprehensive study was conducted, by taking advantage of the PS I 3D structures and the TSR-based algorithm, to answer three questions: (i) Are electron cofactors including P700, A -1 and A 0 , which are chemically identical chlorophylls, structurally different? (ii) There are two electron transfer chains (A and B branches) in PS I. Are the cofactors on both branches structurally different? (iii) Are the amino acids in cofactor binding sites structurally different from those not in cofactor binding sites? The key contributions and important findings include: (i) a novel TSR-based method for representing 3D structures of pigments as well as for quantifying pigment structures was developed; (ii) the results revealed that the redox cofactor, P700, are structurally conserved and different from other redox factors. Similar situations were also observed for both A -1 and A 0 ; (iii) the results demonstrated structural differences between A and B branches for the redox cofactors P700, A -1 , A 0 and A 1 as well as their cofactor binding sites; (iv) the tryptophan residues close to A 0 and A 1 are structurally conserved; (v) The TSR-based method outperforms the Root Mean Square Deviation (RMSD) and the Ultrafast Shape Recognition (USR) methods. The structural analyses of redox cofactors and their binding sites provide a foundation for understanding the unique chemical and physical properties of each redox cofactor in PS I, which are essential for modulating the rate and direction of energy and electron transfers.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Exposed Phosphatidylserine as a Biomarker for Clear Identification of Breast Cancer Brain Metastases in Mouse Models

Brain metastasis is the most common intracranial malignancy in adults. The prognosis is extremely poor, partly because most patients have more than one brain lesion, and the currently available therapies are nonspecific or inaccessible to those occult metastases due to an impermeable blood–tumor barrier (BTB). Phosphatidylserine (PS) is externalized on the surface of viable endothelial cells (ECs) in tumor blood vessels. In this study, we have applied a PS-targeting antibody to assess brain metastases in mouse models. Fluorescence microscopic imaging revealed that extensive PS exposure was found exclusively on vascular ECs of brain metastases. The highly sensitive and specific binding of the PS antibody enables individual metastases, even micrometastases containing an intact BTB, to be clearly delineated. Furthermore, the conjugation of the PS antibody with a fluorescence dye, IRDye 800CW, or a radioisotope, 125I, allowed the clear visualization of individual brain metastases by optical imaging and autoradiography, respectively. In conclusion, we demonstrated a novel strategy for targeting brain metastases based on our finding that abundant PS exposure occurs on blood vessels of brain metastases but not on normal brain, which may be useful for the development of imaging and targeted therapeutics for brain metastases.

Oncology↗
NASA NTRS2019

Photon Sieve Design and Fabrication for Imaging Characteristics Using UAV Flight

The Photon Sieve (PS) team at NASA Langley Research Center (LaRC) began receiving support for the development and characterization of PS devices through the NASA Internal Research & Development Program (IRAD) in 2015. The project involves ascertaining the imaging characteristics of various PS devices. These devices hold the potential to significantly reduce mission costs and improve imaging quality by replacing traditional reflector telescopes. The photon sieve essentially acts as a lens to diffract light to a concentrated point on the focal plane like a Fresnel Zone Plate (FZP). PS’s have the potential to focus light to a very small spot which is not limited by the width of the outermost zone as for the FZP and offers a promising solution for high resolution imaging. In the fields of astronomy, remote sensing, and other applications that require imaging of distant objects both on the ground and in the sky, it is often necessary to perform post-process filtering in order to separate noise signals that arise from multiple scattering events near the collection optic. The PS exhibits a novel filtering technique that rejects the unwanted noise without the need for time consuming post processing of the images. This project leverages key Langley resources to design, manufacture, and characterize a series of photon sieve specimens. After a prototype was developed and characterized in the Langley ISO5 optical cleanroom and laboratory, outside testing was conducted via the capture of images of the moon by using a telescopic setup. This next goal of the project is to design and develop a telescope and image capture system as a drone-based instrument payload. The vehicle utilized for the initial demonstration was a NASA hive model 1200 XE-8 research Unmanned Aerial Vehicle (UAV), capable of handling a 20-pound maximum payload with a 25-minute flight time. This NASA Technical Memorandum (NASA-TM) introduces preliminary results obtained using a PS-based imaging system on the UAV. The next version of the telescope structure will be designed around diffractive optical components and commercially available camera electronics to create a lightweight payload.

Kim, Hyun Jung↗
NASA NTRS2018

Technology and Opportunities of Photon Sieve CubeSat with Deployable Optical Membrane

A photon sieve (PS) is a revolutionary optical instrument that provides high resolution imaging at a fraction of the weight of typical telescopes, with an areal density of 0.3 kg/m2 compared to 25 kg/m2 for the James Webb Space Telescope. The photon sieve is a variation of a Fresnel Zone Plate consisting of many small holes arranged in a series of concentric rings. The sieve works by diffracting light of a certain wavelength to a specified focal point for imaging, so that only a specific wavelength can be imaged. Moreover, the better image contrast and higher signal-to-noise ratios come from suppressing higher diffracted orders by apodizing the number of pinholes in the outer rings. Finally, a photon sieve requires less supports and can withstand more deformation without a reduction in the imaging qualities. Due to these properties, various groups have created PS CubeSats for Earth and Sun imaging at a low cost and weight specifically using deployable technology. A team at the Air Force Research Laboratory created a design and prototype of a mechanism that deploys a 20 cm diameter photon sieve. The United States Air Force Laboratory used a similar design to create a CubeSat-based deployable photon sieve. The team at NASA Langley Research Center has researched photon sieves for conducting an Earth-observing experiment using LIDAR (Light Detection and Ranging) with a higher signal-to-noise ratio benefit from the PS. This paper provides a state of the art overview on existing PS CubeSat technology with deployable structures and applications. Especially, the paper introduces PS for LIDAR applications and discusses the CubeSat-based PS challenge being worked at the NASA Langley Research Center.

Hyun Jung Kim↗
NASA NTRS2022

Polarization performance simulation for the GeoXO atmospheric composition instrument: NO2 retrieval impacts

NOAA’s Geostationary Extended Observations (GeoXO) constellation will continue and expand on the capabilities of the current generation of geostationary satellite systems to support US weather, ocean, atmosphere, and climate operations. It is planned to consist of a dedicated atmospheric composition instrument (ACX) to support air quality forecasting and monitoring by providing similar capabilities to missions such as TEMPO (Tropospheric Emission: Monitoring Pollution), currently planned to launch in 2023, and Ozone Monitoring Instrument (OMI), TROPOMI (TROPOspheric Monitoring Instrument), and GEMS (Geostationary Environment Monitoring Spectrometer) currently in operation. As the early phases of ACX development are progressing, design trade-offs are being considered to understand the relationship between instrument design choices and trace gas retrieval impacts. Some of these choices will affect the instrument polarization sensitivity (PS), which can have radiometric impacts on environmental satellite observations. We conducted a study to investigate how such radiometric impacts can affect NO2 retrievals by exploring their sensitivities to time of day, location, and scene type with an ACX instrument model that incorporates PS. The study addresses the basic steps of operational NO2 retrievals: the spectral fitting step and the conversion of slant column to vertical column via the air mass factor (AMF). The spectral fitting step was performed by generating at-sensor radiance from a clear sky scene with a known NO2 amount, the application of an instrument model including both instrument PS and noise, and a physical retrieval. The spectral fitting step was found to mitigate the impacts of instrument PS. The AMF-related step was considered for clear sky and partially cloudy scenes, where instrument PS can lead to errors in interpreting the cloud content, propagating to AMF errors and finally to NO2 retrieval errors. For this step, the NO2 retrieval impacts were small but non-negligible for high NO2 amounts; we estimated that a typical high NO2 amount can cause maximum of 0.25 x 10^15 molecules/cm^2 for a PS of 5%. These simulation capabilities were designed to aid in the development of a GeoXO atmospheric composition instrument that will improve our ability to monitor and understand the Earth’s atmosphere.

trace gases↗
NASA NTRS2022

Polarization Performance Simulation for the GeoXO Atmospheric Composition Instrument: NO2 Retrieval Impacts

NOAA's Geostationary Extended Observations (GeoXO) constellation will continue and expand on the capabilities of the current generation of geostationary satellite systems to support US weather, ocean, atmosphere, and climate operations. It is planned to consist of a dedicated atmospheric composition instrument (ACX) to support air quality forecasting and monitoring by providing capabilities similar to missions such as TEMPO (Tropospheric Emission: Monitoring Pollution), currently planned to launch in 2023, as well as OMI (Ozone Monitoring Instrument), TROPOMI (TROPOspheric Monitoring Instrument), and GEMS (Geostationary Environment Monitoring Spectrometer) currently in operation. As the early phases of ACX development are progressing, design trade-offs are being considered to understand the relationship between instrument design choices and trace gas retrieval impacts. Some of these choices will affect the instrument polarization sensitivity (PS), which can have radiometric impacts on environmental satellite observations. We conducted a study to investigate how such radiometric impacts can affect NO2 retrievals by exploring their sensitivities to time of day, location, and scene type with an ACX instrument model that incorporates PS. The study addresses the basic steps of operational NO2 retrievals: the spectral fitting step and the conversion of slant column to vertical column via the air mass factor (AMF). The spectral fitting step was performed by generating at-sensor radiance from a clear-sky scene with a known NO2 amount, the application of an instrument model including both instrument PS and noise, and a physical retrieval. The spectral fitting step was found to mitigate the impacts of instrument PS. The AMF-related step was considered for clear-sky and partially cloudy scenes, for which instrument PS can lead to errors in interpreting the cloud content, propagating to AMF errors and finally to NO2 retrieval errors. For this step, the NO2 retrieval impacts were small but non-negligible for high NO2 amounts; we estimated that a typical high NO2 amount can cause a maximum retrieval error of 0.25×1015 molec. cm−2 for a PS of 5 %. These simulation capabilities were designed to aid in the development of a GeoXO atmospheric composition instrument that will improve our ability to monitor and understand the Earth's atmosphere.

Aaron Pearlman↗
DOE OSTI2023

Establishing the accuracy of position–specific carbon isotope analysis of propane by GC–pyrolysis–GC–IRMS

Rationale: Position-specific (PS) δ 13 C values of propane have proven their ability to provide valuable information on the evolution history of natural gases. Two major approaches to measure PS δ 13 C values of propane are isotopic 13 C nuclear magnetic resonance (NMR) and gas chromatography-pyrolysis-gas chromatography-isotope ratio mass spectrometry (GC-Py-GC-IRMS). Measurement accuracy of the isotopic 13 C NMR has been verified, but the requirements of large sample size and long experimental time limit its applications. GC-Py-GC-IRMS is a more versatile method with a small sample size, but its accuracy has not been demonstrated. Methods: We measured the PS δ 13 C values of propane from nine natural gases using both 13 C NMR and GC-Py-GC-IRMS, then evaluated the accuracy of the GC-Py-GC-IRMS method. Results: The results show that large carbon isotope fractionations occurred for both terminal and central carbons within propane during pyrolysis. The isotope fractionations during the pyrolysis are reproducible at optimum conditions, but vary between the two GC-Py-GC-IRMS systems tested, affected by experimental conditions (e.g., pyrolysis temperature, flow rate, and reactor conditions). Conclusions: It is necessary to evaluate and calibrate each GC-Py-GC-IRMS system using propane gases with accurately determined PS δ 13 C values. Finally, this study also highlights a need for PS isotope standards for propane and other molecules (e.g., butane and acetic acid).

03 NATURAL GAS↗
DOE OSTI2025

Persistent Sampling: Enhancing the Efficiency of Sequential Monte Carlo

Sequential Monte Carlo (SMC) samplers are powerful tools for Bayesian inference but suffer from high computational costs due to their reliance on large particle ensembles for accurate estimates. We introduce persistent sampling (PS), an extension of SMC that systematically retains and reuses particles from all prior iterations to construct a growing, weighted ensemble. By leveraging multiple importance sampling and resampling from a mixture of historical distributions, PS mitigates the need for excessively large particle counts, directly addressing key limitations of SMC such as particle impoverishment and mode collapse. Crucially, PS achieves this without additional likelihood evaluations-weights for persistent particles are computed using cached likelihood values. This framework not only yields more accurate posterior approximations but also produces marginal likelihood estimates with significantly lower variance, enhancing reliability in model comparison. Furthermore, the persistent ensemble enables efficient adaptation of transition kernels by leveraging a larger, decorrelated particle pool. Experiments on high-dimensional Gaussian mixtures, hierarchical models, and non-convex targets demonstrate that PS consistently outperforms standard SMC and related variants, including recycled and waste-free SMC, achieving substantial reductions in mean squared error for posterior expectations and evidence estimates, all at reduced computational cost. PS thus establishes itself as a robust, scalable, and efficient alternative for complex Bayesian inference tasks.

Karamanis, Minas↗
DOE OSTI2022

Kinetic and equilibrium reactions on natural and laboratory generation of thermogenic gases from Type II marine shale

The phenomenon that laboratory pyrolysis experiments produce much wetter gases than those in natural reservoirs is a long-recognized and debated problem in the investigation of natural gases in sedimentary basins. In this study, we explore the discrepancy by pyrolyzing a type II kerogen from the Woodford Shale in Oklahoma, compared with the previous results on the produced natural gases from the Arkoma Basin generated from the same source rock (Liu et al., 2019) with the discussion of gas and isotopic compositions at bulk and position-specific (PS) levels. An improved GC-pyrolysis-GC IRMS method is applied for the determination of PS δ 13 C of propane produced in the pyrolysis of the Woodford Shale at Easy %R o from 0.76 to 3.27. Kinetic and thermodynamic considerations of the chemical and isotopic compositions of the natural and laboratory pyrolysis gases suggest that the generation of light hydrocarbons involves uni-directional cracking reactions, exchange reactions with water, and likely reversible reactions among light hydrocarbons and other H-containing volatiles. After the gas generation in the unconventional Woodford Shale reservoirs, the C 1 -C 4 gases might have approached close to chemical equilibrium of C 1 -C 3 and isotope equilibrium of C 2 -C 1 and C 3 -C 1 pairs at their peak temperatures. The capping H for the generation of C 1 -C 4 in the Woodford Shale gases appears to have experienced at least partial exchange with the water, while that in the pyrolysis gases is only originated from organic-bound compounds with large kinetic isotope effects (KIE). Our findings indicate that elevated compound-specific and PS δ 13 C values of propane in the wet-gas cracking stage are significantly influenced by the breakdown of the thermally stable compounds (e.g., remaining kerogen, residues). A first synthesis of PS δ 13 C and δ 2 H isotopic compositions of propane from this study and the literature data suggests relatively similar isotopic structures of propane precursors in kerogens. Finally, this study demonstrates that PS isotope analysis of propane can contribute to identifying various geological (e.g., maturation, wet-gas cracking, H exchange, diffusion) and biodegradation processes.

58 GEOSCIENCES↗
DOE OSTI2024

Nanoconfinement-induced shift in photooxidative degradation pathway of polystyrene

Polymer nanocomposites with high concentrations of nanoparticles (NPs) possess exceptional mechanical, transport, and thermal properties. To enable their widespread use in structural applications and functional coatings, it is crucial to understand how nanoconfinement and the polymer-NP interface influence polymer degradation under various environmental conditions, including prolonged UV exposure. In this study, we investigate the photooxidative degradation of polystyrene (PS)-confined in the interstices of SiO 2 NP films. These nanocomposite films are prepared by the capillary rise infiltration (CaRI) of PS into interstices of SiO 2 NP packings, and subsequently subjected to UV irradiation. Our investigation reveals that PS degradation progresses uniformly across the thickness, with degradation initiating from the center of the NP interstitial pores and extending towards the NP surface. We rationalize this degradation mechanism based on the disparity in the surface energies of PS and the NP surface, as well as slow oxygen diffusion through confined PS. Here, we also demonstrate that packing smaller NPs at a given thickness or thicker packing of a specific NP size facilitates photooxidative degradation, highlighting the critical role of the number of interstitial pores in influencing degradation processes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Gas generation and intramolecular isotope study in laboratory pyrolysis of the Springfield coal from the Illinois Basin

Position-specific (PS) isotopes of propane have been proposed as a potential geochemical tool to decipher various geological processes (e.g., thermal cracking, biodegradation, H exchange) in natural reservoirs. The limited studies have been conducted on the PS isotopes of propane from the pyrolysis gases from marine shales, and natural gases sourced from lacustrine and marine kerogens, but little is known on gases produced from the humic kerogen. Here, this study investigated the PS δ 13 C of propane in the closed-system pyrolysis of the Springfield coal, Illinois Basin, Indiana, at 310 to 470 °C (Easy %Ro: 0.76 to 3.07). The C kinetic isotope effect (KIE) of CH 4 produced in both this study and previous low-temperature pyrolysis of the same coal indicates the cleavage of C—O bonds is the main generation pathway at the early kerogen cracking stage, followed by the breakdown of alkyl groups. At the wet-gas cracking stage, C 3 H 8 production from thermally stable compounds has a significant influence on the bulk and position-specific C KIE in the pyrolysis of marine Woodford kerogen and Springfield coal. According to the PS δ 13 C of propane, the central site is likely more enriched in 13 C and the δ 13 C of the terminal site is relatively heterogeneous within the propyl group attached to different functional groups of the gas-prone kerogen. Our findings based on the pyrolysis experiments and natural gas samples indicate thermal cracking and biodegradation appear to alter the δ 13 C cen values more significantly than the δ 13 C ter values of propane. The larger magnitude of ΔC c-t in the kMC simulations (Peterson et al., 2018) compared with those from the marine shale and coal possibly implies the non-random distributions of 13 C of propane precursors in the kerogens. As a new dimension of intramolecular isotopic information of propane, the PS δ 13 C values can contribute to fingerprinting the gas origins and identifying the various geological processes (e.g., kerogen cracking, wet-gas cracking, microbial activities) in sedimentary basins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗