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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Additive‐Free Aqueous MXene Inks for Thermal Inkjet Printing on Textiles

Abstract Direct printing of functional inks onto flexible substrates allows for scalable fabrication of wearable electronics. However, existing ink formulations for inkjet printing require toxic solvents and additives, which make device fabrication more complex, limit substrate compatibility, and hinder device performance. Even water‐based carbon or metal nanoparticle inks require supplemental surfactants, binders, and cosolvents to produce jettable colloidal suspensions. Here, a general approach is demonstrated for formulating conductive inkjet printable, additive‐free aqueous Ti 3 C 2 T x MXene inks for direct printing on various substrates. The rheological properties of the MXene inks are tuned by controlling the Ti 3 C 2 T x flake size and concentration. Ti 3 C 2 T x ‐based electrical conduits and microsupercapacitors (MSCs) are printed on textile and paper substrates by optimizing the nozzle geometry for high‐resolution inkjet printing. The chemical stability and electrical properties of the printed devices are also studied after storing the devices for six months under ambient conditions. Current collector‐free, textile‐based MSCs show areal capacitance values up to 294 mF cm −2 (2 mV s −1 ) in poly(vinyl alcohol)/sulfuric acid gel electrolyte, surpassing reported printed MXene‐based MSCs and inkjet‐printed MSCs using other 2D nanomaterials. This work is an important step toward increasing the functional capacity of conductive inks and simplifying the fabrication of wearable textile‐based electronics.

Uzun, Simge↗
DOE OSTI2021

Electrolysis on a Chip with Tunable Thin Film Nanostructured PGM Electrocatalysts Generated from Self-Assembled Block Copolymer Templates

Self-assembled block copolymers are promising templates for fabricating thin film materials with tuned periodic feature sizes and geometry at the nanoscale. Here, a series of nanostructured platinum and iridium oxide electrocatalysts templated from poly(styrene)-block-poly(vinyl pyridine) (PSbPVP) block copolymers via an incipient wetness impregnation (IWI) pathway is reported. Both nanowire and nanocylinder electrocatalysts of varying feature sizes are assessed and higher catalyst loadings are achieved by the alkylation of the pyridine moieties in the PVP block prior to IWI. Electrocatalyst evaluations featuring hydrogen pump and water electrolysis demonstrations are carried out on interdigitated electrode (IDE) chips flexible with liquid supporting electrolytes and thin film polymer electrolytes. Notably, the mass activities of the nanostructured electrocatalysts from alkylated block copolymer templates are 35%–94% higher than electrocatalysts from non-alkylated block copolymer templates. Standing cylinder nanostructures lead to higher mass activities than lamellar variants despite their not having the largest surface area per unit catalyst loading demonstrating that mesostructure architectures have a profound impact on reactivity. Overall, IDE chips with model thin film electrocatalysts prepared from self-assembled block copolymers offer a high-throughput experimental method for correlating electrocatalyst nanostructure and composition to electrochemical reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Large-scale reactive thermoset printing: Complex interactions between temperature evolution, viscosity, and cure shrinkage

Thermoset composites are strong candidates for large-scale material extrusion additive manufacturing (AM). However, uncured thermoset composites become unstable as print height increases. Here, chemical initiation of vinyl ester immediately before deposition was used to suppress collapse and enable large-scale thermoset printing. Structural stability was assessed by printing thin walls at various layer times and monitoring thermal gradients with an infrared camera. Stable printing was observed at a layer time of 4.50 min, approximately half the gel time of the material (8 min). Self-weight collapse occurred at short layer time (0.68 min), whereas warpage occurred at long layer time (6.50 min). Here, a new behavior was discovered at intermediate layer time (2.25 min) where the heat generated by the reaction causes new, un-gelled layers to flow. Forced convection eliminates this behavior, stabilizing the 2.25-min layer time print. These findings motivated development of a less exothermic material system, which was used to print a large-scale mold and demonstrate the value of this understanding. By presenting these challenges of large-scale reactive thermoset AM for the first time, this work motivates focused studies of the complex interplay between rheological, thermal, and chemical behaviors to improve the feasibility of large-scale thermoset AM. Tensile properties of the printed material were also measured. Longitudinal and transverse elastic moduli are 3.79 and 2.95 GPa, respectively, and corresponding tensile strengths are 36.11 and 18.83 MPa. The glass transition temperature is 93.13 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Predictive binder jet additive manufacturing enabled by clean burn-off binder design

Binder jet additive manufacturing (BJAM) presents an avenue for advanced manufacturing of various high-value materials due to high deposition rates, scalability, and geometric flexibility. However, conventional organic binders in BJAM introduce residual carbon upon pyrolysis, often leading to imprecise alloy composition in the final sintered part. The undesirable residual carbon from binder burn-off limits the application of BJAM for high-performance alloys due to their high sensitivity to carbon addition. In this study, we have designed poly(vinylpyrrolidone-co-vinyl acetate) (PVP-VAc) as a clean burn-off binder for BJAM, where excess oxygen groups in VAc enable cleaner burn-off and reduce residual carbon retention. Compared to a widely used commercial binder, the optimized PVP-VAc binder reduced residual carbon retention by over 90% in H13 tool steel. The significant reduction in residual carbon enables predictable printing and subsequent sintering of complex H13 tool steel geometries, an alloy known to have substantial challenges around distortion due to the sintering window shifting from carbon addition. The design of a clean burnout binder provides a major path forward for BJAM by enabling new AM designs and applications for composition-sensitive high-performance alloys, such as nickel-based superalloys, titanium alloys, and high alloyed steels.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Multiscale modeling of hydrogenolysis of ethane and propane on Ru(0001): Implications for plastics recycling

Plastic waste presents an environmental threat. Chemical recycling via hydrogenolysis can convert plastic waste into waxes, lubricants, and fuels. Among catalysts, Ru stands out for its superior activity and selectivity. The chemistry of light alkane hydrogenolysis can help understanding plastics deconstruction. Here, we perform first-principles calculations, develop descriptor-based relations, and conduct microkinetic modeling and analysis on ethane and propane. Predictions are in excellent agreement with experimental data. We identify a similar cracking pattern for both hydrocarbons entailing a deeply dehydrogenated species with the removal of four hydrogen atoms: CHCH*+* → 2CH* for ethane and CH 3 CCH*+2* → CH 3 C* + CH* for propane. We find that the rate-determining step is the C-C cracking for ethane and the first dehydrogenation from the terminal carbon (CH 3 CH 2 CH 3 *+* → CH 3 CH 2 CH 2 *+H*) for propane. The vinyl species CH 2 CH* produced from propane cracking is responsible for whether a single or multiple cracking events occur and effectively controls the selectivity. Specifically, ethane formation in propane hydrogenolysis is suppressed at elevated temperatures due to over-cracking via multiple (two here) cracking events being preferred over hydrogenation and desorption of ethane from the catalyst. Our workflow and models provide a baseline for future studies on heavier hydrocarbons. Insights into recent experimental studies of polyethylene over Ru-based catalysts are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Pragmatic protocols for working cleanly when measuring ice nucleating particles

We report that measuring ice nucleating particles (INPs) is critical for understanding, and modeling, cloud formation, reflectivity, and precipitation patterns. However, because INPs are very rare in the atmosphere, but abundant—sometimes alarmingly so—in the dust that covers all work surfaces, contamination during processing of collected aerosol samples can be a significant hindrance to obtaining accurate measures of INPs. In preparing this technical note, we questioned the cleanliness of every collection and processing step involved in making immersion freezing measurements of INPs re-suspended from filter samples. The aim was to identify, and then minimize, all potential sources of significant contamination, including containers and tools used to store filters and prepare liquid suspensions, gloves, work surfaces, and the polymerase chain reaction (PCR) trays commonly used for sample analysis. While plasticware released few INPs, most gloves readily shed them, but this can be mitigated by using washed cleanroom vinyl or polyethylene gloves. Work surfaces, even those that had been cleaned, were prodigious reservoirs of contaminating INPs, but simply covering them with aluminum foil will provide an INP-free surface. By applying these practices, we developed a method to reduce the background level of INPs on Nuclepore™ polycarbonate filters in our tests to 0 at -25 °C and < 20 at -27 °C, making them suitable for use in all sampling environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Surface-modified and oven-dried microfibrillated cellulose reinforced biocomposites: Cellulose network enabled high performance

Microfibrillated cellulose (MFC) is widely used as a reinforcement filler for biocomposites due to its unique properties. However, the challenge of drying MFC and the incompatibility between nanocellulose and polymer matrix still limits the mechanical performance of MFC-reinforced biocomposites. In this study, we used a water-based transesterification reaction to functionalize MFC and explored the capability of oven-dried MFC as a reinforcement filler for polylactic acid (PLA). Remarkably, this oven-dried, vinyl laurate–modified MFC improved the tensile strength by 38 % and Young’s modulus by 71 % compared with neat PLA. Our results suggested improved compatibility and dispersion of the fibrils in PLA after modification. This study demonstrated that scalable water-based surface modification and subsequent straightforward oven drying could be a facile method for effectively drying cellulose nanomaterials. We find that the method helps significantly disperse fibrils in polymers and enhances the mechanical properties of microfibrillar cellulose-reinforced biocomposites.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Chemically and mechanically recyclable polyester-based multilayer plastics

Approximately 100 million tons of multilayered plastics (MLPs) are produced each year worldwide but are not recycled due to their complex structure. Here, this work aims to design polyester-based multilayer plastics (80–100 % polyester) that provide barrier performance comparable to typical 9–12-layer commercial MLPs, while also enabling both chemical recycling (back to parent monomer) and mechanical recycling (grind-and-melt reprocessing). Such dual recyclability is not achievable with non-polyester multilayers, such as all-polyolefin systems. Furthermore, we emphasize how the multilayer architecture was tailored to balance barrier properties, mechanical integrity, and end-of-life recyclability for both flexible and rigid packaging applications. Two main categories of polyester-based MLPs are reported; in the first type, poly(butylene adipate-co-terephthalate) (PBAT)-70 % polyglycolic acid (PGA) is used as middle barrier layer, while in second type, middle barrier layer is Ethylene-vinyl alcohol (EVOH) copolymers. Polyethylene terephthalate (PET) was used as a structural layer, while either PBAT or poly(butylene succinate) (PBS) was used to enable thermal sealing and serve as the product contact layer. These MLPs are recycled by both chemical and mechanical recycling processes. Techno-economic analysis (TEA) shows that MLPs incorporating EVOH as barrier layer have similar or lower selling costs (0.32 $\$$/m 2 ) than commercial MLPs. Life cycle assessment (LCA) indicates EVOH-based MLPs have a lower carbon footprint and lower energy consumption relative to commercial MLP benchmarks. This work offers simplified MLPs that are easy to manufacture and ready to recycle, which will significantly reduce environmental impact of MLP packaging while also providing a cost-effective and practical solution for industry.

Barrier properties↗
DOE OSTI2022

Evaluation of different getter substrates using two-dimensional gas chromatography with time of flight mass spectrometry

We report while understanding hydrogen uptake by organic based getters such as 1,4-bis(phenylethynyl)benzene (DEB) combined with a palladium(0)bis(dibenzylideneacetone) (Pd(dba) 2 ) catalyst is essential, another crucial element to understand is the decomposition of the DEB, Pd(dba) 2 , and/or substrate material. The breakdown of these materials may create unwanted volatiles, which may interact with and lead to deterioration of sensitive materials. Moreover, it is critical to understand if different substrates cause the getter and/or catalyst to degrade in different manners. Utilizing comprehensive two-dimensional gas chromatography (GC×GC) with time-of-flight mass spectrometry (TOFMS), the presence of volatiles located in the headspace of various DEB/Pd(dba) 2 getter substrates is examined. These samples include a getter infused silicone foam, a hydrogenated getter infused silicone foam, an activated carbon getter pellet, and a hydrogenated activated carbon getter pellet. Application of Fisher ratio (F-ratio) analyses lead to the identification of several compounds that are generated or consumed through the hydrogenation process. These include benzene derivatives such as bibenzyl, benzaldehyde, and vinyl benzoate in the activated carbon pellets and 1,5-diphenyl-3-pentanone, toluene, styrene, and 1–1'(2-pentene 1,5-diyl)bis benzene in the silicone foams, and alkane/alkene derivatives such undecane, 4-tridecene, and decane in the activated carbon pellets and 2,6-dimethyl undecane in the silicone foams. Further comparison of the different hydrogenated getter substrates (e.g. activated carbon pellet and silicone foam) indicates that the different substrates alter the decomposition products created from the degradation of the DEB and Pd(dba) 2 .

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

O 2 -Dependence of reactions of 1,2-dimethoxyethanyl and 1,2-dimethoxyethanylperoxy isomers

Reaction mechanisms of Ṙ and ROȮ radicals derived from low-temperature oxidation of 1,2-dimethoxyethane (CH 3 O(CH 2 ) 2 OCH 3 ) were investigated using speciation from multiplexed photoionization mass spectrometry (MPIMS) measurements via Cl-initiated oxidation, in conjunction with electronic structure calculations. The experiments were conducted at 5 bar, from 450 K – 650 K, and O 2 concentrations from 1 · 10 14 cm –3 – 6 · 10 18 cm –3 to probe the effects on competing reaction channels of 1,2-dimethoxyethanyl (Ṙ) and 1,2-dimethoxyethanylperoxy (ROȮ) isomers. Several species were detected with photoionization spectral fitting – ethene, formaldehyde, methyl vinyl ether, and 2-methoxyacetaldehyde – and, as determined by electronic structure calculations, may form via unimolecular decomposition of 1,2-dimethoxyethanyl or 1,2-dimethoxyethanylperoxy. O 2 -dependent yield ratios show that the formation pathways for all species undergo a competition between O 2 -addition and unimolecular decomposition. Here, adiabatic ionization energies were also calculated and utilized along with exact mass determinations to infer contributions for other species derived exclusively from first- and second-O 2 -addition, including 1,2-dimethoxyethene, cyclic ethers, and dicarbonyls.

1,2-dimethoxyethane↗
DOE OSTI2025

Screening green solvents for multilayer plastic film recycling processes

Multilayer (ML) plastic films are essential packaging materials that help protect products from diverse external factors; however, only 5% of all ML films are recycled in the United States. Solvent-based technologies are a promising alternative for recycling ML films because they enable recovery of constituent polymer resins. For example, the Solvent Targeted Recovery and Precipitation (STRAPTM) process sequentially dissolves and separates polymer components using a series of targeted solvent washes. A crucial design aspect of this process is the impact of selected solvents on human health and on the environment. Here, this work introduces a computational framework that integrates molecular modeling, process modeling, techno-economic analysis (TEA), and life-cycle analysis (LCA) to quickly screen green solvents for solvent-based ML recycling processes. Initial screening for solvents based on selectivity is performed by estimating temperature-dependent solubilities using molecular-scale models. Subsequent screening uses basic estimates of energy use and octanol-water partition coefficients (logP) as key measures of health, safety, and environmental hazards. Detailed process modeling, TEA, and LCA are used on a reduced set of promising solvents identified in early screening steps to more accurately determine how solvent selection and associated operating conditions impact overall economics and environmental impacts. The framework is used for the identification of green solvents (from a database of 1,000 solvents) that separate an industrial ML film composed of polyethylene (PE), ethylene vinyl alcohol (EVOH), and polyethylene terephthalate (PET). Our analysis shows the effectiveness of the framework and reveals fundamental trade-offs between solvent greenness, solubility, and economics. Our work emphasizes the importance of taking a holistic systems view during solvent design and aims to inform the development of new processes for ML film recycling and the identification of new ML films that are easier to recycle.

economics↗
DOE OSTI2025

Experimental characterization and potential energy savings of insulated cladding for U.S. residential buildings

This study evaluates a novel insulated cladding composed of foamed cement and vinyl siding that is designed as a retrofit product to enhance thermal performance in U.S. residential buildings. Experimental measurements showed that foamed cement exhibits a thermal conductivity of 0.0334–0.0365 W/m-K (R-value of 4.0–4.3 °F⋅ft 2 ⋅h/BTU), which is significantly higher than that of conventional fiber cement boards. Although mechanical testing confirmed the material’s brittleness and low strength, it also indicated its suitability for nonstructural insulation applications. Water vapor permeability testing demonstrated effective moisture resistance with the polymer coating. To evaluate the insulated cladding’s energy performance, we used the U.S. Department of Energy’s prototype single-family building model and simulated across 50 locations spanning 16 International Energy Conservation Code climate zones. The R-7 (R-value of 7 °F⋅ft 2 ⋅h/BTU per inch) retrofit cladding resulted in heating energy savings up to 275 therms (Fairbanks, AK) and cooling energy savings up to 1,547 kWh (Phoenix, AZ). The energy cost savings varied by region, but the highest annual cost savings ($\$$434/year) were observed in Santa Maria, CA, and the highest annual cost savings percentage (37 %) were noted in Monterey, CA. On a national scale, the insulated retrofit provided an average annual energy cost reduction of 16 %, highlighting the cladding system’s broad applicability and financial viability.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Tunable structure and reinforcement of polyvinyl alcohol (PVA) hydrogels using fungal chitin particles

Polysaccharides, including chitin, are one of the most abundant biopolymers in nature and are increasingly recognized as a sustainable alternative to petroleum-derived plastics and synthetic fillers in polymer composites. Traditionally sourced from crustacean shells, chitin offers mechanical strength and biocompatibility with limitations also in processability and functionality. Fungal-derived chitin material represents a promising alternative, with advantages including scalable fermentation on low-cost substrates, absence of shellfish allergens, and tunable molecular architectures that vary by species, developmental stage, and growth environment. Here, in this study, we systematically examined chitinous materials obtained from taxonomically and functionally distinct fungi, Laccaria bicolor, Trichoderma reesei and Rhizopus oryzae, to assess their structural, chemical, and morphological properties as reinforcement agents in polymer composites. Mild alkaline pretreatment was employed to obtain mycelium chitin particles, thereby improving accessibility to chitin and co-occurring β-D-glucans while maintaining microparticle integrity. Comprehensive FTIR and solid-state NMR analyses revealed species-specific differences in chemical composition and microstructure, with R. oryzae exhibiting a unique spectral signature. These fungal-derived chitin were then incorporated into poly(vinyl alcohol) (PVA) hydrogels, where they acted as reinforcing fillers without the need for additional chemical crosslinkers. Comparative evaluation of hydrogel properties demonstrated that fungal chitin significantly enhanced mechanical performance, with all mycelium fillers mitigating the water weakening in PVA hydrogels. R. oryzae-derived composites tripled the hydrogel tensile strength while the submicron fibrous morphology in L. bicolor contributes to over 45 % tensile improvement in dry PVA composites. Our findings highlight the potential of fungal biomass as a tunable, sustainable platform for producing chitin-based reinforcing agents.

Chitin↗
DOE OSTI2023

Mechanistic study of heterogeneous propene metathesis on WO x /SiO 2 catalysts

Silica-supported tungsten oxides are widely used industrial catalysts for olefin metathesis due to their low cost and robustness, yet the mechanisms for heterogeneously catalyzed metathesis reactions remain comparatively less understood. In this work, density-functional theory (DFT) calculations were used to study the model reactions of propene metathesis. Our calculations confirm that the metathesis reactions catalyzed by WO x /SiO 2 largely follow the Chauvin cycle, with an overall energetic barrier of 142 kJ/mol. To understand how the initial alkylidene active sites are generated, three mechanisms were examined: The pseudo-Wittig mechanism was found to be most favorable and proceeds with a metallacycle intermediate, while the allylic and vinylic C-H activations are much more difficult and require the reduction of surface sites to W(+4). Relative to the adsorbed reactant state, the overall intrinsic barriers for three mechanisms were computed to be 193, 261, and 355 kJ/mol, respectively. In conclusion, the higher barriers for active-site formation than for the metathesis cycle are consistent with the difficult, high-temperature pretreatment required in experiments to activate WO x /SiO 2 catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Understanding the effect of organic coatings on 4-nitrostyrene hydrogenation selectivity over Pt/TiO 2 catalysts

The hydrogenation of 4-nitrostyrene was investigated over Pt/TiO 2 catalysts to understand the effects of different catalyst coatings on product selectivity and reaction rates. This reaction is a much-investigated selectivity probe due to difficulty in controlling reactivity between the nitro and vinyl groups of 4-nitrostyrene, with C=C reduction generally being more favorable. 4-Nitrostyrene hydrogenation reactions were carried out in a batch reactor using uncoated, organothiol coated, phosphonic acid (PA) coated, and ion-conducting polymer (ionomer) coated catalysts. Thiols form dense coatings on Pt surfaces, whereas PAs preferentially accumulate on TiO 2 ; ionomer binding preference is unknown for this type of catalyst. The coating densities of the thiols and PAs were varied to observe the effects of loading on catalytic activity and reaction selectivity relative to the uncoated catalyst. Changes in selectivity were observed for catalysts with all coatings, with thiol coatings shifting selectivity towards the nitro reduction product, 4-vinylaniline (4-VA), and both ionomer and PA coatings shifting towards 4-ethylnitrobenzene, the olefin hydrogenation product. It was observed that selectivity toward 4-VA increased with thiol coating density, where 1,2-benzenedithiol (BDT) coated catalysts exhibited a selectivity of >99%. These changes were attributed to the identity of the adsorption sites blocked by the different coatings: blocking of metal sites via thiols decreased the rate of C=C hydrogenation, whereas blocking of TiO 2 sites by PAs decreased the rate of nitro group hydrogenation. The changes observed for ionomer and PA coatings suggested that ionomers, like PAs, bind preferentially to the metal oxide support rather than the active metal. This work provides new support to the proposal that nitro group hydrogenation preferentially occurs on TiO 2 sites after hydrogen spillover and underscores how selection of ligand functionality can be used to tune catalyst selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Facile polymerization in a bicellar template to produce polymer nano-rings

We report a well-defined discoidal bicelle composed of three lipids, specifically zwitterionic long-chain 1,2-dipalmitoyl phosphocholine (DPPC) and short-chain 1,2-dihexanoyl phosphocholine (DHPC) doped with anionic 1,2-dipalmitoyl phosphoglycerol (DPPG) provides a generalized template for the synthesis of hydrophobic polymer nano-rings. The lipid molar ratio of DPPC/DHPC/DPPG is 0.71/0.25/0.04. The detailed investigation and discussion were based on styrene but tested on three other vinyl monomers. The structure of nano-rings is identified through the detailed analysis of small angle X-ray/neutron scattering (SAXS and SANS) data and transmission electron micrographs (TEM), supported by the differential scanning calorimetric (DSC) data before and after polymerization. The investigation covers samples with a styrene-to-lipid ratio ranged varied from 1:50 to 1:10.The styrene monomers are initially located at both the discoidal planar (long-chain lipid rich) and rim (short-chain lipid rich) regions. During polymerization, they migrate to the more fluid rim region-section. The formation mechanism involves the interplay of hydrophobic interaction, mismatched miscibility of polystyrene between the ordered and disordered phases, and crystallinity of the long lipid acyl chains. This facile synthesis is proven applicable for several hydrophobic monomers. The well-defined nano-rings greatly enhance the interfacial area and have the potential to be the building blocks for functional materials, if monomers are incorporated with desirable functions, for future applications. Crosslinked polymer nano-rings are produced in well-defined discoidal bicelles. The enhanced immiscibility in the planar region drives the hydrophobic polymers to the fluidic rim. The platform can be generalized for synthesis of other hydrophobic polymer nano-rings.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Machine Learning Models for Binary Molecular Classification using VUV Absorption Spectra

Machine learning methods were combined with differential absorption spectroscopy measurements in the vacuum-ultraviolet region (5.167 – 9.920 eV) in order to develop predictive capabilities for inferring molecular structure from the spectra. Several types of species were analyzed and, for modeling purposes, were defined using a single classification: (1) alkane, (2) conjugation with oxygen (e.g. diacetyl, ethyl vinyl ether), (3) non-conjugated alkene (e.g. 1-butene, 1,4-cyclohexadiene), (4) oxygen-containing (e.g. 1-butanol, tetrahydrofuran), or (5) cyclic (e.g. cyclopentane, cyclohexanone). The latter molecular classification excluded cyclic ethers. Several modeling methods were employed in the analysis of 102 absorption spectra, 24 of which were measured for the first time. The primary objective was to identify suitable methods that enable accurate predictions of molecular structure classifications with minimized statistical uncertainties. Rather than identifying a single, unifying method to reliably predict molecular structure contributions to VUV absorption spectra, coordination is required among a particular method, the type of molecular structure detail (e.g. conjugation), and absorption region of interest. The latter is accomplished using a binning approach, wherein absorption regions of ~0.5 eV were utilized rather than the entire ~4.8 eV range. Photon energy binning enabled analysis of region-specific predictions of accuracy, precision, and recall. The outcome from the binning approach is that, rather than utilizing the entire spectrum, optimal determination of molecular structure using machine learning methods depends on the absorption region. Furthermore, the present work provides separate machine learning models for each molecular classification, which enables the identification of multi-functional species relevant to atmospheric chemistry and combustion chemistry, where isomer-resolved speciation is critical to understanding complex reaction networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrostatic limits on charge selectivity in ultrahigh charge density polymer membranes

Ion-exchange membranes (IEMs) with ultrahigh charge densities offer the promise of enhanced ion transport for electrochemical technologies, yet the fundamental limits of this membrane design strategy are not yet understood. In this work, we present a systematic study of bis(1-vinyl-3-imidazolium) cross-linked polymer membranes with fixed charge contents ranging from 6 to 9 mol/L[dry polymer], synthesized to isolate the effects of charge density at constant membrane water content. While ionic conductivity increases monotonically with increasing charge density, a sharp decline in charge selectivity is observed for the most densely charged membranes, defying conventional expectations. Structural, thermal, and mechanical analyses reveal a critical onset of network disruption and anomalous ion partitioning behavior in these densely charged membranes. With proper consideration of cross-linker geometry, these results are interpreted using Manning's counter-ion condensation theory, which suggests that closely packed charged cross-linkers amplify inter-chain electrostatic interactions and trigger excess counter-ion condensation. Our findings suggest that, beyond a threshold spacing between fixed charges, increased functionalization may harm rather than help charge selectivity of IEMs.

36 MATERIALS SCIENCE↗