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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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576 records · Page 32

Examination of Solvent- Room Temperature Ionic Liquid Interactions using 2D NMR and Computational Chemistry

Rare earth metals (REMs) are the key functioning material found in microelectronics, advanced batteries, and high-efficiency electrical motors. Current methods for producing REMs require high temperatures (i.e. energy intensive) and produce an abundance of hazardous fluoride waste. Room temperature ionic liquids (RTILs) are an ideal alternative electrolyte because they allow for a low-temperature, energy-efficient electrochemical process. RTIL properties such as viscosity and conductivity determine how effective they can be in this process. Since viscosity is directly related to both intra and intermolecular forces, this study sets out to investigate two RTILs-Trihexyltetradecylphosphonium dicyanamide (Cyphos 105) and Trihexyltetradecylphosphonium bistrifimide (Cyphos 109) and their interactions. Results from 2-dimensional nuclear magnetic resonance (2D NMR) spectroscopy show that there is an interaction between the tetradecyl tail and the phosphorus atom of the Cyphos RTIL. In order to establish whether this is an intra or an inter-molecular interaction, DFT-based computational calculations were performed to determine the optimized geometry. Calculations were done both in the gas phase and with propylene carbonate as an augmenting solvent. Preliminary results show that there is minimal intramolecular interaction between the tetradecyl tail and the phosphorus atom of the RTILs, and that the interaction seen in the 2D NMR experiment is likely of an intermolecular nature instead.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Swell Behavior of Elastomers with a Hydrothermal Liquefaction Bio-Crude and a Fast Pyrolysis Bio-Oil

The compatibility of seventeen elastomer materials with two heavy biofuels (fast pyrolysis bio-oil and hydrothermal liquefaction (HTL) bio-crude) and diesel was assessed through volume change measurements. The elastomers included two fluorocarbons, six acrylonitrile rubbers (NBRs), and one each of fluorosilicone, neoprene, polyurethane, silicone, epichlorohydrin rubber (ECO), a blend of polyvinyl chloride and NBR (OZO), styrene butadiene rubber (SBR), hydrogenated NBR (HNBR) and ethylene propylene diene monomer (EPDM). The specimens were immersed in each test fuel for four weeks at 50°C and then measured for volume change. Afterwards, the specimens were dried, and the volume was remeasured. Ingeneral, the bio-oil produced unacceptable swelling in the fluoroelastomers, ECO, OZO, neoprene, polyurethane, SBR, HNBR, EPDM, silicone and five of the NBRs. In most cases, the HTL bio-crude produced lower (though still unacceptable) swelling than the bio-oil. Materials that showed good compatibility with the HTL biocrude were the fluoroelastomers, OZO, and silicone.

Kass, Michael↗

Monitoring Degradation of Nuclear Cable Insulation Subjected To Sequential and Simultaneous Thermal and Radiation Aging

Predicting useful remaining life of cables in nuclear power plants is a topic of growing interest as plant continue to age. A typical electrical cable consists of polymeric materials, such as the cable jacket and insulation, which are susceptible to degradation due to exposure to both elevated temperatures and gamma irradiation over decades of service. In this work two insulation materials, crosslinked polyethylene (XLPE) and ethylene propylene diene (EPDM) elastomer, were characterized to quantify aging using total color difference and indenter modulus. Since the effects of thermal and gamma radiation are not additive but coupled, the effects of different aging scenarios including sequential and simultaneous aging were also evaluated. In the case of sequential aging, two aging scenarios were explored where the order in which thermal and gamma radiation received were altered. Total color difference of XLPE showed that sequentially aged insulation specimens, which received radiation first, degraded slightly more at maximum exposure than specimens which received thermal first. Similarly, in the case of EPDM, the extent of degradation evaluated using total color difference was found to be most severe in the case of sequentially aged insulation specimens which received radiation first. Indenter modulus was found to be insensitive to aging for XLPE but trended for EPDM. The largest variations were observed for the sequentially aged insulation specimens which received radiation first, similar to what was observed for total color difference.

Pallaka, Madhusudhan Reddy↗

Nanocomposite membranes and methods of forming the same

A nanocomposite including a mesoporous, macroporous, or a combination thereof oxide and a zeolitic imidazolate framework (ZIF) that is filling the pores of the oxide to form a ZIF phase embedded and at least substantially confined mostly within the oxide. Methods of making nanocomposites including the steps of depositing an oxide in the pores of a mesoporous oxide; and further treating the resulting material with vapor, liquid, or supercritical CO2 comprising an azole-based compound, a carboxylate based compound, or a combination thereof. Use of disclosed articles to separate propylene and propane in a mixture thereof.

Tsapatsis, Michael↗

Direct catalytic conversion of alcohols to olefins of higher carbon number with reduced ethylene production

A catalyst composition for converting an alcohol to olefins, the catalyst composition comprising the following components: (a) a support (e.g., particles) comprising silicon and oxygen; (b) at least one of copper and silver residing on and/or incorporated into said support; and (c) at least one lanthanide element residing on and/or incorporated into said support. The catalyst may also further include component (d), which is zinc. Also described herein is a method for converting an alcohol to one or more olefinic compounds (an olefin fraction) by contacting the alcohol with a catalyst at a temperature of at least 100° C. and up to 500° C. to result in direct conversion of the alcohol to an olefin fraction containing one or more olefinic compounds containing at least three carbon atoms; wherein ethylene and propylene are produced in a minor proportion of the olefin fraction, and butenes and higher olefins are produced in major proportion.

Li, Zhenglong↗

Catalytic conversion of bio-mass derivable aliphatic alcohols to valuable alkenes or oxygenates

Disclosed is a catalyst system, its methods of preparation and its use for producing, among others, alkenes and/or saturated or unsaturated oxygenates and, which include at least one of an aldehyde and an acid (such as propyl aldehyde, acrolein, acrylic acid, isobutyl aldehyde, methacrolein, methacrylic acid), comprising subjecting the corresponding an alcohol or a diol selected from the group consisting of propanol, propanediol and isobutanol that is derivable from biomass, to a vapor phase process over the catalytic system described herein in the presence of a gas mixture of oxygen, air or nitrogen and/or other suitable diluting gas. In the case where one of 1-propanol, or 1,2-propanediol or 1,3-propanediol or a mixture thereof is subjected to a vapor phase catalytic process over the said catalytic system in the presence of air or oxygen, and a co-fed gas, such as nitrogen or other diluting gas, the product is at least one of propylene, propyl aldehyde, acrolein and acrylic acid. In the case where isobutanol is subjected to such a process, the product is at least one of isobutylene, isobutyl aldehyde, methacrolein and methacrylic acid. The catalyst system comprises a single catalytic zone or multi-catalytic zones, in each of which the composition of the co-feed and other reaction parameter can be independently controlled.

Lin, Manhua↗

Ga speciation in Ga/H-ZSM-5 by in-situ transmission FTIR spectroscopy

H-ZSM-5 supported Ga (Ga/H-ZSM-5) has long been recognized as a promising catalyst for nonoxidative dehydrogenation and dehydroaromatization of alkanes. However, Ga speciation under reaction conditions remains controversial. In this work, in-situ transmission Fourier Transform infrared (FTIR) spectroscopy is employed to systematically investigate Ga speciation in Ga/H-ZSM-5 with three Si/Al ratios (15, 28 and 39) and a wide range of Ga/Al ratios (0–1.7). Quantitative FTIR spectroscopy with pyridine reveals that one Ga atom roughly replaces one Brønsted acid site (BAS) at Ga/BAS ratio up to 0.7, however, only up to ~80% of the BAS on the H-ZSM-5 can be exchanged even with excess amounts of Ga. At a low Si/Al ratio of 15, the intensity of GaH x bands on reduced Ga/H-ZSM-5 at 550 °C increases almost linearly at low Ga loadings (Ga/Al < 0.13), and then levels off. In contrast, no detectable GaH x bands are observed on Ga/H-ZSM-5 with a high Si/Al ratio of 39, with Ga/Al ratios up to 1.3. The dependence of GaH x bands on both the Si/Al ratios and the Ga/Al ratios shows that Ga speciation varies with BAS density in the zeolite. We hypothesize that paired BAS sites are preferentially exchanged with Ga + , leading to the formation of Ga + –H + pair sites, while the exchange of isolated BAS form isolated Ga+ species. Using water as a probe molecule, we show that isolated Ga + and Ga + –H + pair sites have distinct properties, i.e., the former can be easily oxidized by water at 150 °C to form GaOOH species, while the latter is inactive under the same conditions. Furthermore, these results provide direct experimental evidence for the existence of two types of Ga species on reduced Ga/H-ZSM-5, highlighting the possibility that they have different catalytic activities in alkane dehydrogenation reactions.

03 NATURAL GAS↗

Understanding the Correlation between Ga Speciation and Propane Dehydrogenation Activity on Ga/H-ZSM-5 Catalysts

H-ZSM-5 zeolite-supported Ga (Ga/H-ZSM-5) has been considered as a selective catalyst for nonoxidative propane dehydrogenation (PDH) for decades; however, the reaction mechanism remains a topic of considerable discussion. In particular, the correlation between various Ga species present on the catalyst at the reaction conditions and the PDH activity has yet to be established. In this work, intrinsic PDH rates and activation energies were determined on Ga + –H + pair sites and isolated Ga + sites on Ga/H-ZSM-5 samples with a wide range of Si/Al and Ga/Al ratios. Here, the turnover frequency on Ga + –H + pair sites in the PDH is higher than that of isolated Ga + sites by a factor of ~15. Experimental measurements combined with a dual-site model show the activation energy in the PDH on the Ga + –H + pair sites and isolated Ga + sites to be 90.8 ± 1.5 and 117 ± 4.7 kJ·mol –1 , respectively. These results demonstrate that Ga+–H+ pair sites are much more active in the PDH than isolated Ga + sites. The activation energy of GaH x decomposition to form H 2 was determined to be 40–60 kJ·mol –1 higher than that of the PDH on Ga species, suggesting that the GaH x decomposition is unlikely to be part of the PDH mechanism. Although both Brønsted acid and Ga sites interact with propane, Fourier transform infrared spectroscopy results provide strong evidence suggesting that the alkyl mechanism is more likely in the PDH on Ga/H-ZSM-5 catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning the Molecular Structure and Reaction Mechanism of Olefin Metathesis by Model Bilayered Supported MoO x /AlO x /SiO 2 Catalysts

The molecular structure and activity of supported MoO x olefin metathesis catalysts are heavily impacted by the choice of catalyst support. In this study, surface modification of the SiO 2 support with AlO x and selective anchoring of the MoO x on the surface AlO x sites were used to tune the structure, activation, and reactivity of the resulting surface MoO x sites. Extensive in situ molecular characterization, chemical probe studies, and density functional theory (DFT) calculations reveal that the enhanced activity of the supported MoO x /AlO x /SiO 2 catalyst over the MoO x / SiO 2 catalyst is associated with more favorable activation and kinetics of surface MoO x anchored at AlO x sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Carbon Anode for Rechargeable Lithium Cells

Conventionally, rechargeable lithium cells employ a pure lithium anode. To overcome problems associated with the pure lithium electrode, it has been proposed to replace the conventional electrode with an alternative material having a greater stability with respect to the cell electrolytes. For this reason, several graphitic and coke based carbonaceous materials were evaluated as candidate anode materials...In this paper, we summarize the results of the studies on Li-ion cell development.

rechargeable batteries batteries lithium cells lit↗

Thermal Cycle and Capacitance Testing of Mezzo Industries Phase Changer Material Heat Capacitor

Effective Thermal management is essential for the safety and performance of human spacecraft, especially during long-duration missions with fluctuating heat loads. Phase Change Material (PCM) heat exchangers offer a compact, efficient solution by storing and releasing thermal energy through latent heat during phase transitions. This allows PCM systems to buffer transient thermal loads without immediate heat rejection, reducing the need for oversized radiators – particularly critical during ascent and re-entry when radiators are stowed. By maintaining stable temperatures in crew cabins and equipment bays, PCM technology enhances crew comfort, protects sensitive systems, and supports long-term mission sustainability with minimal mass and volume impact. A phase change material heat capacitor prototype, designed and built under a NASA Small Business Innovation Research grant by Mezzo Technologies, utilizes a laser welding microtube manufacturing process that promises increased reliability and performance over current manufacturing methods like brazing. This heat exchanger was tested through coolant thermal cycling within the expected flow rates and temperature range of the Orion spacecraft, the crewed spacecraft taking NASA astronauts to the moon under the Artemis Program. The useful heat storage capacitance was measured and compared to Orion spacecraft requirements.

Active Thermal Control Systems↗