Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Chemical modification”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Development of Metal-Free Photocatalysts

Solar fuels show great promise as clean, sustainable energy sources; however, established technologies are still plagued by high price, toxicity concerns, or low efficiencies. There is a critical need for inexpensive, benign materials that can effectively harness the sun’s energy. The overarching objective of this project is to evaluate the compatibility of novel material combinations for use as metal-free, heterojunction photocatalysts. Our central hypothesis is that by tuning the electronic structure of individual components in hybrid composites, via selective chemical modifications and physical stimuli to the interface, we can improve the photocatalytic properties of the overall assembly. We will determine factors that affect energy band gaps and band edge positions in isolated photocatalyst systems as well as explore routes to modulate heterojunction band alignments in composite assemblies. Our results will predict accessible pathways for charge carriers in new composite photocatalysts, facilitating access to more of the solar spectrum via inexpensive, environmentally-friendly material combinations.

14 SOLAR ENERGY↗
DOE OSTI2023

Combined Experimental and Computational Efforts to Establish Ion Mobility, Solubility and Stability of Functional Liquids for Electrochemical Energy Storage

This work provides a computation-driven investigation of the stability of organic electrolytes for lithium-air batteries. Electrolyte instability is currently a key challenge that limits practical use of aprotic Li-air batteries, and the chemical processes that cause this instability are often kinetically-driven. Computational screening for kinetic stability involves the determination of reaction barriers for the numerous potential reaction mechanisms, barriers that are challenging to calculate due to the difficulty of locating transition state structures. Here we screen a broad set of substituted electrolytes for susceptibility to nucleophilic attack by superoxide. We find that carbonates are not typically expected to be stable and that sulfones are generally stable, validating literature trends. We study the effects of chemical functionalization with electron-donating and withdrawing groups and their interplay with steric factors, identifying functional groups and other chemical modifications that increase stability in these groups. User-input driven transition state identification is used for these initial calculations, and an automated computational pipeline is subsequently presented and validated as a means to perform further high-throughput searches across mechanisms and chemistries. The pipeline integrates cheminformatics-based reaction encoding, relaxed potential energy scans, and nudged elastic band calculations for an end-to-end approach to barrier calculations. We review this automated search approach and its current limitations, and discuss challenges and further work.

25 ENERGY STORAGE↗
DOE OSTI2025

Abbr. Final report: Self-assembled molecular containers as artificial water channels: towards biomimetic desalination membranes

Global water scarcity demands advances in desalination technologies that can deliver more fresh water with less energy. Current reverse osmosis membranes are fundamentally limited by a trade-off between how much water they can pass and how well they block salts. To address this challenge, we developed a bottom-up strategy to design and test artificial water channels that mimic the efficiency of biological proteins but are built from robust synthetic molecules. Over two years, we synthesized and evaluated more than twenty molecular channel candidates, including supramolecular macrocycles and nanographene pores with atomically precise structures. We showed that small chemical modifications allow direct control over pore size and chemistry, which in turn govern water permeability and salt rejection. In collaboration with university partners, we reported the first experimental demonstration of water transport through a nanographene pore, bridging a long-standing gap between simulation and experiment. Several of the artificial channels we developed achieved water–salt selectivity beyond conventional polymer membranes, highlighting their potential for next-generation desalination and precision separations.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Recent Progress on Emerging Applications of Hydrochar

Hydrothermal carbonization (HTC) is a prominent thermochemical technology that can convert high-moisture waste into a valuable product (called hydrochar) at a relatively mild treatment condition (180–260 °C and 2–10 MPa). With rapidly growing research on HTC and hydrochar in recent years, review articles addressing the current and future direction of this research are scarce. Hence, this article aims to review various emerging applications of hydrochars, e.g., from solid fuel to soil amendment, from electron storage to hydrogen storage, from dye adsorption, toxin adsorption, heavy metal adsorption to nutrient recovery, and from carbon capture to carbon sequestration, etc. This article further provides an insight in the hydrochar’s working mechanism for various applications and how the applications can be improved through chemical modification of the hydrochar. Finally, new perspectives with appropriate recommendations have been made to further unveil potential applications and its improvement through hydrochar and its modified version.

09 BIOMASS FUELS↗
DOE OSTI2025

Investigations on the Thermal Stability and Kinetics of Biolubricants Synthesized from Different Types of Vegetable Oils

Petroleum-based lubricants raise environmental concerns due to their non-biodegradability and toxicity, whereas biobased lubricants underperform owing to low thermal stability. This study examined and compared three vegetable oils, along with their chemically modified versions, to better understand their suitability as biolubricants. High oleic soybean oil (HOSOY), regular soybean oil (RSOY), and waste cooking oil (WCO) were subjected to chemical modification, where isopropyl groups were attached to the fatty acid chains of the oils to produce branched oils, i.e., b-HOSOY, b-RSOY, and b-WCO. The detailed kinetic study of each regular and modified sample was investigated using thermogravimetric analysis. The kinetic parameters, such as the activation energies, reaction rate, and pre-exponential factor, were generated via Friedman methods. The differential thermal gravimetric (DTG) analysis showed low volatilization at the onset temperature in each modified oil as compared with the unmodified samples under an oxidative environment. Furthermore, the comparative kinetic studies demonstrated the enhanced thermoxidative stability of the modified products relative to their unaltered counterparts. Among the tested oils, the b-RSOY showed an average activation energy of 325 kJ/mol, followed by the b-WCO: 300 kJ/mol and the b-HOSOY: 251 kJ/mol, indicating the most stable modified product under an oxidative environment. For all the samples, the pre-exponential factors were in good agreement with the activation energies, which validates that finding the pre-exponential components is crucial to the kinetic analysis.

Sarker, Majher I. (ORCID:0000000299509274)↗
DOE OSTI2022

Tailoring Mesopores and Nitrogen Groups of Carbon Nanofibers for Polysulfide Entrapment in Lithium–Sulfur Batteries

In the current work, we combined different physical and chemical modifications of carbon nanofibers through the creation of micro-, meso-, and macro-pores as well as the incorporation of nitrogen groups in cyclic polyacrylonitrile (CPAN) using gas-assisted electrospinning and air-controlled electrospray processes. We incorporated them into electrode and interlayer in Li–Sulfur batteries. First, we controlled pore size and distributions in mesoporous carbon fibers (mpCNF) via adding polymethyl methacrylate as a sacrificial polymer to the polyacrylonitrile carbon precursor, followed by varying activation conditions. Secondly, nitrogen groups were introduced via cyclization of PAN on mesoporous carbon nanofibers (mpCPAN). We compared the synergistic effects of all these features in cathode substrate and interlayer on the performance Li–Sulfur batteries and used various characterization tools to understand them. Our results revealed that coating CPAN on both mesoporous carbon cathode and interlayer greatly enhanced the rate capability and capacity retention, leading to the capacity of 1000 mAh/g at 2 C and 1200 mAh/g at 0.5 C with the capability retention of 88% after 100 cycles. The presence of nitrogen groups and mesopores in both cathodes and interlayers resulted in more effective polysulfide confinement and also show more promise for higher loading systems.

25 ENERGY STORAGE↗
NASA NTRS1971

Development of a low void polyimide resin for autoclave processing of glass and graphite reinforced composites.

Experimental studies are described in which new A-type polyimide prepolymer chemical modifications were investigated with the aim of increasing the melt phase duration and temperature range permitting autoclave processing, yet retaining the addition-type cure mechanism required for low-void content composites. Several modification candidates were examined, and one specific formulation was selected for detailed investigation. This A-type polyimide prepolymer formulation is shown to possess the desired characteristics.

Vaughan, R. W.↗
NASA NTRS1974

Three-dimensional tertiary structure of yeast phenylalanine transfer RNA

Results of an analysis and interpretation of a 3-A electron density map of yeast phenylalanine transfer RNA. Some earlier detailed assignments of nucleotide residues to electron density peaks are found to be in error, even though the overall tracing of the backbone conformation of yeast phenylalanine transfer RNA was generally correct. A new, more comprehensive interpretation is made which makes it possible to define the tertiary interactions in the molecule. The new interpretation makes it possible to visualize a number of tertiary interactions which not only explain the structural role of most of the bases which are constant in transfer RNAs, but also makes it possible to understand in a direct and simple fashion the chemical modification data on transfer RNA. In addition, this pattern of tertiary interactions provides a basis for understanding the general three-dimensional folding of all transfer RNA molecules.

Kim, S. H.↗
NASA NTRS1975

Depletion of the F2 region ionosphere and the protonosphere by the release of molecular hydrogen

Theoretical models have been used to investigate the effects of artificially injected H2 gas on plasma densities in the ionospheric F region and the overlying protonosphere. Owing to large reaction rates between H2 and ionospheric O(+) ions, plasma densities in both daytime and nighttime ionospheres can be greatly reduced by modest amounts of released H2 gas. One hundred kg of H2 released at 300-km altitude reduces local O(+) densities by more than three orders of magnitude and produces about a 5% depression in H(+) densities in the overlying protonosphere. These results suggest that it should be possible to conduct controlled chemical-modification experiments for investigation of many outstanding ionospheric and magnetospheric problems.

Bernhardt, P. A.↗
NASA NTRS1977

Results of analyses performed on soil adjacent to penetrators emplaced into sediments at McCook, Nebraska, January 1976

During 1976 several penetrators (full and 0.58 scale) were dropped into a test site McCook, Nebraska. The McCook site was selected because it simulated penetration into wind-deposited sediments (silts and sands) on Martian plains. The physical and chemical modifications found in the sediment after the penetrators' impact are described. Laboratory analyses have shown mineralogical and elemental changes are produced in the sediment next to the penetrator. Optical microscopy studies of material next to the skin of the penetrator revealed a layer of glassy material about 75 microns thick. Elemental analysis of a 0-1-mm layer of sediment next to the penetrator revealed increased concentrations for Cr, Fe, Ni, Mo, and reduced concentrations for Mg, Al Si, P, K, and Ca. The Cr, Fe, Ni, and Mo were in fragments abraded from the penetrator. Mineralogical changes occurring in the sediment next to the penetrator included the introduction of micron-size grains of alpha iron and several hydrated iron oxide minerals. The newly formed silicate minerals include metastable phases of silica (cristobalite, lechatelierite, and opal). The glassy material was mostly opal which formed when the host minerals (mica, calcite, and clay) decomposed. In summary, contaminants introduced by the penetrator occur up to 2 mm away from the penetrator's skin. Although volatile elements do migrate and new minerals are formed during the destruction of host minerals in the sediment, no changes were observed beyond the 2-mm distance. The analyses indicate 0.58-scale penetrators do effectively simulate full-scale testing for soil modification effects.

Blanchard, M.↗
NASA NTRS1977

Results of analyses performed on basalt adjacent to penetrators emplaced into volcanic rock at Amboy, California, April 1976

The physical and chemical modifications found in the basalt after impact of four penetrators were studied. Laboratory analyses show that mineralogical and elemental changes are produced in the powdered and crushed basalt immediately surrounding the penetrator. Optical microscopy studies of material next to the skin of the penetrator revealed a layer, 0-2 mm thick, of glass and abraded iron alloy mixed with fractured mineral grains of basalt. Elemental analysis of the 0-2 mm layer revealed increased concentrations of Fe, Cr, Ni, No, and Mn, and reduced concentrations of Mg, Al, Si, and Ca. The Fe, Cr, Ni, and Mo were in fragments abraded from the penetrator. Mineralogical changes occurring in the basalt sediment next to the penetrator include the introduction of micron-size grains of alpha-iron, magnetite, and hematite. The newly formed silicate minerals include metastable phases of silica (tridymite and cristobalite). An increased concentration of Fe, Cr, Ni, and Mo occurred in the 2-mm to 1-cm layer of penetrator no. 1, which impacted at the highest velocity. No elemental concentration increase was noted for penetrators nos. 2 and 3 in the 2-mm to 1-cm layer. Contaminants introduced by the penetrator occur up to 1 cm away from the penetrator's skin. Although volatile elements do migrate and new minerals are formed during the destruction of host minerals in the crushed rock, no changes were observed beyond the 1-cm distance.

Blanchard, M.↗
NASA NTRS1978

Development of flame resistant treatment for nomex fibrous structures

Technology which renders aramid fibrous structures flame resistant through chemical modification was developed. The project scaled up flame resistant treatment from laboratory fabric swatches of a few inches to efficiently producing ten yards of commercial width (41 inches) aromatic polyamide. The radiation intensity problem of the processor was resolved. Further improvement of the processor cooling system was recommended for two reasons: (1) To advance current technology of flame proofing Nomex fabric to higher oxygen enriched atmospheres; and (2) To adapt the processor for direct applicability to low cost commercial fabrics.

Toy, M. S.↗
NASA NTRS1980

LARC-13 adhesive development

A LARC-13 type adhesive system was developed and property data obtained that demonstrated improved thermomechanical properties superior to base LARC-13 adhesive. An improved adhesive for 589 K (600 F) use was developed by physical or chemical modification of LARC-13. The adhesive was optimized for titanium and composite bonding, and a compatible surface preparation for titanium and composite substrates was identified. The data obtained with the improved adhesive system indicated it would meet the 589 K (600 F) properties desired for application on space shuttle components. Average titanium lap shear data were: (1) 21.1 MPa (3355 psi) at RT, (2) 13.0 MPa (1881 psi) at 600 F, and (3) 16.4 MPa (2335) after aging 125 hours at 600 F and tested at 600 F.

Hill, S. G.↗
NASA NTRS1983

Mechanical and spectroscopic properties of metal-containing polyimides

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymerization or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

Taylor, L. T.↗
NASA NTRS1984

Chemical approach for controlling nadimide cure temperature and rate

Polyimide resins suitable for use as composite matrix materials are formed by copolymerization of maleic and norbornenyl endcapped monomers and oligomers. The copolymers can be cured at temperatures under about 300 C by controlling the available concentration of the maleic capped reactant. This control can be achieved by adding sufficient amounts of said maleic reactant, or by chemical modification of either copolymer, so as to either increase Diels-Alder retrogression of the norbornenyl capped reactant and/or holding initiation and polymerization to a rate compatible with the availability of the maleic capped reactant.

Lauver, R. W.↗
NASA NTRS1985

Chemical approach for controlling nadimide cure temperature and rate with maleimide

Polyimide resins suitable for use as composite matrix materials are formed by copolymerization of maleic and norbornenyl endcapped monomers and oligomers. The copolymers can be cured at temperatures under about 300 C by controlling the available concentration of the maleic end-capped reactant. Control can be achieved by adding sufficient amounts of said maleic reactant, or by chemical modification of either copolymers, so as to either increase Diels-Alder retrogression of the norbornenyl capped reactant and/or holding initiation and polymerization to a rate compatible with the availability of the maleic-capped reactant.

Lauver, R. W.↗
NASA NTRS1985

Chemical approach for controlling nadimide cure temperature and rate with maleimide

Polyimide resins suitable for use as composite matrix materials are formed by copolymerization of maleic and norbornenyl endcapped monomers and oligomers. The copolymers can be cured at temperatures under about 300 C by controlling the available concentration of the maleic end-capped reactant. This control can be achieved by adding sufficient amounts of said maleic reactant, or by chemical modification of either copolymer, so as to either increase Diels-Alder retrogression of the norbornenyl capped reactant and/or holding initiation and polymerization to a rate compatible with the available of the maleic-capped reactant.

Lauver, R. W.↗