Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Chemical Bonds”

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 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Combustion chemistry of alkenes and alkadienes

Alkenes formed, during the refining of crude oil, by cracking the heavier fractions are present in transportation fuels in significant amounts, up to as much as 15–20% in gasoline. Moreover, alkenes are also the major intermediate products of the oxidation of alkanes, which play a significant role in autoignition chemistry. This review has assessed the recent progress in gas-phase detailed kinetic model development for species with C=C double bond, mostly C2–C10 alkenes and 1,3-butadiene. The compiled knowledge on alkene combustion chemistry enabled a better understanding of the influence of the number and the position of the C=C double bond on the chemical kinetics and hence combustion behavior of alkenes in engines. At first, the article gives an extensive overview of fundamental combustion experiments by considering studies of C2–C10 alkenes and 1,3-butadiene in shock tubes, rapid compression machines, laminar flames, and jet-stirred and flow reactors. The value of the data from such experiments is critically discussed. Secondly, this article highlights the important reaction classes involved in alkene oxidation over low-, intermediate- and high-temperature ranges. Combustion chemistry covering C2 to C10 alkenes, with a special emphasis on C2 to C7 isomers is discussed by presenting a large body of experimental and modeling investigations. Detailed chemistry differences between alkene isomers and also between alkenes and alkanes are also addressed. Thirdly, the article presents important reaction pathways for PAH precursor formation in different alkenes. Finally, a summary of the distinguishing features of alkene combustion chemistry and an outlook towards future research in this area are presented. In conclusion, this review is focused on linear and branched chain alkenes, and the chemistry of cyclo-alkenes is not included.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Structural, Optical, and Electronic Properties of Two Quaternary Chalcogenide Semiconductors: Ag 2 SrSiS 4 and Ag 2 SrGeS 4

Quaternary chalcogenide materials have long been a source of semiconductors for optoelectronic applications. Recent studies on the I2-II-IV-X4 (I = Ag, Cu, Li; II = Ba, Sr, Eu, Pb; IV = Si, Ge, Sn; X = S, Se) materials have shown particular versatility and promise among these compounds. These semiconductors take advantage of a diverse bonding scheme and chemical differences among cations to target a degree of anti-site defect resistance. Within this set of compounds, the materials containing both Ag and Sr have not been experimentally studied and leave a gap in the full understanding of the family. Here, we have synthesized powders and single crystals of two Ag- and Sr-containing compounds, Ag 2 SrSiS 4 and Ag 2 SrGeS 4 , each found to form in the tetragonal I4¯2m structure of Ag 2 BaGeS 4 . During the synthesis targeting the title compounds, two additional materials, Ag 2 Sr 3 Si 2 S 8 and Ag 2 Sr 3 Ge 2 S 8 , have also been identified. Furthermore, these cubic compounds represent impurity phases during the synthesis of Ag 2 SrSiS 4 and Ag 2 SrGeS 4 . We show through hybrid density functional theory calculations that Ag 2 SrSiS 4 and Ag 2 SrGeS 4 have highly dispersive band edge states and indirect band gaps, experimentally measured as 2.08(1) and 1.73(2) eV, respectively. Second-harmonic generation measurements on Ag 2 SrSiS 4 and Ag 2 SrGeS 4 powders show frequency doubling capabilities in the near-infrared range.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Effects of irradiation damage on the hardness and elastic properties of quaternary and high entropy transition metal diborides

Multi-principal component transition metal (TM) diborides represent a class of high-entropy ceramics (HECs) that have received considerable interest in recent years owing to their promising properties for extreme environment applications that include thermal/ environmental barriers, hypersonic vehicles, turbine engines, and next-generation nuclear reactors. While the addition of chemical disorder through the random distribution of TM elements on the cation sublattice has offered opportunities to tailor elastic stiffness and hardness, the effects of irradiation-induced structural damage on the physical properties of these complex materials have remained largely unexplored. To this end, changes in the hardness and elastic moduli of a high-entropy TM diboride (Hf 0.2 Nb 0.2 Ta 0.2 Ti 0.2 Zr 0.2 )B 2 and three of its quaternary subsets following irradiation with 10 MeV gold (Au) ions to fluences of up to 6 × 10 15 Au cm -2 are investigated at the micrometer and sub-micrometer length-scales via the dispersion of laser-generated surface acoustic waves (SAW) and nanoindentation, respectively. The nanoindentation measurements show that the TM diborides exhibit an initial increase in hardness following irradiation with energetic Au ions, with a subsequent decrease in hardness following further irradiation. One quaternary composition, (Hf 1/3 Ta 1/3 Ti 1/3 )B 2 , exhibits a notable exception to the trend and continues to exhibit an increase in hardness with ion irradiation fluence. Although differences in the absolute values of the effective elastic moduli obtained from the measured SAW dispersion and nanoindentation are observed (and attributed to microstructural variations at the measurement length-scale), both techniques yield similar trends in the form of an initial reduction and subsequent saturation in the elastic modulus with increasing ion irradiation fluence. The quaternary TM diboride (Hf 1/3 Ta 1/3 Ti 1/3 )B 2 again exhibits a departure from this trend. The high-entropy TM diboride (Hf 0.2 Nb 0.2 Ta 0.2 Ti 0.2 Zr 0.2 )B 2 exhibits the greatest recovery in hardness and modulus when irradiated to high ion fluences following initial changes at low fluence, indicating superior resistance to radiation-induced damage over its quaternary counterparts. Opportunities for designing HECs with superior hardness and modulus for enhanced radiation resistance (compared to their single constituent counterparts) by tailoring chemical disorder and bond character in the lattice are discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Control of the Plasma-Material Interface for Long Pulse Optimization in the Experimental Advanced Superconducting Tokamak (EAST) (Final Report)

This project involved a collaborative effort, led by Dr. Rajesh Maingi of Princeton Plasma Physics Laboratory, to understand and control the plasma-material interface to improve long pulse discharge control and performance in the EAST devices. The focus is on long pulse recycling control and optimization, which can be challenging because of their broad range of materials used for plasma-facing components (PFC) and wall conditioning techniques. The purpose of the EAST device is to demonstrate long-pulse, stable, high performance plasma operation, providing a test-bed for key physics and technology issues for next step devices. As part of these tests, EAST has deployed carbon for the lower divertor PFC, tungsten for the upper divertor, and molybdenum for the main wall. In addition wall coatings are deployed for long pulse recycling control: lithium (Li) via several delivery tools, boronization, and recently also siliconization; for example, in 2013, a layer of SiC was deposited on all of the graphite tiles. Oxygen is also present at trace levels, making for a complex mix of materials and plasma-materials interactions (PMI). This mix of materials and the limited durability of wall coatings, coupled to partially optimized cryo-pumping, lead to evolution of the recycling off the PFCs, which restricts the duration of stationary, high performance, long pulse discharges. Comparing the wall conditioning techniques, Li enables the highest energy confinement and lowest recycling for the longest duration, while also suppressing ELMs in certain discharges. More specifically, research activities at the University of Tennessee focused on heat flux profile measurements in EAST, modeling the surface response, including the bonding energetics and chemical interactions between Li with carbon, tungsten, hydrogen and impurities, in addition to post situ experimental characterization and analysis of the divertor plasma facing components in EAST. This final report describes the overall progress within each of these tasks at the University of Tennessee within the project.

36 MATERIALS SCIENCE↗
NASA NTRS1977

Two-phase working fluids for the temperature range 100-350 C

The decomposition and corrosion of two-phase heat transfer liquids and metal envelopes have been investigated on the basis of molecular, bond strengths and chemical thermodynamics. Potentially stable heat transfer fluids for the temperature range 100 to 350 C have been identified, and reflux heat pipe tests initiated with 10 fluids and carbon steel and aluminum envelopes to experimentally establish corrosion behavior and noncondensable gas generation rates.

Saaski, E. W.↗
NASA NTRS1977

Two-Phase Working Fluids for the Temperature Range 50 to 350 C

The decomposition and corrosion of two-phase heat transfer liquids and metal envelopes have been investigated on the basis of molecular bond strengths and chemical thermodynamics. Potentially stable heat transfer fluids for the temperature range 100 C to 350 C have been identified, and reflux heat pipes tests initiated with 10 fluids and carbon steel and aluminum envelopes to experimentally establish corrosion behavior and noncondensable gas generation rates.

Saaski, E. W.↗
NASA NTRS1985

High temperature metal and ceramic composites

The Materials Division at NASA Lewis is engaged in research and development efforts on behalf of fiber-reinforced composite materials that are lighter, stiffer, and more structurally reliable than conventional monolithic alloys and ceramics in applications that range from the cryogenic to the refractory. Attention is presently given to metal matrix composites, in which high performance depends on stiff, strong and thermally stable large diameter fibers, with chemically stable interfacial bonding and good coefficient of thermal expansion matching between fibers and matrices, and to ceramic matrix composites, in which intermediate strength interfacial bonds must allow cracks to propagate through the matrix only, while retaining good load transfer characteristics between fiber and matrix.

Signorelli, R. A.↗
NASA NTRS1986

Antisoiling Coatings for Solar-Energy Devices

Fluorocarbons resist formation of adherent deposits. Promising coating materials reduce soiling of solar photovoltaic modules and possibly solar thermal collectors. Contaminating layers of various degrees of adherence form on surfaces of devices, partially blocking incident solar energy, reducing output power. Loose soil deposits during dry periods but washed off by rain. New coatings help prevent formation of more-adherent, chemically and physically bonded layers rain alone cannot wash away.

Cuddihy, E. F.↗
NASA NTRS1987

EXAFS: New tool for study of battery and fuel cell materials

Extended X ray absorption fine structure (EXAFS) is a powerful technique for probing the local atomic structure of battery and fuel cell materials. The major advantages of EXAFS are that both the probe and the signal are X rays and the technique is element selective and applicable to all states of matter. This permits in situ studies of electrodes and determination of the structure of single components in composite electrodes, or even complete cells. EXAFS specifically probes short range order and yields coordination numbers, bond distances, and chemical identity of nearest neighbors. Thus, it is ideal for structural studies of ions in solution and the poorly crystallized materials that are often the active materials or catalysts in batteries and fuel cells. Studies on typical battery and fuel cell components are used to describe the technique and the capability of EXAFS as a structural tool in these applications. Typical experimental and data analysis procedures are outlined. The advantages and limitations of the technique are also briefly discussed.

Mcbreen, James↗
NASA NTRS1998

Effect of Composite Fabrication on the Strength of Single Crystal Al2O3 Fibers in Two Fe-Base Alloy Composites

Continuous single-crystal Al2O3 fibers have been incorporated into a variety of metal and intermetallic matrices and the results have consistently indicated that the fiber strength had been reduced by 32 to 50% during processing. Two iron-based alloys, FeNiCoCrAl and FeAlVCMn, were chosen as matrices for Al2O3 fiber reinforced metal matrix composites (MMC) with the goal of maintaining Al2O3 fiber strength after composite processing. The feasibility of Al2O3/FeNiCoCrAl and Al2O3/FeAlVCMn composite systems for high temperature applications were assessed in terms of fiber-matrix chemical compatibility, interfacial bond strength, and composite tensile properties. The strength of etched-out fibers was significantly improved by choosing matrices containing less reactive elements. The ultimate tensile strength (UTS) values of the composites could generally be predicted with existing models using the strength of etched-out fibers. However, the UTS of the composites were less than desired due to a low fiber Weibull modulus. Acoustic emission analysis during tensile testing was a useful tool for determining the efficiency of the fibers in the composite and for determining the failure mechanism of the composites.

Draper, Susan L.↗
NASA NTRS1997

Advanced Lightweight Optics Development for Space Applications

A considerable amount of effort over the past year has been devoted to exploring ultra-lightweight optics for two specific NASA programs, the Next Generation Space Telescope (NGST), and the High Throughput X-ray Spectrometer (HTXS). Experimental investigations have been undertaken in a variety of materials including glass, composites, nickel, beryllium, Carbon Silicon Carbide, Reaction Bonded Silicon Carbide, Chemical Vapor Deposited Silicon Carbide, and silicon. Overall results of these investigations will be summarized, and specific details will be provided concerning the in-house development of ultra-lightweight nickel replication for both grazing incidence and normal incidence optics. This will include x-ray test results of the grazing incidence optic and cryogenic test results of the normal incidence optic. The status of two 1.5 meter diameter demonstration mirrors for NGST will also be presented. These two demonstrations are aimed at establishing the capability to manufacture and test mirrors that have an areal density of 15 kilograms per square meter.

Bilbro, James W.↗
NASA NTRS1990

Longer Life for Steel Structures

IC 531 is a coating manufactured and marketed by Inorganic Coatings, Inc. The coating was developed by Goddard to protect structures at Kennedy Space Center. It is a high ratio potassium silicate formula. The coating is water based, nontoxic, and nonflammable. It generates no volatile organic compounds nor hazardous chemical waste, and bonds to steel in 30 minutes. At the present time, no one can say for sure how long IC 531's effective lifetime is. Some of the original Goddard test applications of 1976 are still going strong after lengthy exposure to the Sun, salt and moisture. Says IC in company literature: 'IC 531 offers virtually permanent protection for steel. We predict it will protect structures for well beyond 25 years. If necessary, it is infinitely maintainable; if damaged, it can easily be touched up with more IC 531.'

Source record↗
NASA NTRS2011

Demonstration/Validation of Environmentally-Preferable Coatings for Launch Facilities

Kennedy Space Center (KSC) is responsible for a number of facilities/structures with metallic structural and non-structural components in a highly corrosive environment. Metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that structures meet or exceed design or performance life. The standard practice for protecting metallic substrates in atmospheric environments is the application of an applied coating system. Applied coating systems work via a variety of methods (barrier, galvanic and/or inhibitor) and adhere to the substrate through a combination of chemical and physical bonds. Maintenance at KSC and other NASA Centers is governed by NASA-STD-50088 (Protective Coating of Carbon Steel, Stainless Steel, and Aluminum on Launch Structures, Facilities, and Ground Support Equipment) which establishes practices for the protective coating of ground support equipment and related facilities used by or for NASA programs and projects. The Standard is for the design of non-flight hardware used to support the operations of receiving, transportation, handling, assembly, inspection, test, checkout, service, and launch of space vehicles and payloads at NASA launch, landing, or retrieval sites. These criteria and practices contained within the Standard may be used for items used at the manufacturing, development, and test sites upstream of the launch, landing, or retrieval sites. The objective of this effort is to demonstrate and validate environmentally-preferable alternatives in accordance with NASA-STD-50088 and KSC requirements which can then be added to the Approved Products List. This Test Protocol contains the critical requirements and tests necessary to qualify alternatives for structural steel applications. These tests were derived from engineering, performance, and operational impact (supportability) requirements defined by a consensus of KSC participants. A Test Report will document the results of the testing as well as any test modifications made during the execution of the testing. Users of this Test Protocol should check the project's Test Report for additional test details or minor modifications that may have been necessary in the execution of the testing. The technical stakeholders will have agreed upon test procedures modifications documented in the Test Report.

Lewis, Pattie↗
NASA NTRS2012

Hexavalent Chrome Free Coatings for Electronics Applications: Joint Test Report

Regardless of the corrosivity of the environment, all metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that alloys meet or exceed design or performance life. The standard practice for protecting metallic substrates is the application of a coating system. Applied coating systems work via a variety of methods (barrier, galvanic, and/or inhibitor) and adhere to the substrate through a combination of chemical and physical bonds. For years hexavalent chromium has been a widely used element within applied coating systems because of its self healing and corrosion resistant properties. Occupational Safety and Health Administration (OSHA) studies have concluded that hexavalent chromium (hex chrome) is carcinogenic and poses significant risk to human health. On May 5, 2011 amendments to the Defense Federal Acquisition Regulation Supplement (DFARS) were issued in the Federal Register. Subpart 223.73 prohibits contracts from requiring hexavalent chromium in deliverables unless certain exceptions apply. These exceptions include authorization from a general or flag officer and members of the Senior Executive Service from a Program Executive Office, and unmodified legacy systems. Otherwise, Subpart 252.223-7008 provides the contract clause prohibiting contractors from using or delivering hexavalent chromium in a concentration greater than 0.1 percent by weight for all new contracts and to be included down to subcontractors for supplies, maintenance and repair services, and construction materials. National Aeronautics and Space Administration (NASA), Department of Defense (DoD), and industry stakeholders continue to search for alternatives to hex chrome in coatings applications that meet their performance requirements in corrosion protection, cost, operability, and health and safety, while typically specifying that performance must be equal to or greater than existing systems.

Kessel, Kurt↗
DOE OSTI2026

Ensemble Effects on Hydroxide Bond Dissociation Free Energies in Polyoxovanadate Clusters

Understanding structure-property relationships is foundational to numerous modern chemistries, such as proton-coupled electron transfer (PCET). However, an experimentally measured property is the result of the behavior from an ensemble of molecules. Neglecting ensemble effects, especially under complex chemical environments, may obfuscate these relationships and lead to discrepancies between theory and experiment. In this work, we demonstrate the impact of configurational entropy and local chemical environments on hydroxide bond dissociation free energies [BDFE- (O−H)] for a set of polyoxovanadate nanoclusters, at ambient conditions. The O−H bond strengths are investigated via density functional theory (DFT) coupled with statistical thermodynamic analysis and bilinear modeling, and compared with previous experimental results on the same systems, namely electrochemical solutions of: [V 6 O 13−x (OH) x (TRIOL R ) 2 ] −2 (x = 2, 4, 6; R = NO 2 , Me) and [V 6 O 11−x (OMe) 2 (OH) x (TRIOL NO 2 ) 2 ] −2 (x = 2, 4). Interestingly, we find that ensemble effects, even at room temperature, can account for a significant portion of the BDFE(O−H) trend with the degree of reduction via H atom binding, which cannot be fully captured by single-structure, static DFT calculations. Moreover, we find that the ensemble effects may be replicated statistically, requiring only enumeration of energetically accessible H-binding sites. With the ensemble effects resolved, we present a simple bilinear model to reconcile remaining biases between experiment and ensemble-informed theory, which corelate with clusterspecific electronic environment differences. The bilinear model achieves outstanding accuracy vs experiments with a root-mean squared error of 0.4 kcal/mol. Finally, based on the physicochemical characteristics of hydrogen interaction with polyoxometalates, we present a simple methodology that captures the BDFE(O−H) trend while dramatically reducing required DFT calculations by 98% and achieving accuracy within 1 kcal/mol. Overall, this work elucidates the roles and structural origins of configurational entropy and chemical effects on polyoxometalate hydroxide bond energies, with potential applicability to various atomically precise metal oxide systems. Importantly, it introduces models for rapid and highly accurate property calculations in connection with experiments.

Cluster chemistry↗
DOE OSTI2024

The Catabolism of Lignin-Derived p-Methoxylated Aromatic Compounds by Rhodococcus jostii RHA1

Emergent strategies to valorize lignin, an abundant but underutilized aromatic biopolymer, include tandem processes that integrate chemical depolymerization and biological catalysis. To date, aromatic monomers from C-O bond cleavage of lignin have been converted to bioproducts, but the presence of recalcitrant C-C bonds in lignin limits the product yield. A promising chemocatalytic strategy that overcomes this limitation involves phenol methyl protection and autoxidation. Incorporating this into a tandem process requires microbial cell factories able to transform the p-methoxylated products in the resulting methylated lignin stream. In this study, we assessed the ability of Rhodococcus jostii RHA1 to catabolize the major aromatic products in a methylated lignin stream and elucidated the pathways responsible for this catabolism. RHA1 grew on a methylated pine lignin stream, catabolizing the major aromatic monomers: p-methoxybenzoate (p-MBA), veratrate, and veratraldehyde. Bioinformatic analyses suggested that a cytochrome P450, PbdA, and its cognate reductase, PbdB, are involved in p-MBA catabolism. Gene deletion studies established that both pbdA and pbdB are essential for growth on p-MBA and several derivatives. Furthermore, a deletion mutant of a candidate p-hydroxybenzoate (p-HBA) hydroxylase, ..delta..pobA, did not grow on p-HBA. Veratraldehyde and veratrate catabolism required both vanillin dehydrogenase (Vdh) and vanillate O-demethylase (VanAB), revealing previously unknown roles of these enzymes. Finally, a ..delta..pcaL strain grew on neither p-MBA nor veratrate, indicating they are catabolized through the ..beta..-ketoadipate pathway. This study expands our understanding of the bacterial catabolism of aromatic compounds and facilitates the development of biocatalysts for lignin valorization.

aromatic biopolymers↗
NASA NTRS1987

Full CI benchmark calculations on N2, NO, and O2 - A comparison of methods for describing multiple bonds

Full configuration interaction (CI) calculations on the ground states of N2, NO, and O2 using a DZP Gaussian basis are compared with single-reference SDCI and coupled pair approaches (CPF), as well as with CASSCF multireference CI approaches. The CASSCF/MRCI technique is found to describe multiple bonds as well as single bonds. Although the coupled pair functional approach gave chemical accuracy (1 kcal/mol) for bonds involving hydrogen, larger errors occur in the CPF approach for the multiple bonded systems considered here. CI studies on the 1Sigma(g +) state of N2, including all single, double, triple, and quadruple excitations show that triple excitations are very important for the multiple bond case, and accounts for most of the deficiency in the coupled pair functional methods.

Bauschlicher, Charles W., Jr.↗
DOE OSTI2025

Activation of Semicore Electrons in Alkali Metals and Their Role in the B1–B2 Phase Transition under Pressure

Alkali fluorides are often thought of as archetypical ionic compounds whose structures can be understood in terms of the packing of rigid spheres. At ambient pressure, they assume the rocksalt (B1) structure, while under only a few GPa of pressure, the cesium chloride (B2) structure, with higher coordination numbers, is assumed for KF, RbF, and CsF. NaF requires almost 10 times more pressure to undergo this same phase transition, which has not been observed for LiF. Herein, we provide a detailed analysis, based upon quantum chemical calculations, explaining this behavior. We show that for the heavier alkali metals, the semicore p orbitals engage in metal-metal bonding in the B2 phase, facilitating the pressure-induced B1 → B2 structural transition. Furthermore, these findings suggest that the semicore orbitals of heavy alkali metals can be activated without the need of strong oxidants at very mild levels of compression, resulting in the formation of chemical bonds, challenging both traditional and modern core-valence distinctions. In addition, we argue that Cs 5p-5p bonding in CsCl occurs already at ambient pressure, stabilizing the B2 phase, and suggest experiments that may be able to detect signatures of such bonding.

Anions↗