Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Chemical structures”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17): Site-Selective Substitution, Electronic Structure, Chemical Bonding, and Structural Transformation

CoSn-type intermetallic compounds have emerged as a model platform for Kagome-derived flat-band physics, where subtle chemical perturbations can strongly influence electronic structure and phase stability. Here, we present a combined experimental and theoretical study of Sb-substitution in CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17) to elucidate the interplay between site selectivity, solubility limit, chemical bonding, and electronic structure. Rietveld refinements on Neutron powder diffraction data confirmed the selective Sb-substitution at the electron-rich In2 (2d) site forming the honeycomb substructure, while the In1 (1a) site within the Kagome layer remains exclusively occupied by In. Density functional theory (DFT) calculations revealed that pristine CoSn-type NiIn hosts Ni 3d-dominated flat bands near the Fermi level (EF), originating from the Kagome-like Ni substructure. Partial replacement of In by Sb within the honeycomb layer alters these flat-band features below EF, reducing the density of states and suppressing the flat-band topology near the Fermi level. Orbital-resolved electronic structure and chemical-bonding analyses show that Sb-substitution enhances Ni-p-block (In/Sb) covalency and optimizes charge compensation, stabilizing the CoSn-type structure up to the solubility limit x ≈ 0.17. Beyond the limit, the higher-Sb compositions show satellite reflections consistent with an incommensurately modulated phase. These results establish a link between site-selective chemical substitution, bonding optimization, and flat-band electronic structure evolution, providing fundamental insights into how chemical substitution influences the electronic properties of Kagome-based intermetallic compounds.

Roy, Nilanjan [National Institute of Technology Si↗
DOE OSTI2019

Examination of gamma-irradiated calcium silicate hydrates. Part I: Chemical-structural properties

The chemical-structural properties of synthetic calcium silicate hydrate (C-S-H) with C/S (Ca/Si) ratios of 0.75, 1 and 1.33 were studied after gamma irradiation-absorbed doses ranging from 0.145 to 0.784 MGy and compared with those of control specimens. The results showed that the total water content given by thermogravimetric analysis and the dimension of the basal spacing given by x-ray diffraction were comparable for control and irradiated samples, which indicate that the interlayer water content did not change. The morphology, C/S ratios, and silicate mean chain length were also found to be unaltered by the absorbed gamma doses.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Predicting Energetics Materials’ Crystalline Density from Chemical Structure by Machine Learning

To expedite new molecular compound development, a long-sought goal within the chemistry community has been to predict molecules’ bulk properties of interest a priori to synthesis from a chemical structure alone. In this work, we demonstrate that machine learning methods can indeed be used to directly learn the relationship between chemical structures and bulk crystalline properties of molecules, even in the absence of any crystal structure information or quantum mechanical calculations. We focus specifically on a class of organic compounds categorized as energetic materials called high explosives (HE) and predicting their crystalline density. An ongoing challenge within the chemistry machine learning community is deciding how best to featurize molecules as inputs into machine learning models—whether expert handcrafted features or learned molecular representations via graph-based neural network models—yield better results and why. We evaluate both types of representations in combination with a number of machine learning models to predict the crystalline densities of HE-like molecules curated from the Cambridge Structural Database, and we report the performance and pros and cons of our methods. Our message passing neural network (MPNN) based models with learned molecular representations generally perform best, outperforming current state-of-the-art methods at predicting crystalline density and performing well even when testing on a data set not representative of the training data. However, these models are traditionally considered black boxes and less easily interpretable. Here, to address this common challenge, we also provide a comparison analysis between our MPNN-based model and models with fixed feature representations that provides insights as to what features are learned by the MPNN to accurately predict density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Influence of Chemical Structure of Petrochemical Polyol on Properties of Bio-polyurethane Foams

In this study, the influence of the chemical structures of petrochemical polyols on the foaming process of polyurethane compositions as well as on selected properties of the foams obtained has been investigated. Two types of petrochemical polyols were used—polyester and polyether polyols as well as their blends with a rapeseed oil-based polyol. Dielectric polarization, temperature and expansion velocity were determined during the foaming process of the polyurethane systems with different polyol components. The results show the highest reactivity of the polyester polyol and a decrease of the polyurethane system’s reactivity as a result of a partial replacement of the petrochemical polyol with the bio-based polyol. The content of the closed cells in the materials obtained strongly depends on the petrochemical polyol used. The results indicate that the chemical structure of the petrochemical polyol had a significant effect on the cellular structure as well as the physical–mechanical properties of the final products. A significant worsening of the foams’ mechanical properties was observed as an effect of a partial replacement of the polyester polyol with the rapeseed oil-based polyol. In contrast, a partial replacement of the polyether polyol caused an improvement of the cell structure keeping the mechanical properties of the modified foams at the same level.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Structural, chemical and optical evaluation of Cu-doped ZnO nanoparticles synthesized by an aqueous solution method

Highlights: • Cu-doped ZnO nanoparticles obtained by chemical synthesis. • Substitutional or interstitial Cu into ZnO lead specific structural, chemical, and optical changes. • Incorporation efficiency of Cu atoms in ZnO as a function of the Cu concentration in the precursor dissolution. - Abstract: In this work a study of ZnO and Cu-doped ZnO nanoparticles obtained by chemical synthesis in aqueous media was carried out. Structural analysis gave the dominant presence of wurtzite ZnO phase forming a solid solution Zn{sub 1−x}Cu{sub x}O. For high Cu doping CuO phase is also present. For low Cu concentration the lattice shrinks due to Cu atoms substitute Zn atoms. For high Cu concentration the lattice enlarges due to predominance of interstitial Cu. From elemental analysis we determined and analyzed the incorporation efficiency of Cu atoms in Zn{sub 1−x}Cu{sub x}O as a function of the Cu concentration in the precursor dissolution. Combining structural and chemical results we described the Cu/Zn precursor concentrations r{sub w} in which the solid solution of Cu in ZnO is predominant. In the region located at r{sub w} ≈ 0.2–0.3 it is no longer valid. For Cu/Zn precursor concentration r{sub w} > 0.3 interstitial Cu dominates, and some amount of copper oxide appears. As the Cu concentration increases, the effective size of nanoparticles decreases. Photoluminescence (PL) measurements of the Cu-doped ZnO nanoparticles were carried out and analyzed.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Understanding how chemical structure affects ignition-delay-time $\phi$-sensitivity

$\phi$-sensitivity is the change in ignition delay time (IDT) with respect to the fuel-to-air equivalence ratio ($\phi$). High $\phi$-sensitivity is a desirable fuel property for applications in advanced compression ignition and multi-mode engine designs. Understanding how $\phi$-sensitivity depends on chemical structure is essential for selecting promising biofuels from the ever-growing list of proposed candidates. Here, we investigate the effect of chemical structure on $\phi$-sensitivity with experiment, simulation, and theory. Experimental Advanced Fuel Ignition Delay Analyzer (AFIDA) measurements for 2,4-dimethylpentane and diisopropyl ether provide evidence that branching and functional groups strongly impact $\phi$-sensitivity. Further insights into this dependence are obtained with 0-D kinetic simulations with existing mechanisms for n-pentane, diethyl ether, 3-pentanone, n-heptane, 2-methylhexane, 2,4-dimethylpentane, and 2,2,3-trimethylbutane. Quantum mechanical (QM) G4 calculations of low-temperature reactions help explain the observed experimental and simulation trends. Specifically, these QM calculations provide theoretical estimates of the ketohydroperoxide (KHP) dissociation rates, the HO 2 formation rates from peroxy radical (ROO), and the “cross-over” temperatures, i.e., the temperature at which ROO dissociation is favored compared to hydroperoxyl radical (QOOH) formation. Each of these reaction rates is compared to the n-alkane reference point to determine the impact of branching and different functional groups. Although kinetic mechanisms typically assume that KHP dissociation rates are invariant of chemical environment, our QM results suggest that this rate can span a range of roughly two orders of magnitude. We also discuss the importance of including the peroxy-hydroperoxy (OO-OOH) hydrogen transfer reaction for branched ethers. Finally, the insights gained assist in proposing a highly $\phi$-sensitive compound, namely, isopropyl propyl ether.

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

Chemical structure–property relationships in nanocelluloses

Abstract Nanocelluloses, nanoscale cellulosic particles or fibrils, are an appealing class of nanomaterials with enormous potential for sustainable development. They have great promise to target some of the 17 Sustainable Development Goals outlined by the United Nations. Nanocelluloses are derived from the most abundant biopolymer in the world, cellulose, which have multiple hydroxyl groups on their surface, enabling a vast range of chemical modifications. The interplay between the chemical structure and physicochemical properties of nanocelluloses is crucial to engineering the next generation of green, functional nanomaterials. In this review paper, we provide a comprehensive account of the structure–property relationships in nanocelluloses, which may establish the basis for the design of precision bio‐based materials. Chemical modifications of nanocelluloses, including hydrolysis, oxidation, esterification, amidation, and polymer grafting, provide an array of chemical and physical properties that open opportunities in a diverse spectrum of applications. We review how chemical modifications affect the physicochemical properties of nanocelluloses, such as thermal stability, hydrophobicity, and dispersibility in nonpolar media. Understanding nanocellulose chemical structure–property relationships is integral to the development of sustainable material platforms based on the most renewable biopolymer on earth.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Small angle X-ray studies of short-range order in non-stoichiometric pseudoprotic ionic liquids: the influence of chemical structure

Mixtures of organic acids and amines have been studied extensively owing to their unusual physicochemical properties and applications as solvents for extraction. In equimolar ratios they represent pseudoprotic ionic liquids, and in other, “nonstoichiometric” ratios they display a range of odd physicochemical behaviors. We report the results of small-angle X-ray scattering studies of a series of such systems with a range of chemical structures chosen to explore the link between molecular geometry and the character of the emergent nanoscale local liquid structure. We find that while the details vary, structure can emerge even when the hydrogen-bonding character of the components is changed significantly, and the character of their hydrocarbon substituents is altered. The consistent emergence of local order in the face of varying chemical structures indicates that the process is robust. Furthermore, this implies that the emergence of such structure may in fact be far more common in liquid mixtures than is currently recognized, and a great many structures may be suitable for the synthesis of pseudoprotic ionic liquids.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Structural, Chemical, Electrical, and Thermal Properties of n -Type NbFeSb

Here, we report on the structural, chemical, electrical, and thermal properties of n -type polycrystalline NbFeSb synthesized by induction melting of the elements. Although several studies on p -type conduction of this half-Heusler composition have recently been reported, including reports of relatively high thermoelectric properties, very little has been reported on the transport properties of n-type compositions. We combine transport property investigations together with short- and long-range structural data obtained by Mössbauer spectroscopy of iron-57 and antimony-121 and by neutron total scattering, as well as first-principles calculations. In our investigation, we show that n -type conduction can occur from antiphase boundaries in this material. This work is intended to provide a greater understanding of the fundamental properties of NbFeSb as this material continues to be of interest for potential thermoelectric applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Rubidium Fluoride Post-Deposition Treatment: Impact on the Chemical Structure of the Cu(In,Ga)Se 2 Surface and CdS/Cu(In,Ga)Se 2 Interface in Thin-Film Solar Cells

Here, we present a detailed characterization of the chemical structure of the Cu(In,Ga)Se 2 thin-film surface and the CdS/Cu(In,Ga)Se 2 interface, both with and without a RbF post-deposition treatment (RbF-PDT). For this purpose, X-ray photoelectron and Auger electron spectroscopy, as well as synchrotron-based soft X-ray emission spectroscopy have been employed. Although some similarities with the reported impacts of light-element alkali PDT (i.e., NaF- and KF-PDT) are found, we observe some distinct differences, which might be the reason for the further improved conversion efficiency with heavy-element alkali PDT. In particular, we find that the RbF-PDT reduces, but not fully removes, the copper content at the absorber surface and does not induce a significant change in the Ga/(Ga + In) ratio. Additionally, we observe an increased amount of indium and gallium oxides at the surface of the treated absorber. These oxides are partly (in the case of indium) and completely (in the case of gallium) removed from the CdS/Cu(In,Ga)Se 2 interface by the chemical bath deposition of the CdS buffer.

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

Bringing chemical structures to life with augmented reality, machine learning, and quantum chemistry

Visualizing 3D molecular structures is crucial to understanding and predicting their chemical behavior. However, static 2D hand-drawn skeletal structures remain the preferred method of chemical communication. Here, we combine cutting-edge technologies in augmented reality (AR), machine learning, and computational chemistry to develop MolAR, an open-source mobile application for visualizing molecules in AR directly from their hand-drawn chemical structures. Users can also visualize any molecule or protein directly from its name or protein data bank ID and compute chemical properties in real time via quantum chemistry cloud computing. MolAR provides an easily accessible platform for the scientific community to visualize and interact with 3D molecular structures in an immersive and engaging way.

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

Chemical structure and genetic organization of the E. coli O6:K15 capsular polysaccharide

Capsular polysaccharides are important virulence factors in pathogenic bacteria. Characterizing the structural components and biosynthetic pathways for these polysaccharides is key to our ability to design vaccines and other preventative therapies that target encapsulated pathogens. Many gramnegative pathogens such as Neisseria meningitidis and Escherichia coli express acidic capsules. The E. coli K15 serotype has been identifed as both an enterotoxigenic and uropathogenic pathogen. Despite its relevance as a disease-causing serotype, the associated capsular polysaccharide remains poorly characterized. We describe in this report the chemical structure of the K15 polysaccharide, based on chemical analysis and nuclear magnetic resonance (NMR) data. The repeating structure of the K15 polysaccharide consists of 4)-α-GlcpNAc-(1→5)-α-KDOp-(2→partially O-acetylated at 3-hydroxyl of GlcNAc. We also report, the organization of the gene cluster responsible for capsule biosynthesis. We identify genes in this cluster that potentially encode an O-acetyltransferase, an N-acetylglucosamine transferase, and a KDO transferase consistent with the structure we report.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Chemical structure and complex growth modes of magnesium silicate hydrate: Nanoparticle orientation, aggregation, and fusion

The extent of utilization of magnesium silicate hydrate (MSH) in construction is limited partly because of insufficient data ascertaining the kinetics of its precipitation. In this report MSH grown homogeneously or heterogeneously in the range of magnesium to silicon solution molar concentration ratios, [Mg]/[Si] = 0.5-1.5, and temperature = 25-80 °C was analyzed for its chemical structure and morphology. Infrared spectroscopy and geochemical modeling show that increasing the [Mg]/[Si] ratio results in less silicate polymerization in MSH. Atomic force microscopy reveals the presence of nanoparticles that aggregate and fuse to form films. Oriented attachment of nanoparticles and features indicative of enhanced crystallinity were observed at higher temperatures and longer reaction times. These data provide direct evidence for the persistence of hierarchical structures (i.e., nanoparticles forming 3D microparticles and 2D film layers) at the nanoscale to mesoscale. These findings offer insights into the precise chemical synthesis of MSH and its widespread use as a binder for construction purposes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Structural, Chemical, and Dynamical Frustration: Origins of Superionic Conductivity in closo -Borate Solid Electrolytes

Li 2 B 12 H 12 , Na 2 B 12 H 12 , and their closo-borate relatives exhibit unusually high ionic conductivity, making them attractive as a new class of candidate electrolytes in solid-state Li- and Na-ion batteries. However, further optimization of these materials requires a deeper understanding of the fundamental mechanisms underlying ultrafast ion conduction. To this end, we use ab initio molecular dynamics simulations and density-functional calculations to explore the motivations for cation diffusion. We find that superionic behavior in Li 2 B 12 H 12 and Na 2 B 12 H 12 results from a combination of key structural, chemical, and dynamical factors that introduce intrinsic frustration and disorder. A statistical metric is used to show that the structures exhibit a high density of accessible interstitial sites and site types, which correlates with the flatness of the energy landscape and the observed cation mobility. Furthermore, cations are found to dock to specific anion sites, leading to a competition between the geometric symmetry of the anion and the symmetry of the lattice itself, which can facilitate cation hopping. Finally, facile anion reorientations and other low-frequency thermal vibrations lead to fluctuations in the local potential that enhance cation mobility by creating a local driving force for hopping. In conclusion, we discuss the relevance of each factor for developing new ionic conductivity descriptors that can be used for discovery and optimization of closo-borate solid electrolytes, as well as superionic conductors more generally.

25 ENERGY STORAGE↗
DOE OSTI2021

Nitrogen-doped graphene nanomaterials for electrochemical catalysis/reactions: A review on chemical structures and stability

The electronic structure of the carbon-based nanomaterials can be modulated by doping heteroatoms into them. When nitrogen is doped into the graphene structure with different bonding configurations, it changes the material's electronic properties in a variety of ways. Because of the tuned electronic properties, nitrogen-doped graphene (N-G) is applicable in electrochemical systems as catalyst. Despite having tremendous prospects, a holistic view of the structural and functional properties of N-G is still unclear. Moreover, to our knowledge, significant findings on the properties of N-G are not well documented yet, which creates an obstacle to the further improvement of this nanomaterial. Keeping our focus on the catalytic activities, in this paper, we presented an in-detailed review of the overall chemical structure and functional properties of N-G nanomaterials. Starting from the structural properties of major precursor materials for N-G synthesis, we reviewed the physical features and its dependence on the synthesis parameters. Also, a detailed study has been conducted on the key nitrogen functional groups' structural properties, favorable formation environment, influence on the electronic structure of N-G, and role in the catalytic activity. Finally, current progress on the stability of N-G nanocatalysts is reported with an insight into the degradation mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Predicting Sooting Tendencies from Chemical Structure with Experimental and Theoretical Insight

Particulate matter (PM) emissions from internal combustion engines negatively impact public health and global climate. These problems are exacerbated by newer gasoline direct injection engines, which are more fuel-efficient, but also produce more soot than traditional spark ignited engines. Reducing soot formation is therefore of paramount importance in the development of new fuels. A fuel's sooting tendency is a quantitative parameter that describes the sooting behavior of a pure compound or fuel mixture. The yield sooting index (YSI), developed by McEnally and Pfefferle, accurately measures sooting tendencies using small sample quantities. Using an experimental sooting tendency database, we have developed a predictive model for sooting behavior from a quantitative structure-activity relationship (QSAR). It was developed so that input molecules are first decomposed into individual carbon-type fragments for which the sooting tendency contribution can be assigned based on a Bayesian linear regression against the experimental database. The model's predictive accuracy is comparable to its training performance using leave-one-out cross-validation. We have used this model to provide quantitative insights into the effects of chemical structure on soot formation, but excitingly, we have also been able to readily identify the presence of more complicated kinetic sooting mechanisms for structures which are extreme outliers. Oxygenated aromatics can be produced readily from biomass as renewable sources and oxygenated aromatics with very similar structures tend to have a much lower sooting tendency, for example methoxybenzene (anisole, 107), 2-methylphenol (m-cresol, 103), 2-ethylphenol (120), 3-ethylphenol (138) and 1-phenylethanol (142). Thus, the presence of just one oxygen atom in an aromatic compound can drastically alter the reaction pathways leading to soot precursors. We have applied density functional theory (DFT) calculations and flow reactor experiments to examine how oxygenation alters reaction pathways in a combustion environment. This study has allowed us to gain understanding on how the location of an oxygenated functional group influences soot formation. Our work provides a blueprint for the design of oxygenated fuels from biomass, which minimize the production of soot in low oxygen environments.

09 BIOMASS FUELS↗
DOE OSTI2025

Structural, chemical, and electronic control in Co–SiNx granular metals for high-pass filter applications

Granular metals, consisting of nanoscale conducting and insulating regions, have been studied for more than 50 years for fundamental and applied research. Granular metals exhibit non-linear conductivity vs frequency behavior, consistent with the universal power law response, and have recently been suggested for high-pass filter applications. Here, we report that cobalt–silicon nitride (Co–SiNx) granular metals with optimized sputter conditions and post-growth annealing exhibit an exceptional 109 increase in conductivity at 1 MHz compared to the DC conductivity. The improved frequency response is correlated with structural and chemical improvements examined via scanning transmission electron microscopy and x-ray photoemission spectroscopy. While we focus on improvements for high-pass filter applications, the structural, chemical, and electronic control demonstrated here will benefit a variety of granular metal and nanoparticle applications.

Annealing↗