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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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49 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1982

Fracture mechanics in fiber reinforced composite materials, taking as examples B/A1 and CRFP

The validity of linear elastic fracture mechanics and other fracture criteria was investigated with laminates of boron fiber reinforced aluminum (R/A1) and of carbon fiber reinforced epoxide (CFRP). Cracks are assessed by fracture strength Kc or Kmax (critical or maximum value of the stress intensity factor). The Whitney and Nuismer point stress criterion and average stress criterion often show that Kmax of fiber composite materials increases with increasing crack length; however, for R/A1 and CFRP the curve showing fracture strength as a function of crack length is only applicable in a small domain. For R/A1, the reason is clearly the extension of the plastic zone (or the damage zone n the case of CFRP) which cannot be described with a stress intensity factor.

Peters, P. W. M.↗
DOE OSTI2026

Direct Observation of Hydroxyls Formed from Water and Oxygen on Ag(100)

The interaction of oxygen with silver is a key descriptor of the catalytic reactivity of silver nanoparticles which are ubiquitous in large-scale partial oxidation reactions like ethylene epoxidation. Despite Ag(100) being proposed as the most selective facet, it is less studied than (111) and (110) surfaces. Using scanning tunneling microscopy and synchrotron X-ray photoelectron spectroscopy, we report that, in addition to the well-known O adatoms formed from O 2 dissociation on Ag(100), hydroxyl groups (OH), at a binding energy of ∼ 531 eV, are also present. The O/OH ratio depends on exposure to water and surface temperature. These assignments are consistent with our density functional theory calculations, which indicate that the formation of two OH groups from an O atom and H 2 O molecule is exothermic. These results indicate that, in addition to O, OH is present even under ultrahigh vacuum conditions and therefore should be considered in proposed catalytic pathways.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Polyhydroxybutyrate laminated trilayer films with enhanced barrier and mechanical properties for active food packaging

Polysaccharides such as starch and chitosan have been explored for sustainable food packaging films. However, their inherent hydrophilicity and brittleness cause poor water vapor barrier performance and limited mechanical properties. To address these issues, starch was first functionalized with acetoacetate groups and subsequently blended with chitosan. Dynamic cross-linking occurred between the acetoacetate groups and the primary amine groups of chitosan, forming vinylogous urethane linkages that reduced the water solubility of the films while preserving high mechanical strength. With 30 wt% of glycerol as a plasticizer, the resulting films showed a tensile strength of up to 24.68 MPa and an elongation at break of up to 83.96%. To improve the barrier properties, poly(3-hydroxybutyrate) (PHB), plasticized with 5-15 wt% epoxidized vegetable oil, was laminated on top of the chitosan/modified starch films, resulting in a significantly reduced water vapor transmission rate (WVTR) of 66%. Additional components, such as food colors like β-carotene were incorporated into this layer to make UV-protective films. A third layer of PHB without active additives was then coated to further reduce WVTR by 99%. Therefore, this multilayer lamination strategy effectively enhanced the barrier and mechanical properties of the polysaccharide-based packaging films.

Active packaging↗
DOE OSTI2025

Benchmarking DFT Accuracy in Predicting O 1s Binding Energies on Metals

X-ray photoelectron spectroscopy (XPS) is a powerful tool for probing the electronic structure and composition of materials, particularly metals and metal oxides of relevance to solar cells and catalysis. Density functional theory (DFT) is often used to support XPS peak assignments, but its reliability for predicting oxygen species is not well established. Here, we compile a large data set of experimental oxygen binding energies and evaluate corresponding DFT predictions. We find that as the binding energies of metal-bound atomic oxygen species increase, especially above ≈530 eV, there is a general decrease in the accuracy of DFTpredicted values. Thus, high-binding-energy atomic oxygen species, such as those proposed as active for selective Ag-catalyzed epoxidation, are less well represented. The chemical nature of the oxygen species also influences accuracy, with molecularly bound species more reliably captured across the entire range of energies. These findings illustrate the limitations of DFT for interpreting XPS spectra and provide a benchmark for improving computational methods.

Adsorption↗
DOE OSTI2026

Low Temperature Oxygen Activation on the NiAg(100) Single-Atom Alloy Surface

Silver-catalyzed ethylene epoxidation remains the only industrially viable route for ethylene oxide (EO) production. However, this process requires chlorine and other promoters to achieve a high EO selectivity while still generating substantial CO 2 emissions. A recent theory-guided approach identified Ni, in single-atom alloy (SAA) form, as a new promoter of this reaction. Specifically, the addition of Ni to Ag nanoparticles supported on α-Al 2 O 3 at a highly diluted ratio (1 Ni per 200 Ag atoms) increased catalyst selectivity to EO by ∼25%, the same increase afforded by the ubiquitous industrial promoter chlorine. To better understand the effect of Ni, we investigated the interaction of O 2 with NiAg(100) SAA surfaces by using scanning tunneling microscopy (STM) and density functional theory (DFT). While only molecular O 2 was present when pure Ag(100) was exposed to O 2 at 78 K, a distinct NiO 2 species, indicative of O 2 dissociation at Ni atom sites, was identified on the NiAg(100) SAA under the same conditions. High-resolution STM imaging backed by DFT simulations elucidated the formation of an O−Ni−O species with the oxygen atoms in 4-fold hollow sites. These findings provide direct experimental evidence that Ni atoms are very effective at O 2 activation, even at cryogenic temperatures. This suggests that, in addition to the known role of Ni in stabilizing the unselective nucleophilic oxygen on Ag, it could also accelerate O 2 dissociation, which can be rate limiting.

Catalysts↗
DOE OSTI2021

Effects of surface species and homogeneous reactions on rates and selectivity in ethane oxidation on oxide catalysts

Selective alkane oxidations on metal oxide catalysts involve complex mechanisms with multiple reactions in series and parallel, different types of reduced and oxidized surface species, and potential contributions from gas-phase reactions. We report kinetics and thermodynamics of elementary steps involved in C 2 H 6 -O 2 reactions on SiO 2 -supported small vanadium oxide domains are determined using density functional theory. These surface reactions together with gas-phase mechanisms are incorporated in kinetic simulations to determine how surface and gaseous reactions interact and contribute to rates and selectivity. The results show that gas-phase reactions within pore volumes in contact with the catalyst contribute significantly to C 2 H 6 activation rates, even at conditions where gas-phase reactions in empty volumes without catalyst are negligible. The majority of C 2 H 6 activations occur on the surface, via H abstraction by vanadium oxo species present at terminal lattice oxygens. The gas-phase activations via H-abstraction by OH radicals also exhibit significant contributions. The reduced centers formed by reactions at vanadium oxo species are re-oxidized rapidly and, therefore, are present in very small concentrations at reaction conditions. The re-oxidation steps lead to the formation of HO 2 radicals and surface peroxo species that are also rapidly consumed and are present in small concentrations. The peroxo species preferentially convert C 2 H 4 to its epoxide product and influence selectivity even at low concentrations. The gas-phase reactions decrease the concentrations of peroxo species and improve selectivity slightly. The effects of reaction conditions and catalyst site density provide further insights into how factors beyond conversions at lattice oxygens influence rates and selectivity in alkane oxidation reactions of significant industrial importance.

42 ENGINEERING↗
DOE OSTI2026

Effect of Solvent on the Local Structure, Dynamics, and Vibrational Density of States in Sn-BEA Zeolite

Lewis acid zeolites are attractive catalysts for epoxidation and biomass valorization, as they are highly active and selective in the liquid phase and can operate at or near ambient conditions. While a rich experimental literature exists on liquid-phase Lewis acid zeolite catalysis, our understanding of the molecular organization and solvent dynamics in the vicinity of Lewis acid sites with differing metal site speciation remains limited. In this work, we investigate the molecular coordination and diffusion of two common solvents (methanol and water) around the closed and open Sn-BEA zeolite active sites using molecular dynamics simulations with a machine-learned interatomic potential trained on ab initio molecular dynamics trajectories. Molecular dynamics simulations reveal that introducing active sites significantly enhances local order in the first and second solvation shells compared to the pure silica case. For methanol, both closed and open active sites are singly coordinated, while more than two water molecules coordinate the open site. In contrast to methanol, we observed that water molecules dissociate, leading to the formation of additional Sn-OH and silanol groups away from the active site. The diffusion coefficients of water and methanol are functions of the solvent population in the pore. Here, our work provides insights into how active site speciation in Lewis acid zeolites affects solvent coordination, diffusion, and vibrational signature. This information is foundational for catalyst design and optimization of liquid-phase catalytic processes in zeolites. It also demonstrates the suitability of machine-learned interatomic potentials for modeling reactive systems, enabling sufficiently long trajectories for appropriate statistical averaging.

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

Evaluating the Origins of Aerobic Oxidation Catalysis with TAM-3, a MOF with Accessible Co(II) Sites and Large Pores

Metal-organic frameworks (MOFs) are attractive platforms that merge concepts of homogeneous and heterogeneous catalysis. Catalyst design and optimization are enabled by an array of synthetic methods that offer independent control over the local chemical structure of lattice-embedded metal ions (i.e., ligand identity and geometry) and the long-range materials properties (i.e., porosity). Establishing the origin of catalytic activity in MOF-promoted reactions remains a significant challenge: The relative rates of catalyst turnover and substrate diffusion dictate the extent to which interstitial sites are accessible and operational in catalysis. To minimize the contributions of surface sites in catalysis, materials with large pore dimensions are often sought, however, the impact of pore expansion on the origins of catalytic activity is similarly challenging to establish. Here, we describe TAM-3, a Co(II) based MOF with accessible metal sites supported by a facially coordinating tris-tetrazole ligand set. TAM-3 features large channel-like pores (17 × 23 Å) and promotes aerobic C−H oxidation and olefin epoxidation. Using a set of simple kinetics experiments, based on the analysis of kinetic isotope effects and olefin oxidation diastereoselectivities, we demonstrate that despite the large pores, interstitial metal ions do not significantly contribute to the observed substrate oxidation. This study highlights the importance of conducting kinetic experiments to assess the origin of apparent catalytic activity with MOFs and the challenge of harnessing reactive oxidants with microporous catalyst materials.

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

Effects of the method of active site characterization for determining structure-sensitivity in Ag-catalyzed ethylene epoxidation

We report catalysts have been prepared on a low surface area α-Al 2 O 3 support used commercially for previous generation olefin epoxidation catalysts. Prescreening of the low surface area alumina (0.73 m 2 /g) indicated the absence of acid catalyzed isomerization of EO at an evaluation temperature of 210 °C. A 0.1 wt% Ag base material synthesized by incipient wetness impregnation of AgNO 3 was used as a base material for electroless deposition (ED) of additional Ag to increase particle sizes by controlled reduction of Ag + directly onto the preexisting Ag surface to form weight loadings between 0.3 and 5.0 wt% metal. A 12 wt% Ag/α-Al 2 O 3 using Ag 2 C 2 O 4 as the Ag precursor was also prepared to compare performance of the ED samples with a catalyst more typical of industrial formulations. Characterization by SEM, STEM, and hydrogen titration of oxygen precovered Ag characterized before and after catalytic evaluation indicated that microscopy is required to accurately represent distributions of Ag particle sizes, but H 2 titration of O-precovered Ag gives the best representation of active sites since it directly counts the number of Ag surface sites. Larger particles >100 nm are resistant to both Ag sintering and carbon foulant; TOF values were relatively insensitive to particle size with only a 2.2 × difference between the best and worst performing samples. Selectivity, which is not a function of TOF, shows the most significant structure sensitivity effect where particle sizes follow the trend 67 nm ≈ 92 nm (58% EO) < 157 nm (67% EO) < 211–542 nm (73% EO). The lower EO selectivities were also correlated with increased fouling for the smaller Ag sizes, suggesting that more strongly bound EO precursor(s) leads to combustion and CO 2 /H 2 O formation.

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

Similarities and Differences in the Effects of Toxic Concentrations of Cadmium and Chromium on the Structure and Functions of Thylakoid Membranes in Chlorella variabilis

Trace metal contaminations in natural waters, wetlands, and wastewaters pose serious threats to aquatic ecosystems—mainly via targeting microalgae. In this work, we investigated the effects of toxic amounts of chromium and cadmium ions on the structure and function of the photosynthetic machinery of Chlorella variabilis cells. To halt the propagation of cells, we used high concentrations of Cd and Cr, 50–50 mg L –1 , in the forms of CdCl 2 x 2.5 H 2 O and K 2 Cr 2 O 7 , respectively. Both treatments led to similar, about 50% gradual diminishment of the chlorophyll contents of the cells in 48 h, which was, however, accompanied by a small (~10%) but statistically significant enrichment (Cd) and loss (Cr) of ß-carotene. Both Cd and Cr inhibited the activity of photosystem II (PSII)—but with more severe inhibitions with Cr. On the contrary, the PsbA (D1) protein of PSII and the PsbO protein of the oxygen-evolving complex were retained more in Cr-treated cells than in the presence of Cd. These data and the higher susceptibility of P700 redox transients in Cr-treated cells suggest that, unlike with Cd, PSII is not the main target in the photochemical apparatus. These differences at the level of photochemistry also brought about dissimilarities at higher levels of the structural complexity of the photosynthetic apparatus. Circular dichroism (CD) spectroscopy measurements revealed moderate perturbations in the macro-organization of the protein complexes—with more pronounced decline in Cd-treated cells than in the cells with Cr. Also, as reflected by transmission electron microscopy and small-angle neutron scattering, the thylakoid membranes suffered shrinking and were largely fragmented in Cd-treated cells, whereas no changes could be discerned with Cr. The preservation of integrity of membranes in Cr-treated cells was most probably aided by high proportion of the de-epoxidized xanthophylls, which were absent with Cd. It can thus be concluded that beside strong similarities of the toxic effects of Cr and Cd, the response of the photosynthetic machinery of C. variabilis to these two trace metal ions substantially differ from each other—strongly suggesting different inhibitory and protective mechanisms following the primary toxic events.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Stable yet hydrophilic graphene oxide nanomembranes by zwitterionic reduction for dye desalination

Holey graphene oxide (HGO) nanosheets have emerged as a promising membrane platform for dye desalination, and they must be reduced to enhance hydrophobicity and stability for long-term underwater operation, which usually decreases water and salt permeance. Herein, we develop a facile method to stabilize HGO nanosheets while retaining their hydrophilicity by reducing them with sulfobetaine amine (SBAm, a superhydrophilic zwitterion), achieving high water and salt permeance and a high salt/dye separation factor. Specifically, HGO nanosheets react with SBAm via an amine-epoxide reaction, rendering reduced HGO nanosheets containing superhydrophilic zwitterions. The effects of in-plane pores, zwitterion content, and layer thickness on the membrane chemistry, structure, and salt/dye separation properties of the SBAm-reduced HGOs (SHGOs) are thoroughly examined. The membrane achieves a Na 2 SO 4 /Direct red separation factor of up to 850, surpassing the state-of-the-art GO membranes. Moreover, hollow fiber membrane modules based on SHGOs are fabricated and exhibit stable performance in multi-cycle tests over 100 h of operation with mixed dye-salt solutions, demonstrating the scalability of our approach and its potential for practical applications.

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

The interpenetration polymer network in a cement paste–waterborne epoxy system

The formation of the interpenetrating polymer network (IPN) structure within the cement-polymer system has been revealed by experiments from 2 dimensional to 3-dimensional scales. However, the microstructure design and performance prediction of IPN as a function of specific C-S-H/polymer components or ingredients' parameters e.g. water to cement ratios (w/c), polymer to cement ratios (p/c), monomer components, degree of polymerization (DP), etc. is by far not available. Here we developed a mesoscale model for IPN visualization based on the Flory-Huggins interaction theory which was applied to cement science for the first time. All the ingredients in the micro-structure were considered as soluble beads with rational sizes based on their properties obtained by molecular dynamic methods. The interaction parameters of each bead were then determined based on their element ratios and chemical backbones. The model was validated with the waterborne epoxy-cement material (WECM) in which a novel waterborne epoxy resin (WEP) was prepared and impregnated. The verification results on the 2D-3D scale show that the developed model predicts the WECM's IPN structures by rule and line concerning DP, w/c, and p/c in the mixture. The C-S-H beads were progressively scaled in size which alters the C-S-H texture to have completely different dissolution characteristics. Beads of diameter ~6 Å are more unstable and soluble which enable them to form a continuous phase in water or a composite structure with WEP. In contrast, beads with diameters larger than 10 Å have different properties with stronger nucleation effects. The results also suggest the impregnation content of WEP in cement-based material should be limited to 10% vol. to prevent the polymer IPN from decomposing into discrete clusters. The application of Flory-Huggins theory in cement-based composites demonstrates great potential in performance prediction and microstructure design.

36 MATERIALS SCIENCE↗