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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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At least 1,279 records · Page 71
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

The Removal of Acid Violet 90 from Aqueous Solutions Using PANI and PANI/Clinoptilolite Composites: Isotherm and Kinetics

Polyaniline (PANI) and polyaniline/Gördes-clinoptilolite (PANI/GC) composite materials were synthesized by the chemical oxidative polymerization technique and used in the adsorption of Acid Violet 90 metal-complex dye (AV 90). The samples were characterized by X-ray diffractions, nitrogen adsorption–desorption isotherms, scanning electron microscopes and Fourier transform infrared. The effect of initial pH (2–8), sorbent dosage (0.5–4.0 g/L) and initial dye concentrations (50–400 mg/L) on adsorption onto PANI and PANI/GC were examined in a batch system. Langmuir, Freundlich and Temkin isotherm models were used to investigate the adsorption mechanism of AV 90 on PANI and PANI/GC. Langmuir isotherm model for PANI/GC and Freundlich isotherm model for PANI were fitted well with the experimental data. The highest dye uptake capacities were obtained with Langmuir isotherm model as 153.85 mg/g and 72.46 mg/g for PANI and PANI/GC, respectively. In order to determine the adsorption kinetics, pseudo first-order and second-order kinetic models were studied. As a result, the adsorption of AV 90 dye on PANI and PANI/GC was better identified with Pseudo second-order kinetic model than the first one.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Dielectric properties of nickel doped bismuth lithium borate glasses

Glasses with composition xBi{sub 2}O{sub 3}•(30-x)Li{sub 2}O•70B{sub 2}O{sub 3} (x = 0, 2, 5, 7 and 10 mol% with codes BLBN1-5 respectively) containing 2 mol% of NiO were prepared via melt-quenching technique and dielectric properties are discussed. The dielectric properties have been studied using impedance spectroscopy. The frequency dependent conductivity investigations for prepared compositions have been carried out using impedance spectroscopy over a frequency range of 1 KHz to 5 MHz and in the temperature range of 300 K-523 K. The complex impedance data have been analyzed by using both the conductivity and the electric modulus formalisms. Standard dielectric behavior is observed in prepared samples. The ac conductivity variations satisfy the Arrhenius relation. The study of the equivalent circuit analysis up to a temperature of 473 K shows a significant change in the equivalent circuit with change in temperature and composition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Surface Film Formation on Al-V Alloys with Far-From-Equilibrium Microstructure

Nanocrystalline supersaturated Al-V alloys produced by high-energy ball milling have been reported to exhibit enhanced corrosion resistance and mechanical properties compared to commercial Al alloys. Corrosion of passive alloys such as Al-V alloy relies on the characteristics of the surface film, which is studied using scanning/transmission electron microscopy and time-of-flight secondary ion mass spectrometry. The effect of microstructure and composition on the surface film has been investigated after different immersion periods (30 min, 2 h, and 1 day) in 0.1 M NaCl. The surface film was complex and composed of oxidized Al and V. The heterogeneous surface film was observed due to the presence of secondary phases and initiation of localized corrosion. The void formation was observed beneath the surface film that would potentially cause pitting corrosion. The generation of nano-sized voids was dependent on grain orientation. Compared to pure Al, the chloride penetration is suppressed in Al-V alloys. The effect of composition and microstructure on surface film formation and attendant corrosion behavior is discussed herein.

36 MATERIALS SCIENCE↗
DOE OSTI2019

In Operando Visualization of the Electrochemical Formation of Liquid Polybromide Microdroplets

Zinc–bromine flow batteries are promising for stationary energy storage, and bromine-complexing agents have been used to form phase-separated liquid polybromide products. However, an understanding of the dynamics of polybromide nucleation is limited due to the beam sensitivity and complexity of polybromides. Here we report an in operando platform composed of dark-field light microscopy and a transparent electrochemical cell to reveal the dynamics of polybromide formation in their native environment. Using our platform, we confirm and reveal the liquid nature, chemical composition, pinning effect (strong interaction with Pt), residual effect (residual charge products on the surface), self-discharging, and over-oxidation of the polybromide products. Overall, the results provide insights into the role of complexing agents and guide the future design of zinc–bromine flow batteries. Furthermore, our in operando platform can potentially be used to study sensitive species and phases in other electrochemical reactions.

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

Sensor Fusion: Comprehensive Real-Time, On-Line Monitoring for Process Control via Visible, Near-Infrared, and Raman Spectroscopy

On-line monitoring based on optical spectroscopy provides unprecedented insight into the chemical composition of process streams or batches. Amplifying this approach through utilizing multiple forms of optical spectroscopy in sensor fusion can greatly expand the number and type of chemical species that can be identified and quantified. This is demonstrated herein, on the analysis of used nuclear fuel recycling streams: highly complex processes with multiple target and interfering analytes. The optical techniques of visible absorbance, near infrared absorbance, and Raman spectroscopy were combined to quantify plutonium (III, IV, VI), uranium (IV, VI), neptunium (IV, V, VI), and nitric acid. Chemometric modeling was used to quantify analytes in process streams in real-time and results were successfully used to enable immediate process control and generation of a product stream at a set composition ratio. This represents a significant step forward in the ability to monitor and control complex chemical processes occurring in harsh chemical environments.

47 OTHER INSTRUMENTATION↗
DOE OSTI2026

Tailoring Thermal and Mechanical Performance Through Multimaterial Laser Powder Directed Energy Deposition of Copper and 17-4PH Stainless Steel

This study investigates the additive manufacturing (AM) processing, microstructural evolution, and resulting mechanical and thermal properties of multimaterial components combining 17-4PH stainless steel and pure copper (Cu) fabricated via laser powder directed energy deposition (LP-DED). Conventional tooling steels exhibit limited thermal conductivity, significantly constraining production throughput in high-volume processes. Incorporating Cu, with its superior thermal conductivity, could significantly enhance tool performance, though Cu and steel present metallurgical incompatibilities when processed via AM. A systematic investigation was conducted across compositions ranging from 0 to 100 wt% Cu, revealing critical thresholds influencing solidification behavior, defect formation, microstructure, hardness, and thermal transport. Optical microscopy, electron backscatter diffraction (EBSD), hardness testing, and thermal conductivity measurements provided comprehensive process–structure–property correlations. Severe hot cracking occurred at low-Cu contents (6–25 wt%), aligning generally well with crack susceptibility modeling, with an unexpected discrepancy at 25 wt%. Porosity remained low (≥99% dense) throughout the compositional spectrum. EBSD analysis revealed a transformation from columnar martensitic structures at low-Cu contents to equiaxed FCC Cu-dominated structures at higher Cu concentrations, highlighting the complex microstructural transitions driven by Cu-induced changes in solidification and phase stability. Hardness decreased from 330 HV (pure 17-4PH) to 62 HV (pure Cu), consistent with microstructural changes. Concurrently, thermal conductivity improved substantially from 13.5 W/m K to 367.9 W/m K, emphasizing Cu’s dominant role in thermal transport. The findings highlight the feasibility of leveraging compositional gradients between 17-4PH and Cu to achieve tailored tooling with optimized thermal and mechanical performance.

17-4PH↗
DOE OSTI2020

Encoding Multilayer Complexity in Anti‐Counterfeiting Heterometallic MOF‐Based Optical Tags

Abstract Optical tags provide a way to quickly and unambiguously identify valuable assets. Current tag fluorophore options lack the tunability to allow combined methods of encoding in a single material. Herein we report a design strategy to encode multilayer complexity in a family of heterometallic rare‐earth metal–organic frameworks based on highly connected nonanuclear clusters. To impart both intricacy and security, a synergistic approach was implemented resulting in both overt (visible) and covert (near‐infrared, NIR) properties, with concomitant multi‐emissive spectra and tunable luminescence lifetimes. Tag authentication is validated with a variety of orthogonal detection methodologies. Importantly, the effect induced by subtle compositional changes on intermetallic energy transfer, and thus on the resulting photophysical properties, is demonstrated. This strategy can be widely implemented to create a large library of highly complex, difficult‐to‐counterfeit optical tags.

Deneff, Jacob I.↗
DOE OSTI2017

Strength, toughness, and reliability of a porous glass/biopolymer composite scaffold

Abstract Development of bioactive glass and ceramic scaffolds intended for the reconstruction of large segmental bone defects remains a challenge for materials science due to the complexities involved in clinical implantation, bone–implant reaction, implant degradation and the multiple loading modes the implants subjected to. A comprehensive evaluation of the mechanical properties of inorganic scaffolds and exploration of new ways to toughen brittle constructs are critical prior to their successful application in loaded sites. A simple and widely adopted approach involves the coating of an inorganic scaffold with a polymeric material. In this work, a systematic evaluation of the influence of a biopolymer, polycaprolactone (PCL), coating on the mechanical performance of bioactive glass scaffolds was carried out. Results from this work indicate that a biopolymer PCL coating was more effective in increasing the compressive strength and reliability of the glass scaffold under compression, but less effective in improving its flexural strength or fracture toughness. This is the first report that reveals the limited successfulness of a polymer coating in improving the toughness of strong scaffolds, suggesting that new and novel ways of toughening inorganic scaffolds should be future research directions for scaffolds applied in loaded sites. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1209–1217, 2018.

Fu, Qiang↗
DOE OSTI2023

Freeform thermoelectrics in single-step manufacturing: additive manufacturing of bismuth-telluride thermoelectrics

The project succeeded in producing crack-free Bismuth Telluride thermoelectric parts with density exceeding 98% through laser powder bed fusion (LPBF) additive manufacturing (AM). This greatly exceeded the highest previously reported density of 88% and is the highest among all semiconducting materials processed by LPBF. The additively manufactured material shows comparable Seebeck coefficient as conventional form and can be made into complex geometries with reduced material loss. On the other hand, measured properties are dramatically sensitive to the AM process parameters used, such that with identical composition, the Seebeck coefficient can be controllably tuned from +120 µV/K to -207 µV/K, which means the material switches between an n-type to a p-type semiconductor depending on processing. These changes are accompanied by significant differences in the as-processed microstructure due to rapid solidification. A machine learning protocol was developed and greatly reduced the experimental burden of the project, reducing the typical process optimization period of 2 years to 6 months. The project was fully successful in the objective of producing defect-free, complex geometry of bismuth-telluride parts through LPBF, but only partially successful in achieving performance goals. First, cost reduction of manufacturing, as measured by material waste, was successfully reduced by up to 70% compared to conventional manufacturing methods. This exceeded the proposed 30% reduction in materials waste needed to reach the 20% cost reduction goal of the project. On the other hand, the device performance, as measured by Seebeck coefficient, failed to reach the 40% improvement in efficiency. Rather, we observe comparable Seebeck coefficient between AM samples and conventionally processed counterparts. The device-level efficiency improvement does exceed 40% for complex geometry samples due to shape-induced increase in temperature gradients, but this was not the originally proposed metric. The machine learning approach developed in this project greatly accelerated the process optimization and can be adopted for fast development of AM processing parameters for other brittle and otherwise difficult-to-print materials. For the public, we deliver an efficient and widely adoptable process for incorporating waste-heat harvesting thermoelectric devices in both industrial and commercial heat exchangers. The geometric flexibility allows the capturing device to conform to the shape of the heat source to improve the system-level conversion efficiency. The technique can be deployed on any commercial LBPF systems with zero modifications, thus poses minimal adoption barrier for any manufacturer that already employed AM technology. Beyond bismuth-telluride, the machine-learning guided optimization protocol can be used in the future to reduce both the time and cost of process development for AM of other energy conversion and harvesting materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Geographic patterns and determinants of antibiotic resistomes in coastal sediments across complex ecological gradients

Coastal areas are highly influenced by terrestrial runoffs and anthropogenic disturbances, commonly leading to ecological gradients from bay, nearshore, to offshore areas. Although the occurrence and distribution of sediment antibiotic resistome are explored in various coastal environments, little information is available regarding geographic patterns and determinants of coastal sediment antibiotic resistomes across ecological gradients at the regional scale. Here, using high-throughput quantitative PCR, we investigated the geographic patterns of 285 antibiotic resistance genes (ARGs) in coastal sediments across a ~ 200 km scale in the East China Sea. Sediment bacterial communities and physicochemical properties were characterized to identify the determinants of sediments antibiotic resistome. Higher richness and abundance of ARGs were detected in the bay samples compared with those in nearshore and offshore samples, and significant negative correlations between the richness and/or abundance of ARGs and the distance to coastline (DTC) were identified, whereas different types of ARGs showed inconsistency in their relationships with DTC. The composition of antibiotic resistome showed significant correlations with nutrition-related variables (including NH 4 + -N, NO 3 − -N, and total phosphorus) and metals/metalloid (including As, Cu, Ni, and Zn), suggesting that terrestrial disturbances largely shape the antibiotic resistome. The Bipartite network showed strong associations between ARGs and mobile genetic elements (MGEs), and Partial Least Squares Path Modeling further revealed that terrestrial disturbance strength (as indicated by DTC) directly affected abiotic environmental conditions and bacterial community composition, and indirectly affected antibiotic resistome via MGEs. These findings provide insights into regional variability of sediment antibiotic resistome and its shaping path across complex ecological gradients, highlighting terrestrial disturbances as determinative forces in shaping coastal sediment antibiotic resistomes.

Xiong, Shangling↗
DOE OSTI2025

Dynamics and lipid membrane coupling of the RAS-RAF complex revealed via multiscale simulations

To gain molecular and mechanistic insights into initiation of the RAS-RAF signaling cascade, we developed and used a combination of multiscale simulation and experimental approaches. The influence and impact of the membrane on RAS and RAF proteins is a factor we are just beginning to understand and appreciate in more detail. Molecular simulation is an ideal methodology to further study this complicated relationship between the membrane and associated proteins. Our previous work using Multiscale Machine-learned Modeling Infrastructure investigated different lipid compositions solely around the KRAS4b protein and the interplay between protein behavior and these membrane environments. Multiscale Machine-learned Modeling Infrastructure uses machine learning to couple adjacent simulation scales and has been efficiently scaled across some of the world’s largest high-performance computers. Recently, we have expanded this multiresolution framework to include the all-atom simulation scale and to incorporate the RAF RBDCRD domains. Here, we present the overall analysis results from this new simulation campaign comprising a mixture of RAS and RAF RBDCRD proteins. Approximately 35,000 coarse-grained and 10,000 all-atom molecular dynamics simulations were completed, sampled from a variety of protein/lipid composition configurations that were generated from a micron-scale continuum simulation containing hundreds of copies of the proteins. Our studies suggest that orientations of the RAS-RBDCRD complex on the membrane occupy distinct configurational states, and the spatial patterns of lipid arrangements around these different protein states are unique to each state. The extent and size of lipid “fingerprints” imposed on the membrane by the RAS-RBDCRD protein complex are significantly larger than observed for just the RAS protein on its own. These protein complexes strongly associate, but we do not observe statistically significant preferred protein-protein orientations. These observations indicate that spatial colocalization of RAS-RBDCRD proteins in the same vicinity may be assisted by specific membrane environments, acting to increase the probability of signaling complex formation.

Carpenter, Timothy S. [Lawrence Livermore National↗
DOE OSTI2020

Progress in Understanding the Origins of Excellent Corrosion Resistance in Metallic Alloys: From Binary Polycrystalline Alloys to Metallic Glasses and High Entropy Alloys

Some of the factors responsible for good corrosion resistance of select polycrystalline and emerging alloys in chloride solutions are discussed with a goal of providing some perspectives on the current status and future directions. Traditional metallic glass alloys, single phase high entropy alloys (HEAs), early metallic glasses, and high entropy metallic glasses are all emerging corrosion-resistant alloys (CRAs) that utilize traditional strategies for improved corrosion resistance as well as take advantage of some other novel beneficial attributes. These materials enjoy many degrees of freedom as far as choice of both composition and structure, providing great flexibility in the pursuit of superior corrosion resistance. The new materials depart from classical solvent-solute type polycrystalline binary or ternary alloys. Thus, such emerging materials provide significant opportunities to achieve even greater improvements in corrosion resistance in harsh environments. Several examples of the unique corrosion properties of selected materials in the context of modern theories of corrosion are discussed herein. Discussion is restricted to solid-solution binary or ternary polycrystalline alloys, several metallic glass alloys, and single phase HEAs. A common feature of many CRAs is that composition and microstructure often affect both passivity and resistance to localized corrosion that can be divided into initiation, stabilization, and propagation stages. Enormous complexities in protective oxide structures and chemistries and the large number of combinatorial possibilities in newer materials such as HEAs preclude trial-and-error approaches and perhaps even combinatorial experimental design. Computational materials methodologies will be required in the search for new corrosion-resistant alloys in these material classes. The search must consider the best scientific insights available regarding how major and minor alloy additions, as well as various microstructural attributes, contribute to corrosion mitigation. Additional scientific insights, as they emerge, will enable choices beyond the reliance on high concentrations of alloying elements that are known to affect passivity breakdown and pit stabilization. A challenge is to connect the “basic attributes” of an alloy with its properties. The strength of this connection will likely require new scientific principles enabling deep multiphysics insights in order to link feature(s) such as composition and metallurgical phases to the desired corrosion properties. Application of data informatics will likely also play a role given the plethora of variables that are important in corrosion and the difficulty in assessing all relationships. Here, the opportunity exists to accelerate the design of emerging materials for high corrosion resistance.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Encoding Multilayer Complexity in Anti-Counterfeiting Heterometallic MOF-based Optical Tags

Optical tags provide a way to quickly and unambiguously identify valuable assets. Current tag fluorophore options lack the tunability to allow combined methods of encoding in a single material. Here we report a design strategy to encode multilayer complexity in a family of heterometallic rare-earth metal-organic frameworks based on highly connected nonanuclear clusters. To impart both intricacy and security, a synergistic approach was implemented resulting in both overt (visible) and covert (near infrared, NIR) properties, with concomitant multi-emissive spectra and tunable luminescence lifetimes. Tag authentication is validated with a variety of orthogonal detection methodologies. Importantly, the effect induced by subtle compositional changes on intermetallic energy transfer, and thus on the resulting photophysical properties, is demonstrated. This strategy can be widely implemented to create a large library of highly complex, difficult to counterfeit optical tags.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Directing the phase behavior of polyelectrolyte complexes using chiral patterned peptides

Polyelectrolyte complexes (PECs) have a broad range of promising applications as soft materials due to their self-assembly and diversity of structure and chemical composition. Peptide polymer PECs are highly biocompatible and biodegradable, making them particularly useful for encapsulation of food additives and flavors, micellar drug delivery, medical and underwater adhesives, fetal membrane patches, and scaffolds for cell growth in tissue engineering. While parameters affecting PEC formation and stability in regards to charge effects are well researched, little is known about the effects of van der Waals interactions, hydrogen bonding, and secondary structure in these materials. Peptide chirality provides a unique opportunity to manipulate PEC phase to modulate the amount of solid-like (precipitate) or liquid-like (coacervate) character by influencing hydrogen bonding interactions among peptide chains. In previous work, we showed that chiral peptides form solid complexes, while complexes with even one racemic peptide were fluid. This raised the interesting question of how long a homochiral sequence must be to result in solid phase formation. In this work, we designed chiral patterned peptides of polyglutamic acid and polylysine ranging from 50 to 90% L-chiral residues with increasing numbers of sequential L-chiral residues before a chirality change. These polymers were mixed together to form PECs. We observed that 8 or more sequential L-chiral residues are necessary to achieve both the appearance of a precipitate phase and sustained beta-sheets in the complex, as determined by optical imaging and FTIR Spectroscopy. Less homochiral content results in formation of a coacervate phase. Thus, we show that chiral sequence can be used to control the phase transition of PECs. Understanding how to manipulate PEC phase using chiral sequence as presented here may enable tuning of the material properties to achieve the desired mechanical strength for coatings and polymer brushes, or the most effective molecular release kinetics for drug delivery applications, for example.

Pacalin, Naomi M.↗
DOE OSTI2022

Probing multiscale dissolution dynamics in natural rocks through microfluidics and compositional analysis

Mineral dissolution significantly impacts many geological systems. Carbon released by diagenesis, carbon sequestration, and acid injection are examples where geochemical reactions, fluid flow, and solute transport are strongly coupled. The complexity in these systems involves interplay between various mechanisms that operate at timescales ranging from microseconds to years. Current experimental techniques characterize dissolution processes using static images that are acquired with long measurement times and/or low spatial resolution. These limitations prevent direct observation of how dissolution reactions progress within an intact rock with spatially heterogeneous mineralogy and morphology. We utilize microfluidic cells embedded with thin rock samples to visualize dissolution with significant temporal resolution (100 ms) in a large observation window (3 × 3 mm). Here we injected acidic fluid into eight shale samples ranging from 8 to 86 wt % carbonate. The pre- and postreaction microstructures are characterized at the scale of pores (0.1 to 1 µm) and fractures (1 to 1,000 µm). We observe that nonreactive particle exposure, fracture morphology, and loss of rock strength are strongly dependent on both the relative volume of reactive grains and their distribution. Time-resolved images of the rock unveil the spatiotemporal dynamics of dissolution, including two-phase flow effects in real time and illustrate the changes in the fracture interface across the range of compositions. Moreover, the dynamical data provide an approach for characterizing reactivity parameters of natural heterogeneous samples when porous media effects are not negligible. The platform and workflow provide real-time characterization of geochemical reactions and inform various subsurface engineering processes.

58 GEOSCIENCES↗
DOE OSTI2023

On the Interfacial Assembly of Anisotropic Amphiphilic Janus Particles

It has been shown both theoretically and experimentally that amphiphilic Janus particles are the most effective solid surfactants to stabilize interfaces. In most cases, the Janus particles investigated have uniform morphologies with Janus boundaries dividing the particle into halves. However, there are many examples of Janus particles where the hydrophilic and hydrophobic domains are not equally distributed. The effects of this uneven domain distribution on the mechanism and kinetics of Janus particle assembly, and final equilibrium state are not well-understood. Dynamic pendant drop tensiometry offers a means to probe both the equilibrium assembly and the kinetics and mechanism of assembly. Here, in this work, the interfacial kinetics and assembly of spherical anisotropic Janus particles are investigated using dynamic pendant drop tensiometry. Systematic studies quantifying the time-dependent interfacial behavior as a function of Janus particle morphology, chemical composition, particle concentration, and NaOH and HCl concentration are performed. These studies shed light on the assembly mechanism of more complex Janus particle morphologies and highlight their effectiveness as interface stabilizers.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Divergent Stabilities of Tetravalent Cerium, Uranium, and Neptunium Imidophosphorane Complexes**

Abstract The study of the redox chemistry of mid‐actinides (U−Pu) has historically relied on cerium as a model, due to the accessibility of trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts of lanthanide 4+/3+ non‐aqueous redox couples have been established within a homoleptic imidophosphorane ligand framework. Herein we extend the chemistry of the imidophosphorane ligand (NPC=[N=P t Bu(pyrr) 2 ] − ; pyrr=pyrrolidinyl) to tetrahomoleptic NPC complexes of neptunium and cerium ( 1‐M , 2‐M , M=Np, Ce) and present comparative structural, electrochemical, and theoretical studies of these complexes. Large cathodic shifts in the M 4+/3+ (M=Ce, U, Np) couples underpin the stabilization of higher metal oxidation states owing to the strongly donating nature of the NPC ligands, providing access to the U 5+/4+ , U 6+/5+ , and to an unprecedented, well‐behaved Np 5+/4+ redox couple. The differences in the chemical redox properties of the U vs . Ce and Np complexes are rationalized based on their redox potentials, degree of structural rearrangement upon reduction/oxidation, relative molecular orbital energies, and orbital composition analyses employing density functional theory.

Otte, Kaitlyn S.↗