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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Inkless, dry printing nanographene via in-Situ Coordinated laser ablation and sintering processes

Printing carbon, such as graphene and other carbon structures, for flexible and printed electronics currently relies on either ink-based printing, laser-induced forward transfer (LIFT), or laser-induced graphitization (LIG) to convert carbon-rich precursor materials, such as polymers, to graphene-like carbon structures. Liquid inks contain toxic solvents, surfactants, and stabilizing additives that degrade electrical conductivity and require high-temperature post-processing. On the other hand, LIG is limited by the substrate. Here, this study introduces an additive manufacturing method for dry-printing carbon nanomaterials, ranging from amorphous carbon to crystalline graphene-like structures, on various substrates. The system utilizes laser ablation of a solid graphite target to create pure carbon nanoparticles in situ and on demand. An inert gas carries the nanoparticles onto the substrate, where they can be deposited either as amorphous structures or laser-sintered in real time to form various graphitic structures. The study of laser processing parameters, specifically fluence and pulse repetition frequency, revealed three unique regimes of nanostructure evolution that influence the morphological and electrical properties of these printed structures. Raman spectroscopy confirmed graphitization with a resistivity slightly higher than that of the bulk graphite target. The conductivity/resistivity could be tuned as a function of sintering laser power. Scanning transmission electron microscopy (STEM) revealed that turbostratic nanographene formed with an interlayer spacing of 0.40 nm. Despite ink-based printing methods, such as screen printing, inkjet printing (IJP), and aerosol jet printing (AJP), this eco-friendly and green manufacturing technique could eliminate toxic chemicals, reduce environmental impact, and enable single-step fabrication of carbon-based devices for applications in wearable sensors, energy storage, flexible electronics, and Internet of Things (IoT) devices.

Additive nanomanufacturing↗
DOE OSTI2022

Closo ‐Borate Gel Polymer Electrolyte with Remarkable Electrochemical Stability and a Wide Operating Temperature Window

Abstract A major challenge in the pursuit of higher‐energy‐density lithium batteries for carbon‐neutral‐mobility is electrolyte compatibility with a lithium metal electrode. This study demonstrates the robust and stable nature of a closo ‐borate based gel polymer electrolyte (GPE), which enables outstanding electrochemical stability and capacity retention upon extensive cycling. The GPE developed herein has an ionic conductivity of 7.3 × 10 −4 S cm −2 at room temperature and stability over a wide temperature range from −35 to 80 °C with a high lithium transference number ( = 0.51). Multinuclear nuclear magnetic resonance and Fourier transform infrared are used to understand the solvation environment and interaction between the GPE components. Density functional theory calculations are leveraged to gain additional insight into the coordination environment and support spectroscopic interpretations. The GPE is also established to be a suitable electrolyte for extended cycling with four different active electrode materials when paired with a lithium metal electrode. The GPE can also be incorporated into a flexible battery that is capable of being cut and still functional. The incorporation of a closo ‐borate into a gel polymer matrix represents a new direction for enhancing the electrochemical and physical properties of this class of materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Gravitational Effects on Distortion in Sintering

During sintering a powder compact gains strength through low-temperature interparticle bonding, usually induced by solid-state surface diffusion, followed by further strength contributions from high-temperature densification. In cases where a liquid phase forms, sintering densification is accelerated and shape retention is sustained while open pores remain and contribute capillary forces. Unfortunately, sintering densification requires the compact become thermally softened to a point where creep strain rates reach levels near 10(exp -2)/s when the liquid forms. On the other hand, thermal softening of the powder compact substantially reduces the strength at high temperatures. Therefore, the in situ strength evolution during sintering is a primary focus to separate compact densification (as required for high performance) with minimized distortion (as required for net-shaping). With respect to gravitation effects on distortion during sintering there are two points of substantial weakness - prior to significant interparticle bonding and during final pore closure. This research is focused on understanding the competition among interparticle neck growth, densification, thermal softening, grain boundary wetting, capillary effects associated with liquid wetting and residual porosity, and gravity. Most surprising is the apparent role of gravity, where the deviatoric stress acting on the powder structure induces skeletal formation that reduces distortion. In contrast with theory, microgravity samples exhibit more distortion yet fail to fully densify. Results are presented on the experimental concepts supporting an emerging model of sintering strength evolution that enables understanding of both distortion and densification. The experiments have relied on tungsten heavy alloys, various combinations of dihedral angle, pore size, initial porosity, liquid:solid ratio, and heating rates. On Earth, the dominant factor with respect to distortion is the starting body heterogeneity. Current modeling efforts are seeking some means to uniformly predict the distortion based on a starting pore structure heterogeneity parameter. Densification is largely unaffected by the initial pore structure, but distortion is highly variable, suggesting that nonuniform pore closure might be a significant parameter during sintering. With respect to flight experiments, plans include removal of the solid body forces acting on the solid grains, allowing stabilization of the pore structure and examination of the buoyancy effects with regard to distortion. In microgravity there is the surprising result that compacts do not densify, yet distort a factor that is contrary to all current sintering models. Densification without distortion during liquid phase sintering was achieved by manipulating microstructure and its evolution during sintering. Microstructure parameters such as the solid volume fraction, dihedral angle, initial porosity, and pore size were varied to measure densification and distortion behavior during LPS using W-Ni-Cu alloys. Green compacts were formed using ethylene-bis-stearamide as a pore-forming agent with the amount of polymer controlling the initial porosity. Different initial pore sizes were generated by varying the polymer particle size. Dihedral angle was varied by changing the Ni:Cu ratio in the alloys. Finally, the solid volume fraction was adjusted via the tungsten content. Distortion was quantified using profiles determined with a coordinate measuring machine to calculate a distortion parameter. Sintering results showed that solid volume fraction and dihedral angle are the dominant factors on densification and distortion during liquid phase sintering. Distortion decreases with increasing solid volume fraction and dihedral angle, while initial porosity and pore size have no observable effect on distortion at nearly full densification. Various strategies emerge to improve distortion control in liquid phase sintering.

German, Randall M.↗
DOE OSTI2024

Vapor Phase Infiltration of Titanium Oxide into P3HT to Create Organic–Inorganic Hybrid Photocatalysts

Herein, we report for the first time the use of vapor phase infiltration (VPI) to infuse conducting polymers with inorganic metal oxide clusters that together form a photocatalytic material. While vapor infiltration has previously been used to electrically dope conjugated polymers, this is the first time, to our knowledge, that the resultant hybrid material has been demonstrated to have photocatalytic properties. The system studied is poly(3-hexylthiophene-2,5-diyl) (P3HT) vapor infiltrated with TiCl 4 and H 2 O to create P3HT-TiO x organic–inorganic hybrid photocatalytic materials. X-ray photoelectron spectroscopy analysis shows that P3HT-TiO x VPI films consist of a partially oxidized P3HT matrix, and the infiltrated titanium inorganic is in a 4+ oxidation state with mostly oxide coordination. Upon visible light illumination, these P3HT-TiO x hybrids degrade methylene blue dye molecules. The P3HT-TiO x hybrids are 4.6× more photocatalytically active than either the P3HT or TiO 2 individually or when sequentially deposited (e.g., P3HT on TiO 2 ). On a per surface area basis, these hybrid photocatalysts are comparable or better than other best in class polymer semiconductor photocatalysts. VPI of TiCl 4 + H 2 O into P3HT makes a unique hybrid structure and idealized photocatalyst architecture by creating nanoscale TiO x clusters concentrated toward the surface achieving extremely high catalytic rates. The mechanism for this enhanced photocatalytic rate is understood using photoluminescence spectroscopy, which shows significant quenching of excitons in P3HT-TiO x as compared to neat P3HT, indicating that P3HT acts as a photosensitizer for the TiO x catalyst sites in the hybrid material. This work introduces a new approach to designing and synthesizing organic–inorganic hybrid photocatalytic materials, with expansive opportunities for further exploration and optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Chromium Ions Improve Moisure Resistance of Epoxy Resins

Broad spectrum of thermosetting epoxy resins used on commercial and military aircraft, primarily as composite matrices and adhesives. In new technique, chromium-ion containing epoxy with improved resistance to moisture produced where chromium ions believed to prevent absorption of water molecules by coordinating themselves to hydroxyl groups on epoxy chain. Anticipated that improved epoxy formulation useful as composite matrix resin, adhesive, or casting resin for applications on commercial and advanced aircraft. Improvement made without sacrifice in mechanical properties of polymer.

St. Clair, A. K.↗
DOE OSTI2021

Role of Molecular Architecture on Ion Transport in Ethylene oxide-Based Polymer Electrolytes

This work aims to develop a detailed mechanistic understanding of the role of a graft polymer architecture on lithium ion (Li + ) transport in poly(ethylene oxide)-based polymer electrolytes. Specifically, we compare Li + transport in poly-(ethylene oxide) (PEO) versus poly(oligo oxyethylene methacrylate) (POEM) polymers doped with lithium bis( trifluoromethanesulfonyl) (LiTFSI) salts, using both experimental electrochemical characterization and molecular dynamics (MD) simulations. Furthermore, our results indicate that POEM exhibits a range of relaxation processes that cannot be interpreted solely in terms of glass-transition temperature (T g ) effects. Due to its side-chain architecture, the segmental relaxation of POEM is nonuniform across ether oxygens (EOs) and shows a more pronounced sensitivity to temperature above T g compared to PEO. Moreover, POEM also exhibits a nonuniform Li + coordination behavior, in which Li + is primarily solvated by two different chains in POEM, compared to a single chain in PEO. Li + transport in POEM occurs via two events with distinct characteristic times: a fast intrachain hopping along side chains and a slow interchain hopping between side chains. Taken together, the relaxation processes and ion transport mechanisms identified in POEM provide useful insights into design of more effective solid polymer electrolytes.

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

Dependence of Linker Length and Composition on Ionic Conductivity and Lithium Deposition in Single-Ion Conducting Network Polymers

In this report, single-ion conducting electrolytes stand as promising alternatives to state-of-the-Art electrolytes in lithium batteries, although a single-ion conducting material with high Li + conductivity, stability in contact with lithium, and suitable mechanical properties has been slow to emerge. Here, we describe the synthesis of a series of single-ion conducting network polymers from the reaction of tetrakis(4-(chloromethyl)-2,3,5,6-Tetrafluorophenyl)borate with oligoethylene glycoxide linkers Li 2 O[(CH 2 CH 2 )O] n (n = 1, 2, 3, 9, and 22). Polymers with the longest linkers (n = 9 and 22; ANP-9 and ANP-10, respectively) form materials with conductivities of ~ 10 -6 S cm -1 at 100 °C. With the addition of 65 wt % propylene carbonate (PC), all the network polymers in the series exhibit high conductivities at ambient temperatures, with the n = 1 material (ANP-6) achieving a bulk ionic conductivity of 2.5 x 10 -4 S cm -1 at 25 °C. More conductive single-ion conducting gels could be prepared by using the less coordinating pentanediol dilithium salt as a linker (ANP-11; σ = 3.5 x 10 -4 S cm -1 at 25 °C), although this material exhibited a surprisingly high interfacial resistance in contact with a lithium electrode. In contrast, the gel formed with ANP-6 is notably stable in contact with metallic lithium electrodes, displays a lithium-ion transference number of unity, and boasts a wide electrochemical stability window of greater than 4.5 V. Temperature-dependent ac impedance analysis reveals that the ionic conductivity of this material-and likely the other gels in the series-matches closely to a Vogel-Tamman-Fulcher temperature model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1988

Computer modeling of polymers

A Polymer Molecular Analysis Display System (p-MADS) was developed for computer modeling of polymers. This method of modeling allows for the theoretical calculation of molecular properties such as equilibrium geometries, conformational energies, heats of formations, crystal packing arrangements, and other properties. Furthermore, p-MADS has the following capabilities: constructing molecules from internal coordinates (bonds length, angles, and dihedral angles), Cartesian coordinates (such as X-ray structures), or from stick drawings; manipulating molecules using graphics and making hard copy representation of the molecules on a graphics printer; and performing geometry optimization calculations on molecules using the methods of molecular mechanics or molecular orbital theory.

Green, Terry J.↗
DOE OSTI2023

ElectroCat: Platinum-Group-Metal-Free Engineered Framework Nano-Structure Catalyst (Final Technical Report)

Traditional synthesis methodologies that produce durable, highly active PGM-free electrocatalysts typically consist of a top-down approach utilizing a nitrogen-coordinating precursor, a metal precursor, and a support material. Nitrogen-coordinated transition metal complexes typically are absorbed onto a support material, which is then activated via high-temperature pyrolysis. Selection of the support and the nitrogen coordinating precursor has long been the focal point of efforts to maximize the number of accessible, catalytically active sites. In this project, GWE in collaboration with SRNL and NU will develop durable, highly active, low-cost, PGM-free electrocatalysts for polymer electrolyte membrane fuel cells designed and synthesized using a unique, bottom-up, rationally designed approach. Electrocatalysts are produced via polymerization reaction followed by a high-temperature pyrolysis step. Additionally, this project focuses on catalyst site and ORR mechanistic modeling to better understand the structure-property relationship.

08 HYDROGEN↗
NASA NTRS1985

A consideration of atomic oxygen interactions with space station

A computer model is developed in order to calculate fluence for a generalized spacecraft in orbital flight based on mass spectrometer and incoherent scatter (MSIS) measurements of ambient density. The calculations are used to identify criteria for the selection of materials for the construction of an LEO Space Station. The model is generalized such that the surfaces for study can be oriented in any direction with respect to: a body coordinate system fixed to the spacecraft (E surfaces); and a solar inertial coordinate system. A parametric study was performed in order to evaluate the effects of altitude, inclination, and solar activity on atomic oxygen fluence. Values are obtained for samples of Mylar, Kevlar, Kapton, Tedlar, Teflon and sulfone, as well as for some ethylene polymers. The range of values for material reactivities is from 360 microns for ram-facing surfaces to 200 microns for solar power surfaces during each cycle of solar activity. The possibility of improving reactivity by employing certain chemical coatings is also discussed.

Leger, L. J.↗
DOE OSTI2025

Role of Histidine‐Containing Peptoids in Accelerating the Kinetics of Calcite Growth

Carbonate mineralization, the conversion of CO 2 into stable, thermodynamically favorable carbonate minerals, offers a promising strategy for permanent and environmentally friendly carbon storage, with minimal risk of long-term leakage and minimal monitoring requirements. Drawing inspiration from carbonic anhydrase (CA), a family of zinc-containing metalloenzymes that catalyze the hydration of CO 2 to bicarbonate and promote carbonate precipitation, a class of histidine-containing peptoids was designed that is capable of coordinating with Zn 2+ ions to act as CA mimetics for accelerating calcite step growth. In situ atomic force microscopy (AFM) measurements reveal that these peptoids significantly enhance step advancement, with a more pronounced effect observed when combined with Zn 2+ ions and under higher calcium-to-carbonate activity ratios, indicating that peptoids facilitate the incorporation of CO 3 2− ions at step edges. Solution NMR and 3D atomic force microscopy (3D AFM) analyses show that the coordination of peptoids with Zn 2+ promotes both the deprotonation of HCO 3 − to CO 3 2− and restructures the interfacial hydration layers of calcite, collectively lowering the activation barrier for step growth. These findings establish a design framework for sequence-defined polymers to regulate carbonate mineralization, offering promising applications in CO 2 capture and long-term storage.

CO2 mineralization↗
DOE OSTI2020

Phase behavior of continuous-space systems: A supervised machine learning approach

The phase behavior of complex fluids is a challenging problem for molecular simulations. Supervised machine learning (ML) methods have shown potential for identifying the phase boundaries of lattice models. In this work, we extend these ML methods to continuous-space systems. We propose a convolutional neural network model that utilizes grid-interpolated coordinates of molecules as input data of ML and optimizes the search for phase transitions with different filter sizes. We test the method for the phase diagram of two off-lattice models, namely, the Widom–Rowlinson model and a symmetric freely jointed polymer blend, for which results are available from standard molecular simulations techniques. The ML results show good agreement with results of previous simulation studies with the added advantage that there is no critical slowing down. We find that understanding intermediate structures near a phase transition and including them in the training set is important to obtain the phase boundary near the critical point. The method is quite general and easy to implement and could find wide application to study the phase behavior of complex fluids.

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

Coordinated Multiscale Modeling and Synthesis of Novel Nanostructured Composite Membranes for Solar Fuels Generation (Final Report)

Generation of carbon-based liquid fuels from reduction of CO 2 using solar energy requires the development of improved membranes that provide good ionic conductivity and mechanical properties while minimizing the crossover of gases and reduction products. Using closely coordinated multiscale modeling, synthesis and characterization studies we propose to investigate and develop novel nanostructured composite membranes with applications to conversion of carbon dioxide to storable chemical fuels. The envisioned proton exchange membranes (PEMs) will be based on a support of self- assembling polymer-modified nanoparticles with controllable porosity and tortuosity. The use of a nanoparticle support will provide control of transport and mechanical properties of the membranes. Tuning the copolymer modification of nanoparticles (polymer architectures, brush grafting density) will allow to optimize the ion (proton) transport via the Grotthuss mechanism through narrow hydrated channels while minimizing crossover of gases and reaction products due to the high density of the grafted brush and use of a non-ionic conducting glassy polymers to fill spaces between polymer-grafted nanoparticles. In Phase I synthesis of the copolymers and their attachment to the nanoparticle support will be guided by multiscale simulations that include atomistic molecular dynamics and continuum-level transport simulations. The former will include reactive and non-reactive atomistic simulations that will provide key insight into nanoscale polymer morphology and ion/molecular transport mechanisms need to optimize the copolymer structure. The latter will provide insight into the role of nanoparticle self-assembly on the global transport of ionic and molecular species. The proton conduction and CO 2 /methanol permeability of the membranes will be experimentally characterized as well as simulated and will be correlated with morphology and polymer structure. Prototypes of optimal membranes will be fabricated and characterized at the end of the project. Successful development of improved nanostructured composite PEMs and demonstration of the simulation-guided materials-by-design paradigm will result in our ability to design and synthesize membranes for a wide variety of solar fuels generation and related electrochemical applications.

14 SOLAR ENERGY↗
DOE OSTI2022

Deep eutectic solvent-based polymer electrolyte for solid-state lithium metal batteries

Poly(ethylene) oxide (PEO)-based electrolytes have been widely studied for solid-state lithium batteries while their ionic conductivity and lithium-ion transference number still need to be further improved. Herein, using the combined experimental and theoretical approach, we demonstrate a novel, solid-state PEO-deep eutectic solvent (DES) electrolyte for the first time. We found that the in situ formation of DES can reduce the crystallinity of PEO matrix and more Li + ions can move freely owing to the weakened coordination between ether oxygens and Li-ions. Besides, we show that more Li + ions can be dissociated from Li salts in PEO-DES electrolyte using the molecular dynamics simulations. Such liquid-free PEO-DES electrolytes showed good ionic conductivity (2.1 × 10 −4 S cm −1 ) which is 160% higher than that of conventional PEO-LiTFSI (8.1 × 10 −5 S cm −1 ) electrolyte at 60 °C. Additionally, the PEO-DES electrolyte showed 136% increase of Li-ion transference number (0.33) compared with ionic liquid-doped PEO-LiTFSI (0.14) at 60 °C. Moreover, the PEO-DES exhibited good compatibility with Li metal and stable Li plating/stripping behavior with little morphology change of Li metal. In conclusion, this research also provides new insights into the enhancement mechanisms of novel polymer electrolytes, improving our fundamental understanding of critical challenges that have impeded the adoption of solid-state lithium metal batteries.

Deep eutectic solvent↗
DOE OSTI2022

A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species

Abstract The silylium‐like surface species [ i Pr 3 Si][(R F O) 3 Al−OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH 3 ][(R F O) 3 Al−OSi≡)] ( 1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH 3 + and [(R F O) 3 Al−OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH 3 ] + in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.

Gao, Jiaxin↗
DOE OSTI2023

Polymer Architecture-Induced Trade-off between Conductivities and Transference Numbers in Salt-Doped Polymeric Ionic Liquids

Recent experiments have demonstrated that polymeric ionic liquids that share the same cation and anion but possess different architectures can exhibit markedly different conductivity and transference number characteristics when doped with lithium salt. In this study, we used atomistic molecular simulations on polymer chemistries inspired by the experiments to probe the mechanistic origins underlying the competition between conductivity and transference numbers. Our results indicate that the architecture of the polycationic ionic liquid plays a subtle but crucial role in modulating the anion–cation interactions, especially their dynamical coordination characteristics. Chemistries leading to longer-lived anion–cation coordinations relative to lithium–anion coordinations lead to lower conductivities and higher transference numbers. Furthermore, our results suggest that higher conductivities are accompanied by lower transference numbers and vice versa, revealing that alternative approaches may need to be considered to break this trade-off in salt-doped polyILs.

33 ADVANCED PROPULSION SYSTEMS↗
NASA NTRS2015

Incorporation of Plasticity and Damage Into an Orthotropic Three-Dimensional Model with Tabulated Input Suitable for Use in Composite Impact Problems

The need for accurate material models to simulate the deformation, damage and failure of polymer matrix composites under impact conditions is becoming critical as these materials are gaining increased usage in the aerospace and automotive industries. While there are several composite material models currently available within commercial transient dynamic finite element codes, several features have been identified as being lacking in the currently available material models that could substantially enhance the predictive capability of the impact simulations. A specific desired feature pertains to the incorporation of both plasticity and damage within the material model. Another desired feature relates to using experimentally based tabulated stress-strain input to define the evolution of plasticity and damage as opposed to specifying discrete input properties (such as modulus and strength) and employing analytical functions to track the response of the material. To begin to address these needs, a combined plasticity and damage model suitable for use with both solid and shell elements is being developed for implementation within the commercial code LS-DYNA. The plasticity model is based on extending the Tsai-Wu composite failure model into a strain-hardening based orthotropic plasticity model with a non-associative flow rule. The evolution of the yield surface is determined based on tabulated stress-strain curves in the various normal and shear directions and is tracked using the effective plastic strain. The effective plastic strain is computed by using the non-associative flow rule in combination with appropriate numerical methods. To compute the evolution of damage, a strain equivalent semi-coupled formulation is used, in which a load in one direction results in a stiffness reduction in multiple coordinate directions. A specific laminated composite is examined to demonstrate the process of characterizing and analyzing the response of a composite using the developed model.

Impact↗