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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Improved interfacial li-ion transport in composite polymer electrolytes via surface modification of LLZO

Composite polymer electrolytes that incorporate ceramic fillers in a polymer matrix offer mechanical strength and flexibility as solid electrolytes for lithium metal batteries. However, fast Li + transport between polymer and Li + -conductive filler phases is not a simple achievement due to high barriers for Li + exchange across the interphase. This study demonstrates how modification of Li 7 La 3 Zr 2 O 12 (LLZO) nanofiller surfaces with silane chemistries influences Li + transport at local and global electrolyte scales. Anhydrous reactions covalently link amine-functionalized silanes [(3-aminopropyl)triethoxysilane (APTES)] to LLZO nanoparticles, which protects LLZO in air. APTES functionalization lowers the poly (ethylene oxide) (PEO)-LLZO interphase resistance to half that of unmodified LLZO and increases effective Li + transference number, while insulating Al 2 O 3 completely blocks ion exchange and lowers transference number and conductivity in PEO-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-LLZO composites. Modeling an inner resistive interphase between LLZO and PEO surrounded by an outer conductive interphase explains non-linear conductivity trends. Solid-state 7 Li & 6 Li nuclear magnetic resonance shows Li + only exchanges between PEO-LiTFSI and some LLZO interphase, with no appreciable Li + transport through bulk LLZO. Surface functionalization is a promising path toward lowering the polymer-ceramic interphase resistance. This work demonstrates that local changes in Li + transport affect macroscopic performance, highlighting the intricate relationships between all interfaces in inherently heterogeneous composite polymer electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2022

Effect of Tethering Anions in Block Copolymer Electrolytes via Molecular Dynamics Simulations

Ion-containing block copolymers (BCPs) are promising solid-state electrolytes as they can combine ion conduction and mechanical robustness via multiple microphases. However, salt-doped BCPs can have low ion conduction and transference number. One strategy to increase transference number is to tether anions to the polymer backbone (creating a single-ion conductor), though this may impact cation mobility. Leveraging coarse-grained molecular dynamics simulations, we compare the effects of ion concentration and polymer dielectric constant on BCPs with and without bonding anions to the chain (without changing any other chemical properties). We find that single-ion BCPs have higher cation conductivity than analogous salt-doped BCPs, especially at moderate ion concentrations. Furthermore, we also compare several structural features of these systems; notably, tethering anions causes the ions to spread more evenly throughout the conducting phase, which is related to improved cation conduction.

25 ENERGY STORAGE↗
DOE OSTI2025

Revealing systematic changes in the transcriptome during the transition from exponential growth to stationary phase

ABSTRACT The composition of bacterial transcriptomes is determined by the transcriptional regulatory network (TRN). The TRN regulates the transition from one physiological state to another. Here, we use independent component analysis to monitor the composition of the transcriptome during the transition from the exponential growth phase to the stationary phase. With Escherichia coli K-12 MG1655 as a model strain, we trigger the transition using carbon, nitrogen, and sulfur starvation. We find that (i) the transition to the stationary phase accompanies common transcriptome changes, including increased stringent responses and reduced production of cellular building blocks and energy regardless of the limiting element; (ii) condition-specific changes are strongly associated with transcriptional regulators ( e.g. , Crp, NtrC, CysB, Cbl) responsible for metabolizing the limiting element; and (iii) the shortage of each limiting element differentially affects the production of amino acids and extracellular polymers. This study demonstrates how the combination of genome-scale datasets and new data analytics reveals the fundamental characteristics of a key transition in the life cycle of bacteria. IMPORTANCE Nutrient limitations are critical environmental perturbations in bacterial physiology. Despite its importance, a detailed understanding of how bacterial transcriptomes are adjusted has been limited. By utilizing independent component analysis (ICA) to decompose transcriptome data, this study reveals key regulatory events that enable bacteria to adapt to nutrient limitations. The findings not only highlight common responses, such as the stringent response, but also condition-specific regulatory shifts associated with carbon, nitrogen, and sulfur starvation. The insights gained from this work advance our knowledge of bacterial physiology, gene regulation, and metabolic adaptation.

Lim, Hyun Gyu (ORCID:0000000204692388)↗
DOE OSTI2024

Exploiting Saturation Regimes and Surface Effects to Tune Composite Design: Single Platelet Nanocomposites of Peptoid Nanosheets and CaCO 3

Mineral-polymer composites found in nature exhibit exceptional structural properties essential to their function, and transferring these attributes to the synthetic design of functional materials holds promise across various sectors. Biomimetic fabrication of nanocomposites introduces new pathways for advanced material design and explores biomineralization strategies. This study presents a novel approach for producing single platelet nanocomposites composed of CaCO 3 and biomimetic peptoid (N-substituted glycines) polymers, akin to the bricks found in the brick-and-mortar structure of nacre, the inner layer of certain mollusc shells. The significant aspect of the proposed strategy is the use of organic peptoid nanosheets as the scaffolds for brick formation, along with their controlled mineralization in solution. Here, we employ the B28 peptoid nanosheet as a scaffold, which readily forms free-floating zwitterionic bilayers in aqueous solution. The peptoid nanosheets were mineralized under consistent initial conditions (σ calcite = 1.2, pH 9.00), with variations in mixing conditions and supersaturation profiles over time aimed at controlling the final product. Nanosheets were mineralized in both feedback control experiments, where supersaturation was continuously replenished by titrant addition and in batch experiments without a feedback loop. Complete coverage of the nanosheet surface by amorphous calcium carbonate was achieved under specific conditions with feedback control mineralization, whereas vaterite was the primary CaCO 3 phase observed after batch experiments. Thermodynamic calculations suggest that time-dependent supersaturation profiles as well as the spatial distribution of supersaturation are effective controls for tuning the mineralization extent and product. We anticipate that the control strategies outlined in this work can serve as a foundation for the advanced and scalable fabrication of nanocomposites as building blocks for nacre-mimetic and functional materials.

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

Trace Adsorptive Removal of PFAS from Water by Optimizing the UiO‐66 MOF Interface

Abstract The confluence of pervasiveness, bioaccumulation, and toxicity in freshwater contaminants presents an environmental threat second to none. Exemplifying this trifecta, per‐ and polyfluoroalkyl substances (PFAS) present an alarming hazard among the emerging contaminants. State‐of‐the‐art PFAS adsorbents used in drinking water treatment, namely, activated carbons and ion‐exchange resins, are handicapped by low adsorption capacity, competitive adsorption, and/or slow kinetics. To overcome these shortcomings, metal–organic frameworks (MOFs) with tailored pore size, surface, and pore chemistry are promising alternatives. Thanks to the compositional modularity of MOFs and polymer–MOF composites, herein we report on a series of water‐stable zirconium carboxylate MOFs and their low‐cost polymer‐grafted composites as C 8 –PFAS adsorbents with benchmark kinetics and “parts per billion” removal efficiencies. Bespoke insights into the structure–function relationships of PFAS adsorbents are obtained by leveraging interfacial design principles on solid sorbents, creating a synergy between the extrinsic particle surfaces and intrinsic molecular building blocks.

Ilić, Nebojša↗
DOE OSTI2021

Polyelectrolyte Complex Coacervation across a Broad Range of Charge Densities

Polyelectrolyte complex coacervates of homologous (co)polyelectrolytes with a near-ideally random distribution of a charged and neutral ethylene oxide comonomer were synthesized. The unique platform provided by these building blocks enabled an investigation of the phase behavior across charge fractions 0.10 ≤ f ≤ 1.0. Experimental phase diagrams for f = 0.30–1.0 were obtained from thermogravimetric analysis of complex and supernatant phases and contrasted with molecular dynamics simulations and theoretical scaling laws. At intermediate to high f, a dependence of polymer weight fraction in the salt-free coacervate phase (w P,c ) of w P,c ~ f 0.37±0.01 was extracted; this trend was in good agreement with accompanying simulation predictions. Below f = 0.50, w P,c was found to decrease more dramatically, qualitatively in line with theory and simulations predicting an exponent of 2/3 at f ≤ 0.25. Preferential salt partitioning to either coacervate or supernatant was found to be dictated by the chemistry of the constituent (co)polyelectrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Crystalline 1D Coordination Polymer Inhibitor Layer Leads to Vertical Sidewalls in Selectively Deposited ZnO on Nanoscale Patterns

Area-selective atomic layer deposition (AS-ALD) is a promising technique for the fabrication of next-generation nanoelectronics. There are two main challenges in AS-ALD: (1) achieving high selectivity of deposition on the growth regions, and (2) preventing mushrooming of the growth material onto the nongrowth regions and achieving well-defined interfaces. In this work, we use benzenethiol (BT) as an inhibitor in the selective deposition of ZnO on SiO 2 in the presence of copper with and without a native oxide (Cu/CuO x ). We observe that BT forms a monolayer on the Cu surface and a Cu-thiolate multilayer structure on CuO x . Using grazing incidence X-ray diffraction combined with simulations, we find that the multilayer structure is crystalline and composed of 1D coordination polymers of Cu-thiolate. Here, using ellipsometry and X-ray photoelectron spectroscopy, we show that the BT consumes the entirety of the CuO x during multilayer formation, allowing the multilayer thickness to be tuned by the thickness of the original oxide. Both the monolayer BT and the multilayer BT prove to be effective inhibitors of ZnO ALD, blocking nearly 500 ALD cycles, which is more than twice that achieved with other thiol inhibitors. Finally, we demonstrate that the multilayer structure can prevent mushrooming of the ALD material onto the nongrowth surface of nanoscale patterns, creating vertical sidewalls with well-defined material interfaces and providing excellent pattern transfer, even for a relatively thick deposited film. As such, these results demonstrate that BT is not only an effective inhibitor but also that its ability to form tunable multilayers makes it well-suited for highly precise nanopatterning applications.

Layers↗
DOE OSTI2023

Functional composites by programming entropy-driven nanosheet growth

Here, nanomaterials must be systematically designed to be technologically viable. Driven by optimizing intermolecular interactions, current designs are too rigid to plug in new chemical functionalities and cannot mitigate condition differences during integration. Despite extensive optimization of building blocks and treatments, accessing nanostructures with the required feature sizes and chemistries is difficult. Programming their growth across the nano-to-macro hierarchy also remains challenging, if not impossible. To address these limitations, we should shift to entropy-driven assemblies to gain design flexibility, as seen in high-entropy alloys, and program nanomaterial growth to kinetically match target feature sizes to the mobility of the system during processing. In tis report, following a micro-then-nano growth sequence in ternary composite blends composed of block-copolymer-based supramolecules, small molecules and nanoparticles, we successfully fabricate high-performance barrier materials composed of more than 200 stacked nanosheets (125 nm sheet thickness) with a defect density less than 0.056 µm -2 and about 98% efficiency in controlling the defect type. Contrary to common perception, polymer-chain entanglements are advantageous to realize long-range order, accelerate the fabrication process (<30 min) and satisfy specific requirements to advance multilayered film technology. This study showcases the feasibility, necessity and unlimited opportunities to transform laboratory nanoscience into nanotechnology through systems engineering of self-assembly.

42 ENGINEERING↗
DOE OSTI2020

Measurement of Three Transport Coefficients and the Thermodynamic Factor in Block Copolymer Electrolytes with Different Morphologies

The design and engineering of composite materials is one strategy to satisfy the materials needs of systems with multiple orthogonal property requirements. In the case of rechargeable batteries with lithium metal anodes, the system requires a separator with fast lithium ion transport and good mechanical strength. In this work, we focus on the system polystyrene-block-poly(ethylene oxide) (SEO) with bis(trifluoromethane)sulfonimide lithium salt (LiTFSI). Ion transport occurs in the salt-containing poly(ethylene oxide)-rich domains. Mechanical rigidity arises due to the glassy nature of polystyrene (PS). If we assume that the salt does not interact with the PS-rich domains, we can describe ion transport in the electrolyte by three transport parameters (ionic conductivity, κ, salt diffusion coefficient, D, and cation transference number, t + 0 ) and a thermodynamic factor, T f . By systematically varying the volume fraction of the conducting phase, Φ c between 0.29 and 1.0, and chain length, N between 80 and 8000, we elucidate the role of morphology on ion transport. We find that κ is the strongest function of morphology, varying by three full orders of magnitude, while D is a weaker function of morphology. To calculate t + 0 and T f , we measure the current fraction, ρ + , and the open circuit potential, U, of concentration cells. We find that ρ + and U follow universal trends as a function of salt concentration, regardless of chain length, morphology, or Φ c , allowing us to calculate t + 0 for any SEO/LiTFSI or PEO/LiTFSI mixture when κ and D are known. Finally, the framework developed in this paper enables predicting the performance of any block copolymer electrolyte in a rechargeable battery.

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

Thermal and Electrical Properties of Isocyanate Derived Organic Aerogels for Cryogenic Insulation Applications

The use and storage of cryogens such as liquefied nitrogen, helium, hydrogen among others requires reliable and efficient thermal insulation systems. Passive insulation from high performance materials that are well-known for their inherent low thermal conductivity would reduce the overall costs involved in design, manufacture and maintenance of such systems. One such class of materials are referred to as aerogels. These materials are known for their low density, high mesoporosity, high surface areas, low thermal conductivity and high acoustic impedance. Aerogels were invented by S.S. Kistler in 1931 and the most common type are those made of silica. However, the inherent fragility of silica aerogels makes them hard to mass produce, and therefore applications have been limited. A major breakthrough was introduced by our team almost 20 years ago with the invention of polymer crosslinked silica aerogels. Those materials shifted attention to all-polymer aerogels that have overcome all fragility issues associated with their inorganic counterparts. This study focuses on such polymeric aerogels that can be mass produced as large monoliths while maintaining the low thermal conductivity of traditional silica aerogels over a wide temperature range. Manufacturing flexibility of polymeric aerogels allows fabrication of blocks and sheets that can be applied in various configurations to insulate cryogenic and superconducting devices. The thermal conductivity with 80 K and room temperature boundary are reported as well as other properties (electrical), that need to be considered when designing devices for cryogenic applications.

Churu, Gitogo↗
DOE OSTI2022

Chain Redistribution Stabilizes Coexistence Phases in Block Copolymer Blends

The nanoscale morphologies of block copolymer (BCP) thin films are determined by chain architecture. Experimental studies of thin film blends of different BCP chain types have demonstrated that blending can stabilize new motifs, such as coexistence phases. Here, we deploy coarsegrained molecular dynamics (MD) simulations in order to better understand the self-assembly behavior of BCP blend thin films. Here, we consider blends of lamella- and cylinder-forming BCP chains, studying their morphological makeup, the chain distribution within the morphology, and the underlying polymer chain conformations. Our simulations show that there are local concentration deviations at the scale of the morphological objects that dictate the local structure, and that BCP chains redistribute within the morphology so as to stabilize the structure. Underlying these effects are measurable distortions in the BCP chain conformations. The conformational freedom afforded by BCP blending stabilizes defects and allows coexistence phases to appear, while also leading to kinetic trapping effects. These results highlight the power of blending in designing the morphology that forms.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Crystal structures of polymerized lithium chloride and dimethyl sulfoxide in the form of {2LiCl·3DMSO} n and {LiCl·DMSO} n

Two novel LiCl·DMSO polymer structures were created by combining dry LiCl salt with dimethyl sulfoxide (DMSO), namely, catena-poly[[chlorido­lithium(I)]-μ-(dimethyl sulfoxide)-κ 2 O:O-[chlorido­lithium(I)]-di-μ-(dimethyl sulfoxide)-κ 4 O:O], [Li 2 Cl 2 (C 2 H 6 OS) 3 ]n, and catena-poly[lithium(I)-μ-chlorido-μ-(dimethyl sulfoxide)-κ 2 O:O], [LiCl(C 2 H 6 OS)]n. The initial synthesized phase had very small block-shaped crystals (<0.08 mm) with monoclinic symmetry and a 2 LiCl: 3 DMSO ratio. As the solution evaporated, a second phase formed with a plate-shaped crystal morphology. After about 20 minutes, large (>0.20 mm) octa­hedron-shaped crystals formed. The plate crystals and the octa­hedron crystals are the same tetra­gonal structure with a 1 LiCl: 1 DMSO ratio. These structures are reported and compared to other known LiCl·solvent compounds.

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

Protein Assembly by Design

Proteins are nature’s primary building blocks for the construction of sophisticated molecular machines and dynamic materials, ranging from protein complexes such as photosystem II and nitrogenase that drive biogeochemical cycles to cytoskeletal assemblies and muscle fibers for motion. Such natural systems have inspired extensive efforts in the rational design of artificial protein assemblies in the last two decades. As molecular building blocks, proteins are highly complex, in terms of both their three-dimensional structures and chemical compositions. To enable control over the self-assembly of such complex molecules, scientists have devised many creative strategies by combining tools and principles of experimental and computational biophysics, supramolecular chemistry, inorganic chemistry, materials science, and polymer chemistry, among others. Owing to these innovative strategies, what started as a purely structure-building exercise two decades ago has, in short order, led to artificial protein assemblies with unprecedented structures and functions and protein-based materials with unusual properties. Furthermore, our goal in this review is to give an overview of this exciting and highly interdisciplinary area of research, first outlining the design strategies and tools that have been devised for controlling protein self-assembly, then describing the diverse structures of artificial protein assemblies, and finally highlighting the emergent properties and functions of these assemblies.

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

Enhanced Ion Conductivity through Hydrated, Polyelectrolyte-Grafted Cellulose Nanocrystal Films

Here,iIonically conductive, hydrated polyelectrolyte nanocomposites are prepared from iodomethane-treated poly(2-vinylpyridine) (mPV)-grafted cellulose nanocrystals (MxG-CNC-g-mPV). These polyelectrolyte-grafted nanoparticle (PEGN) films exhibit an order-of-magnitude higher iodide ion conductivity relative to mPV films and a high in-plane/through-plane anisotropy. The PEGN architecture prevents CNC aggregation, maximizing the CNC/polyelectrolyte interface. PEGN films were prepared with varying polymer graft density (0.03-0.12 chains/nm 2 ) and molecular weight (7k-30k g/mol). The greatest ion conductivity enhancement is observed with lower molecular weight, higher density grafts: ca. 89 ± 6 mS/cm (140 ±10 mS/cm accounting for the volume of the CNC) versus 3.3 ± 0.4 mS/cm for ungrafted mPV. Poly(styrene-block-2-vinylpyridine)-grafted CNCs were prepared in which the insulating polystyrene block or the conducting mPV block was directly attached to the CNCs; only the films with the mPV block closest to the CNCs exhibited an enhancement in conductivity relative to mPV. Together, these data point to beneficial CNC/polyelectrolyte interfacial effects, resulting in significant ionic conductivity enhancement along the length of the CNCs in these films.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Mixed-Polarity Copolymers Based on Ethylene Oxide and Cyclic Carbonate: Insights into Li-Ion Solvation and Conductivity

Here, this study investigates the relationship between polarity and ionic conductivity in random and block copolymer electrolytes comprising highly flexible oligo(ethylene oxide) methyl ether methacrylate (OEM) and highly polar but glassy glycerol carbonate methacrylate (GCMA) monomers, blended with either lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) or lithium triflate. Interestingly, the high polarity of GCMA did not significantly enhance ionic dissociation, and the random copolymers (POEM-r-PGCMA) showed similar or lower ionic conductivities than the POEM homopolymer. Further analysis revealed that Li + only interacts with OEM and its counterion, not with GCMA. The less-intermixed and weakly phase-separated block copolymer (POEM-b-PGCMA) exhibited even lower conductivities than the random copolymer. Our results suggest that Li + solvation occurs only in the POEM-rich phase and that the larger PGCMA regions, depleted of Li + , disrupt long-range ion transport. These findings provide valuable insights into the design of polymer electrolytes and how segmental mobility and functional groups with contrasting polarities affect ion transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗