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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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65 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Nonane and Hexanol Adsorption in the Lamellar Phase of a Nonionic Surfactant: Molecular Simulations and Comparison to Ideal Adsorbed Solution Theory

Adsorption of n-nonane/1-hexanol (C9/C6OH) mixtures into the lamellar phase formed by a 50/50 w/w triethylene glycol mono-n-decyl ether (C10E3)/water system was studied using configurational-bias Monte Carlo simulations in the osmotic Gibbs ensemble. The interactions were described by the Shinoda–Devane–Klein coarse-grained force field. Prior simulations probing single-component adsorption indicated that C9 molecules preferentially load near the center of the bilayer increasing the bilayer thickness, whereas C6OH molecules are more likely to be found near the interface of the polar and non-polar moieties swelling the bilayer in the lateral dimension. Here, we extend this work to binary C9/C6OH adsorption to probe whether the difference in the spatial preferences may lead to a synergistic effect and enhanced loadings for the mixture. Comparing loading trends and the thermodynamics of binary adsorption to unary adsorption reveals that C9–C9 interactions lead to the largest enhancement, whereas C9–C6OH and C6OH–C6OH interactions are less favorable for this bilayer system. As a result, ideal adsorbed solution theory yields satisfactory predictions of the binary loading.

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

Molar-Mass-Dependent Partitioning of Polyethylene in Nanopores of Model Catalyst Supports from Small-Angle Neutron Scattering

Heterogeneous catalysis offers opportunities to enhance valorization of plastic waste via chemical recycling through control of the upcycled product distributions. Minimizing low-value light hydrocarbons is desired; however, fundamental insights into how to control selectivity are lacking. Here we use contrast variation with small-angle neutron scattering (SANS), model perdeuterated polyethylenes (dPEs), and a model liquid hydrocracking product (tetradecane) to quantify polymer partitioning within mesoporous silica (SBA-15). Polyethylene concentration within the mesopores is increased relative to the bulk solution, and this partitioning increases as the temperature increases. However, this polyethylene partitioning is maximized when the radius of gyration of the polymer chains is comparable to the SBA-15 pore size (10 nm). An increased partitioning at higher temperatures is attributed to entropically driven adsorption of PE within the mesopores. There is no observed preferential partitioning of hexatriacontane (a model oligomer) within the mesopores at the temperatures examined. Furthermore, these results suggest that pore size could promote the selective partitioning of polymer species into the mesopores by size. For plastic upcycling, pore-size-dependent partitioning should increase the probability for the reaction of long polymers over oligomeric and small-molecule polyolefin depolymerization products.

Adsorption↗
DOE OSTI2022

Investigation of the Self-Assembly Behavior of Statistical Bottlebrush Copolymers via Self-Consistent Field Theory Simulations

Bottlebrush copolymers, a class of high-density side-chain-grafted copolymers with high molecular weights, have recently attracted extensive research attention due to the dramatic reduction of chain entanglement in these copolymers, unique self-assembly behaviors, and distinctive physical properties. In this study, we employ self-consistent field theory simulations to systemically investigate the phase behavior of statistical bottlebrush copolymers A-stat-B, an intriguing subclass of bottlebrush copolymers with random or alternating sequences of A and B side chains. We find that a broader variety of ordered mesophases can be stabilized in the melts of these copolymers relative to the more extensively studied bottlebrush block copolymers. In particular, we observe that these statistical copolymers can stabilize sphere phases over a larger range of species volume fractions than their diblock and tetrablock counterparts but require much higher segregation strength to achieve this. The sphere and hexagonally packed cylinder phases formed by conformationally symmetric statistical bottlebrush copolymers possess interesting discrete core–shell structures with the backbone and lower volume fraction side-chain species forming shells and cores, respectively. Moreover, we uncover a new strategy of stabilizing the Frank–Kasper phase A15 by introducing conformational asymmetry through different side-chain lengths and also observe deflection of order–order phase boundaries and significant mixing between the backbones and short side chains as conformational asymmetry is introduced.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation

Understanding the solution-state aggregate structure and the consequent hierarchical assembly of conjugated polymers is crucial for controlling multiscale morphologies during solid thin-film deposition and the resultant electronic properties. However, it remains challenging to comprehend detailed solution aggregate structures of conjugated polymers, let alone their chiral assembly due to the complex aggregation behavior. Herein, we present solution-state aggregate structures and their impact on hierarchical chiral helical assembly using an achiral diketopyrrolopyrrole-quaterthiophene (DPP-T4) copolymer and its two close structural analogues wherein the bithiophene is functionalized with methyl groups (DPP-T2M2) or fluorine atoms (DPP-T2F2). Combining in-depth small-angle X-ray scattering analysis with various microscopic solution imaging techniques, we find distinct aggregate in each DPP solution: (i) semicrystalline 1D fiber aggregates of DPP-T2F2 with a strongly bound internal structure, (ii) semicrystalline 1D fiber aggregates of DPP-T2M2 with a weakly bound internal structure, and (iii) highly crystalline 2D sheet aggregates of DPP-T4. These nanoscopic aggregates develop into lyotropic chiral helical liquid crystal (LC) mesophases at high solution concentrations. Intriguingly, the dimensionality of solution aggregates largely modulates hierarchical chiral helical pitches across nanoscopic to micrometer scales, with the more rigid 2D sheet aggregate of DPP-T4 creating much larger pitch length than the more flexible 1D fiber aggregates. Combining relatively small helical pitch with long-range order, the striped twist-bent mesophase of DPP-T2F2 composed of highly ordered, more rigid 1D fiber aggregate exhibits an anisotropic dissymmetry factor (g-factor) as high as 0.09. This study can be a prominent addition to our knowledge on a solution-state hierarchical assembly of conjugated polymers and, in particular, chiral helical assembly of achiral organic semiconductors that can catalyze an emerging field of chiral (opto)electronics.

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

Low-Voltage Haze Tuning with Cellulose-Network Liquid Crystal Gels

Being key components of the building envelope, glazing products with tunable optical properties are in great demand because of their potential for boosting energy efficiency and privacy features while enabling the main function of allowing natural light indoors. However, windows and skylights with electric switching of haze and transparency are rare and often require high voltages or electric currents, as well as not fully meet the stringent technical requirements for glazing applications. Here, by introducing a predesigned gel material we describe an approach dubbed “Haze-Switch” that involves low-voltage tuning of the haze coefficient in a broad range of 2–90% while maintaining high visible-range optical transmittance. The approach is based on a nanocellulose fiber gel network infiltrated by a nematic liquid crystal, which can be switched between polydomain and monodomain spatial patterns of optical axis via a dielectric coupling between the nematic domains and the applied external electric field. By utilizing a nanocellulose network of nanofibers ~10 nm in diameter we achieve <10 V dielectric switching and <2% haze in the clear state, as needed for applications in window products. Finally, we characterize physical properties relevant to window and smart glass technologies, like the color rendering index, haze coefficient, and switching times, demonstrating that our material and envisaged products can meet the stringent requirements of the glass industry, including applications such as privacy windows, skylights, sunroofs, and daylighting.

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

Mechanism of Mesoscale Woodpile Development via Photoelectrochemical Deposition of Se–Te

A combination of experiments and optical modeling provided insight into the mechanism of mesoscale woodpile formation in response to an orthogonal shift in polarization during photoelectrochemical deposition of Se–Te. Cathodic deposition of semiconducting Se–Te using spatially uniform, linearly polarized illumination produced arrays of lamellae that were aligned parallel to the optical E-field oscillation. Continued deposition in conjunction with an orthogonal shift in the polarization direction then produced aligned bridging features that spanned the void space between, and were orthogonal to, the preexisting lamellae. The height and pitch, respectively, in each layer of the woodpile were a function of the charge density and illumination wavelength during deposition. A Monte Carlo model, in which material addition was scaled by the absorption magnitude obtained from electromagnetic simulations, produced morphologies that were nominally identical to those observed experimentally. Here, the formation of mesoscale woodpiles is consistent with a mechanism that involves a series of spontaneously initiated, concerted light–matter interactions during the photoelectrochemical deposition process.

absorption↗
DOE OSTI2020

Planar Hall Driven Torque in a Ferromagnet/Nonmagnet/Ferromagnet System

An important goal of spintronics is to covert a charge current into a spin current with a controlled spin polarization that can exert torques on an adjacent magnetic layer. Here we demonstrate such torques in a two ferromagnet system. A CoNi multilayer is used as a spin current source in a sample with structure CoNi/Au/CoFeB. Spin torque ferromagnetic resonance is used to measure the torque on the CoFeB layer. The response as a function of the applied field angle and current is consistent with the symmetry expected for a torque produced by the planar Hall effect originating in CoNi. We find the strength of this effect to be comparable to that of the spin Hall effect in platinum, indicating that the planar Hall effect holds potential as a spin current source with a controllable polarization direction.

ferromagnetic resonance↗
DOE OSTI2020

Water Treatment: Are Membranes the Panacea?

Alongside the rising global water demand, continued stress on current water supplies has sparked interest in using nontraditional source waters for energy, agriculture, industry, and domestic needs. Membrane technologies have emerged as one of the most promising approaches to achieve water security, but implementation of membrane processes for increasingly complex waters remains a challenge. The technical feasibility of membrane processes replacing conventional treatment of alternative water supplies (e.g., wastewater, seawater, and produced water) is considered in the context of typical and emerging water quality goals. This review considers the effectiveness of current technologies (both conventional and membrane based), as well as the potential for recent advancements in membrane research to achieve these water quality goals. We envision the future of water treatment to integrate advanced membranes (e.g., mixed-matrix membranes, block copolymers) into smart treatment trains that achieve several goals, including fit-for-purpose water generation, resource recovery, and energy conservation.

catalysis (heterogeneous)↗
DOE OSTI2020

Water Structure and Properties at Hydrophilic and Hydrophobic Surfaces

The properties of water on both molecular and macroscopic surfaces critically influence a wide range of physical behaviors, with applications spanning from membrane science to catalysis to protein engineering. Yet, our current understanding of water interfacing molecular and material surfaces is incomplete, in part because measurement of water structure and molecular-scale properties challenges even the most advanced experimental characterization techniques and computational approaches. This review highlights progress in the ongoing development of tools working to answer fundamental questions on the principles that govern the interactions between water and surfaces. One outstanding and critical question is what universal molecular signatures capture the hydrophobicity of different surfaces in an operationally meaningful way, since traditional macroscopic hydrophobicity measures like contact angles fail to capture even basic properties of molecular or extended surfaces with any heterogeneity at the nanometer length scale. Resolving this grand challenge will require close interactions between state-of-the-art experiments, simulations, and theory, spanning research groups and using agreed-upon model systems, to synthesize an integrated knowledge of solvation water structure, dynamics, and thermodynamics.

catalysis (heterogeneous)↗