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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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156 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Relaxation dynamics of water in the vicinity of cellulose nanocrystals

Water molecules near cellulose nanocrystals (CNCs; produced via the sulfuric acid-catalyzed hydrolysis of wood pulp) are believed to relax slower than those in the bulk liquid, which may result in unique properties of CNC aqueous dispersions. Herein this study analyzed the polarization behavior of water molecules in CNC aqueous dispersions and other reference samples using a dielectric relaxation spectroscopy (DRS) technique in the microwave frequency range (0.2–20 GHz). As the CNC concentration increases, two slow relaxation components become prominent. The comparison with DRS data of aqueous dispersions of nanoporous silica, polyvinyl alcohol (PVA), and hairy CNC (HCNC) with amorphous chains protruding from both ends suggested that these slow relaxation modes of water near CNC surfaces cannot be attributed to direct hydrogen bonding interactions with the hydroxyl (OH) groups exposed and immobilized at the solid surface. Instead, they are similar to the water molecules interacting with OH groups attached to flexible polymer chains. Molecular dynamics (MD) simulations of the polarization behavior of water near the (110) facet of cellulose Iβ crystals confirmed that the interactions of water molecules with the cellulose crystal surface do not cause slower relaxations in the frequency range studied via the DRS. These results indicated that the CNC surface cannot be depicted with the crystallographic facets of cellulose Iβ; instead, it resembles a polymer-brush surface on which the short glucan residues or fragments of the strong acid-catalyzed hydrolysis process are swollen and extended into the aqueous phase.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Functional soft materials from blue phase liquid crystals

Blue phase (BP) liquid crystals are chiral fluids wherein millions of molecules self-assemble into cubic lattices that are on the order of hundred nanometers. As the unit cell sizes of BPs are comparable to the wavelength of light, they exhibit selective Bragg reflections in the visible. The exploitation of the photonic properties of BPs for technological applications is made possible through photopolymerization, a process that renders mechanical robustness and thermal stability. We review here the preparation and characterization of stimuli-responsive, polymeric photonic crystals based on BPs. We highlight recent studies that demonstrate the promise that polymerized BP photonic crystals hold for colorimetric sensing and dynamic light control. We review using Landau–de Gennes simulations for predicting the self-assembly of BPs and the potential for using theory to guide experimental design. Finally, opportunities for using BPs to synthesize new soft materials, such as highly structured polymer meshes, are discussed.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Liquid crystalline order in mucus

Mucus plays an exceptionally wide range of important biological roles. It operates as a protective, exchange, and transport medium in the digestive, respiratory, and reproductive systems of humans and other vertebrates. Mucus is a polymer hydrogel. It is secreted as discrete packages (secretory granules) by specialized secretory cells. Mucus hydrogel is stored in a condensed state inside the secretory granules. Depending upon the architecture of their constituent macromolecules and on the composition of the solvent, polymer gels can form liquid crystalline microstructures, with orientational order being exhibited over optically resolvable distances. Individual mucin molecules consist of alternating rigid segments (heavily glycosylated; hydrophilic) and flexible segments (nonglycosylated; hydrophobic). Polymer molecules consisting of rigid units linked by flexible spacers are frequently associated with liquid crystalline behavior, which again raises the possibility that mucus could form anisotropic fluid phases. Suggestions that mucins may be self-associating in dilute solution have previously been challenged on the basis of sedimentation-equilibrium studies performed on mucus in which potential sites of association were competitively blocked with inhibitors. However, the formation of stable liquid crystalline phases does not depend on the existence of inter- or intramolecular associations; these phases can form on the basis of steric considerations alone.

NASA Discipline Number 40-20↗
NASA NTRS1997

Crystalline Colloidal Arrays in Polymer Matrices

Crystalline Colloidal Arrays (CCA, also known as colloidal crystals), composed of aqueous or nonaqueous dispersions of self-assembled nanosized polymer colloidal spheres, are emerging toward the development of advanced optical devices for technological applications. The spontaneous self assembly of polymer spheres in a dielectric medium results from the electrostatic repulsive interaction between particles of uniform size and charge distribution. In a way similar to atomic crystals that diffract X-rays, CCA dispersions in thin quartz cells selectively and efficiently Bragg diffract the incident visible light. The reason for this diffraction is because the lattice (body or face centered cubic) spacing is on the order of the wavelength of visible light. Unlike the atomic crystals that diffract a fixed wavelength, colloidal crystals in principle, depending on the particle size, particle number and charge density, can diffract W, Vis or IR light. Therefore, the CCA dispersions can be used as laser filters. Besides, the diffraction intensity depends on the refractive index mismatch between polymer spheres and dielectric medium; therefore, it is possible to modulate incident light intensities by manipulating the index of either the spheres or the medium. Our interest in CCA is in the fabrication of all-optical devices such as optical switches, limiters, and spatial light modulators for optical signal processing. The two major requirements from a materials standpoint are the incorporation of suitable nonlinear optical materials (NLO) into polymer spheres which will allow us to alter the refractive index of the spheres by intense laser radiation, and preparation of solid CCA filters which can resist laser damage. The fabrication of solid composite filters not only has the advantage that the films are easier to handle, but also the arrays in solid films are more robust than in liquid media. In this paper, we report the photopolymerization process used to trap CCA in polymer matrices, the factors which affect the optical diffraction qualities of resulting polymer films, and methods to improve the efficiencies of solid optical filters. Before this, we also present the experimental demonstration, of controlling the optical diffraction intensities from aqueous CCA dispersions by varying the temperature, which establishes the feasibility of fabricating all-optical switching devices with nonlinear periodic array structures.

Sunkara, Hari B.↗
NASA NTRS1999

Ultrasound Thermal Field Imaging of Opaque Fluids

We have initiated an experimental program to develop an ultrasound system for non-intrusively imaging the thermal field in opaque fluids under an externally imposed temperature gradient. Many industrial processes involve opaque fluids, such as molten metals, semiconductors, and polymers, often in situations in which thermal gradients are important. For example, one may wish to understand semiconductor crystal growth dynamics in a Bridgman apparatus. Destructive testing of the crystal after the process is completed gives only indirect information about the fluid dynamics of the formation process. Knowledge of the coupled thermal and velocity fields during the growth process is then essential. Most techniques for non-intrusive velocity and temperature measurement in fluids are optical in nature, and hence the fluids studied must be transparent. In some cases (for example, LDV (laser Doppler velocimetry) and PIV (particle imaging velocimetry)) the velocities of small neutrally buoyant seed particles suspended in the fluid, are measured. Without particle seeding one can use the variation of the index of refraction of the fluid with temperature to visualize, through interferometric, Schlieren or shadowgraph techniques, the thermal field. The thermal field in turn gives a picture of the pattern existing in the fluid. If the object of study is opaque, non-optical techniques must be used. In this project we focus on the use of ultrasound, which propagates easily through opaque liquids and solids. To date ultrasound measurements have almost exclusively relied on the detection of sound scattered from density discontinuities inside the opaque material of interest. In most cases it has been used to visualize structural properties, but more recently the ultrasound Doppler velocimeter has become available. As in the optical case, it relies on seed particles that scatter Doppler shifted sound back to the detector. Doppler ultrasound techniques are, however, not useful for studying convective fluid flow in crystal growth, because particle seeding is unacceptable and flow velocities are typically too low to be resolved, and may be even lower in microgravity conditions where buoyancy forces are negligible. We will investigate a different use of ultrasound to probe the flows of opaque fluids non-intrusively and without the use of seed particles: our goal is to ultrasonically visualize the thermal field of opaque fluids with relatively high spatial resolution. The proposed technique relies upon the variation of sound speed with temperature of the fluid. A high frequency ultra-sound pulse passing through a fluid-filled chamber will traverse the chamber in a time determined by the relevant chamber dimension and the temperature of the fluid through which the pulse passes. With high time-resolution instrumentation that compares the excitation signal with the received pulse we can detect the influence of the fluid temperature on the pulse travel time. This is effectively an interferometric system, which in its optical form is an extremely sensitive approach to measuring thermal fields in fluids. Moreover, the temperature dependence of sound velocity in liquid metals is comparable to the temperature dependence of the speed of light required for accurate interferometric thermal images in transparent fluids. With an array of transducers scanned electronically a map of the thermal field over the chamber could be produced. An alternative approach would be to use the ultrasound analog of the shadowgraph technique. In the optical version, collimated light passes through the fluid, where it is focused or defocused locally by temperature field induced variations of the index of refraction. The resulting image reveals the thermal field through the spatial pattern of light intensity variations. By analogy, an ultrasound plane wave traversing an opaque fluid sample would be also locally focused or defocused depending on the speed of sound variations, giving rise to spatial variations in sound intensity that will reveal the thermal field pattern. These approaches could be applied to any situation in which temperature differences are expected to occur, and will rapidly provide information about the flow that simply cannot be obtained by any current intrusive or non-intrusive diagnostic technique. As materials processing in microgravity matures it will become increasingly important to have available simple and versatile diagnostic tools, such as we will develop, for studying the flows of opaque fluids under thermal forcing.

Andereck, C. David↗
DOE OSTI2021

Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern

Solution self-assembly of coil-crystalline diblock copolypeptoids has attracted increasing attention due to its capability to form hierarchical nanostructures with tailorable morphologies and functionalities. While the N-substituent (or side chain) structures are known to affect the crystallization of polypeptoids, their roles in dictating the hierarchical solution self-assembly of diblock copolypeptoids are not fully understood. Herein, we designed and synthesized two types of diblock copolypeptoids, i.e., poly(N-methylglycine)-b-poly(N-octylglycine) (PNMG-b-PNOG) and poly(N-methylglycine)-b-poly(N-2-ethyl-1-hexylglycine) (PNMG-b-PNEHG), to investigate the influence of N-substituent structure on the crystalline packing and hierarchical self-assembly of diblock copolypeptoids in methanol. With a linear aliphatic N-substituent, the PNOG blocks pack into a highly ordered crystalline structure with a board-like molecular geometry, resulting in the self-assembly of PNMG-b-PNOG molecules into a hierarchical microflower morphology composed of radially arranged nanoribbon subunits. By contrast, the PNEHG blocks bearing bulky branched aliphatic N-substituents are rod-like and prefer to stack into a columnar hexagonal liquid crystalline mesophase, which drives PNMG-b-PNEHG molecules to self-assemble into symmetrical hexagonal nanosheets in solution. A combination of time-dependent small/wide-angle X-ray scattering and microscopic imaging analysis further revealed the self-assembly mechanisms for the formation of these microflowers and hexagonal nanosheets. These results highlight the significant impact of the N-substituent architecture (i.e., linear versus branched) on the supramolecular self-assembly of diblock copolypeptoids in solution, which can serve as an effective strategy to tune the geometry and hierarchical structure of polypeptoid-based nanomaterials.

99 GENERAL AND MISCELLANEOUS↗
NASA NTRS2009

Filtering Water by Use of Ultrasonically Vibrated Nanotubes

Devices that could be characterized as acoustically driven molecular sieves have been proposed for filtering water to remove all biological contaminants and all molecules larger than water molecules. Originally intended for purifying wastewater for reuse aboard spacecraft, these devices could also be attractive for use on Earth in numerous settings in which there are requirements to obtain potable, medical-grade, or otherwise pure water from contaminated water supplies. These devices could also serve as efficient means of removing some or all water from chemical products . for example, they might be useful as adjuncts or substitutes for stills in the removal of water from alcohols and alcoholic beverages. These devices may be constructed using various materials, such as ceramics, metallics, or polymers, depending on end-use requirements. A representative device of this type (see figure) would include a polymeric disk, about 1 mm in diameter and between 1 and 40 microns thick, within which would be embedded single-wall carbon nanotubes aligned along the thickness axis. The polymeric disk would be part of a unitary polymeric ring assembly. An acoustic transducer in the form of a piezoelectric-film-and-electrode subassembly - typically 9 microns thick and made of poly(vinylidene fluoride) coated with copper 150 nm thick -. would be affixed to the outside of the outer polymeric ring by means of an electrically nonconductive epoxy. The nanotubes would be chosen to have diameters between about 8 and about 13.5 A because water molecules could fit into the nanotubes, but larger molecules could not. Water to be purified would be placed in contact with one face (typically, the upper face) of the filter disk. The surface tension of water is low enough that water molecules should enter and travel along the nanotubes, and computational simulations of molecular dynamics and experimental measurements have shown that the water molecules inside the nanotubes in this size range can be expected to become aligned into helical columns that exhibit properties of both hexagonal ice crystals and liquid water

Gavalas, Lillian Susan↗
DOE OSTI2025

The Effects of Morphology and Hydration on Anion Transport in Self-Assembled Nanoporous Membranes

Ordered nanoporous polymer membranes offer opportunities for systematically probing the mechanisms of ion transport under confinement and for realizing useful materials for electrochemical devices. Here, we examine the impact of morphology and ion hydration on the transport of hydroxide and bromide anions in nanostructured polymer membranes with 1 nm scale pores. We use aqueous lyotropic self-assembly of an amphiphilic monomer, with a polymerizable surfactant to create direct hexagonal (H I ) and gyroid mesophases. UV-induced cross-linking leads to the formation of nanoporous polymers with water continuous channels. The membranes are mechanically robust and chemically durable, resisting degradation during extended exposure to 1 M NaOH solutions. We use a combination of electrochemical impedance spectroscopy, pulsed-field gradient NMR spectroscopy, and molecular simulations to elucidate anion and water transport. The as-prepared hexagonal systems display higher conductivity and lower activation energies for both anions relative to the gyroid system. When compared at equivalent hydration, however, gyroid and hexagonal membranes show similar activation energies, with nearly identical conductivities at ambient temperatures. Both ionic conductivity and water diffusivity increase with increasing hydration. Here, the water uptake as a function of relative humidity for the hexagonal and gyroid mesophases ultimately dictates the water diffusion and magnitude of the ionic conductivity, with the hexagonal system showing overall higher capacity for hydration and thus faster ion transport. The durability of these materials under aggressive alkaline conditions and their relatively high hydroxide ion conductivity suggest that these nanostructured polymers could be of interest as membranes for alkaline fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

All-Optical Micro Motors Based on Moving Gratings in Photosensitive Media

An all-optical micromotor with a rotor driven by a traveling wave of surface deformation of a stator being in contact with the rotor is being studied. Instead of an ultrasonic wave produced by an electrically driven piezoelectric actuator as in ultrasonic motors, the wave is a result of a photo-induced surface deformation of a photosensitive material produced by an incident radiation. A thin piezoelectric polymer will deform more easily LiNbO3 or metal when irradiated with light. The type of photosensitive material studied are piezoelectric polymers with and without coatings for connecting electrodes. In order to be considered as a possible candidate for micromotors, the material should exhibit surface deformation produced by a laser beam of the order of 10 microns. This is compared to the deformations produced by static holographic gratings studied in photorefractive crystals of LiNbO3 using high vertical resolution surface profilometer Dektak 3 and surface interferometer WYKO. An experimental setup showing the oscillations has been developed. The setup uses a chopped beam from an Argon ion laser to produce the deformation while a probe beam is reflected by the thin film into a fiber which is then detected on an oscilloscope. A ramp voltage signal generator will drive the piezoelectric film in another experiment to determine the resonance of the film. A current is generated when light is incident upon the film and this current can be measured. The reverse process has already been demonstrated in other piezoelectric actuators. Changing voltage, polarity, and frequency of the signal can easily generate vibrations similar to those when light is incident on the film. This can be compared to the effects of laser interaction with light absorbing fluids such as solutions of 2,9,16,23-Tetrakis(phenylthio)-29H, 31 H-phthalocyanine in chlorobenzene in capillary tubes, The possibility of using a liquid with the piezoelectric film would be a novel idea for a micromotor since the interaction of a single low power focused laser beam at 633 nm with such fluid produced an intensive circular motion.

Curley, M.↗
DOE OSTI2023

Topological solitonic macromolecules

Being ubiquitous, solitons have particle-like properties, exhibiting behaviour often associated with atoms. Bound solitons emulate dynamics of molecules, though solitonic analogues of polymeric materials have not been considered yet. Here we experimentally create and model soliton polymers, which we call “polyskyrmionomers”, built of atom-like individual solitons characterized by the topological invariant representing the skyrmion number. With the help of nonlinear optical imaging and numerical modelling based on minimizing the free energy, we reveal how topological point defects bind the solitonic quasi-atoms into polyskyrmionomers, featuring linear, branched, and other macromolecule-resembling architectures, as well as allowing for encoding data by spatial distributions of the skyrmion number. Application of oscillating electric fields activates diverse modes of locomotion and internal vibrations of these self-assembled soliton structures, which depend on symmetry of the solitonic macromolecules. Our findings suggest new designs of soliton meta matter, with a potential for the use in fundamental research and technology.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Understanding the Interactions of Seawater Ions with Amidoxime through X-Ray Crystallography

Insoluble polymer substrates functionalized with the amidoxime (R-C(NH 2 )=NOH) functional group have been demonstrated as a technically feasible platform for extracting uranium from seawater, a potential source of extremely abundant uranium for use as nuclear fuel. While it is possible to isolate macroscopic amounts of uranium from the ocean with a positive energy return on investment using these materials, both the economic and energetic costs are many times greater than those of terrestrial uranium mining. Currently, the major contribution to this cost is the production of the sorbent itself, so being able to recycle the sorbent even a small number of times will have a huge impact on lowering the cost of their use. However, amidoxime resins show capacity fading when stripped by strong acids, presently limiting their recyclability. Both alternative extractants and alternative elution chemistries are under development with promising results but are yet at too early a stage to make predictions about their ultimate success. Given the potentially huge impact of a successful recycling process on the viability of seawater extraction of uranium, there is a strong need to pursue additional routes to elution chemistry. During the course of this project, we studied the interactions of amidoxime-containing small molecules with the abundant metal ions in seawater, including Li, Na, K, Mg, Ca, Fe, Cu, and V, to understand the interactions of [UO 2 ] 2+ with amidoxime. By using small molecules with multiple adjacent functional groups, we crystallized the resulting metal complexes and used single crystal X-ray diffraction (SCXRD) as our primary tool for structural characterization. We also investigated the use of solutions of hydroxylammonium salts in weak acids as eluents for stripping and recycling amidoxime-based sorbents. The replacement of strong acids, which react with and destroy the amidoxime functional groups, with weak acids based on hydroxylammonium, a reagent that is actually used to make the amidoxime groups, is expected to avoid capacity loss on recycling and possibly even regenerate functionality that was lost due to exposure to the marine environment.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗