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At least 73 records · Page 4

Static and dynamical Meissner force fields

The coupling between copper-based high temperature superconductors (HTS) and magnets is represented by a force field. Zero-field cooled experiments were performed with several forms of superconductors: 1) cold-pressed sintered cylindrical disks; 2) small particles fixed in epoxy polymers; and 3) small particles suspended in hydrocarbon waxes. Using magnets with axial field symmetries, direct spatial force measurements in the range of 0.1 to 10(exp 4) dynes were performed with an analytical balance and force constants were obtained from mechanical vibrational resonances. Force constants increase dramatically with decreasing spatial displacement. The force field displays a strong temperature dependence between 20 and 90 K and decreases exponentially with increasing distance of separation. Distinct slope changes suggest the presence of B-field and temperature-activated processes that define the forces. Hysteresis measurements indicated that the magnitude of force scales roughly with the volume fraction of HTS in composite structures. Thus, the net force resulting from the field interaction appears to arise from regions as small or smaller than the grain size and does not depend on contiguous electron transport over large areas. Results of these experiments are discussed.

Weinberger, B. R.

Aerogel-Based Insulation Materials for Cryogenic Applications

Many different aerogel-based materials are now being used in thermal insulation systems for cryogenic applications. These materials include flexible composite blankets, bulk-fill particles, and polymer composites in both evacuated and non-evacuated environments. In ambient environments, aerogels provide superior thermal performance compared to conventional polymeric foam and cellular glass insulations while offering unique advantages in avoiding problems with weathering, moisture, and mechanical damage. Aerogels are also used as spacer materials in multilayer insulation systems. These layered systems provide combined structural-thermal capability for cryogenic systems in either vacuum-jacketed or externally-applied insulation designs. Test data (effective thermal conductivity) include a wide range of both commercial and experimental aerogel materials. Testing was performed using laboratory cryostats and standard methods including full range vacuum (from ambient pressure to high vacuum) and boundary temperatures 293 K and 78 K. Examples of aerogel-based insulation systems are given for both evacuated and non-evacuated applications.

heat transfer

Aerogel-Based Insulation Materials for Cryogenic Applications

Many different aerogel-based materials are now being used in thermal insulation systems for cryogenic applications. These materials include flexible composite blankets, bulk-fill particles, and polymer composites in both evacuated and non-evacuated environments. In ambient environments, aerogels provide superior thermal performance compared to conventional polymeric foam and cellular glass insulations while offering unique advantages in solving problems with weathering, moisture, and mechanical damage. Aerogels are also used as spacer materials in multilayer insulation systems. These layered systems provide combined structural-thermal capability for cryogenic systems in either vacuum-jacketed or externally-applied insulation designs. Test data (effective thermal conductivity) include a wide range of both commercial and experimental aerogel materials. Testing was performed using laboratory cryostats and standard methods including full range vacuum (from ambient pressure to high vacuum) and boundary temperatures 293 K and 78 K. Examples of aerogel-based insulation systems are given for both evacuated and non-evacuated applications.

aerogel layered composites

Cracks in Glass Polymers Induced by Solvent Absorption

Combination of soluble particles and absorbed solvents cause polymer cracking. New failure mechanism in glassy polymers identified. Cracking caused by presence of particles insoluble in polymer matrix but soluble in solvent. Experiments performed and equations describe cracking phenomenon set forth in concise report.

Fedors, R. F.

Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have optical constants more comparable to those of the Titan haze.

Non-NASA Center

Patchy nanoparticles by atomic stencilling

Stencilling, in which patterns are created by painting over masks, has ubiquitous applications in art, architecture and manufacturing. Modern, top-down microfabrication methods have succeeded in reducing mask sizes to under 10 nm, enabling ever smaller microdevices as today’s fastest computer chips. Meanwhile, bottom-up masking using chemical bonds or physical interactions has remained largely unexplored, despite its advantages of low cost, solution-processability, scalability and high compatibility with complex, curved and three-dimensional (3D) surfaces. Here we report atomic stencilling to make patchy nanoparticles (NPs), using surface-adsorbed iodide submonolayers to create the mask and ligand-mediated grafted polymers onto unmasked regions as ‘paint’. We use this approach to synthesize more than 20 different types of NP coated with polymer patches in high yield. Polymer scaling theory and molecular dynamics (MD) simulation show that stencilling, along with the interplay of enthalpic and entropic effects of polymers, generates patchy particle morphologies not reported previously. These polymer-patched NPs self-assemble into extended crystals owing to highly uniform patches, including different non-closely packed superlattices. We propose that atomic stencilling opens new avenues in patterning NPs and other substrates at the nanometre length scale, leading to precise control of their chemistry, reactivity and interactions for a wide range of applications, such as targeted delivery, catalysis, microelectronics, integrated metamaterials and tissue engineering.

36 MATERIALS SCIENCE

Large-format battery anodes comprising silicon particles

Large-scale anodes containing high weight percentages of silicon suitable for use in lithium-ion energy storage devices and batteries, and methods of manufacturing the same, are described. The anode material described herein can include a film cast on a current collector substrate, with the film including a plurality of active material particles and a conductive polymer membrane coated over the active material particles. In some embodiments, the conductive polymer membrane comprises polyacrylonitrile (PAN). The method of manufacturing the anode material can include preparation of a slurry including the active material particles and the conductive polymer material, casting the slurry on a current collector substrate, and subjecting the composite material to drying and heat treatments.

Evans, Tyler

Potential health effects of fume particles on the crew of spacecrafts

The effect of the size of polymer (e.g., Teflon) particles in fumes inhaled by spacecraft personnel on the condition of the lung tissue and on the recovery of the exposed subjects was investigated in rats receiving a single intrapulmonary instillation, or repeated inhalation exposures to either TiO2 particles with primary particle diameter 20 nm, or TiO2 particles with primary particle diameter 250 nm. It was found that rats exposed to 20-nm-diam particles showed a dramatically higher toxicity and slower recovery compared to the group exposed to the 250-nm-diam particles, due to a larger extent of penetration of the interstitium of the lung by the finer particles.

Ferin, Juraj

Mass spectra of neutral particles released during electrical breakdown of thin polymer films

A special type of time-of-flight mass spectrometer triggered from the breakdown event was developed to study the composition of the neutral particle flux released during the electrical breakdown of polymer films problem. Charge is fed onto a metal-backed polymer surface by a movable smooth platinum contact. A slowly increasing potential from a high-impedance source is applied to the contact until breakdown occurs. The breakdown characteristics is made similar to those produced by an electron beam charging system operating at similar potentials. The apparatus showed that intense instantaneous fluxes of neutral particles are released from the sites of breakdown events. For Teflon FEP films of 50 and 75 microns thickness the material released consists almost entirely of fluorocarbon fragments, some of them having masses greater than 350 atomic mass units amu, while the material released from a 50 micron Kapton film consists mainly of light hydrocarbons with masses at or below 44 amu, with additional carbon monoxide and carbon dioxide. The apparatus is modified to allow electron beam charging of the samples.

Kendall, B. R. F.

Structure and Flow-Viscosity of Filled-Polymer-Based 3D Printing Ink: Exploration through Coarse-Grained Molecular Dynamics

The addition of nanofiller particles to a polymer matrix has long been known to enhance or modify the composite’s mechanical and rheological properties. However, quantitatively capturing such changes with molecular level simulations remains computationally challenging. Toward that goal, we performed coarse-grained molecular dynamics of a nanocomposite system at a fixed (25 vol %) filler loading under nonspecific, weak polymer–filler interactions representative of a broad class of technologically important materials. We report several interesting results, including: (1) the equilibrium chain-configuration remains Gaussian-like as in an unfilled melt; (2) smaller filler particles display a stronger tendency to cluster; (3) larger fillers act as plasticizers by reducing the entanglement density and accelerating the chain mobility; and (4) fillers enhance the tensile response modulus, with the effect being stronger for larger particles. We also simulate cluster breakup, yielding, and elongational flow under an applied time-linear tensile strain and study the flow viscosity as a function of filler-size and chain-length.

Materials science

Composite fiber electrodes and applications of same

A composite electrode includes two or more types of fibers forming a fiber network, comprising at least a first type of fibers and a second type of fibers. The first type of fibers comprises a first polymer and a first type of particles. The second type of fibers comprises a second polymer and a second type of particles. The second polymer is same as or different from the first polymer. The second type of particles are same as or different from the first type of particles.

Pintauro, Peter N.

Generating forces in confinement via polymerization

Understanding how to produce forces using biomolecular building blocks is essential for the development of adaptive synthetic cells and living materials. Here we ask whether a dynamic polymer system can generate deformation forces in soft shells by pure self-assembly, motivated by the fact that biological polymer networks like the cytoskeleton can exert forces, move objects, and deform membranes by simply growing, even in the absence of molecular motors. We address this question by investigating polymer force generation by varying the release rate, the structure, and the interactions of self-assembling monomers. First, we develop a toy computational model of polymerization in a soft elastic shell that reveals the emergence of spontaneous bundling which enhances shell deformation. We then extend our model to account more explicitly for monomer binding dynamics. We find that the rate at which monomers are released into the interior of the shell is a crucial parameter for achieving deformation through polymer growth. Lastly, we demonstrate that the introduction of multivalent particles that can join polymers can either improve or impede polymer performance, depending on the amount and on the structure of the multivalent particles. Our results provide guidance for the experimental realization of polymer systems that can perform work at the nanoscale, for example through rationally designed self-assembling proteins or nucleic acids.

Osmanović, Dino [University of California at Los A

Impact of Grafting Density on the Assembly and Mechanical Properties of Self-Assembled Metal–Organic Framework Monolayers

Polymer-grafted metal–organic frameworks (MOFs) can be used to form free-standing self-assembled MOF monolayers (SAMMs). Polymer chains can be introduced onto MOF surfaces through either the ligands or metal nodes using both grafting-to and grafting-from approaches. However, controlling the grafting density of polymer-grafted MOFs has not yet been achieved, because a means to control the density of grafting sites on the MOF surface has not been developed. In this study, the grafting density of polymer-grafted UiO-66 (UiO = University of Oslo) was controlled by functionalizing a portion of the Zr(IV) secondary building units (SBUs) on a UiO-66 surface with a so-called blocking agent. The remaining sites on the UiO-66 SBUs were functionalized with polymerization initiation groups, and polymers were grown from these sites to obtain particles with variable grafting densities and chain lengths that form SAMMs at an air–water interface. Even under conditions of low grafting density, these materials retain the ability to form SAMMs and their free-standing ability. Changes in particle arrangement within the monolayers were investigated using SEM imaging, and the toughness of the monolayers was evaluated using a film-on-water (FOW) method. Furthermore, coarse-grained molecular dynamics simulations were carried out to elucidate the morphology and mechanical properties of the monolayers. Findings from both experiments and simulations indicate that the toughness of SAMMs is more heavily influenced by the chain length of the grafted polymers than by the overall polymer content in the composite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Three-Dimensional (3D) Additive Construction: Printing with Regolith

Three dimensional (3D) printing is a new and booming topic in many realms of research and engineering technology. When it comes to space science and aerospace engineering, it can be useful in numerous ways. As humans travel deeper into space and farther from Earth, sending large quantities of needed supplies from Earth for a mission becomes astronomically expensive and less plausible. In order to reach further to new places, In Situ Resource Utilization (ISRU), a project that pushes for technologies to use materials already present in the destination's environment, is necessary. By using materials already available in space such as regolith from the Moon, Mars, or an asteroid's surface, fewer materials need to be brought into space on a launched vehicle. This allows a vehicle to be filled with more necessary supplies for a deep space mission that may not be found in space, like food and fuel. This project's main objective was to develop a 3D printer that uses regolith to "print" large structures, such as a dome, to be used as a heat shield upon a vehicle's reentry into the atmosphere or even a habitat. 3D printing is a growing technology that uses many different methods to mix, heat, and mold a material into a specific shape. In order to heat the regolith enough to stick together into a solid shape, it must be sintered at each layer of material that is laid. Sintering is a process that heats and compresses a powdered material until it fuses into a solid, which requires a lot of energy input. As an alternative, a polymer can be mixed with the regolith before or as it is sent to the 3D printer head to be placed in the specific shape. The addition of the polymer, which melts and binds at much lower temperatures than sintering temperatures, greatly decreases the required heating temperature and energy input. The main task of the project was to identify a functional material for the printer. The first step was to find a miscible. polymer/solvent solution. This solution was added to the regolith and the solvent was evaporated essentially leaving polymer-coated regolith particles. This material would be sent through the printer head and heated layer by layer to melt the polymer and bind the regolith. This method was one of many in a large goal to utilize materials in space with a custom-made 3D printer that builds dome-shaped habitats and other essential equipment for future deep space missions.

Tsoras, Alexandra

Atomic Oxygen Erosion Yield Dependence Upon Texture Development in Polymers

The atomic oxygen erosion yield (volume of a polymer that is lost due to oxidation per incident atom) of polymers is typically assumed to be reasonably constant with increasing fluence. However polymers containing ash or inorganic pigments, tend to have erosion yields that decrease with fluence due to an increasing presence of protective particles on the polymer surface. This paper investigates two additional possible causes for erosion yields of polymers that are dependent upon atomic oxygen. These are the development of surface texture which can cause the erosion yield to change with fluence due to changes in the aspect ratio of the surface texture that develops and polymer specific atomic oxygen interaction parameters. The surface texture development under directed hyperthermal attack produces higher aspect ratio surface texture than isotropic thermal energy atomic oxygen attack. The fluence dependence of erosion yields is documented for low Kapton H (DuPont, Wilmington, DE) effective fluences for a variety of polymers under directed hyperthermal and isotropic thermal energy attack.

oxygen atoms

Modifying Silicates for Better Dispersion in Nanocomposites

An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained.

Campbell, Sandi

Operando Optical Microscopy for Visualization of Dendrite Growth in an Argyrodite LPSCl–Polymer Composite Electrolyte

Herein, we demonstrate the utility of optical microscopy as an accessible technique for the in situ visualization of dendrite growth within polymer–sulfide composite solid-state electrolytes. The composite electrolyte features in situ polymerization and cross-linking of the polymer between ceramic particles, which opens up extensive opportunities for accelerated materials discovery, given the vast array of acrylate/methacrylate monomers available. Specifically, the cross-linked polymer poly(triethylene glycol dimethacrylate) (poly(TEGDMA)) was observed to effectively fill pores and inhibit dendrite growth at the lithium metal interface, attributed to its glassy state at room temperature. This work represents the first application of optical microscopy to illustrate that the incorporation of glassy, undoped polymers such as poly(TEGDMA) can serve as a viable strategy for dendrite suppression in solid-state composite electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Solvent-Free Melt-Processed Cathode Mitigates Li Anode Instability in Polymer-Based Solid-State Batteries

Solvent-free manufacturing of battery components is a promising alternative to traditional slurry processing for reducing the cost and environmental impact. In this work, we used twin-screw melt extrusion to fabricate a polymer-based high voltage composite cathode. The melt-processed cathode is dense (near zero porosity) and thick (65 μm) and has high active material loading (80 wt %). The active particles are distributed uniformly throughout the melt-processed cathode, unlike the traditional slurry-cast cathode, which exhibits inhomogeneous particle distribution. In the melt-processed cathode, polymer and carbon form separate phases, whereas in the slurry-cast cathode they blend into a single phase. Due to these structural differences, the melt-processed cathode shows smooth charge–discharge profiles, while the slurry-cast cathode shows noisy charging and soft-shorting behavior. In conclusion, this work highlights that twin-screw extrusion as a scalable, solvent-free manufacturing method is advantageous in producing uniform cathodes, which mitigates anode instability.

25 ENERGY STORAGE