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At least 73 records · Page 4

Post polymerization cure shape memory polymers

This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

Wilson, Thomas S.↗

In situ deposits of copper and copper oxide containing condensation polyimide films

Novel copper-polyimide composites have been synthesized via simultaneous thermal decomposition of solid solutions of bis (trifluoroacetylacetonato) copper (II) and thermal cyclodehydration of polyimide acid. In contrast to conventional filled polymer composites which are prepared by dispersion of particles or fibers in a polymer matrix this study has yielded in general uniform Cu or CuO dispersions of very small particle size that reside near the film surface that was exposed to the atmosphere during curing. The nature of the copper deposit, the thickness of the copper deposit, and the polyimide overlayer which bonds the copper to the polymer substrate depend on the curing atmosphere used. A variety of analytical surface methods along with thermogravimetric analysis and variable temperature (surface and volume) electrical resistivity measurements have been used to characterize these thin, flexible copper doped polyimide films.

Porta, G. M.↗

Molecular-level design of alternative media for energy-saving pilot-scale fibrillation of nanocellulose

The outstanding mechanical properties, light weight, and biodegradability of cellulose nanofibrils (CNFs) make them promising components of renewable and sustainable next-generation reinforced composite biomaterials and bioplastics. Manufacturing CNFs at a pilot scale requires disc-refining fibrillation of dilute cellulose fibers in aqueous pulp suspensions to shear the fibers apart into their nanodimensional forms, which is, however, an energy-intensive process. Here, in this study, we used atomistic molecular dynamics (MD) simulation to examine media that might facilitate the reduction of interactions between cellulose fibers, thereby reducing energy consumption in fibrillation. The most suitable medium found by the simulations was an aqueous solution with 0.007:0.012 wt.% NaOH:urea, and indeed this was found in pilot-scale experiments to reduce the fibrillation energy by ~21% on average relative to water alone. The NaOH:urea-mediated CNFs have similar crystallinity, morphology, and mechanical strength to those formed in water. The NaOH and urea act synergistically on CNFs to aid fibrillation but at different length scales. NaOH deprotonates hydroxyl groups leading to mesoscale electrostatic repulsion between fibrils, whereas urea forms hydrogen bonds with protonated hydroxyl groups thus disrupting interfibril hydrogen bonds. This suggests a general mechanism in which an aqueous medium that contains a strong base and a small organic molecule acting as a hydrogen-bond acceptor and/or donor may be effectively employed in materials processes where dispersion of deprotonable polymers is required. The study demonstrates how atomic-detail computer simulation can be integrated with pilot-scale experiments in the rational design of materials processes for the circular bioeconomy.

36 MATERIALS SCIENCE↗

Versatile Coating

A radome at Logan Airport and a large parabolic antenna at the Wang Building in Massachusetts are protected from weather, corrosion and ultraviolet radiation by a coating, specially designed for antennas and radomes, known as CRC Weathertite 6000. The CRC 6000 line that emerged from Boyd Coatings Research Co., Inc. is a solid dispersion of fluorocarbon polymer and polyurethane that yields a tough, durable film with superior ultraviolet resistance and the ability to repel water and ice over a long term. Additionally, it provides resistance to corrosion, abrasion, chemical attacks and impacts. Material can be used on a variety of substrates, such as fiberglass, wood, plastic and concrete in addition to steel and aluminum. In addition Boyd Coatings sees CRC 6000 applicability as an anti-icing system coated on the leading edge of aircraft wings.

Source record↗

Multifunctional, High-Temperature Nanocomposites

In experiments conducted as part of a continuing effort to incorporate multifunctionality into advanced composite materials, blends of multi-walled carbon nanotubes and a resin denoted gPETI-330 h (wherein gPETI h is an abbreviation for gphenylethynyl-terminated imide h) were prepared, characterized, and fabricated into moldings. PETI-330 was selected as the matrix resin in these experiments because of its low melt viscosity (<10 poise at a temperature of 280 C), excellent melt stability (lifetime >2 hours at 280 C), and high temperature performance (>1,000 hours at 288 C). The multi-walled carbon nanotubes (MWCNTs), obtained from the University of Kentucky, were selected because of their electrical and thermal conductivity and their small diameters. The purpose of these experiments was to determine the combination of thermal, electrical, and mechanical properties achievable while still maintaining melt processability. The PETI-330/MWCNT mixtures were prepared at concentrations ranging from 3 to 25 weight-percent of MWCNTs by dry mixing of the constituents in a ball mill using zirconia beads. The resulting powders were characterized for degree of mixing and thermal and rheological properties. The neat resin was found to have melt viscosity between 5 and 10 poise. At 280 C and a fixed strain rate, the viscosity was found to increase with time. At this temperature, the phenylethynyl groups do not readily react and so no significant curing of the resin occurred. For MWCNT-filled samples, melt viscosity was reasonably steady at 280 C and was greater in samples containing greater proportions of MWCNTs. The melt viscosity for 20 weightpercent of MWCNTs was found to be .28,000 poise, which is lower than the initial estimated allowable maximum value of 60,000 poise for injection molding. Hence, MWCNT loadings of as much as 20 percent were deemed to be suitable compositions for scale-up. High-resolution scanning electron microscopy (HRSEM) showed the MWCNTs to be well dispersed in the polymer matrices, while high-resolution transmission electron microscopy shows splits in the walls of the MWCNTs but no catastrophic breakage of tubes. To further assess processing characteristics prior to scale-up, samples containing 10, 15, and 20 weight-percent of MWCNTs were processed through a laboratory melting extruder. HRSEM of the extruded fibers shows significant alignment of MWCNTs in the flow direction (see figure). For the samples containing 20 weight-percent of MWCNTs, difficulties were encountered during feeding, and the temperature of a rotor in the extruder rose to 245 C because of buildup of frictional heat; this indicates that materials of this type having MWCNT concentrations .20 weight- percent may not be melt-processable. On the basis of the results from the foregoing characterizations, samples containing 10, 15, and 20 weight-percent of MWCNTs were scaled up to masses of .300 g and used to make specimens having dimensions of 10.2 by 15.2 by 0.32 cm. These specimens were molded by (1) injecting the mixtures, at temperatures between 260 and 280 C, into a tool made of the low-thermal-expansion alloy InvarR and then (2) curing for 1 hour at 371 C. The tool was designed to impart shear during the injection process in an attempt to achieve some alignment of the MWCNTs in the flow direction.

Connell, John W.↗

Layered Electrode Architectures Enabled by Holey Graphene Hosts

Battery electrodes are typically prepared using a slurry-based method, where high boiling point organic solvents are typically used with a polymer binder to disperse active electrode materials and conductive carbon additives followed by casting into current collector sheets. In this process, the use of organic solvents are environmentally hazardous, energy intensive, and time-consuming, while polymeric binders add weight and can undergo parasitic reactions during battery cycling. Here we discuss the use of a unique conductive carbon nanomaterial, namely holey graphene, as a multifunctional host that can be processed via a facile, solvent-free, binder-free, cold pressing method to prepare electrodes with unique architectures. This approach can accommodate a broad range of battery chemistries, such as lithium oxygen/carbon dioxide (Li-O2/CO2), lithium sulfur/selenium (Li-S/Se), and various lithium ion chemistries. The successful use of dry, cold compression allows the convenient modification of electrode mass loading with unique architectures containing active materials randomly mixed or layered with single or multiple layers of one or more active materials. In the conventional slurry-based electrode fabrication method, it is difficult, if not impossible, to achieve such layered architectures. In particular, the layered electrode architectures from the dry, cold press approach are easy to fabricate without significantly sacrificing device performance, and are amenable to continuous roll-to-roll dry processing. In addition, these architectures offer unprecedented perspectives on the battery material loading vs. utilization efficiency, as well as enabling unique characterization opportunities to advance mechanistic understanding of various battery chemistries. Potential applications of this unique electrode fabrication approach for solid-state batteries will also be discussed.

holey graphene, batteries, electrode architecture,↗

Thermodynamic Approach to Boron Nitride Nanotube Solubility and Dispersion

Inadequate dispersion of nanomaterials is a critical issue that significantly limits the potential properties of nanocomposites and when overcome, will enable further enhancement of material properties. The most common methods used to improve dispersion include surface functionalization, surfactants, polymer wrapping, and sonication. Although these approaches have proven effective, they often achieve dispersion by altering the surface or structure of the nanomaterial and ultimately, their intrinsic properties. Co-solvents are commonly utilized in the polymer, paint, and art conservation industries to selectively dissolve materials. These co-solvents are utilized based on thermodynamic interaction parameters and are chosen so that the original materials are not affected. The same concept was applied to enhance the dispersion of boron nitride nanotubes (BNNTs) to facilitate the fabrication of BNNT nanocomposites. Of the solvents tested, dimethylacetamide (DMAc) exhibited the most stable, uniform dispersion of BNNTs, followed by N,N-dimethylformamide (DMF), acetone, and N-methyl-2-pyrrolidone (NMP). Utilizing the known Hansen solubility parameters of these solvents in comparison to the BNNT dispersion state, a region of good solubility was proposed. This solubility region was used to identify co-solvent systems that led to improved BNNT dispersion in poor solvents such as toluene, hexane, and ethanol. Incorporating the data from the co-solvent studies further refined the proposed solubility region. From this region, the Hansen solubility parameters for BNNTs are thought to lie at the midpoint of the solubility sphere: 16.8, 10.7, and 9.0 MPa(exp 1/2) for delta d, delta p, and delta h, respectively, with a calculated Hildebrand parameter of 21.8 MPa)exp 1/2).

Tiano, A. L.↗

Stable powders made from photosensitive polycrystalline complexes of heterocyclic monomers and their polymers

The present invention relates to a low electronic conductivity polymer composition having well dispersed metal granules, a stable powder made from photosensitive polycrystalline complexes of pyrrole, or its substituted derivatives and silver cations for making the polymer composition, and methods of forming the stable powder and polymer composition, respectively. A polycrystalline complex of silver and a monomer, such as pyrrole, its substituted derivatives or combinations thereof, is precipitated in the form of a stable photosensitive powder upon addition of the monomer to a solvent solution, such as toluene containing an electron acceptor. The photosensitive powder can be stored in the dark until needed. The powder may be dissolved in a solvent, cast onto a substrate and photopolymerized.

Hodko, Dalibor↗

Working Toward Nanotube Composites

One of the most attractive applications of single-wall carbon nanotubes (SWNT) is found in the area of structural materials. Nanotubes have a unique combination of high strength, modulus, and elongation to failure, and therefore have potential to significantly enhance the mechanical properties of today's composites. This is especially attractive for the aerospace industry looking for any chance to save weight. This is why NASA has chosen to tackle this difficult application of SWNT. Nanotube properties differ significantly from that of conventional carbon fibers, and a whole new set of problems, including adhesion and dispersion in the adhesive polymer matrix, must be resolved in order to engineer superior composite materials. From recent work on a variety of applications it is obvious that the wide range of research in nanotubes will lead to advances in physics, chemistry, and engineering. However, the possibility of ultralightweight structures is what causes dreamers to really get excited. One of the important issues in composite engineering is aspect ratio of the fibers, since it affects load transfer in composites. Nanotube length was a gray area for years, since they are formed in bundles, making it impossible to monitor individual nanotube length. Even though bundles are observed to be tens and hundreds of microns long, they can be built of relatively short tubes weakly bound by Van der Waals forces. Nanotube length can be affected by subsequent purification and ultrasound processing, which has been necessary in order to disperse nanotubes and introduce them into a polymer matrix. Some calculations show that nanotubes with 10(exp 5) aspect ratio may be necessary to achieve good load transfer. We show here that nanotubes produced in our laser system are as much as tens of microns long and get cut into lengths of hundreds of nanometers during ultrasound processing. Nanotube length was measured by AFM on pristine nanotube specimens as well, as after sonication. In each case great care was taken to measure individual nanotubes, rather than bundles. Pristine nanotubes were collected on quartz substrates placed directly in the laser oven and exposed for 0.5 s. This results in an equal mix of bundles and individual nanotubes. Nanotube length measurements were limited practically by the lateral span of the AFM scanner, but nanotube length is certainly in excess of 20 micrometers.

Arepalli, Sivaram↗

Phase-inversion polymer composite material, fabricating methods and applications of same

A composite film usable as a separator of an electrochemical device includes hBN nanosheets and at least one polymer. The hBN nanosheets are uniformly dispersed within a matrix of said least one polymer to achieve a highly porous microstructure. Said at least one polymer comprises one or more electrically insulating and electrochemically inert polymers.

Hersam, Mark C.↗

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.↗

Anomalous dispersion in coupled surface plasmons and excitons

We studied dispersion in Rhodamine laser dyes in the Kretschmann geometry and found (i) multi-branch “staircase” dispersion curves in singly doped and double doped PMMA polymer, (ii) emergence of the new dispersion “fork” branch, (iii) unparallel dispersion and coupling in the mixture of two different dyes, and (iv) effect of high dye concentration on strong coupling without metal.

36 MATERIALS SCIENCE↗

Imaging Carbon Nanotubes in High Performance Polymer Composites via Magnetic Force Microscope

Application of carbon nanotubes as reinforcement in structural composites is dependent on the efficient dispersion of the nanotubes in a high performance polymer matrix. The characterization of such dispersion is limited by the lack of available tools to visualize the quality of the matrix/carbon nanotube interaction. The work reported herein demonstrates the use of magnetic force microscopy (MFM) as a promising technique for characterizing the dispersion of nanotubes in a high performance polymer matrix.

Lillehei, Peter T.↗

Polymer/Silicate Nanocomposites Developed for Improved Strength and Thermal Stability

Over the past decade, polymer-silicate nanocomposites have been attracting considerable attention as a method of enhancing polymer properties. The nanometer dimensions of the dispersed silicate reinforcement can greatly improve the mechanical, thermal, and gas barrier properties of a polymer matrix. In a study at the NASA Glenn Research Center, the dispersion of small amounts (less than 5 wt%) of an organically modified layered silicate (OLS) into the polymer matrix of a carbon-fiber-reinforced composite has improved the thermal stability of the composite. The enhanced barrier properties of the polymer-clay hybrid are believed to slow the diffusion of oxygen into the bulk polymer, thereby slowing oxidative degradation of the polymer. Electron-backscattering images show cracking of a nanocomposite matrix composite in comparison to a neat resin matrix composite. The images show that dispersion of an OLS into the matrix resin reduces polymer oxidation during aging and reduces the amount of cracking in the matrix significantly. Improvements in composite flexural strength, flexural modulus, and interlaminar shear strength were also obtained with the addition of OLS. An increase of up to 15 percent in these mechanical properties was observed in composites tested at room temperature and 288 C. The best properties were seen with low silicate levels, 1 to 3 wt%, because of the better dispersion of the silicate in the polymer matrix.

Campbell, Sandi G.↗

Carbon Nanotube/Space Durable Polymer Nanocomposite Films for Electrostatic Charge Dissipation

Low solar absorptivity, space environmentally stable polymeric materials possessing sufficient electrical conductivity for electrostatic charge dissipation (ESD) are of interest for potential applications on spacecraft as thin film membranes on antennas, solar sails, large lightweight space optics, and second surface mirrors. One method of imparting electrical conductivity while maintaining low solar absorptivity is through the use of single wall carbon nanotubes (SWNTs). However, SWNTs are difficult to disperse. Several preparative methods were employed to disperse SWNTs into the polymer matrix. Several examples possessed electrical conductivity sufficient for ESD. The chemistry, physical, and mechanical properties of the nanocomposite films will be presented.

Smith, J. G., Jr.↗

Electrospinning of ultra-high molecular weight polymers into aligned nanofibers and their application in chemical separations

Ultra-high molecular weight (UHMW, >10 6 g mol −1 ) vinyl polymers are increasingly accessible through photoiniferter polymerization, yet their behavior in electrospinning has received comparatively little attention. Here, we explore the electrospinning of UHMW poly(methyl acrylate), poly(methyl methacrylate), poly(N,N-dimethylacrylamide), and poly(styrene-co-pentafluorostyrene) synthesized by photoiniferter polymerization, with number-average molecular weights (M n ) greater than 1000 kDa and dispersities below 1.4. UHMW polymers form stable Taylor cones and discrete fibers at solution concentrations as low as 0.5 wt% due to their large number of entanglements, a threshold unachievable with low molecular weight (M n = 20–54 kDa) polymers of the same chemistry. Using poly(methyl methacrylate) and poly(styrene-co-pentafluorostyrene) as model systems, we demonstrate that fiber diameter can be tuned from 350 nm to 20 μm through systematic variation of polymer concentration (0.01 to 4 wt%) and flow rate (0.5 to 10 mL h −1 ). Additionally, we find that collector rotation rate governs fiber alignment, with highly aligned mats obtained with drum rotation speeds of 1000 RPM. Reversing the polarity of the electric field during electrospinning reorients the surface chemistry of these fiber mats without altering their microscale morphology, shifting the water contact angle by 7° (89° to 96°) and providing a two-fold binding capacity enhancement in cationic dye uptake. These results show that the high entanglement densities of UHMW vinyl polymers shift the accessible electrospinning window to dilute solutions and that electric-field polarity is a useful lever to control the surface chemistry in the resulting fibers.

Marquez, Joshua D. [University of Florida, Gainesv↗

Polyimide Nanocomposites Prepared from High-Temperature, Reduced Charge Organoclays

Montmorillonite clays modified with the dihydrochloride salt of 1,3-bis(3-aminophenoxy)benzene (APB) were used in the preparation of polyimide/organoclay hybrid films. Organoclays with varying surface charge based upon APB were prepared and examined for their dispersion behavior in the polymer matrix. High molecular weight poly(amide acid) solutions were prepared in the presence of the organoclays. Films were cast and subsequently heated to 300C to cause imidization. The resulting nanocomposite films, containing 3 wt% of organoclay, were characterized by transmission electron microscopy and X-ray diffraction. The clay's cation exchange capacity (CEC) played a key role in determining the extent of dispersion in the polyimide matrix. Considerable dispersion was observed in some of the nanocomposite films. The most effective organoclay was found to have a CEC of 0.70 meq/g. Nanocomposite films prepared with 3-8 wt% of this organoclay were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and thin-film tensile testing. High levels of clay dispersion could be achieved even at the higher clay loadings. Results from mechanical testing revealed that while the moduli of the nanocomposites increased with increasing clay loadings, both strength and elongation decreased.

Delozier, D. M.↗