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At least 667 records · Page 37

High cycle life secondary lithium battery

A secondary battery (10) of high energy density and long cycle is achieved by coating the separator (18) with a film (21) of cationic polymer such as polyvinyl-imidazoline. The binder of the positive electrode (14) such as an ethylene-propylene elastomer binder (26) containing particles (28) of TiS.sub.2 chalcogenide can also be modified to contain sulfone functional groups by incorporating liquid or solid sulfone materials such as 0.1 to 5 percent by weight of sulfolane into the binder. The negative lithium electrode (14), separator (18) and positive electrode (16) are preferably spirally wound and disposed within a sealed casing (17) containing terminals (32, 34). The modified separator and positive electrode are more wettable by the electrolytes in which a salt is dissolved in a polar solvent such as sulfolane.

Yen, Shiao-Ping S.↗

Large-Strain Transparent Magnetoactive Polymer Nanocomposites

A document discusses polymer nano - composite superparamagnetic actuators that were prepared by the addition of organically modified superparamagnetic nanoparticles to the polymer matrix. The nanocomposite films exhibited large deformations under a magnetostatic field with a low loading level of 0.1 wt% in a thermoplastic polyurethane elastomer (TPU) matrix. The maximum actuation deformation of the nanocomposite films increased exponentially with increasing nanoparticle concentration. The cyclic deformation actuation of a high-loading magnetic nanocomposite film was examined in a low magnetic field, and it exhibited excellent reproducibility and controllability. Low-loading TPU nanocomposite films (0.1-2 wt%) were transparent to semitransparent in the visible wavelength range, owing to good dispersion of the magnetic nanoparticles. Magnetoactuation phenomena were also demonstrated in a high-modulus, high-temperature polyimide resin with less mechanical deformation.

Meador, Michael A.↗

Additive Manufacturing of Frequency-Agile W-Band Packaging

Abstract —In this paper we demonstrate a fully additively manufactured packaged W-band amplifier with integrated bypass capacitors. This package was fabricated using a chip-first approach and aerosol jet printing. Package substrates (dielectrics), conductors and interconnects are printed around a bare die attached to a carrier. This package uses shaped ramp interconnects, allowing for frequency agnostic package performance of the interconnect with no impedance discontinuity, within the physical limits of the printer. High dielectric constant thin films of a polymer-matrix nanocomposite for bypass capacitors were printed using multi-material aerosol jet printing. The maximum measured packaged gain is 14.9 dB in the W-band, compared to the maximum bare die gain of 15.5 dB in the same frequency range. From 75 - 92 GHz, the average package loss is 1.1 dB including 3 mm transmission line, interconnects, and a GSG launch structure correlating to an average loss of 0.37 dB/mm.

Additive manufacturing, aerosol jet printing, hete↗

Variable-Temperature Scattering and Spectroscopy Characterizations for Temperature-Dependent Solution Assembly of PffBT4T-Based Conjugated Polymers

The solution structure of conjugated polymers (CPs) from which the films are cast is critical for tailoring the thin-film morphology thus device performance. Here, we used multimodal variable-temperature scattering and spectroscopy tools to fully quantify the solution assembly of poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-dialkyl-2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PffBT4T) polymers with varying side-chain lengths at different assembly temperatures. The conformational and aggregation behaviors for PffBT4T-based CPs were found to be very sensitive to both temperature and side chain length using ultraviolet–visible (UV–vis) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and small-angle neutron scattering (SANS). We found that with slightly increasing side chain length from 2-octyldodecyl (C8C12) to 2-nonyltridecyl (C9C13), PffBT4T-based CPs show a significant decrease in aggregation-to-dissolved chain transition temperature (10 °C), degree of aggregation, enthalpy change of aggregation, and size of the aggregates in solution. At room temperature, PffBT4T polymer strongly aggregated to form fabric structure with the film thickness of a few nanometers in thickness and hundreds of nanometers in length, as probed by atomic force microscopy (AFM), transmission electronic microscopy (TEM), and dynamic light scattering (DLS). At the elevated temperature above the aggregation-to-dissolved chain transition temperature, PffBT4T is fully dissolved and adopts a semiflexible coil conformation with the persistence length of 3.1 nm for PffBT4T-C8C12 and a slightly increased persistence length of 3.4 nm for PffBT4T-C9C13, according to temperature-dependent SANS measurements. Longer side chains of PffBT4T-C9C13 also lead to less aggregation enthalpy gain compared with PffBT4T-C8C12. This work provides a solution structure manipulating strategy of CPs and thus will inspire the molecular design and processing protocols of CPs toward higher performance electronic devices.

36 MATERIALS SCIENCE↗

Biomimetic/Optical Sensors for Detecting Bacterial Species

Biomimetic/optical sensors have been proposed as means of real-time detection of bacteria in liquid samples through real-time detection of compounds secreted by the bacteria. Bacterial species of interest would be identified through detection of signaling compounds unique to those species. The best-characterized examples of quorum-signaling compounds are acyl-homoserine lactones and peptides. Each compound, secreted by each bacterium of an affected species, serves as a signal to other bacteria of the same species to engage in a collective behavior when the population density of that species reaches a threshold level analogous to a quorum. A sensor according to the proposal would include a specially formulated biomimetic film, made of a molecularly imprinted polymer (MIP), that would respond optically to the signaling compound of interest. The MIP film would be integrated directly onto an opticalwaveguide- based ring resonator for optical readout. Optically, the sensor would resemble the one described in Chemical Sensors Based on Optical Ring Resonators (NPO-40601), NASA Tech Briefs, Vol. 29, No. 10 (October 2005), page 32. MIPs have been used before as molecular- recognition compounds, though not in the manner of the present proposal. Molecular imprinting is an approach to making molecularly selective cavities in a polymer matrix. These cavities function much as enzyme receptor sites: the chemical functionality and shape of a cavity in the polymer matrix cause the cavity to bind to specific molecules. An MIP matrix is made by polymerizing monomers in the presence of the compound of interest (template molecule). The polymer forms around the template. After the polymer solidifies, the template molecules are removed from the polymer matrix by decomplexing them from their binding sites and then dissolving them, leaving cavities that are matched to the template molecules in size, shape, and chemical functionality. The cavities thus become molecular-recognition sites that bind only to molecules matched to the sites; other molecules are excluded. In a sensor according to the proposal, the MIP would feature molecular recognition sites that would bind the specific signaling molecules selectively according to their size, shape, and chemical functionality (see figure). As the film took up the signaling molecules in the molecular recognition sites, the index of refraction and thickness of the film would change, causing a wavelength shift of the peak of the resonance spectrum. It has been estimated that by measuring this wavelength shift, it should be possible to detect as little as 10 picomoles of a peptide signaling compound.

Homer, Margie↗

Recycling of a post-industrial printed multilayer plastic film containing polyurethane inks by solvent-targeted recovery and precipitation

The recently reported Solvent-Targeted Recovery And Precipitation (STRAP) strategy is used to deconstruct multilayer plastic packaging films into their constituent resins by selective polymer dissolution. To broaden the applicability of STRAP, we demonstrate the process with a flexible post-industrial printed multilayer plastic film used for food packaging. The material was a reverse printed film composed of polyethylene (PE), ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), and polyurethane (PU)-based inks. Removal of all colors was observed with biomass-derived gamma-valerolactone (GVL) and the recovered polymers possessed comparable properties to the corresponding virgin resins. A technoeconomic analysis indicates that this STRAP process could be economically feasible at a processing capacity of 6,000 tons per year. Furthermore, the production of plastic films with materials recovered by this STRAP process can have a lower climate change impact than the production of films from virgin polymers.

54 ENVIRONMENTAL SCIENCES↗

Thin Films and Inflatable Applications in Exploration Habitat Structures

NASA's vision to return to the Moon and then extend human exploration to Mars will benefit from human habitat technology development using new and creative applications of polymer materials and concepts. Thin Film and Inflatable (TFVI) materials are particularly interesting for exploration applications due to their light weight and low volume. Whereas TF/I materials can be launched and carried from Earth to multiple and distant exploration sites without the constraints of upmass limitations, eventually, with recycling and reclamation efforts, these materials may be developed using in-situ resources. These materials can be useful for fabricating, patching and repairing vehicles, replacement parts and even habitat structures, as well as for developing stand-alone habitat structure technologies and for nested and integrated applications. TF/Is can also be ideal environmental containment vessels within lunar or Martian regolith walls or as liners inside caves or raw regolith exterior structures for the provisions of atmosphere containment, debris protection and cleanliness. Further, TFOs can be specialized and matured for various and diverse applications. The desired range of applications will require materials specification for such properties as transparency, elasticity, thermal conductivity, mechanical strength, heat capacity, chemical resistance, and permeability. This paper will discuss Marshall Space Flight Center's plans to analyze and prioritize TF/I materials properties and classifications and to develop applications for these highly desirable materials in human habitat construction projects on the Moon and Mars.

Frazier, Donald O.↗

Improved Organic Electrochemical Transistors via Directed Crystallizable Small Molecule Templating

Organic electrochemical transistors (OECTs) are of great interest as biosensors and for flexible electronics applications. Historically, processing techniques have been widely used to improve the performance of polymers in organic electronics but have been underutilized in the field of OECTs. Here, in this work, we study the effects of a crystallizable small molecule template for improving the performance of poly(3-hexylthiophene-2,5-diyl) (P3HT)-based OECTs. We utilize 1,3,5-trichlorobenzene (TCB) as a crystallizable additive to induce directional crystallization during blade coating. This procedure results in an aligned, highly ordered, and moderately porous layer of the semiconducting polymer. We find that compared to neat P3HT solutions, films cast with TCB additive show a greater than 8× improvement in the steady state figure of merit for OECTs. Additionally, the optimum TCB loading produces anisotropic OECTs where the polymer chain aligned parallel to the current outperforms the perpendicular alignment by more than a factor of 10. We investigated the mechanism of this improvement and found that polymer alignment, polymer ordering, and film porosity all play a role in improving the device performance. Overall, these results demonstrate the importance of processing on the optimization of polymers for OECTs and suggest a route to greatly improve the performance of commercially available hydrophobic polymers.

36 MATERIALS SCIENCE↗

Germanium Lift-Off Masks for Thin Metal Film Patterning

A technique has been developed for patterning thin metallic films that are, in turn, used to fabricate microelectronics circuitry and thin-film sensors. The technique uses germanium thin films as lift-off masks. This requires development of a technique to strip or undercut the germanium chemically without affecting the deposited metal. Unlike in the case of conventional polymeric lift-off masks, the substrate can be exposed to very high temperatures during processing (sputter deposition). The reason why polymeric liftoff masks cannot be exposed to very high temperatures (greater than 100 C) is because (a) they can become cross linked, making lift-off very difficult if not impossible, and (b) they can outgas nitrogen and oxygen, which then can react with the metal being deposited. Consequently, this innovation is expected to find use in the fabrication of transition edge sensors and microwave kinetic inductance detectors, which use thin superconducting films deposited at high temperature as their sensing elements. Transition edge sensors, microwave kinetic inductance detectors, and their circuitry are comprised of superconducting thin films, for example Nb and TiN. Reactive ion etching can be used to pattern these films; however, reactive ion etching also damages the underlying substrate, which is unwanted in many instances. Polymeric lift-off techniques permit thin-film patterning without any substrate damage, but they are difficult to remove and the polymer can outgas during thin-film deposition. The outgassed material can then react with the film with the consequence of altered and non-reproducible materials properties, which, in turn, is deleterious for sensors and their circuitry. The purpose of this innovation was to fabricate a germanium lift-off mask to be used for patterning thin metal films.

Brown, Ari↗

Solutions Are the Problem: Ordered Two-Dimensional Covalent Organic Framework Films by Chemical Vapor Deposition

Covalent organic frameworks (COFs) are a promising class of crystalline polymer networks that are useful due to their high porosity, versatile functionality, and tunable architecture. Conventional solution-based methods of producing COFs are marred by slow reactions that produce powders that are difficult to process into adaptable form factors for functional applications, and there is a need for facile and fast synthesis techniques for making crystalline and ordered covalent organic framework (COF) thin films. In this work, we report a chemical vapor deposition (CVD) approach utilizing co-evaporation of two monomers onto a heated substrate to produce highly crystalline, defect-free COF films and coatings with hydrazone, imine, and ketoenamine COF linkages. Further, this all-in-one synthesis technique produces highly crystalline, 40 nm–1 μm-thick COF films on Si/SiO2 substrates in less than 30 min. Crystallinity and alignment were proven by using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and transmission electron microscopy (TEM), and successful conversion of the monomers to produce the target COF was supported by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV–vis measurements. Additionally, we used atomic force microscopy (AFM) to investigate the growth mechanisms of these films, showing the coalescence of triangular crystallites into a smooth film. To show the wide applicability and scope of the CVD process, we also prepared crystalline ordered COF films with imine and ketoenamine linkages. These films show potential as high-quality size exclusion membranes, catalytic platforms, and organic transistors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly Deformable Rigid Glassy Conjugated Polymeric Thin Films

Wearable devices benefit from the use of stretchable conjugated polymers (CPs). Traditionally, the design of stretchable CPs is based on the assumption that a low elastic modulus (E) is crucial for achieving high stretchability. However, this research, which analyzes the mechanical properties of 65 CP thin films, challenges this notion. It is discovered that softness alone does not determine stretchability; rather, it is the degree of entanglement that is critical. This means that rigid CPs can also exhibit high stretchability, contradicting conventional wisdom. To inverstigate further, the mechanical behavior, electrical properties, and deformation mechanism of two model CPs: a glassy poly(3-butylthiophene-2,5-diyl) (P3BT) with an E of 2.2 GPa and a viscoelastic poly(3-octylthiophene-2,5-diyl) (P3OT) with an E of 86 MPa, are studied. Ex situ transmission X-ray scattering and polarized UV–vis spectroscopy revealed that only the initial strain (i.e., <20%) exhibits different chain alignment mechanisms between two polymers, while both rigid and soft P3ATs showed similarly behavior at larger strains. In conclusion, by challenging the conventional design metric of low E for high stretchability and highlighting the importance of entanglement, it is hoped to broaden the range of CPs available for use in wearable devices.

36 MATERIALS SCIENCE↗

Preparation of atomic oxygen resistant polymeric materials

Polyphenyl quinoxalines (PPQs) are an important family of high performance polymers that offer good chemical and thermal stability coupled with excellent mechanical properties. These aromatic heterocyclic polymers are potentially useful as films, coatings, adhesives, and composite materials that demand stability in harsh environments. Our approach was to prepare PPQs with pendent siloxane groups using the appropriate chemistry and then evaluate these polymers before and after exposure to simulated atomic oxygen. Either monomer, the bis(o-diamine)s or the bis(alpha-diketone)s can be synthesized with a hydroxy group to which the siloxane chain will be attached. Several novel materials were prepared.

Tortorelli, Victor J.↗

Detecting Airborne Mercury by Use of Polymer/Carbon Films

Films made of certain polymer/carbon composites have been found to be potentially useful as sensing films for detecting airborne elemental mercury at concentrations on the order of tens of parts per billion or more. That is to say, when the polymer/carbon composite films are exposed to air containing mercury vapor, their electrical resistances decrease by measurable amounts. Because airborne mercury is a health hazard, it is desirable to detect it with great sensitivity, especially in enclosed environments in which there is a risk of a mercury leak from lamps or other equipment. The present effort to develop polymerbased mercury-vapor sensors complements the work reported in NASA Tech Briefs Detecting Airborne Mercury by Use of Palladium Chloride (NPO- 44955), Vol. 33, No. 7 (July 2009), page 48 and De tecting Airborne Mer cury by Use of Gold Nanowires (NPO-44787), Vol. 33, No. 7 (July 2009), page 49. Like those previously reported efforts, the present effort is motivated partly by a need to enable operation and/or regeneration of sensors under relatively mild conditions more specifically, at temperatures closer to room temperature than to the elevated temperatures (greater than 100 C ) needed for regeneration of sensors based on noble-metal films. The present polymer/carbon films are made from two polymers, denoted EYN1 and EYN2 (see Figure 1), both of which are derivatives of poly-4-vinyl pyridine with amine functional groups. Composites of these polymers with 10 to 15 weight percent of carbon were prepared and solution-deposited onto the JPL ElectronicNose sensor substrates for testing. Preliminary test results showed that the resulting sensor films gave measurable indications of airborne mercury at concentrations on the order of tens of parts per billion (ppb) or more. The operating temperature range for the sensing films was 28 to 40 C and that the sensor films regenerated spontaneously, without heating above operating temperature (see Figure 2).

Shevade, Abhijit↗

Zr-Containing 4,4'-ODA/PMDA Polyimide Composites

The objective of this research is to improve the atomic oxygen resistance of Kapton(TM), a polyimide (PI) made from pyromellitic acid dianhydride (PMDA) and 4,4'-oxydianiline (ODA), while retaining or enhancing the desirable properties of the pure polymer. Toward this end, zirconium-containing complexes and polymers were used to make composites and blends. Tetra(acetylacetonato)zirconium(IV), Zr(acac)4, which is commercially available, was identified as the best zirconium-containing complex for enhancing the atomic oxygen resistance of polyimide composites of the 10 complexes screened. Films prepared from the commercially available polyamic acid (PAA) of PMDA-ODA (DuPont) have good uniformity, flexibility, and tensile strength. A 24-layer 10% (mol) Zr(acac)4/PI composite film showed significant improvement (ca. 20 fold) of atomic oxygen resistance over the pure polyimide. However, 10% (mol) Zr(acac)4 represents an upper concentration limit, above which films undergo cracking upon thermal imidization. In order to increase the Zr complex concentration in PMDA-ODA PI films, while retaining good film properties, [Zr(adsp)2-PMDA]n coordination polymer [bis(4-amino-N,N'-disalicylidene- 1,2-phenylenediamino)zirconium(IV)-pyromellitic dianhydride] and [Zr(adsp)2-PMDA-ODA-PMDA]n terpolymer were synthesized and blended with commercial PAA, respectively. Several techniques were used to characterize the films made from the polymer containing Zr(acac)4. Plasma studies of films having 2% (mol) incremental concentrations of Zr in the Kapton up to 10% (mol) show that the overall rate of erosion is reduced about 75 percent.

Illingsworth, M. L.↗

The Effect of Thin Film Adhesives on Mode I Interlaminar Fracture Toughness in Carbon Fiber Composites with Shape Memory Alloy Inserts

Shape Memory Alloy (SMA) was placed within Polymer Matrix Composite (PMC) panels alongside film adhesives to examine bonding. Double cantilever beam (DCB) testing was performed using ASTM D5528. C-scanning was performed before testing, modal acoustic emissions (MAE) were monitored during testing, and microscopy performed post-test. Data was analyzed using modified beam theory (MBT), compliance calibration (CC) and modified compliance calibration (MCC) methods. Fracture toughness for control specimens was higher than previously reported due to fiber-bridging. Specimens with SMAs and adhesives stabilized crack propagation. Results revealed SMA-bridging; a phenomenon mimicking fiber-bridging which increased the load and fracture toughness of SMA specimens.

Derek J Quade↗

Anti-Icing Coatings using Ionomer Film Layer Structuring

This research effort examined the application of Nafion polymers in alcohol solvents as an anti-ice surface coating, as a mixture with hydrophilic polymers and freezing point depressant salt systems. Co-soluble systems of Nafion, polymer and salt were applied using dip coating methods to create smooth films for frost observation over a Peltier plate thermal system in ambient laboratory conditions. Cryo-DSC was applied to examine freezing events of the Nafion-surfactant mixtures, but the sensitivity of the measurement was insufficient to determine frost behavior. Collaborations with the Fog Chamber at Sandia-Albuquerque, and in environmental SAXS measurements with CINT-LANL were requested but were not able to be performed under the research duration. Since experimental characterization of these factors is difficult to achieve directly, computational modeling was used to guide the scientific basis for property improvement. Computational modeling was performed to improve understanding of the dynamic association between ionomer side groups and added molecules and deicing salts. The polyacrylic acid in water system was identified at the start of the project as a relevant system for exploring the effect of varying counterions on the properties of fully deprotonated polyacrylic acid (PAA) in the presence of water. Simulations were modeled with four different counterions, two monovalent counterions (K+ and Na+) and two divalent counterions (Ca2+ and Mg2+). The wt% of PAA in these systems was varied from ~10 to 80 wt% PAA for temperatures from 250K to 400K. In the second set of simulations, the interpenetration of water into a dry PAA film was studied for Na+ or Ca2+ counterions for temperatures between 300K and 400K. The result of this project is a sprayable Nafion film composite which resists ice nucleation at -20 °C for periods of greater than three hours. It is composed of Nafion polymer, hydrophilic polyethylene oxide polymer and CaCl2 anti-ice crosslinker. Durability and field performance properties remain to be determined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication of ultrathin suspended membranes from atomic layer deposition films

In this report, ultrathin films suspended as freestanding membranes are critical to many microelectronic and materials science applications. However, fabrication methods are currently limited in either their flexibility, due to material selectivity issues during the final membrane release, or their scalability. Here, we demonstrate a novel fabrication process for suspending ultrathin films with thicknesses as low as 4 nm and lateral dimensions up to 20 x 1000 μm from a variety of materials grown by atomic layer deposition. A silicon nitride membrane serves as the support for a sacrificial polymer layer and an ultrathin atomic layer deposition film which, after plasma etching, will form the membrane. The high chemical selectivity between atomic layer deposition-grown transition metal nitrides and oxides and the sacrificial polymer means that ultrathin films of a variety of materials can be released without damage using a single process. Electrically conductive titanium nitride membranes can be produced by this method and are of significant interest for electron microscopy applications. Electron transparency of titanium nitride membranes was found to be ~14% higher than silicon nitride of the same thickness, and of similar conductivity to graphite, meaning that ultrathin, conductive, and electron transparent membranes can be fabricated at scale. These membranes are ideal supports for electron and photon characterization techniques, as well as microelectromechanical system applications that require a conductive membrane.

36 MATERIALS SCIENCE↗

Polyenamines for Films, Coatings, and Adhesives

Easy process makes polymers with good mechanical properties. Synthesis involves Michael-type addition polymerization of two diacetylenic diketones, with various aromatic diamines in m-cresol at 60 to 130 degrees C. Technique provides synthetic route to high-molecular-weight polyenamines with moderate thermal stability and good mechanical properties. Polyenamines produced exhibit potential for use as films, coatings, adhesives, molding compounds, and composite matrices.

Hergenrother, Paul M.↗