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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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At least 271 records · Page 15

Preignition reactions of AP-HTPB propellants studied by IR spectrometry

IR absorption spectrometry was used to follow the disappearance of NH and CH bonds during the pyrolysis of a polymer film containing 30 weight percent ammonium perchlorate (AP). The remaining 70 weight percent consisted of a mixture of 92.5 weight percent hydroxyl-terminated polybutadiene (HTPB) and 7.5 weight percent isophrone diisocyanate (IPDI). The results indicate that polymer decomposition is induced by products of AP decomposition, and that about 2.5 CH bonds disappear for each NH bond that disappears. The diffusion process occurring in the later stages of the reaction is analyzed in an attempt to account for the unexpectedly low activation energy.

Law, R. J.↗

Effect of LEO Exposure on Aromatic Polymers Containing Phenylphosphine Oxide Groups

As part of the Materials on The International Space Station Experiment (MISSE), aromatic polymers containing phenylphosphine oxide groups were exposed to low Earth orbit (LEO) for approximately 4 years. All of the aromatic polymers containing phenylphosphine oxide groups survived the exposure despite the high fluence of atomic oxygen that completely eroded other polymer films such as Kapton and Mylar of comparable or greater thickness. The samples consisted of a colorless polyimide film and a poly(arylene ether benzimidazole) film and thread. The samples were characterized for changes in physical properties, thermal/optical properties (i.e. solar absorptivity and thermal emissivity), surface chemistry (X-ray photoelectron spectroscopy), and surface topography (atomic force microscopy). The data from the polymer samples on MISSE were compared to samples from the same batch of material stored under ambient conditions on Earth. In addition, comparisons were made between the MISSE samples and those subjected to shorter term space flight exposures. The results of these analyses will be presented.

Watson, K. A.↗

Conductive Carbon Nanotube Inks for Use with Desktop Inkjet Printing Technology

Inkjet printing is a common commercial process. In addition to the familiar use in printing documents from computers, it is also used in some industrial applications. For example, wire manufacturers are required by law to print the wire type, gauge, and safety information on the exterior of each foot of manufactured wire, and this is typically done with inkjet or laser printers. The goal of this work was the creation of conductive inks that can be applied to a wire or flexible substrates via inkjet printing methods. The use of inkjet printing technology to print conductive inks has been in testing for several years. While researchers have been able to get the printing system to mechanically work, the application of conductive inks on substrates has not consistently produced adequate low resistances in the kilohm range. Conductive materials can be applied using a printer in single or multiple passes onto a substrate including textiles, polymer films, and paper. The conductive materials are composed of electrical conductors such as carbon nanotubes (including functionalized carbon nanotubes and metal-coated carbon nanotubes); graphene, a polycyclic aromatic hydrocarbon (e.g., pentacene and bisperipentacene); metal nanoparticles; inherently conductive polymers (ICP); and combinations thereof. Once the conductive materials are applied, the materials are dried and sintered to form adherent conductive materials on the substrate. For certain formulations, increased conductivity can be achieved by printing on substrates supported by low levels of magnetic field alignment. The adherent conductive materials can be used in applications such as damage detection, dust particle removal, smart coating systems, and flexible electronic circuitry. By applying alternating layers of different electrical conductors to form a layered composite material, a single homogeneous layer can be produced with improved electrical properties. It is believed that patterning alternate layers of different conductors may improve electrical pathways through alignment of the conductors and band gap optimization. One feature of this innovation is that flexible conductive traces could be accomplished with a conductive ink having a surface resistivity of less than 10 ohms/square. Another result was that a composite material comprising a mixture of carbon nanotubes and metallic nanoparticles could be applied by inkjet printing to flexible substrates, and the resulting applied material was one to two orders of magnitude more conductive than a material made by printing inks containing carbon nanotubes alone.

Roberson, Luke↗

Impact of hydrophobic pendant phenyl groups on transport and co-transport of methanol and acetate in PEGDA-SPMAK cation exchange membranes

CO 2 reduction cells are innovative devices that reduce CO 2 into valuable chemicals (i.e. methanol (MeOH) and acetate (OAc – )) on the cathode. A major challenge with such devices is to develop ion exchange membranes that allow ion-selective transport (i.e., protons for cation exchange membranes, CEM) and suppress the crossover of CO 2 reduction products. To design such membranes, it is important to understand multi-solute transport behavior of these solutes. Previously, our group reported acetate diffusivities in co-transport with MeOH increase in sulfonated CEMs, where we speculated charge screening of the electrostatic interactions by co-diffusing MeOH has an impact. Here, crosslinked membranes fabricated by photopolymerization of poly(ethylene glycol) diacrylate (PEGDA), 3-sulfopropyl methacrylate potassium (SPMAK, SO 3 – -containing ionomer), and a phenyl-containing comonomer either phenoxyethyl acrylate (PEA) or poly(ethylene glycol) phenyl ether acrylate (PEGPEA)) are investigated. We observe OAc – diffusivities to both (1) PEGDA-SPMAK and (2) PEGDA-PEGPEA increase in co-diffusion with MeOH and those to (3) PEGDA-SPMAK/PEGPEA decrease. To rationalize this emergent co-transport behavior, we speculate (1) electrostatic interactions are interfered with by co-diffusing MeOH, (2) chain mobility (segmental dynamics) increases in the presence of MeOH and (3) for films with both hydrophobic (PEGPEA) and hydrophilic (SPMAK) comonomers chain mobility (segmental dynamics) decrease due to interactions between the comonomer sidechains depressing overall solute diffusivities. Finally, while further investigations are needed, this work contributes to improving our fundamental understanding of the relationships between polymer film chemistry, solute chemistry, and emergent cotransport behavior observed and described in this work (and others) towards enabling the design of improved membrane materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Automated Fiber Placement of PEEK/IM7 Composites with Film Interleaf Layers

The incorporation of thin discrete layers of resin between plies (interleafing) has been shown to improve fatigue and impact properties of structural composite materials. Furthermore, interleafing could be used to increase the barrier properties of composites used as structural materials for cryogenic propellant storage. In this work, robotic heated-head tape placement of PEEK/IM7 composites containing a PEEK polymer film interleaf was investigated. These experiments were carried out at the NASA Langley Research Center automated fiber placement facility. Using the robotic equipment, an optimal fabrication process was developed for the composite without the interleaf. Preliminary interleaf processing trials indicated that a two-stage process was necessary; the film had to be tacked to the partially-placed laminate then fully melted in a separate operation. Screening experiments determined the relative influence of the various robotic process variables on the peel strength of the film-composite interface. Optimization studies were performed in which peel specimens were fabricated at various compaction loads and roller temperatures at each of three film melt processing rates. The resulting data were fitted with quadratic response surfaces. Additional specimens were fabricated at placement parameters predicted by the response surface models to yield high peel strength in an attempt to gage the accuracy of the predicted response and assess the repeatability of the process. The overall results indicate that quality PEEK/lM7 laminates having film interleaves can be successfully and repeatability fabricated by heated head automated fiber placement.

Hulcher, A. Bruce↗

Interfacial Response and Structural Adaptation of Structured Polyelectrolyte Thin Films

Ionizable block copolymers with distinctive block characteristics display the diversity crucial for the design of macromolecules for targeted applications. In contrast to van der Waals copolymers, their interfaces, which are critical to their function, consist of nanodomains, each of a different nature and thus unique interfacial behavior. Here, the interfacial response of a symmetric block copolymer with a sulfonated polystyrene polyelectrolyte center, tethered to polyethylene-r-propylene and terminated by poly(t-butyl styrene) is probed as polymer films are exposed to three polar solvents, water, propanol, and tetrahydrofuran (THF), using molecular dynamics simulations. Each of the solvents captures a distinctive interaction with the individual blocks. We find that at the film boundary, the interfacial response is initially dominated by that of the hydrophobic blocks to all solvents. At later times, the solvent distribution among the blocks, where water molecules associate predominantly with the sulfonated groups and propanol and THF reside at multiple different sites, determines the chemical composition and the polymer conformation at the interface. Altogether, these simulations provide the first direct molecular insight into the interfacial response of ionizable copolymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge-flow structures as polymeric early-warning fire alarm devices

The charge-flow transistor (CFT) and its applications for fire detection and gas sensing were investigated. The utility of various thin film polymers as possible sensing materials was determined. One polymer, PAPA, showed promise as a relative humidity sensor; two others, PFI and PSB, were found to be particularly suitable for fire detection. The behavior of the charge-flow capacitor, which is basically a parallel-plate capacitor with a polymer-filled gap in the metallic tip electrode, was successfully modeled as an RC transmission line. Prototype charge-flow transistors were fabricated and tested. The effective threshold voltage of this metal oxide semiconductor was found to be dependent on whether surface or bulk conduction in the thin film was dominant. Fire tests with a PFI-coated CFT indicate good sensitivity to smouldering fires.

Sechen, C. M.↗

Optically transparent/colorless polyimides

Several series of linear aromatic polyimide films have been synthesized and characterized with the objective of obtaining maximum optical transparency. Two approaches have been used as part of this structure-property relationship study. The first approach is to vary the molecular structure so as to separate chromophoric centers and reduce electronic interactions between polymer chains to lower the intensity of color in the resulting polymer films. A second and concurrent approach is to perform polymerizations with highly purified monomers. Glass transition temperatures of thermally cured polyimide films are obtained by thermomechanical analysis and thermal decomposition temperatures are determined by thermogravimetric analysis. Transmittance UV-visible spectra of the polyimide films are compared to that of a commercial polyimide film. Fully imidized films are tested for solubility in common organic solvents. The more transparent films prepared in this study are evaluated for use on second-surface mirror thermal control coating systems. Lightly colored to colorless films are characterized by UV-visible spectroscopy before and after exposure to 300 equivalent solar hours UV irradiation and varying doses of 1 MeV electron irradiation. The effects of monomer purity, casting solvent and cure atmosphere on polyimide film transparency are also investigated.

Stclair, A. K.↗

Sequential Doping of Ladder-Type Conjugated Polymers for Thermally Stable n-Type Organic Conductors

Doping of organic semiconductors is a powerful tool to optimize the performance of various organic (opto)electronic and bioelectronic devices. Despite recent advances, the low thermal stability of the electronic properties of doped polymers still represents a significant obstacle to implementing these materials into practical applications. Hence, the development of conducting doped polymers with excellent long-term stability at elevated temperatures is highly desirable. Here, we report on the sequential doping of the ladder-type polymer poly(benzimidazobenzophenanthroline) (BBL) with a benzimidazole-based dopant (i.e., N-DMBI). By combining electrical, UV–vis/infrared, X-ray diffraction, and electron paramagnetic resonance measurements, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and microstructure of the sequentially doped polymer films as a function of the thermal annealing temperature. Importantly, we observed that the electrical conductivity of N-DMBI-doped BBL remains unchanged even after 20 h of heating at 190 °C. This finding is remarkable and of particular interest for organic thermoelectrics.

36 MATERIALS SCIENCE↗

Space Durable Polyimide/Carbon Nanotube Composite Films for Electrostatic Charge Mitigation

Low color, space environmentally durable polymeric films with sufficient electrical conductivity to mitigate electrostatic charge (ESC) build-up have been under investigation as part of a materials development activity. These materials have potential applications on advanced spacecraft, particularly on large, deployable, ultra-light weight Gossamer spacecraft. The approach taken to impart sufficient electrical conductivity into the polymer film is based on the use of single walled carbon nanotubes (SWNT) as conductive additives. Earlier approaches investigated in our lab involved both an in-situ polymerization approach and addition of SWNT to an oligomer containing reactive end-groups as methods to improve SWNT dispersion. The work described herein is based on the spray coating of a SWNT/solvent dispersion onto the film surface. Two types of polyimides were investigated, one with reactive end groups that can lead to bond formation between the oligomer chain and the SWNT surface and those without reactive end-groups. Surface conductivities (measured as surface resistance) in the range sufficient for ESC mitigation were achieved with minimal effects on the mechanical, optical, thermo-optical properties of the film as compared to the other methods. The chemistry and physical properties of these nanocomposites will be discussed.

Watson, Kent A.↗

Temperature and Humidity Dependence of a Polymer-Based Gas Sensor

This paper quantifies the temperature and humidity dependence of a polymer-based gas sensor. The measurement and analysis of three polymers indicates that resistance changes in the polymer films, due to temperature and humidity, can be positive or negative. The temperature sensitivity ranged from +1600 to -320 ppm/nd the relative sensitivity ranged from +1100 to -260 ppm/%.

temperature humidity gas sensor polymers↗

Electronically conducting polymers with silver grains

The present invention provides electronically conducting polymer films formed from photosensitive formulations of pyrrole and an electron acceptor that have been selectively exposed to UV light, laser light, or electron beams. The formulations may include photoinitiators, flexibilizers, solvents and the like. These solutions can be used in applications including printed circuit boards and through-hole plating and enable direct metallization processes on non-conducting substrates. After forming the conductive polymer patterns, a printed wiring board can be formed by sensitizing the polymer with palladium and electrolytically depositing copper.

Murphy, Oliver J.↗

Method of forming electronically conducting polymers on conducting and nonconducting substrates

The present invention provides electronically conducting polymer films formed from photosensitive formulations of pyrrole and an electron acceptor that have been selectively exposed to UV light, laser light, or electron beams. The formulations may include photoinitiators, flexibilizers, solvents and the like. These solutions can be used in applications including printed circuit boards and through-hole plating and enable direct metallization processes on non-conducting substrates. After forming the conductive polymer patterns, a printed wiring board can be formed by sensitizing the polymer with palladium and electrolytically depositing copper.

Murphy, Oliver J.↗

An overview of the first results on the solar array passive LDEF experiment (sample), AO171

Space environmental effects were visibly obvious on components of experiment AO171 which contained solar cells, composites, polymeric thin films, solar reflectors, protective coatings, metals, paints , and elastomers. Micrometeoroid/space debris impacts were observed on all experiment elements. Luminescence of polyimide, silicone, and polyurethane materials occurred under black light examination. Outgassing of RTV511 occurred mainly as a result of insufficient thermal vacuum bakeout. Solar cell degradation was predominantly below 10 percent. Elastomers lost mass and discolored; composites showed evidence of atomic oxygen attack, and unprotected thin polymer films eroded away.

Whitaker, Ann F.↗

Electrolysis on a Chip with Tunable Thin Film Nanostructured PGM Electrocatalysts Generated from Self-Assembled Block Copolymer Templates

Self-assembled block copolymers are promising templates for fabricating thin film materials with tuned periodic feature sizes and geometry at the nanoscale. Here, a series of nanostructured platinum and iridium oxide electrocatalysts templated from poly(styrene)-block-poly(vinyl pyridine) (PSbPVP) block copolymers via an incipient wetness impregnation (IWI) pathway is reported. Both nanowire and nanocylinder electrocatalysts of varying feature sizes are assessed and higher catalyst loadings are achieved by the alkylation of the pyridine moieties in the PVP block prior to IWI. Electrocatalyst evaluations featuring hydrogen pump and water electrolysis demonstrations are carried out on interdigitated electrode (IDE) chips flexible with liquid supporting electrolytes and thin film polymer electrolytes. Notably, the mass activities of the nanostructured electrocatalysts from alkylated block copolymer templates are 35%–94% higher than electrocatalysts from non-alkylated block copolymer templates. Standing cylinder nanostructures lead to higher mass activities than lamellar variants despite their not having the largest surface area per unit catalyst loading demonstrating that mesostructure architectures have a profound impact on reactivity. Overall, IDE chips with model thin film electrocatalysts prepared from self-assembled block copolymers offer a high-throughput experimental method for correlating electrocatalyst nanostructure and composition to electrochemical reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strong Reduction in Amplitude of the Interfacial Segmental Dynamics in Polymer Nanocomposites

Despite the wide use of polymer nanocomposites (PNCs) in various applications, our understanding of the microscopic parameters controlling their macroscopic properties remains limited. In this study, we examine the dielectric strength of segmental dynamics, Δε IL (T) in the interfacial polymer layer surrounding the nanoparticles in PNCs. The presented analysis reveals a significant drop in Δε IL (T) and its anomalous temperature dependence in the polymer layer adsorbed to nanoparticles. The drop in Δε IL (T) was observed in all samples regardless of whether segmental relaxation time in the interfacial layer was slower or faster than in the bulk polymer, excluding interpretation of the “dead” layer. We ascribe the observed decrease in the dielectric strength to the restricted amplitude of segmental relaxation in the interfacial/adsorbed layer. Our results provide a new perspective on discussion of dynamics in the interfacial layer in PNCs and thin polymer films, demonstrating that not only segmental relaxation time but also its amplitude can be strongly affected by the interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Effect of Journal Roughness and Foil Coatings on the Performance of Heavily Loaded Foil Air Bearings

Foil air bearing load capacity tests were conducted to investigate if a solid lubricant coating applied to the surface of the bearing's top foil can function as a break-in coating. Two foil coating materials, a conventional soft polymer film (polyimide) and a hard ceramic (alumina), were independently evaluated against as-ground and worn (run-in) journals coated with NASA PS304, a high-temperature solid lubricant composite coating. The foil coatings were evaluated at journal rotational speeds of 30,000 rpm and at 25 C. Tests were also performed on a foil bearing with a bare (uncoated) nickel-based superalloy top foil to establish a baseline for comparison. The test results indicate that the presence of a top foil solid lubricant coating is effective at increasing the load capacity performance of the foil bearing. Compared to the uncoated baseline, the addition of the soft polymer coating on the top foil increased the bearing load coefficient by 120% when operating against an as-ground journal surface and 85 percent against a run-in journal surface. The alumina coating increased the load coefficient by 40% against the as-ground journal but did not have any affect when the bearing was operated with the run-in journal. The results suggest that the addition of solid lubricant films provide added lubrication when the air film is marginal indicating that as the load capacity is approached foil air bearings transition from hydrodynamic to mixed and boundary lubrication.

Radil, Kevin C.↗

Distinguishing photo-induced oxygen attack on alkyl chain versus conjugated backbone for alkylthienyl-benzodithiophene (BDTT)-based push–pull polymers

Synthetic design has enabled increasing power conversion efficiency advances in organic photovoltaics (OPV). One continuing knowledge gap is detailed understanding of single-material chemical (photo)stability. Many considerations are based on prior OPV-relevant donor homopolymer systems rather than the next-generation push–pull architectures. Generally, energetic offsets between the lowest occupied molecular orbital of the donor and molecular oxygen are assumed to dictate kinetics of photo-induced charge transfer to a super oxide radical. Herein we determine the ambient-induced photo-degradation pathways, presented as proposed site-specific arrow-pushing mechanisms, for five donor polymers all containing the same push unit – alkylthienyl-substituted-benzodithiophene (BDTT) – but with chemically distinct pull units. The donor-only polymer films were subject to controlled photobleaching in air as an accelerated degradation approach, coupled with simultaneous monitoring of absorptance. Sample subsets were periodically removed and analyzed with X-ray photoelectron spectroscopy, to evaluate near-surface chemical composition and oxygen additions to hetero reporter atoms on either the BDTT push unit or distinct pull unit (i.e., sulphur and nitrogen). Here, this methodology allows us to distinguish between different mechanisms of bond cleavage and formation. Overall, we find that neither polymer redox properties nor individual push or pull unit stability are sufficient to predict photo-oxidative degradation of these polymers. Rather, there is a greater dependence on the susceptibility of unique structural groups within a polymeric system. Alkyl chain oxygen addition is generally the first attack site and direct sulfur oxidation on the conjugated backbone occurs after saturation of the alkyl chain initiation sites. This work provides a standard that could be used to evaluate relative photo-oxidative (in)stability for new OPV materials quickly – prior to time-consuming device optimization – and demonstrates an effective methodology for correlating optical degradation with chemical structure alterations via spectroscopic signatures to guide synthetic design.

14 SOLAR ENERGY↗