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138 records · Page 8

Novel Low-Temperature Poss-Containing Siloxane Elastomers

One route to increased aircraft performance is through the use of flexible, shape-changeable aerodynamics effectors. However, state of the art materials are not flexible or durable enough over the required broad temperature range. Mixed siloxanes were crosslinked by polyhedral oligomeric silsesquioxanes (POSS) producing novel materials that remained flexible and elastic from -55 to 94 C. POSS molecules were chemically modified to generate homogeneous distributions within the siloxane matrix. High resolution scanning electron microscope (HRSEM) images indicated homogenous POSS distribution up to 0.8 wt %. Above the solubility limit, POSS aggregates could be seen both macroscopically and via SEM (approx.60-120 nm). Tensile tests were performed to determine Young s modulus, tensile strength, and elongation at break over the range of temperatures associated with transonic aircraft use (-55 to 94 C; -65 to 200 F). The siloxane materials developed here maintained flexibility at -55 C, where previous candidate materials failed. At room temperature, films could be elongated up to 250 % before rupturing. At -55 and 94 C, however, films could be elongated up to 400 % and 125 %, respectively.

Belcher, Marcus A.↗

Oxygen Plasma Modification of Poss-Coated Kapton(Registered TradeMark) HN Films

The surface energy of a material depends on both surface composition and topographic features. In an effort to modify the surface topography of Kapton(Registered TradeMark) HN film, organic solutions of a polyhedral oligomeric silsesquioxane, octakis(dimethylsilyloxy)silsesquioxane (POSS), were spray-coated onto the Kapton(Registered TradeMark) HN surface. Prior to POSS application, the Kapton(Registered TradeMark) HN film was activated by exposure to radio frequency (RF)-generated oxygen plasma. After POSS deposition and solvent evaporation, the films were exposed to various durations of RF-generated oxygen plasma to create a topographically rich surface. The modified films were characterized using optical microscopy, attenuated total reflection infrared (ATR-IR) spectroscopy, and high-resolution scanning electron microscopy (HRSEM). The physical properties of the modified films will be presented.

Wohl, C. J.↗

Modification of the Surface Properties of Polyimide Films using POSS Deposition and Oxygen Plasma Exposure

Topographically rich surfaces were generated by spray-coating organic solutions of a polyhedral oligomeric silsesquioxane, octakis (dimethylsilyloxy) silsesquioxane (POSS), on Kapton HN films and exposing them to radio frequency generated oxygen plasma. Changes in both surface chemistry and topography were observed. High-resolution scanning electron microscopy indicated substantial modification of the POSS-coated polyimide surface topographies as a result of oxygen plasma exposure. Water contact angles varied from 104 deg for unexposed POSS-coated surfaces to approximately 5 deg, for samples exposed for 5 h. Modulation of the dispersive and polar contributions to the surface energy was determined using van Oss Good Chaudhury theory.

Wohl, Christopher J.↗

Distinct Distribution of Purines in CM and CR Carbonaceous Chondrites

Carbonaceous meteorites contain a diverse suite of organic molecules and delivered pre biotic organic compounds, including purines and pyrimidines, to the early Earth (and other planetary bodies), seeding it with the ingredients likely required for the first genetic material. We have investigated the distribution of nucleobases in six different CM and CR type carbonaceous chondrites, including fivc Antarctic meteorites never before analyzed for nucleobases. We employed a traditional formic acid extraction protocol and a recently developed solid phase extraction method to isolate nucleobases. We analyzed these extracts by high performance liquid chromatography with UV absorbance detection and tandem mass spectrometry (HPLC-UV -MS/MS) targeting the five canonical RNAIDNA bases and hypoxanthine and xanthine. We detected parts-per-billion levels of nucleobases in both CM and CR meteorites. The relative abundances of the purines found in Antarctic CM and CR meteorites were clearly distinct from each other suggesting that these compounds are not terrestrial contaminants. One likely source of these purines is formation by HCN oligomerization (with other small molecules) during aqueous alteration inside the meteorite parent body. The detection of the purines adenine (A), guanine (0), hypoxanthine (HX), and xanthine (X) in carbonaceous meteorites indicates that these compounds should have been available on the early Earth prior to the origin of the first genetic material.

Callahan, Michael P.↗

Polyimide Aerogels with Three-Dimensional Cross-Linked Structure

Polyimide aerogels with three-dimensional cross-linked structure are made using linear oligomeric segments of polyimide, and linked with one of the following into a 3D structure: trifunctional aliphatic or aromatic amines, latent reactive end caps such as nadic anhydride or phenylethynylphenyl amine, and silica or silsesquioxane cage structures decorated with amine. Drying the gels supercritically maintains the solid structure of the gel, creating a polyimide aerogel with improved mechanical properties over linear polyimide aerogels. Lightweight, low-density structures are desired for acoustic and thermal insulation for aerospace structures, habitats, astronaut equipment, and aeronautic applications. Aerogels are a unique material for providing such properties because of their extremely low density and small pore sizes. However, plain silica aerogels are brittle. Reinforcing the aerogel structure with a polymer (X-Aerogel) provides vast improvements in strength while maintaining low density and pore structure. However, degradation of polymers used in cross-linking tends to limit use temperatures to below 150 C. Organic aerogels made from linear polyimide have been demonstrated, but gels shrink substantially during supercritical fluid extraction and may have lower use temperature due to lower glass transition temperatures. The purpose of this innovation is to raise the glass transition temperature of all organic polyimide aerogel by use of tri-, tetra-, or poly-functional units in the structure to create a 3D covalently bonded network. Such cross-linked polyimides typically have higher glass transition temperatures in excess of 300 400 C. In addition, the reinforcement provided by a 3D network should improve mechanical stability, and prevent shrinkage on supercritical fluid extraction. The use of tri-functional aromatic or aliphatic amine groups in the polyimide backbone will provide such a 3D structure.

Panek, John↗

Multiscale Modeling of Thermal Conductivity of Polymer/Carbon Nanocomposites

Molecular dynamics simulation was used to estimate the interfacial thermal (Kapitza) resistance between nanoparticles and amorphous and crystalline polymer matrices. Bulk thermal conductivities of the nanocomposites were then estimated using an established effective medium approach. To study functionalization, oligomeric ethylene-vinyl alcohol copolymers were chemically bonded to a single wall carbon nanotube. The results, in a poly(ethylene-vinyl acetate) matrix, are similar to those obtained previously for grafted linear hydrocarbon chains. To study the effect of noncovalent functionalization, two types of polyethylene matrices. -- aligned (extended-chain crystalline) vs. amorphous (random coils) were modeled. Both matrices produced the same interfacial thermal resistance values. Finally, functionalization of edges and faces of plate-like graphite nanoparticles was found to be only modestly effective in reducing the interfacial thermal resistance and improving the composite thermal conductivity

Clancy, Thomas C.↗

PETIs as High-Temperature Resin-Transfer-Molding Materials

Compositions of, and processes for fabricating, high-temperature composite materials from phenylethynyl-terminated imide (PETI) oligomers by resin-transfer molding (RTM) and resin infusion have been developed. Composites having a combination of excellent mechanical properties and long-term high-temperature stability have been readily fabricated. These materials are particularly useful for the fabrication of high-temperature structures for jet-engine components, structural components on highspeed aircraft, spacecraft, and missiles. Phenylethynyl-terminated amide acid oligomers that are precursors of PETI oligomers are easily made through the reaction of a mixture of aromatic diamines with aromatic dianhydrides at high stoichiometric offsets and 4-phenylethynylphthalic anhydride (PEPA) as an end-capper in a polar solvent such as N-methylpyrrolidinone (NMP). These oligomers are subsequently cyclodehydrated -- for example, by heating the solution in the presence of toluene to remove the water by azeotropic distillation to form low-molecular-weight imide oligomers. More precisely, what is obtained is a mixture of PETI oligomeric species, spanning a range of molecular weights, that exhibits a stable melt viscosity of less than approximately 60 poise (and generally less than 10 poise) at a temperature below 300 deg C. After curing of the oligomers at a temperature of 371 deg C, the resulting polymer can have a glass-transition temperature (Tg) as high as 375 C, the exact value depending on the compositions.

Connell, John N.↗

Marshall Convergent Spray Formulation Improvement for High Temperatures

The Marshall Convergent Coating-1 (MCC-1) formulation was produced in the 1990s, and uses a standard bisphenol A epoxy resin system with a triamine accelerator. With the increasing heat rates forecast for the next generation of vehicles, higher-temperature sprayable coatings are needed. This work substitutes the low-temperature epoxy resins used in the MCC-1 coating with epoxy phenolic, epoxy novalac, or resorcinolinic resins (higher carbon content), which will produce a higher char yield upon exposure to high heat and increased glass transition temperature. High-temperature filler materials, such as granular cork and glass ecospheres, are also incorporated as part of the convergent spray process, but other sacrificial (ablative) materials are possible. In addition, the use of polyhedral oligomeric silsesquioxanes (POSS) nanoparticle hybrids will increase both reinforcement aspects and contribute to creating a tougher silacious char, which will reduce recession at higher heat rates. Use of expanding epoxy resin (lightweight MCC) systems are also useful in that they reduce system weight, have greater insulative properties, and a decrease in application times can be realized.

Scarpa, Jack↗

Characterization of Modern Spacecraft Materials under Space-simulated Environment

External spacecraft materials play an important role in satellite protection from the harsh space environment. Research has shown that the physical, chemical, and optical properties of matter change continuously as a result of exposure to solar radiation and aggressive chemical species produced in Earth’s upper atmosphere. Thorough knowledge of the material properties evolution throughout a planned mission lifetime helps to improve the reliability of spacecraft. Moreover, the establishment of correlation factors between true space exposure and accelerated space weather experiments at ground facilities enables accurate prediction of on-orbit material performance based on laboratory-based testing. The presented work aims to evaluate the radiation effects of low Earth orbit (LEO) environment, namely, exposure to the high-energy electrons, atomic oxygen (AO), and vacuum ultraviolet (VUV), of several modern spacecraft materials. The studied materials represent the “flight duplicates” of samples that will be launched as a part of the Materials International Space Station Experiment Flight Facility (MISSE-FF) mission in 2022. MISSE-FF flight sample collection comprises different classes of polymers, including polyimides from the Kapton family, manufactured by E.I du Pont de Nemours and Co., Polyethylene terephthalate (PET) materials, liquid crystal polymers, PI/Polyhedral Oligomeric Silsesquioxanes (POSS), and carbon and glass fiber reinforced polymers. A sequential exposure approach was undertaken to allow monitoring of degradation induced by each environmental component (electrons, AO, and VUV) separately. Surface morphology, optical, and charge transport properties of selected materials were characterized using different techniques, namely, atomic force and scanning electron microscopy, ultraviolet visible (UV/Vis) transmission, reflectance, Bidirectional Reflectance Distribution Function (BRDF), and surface potential decay measurements.

Elena Plis↗

Local frustration around enzyme active sites

Conflicting biological goals often meet in the specification of protein sequences for structure and function. Overall, strong energetic conflicts are minimized in folded native states according to the principle of minimal frustration, so that a sequence can spontaneously fold, but local violations of this principle open up the possibility to encode the complex energy landscapes that are required for active biological functions. We survey the local energetic frustration patterns of all protein enzymes with known structures and experimentally annotated catalytic residues. In agreement with previous hypotheses, the catalytic sites themselves are often highly frustrated regardless of the protein oligomeric state, overall topology, and enzymatic class. At the same time a secondary shell of more weakly frustrated interactions surrounds the catalytic site itself. We evaluate the conservation of these energetic signatures in various family members of major enzyme classes, showing that local frustration is evolutionarily more conserved than the primary structure itself.

Maria I. Freiberger↗

Overview of the MISSE-16 Mission and Preliminary Characterization of Novel Space Weathered Materials

The Materials International Space Station Experiment (MISSE) project is a series of experiments that began in 2001, involving the deployment of external experiment platforms on the International Space Station (ISS). Since then, more than 4,000 materials were tested yielding valuable data and insights into the performance of materials and coatings in the harsh space environment, as well as providing a platform for testing and validating new materials and technologies. The results of the MISSE experiments have contributed to the development of more durable and reliable spacecraft and equipment, as well as improving our understanding of the space environment and its effects on human space exploration. To gain deeper insights into the changes in material properties of both novel and heritage spacecraft materials over the course of a mission, we proposed to enhance the MISSE hardware. This was achieved by integrating a high-resolution camera that can capture both RGB and IR color data, along with an updated illumination scheme. The identical sets of selected materials were mounted on the Zenith, Ram, and Wake faces of the ISS to expose them to predominant vacuum ultraviolet (VUV), atomic oxygen, and high-energy electron conditions. In addition, we exposed flight duplicates of these materials to a simulated space environment, which included sequential exposure to the same irradiation species on the ground. This allowed us to study the effects of space exposure on the materials in a controlled manner and to compare their behavior in both real and simulated space environments. The MISSE-FF flight sample collection comprised different classes of polymers, including polyimides from the Kapton family, manufactured by E.I du Pont de Nemours and Co., Polyethylene terephthalate (PET) materials, liquid crystal polymers, PI/Polyhedral Oligomeric Silsesquioxanes (POSS), and carbon and glass fiber reinforced polymers. The experimental cadence during the MISSE-16 mission (~6 months) included daily images of each sample for the first week, weekly for the next 2 months, and monthly the remaining duration of the mission. This paper will focus on the flight duplicate as well as the postflight optical characterization of novel and heritage materials currently under observation on the MISSE-FF.

Jainisha R Shah↗

Atomic Oxygen Impacts on Materials International Space Station Experiment (MISSE)-16 flight Samples

A variety of materials consisting of polyimides, polyethylene terephthalates (PETs), fiber reinforced polymers, and polyhedral oligomeric silsesquioxanes (POSS) were on the exterior of the International Space Station (ISS) as part of Materials International Space Station Experiment (MISSE)-16. Samples on the side of the ISS pointing in the direction of the spacecraft’s motion (the ram direction) were observed for effects due to atomic oxygen (AO). The erosion yield of select materials from MISSE-16 is reported, as well as their variation in surface roughness due to AO erosion. Trade names and trademarks are used in this paper for identification only. Their usage does not constitute an official endorsement, either expressed or implied, by the National Aeronautics and Space Administration.

Samuel A Westrick↗