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At least 1,099 records · Page 61

Actinometric measurement of solar ultraviolet and development of a weighted solar UV integral

An actinometer has been developed to measure outdoor irradiance in the range 295-400 nm. Actinometric measurements of radiation are based on determination of photochemical reaction rates for reactions of known quantum efficiency. Actinometers have the advantage of providing irradiance data over surfaces of difficult accessibility; in addition, actinometrically determined irradiance data are wavelength weighted and therefore provide a useful means of assessing the degradation rates of polymers employed in solar energy systems.

Gupta, A.↗

Viscoelastic properties of entangled polymers - Ternary blends of monodisperse homopolymers

In a previous publication from this laboratory, the Rouse-Bueche-Zimm molecular theory of viscoelasticity has been extended by using a transient network model to apply to binary blends of monodisperse polymers with chain entanglements. The dynamics of the entanglements were modeled both by the enhanced frictional coefficients and by the additional elastic couplings. It was recognized that entanglements not only may form between chains of the same lengths (intracomponent entanglements) but also between those of different lengths (intercomponent entanglements). At a given intercomponent entanglement, the longer chain was assumed to have the frictional coefficient of the shorter chain. Similarly, for blends consisting of several monodisperse components with different molecular weights, such modifications are also required to predict their linear viscoelastic behavior. The frequency of these interactions is assumed to be proportional to the weight ratio of the respective component chains in the blend. Equations of motion are formulated for each component and solved numerically for the relaxation time spectra. Linear viscoelastic properties such as the dynamic mechanical moduli, stress relaxation moduli, and zero-shear viscosity can then be computed for these systems by linear summation of those of the components.

Soong, D.↗

Investigation of test methods, material properties and processes for solar cell encapsulants

The historical development of ethylene vinyl acetate (EVA) is presented, including the functional requirements, polymer selection, curing, stabilization, production and module processing. The construction and use of a new method for the accelerated aging of polymers is detailed. The method more closely resembles the conditions that may be encountered in actual module field exposure and additionally may permit service life to be predicted accurately. The use of hardboard as a low cost candidate substrate material is studied. The performance of surface antisoiling treatments useful for imparting a self cleaning property to modules is updated.

Willis, P. B.↗

Space environmental effects on polymer matrix composites as a function of sample location on LDEF

This paper presents results on the effect of circumferential location on the variation in solar absorptance (alpha(sub S)) and infrared emittance (epsilon) for five different polymer matrix composites (PMC), and variations in erosion depth due to atomic oxygen (AO) for fourteen different PMC materials. In addition, a chemical content design parameter (gamma) has been found that correlates well with the erosion yield obtained from space flight data and hyperthermal AO tests for hydrocarbon polymeric materials. This parameter defines the ratio of the total number of atoms in a repeat monomer unit to the difference between the total carbon content and the total number of intermolecular oxygen atoms in the same repeat unit.

Tennyson, R. C.↗

Oxidative Degradation of Nadic-End-Capped Polyimides: Evidence for Reactions Occurring at High Temperatures - 2

The oxidative degradation of PMR (for polymerization of monomeric reactants) polyimides at elevated temperatures was followed by cross-polarized magic angle spinning (Cp-MAS) NMR. C-13 labeling of selected sites in the polymers allowed for direct observation of the transformations arising from oxidation processes. As opposed to model compound studies, the reactions were followed directly in the polymer. The labeling experiments confirm the previously reported oxidation of the methylene carbon to ketone in the methylenedianiline portion of the polymer chain. They also show the formation of two other oxidized species, acid and ester, from this same carbon. In addition, the technique provides the first evidence of the kind of degradation reactions that are occurring in the nadic end caps. Several PMR formulations containing moieties determined to be present after oxidation, as suggested by the labeling study, were synthesized. Weight loss, FTIR, and natural abundance NMR of these derivatives were followed during aging. In this way, weight loss could be related to the observed transformations.

Meador, Mary Ann B.↗

The Exploration Atmospheres Working Group's Report on Space Radiation Shielding Materials

This part of Exploration Atmospheres Working Group analyses focuses on the potential use of nonmetallic composites as the interior walls and structural elements exposed to the atmosphere of the spacecraft or habitat. The primary drive to consider nonmetallic, polymer-based composites as an alternative to aluminum structure is due to their superior radiation shielding properties. But as is shown in this analysis, these composites can also be made to combine superior mechanical properties with superior shielding properties. In addition, these composites can be made safe; i.e., with regard to flammability and toxicity, as well as "smart"; i.e., embedded with sensors for the continuous monitoring of material health and conditions. The analysis main conclusions are that (1) smart polymer-based composites are an enabling technology for safe and reliable exploration missions, and (2) an adaptive, synergetic systems approach is required to meet the missions requirements from structure, properties, and processes to crew health and protection for exploration missions.

Barghouty, A. F.↗

Space Environmental Effects on Additively Manufactured Materials – Results from MISSE-9 and MISSE-10

The NASA Marshall Space Flight Center (MSFC) Space Environmental Effects (SEE) and Contamination Control (CC) teams prepared and characterized MISSE-9 and MISSE-10’s additively manufactured (AM) materials samples to investigate the effect of ultraviolet (UV) radiation, thermal cycling, outgassing, and temperature and provide data on the durability of these samples. Materials studied were polyetherimide (Ultem 1010 and 9085), electrostatic dissipative polyetherketoneketone (ESD-PEKK), also known commercially as Antero 840CN03, polycarbonate biocompatible per ISO 10993 USP Class VI (PC-ISO), and Inconel 718. Some samples were manufactured at MSFC, while 3D printer manufacturers Stratasys and Made In Space, Inc. (MIS) (now Redwire) participated in this effort to compare different vendors and printing setups. Results from nondestructive analyses and tensile testing are presented.

additive manufacturing↗

Compounds and composition for preparation of lithium-loaded plastic scintillators

A scintillator material includes a polymer matrix, a primary dye in the polymer matrix, the primary dye being a fluorescent dye; a secondary dye, and a Li-containing compound in the polymer matrix, where the Li-containing compound is a Li salt of a short-chain aliphatic acid. In addition, the scintillator material exhibits an optical response signature for thermal neutrons that is different than an optical response signature for fast neutrons.

Zaitseva, Natalia P.↗

Material Interactions with Solar Wind Ion Environments

Solar wind composition is dominated by hydrogen (approx.96%) and helium (approx.3 to 4%) with a minor fraction (less than or equal to 1%) of heavy ions. Hydrogen (helium) ions impact spacecraft surfaces with energies from 0.5 to 5 keV (1.8 to 21 keV) due to variations in solar wind velocity from 300 km/s to 1000 km/sec with extremes of a few 10 s keV during periods of extremely high solar wind velocity exceeding 1000 km/sec. Mean impact energies are typically on the order of approximately 1 keV and 4 keV for hydrogen ions and helium ions, respectively. These energies are typically of the peak of the energy dependent light ion sputter yields for hydrogen and helium on many metals. In addition, light ions with kilovolt energies have been shown to produce blister (or exfoliation) damage to metal surfaces due to formation of high pressure gas bubbles within the materials when exposed to ion fluences on the order of 10(exp 16 to (10(exp 17 ions/sq cm. A number of spacecraft designs for current and future missions include gossamer polymer structures with thin metallic reflection coatings to shield instruments from the Sun or solar sail propulsion systems for use in a variety of locations in the inner solar system from 0.5 to 1 AU. In addition, there is interest in designing spacecraft for solar physics missions requiring operations as close to the Sun as 0.16 to 0.2 AU. Integrity of the metallic coatings is critical in many of these applications since degradation will result in modification of material thermal properties or exposure of polymers to solar UV photons which can compromise mission requirements. This paper will evaluate the relative contributions of sputtering and blister formation to material degradation in solar wind environments over a range of radial distances from the Sun to demonstrate where solar wind environments become important for materials selection. We will first review the physics and results from laboratory measurements of light ion sputtering, blistering, and exfoliation of metallic surfaces to establish the order of magnitude ion fluence required for significant surface damage. Solar wind ion fluence environments will then be evaluated due to variations in solar wind conditions as a function of solar cycle for varying distances from the Sun using models for radial variations in solar wind ion number density, temperature, and velocity to determine where sputtering and blistering is most likely to be an issue. Finally, ion fluence statistics for varying radial distances from the Sun will be shown to establish the mission duration and radial distances from the Sun where missions will encounter sufficient ion fluence to exhibit damage to metallic surfaces.

Minow, Joseph I.↗

Water stable molecular n-doping produces organic electrochemical transistors with high transconductance and record stability

From established to emergent technologies, doping plays a crucial role in all semiconducting devices. Doping could, theoretically, be an excellent technique for improving repressively low transconductances in n-type organic electrochemical transistors – critical for advancing logic circuits for bioelectronic and neuromorphic technologies. However, the technical challenge is extreme: n-doped polymers are unstable in electrochemical transistor operating environments, air and water (electrolyte). Here, the first demonstration of doping in electron transporting organic electrochemical transistors is reported. The ammonium salt tetra-n-butylammonium fluoride is simply admixed with the conjugated polymer poly(N,N’-bis(7-glycol)-naphthalene-1,4,5,8-bis(dicarboximide)-co-2,2’-bithiophene-co-N,N’-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide), and found to act as a simultaneous molecular dopant and morphology-additive. The combined effects enhance the n-type transconductance with improved channel capacitance and mobility. Furthermore, operational and shelf-life stability measurements showcase the first example of water-stable n-doping in a polymer. Overall, the results set a precedent for doping/additives to impact organic electrochemical transistors as powerfully as they have in other semiconducting devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trace Compound Analysis in TATB by Liquid Chromatography coupled with Spectroscopic and Spectrometric Detection

Accurate quantitation of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is important because of its strategic use as an energetic material. A purity determination is also needed for the proper assessment of performance. A fast and sensitive method has been developed to measure the purity of TATB in polymer-bonded materials. The target material is extracted with DMSO, and the extract is separated on a reversed-phase chromatography column. The column effluent is monitored by diode array detection (DAD) at 354 nm. The characteristic UV-Vis response and retention time identify the individual components when compared to pure compound standards. The chemical structures of compounds with no pure standards available have been determined by high-resolution mass spectrometry (MS) and MS/MS. The major component, TATB, along with 1-chloro-3,5-dinitro-2,4,6-triaminobenzene (T4A) and mono-benzofuroxan (FX1) were quantitated directly from pure compound standards. Several trace concentration components, mono-benzofurazan (F1), 1-bromo-3,5-dinitro-2,4,6-triaminobenzene (Br-T4A), 2,4,6-triamino-1-nitroso-3,5-dinitrobenzene (MN-TATB), 2,4,6-triamino-1-hydroxyl-3,5-dinitrobenzene (HO-TATB), and 2,4,6-triamino-1-nitrile-3,5-dinitrobenzene (Nitrile-TATB) were also detected and structures verified via MS/MS. Approximate concentrations were determined using calibrations from standards of similar structures. Additional trace components were also detected by MS. Contained herein are the results of analyses of TATB-based materials characterized for polymer-bonded formulations compared to different preparations of TATB. The accuracy, details, and process of developing this method are reported here.

36 MATERIALS SCIENCE↗

Additive friction stir deposition induced stress ripples in aluminum alloy

In additive manufacturing, modification of the viscosity of softened or molten metal plays a significant role in the development of mechanical properties distribution. Similar to soft polymers, molten or softened metal usually exhibits vastly different viscoelastic properties. During scratching tests, viscoelastic polymers undergo spatiotemporal stress development and relaxation, causing stress ripples to form on their surfaces. Here, it is observed that friction stir-based solid-state manufacturing can yield similar stress ripples on softened aluminum alloys due to the linear motion of the deposition tool. Softened aluminum alloys exhibit viscoelastic and viscoplastic responses similar to polymeric material during the solid-state deposition process. In the final product, residual stress ripples appear on the surface of the metal alloy due to periodic residual stress relaxation, leading to oscillatory behavior from the bulk mechanical properties of the material. The orientation of the in-built stress pattern formed in the bulk of the additively manufactured metal alloy underneath the visually evident onion ring-like surface pattern formation is diametrically in the opposite direction. The experimentally observed results are consistent with analytical calculation and numerical simulations in terms of behaviors.

36 MATERIALS SCIENCE↗

Simulated Galactic Cosmic Ray and Solar Particle Event Radiation Effects on Inflatable Habitat, Composite Habitat, Space Suit and Space Hatch Cover Materials

The effect of particle radiation representative of galactic cosmic ray (GCR) and solar particle event (SPE) radiation on polymeric materials used in deep space mission environments is largely unknown. For NASA, this uncertainty represents an unquantified mission risk. To better quantify this risk, selected polymeric materials used in inflatable habitats, composite habitats, space suits and space hatch covers are irradiated at the Brookhaven National Laboratory, after which changes in relevant end-use properties are measured. The irradiated materials are lightweight candidates having critical functions such as ripstops, permeation barriers, micrometeoroids and orbital debris (MMOD) shield layers and restraint layers.The effect of several types of particle radiation are evaluated. To evaluate GCR effects, high-energy (1 GeV) protons and iron nucleons are used. To evaluate SPE effects, intermediate energy (ca. 20 to 40 MeV) protons are used. In addition, two mission scenarios are evaluated: a Mars mission cycle (space suit materials) and a worst-case 50 year deep space mission cycle (all materials). Lastly, a common polymer (high density polyethylene (HDPE)) is subjected to accelerated aging and radiation exposure to determine if a combined physical aging/radiation effect exists.The level of radiation induced property change observed in this study after exposure of polymers to kGy levels of intermediate and high energy ions is often significant and is quantitatively comparable to the level of change reported for similar materials exposed to MGy levels of low energy protons, electrons and gamma-radiation. This suggests that intermediate and high energy ions encountered in space may cause more damage than low energy forms of radiation due to displacement and linear energy transfer (LET) effects. For these reasons, it is recommended that final approval for mission use be made by the appropriate NASA material and structural review boards to ensure radiation induced changes in candidate materials do not interfere with their engineering function in the intended mission application. Since the materials tested in this report received doses exceeding actual mission doses, the results are considered conservative as a first approximation. However, caution must be exercised when evaluating radiation effects in the absence of other secondary factors know to contribute to degradation. In the addition to radiation type and energy, the results presented in this study show that molecular composition, orientation, stress and physical aging can also contribute to or influence degradation. Other factors such as polymer formulation, secondary radiation effects, stress, exposure to elevated temperature, thermal cycling and exposure to ozone were not investigated here, but must be considered when performing a comprehensive evaluation of a polymeric materials suitability for service in a space radiation environment. Only when the total sum of these factors operating in concert with radiation are accounted for, can accurate assessments of a material's suitability be made.

Jess M. Waller↗

Heterogeneous Supramolecular Catalysis through Immobilization of Anionic M 4 L 6 Assemblies on Cationic Polymers

Although most of the currently developed supramolecular catalysts that emulate enzymatic reactivity with unique selectivity and activity through specific host-guest interactions work under homogeneous conditions, enzymes in nature can operate under heterogeneous conditions as membrane-bound enzymes. In order to develop such a heterogeneous system, an immobilized chiral supramolecular cluster Ga 4 1 6 ( 2 ) was introduced into cross-linked polymers with cationic functionalities. These heterogeneous supramolecular catalysts were used in aza-Prins and aza-Cope reactions and successfully applied to continuous-flow reactions. Additionally, they showed high durability and maintained high turnovers for long periods of time. In sharp contrast to the majority of examples of heterogenized homogeneous catalysts, the newly developed catalysts showed enhanced activity and robustness compared to those exhibited by the corresponding soluble cluster catalyst. An enantioenriched cluster was also immobilized to enable asymmetric catalysis, and activity and enantioselectivity of the supported chiral catalyst were maintained during recovery and reuse experiments and under a continuous-flow process. Significantly, the structure of the ammonium cations in the polymers affected stability, reactivity, and enantioselectivity, which is consistent with the hypothesis that the cationic moieties in the polymer support interact with cluster as an exohedral protecting shell, thereby influencing their catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Additive manufacturing of multiscale NiFeMn multi-principal element alloys with tailored composition

Nanostructured multi-principal element alloys (MPEAs) have been explored as next-generation engineering materials due to unique mechanical and functional properties which have significant advantages over traditional dilute alloys. However, the practical applications of nanostructured MPEAs are still limited due to the lack of scalable processing approaches to prepare a large quantity of nanostructured MPEAs, as well as lack of an efficient pathway for high-throughput discovery of better functional nanostructured MPEAs within their vast compositional space. Here we tackle these challenges by presenting an integrated approach by combining direct-ink-writing-based additive manufacturing, solid-state sintering, and chemical dealloying to manufacture hierarchically porous MPEAs. The hierarchical structure is comprised of macro- and micro-scale pores introduced via extrusion printing and polymer decomposition during sintering, as well as nanoscale pores formed via chemical dealloying. The macro- and micro-scale pores allow efficient dealloying of a large mass of material as the diffusion length that the corroding medium must penetrate remains at the scale of the ligaments formed after sintering (∼10 μm), despite the large volume of the 3D-printed samples. In addition, this integrated approach enables versatile control of the alloy composition via precisely tuning the ratio of elemental powders in the starting ink, thus offering a pathway for high-throughput discovery of novel functional MPEAs. As a case study, multiscale macro/micro/nanoporous NiFeMn MPEAs with three different compositions were investigated as catalysts to reduce the overpotential of oxygen evolution reaction (OER), where NiFeMn-based electrocatalysts display composition-dependent performance such that the overpotential measured at a current of 0.5 A g −1 for OER increases in the order of Ni 58 Fe 29 Mn 13 ⩽ Ni 64 Fe 26 Mn 10 < Ni 76 Fe 18 Mn 6 . This introduced manufacturing process offers new opportunities for scalable fabrication and rapid screening of nanostructured multi-component complex alloys.

36 MATERIALS SCIENCE↗

High Temperature Polymers for use in Fuel Cells

NASA Glenn Research Center (GRC) is currently working on polymers for fuel cell and lithium battery applications. The desire for more efficient, higher power density, and a lower environmental impact power sources has led to interest in proton exchanges membrane fuels cells (PEMFC) and lithium batteries. A PEMFC has many advantages as a power source. The fuel cell uses oxygen and hydrogen as reactants. The resulting products are electricity, heat, and water. The PEMFC consists of electrodes with a catalyst, and an electrolyte. The electrolyte is an ion-conducting polymer that transports protons from the anode to the cathode. Typically, a PEMFC is operated at a temperature of about 80 C. There is intense interest in developing a fuel cell membrane that can operate at higher temperatures in the range of 80 C- 120 C. Operating the he1 cell at higher temperatures increases the kinetics of the fuel cell reaction as well as decreasing the susceptibility of the catalyst to be poisoned by impurities. Currently, Nafion made by Dupont is the most widely used polymer membrane in PEMFC. Nafion does not function well above 80 C due to a significant decrease in the conductivity of the membrane from a loss of hydration. In addition to the loss of conductivity at high temperatures, the long term stability and relatively high cost of Nafion have stimulated many researches to find a substitute for Nafion. Lithium ion batteries are popular for use in portable electronic devices, such as laptop computers and mobile phones. The high power density of lithium batteries makes them ideal for the high power demand of today s advanced electronics. NASA is developing a solid polymer electrolyte that can be used for lithium batteries. Solid polymer electrolytes have many advantages over the current gel or liquid based systems that are used currently. Among these advantages are the potential for increased power density and design flexibility. Automobiles, computers, and cell phones require highly efficient power density for lowering emissions and meeting increasing consumer demands. Many of the solutions can be provided by proton exchange membrane fuel cells and lithium batteries. NASA Glenn Research Center has recognized this need, and is presently engaged in a solution. The goals for the summer include mastering synthesis techniques, understanding the reactions occurring during the synthesis, and characterizing the resulting polymer membranes using NMR, DSC, and TGA for the PEMFC and lithium batteries.

Peplowski, Katherine M.↗

Halophyte biorefinery for polyhydroxyalkanoates production from Ulva sp. Hydrolysate with Haloferax mediterranei in pneumatically agitated bioreactors and ultrasound harvesting

Here, the present study tested the outdoor cultivation of Haloferax mediterranei for PHA production from green macroalgae Ulva sp. in pneumatically agitated bioreactors and applied ultrasonic separation for enhanced settling of archaeal cells. Scaled-up cultivation (40 L) yielded maximum biomass productivity of 50.1 ± 0.11 mg·L -1 ·h -1 with a PHA productivity of 27 ± 0.01 mg·L -1 ·h -1 and conversion yield of 0.107 g PHA per gram UlvaDW. The maximum mass fraction of PHA achieved in biomass was calculated to be 56% w/w. Ultrasonic harvesting of Hfx. mediterranei cells approached 30% removal at energy inputs around 7.8 kWh·m -3 , and indicated no significant aggregation enhancement by Ca 2+ addition. Molecular weight analysis showed an increase in Polydispersity Index (PDI) when the corresponding air velocities were increased suggesting that the polymer was more homogeneous at lower mixing velocities. The current study demonstrated scalable processes for PHA production using Ulva sp. feedstock providing new technologies for halophilic biorefinery.

09 BIOMASS FUELS↗

Multi-technique characterization of spray coated and roll-to-roll coated gas diffusion fuel cell electrodes

Here this work reports the characterization of catalyst layer (CL) structure and composition for a set of gas-diffusion electrodes (GDEs) fabricated by different coating methods with the goal of developing a better understanding of CL processing-structure-property-performance relationships. The CL coating techniques used in this study were ultrasonic spray coating, and two roll-to-roll (R2R) methods - gravure and slot die. Scanning transmission electron microscopy (STEM) coupled with X-ray energy dispersive spectroscopy (EDS) analysis of GDE cross-sections provided bulk information, while scanning electron microscopy (SEM) with EDS and X-ray photoelectron spectroscopy (XPS) were used to investigate the near surface and surface composition of the CLs that will be in direct contact with the membrane once the membrane electrode assembly (MEA) is constructed. This study demonstrates that common quantification parameters, namely the F:Pt ratio extracted from cross-sectional STEM-EDS maps and top-down CL measurements with SEM and XPS, along with roughness parameters quantified from SEM micrographs are useful parameters in explaining and potentially predicting performance trends. Additionally, it highlights the importance of understanding key CL surface properties for advancing the manufacturability of high-performance components for polymer electrolyte membrane (PEM) technologies.

30 DIRECT ENERGY CONVERSION↗