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At least 289 records · Page 16

Effects of Hypervelocity Impacts on Silicone Elastomer Seals and Mating Aluminum Surfaces

While in space silicone based elastomer seals planned for use on NASA's Crew Exploration Vehicle (CEV) are exposed to threats from micrometeoroids and orbital debris (MMOD). An understanding of these threats is required to assess risks to the crew, the CEV orbiter, and missions. An Earth based campaign of hypervelocity impacts on small scale seal rings has been done to help estimate MMOD threats to the primary docking seal being developed for the Low Impact Docking System (LIDS). LIDS is being developed to enable the CEV to dock to the ISS (International Space Station) or to Altair (NASA's next lunar lander). The silicone seal on LIDS seals against aluminum alloy flanges on ISS or Altair. Since the integrity of a seal depends on both sealing surfaces, aluminum targets were also impacted. The variables considered in this study included projectile mass, density, speed, incidence angle, seal materials, and target surface treatments and coatings. Most of the impacts used a velocity near 8 km/s and spherical aluminum projectiles (density = 2.7 g/cubic centimeter), however, a few tests were done near 5.6 km/s. Tests were also performed using projectile densities of 7.7, 2.79, 2.5 or 1.14 g/cubic centimeter. Projectile incidence angles examined included 0 degrees, 45 degrees , and 60 degrees from normal to the plane of the target. Elastomer compounds impacted include Parker's S0383-70 and Esterline's ELA-SA-401 in the as received condition, or after an atomic oxygen treatment. Bare, anodized and nickel coated aluminum targets were tested simulating the candidate mating seal surface materials. After impact, seals and aluminum plates were leak tested: damaged seals were tested against an undamaged aluminum plate; and undamaged seals were placed at various locations over craters in aluminum plates. It has been shown that silicone elastomer seals can withstand an impressive level of damage before leaking beyond allowable limits. In general on the tests performed to date, the diameter of the crater in either the elastomer, or the aluminum, must be at least as big as 80% to 90% of width of the bulb of the seal before significant leakage occurs.

deGroh, Henry C., III↗

Effects of Hypervelocity Impacts on Silicone Elastomer Seals and Mating Aluminum Surfaces

While in space silicone based elastomer seals planned for use on NASA's Crew Exploration Vehicle (CEV) are exposed to threats from micrometeoroids and orbital debris (MMOD). An understanding of these threats is required to assess risks to the crew, the CEV orbiter, and missions. An Earth based campaign of hypervelocity impacts on small scale seal rings has been done to help estimate MMOD threats to the primary docking seal being developed for the Low Impact Docking System (LIDS). LIDS is being developed to enable the CEV to dock to the ISS (International Space Station) or to Altair (NASA's next lunar lander). The silicone seal on LIDS seals against aluminum alloy flanges on ISS or Altair. Since the integrity of a seal depends on both sealing surfaces, aluminum targets were also impacted. The variables considered in this study included projectile mass, density, speed, incidence angle, seal materials, and target surface treatments and coatings. Most of the impacts used a velocity near 8 km/s and spherical aluminum projectiles (density = 2.7 g/cubic cm), however, a few tests were done near 5.6 km/s. Tests were also performed using projectile densities of 7.7, 2.79, 2.5 or 1.14 g/cubic cm. Projectile incidence angles examined included 0 deg, 45 deg, and 60 deg from normal to the plane of the target. Elastomer compounds impacted include Parker's S0383-70 and Esterline's ELA-SA-401 in the as received condition, or after an atomic oxygen treatment. Bare, anodized and nickel coated aluminum targets were tested simulating the candidate mating seal surface materials. After impact, seals and aluminum plates were leak tested: damaged seals were tested against an undamaged aluminum plate; and undamaged seals were placed at various locations over craters in aluminum plates. It has been shown that silicone elastomer seals can withstand an impressive level of damage before leaking beyond allowable limits. In general on the tests performed to date, the diameter of the crater in either the elastomer, or the aluminum, must be at least as big as 80% to 90% of width of the bulb of the seal before significant leakage occurs.

deGroh, Henry C., III↗

Mechanistic Insights on Permeation of Water over Iron Cations in Nanoporous Silicon Oxide Films for Selective H 2 and O 2 Evolution

Electrocatalysts encapsulated by an ultrathin and semipermeable oxide layer offer a promising avenue for efficient, selective, and cost-effective production of hydrogen through photoelectrochemical water splitting. This architecture is especially attractive for Z-scheme water splitting, for which a nanoporous oxide film can be leveraged to mitigate undesired, yet kinetically facile, reactions involving redox shuttles, such as aqueous iron cations, by limiting transport of these species to catalytically active sites. In this work, molecular dynamics simulations were combined with electrochemical measurements to provide a mechanistic understanding of permeation of water and Fe(III)/Fe(II) redox shuttles through nanoporous SiO 2 films. It is shown that even for SiO 2 pores with a width as small as 0.8 nm, water does not experience any energy barrier for permeating into the pores due to a favorable interaction with hydrophilic silanol groups on the oxide surface. In contrast, permeation of Fe(III) and Fe(II) into microporous SiO 2 pores is limited due to high energy barriers, which stem from a combination of distortion and dehydration of the second and third ion solvation shells. Furthermore, our simulations and experimental results show that SiO 2 coatings can effectively mitigate undesired Fe(III)/Fe(II) redox reactions at underlying electrodes by attenuating permeation of iron cations, while allowing water to permeate and thus participate in water splitting reactions. In a broader context, our study demonstrates that selectivity of solvated cations can be manipulated by controlling the pore size and surface chemistry of oxide films.

14 SOLAR ENERGY↗

Fundamental Studies of Crystal Growth of Microporous Materials

Microporous materials are framework structures with well-defined porosity, often of molecular dimensions. Zeolites contain aluminum and silicon atoms in their framework and are the most extensively studied amongst all microporous materials. Framework structures with P, Ga, Fe, Co, Zn, B, Ti and a host of other elements have also been made. Typical synthesis of microporous materials involve mixing the framework elements (or compounds, thereof) in a basic solution, followed by aging in some cases and then heating at elevated temperatures. This process is termed hydrothermal synthesis, and involves complex chemical and physical changes. Because of a limited understanding of this process, most synthesis advancements happen by a trial and error approach. There is considerable interest in understanding the synthesis process at a molecular level with the expectation that eventually new framework structures will be built by design. The basic issues in the microporous materials crystallization process include: (1) Nature of the molecular units responsible for the crystal nuclei formation; (2) Nature of the nuclei and nucleation process; (3) Growth process of the nuclei into crystal; (4) Morphological control and size of the resulting crystal; (5) Surface structure of the resulting crystals; (6) Transformation of frameworks into other frameworks or condensed structures. The NASA-funded research described in this report focuses to varying degrees on all of the above issues and has been described in several publications. Following is the presentation of the highlights of our current research program. The report is divided into five sections: (1) Fundamental aspects of the crystal growth process; (2) Morphological and Surface properties of crystals; (3) Crystal dissolution and transformations; (4) Modeling of Crystal Growth; (5) Relevant Microgravity Experiments.

Dutta, P.↗

Fundamental Studies of Crystal Growth of Microporous Materials

Microporous materials are framework structures with well-defined porosity, often of molecular dimensions. Zeolites contain aluminum and silicon atoms in their framework and are the most extensively studied amongst all microporous materials. Framework structures with P, Ga, Fe, Co, Zn, B, Ti and a host of other elements have also been made. Typical synthesis of microporous materials involve mixing the framework elements (or compounds, thereof) in a basic solution, followed by aging in some cases and then heating at elevated temperatures. This process is termed hydrothermal synthesis, and involves complex chemical and physical changes. Because of a limited understanding of this process, most synthesis advancements happen by a trial and error approach. There is considerable interest in understanding the synthesis process at a molecular level with the expectation that eventually new framework structures will be built by design. The basic issues in the microporous materials crystallization process include: (a) Nature of the molecular units responsible for the crystal nuclei formation; (b) Nature of the nuclei and nucleation process; (c) Growth process of the nuclei into crystal; (d) Morphological control and size of the resulting crystal; (e) Surface structure of the resulting crystals; and (f) Transformation of frameworks into other frameworks or condensed structures.

Singh, Ramsharan↗

Novel in-capsule synthesis of metal–organic framework for innovative carbon dioxide capture system

Metal-Organic Frameworks (MOFs) have been developed as solid sorbents for CO2 capture applications and their properties can be controlled by tuning the chemical blocks of their crystalline units. A number of MOFs (e.g., HKUST-1) have been developed but the question remains how to deploy them for gas–solid contact. Unfortunately, the direct use of MOFs as nanocrystals would lead to serious problems and risks. Here, for the first time, we report a novel MOF-based hybrid sorbent that is produced via an innovative in-situ microencapsulated synthesis. Using a custom-made double capillary microfluidic assembly, double emulsions of the MOF precursor solutions and UV-curable silicone shell fluid are produced. Subsequently, HKUST-1 MOF is successfully synthesized within the droplets enclosed in the gas permeable microcapsules. The developed MOF-bearing microcapsules uniquely allow the deployment of functional nanocrystals without the challenge of handling ultrafine particles, and further, can selectively reject undesired compounds to protect encapsulated MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of organic non-flammable spacecraft potting, encapsulating and conformal coating compounds

The overall program objective was to develop a flexible compound which not only functioned in a manned aerospace environment as an effective electrical insulation, but whose flammability characteristics in 16.5 psia, 60% oxygen/40% nitrogen were evidenced by rapid self-extinguishment and minimal thermal (pyrolysis) degradation. The following polymeric matrices were examined in depth: fluoroelastomers, modified fluoroelastomers, silicone RTV's, and modified silicone and fluorosilicone RTV's. Almost none of these systems burned in air, but all burned in 6.2 psia oxygen. Inorganic, organic, and inorganic/organic additives were evaluated in conjunction with these polymers in order to achieve the required survival in the 16.5 psia 60/40 environment. Depending upon formulations, it was possible to achieve nonflammable products when tested in the 1/4 in. x 1/4 in. x 1 in. configuration, even up to and including 16.5 psia oxygen. However, in order to assure this level of flame resistance, it was found necessary to heavily load the matrix with the additives. This resulted in a significant reduction in mechanical properties and large increases in viscosities. Optimization of formulations to obtain a suitable balance between these properties and flammability resistance led to the final selection of Formulation 387 as the primary system.

Lieberman, S. L.↗

High efficiency compound semiconductor concentrator photovoltaics

Special emphasis was given to the high yield pilot production of packaged AlGaAs/GaAs concentrator solar cells, using organometallic VPE for materials growth, the demonstration of a concentrator module using 12 of these cells which achieved 16.4 percent conversion efficiency at 50 C coolant inlet temperature, and the demonstration of a spectral splitting converter module that achieved in excess of 20 percent efficiency. This converter employed ten silicon and ten AlGaAs cells with a dichroic filter functioning as the beam splitter. A monolithic array of AlGaAs/GaAs solar cells is described.

Borden, P.↗

Applications of plasma-enhanced metalorganic chemical vapor deposition

The use of plasma enhancement for growth of III-V compound semiconductor materials by metalorganic chemical vapor deposition (MOCVD) is examined, to improve control of microstructure, develop understanding of the underlying growth mechanisms, and expand the range of materials combinations for photovoltaic and solid-state lighting applications. Whereas plasma is commonly used with group-IV materials, such as silicon, few studies have examined the impact of plasma-enhanced MOCVD (PE-MOCVD) for III-V materials growth. PE-MOCVD provides improved decomposition of metalorganic precursors, which is driven by hydrogen plasma to augment hydride reactions and thermal pyrolysis, but plasma generation requires low reactor pressure. We have demonstrated elemental Al films grown by PE-MOCVD, which show distinct crystallographic texturing, and assume epitaxial microstructure upon post-growth annealing. We also demonstrate PE-MOCVD of GaAs at temperatures as low as 300 °C. With increasing radio-frequency power, the GaAs growth rate shows a transition from power limited to mass-transport limited. PE-MOCVD grown Ga 0.5 In 0.5 P shows no detectable spontaneous atomic ordering, which offers a mechanism to form order/disorder unicompositional heterostructures, without temperature change or impurity incorporation. In its current implementation, PE-MOCVD grown films have shown microstructural degradation, that we attribute to direct plasma exposure during growth. Improvements in the system design and growth sequences are at the focus of on-going efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Infrared/submillimeter optical properties data base

The general goal was to build a data base containing optical properties, such as reflectance, transmittance, refractive index, in the far infrared to submillimeter wavelength region. This data base would be limited to selected crystalline materials and temperature between 300 and 2 K. The selected materials were: lithium, lead, and strontium; the bromides of potassium and thallium; the carbides of silicone and tungsten; and the materials of KRS5, KRS6, diamond, and sapphire. Last summer, barium fluoride was selected as prototype material for building the data base. This summer the literature search, preparation of the data for barium fluoride was completed. In addition the literature search for data related to the compounds mentioned was completed. The current status is that barium fluoride is in a form suitable for a NASA internal publication. The papers containing the data on the other materials were xeroxed and they are ready to be reduced. On the reverse side, the top figure is a sample combination of data for the index of refraction at 300 K. The lower figure shows the transmittance vs wavelength at 300 and 80 K. These figures are a sample of many which were developed. Since barium fluoride was studied more than most of the materials listed above, it is clear that additional measurements should be made to fill in the gaps present on both temperature and wavelength data.

Alley, Phillip W.↗

FeSi 4 P 4 and CoSi 3 P 3 : Hidden Gems of Ternary Tetrel Pnictides with Outstanding Nonlinear Optical Properties

Metal silicon phosphides have shown promise as nonlinear optical materials. To be practically useful and cheap, earth-abundant 3d transition metals are preferred over their scarcer and more expensive 4d and 5d counterparts. Here, we developed a synthetic method to produce polycrystalline bulk powders and millimeter-sized single crystals of ternary compounds FeSi 4 P 4 and CoSi 3 P 3 . Both studied compounds have noncentrosymmetric and chiral crystal structures with ordered Si/P arrangements as was confirmed by single-crystal X-ray diffraction and solid-state NMR. Despite the presence of the transition metal, FeSi 4 P 4 and CoSi 3 P 3 are semiconductors with direct band gaps of 1.3 and 1.6 eV, respectively, indicating low-spin d 6 electronic configuration for octahedral Fe 2+ and Co 3+ . Relative to reported sulfide materials, FeSi 4 P 4 and CoSi 3 P 3 small band gap semiconductors demonstrate an outstanding combination of second-harmonic generation (SHG) activity and laser damage threshold (LDT). Both studied materials are phase-matchable with a 2.09 μm laser and not only exhibit 2.5–3.0 times stronger SHG signal than that of the state-of-the-art AgGaS 2 standard but also demonstrate an LDT response of 2.3–2.5 times higher than that of AgGaS 2 (at 1.09 μm laser with a pulse width of 10 ns)-which is unprecedented for small band gap semiconductors.

36 MATERIALS SCIENCE↗

Theoretical Investigation of Delafossite-Cu 2 ZnSnO 4 as a Promising Photovoltaic Absorber

In the quest for efficient and cost-effective photovoltaic absorber materials beyond silicon, considerable attention has been directed toward exploring alternatives. One such material, zincblende-derived Cu2ZnSnS4 (CZTS), has shown promise due to its ideal band gap size and high absorption coefficient. However, challenges such as structural defects and secondary phase formation have hindered its development. In this study, we examine the potential of another compound, Cu2ZnSnO4 (CZTO), with a similar composition to CZTS as a promising alternative. Employing ab initio density function theory (DFT) calculations in combination with an evolutionary structure prediction algorithm, we identify that the crystalline phase of delafossite structure is the most stable among the 900 (meta)stable CZTO. Its thermodynamic stability at room temperature is also confirmed by the molecular dynamics study. Excitingly, this new phase of CZTO displays a direct band gap where the dipole-allowed transition occurs, making it a strong candidate for efficient light absorptions. Furthermore, the estimation of spectroscopic limited maximum efficiency (SLME) directly demonstrates the high potential of delafossite-CZTO as a photovoltaic absorber. Our numerical results suggest that delafossite-CZTO holds promise for future photovoltaic applications.

14 SOLAR ENERGY↗

Easy-Processable and Aging-Free All-Polymer Polysiloxane Composites

In this work, we report all-polymer polysiloxane composites that overcome the long-standing processing problems of silica-reinforced silicone rubbers. Polystyrene fillers are dispersed with styrene/dimethylsiloxane symmetric diblock and triblock copolymers that control the filler morphology, filler–matrix interactions, and filler–filler interactions. Surprisingly, the composites not only rival the traditional silica-reinforced polysiloxane in mechanical properties of cured materials but also have better processability and stability than the silica-filled compound before curing. Large amplitude oscillatory shear experiments demonstrate that the triblock copolymer addition strongly affects the rheological properties. We hypothesize that the bridges and entangled loops that were formed by the triblock copolymer can connect different PS domains to provide additional reinforcement. The aging effect that originates from PDMS chain adsorption on the filler particle surface is also avoided because of the thermodynamic repulsion between PS and PDMS phases.

36 MATERIALS SCIENCE↗

Variations in the Peak Position of the 6.2 micron Interstellar Emission Feature: A Tracer of N in the Interstellar Polycyclic Aromatic Hydrocarbon Population

This paper presents the results of an investigation of the molecular characteristics that underlie the observed peak position and profile of the nominal 6.2 micron interstellar emission band generally attributed to the CC stretching vibrations of polycyclic aromatic hydrocarbons (PAHs). It begins with a summary of recent experimental and theoretical studies ofthe spectroscopic properties of large (>30 carbon atoms) PAH cations as they relate to this aspect of the astrophysical problem. It then continues with an examination of the spectroscopic properties of a number of PAH variants within the context of the interstellar 6.2 micron emission, beginning with a class of compounds known as polycyclic aromatic nitrogen heterocycles (PANHs; PAHs with one or more nitrogen atoms substituted into their carbon skeleton). In this regard, we summarize the results of recent relevant experimental studies involving a limited set of small PANHs and their cations and then report the results of a comprehensive computational study that extends that work to larger PANH cations including many nitrogen-substituted variants of coronene(+) (C24H12(+)), ovalene(+) (C32H14(+)), circumcoronene(+) (C54H18(+)), and circum-circumcoronene(+) (C96H24(+)). Finally, we report the results of more focused computational studies of selected representatives from a number of other classes of PAH variants that share one or more of the key attributes of the PANH species studied. These alternative classes of PAH variants include (1) oxygen- and silicon-substituted PAH cations; (2) PAH-metal ion complexes (metallocenes) involving the cosmically abundant elements magnesium and iron; and (3) large, asymmetric PAH cations. Overall, the studies reported here demonstrate that increasing PAH size alone is insuEcient to account for the position of the shortest wavelength interstellar 6.2 micron emission bands, as had been suggested by earlier studies. On the other hand, this work reveals that substitution of one or more nitrogen atoms within the interior of the carbon skeleton of a PAH cation induces a significant blueshift in the position of the dominant CC stretching feature of these compounds that is suf6cient to account for the position of the interstellar bands. Subsequent studies of the effects of substitution by other heteroatoms (O and Si), metal ion complexation (Fe(+), Mg(+), and Mg(2+)), and molecular symmetry variation-all of which fail to reproduce the blueshift observed in the PANH cations-indicate that N appears to be unique in its ability to accommodate the position of the interstellar 6.2 micron bands while simultaneously satisfying the other constraints of the astrophysical problem. This result implies that the peak position of the interstellar feature near 6.2 micron traces the degree of nitrogen substitution in the population, that most of the PAHs responsible for the interstellar IR emission features incorporate nitrogen within their aromatic networks, and that a lower limit of 1%-2% of the cosmic nitrogen is sequestered within the interstellar PAH population. Finally, in view of the ubiquity and abundance of interstellar PAHs and the permanent dipoles and distinctive electronic structures of these nitrogen-substituted variants, this work impacts a wide range of observational phenomena outside of the infrared region of the spectrum including the forest of unidentified molecular rotational features and the anomalous Galactic foreground emission in the microwave, and the diffuse interstellar bands (DIBs) and other structure in the interstellar extinction curve in the ulhviolet/visible. These astrophysical ramifications are discussed, and the dipole moments and rotational constants are tabulated to facilitate further investigations of the astrophysical role of nitrogen-substituted aromatic compounds.

Hudgins, Douglas M.↗

The seventh blind test of crystal structure prediction: structure generation methods

A seventh blind test of crystal structure prediction was organized by the Cambridge Crystallographic Data Centre featuring seven target systems of varying complexity: a silicon and iodine-containing molecule, a copper coordination complex, a near-rigid molecule, a cocrystal, a polymorphic small agrochemical, a highly flexible polymorphic drug candidate, and a polymorphic morpholine salt. In this first of two parts focusing on structure generation methods, many crystal structure prediction (CSP) methods performed well for the small but flexible agrochemical compound, successfully reproducing the experimentally observed crystal structures, while few groups were successful for the systems of higher complexity. A powder X-ray diffraction (PXRD) assisted exercise demonstrated the use of CSP in successfully determining a crystal structure from a low-quality PXRD pattern. The use of CSP in the prediction of likely cocrystal stoichiometry was also explored, demonstrating multiple possible approaches. Crystallographic disorder emerged as an important theme throughout the test as both a challenge for analysis and a major achievement where two groups blindly predicted the existence of disorder for the first time. Additionally, large-scale comparisons of the sets of predicted crystal structures also showed that some methods yield sets that largely contain the same crystal structures.

Chemistry↗

Space processing of composite materials

Materials and processes for the testing of aluminum-base fiber and particle composites, and of metal foams under extended-time low-g conditions were investigated. A wetting and dispersion technique was developed, based on the theory that under the absence of a gas phase all solids are wetted by liquids. The process is characterized by a high vacuum environment and a high temperature cycle. Successful wetting and dispersion experiments were carried out with sapphire fibers, whiskers and particles, and with fibers of silicon carbide, pyrolytic graphite and tungsten. The developed process and facilities permit the preparation of a precomposite which serves as sample material for flight experiments. Low-g processing consists then merely in the uniform redistribution of the reinforcements during a melting cycle. For the preparation of metal foams, gas generation by means of a thermally decomposing compound was found most adaptable to flight experiments. For flight experiments, the use of compacted mixture of the component materials limits low-g processing to a simple melt cycle.

Steurer, W. H.↗

Advanced diesel engine component development program, tasks 4-14

This report summarizes the Advanced Diesel Engine Component Development (ADECD) Program to develop and demonstrate critical technology needed to advance the heavy-duty low heat rejection engine concept. Major development activities reported are the design, analysis, and fabrication of monolithic ceramic components; vapor phase and solid film lubrication; electrohydraulic valve actuation; and high pressure common rail injection. An advanced single cylinder test bed was fabricated as a laboratory tool in studying these advanced technologies. This test bed simulates the reciprocator for a system having no cooling system, turbo compounding, Rankine bottoming cycle, common rail injection, and variable valve actuation to achieve fuel consumption of 160 g/kW-hr (.26 lb/hp-hr). The advanced concepts were successfully integrated into the test engine. All ceramic components met their functional and reliability requirements. The firedeck, cast-in-place ports, valves, valve guides, piston cap, and piston ring were made from silicon nitride. Breakthroughs required to implement a 'ceramic' engine included the fabrication of air-gap cylinder heads, elimination of compression gaskets, machining of ceramic valve seats within the ceramic firedeck, fabrication of cast-in-place ceramic port liners, implementation of vapor phase lubrication, and elimination of the engine coolant system. Silicon nitride valves were successfully developed to meet several production abuse test requirements and incorporated into the test bed with a ceramic valve guide and solid film lubrication. The ADECD cylinder head features ceramic port shields to increase insulation and exhaust energy recovery. The combustion chamber includes a ceramic firedeck and piston cap. The tribological challenge posed by top ring reversal temperatures of 550 C was met through the development of vapor phase lubrication using tricresyl phosphate at the ring-liner interface. A solenoid-controlled, variable valve actuation system that eliminated the conventional camshaft was demonstrated on the test bed. High pressure fuel injection via a common rail system was also developed to reduce particulate emissions.

Kaushal, Tony S.↗