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At least 307 records · Page 17

An Approach to Processable Polyimides

The use of polymer matrix composites (PMC's) in aircraft engines can lead to substantial weight savings over metals. This weight reduction correlates into better fuel economy, increased speed, and increased passenger load. Typically, high performance PMC's possess high thermal-oxidative stabilities (TOS) and high glass transition temperatures (Tg's) to withstand temperatures up to 316 C (600 F). One of the leading high temperature resins system available today is PMR-15 (Polymerization of Monomeric Reactants, MW=1500). This thermosetting polyimide utilizes addition curing through polymer endcaps which enables hand lay-up processing of carbon fiber composite parts with low void contents. However, the large amount of hand labor raises manufacturing costs and prohibits the use of PMR-15 in many aerospace applications. Resin Transfer Molding (RTM) provides an economical alternative, but it requires a melt Viscosity of less than 10(exp 3) centipoise (cP). This is much lower than the minimum melt viscosity of PMR-15 (about 10(exp 6) cP). To improve the processability of polyimides, the polymer backbone can be modified by incorporating flexible linkages, such as branching. bulky pendant groups, kinked structures, and twisted or non-coplanar moietes . The focus of this paper will be the introduction of non-coplanar biaryls into the PMR polyimide backbone to increase processability while maintaining high temperature performance.

Gariepy, Christopher A.↗

A Cryogenic Infrared Calibration Target

A compact cryogenic calibration target is presented that has a peak diffuse reflectance, R < or = 0.003, from 800 to 4800/cm (12 − 2 microns ). Upon expanding the spectral range under consideration to 400-10,000/ cm−1 (25 − 1 microns) the observed performance gracefully degrades to R < or = 0.02 at the band edges. In the implementation described, a high-thermal-conductivity metallic substrate is textured with a pyramidal tiling and subsequently coated with a thin lossy dielectric coating that enables high absorption and thermal uniformity across the target. The resulting target assembly is lightweight, has a low-geometric profile, and has survived repeated thermal cycling from room temperature to approx.4 K. Basic design considerations, governing equations, and test data for realizing the structure described are provided. The optical properties of selected absorptive materials-Acktar Fractal Black, Aeroglaze Z306, and Stycast 2850 FT epoxy loaded with stainless steel powder-are characterized and presented

dielectric coating↗

Single Ru(II) Ions on Ceria as a Highly Active Catalyst for Abatement of NO

Atom trapping leads to catalysts with atomically dispersed Ru 1 O 5 sites on (100) facets of ceria, as identified by spectroscopy and DFT calculations. This is a new class of ceria-based materials with Ru properties drastically different from the known M/ceria materials. They show excellent activity in catalytic NO oxidation, a critical step that requires use of large loadings of expensive noble metals in diesel aftertreatment systems. Ru 1 /CeO 2 is stable during continuous cycling, ramping, and cooling as well as the presence of moisture. Furthermore, Ru 1 /CeO 2 shows very high NO x storage properties due to formation of stable Ru–NO complexes as well as a high spill-over rate of NO x onto CeO 2 . Only ~0.05 wt % of Ru is required for excellent NO x storage. Ru 1 O 5 sites exhibit much higher stability during calcination in air/steam up to 750 °C in contrast to RuO 2 nanoparticles. Here we clarify the location of Ru(II) ions on the ceria surface and experimentally identify the mechanism of NO storage and oxidation using DFT calculations and in situ DRIFTS/mass spectroscopy. Moreover, we show excellent reactivity of Ru 1 /CeO 2 for NO reduction by CO at low temperatures: only 0.1–0.5 wt % of Ru is sufficient to achieve high activity. Modulation-excitation in situ infrared and XPS measurements reveal the individual elementary steps of NO reduction by CO on an atomically dispersed Ru ceria catalyst, highlighting unique properties of Ru 1 /CeO 2 and its propensity to form oxygen vacancies/Ce +3 sites that are critical for NO reduction, even at low Ru loadings. Our study highlights the applicability of novel ceria-based single-atom catalysts to NO and CO abatement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fast-Response-Time Shape-Memory-Effect Foam Actuators

Bulk shape memory alloys, such as Nitinol or CuAlZn, display strong recovery forces undergoing a phase transformation after being strained in their martensitic state. These recovery forces are used for actuation. As the phase transformation is thermally driven, the response time of the actuation can be slow, as the heat must be passively inserted or removed from the alloy. Shape memory alloy TiNi torque tubes have been investigated for at least 20 years and have demonstrated high actuation forces [3,000 in.-lb (approximately equal to 340 N-m) torques] and are very lightweight. However, they are not easy to attach to existing structures. Adhesives will fail in shear at low-torque loads and the TiNi is not weldable, so that mechanical crimp fits have been generally used. These are not reliable, especially in vibratory environments. The TiNi is also slow to heat up, as it can only be heated indirectly using heater and cooling must be done passively. This has restricted their use to on-off actuators where cycle times of approximately one minute is acceptable. Self-propagating high-temperature synthesis (SHS) has been used in the past to make porous TiNi metal foams. Shape Change Technologies has been able to train SHS derived TiNi to exhibit the shape memory effect. As it is an open-celled material, fast response times were observed when the material was heated using hot and cold fluids. A methodology was developed to make the open-celled porous TiNi foams as a tube with integrated hexagonal ends, which then becomes a torsional actuator with fast response times. Under processing developed independently, researchers were able to verify torques of 84 in.-lb (approximately equal to 9.5 Nm) using an actuator weighing 1.3 oz (approximately equal to 37 g) with very fast (less than 1/16th of a second) initial response times when hot and cold fluids were used to facilitate heat transfer. Integrated structural connections were added as part of the net shape process, eliminating the need for welding, adhesives, or mechanical crimping. Inexpensive net-shape processing was used, which reduces the cost of the actuator by over a factor of 10 over nonporous TiNi made by hot drawing of tube or electrical discharge machining. By forming the alloy as an open-celled foam, the surface area for heat transfer is dramatically increased, allowing for much faster response times. The technology also allows for netshape fabrication of the actuator, which allows for structural connections to be integrated into the actuator material, making these actuators significantly less expensive. Commercial applications include actuators for concepts such as the variable area chevron and nozzle in jet aircraft. Lightweight tube or rod components can be supplied to interested parties.

Jardine, Peter↗

Stress Corrosion Evaluation of Various Metallic Materials for the International Space Station Water Recycling System

A stress corrosion evaluation was performed on Inconel 625, Hastelloy C276, titanium commercially pure (TiCP), Ti-6Al-4V, Ti-6Al-4V extra low interstitial, and Cronidur 30 steel as a consequence of a change in formulation of the pretreatment for processing the urine in the International Space Station Environmental Control and Life Support System Urine Processing Assembly from a sulfuric acid-based to a phosphoric acid-based solution. The first five listed were found resistant to stress corrosion in the pretreatment and brine. However, some of the Cronidur 30 specimens experienced reduction in load-carrying ability.

Torres, P. D.↗

Fabrication of a Thermally Isolated and Pre-amplified Transistor Module with Polyimide Micro-wires for Cryogenic Detectors

For use in cryogenic applications such as bolometer and x-ray microcalorimeter arrays, pre-amplifying Junction Field Effect Transistors (JFETs) are often required for the readout electronics. The optimum operating temperature of the JFETs is 130 Kelvin while the cryogenic detectors operate in the milli-Kelvin range. Thus, the JFETs must be heated up but thermally isolated from the surrounding cryogenic instruments. In the past, the thermal isolation was accomplished by suspending the JFETs with low conductance wires such as manganium or stainless steel on a Kevlar support platform [I]. This also achieved electrical connections. However, this assembly required manual soldering work, which could raise a reliability issue for the cryogenic applications. In order to eliminate the manual work, polyimide micro-wires were developed [2]. The wires must be of sufficient length to decrease the heat load and in tension to prevent microphonic noise from vibration of the wires: the polyimide wires were patterned into llS"shaped curves over a thin metal wires such as aluminum, titanium, or niobium. The bilayer of the films were then suspended by etching silicon substrate thus to make freestanding air bridges (enough explanation?). In this paper, we present a method to fabricate micromachined JFET mechanical modules suspended by polyimide Pyraline micro-wires and heated up with built-in aluminum micro-heaters.

Oh, L. H.↗

Materials and structures for hypersonic vehicles

The development of low-density materials with higher strength and stiffness, and more efficient engine and airframe structures is considered enabling technology for reusable hypersonic vehicles. Advanced structural concepts are required for minimum weight hot structures that will be fully reusable. Key design drivers are maximum heating rate, duration of heating, total heat load, flight envelope and type of propulsion system, mission life requirements, and containment of liquid hydrogen. For hot-structures applications in the range from 600-1800°F, advanced alloys of titanium, titanium and nickel aluminides, and metal-matrix composites are leading candidates because of their high specific properties. For temperatures in excess of 2000°F carbon-carbon and ceramic-matrix composites are the most structurally efficient materials. This paper addresses the technology issues for light weight hot structures, gives brief assessments of the state of the art, presents selected highlights of current research, and identifies areas requiring additional development.

Hypersonic Vehicles↗

Materials and structures for hypersonic vehicles

The development of low-density materials with higher strength and stiffness, and more efficient engine and airframe structures is considered enabling technology for reusable hypersonic vehicles. Advanced structural concepts are required for minimum weight hot structures that will be fully reusable. Key design drivers are maximum heating rate, duration of heating, total heat load, flight envelope and type of propulsion system, mission life requirements, and containment of liquid hydrogen. For hot-structures applications in the range from 600-1800°F, advanced alloys of titanium, titanium and nickel aluminides, and metal-matrix composites are leading candidates because of their high specific properties. For temperatures in excess of 2000°F carbon-carbon and ceramic-matrix composites are the most structurally efficient materials. This paper addresses the technology issues for light weight hot structures, gives brief assessments of the state of the art, presents selected highlights of current research, and identifies areas requiring additional development.

Hypersonic Vehicles↗

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High‐Energy Li‐S Batteries

Abstract Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium–sulfur (Li‐S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li‐S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core–shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm −2 ) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm −2 ) with a low electrolyte/sulfur ratio (10 μL mg −1 ). This research further demonstrates a durable Li‐Se/S pouch cell with high specific capacity, validating the potential practical applications.

Zhao, Chen↗

Recrystallization as a controlling process in the wear of some f.c.c. metals

Detailed examination of copper specimens after sliding against 440 C steel in liquid methane at speeds up to 25 m/s and loads of up to 2 kg showed the metal comprising the wear surface to possess a fine cell recrystallized structure. Wear proceeded by the plastic shearing of metal in this near surface region without the occurrence of visible metal transfer. A dynamic balance between the intense shear process at the surface and the nucleation of recrystallized grains was proposed to account for the behavior of the metal at the wear surface. Sliding wear experiments were also conducted on Ag, Cu-10% Al, Cu-10% Sn, Ni and Al. It was found that low wear and the absence of heavy metal transfer were associated with those metals observed to undergo recrystallization nucleation without prior recovery.

Bill, R. C.↗

The Influence of Yttria Content on the Thermal Stability of Yttria-Stabilized Zirconia Aerogels

Aerogels demonstrate extraordinarily low thermal conductivity and low density, presenting a promising form of lightweight insulation for aerospace applications. The primary challenge is stabilization of the highly porous structure at temperatures to 1200 °C. Upon collapse of the pore structure, the favorable thermal properties and low density are diminished. Yttria-stabilized zirconia (YSZ) aerogels are synthesized to investigate the effect of composition on morphology, phase behavior, and thermal stability (specific surface area, pore size distribution). This work demonstrates the improvement in thermal stability of zirconia aerogels with increased yttria content. To develop insight on the influence of structure on thermal stability, the effects of water content and solids loading are studied and in elucidation of the mechanism by which yttria stabilizes the pore structure. With an improved understanding of aerogel structure and performance, metal oxide aerogels can be developed to withstand the extreme environments of space exploration.

Nathaniel Olson↗

Isothermal and nonisothermal fatigue behavior of a metal matrix composite

The isothermal and nonisothermal fatigue resistance of a metal matrix composite (MMC) consisting of Ti-15V-3Cr-3Al-3Sn (Ti-15-3) matrix reinforced by 33 vol pct continuous SiC fibers was investigated. The fibers were nominally oriented parallel to the specimen axis. Isothermal fatigue tests were performed in air at 300 and 550 C. The MMC had good isothermal fatigue resistance at low cyclic stress, with fatigue cracks initiating from fiber-matrix interfaces and foil laminations. At high cyclic stresses, stress relaxation in the matrix reduced isothermal composite fatigue resistance at 550 C. Nonisothermal fatigue loading substantially degraded composite fatigue resistnce. This degradation was produced by a thermomechanical fatigue damage mechanism associated with the fiber-matrix interfaces.

Gabb, T. P.↗

Boosting Hydrogen Evolution in Neutral Medium by Accelerating Water Dissociation with Ru Clusters Loaded on Mo 2 CTx MXene

Abstract Electrocatalytic hydrogen evolution reaction (HER) in mild neutral medium is a compelling goal for environmentally sustainable energy conversion, but its development is greatly limited by slow kinetics. Platinum group noble metals exhibit ultra‐high HER activities, but their scarcity and performance instability restrict wide application. Herein, taking advantage of excellent catalyst carrier properties of 2D‐layered transition metal carbides (MXenes), highly dispersed of Ru clusters anchored on Mo 2 CT x MXene are demonstrated as a superior HER electrocatalyst, which is prepared by a facile in situ reduction strategy. The as‐prepared Ru/Mo 2 CT x catalyst exhibits a very low overpotential of 73 mV to achieve a current density of −10 mA cm −2 and Tafel slope of 57 mV dec −1 in neutral medium, surpassing performance of most previously reported MXene‐based catalysts. In addition, Ru/Mo 2 CT x catalyst also presents superior stability compared to commercial Pt/C. Experimental results and theoretical calculations indicate that the interaction between Ru clusters modulates the electronic structure of active sites and promotes H 2 O dissociation and hydrogen desorption.

Wu, Yanze↗

Inelastic response of metal matrix composites under biaxial loading

Theoretical predictions and experimental results were obtained for inelastic response of unidirectional and angle ply composite tubes subjected to axial and torsional loading. The composite material consist of silicon carbide fibers in a titanium alloy matrix. This material is known to be susceptible to fiber matrix interfacial damage. A method to distinguish between matrix yielding and fiber matrix interfacial damage is suggested. Biaxial tests were conducted on the two different layup configurations using an MTS Axial/Torsional load frame with a PC based data acquisition system. The experimentally determined elastic moduli of the SiC/Ti system are compared with those predicted by a micromechanics model. The test results indicate that fiber matrix interfacial damage occurs at relatively low load levels and is a local phenomenon. The micromechanics model used is the method of cells originally proposed by Aboudi. Finite element models using the ABACUS finite element program were used to study end effects and fixture specimen interactions. The results to date have shown good correlation between theory and experiment for response prior to damage initiation.

Lissenden, C. J.↗

Fatigue behavior and life prediction of a SiC/Ti-24Al-11Nb composite under isothermal conditions

Metal Matrix Composites (MMC) and Intermetallic Matrix Composites (IMC) were identified as potential material candidates for advanced aerospace applications. They are especially attractive for high temperature applications which require a low density material that maintains its structural integrity at elevated temperatures. High temperature fatigue resistance plays an important role in determining the structural integrity of the material. This study attempts to examine the relevance of test techniques, failure criterion, and life prediction as they pertain to an IMC material, specifically, unidirectional SiC fiber reinforced titanium aluminide. A series of strain and load controlled fatigue tests were conducted on unidirectional SiC/Ti-24Al-11Nb composite at 425 and 815 C. Several damage mechanism regimes were identified by using a strain-based representation of the data, Talreja's fatigue life diagram concept. Results of these tests were then used to address issues of test control modes, definition of failure, and testing techniques. Finally, a strain-based life prediction method was proposed for an IMC under tensile cyclic loadings at elevated temperatures.

Bartolotta, Paul A.↗

Syntheses of gold supported on metal oxides and their application in organic transformations

Herein, we report a general and straightforward synthesis method for gold supported on mesoporous and microporous metal oxides. Supported materials, in general, show higher crystallinity compare to unsupported systems as verified through powder X-ray diffraction (XRD). Also, through XRD, most of the metal is observed to be in its oxide form, whereas the gold support was found to be in its metallic state, which has been further confirmed from TEM. In terms of surface area, the catalyst was not found to follow any trend. Morphology wise, there are no changes observed after doping except in few cases. Combined results from XRD, X-ray fluorescence spectroscopy, Auger, and X-ray photoelectron spectroscopy suggest that gold is mainly in the bulk and very little (0.04% in case of gold doped calcium oxide) or non (in case of gold doped mixed manganese-cerium oxide) on the surface. The presence of Au (0) 4f peaks in XPS further confirms the metallic state of the gold. Oxides of indium, magnesium and calcium have been studied for the organic transformation reactions. An enhancement in activity and product selectivity was observed in the case of the gold supported catalysts. Indium serves as a great catalyst for C–C coupling and electrophilic aromatic substitution reactions and gives >99% conversion. Interestingly, 88% selectivity for C–C coupling and >99% selectivity for aromatic substitution have been achieved at 100 °C and room temperature respectively. Magnesium and calcium give Knoevenagel condensation products. At room temperature with very low catalyst loading, >99% conversion and selectivity were observed for the Knoevenagel reaction with as high as 35.30 TOF. Finally, a mechanism for the C–C coupling reaction has been proposed based on these results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Ordered Mesoporous Oxides in Plasma-Assisted Ammonia Synthesis

Widespread implementation of dielectric barrier discharge (DBD)-assisted NH 3 synthesis, a nascent technology operating under sustainable, ambient conditions, is hindered by low energy yields due to, in part, poor fundamental understanding. Porous oxides used to support metal nanoparticle catalysts have shown significant energy yield contributions for DBD-assisted NH 3 synthesis even without metal. Using an AC-powered, coaxial, single-stage reactor at 16 kV with equimolar (N 2 /H 2 ) feed, we measured NH 3 synthesis rates in the presence of different nonordered oxides, ordered SiO 2 structures (SBA-15 and MCM-41), and ordered Al-incorporated analogues (γ-Al 2 O 3 -coated with varying Al-loadings and Al-substitution, respectively: Al 2 O 3 -SBA-15 and Al-MCM-41). We systematically quantified NH 3 energy yield dependence on pore structures and material identities (i.e., ordered pores and Al incorporation) known to facilitate higher DBD-assisted NH 3 synthesis rates. SBA-15 displayed a higher steady-state energy yield than MCM-41, indicating that framework type is a crucial factor, with both ordered porous systems outperforming fumed SiO 2 . 10 wt % Al maximized in situ NH 3 uptake among the various Al loadings, exhibiting a higher steady-state energy yield and similar power to SBA-15. However, Al-MCM-41 had a similar steady-state energy yield and lower power than MCM-41, likely due to the extended γ-Al 2 O 3 surface that has a dielectric constant higher than that of SiO 2 . Both Al-incorporated analogues benefit from surface acid sites that can adsorb NH 3 in situ, resulting in higher overall NH 3 energy yields than that of their parent ordered SiO 2 . Al 2 O 3 -SBA-15 shielded more NH 3 than Al-MCM-41, likely due to a higher acid site density than the acid site identity. Furthermore, Al incorporation via γ-Al 2 O 3 coating more successfully improves the NH 3 energy yield; together with the high-performing ordered framework, these analogues are potential metal catalyst supports with promising energy yields for DBD-assisted synthesis of NH 3 and other chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗