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Furfural Acetalization with Ethanol over Hierarchical vs. Conventional Beta Zeolites
A set of hierarchical Beta zeolites was synthesized using concentrated reaction mixtures and compared to conventional materials with a similar composition. The obtained zeolite catalysts were investigated in acetalization of furfural with ethanol at room temperature yielding a commercially valuable fuel additive (furfural diethyl acetal). The highest yield of the desired product (91 %) was achieved over a zeolite catalyst possessing developed mesoporosity (V meso 0.75 cm 3 /g) and a high external surface area (280 m 2 /g). Here, the concentration of accessible acid sites was found to be responsible for high catalytic performance of the tested zeolitic catalysts.
Surface areas and porosities of ices used to simulate stratospheric clouds
Surface areas, bulk densities, and porosities of ices formed at 85 or 200 K are measured to study the morphology of the vapor-deposited ices that have been used to simulate ice clouds in the laboratory. Surface areas are measured from the Brunauer, Emmett, and Teller (BET) analysis of absorption isotherms obtained at 72.2 K. Bulk densities and porosities are determined photogrammetrically. Results show that water ice and HNO3-H2O ice films deposited from the vapor at temperatures below 200 K exhibit large BET surface areas and are highly porous. For the ices annealed at temperatures above 200 K, external surface areas calculated from the observed particle sizes agree reasonably well with the BET areas, which indicates that the annealed ices are composed of nonporous particles and that the porosity of these ices is due to interstices among the particles.
Boron Nitride Nanoribbons from Exfoliation of Boron Nitride Nanotubes
Two types of boron nitride nanotubes (BNNTs) were exfoliated into boron nitride nanoribbons (BNNR), which were identified using transmission electron microscopy: (1) commercial BNNTs with thin tube walls and small diameters. Tube unzipping was indicated by a large decrease of the sample's surface area and volume for pores less than 2 nm in diameter. (2) BNNTs with large diameters and thick walls synthesized at NASA Glenn Research Center. Here, tube unraveling was indicated by a large increase in external surface area and pore volume. For both, the exfoliation process was similar to the previous reported method to exfoliate commercial hexagonal boron nitride (hBN): Mixtures of BNNT, FeCl3, and NaF (or KF) were sequentially treated in 250 to 350 C nitrogen for intercalation, 500 to 750 C air for exfoliation, and finally HCl for purification. Property changes of the nanosized boron nitride throughout this process were also similar to the previously observed changes of commercial hBN during the exfoliation process: Both crystal structure (x-ray diffraction data) and chemical properties (Fourier-transform infrared spectroscopy data) of the original reactant changed after intercalation and exfoliation, but most (not all) of these changes revert back to those of the reactant once the final, purified products are obtained.
Noncovalent Surface Modification of Metal–Organic Frameworks: Unscrambling Adsorption Properties via Isothermal Titration Calorimetry
Despite the importance of noncovalent interactions in the utilization of metal–organic frameworks (MOFs), using these interactions to functionalize MOFs has rarely been explored. The ease of functionalization and potential for surface-selective functionalization makes modification via noncovalent interactions promising for the creation of porous photocatalytic assemblies. Here, using isothermal titration calorimetry, photoluminescence measurements, and desorption experiments, we have explored the nature and magnitude of the interactions of [Ru(bpy) 2 (bpy-R)] 2+ -functionalized dyes with the surface of MIL-96, where R = C 3 , C 8 , C 12 , and C 18 alkyl chains of either straight-chain or cyclic conformations. The orientation of the dyes appears to be flat against the surface with respect to the long alkyl chains, and the surface concentration approaches a monolayer at high initial concentrations of dye. Strangely, the dodecyl-functionalized dye, despite having a smaller interaction energy and larger footprint than either octyl-functionalized dye, achieves the highest maximum surface concentration. Based on photoluminescence spectra, desorption experiments, and ITC data, we believe this is due to the core of the dye being lifted from the surface as the chain length increases. Our understanding of these interactions is important for further utilization of this method for the functionalization of the internal and external surface areas of MOFs.
Optimum subsonic, high-angle-of-attack nacelles
The optimum design of nacelles that operate over a wide range of aerodynamic conditions and their inlets is described. For low speed operation the optimum internal surface velocity distributions and skin friction distributions are described for three categories of inlets: those with BLC, and those with blow in door slots and retractable slats. At cruise speed the effect of factors that reduce the nacelle external surface area and the local skin friction is illustrated. These factors are cruise Mach number, inlet throat size, fan-face Mach number, and nacelle contour. The interrelation of these cruise speed factors with the design requirements for good low speed performance is discussed.
Optimum subsonic, high-angle-of-attack nacelles
Many proposed advanced aircraft - but especially tilt-nacelle, subsonic-cruise, V/STOL aircraft - require nacelles that operate over a wide range of aerodynamic conditions. The optimum design of such nacelles and their inlets is described, including how the inlet low-speed design conditions are selected, the conditions for which the various regions of the inlet are designed, and appropriate criteria of merit. For low-speed operation the optimum internal surface velocity distributions and skin friction distributions are described for three categories of inlets: those without boundary-layer control (BLC), those with BLC, and those with blow-in door slots and retractable slats. Experimental results are presented that show the performance of the various types of inlets. At cruise speed the effect of factors that reduce the nacelle external surface area and the local skin friction is illustrated. These factors are cruise Mach number, inlet throat size, fan-face Mach number, and nacelle contour. The interrelation of these cruise-speed factors with the design requirements for good low-speed performance is discussed. Finally an inlet design without BLC and an optimized inlet design with slots and slats are compared to illustrate the possible reductions in nacelle size.
Capillary-Condenser-Pumped Heat-Transfer Loop
Heat being transferred supplies operating power. Capillary-condenser-pumped heat-transfer loop similar to heat pipe and to capillary-evaporator-pumped heat-transfer loop in that heat-transfer fluid pumped by evaporation and condensation of fluid at heat source and sink, respectively. Capillary condenser pump combined with capillary evaporator pump to form heat exchanger circulating heat-transfer fluids in both loops. Transport of heat more nearly isothermal. Thermal stress in loop reduced, and less external surface area needed in condenser section for rejection of heat to heat sink.
Co-Flow Hollow Cathode Technology
Hall thrusters utilize identical hollow cathode technology as ion thrusters, yet must operate at much higher mass flow rates in order to efficiently couple to the bulk plasma discharge. Higher flow rates are necessary in order to provide enough neutral collisions to transport electrons across magnetic fields so that they can reach the discharge. This higher flow rate, however, has potential life-limiting implications for the operation of the cathode. A solution to the problem involves splitting the mass flow into the hollow cathode into two streams, the internal and external flows. The internal flow is fixed and set such that the neutral pressure in the cathode allows for a high utilization of the emitter surface area. The external flow is variable depending on the flow rate through the anode of the Hall thruster, but also has a minimum in order to suppress high-energy ion generation. In the co-flow hollow cathode, the cathode assembly is mounted on thruster centerline, inside the inner magnetic core of the thruster. An annular gas plenum is placed at the base of the cathode and propellant is fed throughout to produce an azimuthally symmetric flow of gas that evenly expands around the cathode keeper. This configuration maximizes propellant utilization and is not subject to erosion processes. External gas feeds have been considered in the past for ion thruster applications, but usually in the context of eliminating high energy ion production. This approach is adapted specifically for the Hall thruster and exploits the geometry of a Hall thruster to feed and focus the external flow without introducing significant new complexity to the thruster design.
Adsorption Mechanisms of Glyphosate on Ferrihydrite: Effects of Al Substitution and Aggregation State
Ferrihydrite is one of the most reactive iron (Fe) (oxyhydr)oxides in soils, but the adsorption mechanisms of glyphosate, the most widely used herbicide, on ferrihydrite remain unknown. Here, we determined the adsorption mechanisms of glyphosate on pristine and Al-substituted ferrihydrites with aggregated and dispersed states using macroscopic adsorption experiments, zeta potential, phosphorus K-edge X-ray absorption near-edge structure spectroscopy, in situ attenuated total reflectance Fourier transform infrared spectroscopy coupled with two-dimensional correlation spectroscopy, and multivariate curve resolution analyses. Aggregation of ferrihydrite decreases the glyphosate adsorption capacity. The partial substitution of Al in ferrihydrite inhibits glyphosate adsorption on aggregated ferrihydrite due to the decrease of external specific surface area, while it promotes glyphosate adsorption on dispersed ferrihydrite, which is ascribed to the increase of surface positive charge. Glyphosate predominately forms protonated and deprotonated, depending on the sorption pH, monodentate-mononuclear complexes (MMH 1 /MMH 0 , 77-90%) on ferrihydrites, besides minor deprotonated bidentate-binuclear complexes (BBH 0 , 23-10%). Both Al incorporation and a low pH favor the formation of the BB complex. The adsorbed glyphosate preferentially forms the MM complex on ferrihydrite and preferentially bonds with the Al-OH sites on Al-substituted ferrihydrite. In conclusion, these new insights are expected to be useful in predicting the environmental fate of glyphosate in ferrihydrite-rich environments.
Impact of Site Identity, Location, and Accessibility on Polyethylene Conversion Rates and Product Selectivities over Metal-Free MFI Zeolites
Brønsted (BAS), Lewis (LAS), and surface Brønsted (SBAS) acid sites have been investigated for polyethylene (PE) upcycling by zeolite catalysts, but there is no clear consensus regarding their catalytic roles, partly due to the complexity of the catalysts used and varying reaction conditions across studies. This work systematically determined how these sites impact PE conversion rates and product distributions by utilizing a suite of microporous MFI catalysts with varying Si/Al ratios, acid site densities, and inherent mesoporosities. PE conversion rates did not trend with total BAS or LAS densities due to a combination of internal mass transfer limitation and the apparent inability of LAS alone to cleave C–C bonds, but a strong, statistically significant correlation was present with respect to SBAS density and mesopore surface area, jointly, owing to accelerated polymer activation on external surfaces to smaller diffusion-limited chains. However, ingress of these SBAS-derived fragments ultimately remained rate limiting, as demonstrated by solid conversion rates that increased with mesopore surface area at similar SBAS density and likewise increased with SBAS density at similar mesopore surface area. In batch PE cracking reactions, light gaseous product selectivities were most sensitive to total BAS, with higher densities generally exhibiting higher selectivity to C 3 and linear C 4 –C 7 products and higher alkane/alkene product ratios, consistent with increased β-scission turnovers. Insights from this work help systematically clarify the roles of BAS, LAS, SBAS, and mesopores in PE cracking reactions and inform the development of tailored zeolite catalysts for efficient polyolefin upcycling.
Annular Internal-External-Expansion Rocket Nozzles for Large Booster Applications
For large-thrust booster applications, annular rocket nozzles employing both internal and external expansion are investigated. In these nozzles, free-stream air flows through the center as well as around the outside of the exiting jet. Flaps for deflecting the rocket exhaust are incorporated on the external-expansion surface for thrust-vector control. In order to define nozzle off-design performance, thrust vectoring effectiveness, and external stream effects, an experimental investigation was conducted on two annular nozzles with area ratios of 15 and 25 at Mach 0, 2, and 3 in the Lewis 10- by 10-foot wind tunnel. Air, pressurized to 600 pounds per square inch absolute, was used to simulate the exhaust flow. For a nozzle-pressure-ratio range of 40 to 1000, the ratio of actual to ideal thrust was essentially constant at 0.98 for both nozzles. Compared with conventional convergent-divergent configurations on hypothetical boost missions, the performance gains of the annular nozzle could yield significant orbital payload increases (possibly 8 to 17 percent). A single flap on the external-expansion surface of the area-ratio-25 annular nozzle produced a side force equal to 4 percent of the axial force with no measurable loss in axial thrust.
Breakdown of organic insulators
Solar cells and their associated electrical interconnects and leads were encapsulated in transparent elastomeric materials. Their purpose in a photovoltaic module, one of the most important for these elastomeric encapsulation materials, is to function as electrical insulation. This includes internal insulation between adjacent solar cells, between other encapsulated electrical parts, and between the total internal electrical circuitry and external metal frames, grounded areas, and module surfaces. Catastrophic electrical breakdown of the encapsulant insulation materials or electrical current through these materials or module edges to external locations can lead to module failure and can create hazards to humans. Electrical insulation stability, advanced elastomeric encapsulation materials are developed which are intended to be intrinsically free of in-situ ionic impurities, have ultralow water absorption, be weather-stable (UV, oxygen), and have high mechanical flexibility. Efforts to develop a method of assessing the life potential of organic insulation materials in photovoltaic modules are described.
Liquid bicontinuous stabilized assemblies by interfacial jamming of nanoparticles
A method for preparing a stabilized assembly includes combining a first liquid phase including nanoparticles and a second, immiscible liquid phase, dissolving in the second phase a first end-functionalized polymer having a first molecular weight, and a second end-functionalized polymer having a second molecular weight, wherein the second molecular weight is greater than the first molecular weight, applying a shearing external deformation field to increase the surface area of the first phase to create a new interface, wherein the nanoparticle surfactants form a disordered, jammed assembly at the new interface, and releasing the shearing external deformation field. The polymer and the nanoparticles can interact at an interface through ligand interactions to form nanoparticle surfactants and upon releasing the external deformation field the jammed assembly at the new interface traps the first phase in a deformed state having the first liquid phase and the second liquid phase as interpenetrating domains.
The role of the Long Duration Exposure Facility in the design of the Space Station Freedom
The Long Duration Exposure Facility (LDEF) satellite retrieved this year by the U.S. Space Shuttle offers spacecraft designers an unprecedented opportunity to examine synergistic, long-term space environmental effects on systems and materials. This paper discusses the strategy for data development and the role its implementation will play in the design of the Space Station Freedom. Examples are provided from three key areas (environments definition, protection of external surfaces, and verification of system components) to illustrate LDEF's potential contribution.
Preliminary Shuttle payload contamination assessment
The paper discusses the molecular induced atmosphere of the Shuttle Orbiter and a payload carrier (Spacelab) configuration - long module and a 3-m pallet) in the Shuttle Orbiter payload bay and compares it to the ambient atmosphere at various orbital altitudes. The density and flux of the contaminants are expressed as a function of distance out of the payload bay for a line-of-sight perpendicular to the payload bay and payload carrier. Isodensity plots about the Shuttle Orbiter for a side and end view for each major source are presented. The major sources considered are the external surface materials mass loss, pressurized habitation area leakage, attitude control engines, and supplemental flash evaporator venting. The resulting plots provide an insight into the extent and spatial variation of the on-orbit contaminant-induced environment.
Photographic Analysis Technique for Assessing External Tank Foam Loss Events
A video camera and recorder were placed inside the solid rocket booster forward skirt in order to view foam loss events over an area on the external tank (ET) intertank surface. In this Technical Memorandum, a method of processing video images to allow rapid detection of permanent changes indicative of foam loss events on the ET surface was defined and applied to accurately count, categorize, and locate such events.
Atmospheric water vapor transport: Estimation of continental precipitation recycling and parameterization of a simple climate model
The advective transport of atmospheric water vapor and its role in global hydrology and the water balance of continental regions are discussed and explored. The data set consists of ten years of global wind and humidity observations interpolated onto a regular grid by objective analysis. Atmospheric water vapor fluxes across the boundaries of selected continental regions are displayed graphically. The water vapor flux data are used to investigate the sources of continental precipitation. The total amount of water that precipitates on large continental regions is supplied by two mechanisms: (1) advection from surrounding areas external to the region; and (2) evaporation and transpiration from the land surface recycling of precipitation over the continental area. The degree to which regional precipitation is supplied by recycled moisture is a potentially significant climate feedback mechanism and land surface-atmosphere interaction, which may contribute to the persistence and intensification of droughts. A simplified model of the atmospheric moisture over continents and simultaneous estimates of regional precipitation are employed to estimate, for several large continental regions, the fraction of precipitation that is locally derived. In a separate, but related, study estimates of ocean to land water vapor transport are used to parameterize an existing simple climate model, containing both land and ocean surfaces, that is intended to mimic the dynamics of continental climates.