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At least 19 records

Design and Characterization of ALD-Based Overcoats for Supported Metal Nanoparticle Catalysts

Supported metal nanoparticle (SMN) catalysts are enormously crucial for many catalytic applications. However, catalyst deactivation, caused by sintering and coke formation, is a ubiquitous problem that significantly undermines catalytic processing economics. The application of material overcoating onto supported metal nanoparticles by atomic layer deposition (ALD) offers the solution to inhibit catalyst deactivation. Herein, we discuss examples in which ALD has been used to stabilize SMN catalysts in gaseous and aqueous-phase reactions. We highlight the ALD tools and methods in coating high-surface-area catalysts. Besides, various techniques are introduced to understand better how to characterize the overcoating layer and the catalyst itself. Finally, the outlook for new techniques to characterize the ALD overcoated catalytic materials is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Space vehicle glow measurements on STS 41-D

A flight experiment using a hand-held, image-intensified spectrographic camera was performed on mission 41-D. The instrument enabled the photographic documentation of the position of the spectral slit on the image to be subjected to spectrographic analysis. Because of this instrument feature, the spectrum of the glow on the Shuttle tail pod could be clearly separated from spectrum of the scattered light from the Orbiter. From the measurements it is clear that the spectrum of the glow is a continuum in the passband of the instrument between 4200 A and 8000 A. The measured spectral resolution of the instrument was 35 A. The scattered light from the Orbiter surfaces distinctly show the components of the earth's airglow at 5577 A and 7620 A. On the same flight material samples were also carried by the Orbiter attached to the Remote Manipulating System arm. These samples were representative of the material overcoatings used on the space telescope. The altitude of the 41-D flight was 290 km, instead of the 220 km which was originally planned for this experiment. The signal to noise ratio in the material glow discrimination experiment was quite low. This made it difficult to draw strong conclusions regarding the glow propensity of the materials. Nevertheless it was clear that polyethylene produces a very weak glow, while most black overcoating materials produce significant glow. MgF2 was also found to produce a relatively intense glow.

Mende, S. B.↗

Oxidation processes in magneto-optic and related materials

The surface oxidation processes of thin films of magneto-optic materials, such as the rare-earth transition metal alloys have been studied, starting in ultrahigh vacuum environments, using surface analysis techniques, as a way of modeling the oxidation processes which occur at the base of a defect in an overcoated material, at the instant of exposure to ambient environments. Materials examined have included FeTbCo alloys, as well as those same materials with low percentages of added elements, such a Ta, and their reactivities to both O2 and H2O compared with materials such as thin Fe films coated with ultrathin adlayers of Ti. The surface oxidation pathways for these materials is reviewed, and XPS data presented which indicates the type of oxides formed, and a critical region of Ta concentration which provides optimum protection.

Lee, Paul A.↗

Tuning acidity in silica-overcoated oxides for hydroalkoxylation

Mixed oxides are ubiquitious solid acid catalysts for a number of transformations. Here, the chemistry of mixed oxide interfaces was experimentally probed by constructing model SiO 2 on MO x interfaces using a liquid-phase, stoichiometrically-controlled deposition of tetraethyl orthosilicate (TEOS). Catalytically active Brønsted sites were generated in four series of overcoated SiO 2 on metal oxide materials prepared by depositing TEOS onto Al 2 O 3 , anatase TiO 2 , Nb 2 O 5 , and ZrO 2 . Pyridine DRIFTS studies indicate that the acidity of deposited silanol groups was enhanced by interaction with the metal oxide surface, suggesting that pseudo-bridging silanol type structures were formed. Trimethylphosphine oxide (TMPO) 31 P NMR experiments showed that Brønsted acid strength varied in the overcoated materials, with increasing strength in the following order: SiO 2 /ZrO 2 < SiO 2 /TiO 2 < SiO 2 /Nb 2 O 5 < SiO 2 /Al 2 O 3 . This order correlated with the Lewis acidity and chemical hardness of the underlying metal oxides. The catalytic performance of the materials was evaluated in the liquid-phase hydroalkoxylation of dihydropyran with n-octanol, revealing that activity was highly dependent on SiO 2 loading, which impacted the density of acid sites, and scaled exponentially with Brønsted acid strength, determined by the core metal oxide identity. Brønsted acid strength appears to be the key driver of the materials’ activity, with the highest areal rate of 2.2 mmol / m 2 – h being measured over SiO 2 /Al 2 O 3 . Furthermore, this study shows that SiO 2 -overcoated materials are a systematically tunable class of catalysts that can be applied to acid catalyzed reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidation of Palladium-Chromium Alloys for High Temperature Applications

An alloy consisting of Pd with 13 wt % Cr is a promising material for high temperature applications. High temperature performance is degraded by the oxidation of the material, which is more severe in the fine wires and thin films used for sensor applications than in the bulk. The present study was undertaken to improve our understanding of the physical and chemical changes occurring at these temperatures and to identify approaches to limit oxidation of the alloy. The alloy was studied in both ribbon and wire forms. Ribbon samples were chosen to examine the role of grain boundaries in the oxidation process because of the convenience of handling for the oxidation studies. Wire samples 25 microns in diameter which are used in resistance strain gages were studied to correlate chemical properties with observed electrical, physical, and structural properties. Overcoating the material with a metallic Cr film did prevent the segregation of Pd to the surface; however, it did not eliminate the oxidation of the alloy.

Piltch, Nancy D.↗

Compact infrared detector

Broadband IR detector integrated into compact package for pollution monitoring and weather prediction is small, highly responsive, and immune to high noise. Sensing material is transparent sheet metalized with reflecting coating and overcoated with black material on same side. Pulse produced by chopping of infrared source beam creates transient "thermal lens" that temporarily defocuses laser beam probe. Detector monitoring beam measures defocusing which parallels infrared intensity.

Gupta, A.↗

Application of diffusion barriers to high modulus fibers

Barrier layers were coated onto high-modulus fibers, and nickel and titanium layers were overcoated as simulated matrix materials. The objective was to coat the high-strength fibers with unreactive selected materials without degrading the fibers. The fibers were tungsten, niobium, and single-crystal sapphire, while the materials used as barrier coating layers were Al2O3, Y2O3, TiC, ZrC, WC with 14% Co, and HfO2. An ion-plating technique was used to coat the fibers. The fibers were subjected to high-temperature heat treatments to evaluate the effectiveness of the barrier layer in preventing fiber-metal interactions. Results indicate that Al2O3, Y2O3, and HfO2 can be used as barrier layers to minimize the nickel-tungsten interaction. Further investigation, including thermal cycling tests at 1090 C, revealed that HfO2 is probably the best of the three.

Veltri, R. D.↗

Retractor Tool for Brain Surgery

Proposed brain-surgery tool has an octogonal fixture for positioning latex tube over incision. Eight stainless-steel wires embedded in latex extend to hold positioning fixture. Another eight are also embedded in the latex. Concentric sleeves are successively inserted into expandable latex tube. The first sleeve is placed over a solid rod. Last sleeve is a stainless-steel tube 1 inch in diameter. It is overcoated with Teflon (or equivalent) material.

Helms, R.↗

Creating Brønsted acidity at the SiO 2 -Nb 2 O 5 interface

Catalytically active acid sites associated with the silica-niobia interface were probed with a series of overcoated SiO 2 on Nb 2 O 5 (SiO 2 /Nb 2 O 5 ) mixed oxide materials prepared by deposition of tetraethyl orthosilicate onto niobic acid (Nb 2 O 5 nH 2 O) or calcined niobia (Nb 2 O 5 ). NH 3 TPD and pyridine DRIFTS studies indicated that the speciation of acid sites in the materials evolved as a function of SiO 2 loading, impacting the quantity and stability of Brønsted sites. Catalyst activity was highly dependent on SiO 2 loading in the liquid phase hydroalkoxylation of dihydropyran with n-octanol. At SiO 2 surface densities corresponding to approximately 1 Si per 2 surface Nb, the activity of these catalysts passed through a maximum approximately 20 times higher than the activity of calcined Nb 2 O 5 . We found that apparent reaction barriers measured over the most active SiO 2 /Nb 2 O 5 catalysts were 10 kJ/mol lower than those measured over niobic acid, suggesting that the OH features unique to the SiO 2 -Nb 2 O 5 interface were slightly more reactive than those on niobic acid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interaction of atomic oxygen with solid surfaces at orbital altitudes (A0114)

The basic approach to this experiment is to expose a wide variety of material surfaces to the atomic flux in orbit. The experiment is passive and depends on preflight and postflight measurements of the test surfaces in the laboratory. The experiment will also include a reflectometer device to measure atomic beam reflection angles and thus momentum accommodations, and a unique passive spacecraft attitude sensor. Samples consisting of solid disks or thin film coatings on substrate disks will be mounted in a panel. The face of this panel will be flown on Long Duration Exposure Facility normal to the incident stream of oxygen atoms. Each disk will have part of its front surface masked so exposure to the atomic-oxygen reaction will be limited to selected areas, the shadowed areas being used as control surfaces in the measurements. A typical sample is an optically flat quartz disk overcoated with a film of the material of interest. These include Ag, Au, Pt, Nb, Ni, Al, C, Si, Ge, LiF, and a few engineering materials. Some materials for which the expected removal rate is high, such as carbon, will be solid disks rather than thin films.

Gregory, J. C.↗

Venus Landsailer Zephyr

Imagine sailing across the hot plains of Venus! A design for a craft to do just this was completed by the COncurrent Multidisciplinary Preliminary Assessment of Space Systems (COMPASS) Team for the NASA Innovative Advanced Concepts (NIAC) project. The robotic craft could explore over 30 kilometers of the surface of Venus, driven by the power of the wind. The Zephyr Venus Landsailer is a science mission concept for exploring the surface of Venus with a mobility and science capability roughly comparable to the Mars Exploration Rovers (MER) mission, but using the winds of the thick atmosphere of Venus for propulsion. It would explore the plains of Venus in the year 2025, near the Venera 10 landing site, where wind velocities in the range of 80 to 120 centimeters per second (cm/s) were measured by earlier Soviet landing missions. These winds are harnessed by a large wing/sail which would also carry the solar cells to generate power. At around 250 kilograms (kg), Zephyr would carry an 8 meter tall airfoil sail (12 square meters area), 25 kg of science equipment (mineralogy, grinder, and weather instruments) and return 2 gigabytes of science over a 30 day mission. Due to the extreme temperatures (450 degrees Centigrade) and pressures (90 bar) on Venus, Zephyr would have only basic control systems (based on high temperature silicon carbide (SiC)electronics) and actuators. Control would come from an orbiter which is in turn controlled from Earth. Due to the time delay from the Earth a robust control system would need to exist on the orbiter to keep Zephyr on course. Data return and control would be made using a 250 megahertz link with the orbiter with a maximum data rate of 2 kilobits per second. At the minimal wind speed required for mobility of 35 cm/s, the vehicle move at a slow but steady 4 cm/s by positioning the airfoil and use of one wheel that is steered for pointing control. Navigation commands from the orbiter will be based upon navigation cameras, simple accelerometers and stability sensors; Zephyr's stability is robust, using a wide wheel base along with controls to "feather" or "luff" the airfoil and apply brakes to stop the vehicle in the case of unexpected conditions. This would be the science gathering configuration. The vehicle itself would need to be made from titanium (Ti) as the structural material, with a corrosion-barrier overcoating due to extreme temperatures on the surface.

Wind Sailing↗

Combined environmental effects on polymers

A series of space simulation tests on FEP Teflon and other polymeric thermal control coatings was conducted using UV, electrons, protons and Lyman-alpha wavelength vacuum UV radiation. Interest was centered on simulating synchronous altitude radiation environment conditions. Physical changes in materials included loss of specularity and introduction of a high density of photographable tracking defects on a microscopic scale. An example shows the discharge of trapped electrons when dielectric strength is exceeded. This leaves a portion of the Teflon volume no longer clear, but diffusely transmitting and reflecting. Thermophysical changes included degradation of solar absorptance coefficients as much as five-fold. The situation that prevails for earth orbit contrasted with polymer performance in the solar wind. It is suggested that conductive overcoatings be developed for polymers and other flexible materials, comparable or superior to those available for fused silica SSMs.

Fogdall, L. B.↗

Monitoring Structural and Electronic Changes of Supported Metal Catalysts Using Combined X‐Ray Techniques

Supported metal nanoparticle catalysts have become increasingly crucial for many catalytic applications. However, long-term catalyst stability remains a problem due to catalyst deactivation caused by coke formation and sintering. The deposition of a thin overcoating via atomic layer deposition (ALD) onto metal-supported nanoparticles has shown to greatly inhibit catalyst deactivation. This work utilizes a model catalyst system comprised of Pt nanoparticles supported on Al 2 O 3 to demonstrate the effect of an atomically thin overcoating on supported metal nanoparticles. Continuous operando small-angle X-ray scattering (SAXS) and X-ray absorption near edge spectroscopy (XANES) monitor structural and electronic changes to the catalyst and overcoating during calcination. SAXS data fitting reveals the formation of nanopores in the overcoating at high temperatures, while XANES monitors the oxidation state of the Pt catalyst. Herein, the usefulness of combined X-ray techniques is demonstrated to characterize supported metal catalysts to further understanding of the synergistic effects of the ALD overcoating to aid in the design of new catalyst materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Durability of reflector materials in the space environment

Various reflector configurations were flown as part of the Long Duration Exposure Facility (LDEF) A0171 experiment. These reflectors consisted of nickel substrates with aluminum, enhanced aluminum (multiple layers of aluminum and silver), silver, and silver alloy coatings with glassy ceramic overcoatings. These samples have been evaluated for changes in reflectance due to 5.8 years in the space environment. The reflector materials have also been evaluated using angstrometer, Rutherford backscattering (RBS), and electron spectroscopy for chemical analysis (ESCA) techniques.

Whitaker, Ann F.↗

Understanding Pore Formation in ALD Alumina Overcoats

AlO X thin films deposited by atomic layer deposition (ALD) have previously been used to increase both stability and selectivity of supported palladium catalysts and are known to develop nanoscale porosity upon heating. Furthermore, understanding the factors that affect ALD thin film porosity would enable future design of layered catalytic structures with tunable nanoscale features on industrially relevant high surface area materials. In this study, porous and nonporous aluminum oxide supports with and without palladium nanoparticles were overcoated with thin films of 2 - 7 nm AlO X by ALD deposited at temperatures of 100 °C, 200 °C and 300 °C. Hydroxyl loss and changes in surface chemistry were observed upon heating the films, and changes in surface area and pore volume of the annealed films were correlated to AlO x deposition temperature and presence of Pd. Crystallization of the overcoat to γ-Al 2 O 3 is shown to occur separately from hydroxyl loss and pore formation. A mechanistic understanding of pore formation in AlO X ALD films is obtained by reference to studies of the structural transformations accompanying the formation of transition aluminas from hydroxide precursors. Additionally, a direct and tunable correlation is established between pore development and the overall hydroxyl content of AlO X ALD coatings.

36 MATERIALS SCIENCE↗

Effects on optical systems from interactions with oxygen atoms in low earth orbits

Modifications of material surface properties due to interactions with ambient atomic oxygen have been observed on surfaces facing the orbital direction in low earth orbits. Some effects are very damaging to surface optical properties while some are more subtle and even beneficial. Most combustible materials are heavily etched, and some coatings, such as silver and osmium, are seriously degraded or removed as volatile oxides. The growth of oxide films on metals and semiconductors considered stable in dry air was measured. Material removal, surface roughness, reflectance, and optical densities are reported. Effects of temperature, contamination, and overcoatings are noted.

Peters, P. N.↗