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At least 307 records · Page 17

The Effect of Solid Constituent Particle Size Distributions on TP-H1148 Propellant Slag

Special aluminum and ammonium perchlorate (AP) particle size distributions were prepared for a matrix of five-inch diameter, center-perforated (CP) motor tests to measure the aluminum oxide slag response in Space Shuttle Reusable Solid Rocket Motor (RSRM) propellant. Previous tests of TP-H1148 propellant in five-inch CP spin motors have shown a correlation between aluminum particle size and generated slag. The motors for this study were cast from thirteen five-gallon propellant mixes which used five particle size levels of aluminum powder, five of unground AP and three of ground AP. Aluminum had the greatest effect on slag formation, the more coarse fractions causing greater slag quantities and larger slag particles. Unground AP had about half the effect of aluminum with the coarser fractions again producing more and larger sized slag particles. The variation in ground AP did not have a significant effect on slag formation. Quench bomb tests showed the same trends as the spin motors, that is, larger aluminum and AP particle size distributions generated larger slag particles leaving the propellant surface. Cured propellant mechanical properties were also impacted by particle size variation.

May, Douglas H.↗

Tracking oxygen vacancy migration in memristor devices using operando hard X-ray photoelectron spectroscopy

Fabrication of ultrathin (sub-2 nm) oxide semiconductor memristors poses the fundamental challenge of achieving oxide growth with atomic precision in terms of electronic structure and defect formation. Recently, ultrathin memristors consisting of bilayers of mixed Al 2 O 3 and MgO atomic layers were fabricated using an in vacuo atomic layer deposition process. This approach offers a unique platform for precise atomic control of oxygen vacancies in the device in which the vacancies are introduced by placing MgO atomic layers between pristine Al 2 O 3 layers. In this work, we present a systematic operando Hard X-ray PhotoElectron Spectroscopy (HAXPES) study of the switching of such memristors, combined with complementary current-voltage and capacitance-voltage (C-V) measurements. We used a memristor stack of Al 2 O 3 /MgO atomic layers, with the MgO-containing oxide deposited on the bottom Al metal electrode and a pure Al 2 O 3 layer below the top Pd electrode. HAXPES analysis shows a substantial change in the chemical shift of the Aluminum oxide when switching between the ”OFF” and ”ON” states indicative of a redistribution of oxygen vacancies in the device active layer. Interestingly, subsequent switching to the OFF state shows hysteretic behavior indicating the retention of some oxygen vacancies in the top Al 2 O 3 layer. This vacancy retention can be correlated with the stochastic behavior of the switching voltage observed in these devices. C–V measurements show a clear frequency-dependent response in the OFF state, consistent with enhanced polarization and vacancy trapping at low frequencies.

47 OTHER INSTRUMENTATION↗

Dynamic Behavior of Platinum Atoms and Clusters in the Native Oxide Layer of Aluminum Nanocrystals

Strong metal–support interactions (SMSIs) are well-known in the field of heterogeneous catalysis to induce the encapsulation of platinum (Pt) group metals by oxide supports through high temperature H 2 reduction. However, demonstrations of SMSI overlayers have largely been limited to reducible oxides, such as TiO 2 and Nb 2 O 5 . In this report we show that the amorphous native surface oxide of plasmonic aluminum nanocrystals (AlNCs) exhibits SMSI-induced encapsulation of Pt following reduction in H 2 in a Pt structure dependent manner. Reductive treatment in H 2 at 300 °C induces the formation of an AlO x SMSI overlayer on Pt clusters, leaving Pt single-atom sites (Ptiso) exposed available for catalysis. The remaining exposed Pt iso species possess a more uniform local coordination environment than has been observed on other forms of Al 2 O 3 , suggesting that the AlO x native oxide of AlNCs presents well-defined anchoring sites for individual Pt atoms. This observation extends our understanding of SMSIs by providing evidence that H 2 -induced encapsulation can occur for a wider variety of materials and should stimulate expanded studies of this effect to include nonreducible oxides with oxygen defects and the presence of disorder. It also suggests that the single-atom sites created in this manner, when combined with the plasmonic properties of the Al nanocrystal core, may allow for site-specific single-atom plasmonic photocatalysis, providing dynamic control over the light-driven reactivity in these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calibration of the reflectance of hard targets for a coherent Doppler lidar

Data on the bihemispherical and directional-hemispherical reflectance were measured on a gold standard, a flowers of sulfur secondary standard, glass bead blasted aluminum, and 120 grade aluminum oxide sandpaper. These reflectances were measured for the P(24) and P(20) 10-micron and R(26), R(20), and P(20) 9-micron CO2 lines. The specular and retroreflection character of scattering from aluminum and sandpaper was evident in the measurements. The results agree reasonably well with previous measurements. Also when the sphere is irradiated with polarized light no difference was noted in the reflectance, which indicates that the integrating sphere is a depolarizer.

Anderson, Richard↗

Dialing in Catalytic Sites on Metal Organic Framework Nodes: MIL-53(Al) and MIL-68(Al) Probed with Methanol Dehydration Catalysis

Many metal organic frameworks (MOFs) incorporate metal oxide clusters as nodes. Node sites where linkers are missing can be catalytic sites. We now show how to dial in the number and occupancy of such sites in MIL-53 and MIL-68, which incorporate aluminum-oxide-like nodes. Here, the methods involve modulators used in synthesis and postsynthesis reactions to control the modulator-derived groups on these sites. We illustrate the methods using formic acid as a modulator, giving formate ligands on the sites, and these can be removed to leave μ 2 -OH groups and open Lewis acid sites. Methanol dehydration was used as a catalytic reaction to probe these sites, with infrared spectra giving evidence of methoxide ligands as reaction intermediates. Control of node surface chemistry opens the door for placement of a variety of ligands on a wide range of metal oxide cluster nodes for dialing in reactivity and catalytic properties of a potentially immense class of structurally well-defined materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Neutron tomography of porous aluminum electrodes used in electrocoagulation of groundwater

In this work, neutron computed tomography (CT) is employed to investigate the dissolution of porous aluminum electrodes during electrocoagulation (EC). Porous electrodes were chosen in efforts to reduce electric power requirements by using larger surface-area electrodes, having both inner and outer surface, for the EC process. Neutron CT allowed 3D reconstruction of the porous electrodes, and image analysis provided the volume of each electrode vs. thickness, which can indicate whether the inner surface is effectively involved in EC reactions. For the anode, the volume decreased uniformly throughout the thickness of the electrode, indicating that both the outer and inner surface participated in electrochemical dissolution, while the volume of the cathode increased uniformly vs. thickness, indicating deposition of material on both the outer and inner surface. The attenuation coefficient vs. thickness, increased for both anode and cathode, indicating surface chemistry changes. For the anode, the attenuation coefficient increased slightly but uniformly, probably due to aluminum oxide formation on the surface of the anode. For the cathode, the attenuation coefficient increased more than for the anode and nonuniformly. The higher increase in the attenuation coefficient for the cathode is due to precipitation of aluminum hydroxide on the electrode surface, which added hydrogen. Image analysis also showed that, although the attenuation coefficient increased throughout the thickness of the electrode, most of the hydroxide deposition occurred on the outer surface. Energy analysis showed that porous electrodes can be used to reduce process energy requirements by as much as 4 times compared to solid electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Material growth and characterization for solid state devices

During this period InGaAs and InGaAsP were grown on (100)InP by liquid phase electroepitaxy (LPEE). Results of the epitaxial growth of InGaAs on sputtered quartz masked substrates are presented. The resulting surface morphology can be related to the current density distribution near the edges of a masked pattern. The quaternary InGaAs was grown with compositions corresponding to 1.3 micron and 1.5 micron emission wavelengths. Growth rates were found to be linearly dependent upon current density, and a strong dependence upon composition was noted. These compositions lie in the miscibility gap region of the alloy phase diagram at the 645 C growth temperature. Growths were performed at 685 C to avoid the miscibility gap. Epilayers were characterized by photoluminescence, X-ray diffraction, secondary ion mass spectrometry, and Hall effect measurements. Aluminum oxide was deposited on silicon and InGaAs substrates for the characterization of this material as an insulator in a field effect transistor structure. It was determined that the results did not warrant further work with the deposition from an aluminum isopropoxide source. A metallographic vapor phase epitaxy system installation is nearing completion for use in hybrid III-V semiconductor epilayer growths.

Collis, Ward J.↗

Friction and wear of ceramics

The adhesion, friction, wear and lubricated behaviors of both oxide and non-oxide ceramics are reviewed. Ceramics are examined in contact with themselves, other harder materials and metals. Elastic, plastic and fracture behavior of ceramics in solid state contact is discussed. The contact load necessary to initiate fracture in ceramics is shown to be appreciably reduced with tangential motion. Both friction and wear of ceramics are anisotropic and relate to crystal structure as with metals. Grit size effects in two- and three-body abrasive wear are observed for ceramics. Both free energy of oxide formation and the d valence bond character of metals are related to the friction and wear characteristics for metals in contact with ceramics. Surface contaminants affect friction and adhesive wear. For example, carbon on silicon carbide and chlorine on aluminum oxide reduce friction while oxygen on metal surfaces in contact with ceramics increases friction. Lubrication increases the critical load necessary to initiate fracture of ceramics both in indentation and with sliding or rubbing.

Buckley, D. H.↗

Tribological properties of structural ceramics

The tribological and lubricated behavior of both oxide and nonoxide ceramics are reviewed in this chapter. Ceramics are examined in contact with themselves, other harder materials and metals. Elastic, plastic and fracture behavior of ceramics in solid state contact is discussed. The contact load necessary to initiate fracture in ceramics is shown to be appreciably reduced with tangential motion. Both friction and wear of ceramics are anisotropic and relate to crystal structure as has been observed with metals. Grit size effects in two and three body abrasive wear are observed for ceramics. Both free energy of oxide formation and the d valence bond character of metals are related to the friction and wear characteristics for metals in contact with ceramics. Surface contaminants affect friction and adhesive wear. For example, carbon on silicon carbide and chlorine on aluminum oxide reduce friction while oxygen on metal surfaces in contact with ceramics increases friction. Lubrication increases the critical load necessary to initiate fracture of ceramics both in indentation and with sliding or rubbing. Ceramics compositions both as coatings and in composites are described for the high temperature lubrication of both alloys and ceramics.

Buckley, D. H.↗

Friction and wear of ceramics

The adhesion, friction, wear, and lubricated behaviors of both oxide and non-oxide ceramics are reviewed. Ceramics are examined in contact with themselves, other harder materials, and metals. Elastic, plastic, and fracture behavior of ceramics in solid state contact is discussed. The contact load necessary to initiate fracture in ceramics is shown to be appreciably reduced with tangential motion. Both friction and wear of ceramics are anisotropic and relate to crystal structure as with metals. Grit size effects in two and three body abrasive wear are observed for ceramics. Both the free energy of oxide formation and the d valence bond character of metals are related to the friction and wear characteristics for metals in contact with ceramics. Surface contaminants affect friction and adhesive wear. For example, carbon on silicon carbide and chlorine on aluminum oxide reduce friction while oxygen on metal surfaces in contact with ceramics increases friction. Lubrication increases the critical load necessary to initiate fracture of ceramics both in indentation and with sliding or rubbing.

Buckley, Donald H.↗

Tribological properties of structural ceramics

The tribological and lubricated behavior of both oxide and nonoxide ceramics are reviewed in this chapter. Ceramics are examined in contact with themselves, other harder materials and metals. Elastic, plastic and fracture behavior of ceramics in solid state contact is discussed. The contact load necessary to initiate fracture in ceramics is shown to be appreciably reduced with tangential motion. Both friction and wear of ceramics are anisotropic and relate to crystal structure as has been observed with metals. Grit size effects in two and three body abrasive wear are observed for ceramics. Both free energy of oxide formation and the d valence bond character of metals are related to the friction and wear characteristics for metals in contact with ceramics. Surface contaminants affect friction and adhesive wear. For example, carbon on silicon carbide and chlorine on aluminum oxide reduce friction while oxygen on metal surfaces in contact with ceramics increases friction. Lubrication increases the critical load necessary to initiate fracture of ceramics both in indentation and with sliding or rubbing. Ceramics compositions both as coatings and in composites are described for the high temperature lubrication of both alloys and ceramics.

Buckley, Donald H.↗

Near-field passive sensor for the monitoring of high-temperature oxidative corrosion of metals

This study reports on the development and testing of a passive wireless device designed to track temperature and corrosion behavior in SS304H stainless steel under elevated temperatures. The ANSYS HFSS software was utilized to model and optimize the design of an inductor-capacitor (LC) resonator passive wireless sensors fabricated using platinum designs printed onto an aluminum oxide support operating at frequencies between (50–190 MHz). The optimal LC wireless sensor designs were then fabricated using screen-printing and sintering methods. Here, the sensors were tested by placing the sensor onto polished SS304H flat substrates and heated to 900–1050 °C in air. Wireless acquisition of sensor data during heating, cooling, and isothermal stages was achieved through a Pt loop antenna connected to an RF signal generator and a network analyzer.

20 FOSSIL-FUELED POWER PLANTS↗

Unveiling the support effect in Pt-based catalysts for the selective catalytic oxidation of NH 3 under realistic diesel engine conditions

Pt catalysts have been widely used for the selective catalytic oxidation of NH 3 (NH 3 -SCO) in practical applications due to their high activity at low temperatures. However, more stringent regulations require further enhancement of low-temperature NH 3 -SCO activity. In this study, we investigated the influence of different supports, including aluminum oxide (Al 2 O 3 ), silica (SiO 2 ), and chabazite (CHA), on the NH 3 -SCO performance of Pt catalysts. Furthermore, our findings demonstrate that the Pt/CHA catalyst exhibited superior NH 3 -SCO performance under realistic diesel engine conditions, characterized by high space velocity and the presence of water vapor. Notably, the Pt/CHA catalyst achieved a significantly lower T 50 (temperature at which 50% NH 3 conversion is achieved) of 218 °C under conditions with both CO 2 and H 2 O, with a 56 °C reduction compared to the state-of-the-art Pt/Al 2 O 3 catalyst. The exceptional NH 3 -SCO performance is attributed to the high abundance of metallic Pt 0 species and the presence of rich and stable acid sites that facilitate NH 3 adsorption and activation. Furthermore, these results highlight CHA as a promising support for the Pt catalyst in NH 3 -SCO applications for diesel engine emission control.

36 MATERIALS SCIENCE↗

Measurements of Total Hemispherical Emissivity of Several Stably Oxidized Metals and Some Refractory Oxide Coatings

A description of the apparatus and methods used for obtaining total hemispherical emissivity is presented, and data for several stably oxidized metals are included. The metals which were tested included type 347 stainless steel, tungsten, and Haynes alloys B, C, X, and 25. No values of emissivity were obtained for tungsten or Haynes alloy B because of the nature of the oxides produced. The refractory oxide coatings tested were flame-sprayed alumina and zirconia. The results of the investigation indicate that strongly adherent, oxidized surfaces of a high stable emissivity can be produced on type 347 stainless steel for which the total hemispherical emissivity varied from 0.87 to 0.91 for temperatures from 600 F to 2,000 F. For this same temperature range, the Haynes alloys tested showed values of total hemispherical emissivity from 0.90 to 0.96 for alloy C, from 0.85 to 0.88 for alloy X, and from 0.85 to 0.89 for alloy 25. Haynes alloy B and tungsten formed nonadherent oxides at elevated temperatures and, therefore, stable emissivities were not obtained. The results obtained for the flame-sprayed ceramics (alumina and zirconia) showed considerably higher values of total emissivity than those measured for coatings applied by other methods. Emissivity values ranging from 0.69 to 0.44 for aluminum oxide and from 0.62 to 0.44 for zirconium oxide were measured for temperatures from 800 F to 2,000 F.

Wade, William R.↗

Active Sites in a Heterogeneous Organometallic Catalyst for the Polymerization of Ethylene

Heterogeneous derivatives of catalysts developed by Ziegler and Natta are important for the industrial production of polyolefin plastics. However, the interaction between precatalysts, alkylaluminum activators, and oxide supports to form catalytically active materials is poorly understood. This is in contrast to homogeneous or well-defined heterogeneous catalysts that 20 contain resolved molecular structures that relate to activity and selectivity in polymerization reactions. This study describes the reactivity of triisobutylaluminum with high surface area aluminum oxide and a zirconocene precatalyst. Triisobutylaluminum reacts with the zirconocene precatalyst to form hydrides and passivates –OH sites on the alumina surface. The combination of passivated alumina and zirconium hydrides formed in this mixture generate ion-pairs that 25 polymerize ethylene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degradation of Aluminum and Tantalum Wet Electrolytic Capacitors during High Temperature Storage

Aluminum electrolytic capacitors (AEC) are available to higher ranges of capacitance and voltage compared to tantalum electrolytic capacitors (TEC). However, evaporation of the electrolyte during operation or storage of conventional AEC that is accelerated with temperature does not allow use of these parts in space electronics. Instead, for systems requiring large value capacitors and high operating voltages, designers must use banks of TECs that increases substantially the size and weight of electronic modules. Development of hermetically sealed AECs might be beneficial for space systems provided the necessary reliability is assured. Increase in leakage current during storage of AEC is well known and is often explained by dissolution of aluminum oxide in electrolyte. However, other possible mechanisms of this effect have not been discussed. Although hermetically sealed TEC have been used in space systems for years, there is a lack of information about the effects of storage on their characteristics that is of great interest as a comparison for aluminum capacitors. This work explores degradation of AC characteristics (capacitance, dissipation factor, and equivalent series resistance) and DC characteristics (leakage and absorption currents) in different types of aluminum and tantalum hermetically sealed capacitors during long-term storage at high temperatures (100 °C, 125 °C, and 150 °C). It is shown that leakage currents are degrading in both types of capacitors, but this degradation is reversible after bias application. Mechanisms of degradation are discussed, and explanations based on the processes common for both types of capacitors are suggested. Problems associated with assessments of hermeticity and evaporation of the electrolyte in hermetically sealed capacitors are analyzed.

Alexander Teverovsky↗

Soil properties explain tree growth and mortality, but not biomass, across phosphorus-depleted tropical forests

We observed strong positive relationships between soil properties and forest dynamics of growth and mortality across twelve primary lowland tropical forests in a phosphorus-poor region of the Guiana Shield. Average tree growth (diameter at breast height) increased from 0.81 to 2.1 mm yr -1 along a soil texture gradient from 0 to 67% clay, and increasing metal-oxide content. Soil organic carbon stocks in the top 30cm ranged from 30 to 118 tons C ha -1 , phosphorus content ranged from 7 to 600 mg kg -1 soil, and the relative abundance of arbuscular mycorrhizal fungi ranged from 0 to 50%, all positively correlating with soil clay, and iron and aluminum oxide and hydroxide content. In contrast, already low extractable phosphorus (Bray P) content decreased from 4.4 to <0.0 mg kg -1 in soil with increasing clay content. A greater prevalence of arbuscular mycorrhizal fungi in more clayey forests that had higher tree growth and mortality, but not biomass, indicates that despite the greater investment in nutrient uptake required, soils with higher clay content may actually serve to sustain high tree growth in tropical forests by avoiding phosphorus losses from the ecosystem. Our study demonstrates how variation in soil properties that retain carbon and nutrients can help to explain variation in tropical forest growth and mortality, but not biomass, by requiring niche specialization and contributing to biogeochemical diversification across this region.

54 ENVIRONMENTAL SCIENCES↗