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At least 127 records · Page 7

Unveiling the Stability of Encapsulated Pt Catalysts Using Nanocrystals and Atomic Layer Deposition

Platinum exhibits desirable catalytic properties, but it is scarce and expensive. Optimizing its use in key applications such as emission control catalysis is important to reduce our reliance on such a rare element. Supported Pt nanoparticles (NPs) used in emission control systems deactivate over time because of particle growth in sintering processes. Here, in this work, we shed light on the stability against sintering of Pt NPs supported on and encapsulated in Al 2 O 3 using a combination of nanocrystal catalysts and atomic layer deposition (ALD) techniques. We find that small amounts of alumina overlayers created by ALD on preformed Pt NPs can stabilize supported Pt catalysts, significantly reducing deactivation caused by sintering, as previously observed by others. Combining theoretical and experimental insights, we correlate this behavior to the decreased propensity of oxidized Pt species to undergo Ostwald ripening phenomena because of the physical barrier imposed by the alumina overlayers. Furthermore, we find that highly stable catalysts can present an abundance of under-coordinated Pt sites after restructuring of both Pt particles and alumina overlayers at a high temperature (800 °C) in C 3 H 6 oxidation conditions. The enhanced stability significantly improves the Pt utilization efficiency after accelerated aging treatments, with encapsulated Pt catalysts reaching reaction rates more than two times greater than those of a control supported Pt catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlled site coverage of strong metal–support interaction (SMSI) on Pd NP catalysts

Here, strong metal–support interaction catalysts have been shown to improve desired product selectivity at the cost of fractional rates due to active site coverage. The goal of this study was to determine if the active site coverage of metallic nanoparticles could be controlled to lower levels than have been previously reported in SMSI catalysts with the aim of improving the rate while maintaining high selectivity. 2Pd–XTi/SiO 2 (2 wt% Pd, X wt% Ti) strong metal–support interaction (SMSI) catalysts with Ti loadings between 0–1.0 wt% were synthesized to control Pd nanoparticle coverage. Calcination at 450 °C and reduction at 550 °C were sufficient for forming ~2 nm sized Pd particles in all catalysts. Increasing the Ti loading from 0.1 to 1.0 wt% increased the surface coverage from 40 to 85% at a fixed reduction temperature of 550 °C. The IR spectra of the SMSI catalysts were similar with a high fraction of linear bonded CO which was much higher than that of Pd nanoparticles of similar size. The SMSI overlayer could be removed by oxidation at 350 °C and re-reduction at 200 °C. EXAFS of the oxidized catalysts indicates that nearly full oxidation of the metallic nanoparticle was required to remove the SMSI overlayer. Oxidation temperatures from 30 to 300 °C partially oxidized the Pd nanoparticles and subsequent re-reduction at 200 °C partially decreases the SMSI coverage. The fractional surface coverage was determined by measuring the rate of propylene hydrogenation with and without the SMSI overlayer. Increasing the reduction temperature from 200 to 550 °C increased the SMSI coverage from 0 to 85% depending on the Ti loading and temperature. In conclusion, after reduction at 550 °C and oxidation at 350 °C, the range of coverages varied between ~10% with 0.1 wt% Ti after re-reduction at 300 °C and ~85% with 1 wt% Ti after reduction at 550 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multi-layering of SU-8 exhibits distinct geometrical transitions from circular to planarized profiles

The negative tone photoresist SU-8 permits the creation of micrometer-scale structures by optical lithography. It is also the most used photoresist in soft lithography for the fast-prototyping of microfluidic devices. Despite its importance, the effect of capillary forces on SU-8 multi-layering onto topographical features has not been thoroughly studied. In particular, the profile of the added layer has not been examined in detail. The overlaying process exhibits a set of distinct behaviors, or regimes, depending on the relative thickness of the overlay and the underlying rectangular pattern. We demonstrate how capillary effects control the profile of multi-layer microchannels in a predictable manner. We derive a simple static model to describe the evolution of the overlay as a function of dimensionless geometric parameters. Our study provides a critical understanding of the parameters that govern multi-layer spin coating.

Sauzade, Martin↗

Evaluation of bacterial hosts for conversion of lignin-derived p-coumaric acid to 4-vinylphenol

Abstract Hydroxycinnamic acids such as p -coumaric acid (CA) are chemically linked to lignin in grassy biomass with fairly labile ester bonds and therefore represent a straightforward opportunity to extract and valorize lignin components. In this work, we investigated the enzymatic conversion of CA extracted from lignocellulose to 4-vinylphenol (4VP) by expressing a microbial phenolic acid decarboxylase in Corynebacterium glutamicum , Escherichia coli, and Bacillus subtilis . The performance of the recombinant strains was evaluated in response to the substrate concentration in rich medium or a lignin liquor and the addition of an organic overlay to perform a continuous product extraction in batch cultures. We found that using undecanol as an overlay enhanced the 4VP titers under high substrate concentrations, while extracting > 97% of the product from the aqueous phase. C. glutamicum showed the highest tolerance to CA and resulted in the accumulation of up to 187 g/L of 4VP from pure CA in the overlay with a 90% yield when using rich media, or 17 g/L of 4VP with a 73% yield from CA extracted from lignin. These results indicate that C. glutamicum is a suitable host for the high-level production of 4VP and that further bioprocess engineering strategies should be explored to optimize the production, extraction, and purification of 4VP from lignin with this organism.

4-hydroxystyrene↗

Off-gas capture: a promising strategy for removal and recovery of toxic bioproducts in aerobic fermentation

In many bioprocesses, maximum achievable titers are limited below economically viable levels by toxic accumulation of the primary end-product. To combat end-product inhibition, a variety of in situ product removal technologies have been developed to selectively remove or partition toxic bioproducts, thereby prolonging fermentation and improving overall process efficiency. Use of an in situ organic overlay to partition toxic hydrophobic products is a commonly employed approach, but this technique occupies valuable space in the fermentor, imposes replacement costs for unrecovered solvent, and increases downstream separation due to formation of stable emulsions. In addition, for many volatile hydrophobic products produced under aerobic conditions—including medium-chain alcohols, esters, monoterpenes, and other aviation fuel precursors—a significant fraction of the product is volatilized to the fermentor off-gas and must be recovered separately to maximize product yield. To address these challenges, we explore the viability of leveraging existing aeration energy to fully strip and recover volatile products from the fermentor off-gas. We compare two strategies of in situ product removal—liquid–liquid extraction and direct recovery from fermentation off-gas—for the production and recovery of intermediates used to generate isoprene and DMCO (1,4-dimethylcyclooctane), a high-performance jet fuel. We evaluate product toxicity, solvent toxicity, solvent partitioning, and the impact of aeration and internal overlay configurations on product volatilization rates. We then optimize product recovery from fermentor off-gas via condensation in chilled solvent, achieving 84% capture efficiency. In addition to greatly simplifying downstream processing, relying on aeration for product volatilization in the absence of an internal overlay enables continuous removal of toxic fermentation products up to maximum isoprenol titers of 20.4 g/L, the highest reported to date.

isoprene↗

LUBRICATING PROPERTIES OF CERAMIC-BONDED CALCIUM FLUORIDE COATINGS ON NICKEL-BASE ALLOYS FROM 75 DEG TO 1900 DEG F

The endurance life and the friction coefficient of ceramic-bonded calcium fluoride (CaF2) coatings on nickel-base alloys were determined at temperatures from 75° to 1900° F. The specimen configuration consisted of a hemispherical rider (3/16-in. rad.) sliding against the flat surface of a rotating disk. Increasing the ambient temperature (up to 1500° F) or the sliding velocity generally reduced the friction coefficient and improved coating life. Base-metal selection was critical above 1500° F. For instance, cast Inconel sliding against coated Inconel X was lubricated effectively to 1500° F, but at 1600° F severe blistering of the coatings occurred. However, good lubrication and adherence were obtained for René 41 sliding against coated René 41 at temperatures up to 1900° F; no blisters developed, coating wear life was fairly good, and the rider wear rate was significantly lower than for the unlubricated metals . Friction coefficients were 0.12 at 1500° F, 0.15 at 1700° F, and 0.17 at 1800° and 1900° F. Because of its ready availability, Inconel X appears to be the preferred substrate alloy for applications in which the temperature does not exceed 1500° F. René 41 would have to be used in applications involving higher temperatures. Improved coating life was derived by either preoxidizing the substrate metals prior to the coating application or by applying a very thin (<0.0002 in.) burnished and sintered overlay to the surface of the coating. Preoxidation did not affect the friction coefficient. The overlay generally resulted i n a higher friction coefficient than that obtained without the overlay. The combination of both modifications resulted in longer coating life and in friction coefficients intermediate between those obtained with either modification alone.

Nickel alloy↗

Natural resources information system.

A computer-based Natural Resources Information System was developed for the Bureaus of Indian Affairs and Land Management. The system stores, processes and displays data useful to the land manager in the decision making process. Emphasis is placed on the use of remote sensing as a data source. Data input consists of maps, imagery overlays, and on-site data. Maps and overlays are entered using a digitizer and stored as irregular polygons, lines and points. Processing functions include set intersection, union and difference and area, length and value computations. Data output consists of computer tabulations and overlays prepared on a drum plotter.

Leachtenauer, J. C.↗

Automated strip-mine and reclamation mapping from ERTS

The author has identified the following significant results. Computer processing techniques were applied to ERTS-1 computer-compatible tape (CCT) data acquired in August 1972 on the Ohio Power Company's coal mining operation in Muskingum County, Ohio. Processing results succeeded in automatically classifying, with an accuracy greater than 90%: (1) stripped earth and major sources of erosion; (2) partially reclaimed areas and minor sources of erosion; (3) water with sedimentation; (4) water without sedimentation; and (5) vegetation. Computer-generated tables listing the area in acres and square kilometers were produced for each target category. Processing results also included geometrically corrected map overlays, one for each target category, drawn on a transparent material by a pen under computer control. Each target category is assigned a distinctive color on the overlay to facilitate interpretation. The overlays, drawn at a scale of 1:250,000 when placed over an AMS map of the same area, immediately provided map locations for each target. These mapping products were generated at a tenth of the cost of conventional mapping techniques.

Rogers, R. H.↗

CARETS: A prototype regional environmental information system. Volume 5: Interpretation, compilation and field verification procedures in the CARETS project

The production of the CARETS map data base involved the development of a series of procedures for interpreting, compiling, and verifying data obtained from remote sensor sources. Level II land use mapping from high-altitude aircraft photography at a scale of 1:100,000 required production of a photomosaic mapping base for each of the 48, 50 x 50 km sheets, and the interpretation and coding of land use polygons on drafting film overlays. CARETS researchers also produced a series of 1970 to 1972 land use change overlays, using the 1970 land use maps and 1972 high-altitude aircraft photography. To enhance the value of the land use sheets, researchers compiled series of overlays showing i cultural features, county boundaries and census tracts, surface geology, and drainage basins. In producing Level I land use maps from Landsat imagery, at a scale I of 1:250,000, interpreters overlaid drafting film directly on Landsat color composite transparencies and interpreted on the film. They found that such interpretation involves pattern and spectral signature recognition. In studies using Landsat imagery, interpreters identified numerous areas of change but also identified extensive areas of "false change," where Landsat spectral signatures but not land use had changed.

Field verification procedures↗

Thermal fatigue and oxidation data for alloy/braze combinations

Thermal fatigue and oxidation data were obtained for 62 brazed specimens of 3 iron-, 3 nickel-, and 1 cobalt-base alloy. Fluidized bed thermal cycling was conducted over the range 740/25 C employing 10 cm long single-edge wedge specimens. Immersion time was always 4 minutes in each bed. Types of test specimens employed in the program include those with brazed overlays on the specimen radius, those butt brazed at midspan and those with a brazed foil overlay on the specimen radius. Of the 18 braze overlay specimens, 5 generated fatigue cracks by 7000 cycles. Thermal cracking of butt brazed specimens occurred exclusively through the butt braze. Of the 23 butt brazed specimens, 7 survived 11,000 thermal cycles without cracking. Only 2 of the 21 foil overlaid specimens exhibiting cracking in 7,000 cycles. Blistering of the foil did occur for 2 alloys by 500 cycles. Oxidation of the alloy/braze combination was limited at the test maximum test temperature of 740 C.

Hill, V. L.↗

The incorporation of plotting capability into the Unified Subsonic Supersonic Aerodynamic Analysis program, version B

The B01 version of the United Subsonic Supersonic Aerodynamic Analysis program is the result of numerous modifications and additions made to the B00 version. These modifications and additions affect the program input, its computational options, the code readability, and the overlay structure. The following are described: (1) the revised input; (2) the plotting overlay programs which were also modified, and their associated subroutines, (3) the auxillary files used by the program, the revised output data; and (4) the program overlay structure.

Winter, O. A.↗

Inventory and analysis of rangeland resources of the state land block on Parker Mountain, Utah

High altitude color infrared (CIR) photography was interpreted to provide an 1:24,000 overlay to U.S.G.S. topographic maps. The inventory and analysis of rangeland resources was augmented by the digital analysis of LANDSAT MSS data. Available geology, soils, and precipitation maps were used to sort out areas of confusion on the CIR photography. The map overlay from photo interpretation was also prepared with reference to print maps developed from LANDSAT MSS data. The resulting map overlay has a high degree of interpretive and spatial accuracy. An unacceptable level of confusion between the several sagebrush types in the MSS mapping was largely corrected by introducing ancillary data. Boundaries from geology, soils, and precipitation maps, as well as field observations, were digitized and pixel classes were adjusted according to the location of pixels with particular spectral signatures with respect to such boundaries. The resulting map, with six major cover classes, has an overall accuracy of 89%. Overall accuracy was 74% when these six classes were expanded to 20 classes.

Jaynes, R. A.↗

High temperature glass thermal control structure and coating

A high temperature stable and solar radiation stable thermal control coating is described which is useful either as such, applied directly to a member to be protected, or applied as a coating on a re-usable surface insulation (RSI). It has a base coat layer and an overlay glass layer. The base coat layer has a high emittance, and the overlay layer is formed from discrete, but sintered together glass particles to give the overlay layer a high scattering coefficient. The resulting two-layer space and thermal control coating has an absorptivity-to-emissivity ratio of less than or equal to 0.4 at room temperature, with an emittance of 0.8 at 1200 F. It is capable of exposure to either solar radiation or temperatures as high as 2000 F without significant degradation. When used as a coating on a silica substrate to give an RSI structure, the coatings of this invention show significantly less reduction in emittance after long term convective heating and less residual strain than prior art coatings for RSI structures.

Stewart, D. A.↗

Diffusion of Si in thin CoSi2 layers

Evidence of silicon diffusion in 100-A CoSi2 layers grown by room-temperature codeposition and annealing on Si(111) substrates was from Auger peak height ratios, which were interpreted in terms of a Si overlayer. It was found that this layer could be removed by chemical etching and reformed by subsequent annealing. By measuring the intensity of the plasmon energy loss peak associated with the CoL23 VV Auger peak, the effective thickness of the Si overlayer was measured as a function of annealing temperature, by calibrating the plasmon loss data against known overlayer thicknesses on unannealed samples. Similar results were found for samples grown both with and without the addition of a 10-A Si cap to prevent pinhole formation in the CoSi2; moreover, Si diffusion was also observed at temperatures well below the point where pinhole formation is first found, suggesting that Si diffusion does not depend on the presence of observable pinholes.

Schowengerdt, F. D.↗

The effect of Sr and Bi on the Si(100) surface oxidation - Auger electron spectroscopy, low energy electron diffraction, and X-ray photoelectron spectroscopy study

The effect of Sr and Bi on the oxidation of the Si(100) surface has been studied by Auger electron spectroscopy, low electron diffraction, and X-ray photoelectron spectroscopy. A dramatic enhancement, by a factor of 10, of the Si oxidation has been observed for Si(100) with a Sr overlayer. The SR-enhanced Si oxidation has been studied as a function of O2 exposure and Sr coverage. In contrast to the oxidation promotion of Sr on Si, it has been also observed that a Bi overlayer on Si(100) reduced Si oxidation significantly. Sr adsorption on the Si(100) with a Bi overlayer enhances Si oxidation only at Sr coverage of greater than 0.3 ML.

Fan, W. C.↗

Better Ohmic Contacts For InP Semiconductor Devices

Four design modifications enable fabrication of improved ohmic contacts on InP-based semiconductor devices. First modification consists of insertion of layer of gold phosphide between n-doped InP and metal or other overlayer of contact material. Second, includes first modification plus use of particular metal overlayer to achieve very low contact resistivities. Third, also involves deposition of Au(2)P(3) interlayer; in addition, refractory metal (W or Ta) deposited to form contact overlayer. In fourth, contact layer of Auln alloy deposited directly on InP. Improved contacts exhibit low electrical resistances and fabricated without exposing devices to destructive predeposition or postdeposition treatments.

Weizer, Victor G.↗

Unoccupied electronic resonances of Sc adsorbed on W(001) by k-resolved inverse photoemission

Scandium adsorbed on the (001) face of tungsten has been studied using Auger-electron spectroscopy, low-energy electron diffraction, k-resolved inverse photoelectron spectroscopy, work-function measurements, and relativistic-electronic-structure calculations. We find that the work function of W(001) does not decrease monotonically as a function of scandium adsorption but reaches a minimum value of Phi = 3.25 eV at 50% coverage. For a complete monolayer, an order 1 X 1 Sc overlayer is formed. Inverse photoemission in the isochromat mode was used to map the unoccupied energy levels of this overlayer along the bar-Gamma(bar-Mu) symmetry direction of the surface Brillouin zone. Local-density-functional calculations using the muffin-tin orbital method were performed for a 1 X 1 Sc overlayer on W and are compared with the experimental two-dimensional band structure.

Lamouri, A.↗

Lubricating Properties of Ceramic-Bonded Calcium Fluoride Coatings on Nickel-Base Alloys from 75 to 1900 deg F

The endurance life and the friction coefficient of ceramic-bonded calcium fluoride (CaF2) coatings on nickel-base alloys were determined at temperatures from 75 F to 1900 F. The specimen configuration consisted of a hemispherical rider (3/16-in. rad.) sliding against the flat surface of a rotating disk. Increasing the ambient temperature (up to 1500 F) or the sliding velocity generally reduced the friction coefficient and improved coating life. Base-metal selection was critical above 1500 F. For instance, cast Inconel sliding against coated Inconel X was lubricated effectively to 1500 F, but at 1600 F severe blistering of the coatings occurred. However, good lubrication and adherence were obtained for Rene 41 sliding against coated Rene 41 at temperatures up to 1900 F; no blisters developed, coating wear life was fairly good, and the rider wear rate was significantly lower than for the unlubricated metals. Friction coefficients were 0.12 at 1500 F, 0.15 at 1700 F, and 0.17 at 1800 F and 1900 F. Because of its ready availability, Inconel X appears to be the preferred substrate alloy for applications in which the temperature does not exceed 1500 F. Rene 41 would have to be used in applications involving higher temperatures. Improved coating life was derived by either preoxidizing the substrate metals prior to the coating application or by applying a very thin (less than 0.0002 in.) burnished and sintered overlay to the surface of the coating. Preoxidation did not affect the friction coefficient. The overlay generally resulted in a higher friction coefficient than that obtained without the overlay. The combination of both modifications resulted in longer coating life and in friction coefficients intermediate between those obtained with either modification alone.

Sliney, Harold E.↗