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At least 73 records · Page 4

Thin film diamond microstructure applications

Selective deposition and abrasion, as well as etching in atomic oxygen or reduced-pressure air, have been used to prepare patterned polycrystalline diamond films which, on further processing by anisotropic Si etching, yield the microstructures of such devices as flow sensors and accelerometers. Both types of sensor have been experimentally tested in the respective functions of hot-wire anemometer and both single- and double-hinged accelerometer.

Roppel, T.↗

Evaluation of the Effect of Microalloying on Cleavage of Monocrystalline NiAl Using a Miniaturized Disk-Bend Test

It was originally proposed to investigate the effect of microalloying on the ductility of monocrystalline NiAl. The idea was to deposit selected elements on oriented crystals of NiAl using magnetron sputtering, followed by annealing at high temperatures to produce the doped specimens. The project was terminated before that stage of the research was reached, but useful results needed for that study were obtained during the lifetime of the program. Those results are described in this report.

Ardell, Alan J.↗

Evaluation of the Effect of Microalloying on Cleavage of Monocrystalline NiAl using a Miniaturized Disk-Bend Test

It was originally proposed to investigate the effect of microalloying on the ductility of monocrystalline NiAl. The idea was to deposit selected elements on oriented crystals of NiAl using magnetron sputtering, followed by annealing at high temperatures to produce the doped specimens. The project was terminated before that stage of the research was reached, but useful results needed for that study were obtained during the lifetime of the program. Those results are described in this resort.

Ardell, Alan J.↗

Magnetic particles

Metal oxide containing polymers and particularly styrene, acrylic or protein polymers containing fine, magnetic iron oxide particles are formed by combining a NO.sub.2 -substituted polymer with an acid such as hydrochloric acid in the presence of metal, particularly iron particles. The iron is oxidized to fine, black Fe.sub.3 O.sub.4 particles which deposit selectively on the polymer particles. Nitrated polymers are formed by reacting functionally substituted, nitrated organic compounds such as trinitrobenzene sulfonate or dinitrofluoro benzene with a functionally coreactive polymer such as an amine modified acrylic polymer or a protein. Other transition metals such as cobalt can also be incorporated into polymers using this method.

Chang, Manchium↗

Developments for Nickel Electroformed X-Ray Optics

This slide presentation reviews the developments at Marshall Space Flight Center in fabricating Electroformed Nickel X-ray Optical devices. Missions that are using the mandrels created using the described process are reviewed, and improvements in the process of creating better quality mandrels are also reviewed. One of the processes, Electrochemically-Enhanced Mechanical Polishing (EEMP), is described. The Alignment and mounting system for full-shell replicated X-Ray Optics is shown, and the selective deposition process is also shown.

Ramsey, B.↗

Abundances of Volatile - Bearing Species from Evolved Gas Analysis of Samples from the Rocknest Aeolian Bedform in Gale Crater

The Sample Analysis at Mars (SAM) instrument suite on board the Mars Science Laboratory (MSL) recently ran four samples from an aeolian bedform named Rocknest. SAM detected the evolution of H2O, CO2, O2, and SO2, indicative of the presence of multiple volatile bearing species (Fig 1). The Rocknest bedform is a windblown deposit selected as representative of both the windblown material in Gale crater as well as the globally-distributed martian dust. Four samples of Rocknest material were analyzed by SAM, all from the fifth scoop taken at this location. The material delivered to SAM passed through a 150 m sieve and is assumed to have been well mixed during the sample acquisition/preparation/handoff process. SAM heated the Rocknest samples to approx.835 C at a ramp rate of 35 C/min with a He carrier gas flow rate of apprx.1.5 standard cubic centimeters per minute and at an oven pressure of ~30 mbar [1]. Evolved gases were detected by a quadrupole mass spectrometer (QMS). This abstract presents the molar abundances of H2O, CO2, O2, and SO2 as well as their concentration in rocknest samples using an estimated sample mass.

Archer, P. D., Jr.↗

Wildfire Smoke Particle Properties and Evolution, from Space-Based Multi-Angle Imaging

Emitted smoke composition is determined by properties of the biomass burning source and ambient ecosystem. However, conditions that mediate the partitioning of black carbon (BC) and brown carbon (BrC) formation, as well as the spatial and temporal factors that drive particle evolution, are not understood adequately for many climate and air-quality related modeling applications. In situ observations provide considerable detail about aerosol microphysical and chemical properties, although sampling is extremely limited. Satellites offer the frequent global coverage that would allow for statistical characterization of emitted and evolved smoke, but generally lack microphysical detail. However, once properly validated, data from the National Aeronautics and Space Administration (NASA) Earth Observing System’s Multi-Angle Imaging Spectroradiometer (MISR) instrument can create at least a partial picture of smoke particle properties and plume evolution. We use in situ data from the Department of Energy’s Biomass Burning Observation Project (BBOP) field campaign to assess the strengths and limitations of smoke particle retrieval results from the MISR Research Aerosol (RA) retrieval algorithm. We then use MISR to characterize wildfire smoke particle properties and to identify the relevant aging factors in several cases, to the extent possible. The RA successfully maps qualitative changes in effective particle size, light absorption, and its spectral dependence, when compared to in situ observations. By observing the entire plume uniformly, the satellite data can be interpreted in terms of smoke plume evolution, including size-selective deposition, new-particle formation, and locations within the plume where BC or BrC dominates.

Noyes, Katherine Junghenn↗

Binderjet Additive Manufacturing for Complex Heat Exchanger Geometries

Concentrated Solar Power (CSP) systems play a role in the worlds development of renewable energy. Mirrors are used to concentrate sunlight that is converted into electricity or other forms of useful energy. CSP impact depends significantly on its overall economics. The U.S. Department of Energy’s (DOE’s) Solar Energy Technology Office (SETO) cost goals for 2030include $0.05/kWh levelized cost of electricity (LCOE) for a baseload plant [1]. The power cycle cost goal is $900/kWe [1]. The envisioned recompression supercritical carbondioxide (sCO2) power cycle includes four heat exchangers, which together are at least ¾ of the total power cycle cost. Meeting the cost target requires reducing the heat exchanger cost. The 260 bar and 588 °C heat exchanger requirements are challenging. Shell and tube heat exchangers can meet the requirements, but the size and cost are prohibitive. State-of-the-art diffusion bonded printed circuit heat exchanger designs are 3 m3 or larger and expensive to manufacture. Additive manufacturing enables novel heat exchanger geometries that can reduce heat exchanger size and mass [2]. Binderjet technology is an additive manufacturing modality. It selectively deposits binder material onto the powder bed to form a solid part one layer at a time. Once applied, the binder is cured, the remaining powder removed, and the part heat treated in steps to remove the binder, sinter the metal powder, and densify the part. The Binderjet printing process is more than 10x faster than the best-known metal additive modality, direct metal laser melting (DMLM), thus enabling 10x the part through-put rate [3]. The high throughput rate results in a low-cost manufacturing process capable of creating complex heat exchanger geometries. This paper introduces a complex heat exchanger geometry and methods of Binderjet processing to fabricate the geometry.

Barua, Ananda↗

Site-Selective Atomic Layer Deposition at Thermally Generated Surface Oxygen Vacancies on Rutile TiO 2

Unique atomic arrangements (i.e., defects) on material surfaces may exhibit distinctive reactivity that affords opportunities for selective surface chemistry exclusively at those sites. While theoretically appealing, site-selective atomic layer deposition (ALD) processes remain largely unrealized experimentally. Here we provide evidence for site-selective ALD that exclusively targets oxygen vacancies thermally generated at the surface of TiO 2 single crystals. High-resolution in situ ellipsometry reveals the nucleation behavior of dimethylaluminum isopropoxide (DMAI) and water at process conditions precisely tuned for selective hydroxylation of surface defects. An island growth model for nucleation and atomic force microscopy (AFM) imaging are consistent with a site-selective growth mechanism that depends on the surface oxygen vacancy density. This approach to direct ALD reactions at defective surface sites may provide future opportunities for targeted remediation of electronically imperfect interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tunable and scalable fabrication of plasmonic dimer arrays with sub-10nm nanogaps by area-selective atomic layer deposition

Nanogaps in metallic nanostructures produce local field enhancements with potential applications in surface enhanced spectroscopy, solar energy conversion, and photocatalysis. Atomic layer deposition is applied as a conformal coating to modify nanogap sizes and tune the optical properties of plasmonic dimer arrays with sub-10 nm nanogaps. Nanostructures are fabricated using layers of gold and palladium to combine features of plasmonics and area-selective atomic layer deposition, where copper metal is deposited on palladium-covered surfaces. Direct measurements of optical extinction for successive smaller nanogaps and thicker copper coatings show that spectral features become broadened at first due to heating-induced shape changes but subsequently sharpen as copper coatings form on palladium structures. Furthermore, longitudinal resonances of plasmonic dimers blue shift for thin coatings due to heating and decreasing aspect ratio, but thicker coatings lead to red shifts due to narrowing nanogaps. Together, these results show that area-selective atomic layer deposition is a promising tool for achieving large area arrays of plasmonic dimers with sub-10 nm nanogaps.

Engineering↗

Microscopic and Metallurgical Aspects of the Space Shuttle Columbia Accident Investigation and Reconstruction

The Space Shuttle Columbia was descending for a landing at the Kennedy Space Center (KSC) on February 1, 2003. Approximately 20 minutes prior to touchdown, the Columbia began disintegrating over the western United States; the majority of debris eventually impacted in eastern Texas and western Louisiana. A monumental effort eventually recovered approximately 84,000 pieces of debris, approximately 38% of the Orbiter's original dry weight. The debris was transported to KSC, where the items were catalogued and evaluated. Critical areas of interest, such as the left and right leading edge surfaces and the underside of the ship, were placed upon a grid to aid in the reconstruction. Items of interest included metallic structures, reinforced carbon-carbon composites, and ceramic heat insulation tiles. Many of the leading edge elements had re-solidified metallic deposits spattered on them. These deposits became known as slag and were one of the main focuses of the investigation. In order to help determine the sequence of events inside the left wing during the accident, the slag's composition, layering order, and directionality of deposition were studied. A myriad of analytical tests were performed in an attempt to ascertain the compositional and depositional characteristics of selected slag deposits, including the ordering of deposited layers within each individual slag deposit harvested. Initially, Scanning Electron Microscopy and Energy Dispersive X-Ray Spectroscopy (SEM/EDX) were performed to quickly characterize the overall composition of individual slag deposits: SEM utilizes a narrowlyfocused high-energy electron beam impinging upon a specimen. The incident beam excites and liberates lower energy secondary electrons, which are detected and analyzed, providing a visual representation of the sample's surface topography. EDX also relies on an incident electron beam, except an EDX unit measures X-ray energies generated by the impinging beam. Each element generates a unique X-ray signature; the EDX detector measures these discreet energies. EDX actually penetrates approximately 2 microns into the bulk of the sample. However, random examination of various portions of slag, coupled with the semiquantitative nature of the SEM/EDX analysis, did not yield convincingly pertinent data. Therefore, X-ray dot mapping was conducted, which provided more understandable data, both in terms of slag layering and composition. An X-ray dot map is generated by performing numerous EDX scans for individual elements, then compiling the scans in a visual representation. Eventually, specimens consisting of not only the slag, but of the adjacent RCC substrate as well were cross-sectioned. X-Ray dot mapping of the materialographicallymounted and -polished cross- sections provided a visual representation of both the layering sequence and compositional characteristics of the slag. Contemporaneously, Electron Spectroscopy for Chemical Analysis/X-Ray Photoelectron Spectroscopy (ESCA/XPS) and powdered X-Ray Diffraction (XRD) were performed to further characterize the deposits and to attempt to identify what, if any, compounds were present. The ESCA/XPS analysis allowed the analyst to "sputter" into the sample with an electron gun, aiding in the identification of the layering sequence. XPS uses photons, rather than electrons, which impinge upon the surface of the sample. XPS measures the electrons emitted from within the first 5 nm of the sample's surface. The XRD measures the scatter angles of incident X-rays; the angle and intensity of scatter depend upon the crystalline structure of the pulverized sample. XRD is considered a qualitative rather than quantitative technique. ESCA/XPS revealed that the final layer to deposit was predominantly carbonaceous. XRD was successful in identifying specific compounds, such as Al 2O3, Al and/or Al3 21SiO47, mullite (3(Al2)O3 -SiO2), and nickel-aluminides. Eventually, Electron MicroProbe Analysis (EMPA) was conducted on the marialographically-prepared cross- sections of selected slag deposits. Microprobe combines SEM and Wavelength Dispersive X-Ray Spectroscopy (WDS), and, like EDX, uses a narrowly-focused high-energy electron beam impinging upon a specimen to elicit, in the case of EPMA, characteristic X-rays with specific wavelengths. This quantitative, analytical tool proved the most useful in determining depositional layering and composition of the slag deposits. This information was utilized in verifying the location of the breach in the left leading edge of the wing of the Columbia.

McDaniels, Steven J.↗

Aggregation of Size-Selected Oxide Clusters Deposited onto Au(111)

Kinetic Monte Carlo (kMC) simulations along with density functional theory (DFT) calculations were used to investigate the aggregation of size-selected Nb 3 O y (y = 5, 6, 7) clusters deposited onto the Au(111) surface. Recent STM experiments showed that the cluster binding sites and sizes of the cluster assemblies on the Nb 3 O y /Au(111) surfaces strongly depend on the stoichiometry of the clusters, i.e., the oxygen-to-niobium ratio. To better understand the origins of these differences, kMC simulations of the nucleation and growth of cluster assemblies were performed using energy barriers for diffusion and intercluster interactions estimated from DFT calculations of cluster binding and dimerization energies, respectively. Comparisons of the kMC simulations with STM images of the as-deposited Nb 3 O y /Au(111) surfaces at RT and after high temperature annealing were used to further optimize the energetics and gauge the importance of nearest neighbor interactions. The kMC simulations demonstrate that the assembly of Nb 3 O y clusters on Au(111) are largely controlled by the magnitude of the barriers for diffusion and interparticle-bond formation, while changes at higher temperatures are sensitive to the binding energies between nearest neighbors. Simulations for the Nb 3 O 5 and Nb 3 O 6 clusters, which exhibit smaller cluster assembly sizes in STM, required larger diffusion barriers as well as different barriers for interparticle binding, which reflected differences in DFT calculated dimerization energies. Furthermore, the results demonstrate the effectiveness of combined DFT and kMC calculations for understanding how the stoichiometry affects the aggregation of small oxide clusters on a metal surface.

36 MATERIALS SCIENCE↗

Mechanistically Informed Strategies for Site-Selective Atomic Layer Deposition

While atomic layer deposition (ALD) processes from across the periodic table have been designed to deposit conformal thin films, an atomistic view of disparate substrate sites reveals the possibility of even greater synthetic control and precision. An understanding of the mechanism by which a particular ALD precursor reacts (or does not react) at myriad surface sites remains in its infancy. Here, in this Perspective, we summarize site-specific chemical reaction strategies that utilize ALD precursors and tailored surface chemistry to discriminate among potential deposition sites as well as describe techniques and tools that can be used to investigate site-selective ALD (SS-ALD). The Perspective is focused on the science of site-selective vapor-phase surface reactions but inevitably reveals the potential utility of such surface synthetic precision.

36 MATERIALS SCIENCE↗

Selective Hydroxylation of In 2 O 3 as A Route to Site-Selective Atomic Layer Deposition

We report that several atomic layer deposition (ALD) processes are now known that leverage the distinct surface chemistry of two disparate substrates (e.g., metal vs oxide) to realize markedly different ALD nucleation rates in an approach referred to as area-selective ALD. In contrast, few ALD processes have been identified that allow selective reaction at distinct surface sites of a single material surface, in a process that might be called site-selective ALD (SS-ALD). We describe one potential strategy to discriminate among several distinct surface sites on bixbyite In 2 O 3 to achieve site selectivity. Using density functional theory, we predict the discriminant hydration and hydroxylation of In 2 O 3 terrace and step-edge sites that depend strongly on the substrate temperature at low water coverage. Infrared measurement of surface hydroxyls on In 2 O 3 nanoparticles supports the predicted temperature dependence. The in situ examination of MgO ALD nucleation also shows results consistent with the predicted temperature dependence of In 2 O 3 hydroxylation. Together, these findings suggest that a selective hydroxylation approach may be a viable route to SS-ALD on In 2 O 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Area-selective atomic layer deposition enabled by competitive adsorption

In this work, we investigate the atomic layer deposition (ALD) of ZrO2 thin films on Cu and SiO2 substrates, using Zr[N(C2H5CH3)]4 as the thin-film precursor, and H2O or O2 as the coreactants. Here, we introduce 3-hexyne as a coadsorbate molecule during the thin-film precursor half-cycle and examine its effect on the selectivity of growth. We find that 3-hexyne strongly inhibits growth on Cu, while having essentially no effect on the growth on SiO2. Calculations using dispersion-inclusive density functional theory verify that 3-hexyne undergoes sp → sp2 rehybridization on Cu, which results in strong chemisorption on the metal surface, while only binding weakly to SiO2 via nonbonded van der Waals/dispersion interactions. After 10 cycles of ALD using 3-hexyne as the coadsorbate, we observed the deposition of ∼1.5 nm of ZrO2 on SiO2. On a Cu substrate, we only detected <0.15 nm of ZrO2 after the same number of cycles of ALD. At this point in the process, we find evidence of the formation of cuprous oxide (Cu2O) from in situ x-ray photoelectron spectroscopy and a significant increase in the roughness of the Cu substrate. We conclude that both factors likely contribute to the loss of selectivity due to the formation of sites (e.g., Cu2O) that bind 3-hexyne less strongly and/or an increase in the density of highly reactive sites (e.g., steps, kinks) that promote dissociative chemisorption of the thin-film precursor.

Suh, Taewon (ORCID:0000000163823811)↗