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This report presents a study on the effect of material processing parameters used in layer-by-layer material construction on the surface finish of a model to be used as an investment casting pattern. The data presented relate specifically to fused deposition modeling using a machinable wax.
Miniaturization of microelectronic devices necessitates atomic precision in manufacturing techniques, particularly in the deposition of thin films. Atomic layer deposition (ALD) is recognized for its precision in controlling film thickness and composition on intricate three-dimensional structures. This study focuses on the ALD nucleation and growth mechanisms of ruthenium (Ru), a metal that has significant future implications for microelectronics. Despite its advantages, the deposition of a high surface-free energy material like Ru on a low surface-free energy material such as an oxide often faces challenges of large nucleation delays and non-uniform growth. To address these challenges, we explored the effectiveness of organometallic surface pretreatments using trimethylaluminum (TMA) or diethylzinc (DEZ) to enhance Ru film nucleation and growth. Our study employed a less-studied Ru precursor, cyclopentadienylethyl(dicarbonyl)ruthenium [RuCpEt(CO)2], which demonstrated promising results in terms of reduced nucleation delay and increased film continuity. Ru ALD was performed on silicon substrates with native oxide, using RuCpEt(CO)2 and O2 as coreactants. Our findings reveal that surface pretreatment significantly improves nucleation density and film thickness within the initial 60 ALD cycles, achieving up to a 3.2-fold increase in Ru surface coverage compared to nonpretreated substrates. Supported by density functional theory calculations, we propose that the enhanced nucleation observed with RuCpEt(CO)2 compared to previously-studied Ru(Cp)2 is due to two key mechanisms: the facilitated removal of CO ligands during deposition, which enhances the reactivity of the precursor, and a hydrogen-abstraction reaction involving the ethyl ligand of RuCpEt(CO)2 and the metal-alkyl groups on the surface. This study not only advances our understanding of Ru ALD processes but also highlights the significant impact of precursor chemistry and surface treatments in optimizing ALD for advanced microelectronic applications.
The origin of the near-infrared photoluminescence (PL) from thiolate-protected gold nanoclusters (Au NCs, <2 nm) has long been controversial, and the exact mechanism for the enhancement of quantum yield (QY) in many works remains elusive. Meanwhile, based upon the sole steady-state PL analysis, it is still a major challenge for researchers to map out a definitive relationship between the atomic structure and the PL property and understand how the Au(0) kernel and Au(I)–S surface contribute to the PL of Au NCs. Herein, we provide a paradigm study to address the above critical issues. By using a correlated series of “mono-cuboctahedral kernel” Au NCs and combined analyses of steady-state, temperature-dependence, femtosecond transient absorption, and Stark spectroscopy measurements, we have explicitly mapped out a kernel-origin mechanism and clearly elucidate the surface–structure effect, which establishes a definitive atomic-level structure–emission relationship. A ~100-fold enhancement of QY is realized via suppression of two effects: (i) the ultrafast kernel relaxation and (ii) the surface vibrations. Furthermore the new insights into the PL origin, QY enhancement, wavelength tunability, and structure–property relationship constitute a major step toward the fundamental understanding and structural-tailoring-based modulation and enhancement of PL from Au NCs.
Structural properties of the anionic surfactant dioctyl sodium sulfosuccinate (AOT or Aerosol-OT) adsorbed on the mica surface were investigated by molecular dynamics simulation, including the effect of surface loading in the presence of monovalent and divalent cations. The simulations confirmed recent neutron reflectivity experiments that revealed the binding of anionic surfactant to the negatively charged surface via adsorbed cations. At low loading, cylindrical micelles formed on the surface, with sulfate head groups bound to the surface by water molecules or adsorbed cations. Cation bridging was observed in the presence of weakly hydrating monovalent cations, while sulfate groups interacted with strongly hydrating divalent cations through water bridges. The adsorbed micelle structure was confirmed experimentally with cryogenic electronic microscopy, which revealed micelles approximately 2 nm in diameter at the basal surface. At higher AOT loading, the simulations reveal adsorbed bilayers with similar surface binding mechanisms. Adsorbed micelles were slightly thicker (2.2–3.0 nm) than the corresponding bilayers (2.0–2.4 nm). Upon heating the low loading systems from 300 K to 350 K, the adsorbed micelles transformed to a more planar configuration resembling bilayers. The driving force for this transition is an increase in the number of sulfate head groups interacting directly with adsorbed cations.
Experimental investigations of the percent polarization of sunlight reflected from the surfaces of each of the Echo 2 Satellite and PAGEOS (Passive Geodetic Earth Orbiting Satellite) were performed to determine the stability of their surfaces in the space environment. The Echo 2 surface material was amorphous phosphate chemically bonded to a rolled aluminum substrate while the PAGEOS 1 surface material is vapor deposited aluminum on a poly (ethylene terephthalate) film. The stability of the satellites' surfaces was analyzed by comparing the light polarizing properties of the satellites, to those of test surfaces representative of the satellites' surfaces. The properties of flat test surfaces were measured experimentally in the laboratory, and the effects of surface strain, surface geometry, and vacuum upon these properties were examined. The laboratory analyses revealed that the polarization properties of the Echo 2 surface were significantly affected by surface geometry and vacuum, and that the properties of the PAGEOS 1 surface were not significantly altered by any of the above mechanisms.
The impact of satisfying satellite quarantine constraints on outer planet missions and spacecraft design are studied by considering the effects of planetary radiation belts, solar wind radiation, and space vacuum on microorganism survival. Post launch recontamination studies evaluate the effects of mission environments on particle distributions on spacecraft surfaces and effective cleaning and decontamination techniques.
The dynamics of the lunar ionosphere and resulting flux of lunar ions to the lunar surface are reviewed. In the Lunar rest frame, ions formed from the neutral lunar atmosphere are accelerated by the interplanetary electric and magnetic fields. The trajectories of heavier ions are primarily along the electric field; the ion flux is in a direction perpendicular to the solar wind flow, correlated to the orientation of the interplanetary magnetic field, and impacts the surface with energies of tens of electron volts to a few keV. Thus we predict a relatively energetic (compared to thermal energies), highly directional, lunar ion flux but with the possibility that light ions such as hydrogen can execute orbits that return them to portions of the lunar surface not directly exposed to the solar wind. The effects of surface electric and magnetic fields are discussed, as is the ion energy spectrum. We calculate the trapping of atmospheric ions which impact the surface and from this the density of neutral Ar 40 in the lunar atmosphere. We show that using the acceleration model, the lunar atmosphere total neutral number density can be calculated from ion detector data.
A technique is proposed for measuring the longitudinal residual stress distribution in commercial CVD (Chemical Vapor Deposition) boron on tungsten fibers of 102, 142, and 203 microns in diameter. The experimental apparatus is so designed that continuous measurements are made of the length changes of a boron fiber specimen as the surface of the fiber is removed by electropolishing. The effects of surface removal on core residual stress and core-initiated fracture are discussed. The three sizes of boron fibers investigated show similar residual stress distributions, i.e., compressive at the surface, tensile near the core, and for the 102-micron fiber compressive again in the core. It is shown that an increase in UTS is due to the increase in the compressive stress at the core produced by fiber contraction during surface removal. An expression is derived for calculating the longitudinal residual stress at a given radius for an as-received fiber of a certain radius from measurements of the axial strain produced by removal of the surface by electropolishing.
Solar system processes are considered along with the origin and evolution of the moon, planetary geophysics, lunar basins and crustal layering, lunar magnetism, the lunar surface as a planetary probe, remote observations of lunar and planetary surfaces, earth-based measurements, integrated studies, physical properties of lunar materials, and asteroids, meteorites, and the early solar system. Attention is also given to studies of mare basalts, the kinetics of basalt crystallization, topical studies of mare basalts, highland rocks, experimental studies of highland rocks, geochemical studies of highland rocks, studies of materials of KREEP composition, a consortium study of lunar breccia 73215, topical studies on highland rocks, Venus, and regional studies of the moon. Studies of surface processes, are reported, taking into account cratering mechanics and fresh crater morphology, crater statistics and surface dating, effects of exposure and gardening, and the chemistry of surfaces.
Results are reported from the initial phase of an effort to provide an adequate technical capability to accurately predict the full scale, flight vehicle, nozzle-afterbody performance of future aircraft based on partial scale, wind tunnel testing. The primary emphasis of this initial effort is to assess the current capability and identify the cause of limitations on this capability. A direct comparison of surface pressure data is made between the results from an 0.1-scale model wind tunnel investigation and a full-scale flight test program to evaluate the current subscale testing techniques. These data were acquired at Mach numbers 0.6, 0.8, 0.9, 1.2, and 1.5 on four nozzle configurations at various vehicle pitch attitudes. Support system interference increments were also documented during the wind tunnel investigation. In general, the results presented indicate a good agreement in trend and level of the surface pressures when corrective increments are applied for known effects and surface differences between the two articles under investigation.
The induced environment is the main source of contamination on a spacecraft. The contamination of surfaces by volatile condensable material (VCM) present on spacecraft is being studied by many investigators both in the laboratory and space. In addition to VCM, the space environment is also a contributing factor in the contamination of surfaces. The effects of the interaction of the solar plasma with surfaces is examined. Plasma particles impact at energies in the multi-kilovolt range and penetrate and become trapped in surfaces. Results show that protons can penetrate up to 600 monolayers into surfaces and reach saturation concentrations of 6%.
Steady convective flows for geometries of varying complexity are described. This in general involves the solution of nonlinear free boundary problems. The stability of these flows were determined to more complicated (perhaps time dependent) modes of fluid motion. These include shear flow and free surface instability modes, with possible coupling between them. The effect of surface chemical species is described, including impurities which act as surfactants and insoluble oxide films, on the convective patterns and their stability.
Technologies exist for construction of antennas with adaptive surfaces that can compensate for many of the larger distortions caused by thermal and gravitational forces. However, as the frequency and size of the reflectors increase, the subtle surface errors become significant and degrade the overall electromagnetic performance. Electronic compensation through an adaptive feed array offers a means for mitigation of surface distortion effects. A pattern synthesis approach for electromagnetic compensation of surface error is presented. The pattern synthesis approach uses a localized algorithm in which pattern corrections are directed toward specific portions of the pattern requiring improvement. The pattern synthesis technique uses radiation pattern data to perform the compensation.
Pressure distributions and erosion patterns on simulated lunar surfaces (hard and soft) and interference effects between the surface and two representative lunar vehicles (cylindrical and spherical) were obtained with cold-air jets at various descent heights and nozzle total-pressure ratios up to 288,000. Surface pressure distributions were dependent on both nozzle area ratio and, nozzle contour. Peak pressures obtained with a sonic nozzle agreed closely with those predicted theoretically for a near-sonic jet expanding into a vacuum. Short bell-shaped nozzles gave annular pressure distributions; the low center pressure resulted from the coalescence of shocks that originated within the nozzle. The high surface pressures were contained within a circle whose diameter was about 16 throat diameters, regardless of nozzle area ratio or contour. The peak pressure increased rapidly as the vehicle approached the surface; for example, at a descent height of 40 throat diameters the peak pressure was 0.4 percent of the chamber pressure, but increased to 6 percent at 13 throat diameters. The exhaust jet eroded a circular concave hole in white sand at descent heights from about 200 to 600 throat diameters. The hole diameter was about 225 throat diameters, while the depth was approximately 60 throat diameters. The sand particles, which formed a conical sheet at a semivertex angle of 50 deg, appeared to follow a ballistic trajectory and at no time struck the vehicle. An increase in pressure was measured on the base of the cylindrical lunar vehicle when it approached to within 14 throat diameters of the hard, flat surface. No interference effects were noted between the spherical model and the surface to descent heights as low as 8 throat diameters.
We investigate the shape of near-Earth asteroid (101955) Bennu by constructing a high-resolution (20 cm) global digital terrain model from laser altimeter data. By modeling the northern and southern hemispheres separately, we find that longitudinal ridges previously identified in the north extend into the south but are obscured there by surface material. In the south, more numerous large boulders effectively retain surface materials and imply a higher average strength at depth to support them. The north has fewer large boulders and more evidence of boulder dynamics (toppling and downslope movement) and surface flow. These factors result in Bennu's southern hemisphere being rounder and smoother, whereas its northern hemisphere has higher slopes and a less regular shape. We infer an originally asymmetric distribution of large boulders followed by a partial disruption, leading to wedge formation in Bennu's history.
The surface of silicon-based high temperature ceramics exhibits thermochemical instabilities when exposed to oxygen-rich high enthalpy flows. These instabilities manifest as sudden temperature jumps of several hundred degrees and rapid material failure, when temperatures exceed 2000 K. Understanding and predicting these phenomena is critical to the design of thermal protection systems for sustained high speed flight vehicles. In this talk we review a series of test cases where surface temperature jumps were observed during plasmatron wind tunnel testing of ceramic materials, including ZrB2-SiC ultra-high temperature ceramics, C/SiC ceramic matrix composites, and silicone-based coatings for low-density carbon phenolic ablators. The underlying physical processes occurring when Si-containing ceramics are exposed to high enthalpy air flow include formation of passivating scales at low temperatures, passive to active oxidation transition, melting of oxide scales, changes in surface radiative properties, formation of porosity and changes in effective conductivity, surface catalytic recombination and transitions in catalytic properties, as well as high-temperature phase changes. The role of these processes in promoting thermochemical instabilities for the different material systems is discussed.
Herein, the effect of surface modification of cellulose nanocrystals (CNC) on the sorption of dyes from waste textile effluent (methylene blue as a model) was achieved. The esterification of the isolated CNC from wood sawdust by acid hydrolysis was performed through melting with succinic anhydride (SA). At using 1:3–1:9 as the feeding ratios of CNC to SA, the succinylated CNC (CNC-SA) was obtained with degree of substitution of 1.6–2.2 and carboxylic content of 286.8–381.7 mmol/kg. Both of diameter size and zeta potential of the prepared CNC-SA were gradually enlarged by increasing the reactant feed ratio, indicating the successful modification of CNC surface with highly stable particles via increasing the negative charges on the outer surface. FTIR and XRD affirmed the change in the chemical structure as well as crystallinity of CNC after succinylation reaction. The prepared succinylated CNC was applied in the removal of methylene blue (MB) dye and the data showed that the sorption capacity is a direct proportional linear relation with the contents of carboxylic group. Within 120 min contact time, the sorption capacity was enlarged from 64.1 mg/g for CNC to 84.1 mg/g for CNC-SA3. The sorption data was fitted well to the first order kinetic model. Due to the esterification, the rate of sorption reaction is accelerated by double factor. These findings will maximize the benefit of esterified CNC in water treatment.
An experimental investigation of hexcomb pattern surface roughness effects on boundary-layer transition and convective heating has been performed. Two representative entry vehicle geometries, a spherical-cap aeroshell and a sphere-cone aeroshell, were considered. Multiple cast ceramic models of each geometry were fabricated with various roughness pattern densities and depths that simulated an ablated hexcomb-structure thermal protection system. Wind tunnel testing was performed at Mach 6 over a range of Reynolds numbers sufficient to produce laminar, transitional, and turbulent flow. Aeroheating and boundary-layer transition onset data were obtained using global phosphor thermography. The experimental heating data are presented herein, as are comparisons to laminar and turbulent smooth-wall heat transfer distributions from computational flow field simulations. The experimental data were used to develop a unified boundary-layer transition correlation for both sandgrain distributed roughness and hexcomb pattern roughness.