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At least 91 records · Page 5

Kinetic Isotope Effect in the Radical Step-Growth Termination of On-Surface Synthesized Graphene Nanoribbons

Bottom-up on-surface synthesis has emerged as a versatile tool to access and finely tune the electronic structure of nanographenes. The controlled generation of reactive intermediates catalyzed and stabilized by a supporting substrate has enabled the design, assembly, and characterization of a wide range of exotic tailor-made quantum materials. Even under these tightly controlled conditions, the growth of extended structures remains limited by termination processes and undesired side reactions. Here, we identify an H atom transfer as one principal contributor to the radical step growth termination that limits the on-surface growth of N = 7 armchair graphene nanoribbons (7-AGNRs) on Au(111) surfaces. Analysis of 7-AGNR lengths grown from protiated and deuterated molecular precursors reveals a primary kinetic isotope effect of KIE ∼ 1.4. First-principles density functional theory calculations suggest that a concerted H atom transfer mechanism that involves the breaking of a C–H/D bond in the transition state is associated with radical chain termination.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Antiphase boundaries in epitaxially grown beta-SiC

When the surface of beta-SiC, grown epitaxially on (001) silicon by chemical vapor deposition, is chemically etched, boundaries appear which may be observed by optical or scanning electron microscopy. Examination by plan-view and cross-sectional transmission electron microscopy shows boundaries in the film which exhibit line or fringe contrast. Convergent beam electron diffraction has been used to show that these boundaries separate domains that are in an antiphase relationship to each other. A model is presented which discusses the formation of these domains from independent nucleation on a stepped substrate surface.

Pirouz, P.↗

Stair-Step Particle Flux Spectra on the Lunar Surface: Evidence for Nonmonotonic Potentials?

We present examples of unusual "stair‐step" differential flux spectra observed by the Apollo 14 Suprathermal Ion Detector Experiment on the lunar dayside surface in Earth's magnetotail. These spectra exhibit a relatively constant differential flux below some cutoff energy and then drop off precipitously, by about an order of magnitude or more, at higher energies. We propose that these spectra result from photoions accelerated on the lunar dayside by nonmonotonic potentials (i.e.,potentials that do not decay to zero monotonically) and present a model for the expected differential flux. The energy of the cutoff and the magnitude of the differential flux are related to the properties of the local space environment and are consistent with the observed flux spectra. If this interpretation is correct, these surface‐based ion observations provide a unique perspective that both complements and enhances the conclusions obtained by remote‐sensing orbiter observations on the Moon's exospheric and electrostatic properties.

Stair-step↗

Flight-measured pressure characteristics of aft-facing steps in high Reynolds number flow at Mach numbers of 2.20, 2.50, and 2.80 and comparison with other data

The YF-12 airplane was studied to determine the pressure characteristics associated with an aft-facing step in high Reynolds number flow for nominal Mach numbers of 2.20, 2.50, and 2.80. Base pressure coefficients were obtained for three step heights. The surface static pressures ahead of and behind the step were measured for the no-step condition and for each of the step heights. A boundary layer rake was used to determine the local boundary layer conditions. The Reynolds number based on the length of flow ahead of the step was approximately 10 to the 8th power and the ratios of momentum thickness to step height ranged from 0.2 to 1.0. Base pressure coefficients were compared with other available data at similar Mach numbers and at ratios of momentum thickness to step height near 1.0. In addition, the data were compared with base pressure coefficients calculated by a semiempirical prediction method. The base pressure ratios are shown to be a function of Reynolds number based on momentum thickness. Profiles of the surface pressures ahead of and behind the step and the local boundary layer conditions are also presented.

Powers, S. G.↗

Low temperature atomic layer deposition of PbO 2 for electrochemical applications

A low temperature atomic layer deposition (ALD) process for PbO 2 was developed using bis(1-dimethylamino-2-methyl-2-propanolate)lead(II), Pb(DMAMP) 2 , and O 3 as the reactants, with a high growth rate of 2.6 Å/cycle. PbO 2 readily reduces under low oxygen partial pressures at moderate temperatures making it challenging to deposit ALD PbO 2 from Pb 2+ precursors. However, thin films deposited with this process showed small crystalline grains of α-PbO 2 and β-PbO 2 , without signs of reduced PbO x phases. The ALD PbO 2 thin films show the high electrical conductivity characteristic of bulk PbO 2 . In situ measurements of ALD PbO 2 film conductivity during growth suggest a reaction mechanism by which sub-surface oxygen mobility contributes to the growth of resistive PbO or PbO x during the Pb(DMAMP) 2 surface reaction step, which is only fully oxidized from Pb 2+ to Pb 4+ during the O 3 reaction step. These films were electrochemically reduced to PbSO 4 in H 2 SO 4 and then reoxidized to PbO 2 , demonstrating their suitability for use as an electrode material for fundamental battery research and other electrochemical applications.

atomic layer deposition↗

Optimal Geometry for Focused Ion Beam-Milled Samples for Direct-Pull Micro-Tensile Testing Performed In Situ in a Scanning Electron Microscope

A thorough procedure was developed to efficiently manufacture dogbone samples using focused ion beam (FIB) milling for micro-tensile testing. A Bruker PI 89 PicoIndenter, Billerica, MA, USA, was used as a case study, although the analysis and results are applicable to other micro-mechanical testing systems capable of mounting a standard, Ø12.7 mm × Ø3.2 mm pin, scanning electron microscopy (SEM) pin stub (Ted Pella, Redding, CA, USA). Nine dogbones were made from an Fe-45Cu alloy additively manufactured using powder-fed laser-directed energy deposition (DED-LB). Testing showed that fracture was confined to the gauge section for all dogbones and that the fracture mode, ductile vs. brittle, was entirely dependent on the grain orientation relative to the loading direction. The analysis showed that the measured plastic strain to failure can vary from >11% (optimal geometry) to <1% (non-optimal geometry) in micro-tensile testing of high-tensile-strength (>1 GPa) metallic materials. Subsequently, a finite element analysis (FEA) was conducted to identify the improved dogbone geometries. A total of ten thousand dogbone geometries were tested, and their dimensions were defined by a set of four adjustable parameters (corner radius, load surface angle, load surface length, and dogbone head length). The gauge width and gauge length were fixed to 4 µm and 10 µm, respectively. Three-dimensional surface plots of the stress concentration as a function of two parameters were used to identify the optimal ranges of parameter values. The addition of maximum width and length constraints, measuring 25 µm and 30 µm, respectively, allowed us to identify an optimal geometry at load surface angles of 30° and 45°. Their respective dimensions (corner radius, load surface length, and dogbone head length) are, in µm, 12, 6, and 7 and 10, 7, and 7. Testing these two optimal geometries with a range of gauge lengths from 4 to 20 µm showed that smaller gauge lengths only slightly reduced the detrimental stress concentration outside the gauge section. However, smaller gauge lengths will notably improve the FIB surface polishing step as tapering is reduced with smaller dogbone lengths.

Chemistry↗

Relation between surface slip topography and stress corrosion cracking in Ti-8 wt % Al

The deformation behavior of Ti-8 wt % Al has been investigated in an inert environment (air), and an aggressive environment (salt water). Details of surface slip geometry were examined by high resolution surface replicas at various stages of deformation in both environments. Specimens aged to contain a fine dispersion of Ti3Al precipitates failed by subcritical crack growth in salt water, whereas specimens in the single phase condition showed no effects of environment on the yield or fracture characteristics. The Ti3Al precipitates produce little change in strength level or slip character compared to the single phase alloy, and there is no evidence of any effects of environment on the character of surface slip. Rather, the presence of trenches along slip bands on the surface of aged specimens suggest that the specific effect of the Ti3Al precipitates is to render the surface slip steps chemically active relative to the surrounding matrix by slip induced dissolution of the particles.

Boyd, J. D.↗

An implicit Navier-Stokes analysis of turbine rotor-stator interaction

An implicit Navier-Stokes analysis using a single deforming mesh has been developed for the unsteady rotor-stator interaction problem. The technique has been used to simulate the flow through a turbine stator-rotor stage. Periodic two-dimensional solutions have been obtained using 1000 time steps per cycle without iteration at each time step. Computed surface pressure distributions compare favorably with experimental data available for this configuration.

Gibeling, Howard J.↗

Coating Carbon Fibers With Platinum

A process for coating carbon fibers with platinum has been developed. The process may also be adaptable to coating carbon fibers with other noble and refractory metals, including rhenium and iridium. The coated carbon fibers would be used as ingredients of matrix/fiber composite materials that would resist oxidation at high temperatures. The metal coats would contribute to oxidation resistance by keeping atmospheric oxygen away from fibers when cracks form in the matrices. Other processes that have been used to coat carbon fibers with metals have significant disadvantages: Metal-vapor deposition processes yield coats that are nonuniform along both the lengths and the circumferences of the fibers. The electrical resistivities of carbon fibers are too high to be compatible with electrolytic processes. Metal/organic vapor deposition entails the use of expensive starting materials, it may be necessary to use a furnace, and the starting materials and/or materials generated in the process may be hazardous. The present process does not have these disadvantages. It yields uniform, nonporous coats and is relatively inexpensive. The process can be summarized as one of pretreatment followed by electroless deposition. The process consists of the following steps: The surfaces of the fiber are activated by deposition of palladium crystallites from a solution. The surface-activated fibers are immersed in a solution that contains platinum. A reducing agent is used to supply electrons to effect a chemical reduction in situ. The chemical reduction displaces the platinum from the solution. The displaced platinum becomes deposited on the fibers. Each platinum atom that has been deposited acts as a catalytic site for the deposition of another platinum atom. Hence, the deposition process can also be characterized as autocatalytic. The thickness of the deposited metal can be tailored via the duration of immersion and the chemical activity of the solution.

Effinger, Michael R.↗

Exploration of Planetary Skylights and Tunnels

While planetary pits and caves have been fiction for a century, they have been seen from orbit only in the last few years. These discoveries exceed the fantasies in diversity, scale, and abundance. For pits and caves, this is the age of discovery, ranging from a few pits on the Moon and Mars in 2009 to hundreds within the time of this research, with many more to come. Pits with subsurface voids have been confirmed on the Moon and Mars and indicated on Venus, Phobos, Eros, Gaspra, Ida, Enceladus, and Europa. Compelling next steps are surface and subsurface exploration.Pits and caves are opportunistic study targets for unique origins, geology, and climate that will broadly impact planetary science. Holes on Mars are of particular interest because their interior caves are relatively protected from the harsh surface, making them good candidates to contain Martian life. Pits are prime targets for possible future spacecraft, robots, and even human interplanetary explorers. Caves and caverns could be ready-_made shelters for future Moon and Mars explorers and colonists. Discoveries to date look down from on high with satellites but cannot reveal the wonders of caves. They cannot enter, touch, or view pits up close. Genuine exploration is only achievable through surface missions. Robotic missions can assess suitability for safe entry and habitation, plus inform techniques for developing subsurface infrastructure.Missions into planetary voids redefine the future of exploration, science, and habitation beyond Earth. We can reach this future only by targeting specific technological advancement now. Prior missions and current roadmap priorities target regions of benign terrain. While in-cave concepts have been postulated, the critical technologies have not been identified and demonstrated.While robotic exploration of skylights and caves can seek out life, investigate geology and origins, and open the subsurface of other worlds to humankind, it is a daunting venture. Planetary voids present perilous terrain requiring innovative technologies for access, exploration, and modeling. These same technologies are broadly applicable to explorations of rough and/or subsurface planetary environments, including caves, craters, cliffs, and rock fields. This research speculates on the possibilities and means of such exploration with fundamental contributions to exploring, modeling, and visualizing this new class of large-scale, highly three-dimensional concave planetary features.

Whittaker, Red↗

Electrocatalytic reduction of oxygen on modified oxide surfaces

A first step which frequently occurs in the reduction of dioxygen, e.g., at the cathode of the alkaline fuel cell, is the two-electron reduction to the peroxyl ion, HO bar 2. For the efficiency of the fuel cell, this ion must be further reduced, or decomposed, to OH(-). Rate constants for HO bar 2 decomposition have been determined in 31 percent KOH at 25 C for the following catalysts in the form of suspended powders and Teflon-bonded electrodes: Pt, Au, cobalt tetrametoxyl phenyl porphyrin (CoTMPP), and La sub 0.5Pb sub 0.5MnO3. Rates were normalized to unit surface area measured by several methods as suitable. Where possible, four methods were used to measure rate constants: gasometric, oxygen probe, rotating disk electrode, and open-circuit potential decay. Steady-state polarization was also tried but was not as satisfactory. Comparisons are given for the methods in regard to reliability, applicability to the material, and convenience.

Chaffins, Scott A.↗

High-precision mass measurement of 103 Sn restores smoothness of the mass surface

As a step towards the ultimate goal of a high-precision mass measurement of doubly magic 100 Sn, the mass of 103 Sn was measured at the Low Energy Beam and Ion Trap (LEBIT) located at the Facility for Rare Isotope Beams (FRIB). Utilizing the time-of-flight ion cyclotron resonance technique, a mass uncertainty of 3.7 keV was achieved, an improvement by more than an order of magnitude compared to a recent measurement performed in 2023 at the Cooler Storage Ring (CSRe) in Lanzhou. Although the LEBIT and CSRe mass measurements of 103 Sn are in agreement, they diverge from the experimental mass value reported in the 2016 version of the Atomic Mass Evaluation (AME2016), which was derived from the measured 𝑄 𝛽 + value and the mass of 103 In. In AME2020, this indirectly measured 103 Sn mass was classified as a “seriously irregular mass” and replaced with an extrapolated value, which aligns with the most recent measured values from CSRe and LEBIT. As such, the smoothness of the mass surface is confidently reestablished for 103 Sn. Here, LEBIT's mass measurement of 103 Sn enabled a significant reduction in the mass uncertainties of five parent isotopes which are now dominated by uncertainties in their respective 𝑄 values.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Jet-Surface Interaction Noise Models Comparison to TMP17 and Next Steps

A set of empirical jet-surface interaction noise models, developed for single-stream round nozzles exhausting over a simple surface in a static ambient, are evaluated for use in more realistic applications that include multi-stream nozzle systems with chevrons and dihedral surface geometries. The simple-single-stream models have several advantages when used in system-level noise studies: they are robust, they are quickly computed, and they are generally applicable to a wide range of configurations. However, these models rely on a fixed noise source distribution that does not account for the presence of chevrons at the nozzle exit. The effect of this omission on the prediction accuracy is shown by this comparison to experimental data. This motivates discussion of future work to develop a more robust modeling framework that can account for generalized source distributions and more complex airframe geometries. Re: Top-Mounted Propulsion (TMP17) Test Plans.

Propulsion Noise↗

Concave-convex growth spirals.

The simple model for introduction of a screw dislocation into a crystal leaves a step in those surfaces of the crystal that intersect the axis of the screw dislocation such that the Burgers vector has a finite component perpendicular to the surfaces. When two parallel surfaces of a crystal intersect the same screw dislocation, the resultant step, on opposite sides of the crystal, face in opposite directions. Consequently, when two such surfaces grow by accretion of the molecules at the steps, the steps wind themselves into spirals that appear to have opposite senses of rotation when viewed along the axis of the screw dislocation. Furthermore, the growth structure that results is a plano convex cone or pyramid centered on the screw dislocation. When growth occurs simultaneously on both sides of a crystal, a doubly convex structure will develop under the control of a singe screw dislocation.

Crystal growth↗

Thermodynamic and Kinetic Modulation of Methylammonium Lead Bromide Crystallization Revealed by In Situ Monitoring

Hybrid organic–inorganic perovskite (HOIP) crystals are promising optoelectronic materials, but little is known about either the thermodynamic and kinetic controls on crystal growth or the underlying growth mechanism(s). Herein, we use fluid cell atomic force microscopy (AFM) and solution nuclear magnetic resonance (NMR) spectroscopy to investigate growth of the model HOIP crystal CH 3 NH 3 PbBr 3 (MAPbBr 3 ) and to determine how formic acid (HCOOH) modulates the thermodynamics and kinetics of growth. The results show that growth of MAPbBr 3 in dimethylformamide (DMF) proceeds through the classical pathway by the spreading of atomic crystal steps generated at screw dislocations on the {100} surface. Temperature dependent step velocity measurements demonstrate that with increasing concentration, HCOOH decreases both the solubility of MAPbBr 3 and the kinetic coefficient (b) of step movement. 1 H-NMR measurements indicate that HCOOH increases the lifetime of the methylammonium (MA + ) ions and promotes the association of MAPbBr 3 , thus tuning the solubility of the perovskite. HCOOH also alters the molecular tumbling motion and bulk diffusion of the MA + ions, possibly via H-bonding. Further, our findings establish a direct correlation between the mesoscale crystal growth kinetics and the molecular-scale interactions between organic additives and constituent ions, providing unprecedented insights for developing predictive syntheses of HOIP crystals with defined size, crystal habit and shape, and defect distribution.

36 MATERIALS SCIENCE↗

The turbulent thermal boundary layer with an abrupt change from a rough to a smooth wall

The work reported here was motivated by concern over the use of smooth heat flux gages for heat transfer measurements on the otherwise rough turbine blades. Stanton number distributions and boundary layer profiles of mean temperature, mean velocity, and turbulence intensity are reported for a surface with a step change from a rough to a smooth surface. In most cases, the Stanton number immediately downstream of the change in roughness drops below the all-smooth-wall data at the same x-Reynolds number. The alignment of the smooth surface between the bases and crests of the roughness elements is shown to have only a weak effect on the Stanton number distribution. It is concluded that the use of smooth heat flux gages on otherwise rough surfaces can cause large errors. It is recommended that heat transfer data collected in this manner be used with caution.

Taylor, Robert P.↗

Surface Reorientation and Settling in Cylinders upon Step Reduction in Gravity

A large literature exists concerning the equilibrium configurations of free liquid/gas surfaces in reduced gravity environments. Such conditions generally yield surfaces of constant curvature contracting the container wall at a particular angle. The time required to reach and stabilize about this configuration is less studied for the case of sudden changes in gravity level; e.g., from normal- to low-gravity, as can occur in many drop tower experiments. The particular interest here was to determine the total reorientation time for such surfaces in cylinders, as a function primarily of contact angle and kinematic viscosity, in order to aid in the development of drop tower experiment design. A large parametric range of tests were performed and, based on an accompanying scale analysis, the complete data set was correlated. The results of other investigations are included for comparison.

Weislogel, Mark M.↗

Surface settling in partially filled containers upon step reduction in gravity

A large literature exists concerning the equilibrium configurations of free liquid/gas surfaces in reduced gravity environments. Such conditions generally yield surfaces of constant curvature meeting the container wall at a particular (contact) angle. The time required to reach and stabilize about this configuration is less studied for the case of sudden changes in gravity level, e.g. from normal- to low-gravity, as can occur in many drop tower experiments. The particular interest here was to determine the total reorientation time for such surfaces in cylinders (mainly), as a function primarily of contact angle and kinematic viscosity, in order to aid in the development of drop tower experiment design. A large parametric range of tests were performed and, based on an accompanying scale analysis, the complete data set was correlated. The results of other investigations are included for comparison.

Weislogel, Marl M.↗