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At least 1,225 records · Page 68

Single-unit-cell layer established Bi 2 WO 6 3D hierarchical architectures: Efficient adsorption, photocatalysis and dye-sensitized photoelectrochemical performance

Single-layer catalysis sparks huge interests and gains widespread attention owing to its high activity. Simultaneously, three-dimensional (3D) hierarchical structure can afford large surface area and abundant reactive sites, contributing to high efficiency. Herein, we report an absorbing single-unit-cell layer established Bi2WO6 3D hierarchical architecture fabricated by a sodium dodecyl benzene sulfonate (SDBS)-assisted assembled strategy. The DBS- long chains can adsorb on the (Bi2O2)2+ layers and hence impede stacking of the layers, resulting in the single-unit-cell layer. We also uncovered that SDS with a shorter chain is less effective than SDBS. Due to the sufficient exposure of surface O atoms, single-unit-cell layer 3D Bi2WO6 shows strong selectivity for adsorption on multiform organic dyes with different charges. Remarkably, the single-unit-cell layer 3D Bi2WO6 casts profoundly enhanced photodegradation activity and especially a superior photocatalytic H2 evolution rate, which is 14-fold increase in contrast to the bulk Bi2WO6. Systematic photoelectrochemical characterizations disclose that the substantially elevated carrier density and charge separation efficiency take responsibility for the strengthened photocatalytic performance. Additionally, the possibility of single-unit-cell layer 3D Bi2WO6 as dye-sensitized solar cells (DSSC) has also been attempted and it was manifested to be a promising dye-sensitized photoanode for oxygen evolution reaction (ORR). Our work not only furnish an insight into designing single-layer assembled 3D hierarchical architecture, but also offer a multi-functional material for environmental and energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of powder layer thickness on the microstructural development of additively manufactured SS316

By Increasing the powder layer thickness we could increase material deposition rates and reduce build times during laser powder bed fusion (LPBF). However, increasing the powder layer thickness could also negatively affect the local melting and subsequent microstructure of the printed material. This study systematically investigated, for the first time, the defect evolution and microstructural changes of LPBF stainless steel 316 (SS316) processed by using various powder layer thicknesses of 40, 80, and 120 μm while also varying the laser dwell time for the pulsed laser. Through image analysis, the pore density was found to increase with increasing powder layer thickness, particularly when the dwell time was too high or too low. The maximum achievable density (>99%) was found over a wide processing window when using the smallest powder layer thickness of 40 μm between dwell times of 60 and 100 μs. Increasing the powder layer thicknesses to 80 and 120 μm resulted in maximum densities of 98.7 and 96.8%, respectively, but the window for acceptable laser dwell times that could achieve these densities narrowed considerably. A microstructural analysis of the melt pools was performed to measure the melt pool depths and widths, both of which increased with increasing dwell time. However, increasing the powder layer thickness did not affect the melt pool depth and only minorly affected the width. A sub-grain cellular structure distinguished the melt pool boundaries. The cell size increased with increasing dwell time and decreasing powder layer thickness. Moreover, the cell size was used to calculate a cooling rate that had a magnitude of 10 7 K/s and increased with increasing powder layer thickness.

36 MATERIALS SCIENCE↗

Enhanced DSSCs performance of TiO2 nanostructure by surface passivation layers

Highlights: • Passivation layers of MgO, CaCO{sub 3}, ZrO{sub 2} and SnO{sub 2} on TiO{sub 2} electrode deposited in copper container by spin coating method. • XRD and EDX analysis give detail information about surface passivation layers deposition on TiO{sub 2} electrode. • Achieved highest efficiency for electrode with MgO passivation layer it is about 6.05%. • Highest electron lifetime of 0.65 ms. - Abstract: Rutile titanium oxide (TiO{sub 2}) synthesized in copper containers, was spin-coated with different surface passivation layers such as magnesium oxide (MgO), calcium carbonate (CaCO{sub 3}), zirconium oxide (ZrO{sub 2}), and tin oxide (SnO{sub 2}). The deposition of these passivation layers on TiO{sub 2} confirmed with the help of XRD and EDX analysis, leads to changes in surface morphology induced by the passivation layers demonstrated by FE-SEM imaging. The highest photoconversion efficiency obtained for TiO{sub 2} electrode with MgO passivation layer (6.05%), respective incident photon conversion efficiency was 52%. After introduction of passivation layers on the TiO{sub 2} nanostructure, electron lifetime increased from 0.48 ms to 0.65 ms and charge transfer resistance decreased from 36.9 Ω cm (pristine TiO{sub 2} electrode) to 20.16 Ω cm (MgO passivation layer).

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Reaction Layer Formation on MgO in the Presence of Humidity

Mineralization by MgO is an attractive potential strategy for direct air capture (DAC) of CO 2 due to its tendency to form carbonate phases upon exposure to water and CO 2 . Hydration of MgO during this process is typically assumed to not be rate limiting, even at ambient temperatures. However, surface passivation by hydrated phases likely reduces the CO 2 capture capacity. Here, we examine the initial hydration reactions that occur on MgO(100) surfaces to determine whether they could potentially impact CO 2 uptake. We first used atomic force microscopy (AFM) to explore changes in reaction layers in water (pH = 6 and 12) and MgO-saturated solution (pH = 11) and found the reaction layers on MgO are heterogeneous and nonuniform. To determine how relative humidity (R.H.) affects reactivity, we reacted samples at room temperature in nominally dry N 2 (~11–12% R.H.) for up to 12 h, in humid (>95% R.H.) N 2 for 5, 10, and 15 min, and in air at 33 and 75% R.H. for 8 days. X-ray reflectivity and electron microscopy analysis of the samples reveal that hydrated phases form rapidly upon exposure to humid air, but the growth of the hydrated reaction layer slows after its initial formation. Reaction layer thickness is strongly correlated with R.H., with denser reaction layers forming in 75% R.H. compared with 33% R.H. or nominally dry N 2 . The reaction layers are likely amorphous or poorly crystalline based on grazing incidence X-ray diffraction measurements. After exposure to 75% R.H. in air for 8 days, the reaction layer increases in density as compared to the sample reacted in humid N 2 for 5–15 min. Further, this may represent an initial step toward the crystallization of the reaction layer. Overall, high R.H. favors the formation of a hydrated, disordered layer on MgO. Based on our results, DAC in a location with a higher R.H. will be favorable, but growth may slow significantly from initial rates even on short timescales, presumably due to surface passivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nutrient transport suggests an evolutionary basis for charged archaeal surface layer proteins

Surface layers (S-layers) are two-dimensional, proteinaceous, porous lattices that form the outermost cell envelope component of virtually all archaea and many bacteria. Despite exceptional sequence diversity, S-layer proteins (SLPs) share important characteristics such as their ability to form crystalline sheets punctuated with nano-scale pores, and their propensity for charged amino acids, leading to acidic or basic isoelectric points. However, the precise function of S-layers, or the role of charged SLPs and how they relate to cellular metabolism is unknown. Nano-scale lattices affect the diffusion behavior of low-concentration solutes, even if they are significantly smaller than the pore size. Here, we offer a rationale for charged S-layer proteins in the context of the structural evolution of S-layers. Using the ammonia-oxidizing archaea (AOA) as a model for S-layer geometry, and a 2D electrodiffusion reaction computational framework to simulate diffusion and consumption of the charged solute ammonium (NH 4 + ), we find that the characteristic length scales of nanoporous S-layers elevate the concentration of NH 4 + in the pseudo-periplasmic space. Our simulations suggest an evolutionary, mechanistic basis for S-layer charge and shed light on the unique ability of some AOA to oxidize ammonia in environments with nanomolar NH 4 + availability, with broad implications for comparisons of ecologically distinct populations.

59 BASIC BIOLOGICAL SCIENCES↗

Topologically-guided continuous protein crystallization controls bacterial surface layer self-assembly

Abstract Many bacteria and most archaea possess a crystalline protein surface layer (S-layer), which surrounds their growing and topologically complicated outer surface. Constructing a macromolecular structure of this scale generally requires localized enzymatic machinery, but a regulatory framework for S-layer assembly has not been identified. By labeling, superresolution imaging, and tracking the S-layer protein (SLP) from C. crescentus , we show that 2D protein self-assembly is sufficient to build and maintain the S-layer in living cells by efficient protein crystal nucleation and growth. We propose a model supported by single-molecule tracking whereby randomly secreted SLP monomers diffuse on the lipopolysaccharide (LPS) outer membrane until incorporated at the edges of growing 2D S-layer crystals. Surface topology creates crystal defects and boundaries, thereby guiding S-layer assembly. Unsupervised assembly poses challenges for therapeutics targeting S-layers. However, protein crystallization as an evolutionary driver rationalizes S-layer diversity and raises the potential for biologically inspired self-assembling macromolecular nanomaterials.

59 BASIC BIOLOGICAL SCIENCES↗

Ultra-thin passivation layers in Cu(In,Ga)Se 2 thin-film solar cells: full-area passivated front contacts and their impact on bulk doping

In the search for highly transparent and non-toxic alternative front layers replacing state-of-the-art CdS in Cu(In,Ga)Se 2 thin-film solar cells, alternatives rarely exceed reference devices in terms of efficiency. Full-area ultra-thin aluminium oxide tunnelling layers do not require any contact patterning and thus overcome the main drawback of insulating passivation layers. Even a few monolayers of aluminium oxide can be deposited in a controlled manner by atomic layer deposition, they show excellent interface passivation properties, low absorption, and suitable current transport characteristics on test devices. Depositing a ZnO-based transparent front contact, however, results in extremely poor solar cell performance. The issue is not necessarily a low quality of the alternative front layer, but rather the intricate relation between front layer processing and electronic bulk properties in the absorber layer. We identify three challenges critical for the development of novel front passivation approaches:(i) both Cd and Zn impurities beneficially reduce the high native net dopant concentration in the space charge region, (ii) sputter deposition of ZnO damages the passivation layer resulting in increased interface recombination, (iii) thermal treatments of devices with ZnO layer result in substantial Zn diffusion, which can penetrate the full absorber thickness already at moderate temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Epitaxially Grown Single-Crystalline SrTiO 3 Membranes Using a Solution-Processed, Amorphous SrCa 2 Al 2 O 6 Sacrificial Layer

Water-soluble sacrificial layers based on epitaxially-grown, single crystalline (Ca, Sr, Ba) 3 Al 2 O 6 layer are widely used for creating free-standing perovskite oxide membranes. However, obtaining these sacrificial layers with intricate stoichiometry remains a challenge, especially for molecular beam epitaxy (MBE). In this study, we demonstrate the hybrid MBE growth of epitaxial, single crystalline SrTiO 3 films using a solution processed, amorphous SrCa 2 Al 2 O 6 sacrificial layer onto SrTiO 3 (001) substrates. Prior to the growth, the oxygen plasma exposure was used to first create the crystalline SrCa 2 Al 2 O 6 layer with well-defined surface crystallinity. Utilizing reflection high energy electron diffraction, x-ray diffraction, and atomic force microscopy, we observe an atomic layer-by-layer growth of epitaxial, single crystalline SrTiO 3 film on the SrCa 2 Al 2 O 6 layer with atomically smooth surfaces. The SrCa 2 Al 2 O6 layer was subsequently dissolved in de-ionized water to create free-standing SrTiO3 membranes that were transferred onto a metal-coated Si wafer. Membranes created with Sr-deficiency revealed ferroelectric-like behavior measured using piezo force microscopy whereas stoichiometric films remained paraelectric-like. Furthermore, these findings underscore the viability of using ex-situ deposited amorphous SrCa2Al2O6 for epitaxial, single crystalline growth, as well as the importance of point defects in determining the ferroic properties in membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic-Layer-Deposited Transparent Electrodes for Silicon Heterojunction Solar Cells

We examine damage-free transparent-electrode deposition to fabricate high-efficiency amorphous silicon/crystalline silicon heterojunction solar cells. Such solar cells usually feature sputtered transparent electrodes, the deposition of which may damage the layers underneath. Using atomic layer deposition, we insert thin protective films between the amorphous silicon layers and sputtered contacts and investigate their effect on device operation. We find that a 20-nm-thick protective layer suffices to preserve, unchanged, the amorphous silicon layers beneath. Insertion of such protective atomic-layer-deposited layers yields slightly higher internal voltages at low carrier injection levels. However, we identify the presence of a silicon oxide layer, formed during processing, between the amorphous silicon and the atomic-layer-deposited transparent electrode that acts as a barrier, impeding hole and electron collection.

14 SOLAR ENERGY↗

Impact of aqueous solution pH on network structure of corrosion–induced surface layers of boroaluminosilicate glass

Understanding of the long-term stability of vitrified nuclear waste glass is critical to its safe storage, but knowledge gaps remain regarding the corrosion mechanism, especially with respect to surface alteration layers whose presence changes the observed corrosion rates. Here, we report the aqueous corrosion of a model boroaluminosilicate glass at ground water relevant pHs as investigated by vibrational spectroscopy to understand the network structure of the alteration layer that we hypothesize controls the corrosion rates. Both specular reflection infrared spectroscopy and infrared variable angle spectroscopic ellipsometry were used to elucidate details of the structure of the alteration layers formed at pH 7 and pH 9. After 2312 days, the thickness of the alteration layer is found to be ~2000 nm for corrosion at pH 7 and ~300 nm for corrosion at pH 9. Here, the interpretation of the vibrational spectra suggests that alteration layers formed at pH 7 and pH 9 both exhibit a porous network with "silica-like" structures, but with differences in the bond lengths and bond angles in the glass network. Moreover, the relative abundance of the hydrous species within the porous network appears to be dependent on pH. Additionally, the spectroscopic data suggest that the B and Ca trapped in the alteration layer during the secondary corrosion of the pH 9 pre-corroded sample in pH 3 solution are hydrated within the nano-porous layer and not bound to the silicate network. However, the precise chemical form remains to be determined. Based on these findings, we propose that the combination of the network structure of the alteration layer and the relative abundance of hydrous species within the alteration layer act to control the transport of ionic species dissolved from the reaction front to the aqueous solution outside the glass.

36 MATERIALS SCIENCE↗

SU-F-I-06: Evaluation of Imaging Dose for Modulation Layer Based Dual Energy Cone-Beam CT

Purpose: Dual energy cone beam CT system is finding a variety of promising applications in diagnostic CT, both in imaging of endogenous materials and exogenous materials across a range of body sites. Dual energy cone beam CT system to suggest in this study acquire image by rotating 360 degree with half of the X-ray window covered using copper modulation layer. In the region that covered by modulation layer absorb the low energy X-ray by modulation layer. Relative high energy X-ray passes through the layer and contributes to image reconstruction. Dose evaluation should be carried out in order to utilize such an imaging acquirement technology for clinical use. Methods: For evaluating imaging dose of modulation layer based dual energy cone beam CT system, Prototype cone beam CT that configured X-ray tube (D054SB, Toshiba, Japan) and detector (PaxScan 2520V, Varian Medical Systems, Palo Alto, CA) is used. A range of 0.5–2.0 mm thickness of modulation layer is implemented in Monte Carlo simulation (MCNPX, ver. 2.6.0, Los Alamos National Laboratory, USA) with half of X-ray window covered. In-house phantom using in this study that has 3 cylindrical phantoms configured water, Teflon air with PMMA covered for verifying the comparability the various material in human body and is implemented in Monte Carlo simulation. The actual dose with 2.0 mm copper covered half of X-ray window is measured using Gafchromic EBT3 film with 5.0 mm bolus for compared with simulative dose. Results: Dose in phantom reduced 33% by copper modulation layer of 2.0 mm. Scattering dose occurred in modulation layer by Compton scattering effect is 0.04% of overall dose. Conclusion: Modulation layer of that based dual energy cone beam CT has not influence on unnecessary scatter dose. This study was supported by the Radiation Safety Research Programs (1305033) through the Nuclear Safety and Security Commission.

60 APPLIED LIFE SCIENCES↗

Modeling Single and Two-Phase Transport in Thin Porous Layers Using a Composite Continuum-Pore Network Formulation

In this work, a composite continuum-pore network formulation is presented to model single and two-phase transport thin porous layers, such as gas diffusion layers in polymer electrolyte fuel cells (PEFCs) and active electrodes in redox flow batteries (RFBs). The formulation can be integrated into CFD codes, thus combining the ease of implementation of continuum-based modeling and the computational power of pore-network modeling. The composite model includes a control volume (CV) mesh at the layer scale, which embeds a cubic pore network [1,2]. The pore-network model is used to determine analytically local anisotropic effective transport properties (local effective diffusivity and permeability), which are mapped onto the CV mesh to simulate transport in the porous transport layer [3,4]. Good agreement is found between the predicted global effective transport properties (global effective diffusivity and permeability) under dry and wet conditions and previous experimental data reported in the literature for Toray TGP-H series carbon paper. Water saturation distributions are also compared with results obtained using X-ray computed tomography [4]. [1] P.A. García-Salaberri, I.V. Zenyuk, J.T. Gostick, A.Z. Weber, Modeling Gas Diffusion Layer in Polymer Electrolyte Fuel Cells Using a Continuum-Based Pore-Network Formulation, ECS Trans. 97 (2020) 615. [2] P.A. García-Salaberri, Modeling diffusion and convection in thin porous transport layers using a composite continuum-network model: Application to gas diffusion layers in polymer electrolyte fuel cells, Int J. Heat Mass Transf. (2020), submitted. [3] P.A. García-Salaberri, J.T. Gostick, G. Hwang, A.Z. Weber, M. Vera, Effective diffusivity in partially-saturated carbon-fiber gas diffusion layers: Effect of local saturation and application to macroscopic continuum models, J. Power Sources 296 (2015) 440–453. [4] P.A. García-Salaberri, G. Hwang, M. Vera, A.Z. Weber, J.T. Gostick, Effective diffusivity in partially-saturated carbon-fiber gas diffusion layers: Effect of through-plane saturation distribution, Int. J. Heat Mass Transf. 86 (2015) 319–333.

Garcia-Salaberri, Pablo↗

Impact of laser-contaminant interaction on the performance of the protective capping layer of 1w high-reflection mirror coatings

In this paper, high dielectric constant multilayer coatings are commonly used on high-reflection mirrors for high-peak-power laser systems because of their high laser-damage resistance. However, surface contaminants often lead to damage upon laser exposure, thus limiting the mirror’s lifetime and performance. One plausible approach to improve the overall mirror resistance against laser damage, including that induced by laser-contaminant coupling, is to coat the multilayers with a thin protective capping (absentee) layer on top of the multilayer coatings. An understanding of the underlying mechanism by which laser-particle interaction leads to capping layer damage is important for the rational design and selection of capping materials of high-reflection multilayer coatings. In this paper, we examine the responses of two candidate capping layer materials, made of SiO 2 and Al 2 O 3 , over silica-hafnia multilayer coatings. These are exposed to a single oblique shot of a 1053 nm laser beam (fluence ~10 J/cm 2 , pulse length 14 ns), in the presence of Ti particles on the surface. We find that the two capping layers show markedly different responses to the laser-particle interaction. The Al 2 O 3 cap layer exhibits severe damage, with the capping layer becoming completely delaminated at the particle locations. The SiO 2 capping layer, on the other hand, is only mildly modified by a shallow depression. Combining the observations with optical modeling and thermal/mechanical calculations, we argue that a high-temperature thermal field from plasma generated by the laser-particle interaction above a critical fluence is responsible for the surface modification of each capping layer. The great difference in damage behavior is mainly attributed to the large disparity in the thermal expansion coefficient of the two capping materials, with that of Al 2 O 3 layer being about 15 times greater than that of SiO 2 .

36 MATERIALS SCIENCE↗

Comparing measurements of the mixing layer height to modeled values

The mixing layer height (MLH) is the top layer of turbulent mixing within the lower atmosphere, above the Earth’s surface. Estimates of the mixing layer height allow us to determine the volume available for the dispersion of pollutants throughout the atmosphere. Our goal is to identify the most suitable mixing layer height input for our dispersion modeling tool (AERMOD). For this project we evaluated two different methods of estimating the local mixing layer height. First, we use 3 estimates of the mixing layer height obtained from a ceilometer, each height estimate corresponds to a different gradient in aerosol backscatter which is used as a proxy for mixing layer height identification. Second, we use AERMET, our AERMOD modeling system preprocessor for meteorological data, which estimates the mixing layer height using several equations combined with measured meteorological data. We evaluate the ceilometer and AERMET estimates over a 5-year period (2015-2019) to see how well aligned the estimated mixing layer heights are. Our results suggest that our model, AERMET, is on average, aligned with ceilometer estimates during the daytime hours. However, daily maximum MLH estimates by AERMET occur earlier in the day than those estimated by the ceilometer. We believe that the ceilometer struggles with accurately measuring the MLH during nighttime hours as a result of sensor limitations.

54 ENVIRONMENTAL SCIENCES↗

Density response of the mesospheric sodium layer to gravity wave perturbations

Lidar observations of the mesospheric sodium layer often reveal wavelike features moving through the layer. It is often assumed that these features are a layer density response to gravity waves. Chiu and Ching (1978) described the approximate form of the linear response of atmospheric layers to gravity waves. In this paper, their results are used to predict the response of the sodium layer to gravity waves. These simulations are compared with experimental observations and a good correlation is found between the two. Because of the thickness of the sodium layer and the density gradients found in it, a linear model of the layer response is not always adequate to describe gravity wave-sodium layer interactions. Inclusion of nonlinearities in the layer response is briefly discussed. Experimental data is seen to contain features consistent with the predicted nonlinearities.

Shelton, J. D.↗

Near-field turbulence properties of single- and two-stream plane mixing layers

Detailed mean-flow and turbulence measurements have been made in the near-field of two plane mixing layers in air with a maximum velocity of 21 m/s. The experimental rig enabled mixing layers of velocity ratios 0 and 0.46 to be generated simultaneously. Cases with both tripped and untripped initial boundary layers were studied. In all cases, it was found that the two-stream layer developed to the self-preserving state in a distance much shorter than the single-stream layer which followed accepted criteria for the development distance. The asymptotic levels of the turbulence quantities in the two-stream layer, and the development of the single-stream layer showed agreement with existing data. The results suggest that the two-stream mixing layer should provide a better test case for the development of turbulence models and calculation methods than the single-stream mixing layer.

Mehta, R. D.↗

An experimental study of plane mixing layer development

Mean flow and turbulence was measured in the near field of two plane mixing layers in air with a maximum velocity of 21 m/sec. The experimental rig enabled mixing layers of velocity ratios 0 and 0.46 to be generated simultaneously. Gases with both tripped and untripped initial boundary layers were studied. It was found that the two stream layer developed to the self preserving state in a distance much shorter than did the single stream layer which followed accepted criteria for the development distance. The asymptotic levels of the turbulence quantities in the two stream layer and the development of the single stream layer showed agreement with existing data. It is suggested that the two stream mixing layer should provide a better test case for the development of turbulence models and calculation methods than the single stream mixing layer.

Mehta, R. D.↗

An experimental investigation of nozzle-exit boundary layers of highly heated free jets

An experimental investigation of the effects of nozzle operating conditions on the development of nozzle-exit boundary layers of highly heated air free jets is reported in this paper. The total pressure measurements in the nozzle-exit boundary layer were obtained at a range of jet Mach numbers from 0.1 to 0.97 and jet total temperatures up to 900 K. The analysis of results shows that the nozzle-exit laminar boundary-layer development depends only on the nozzle-exit Reynolds number. For the nozzle-exit turbulent boundary layer, however, it appears that the effects of the jet total temperature on the boundary-layer integral characteristics are independent from the effects of the nozzle-exit Reynolds number. This surprizing finding has not yet been reported. Further, laminar boundary-layer profiles were compared with the Pohlhausen solution for a flat-wall converging channel and an acceptable agreement was found only for low Reynolds numbers. For turbulent boundary layers, the dependence of the shape factor on relative Mach numbers at a distance of one momentum thickness from the nozzle wall resembles Spence's prediction. Finally, the calculated total pressure loss coefficient was found to depend on the nozzle-exit Reynolds number for the laminar nozzle-exit boundary layer, while for the turbulent exit boundary layer this coefficient appears to be constant.

Lepicovsky, J.↗