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At least 199 records · Page 11

Na-Montmorillonite Edge Structure and Surface Complexes: An Atomistic Perspective

The edges of montmorillonite (MMT) react strongly with metals and organic matter, but the atomic structure of the edge and its surface complexes are not unambiguous since the experimental isolation of the edge is challenging. In this study, we introduce an atomistic model of a Na MMT edge that is suitable for classical molecular dynamics (MD) simulations, in particular for the B edge, a representative edge surface of 2:1 phyllosilicates. Our model possesses the surface groups identified through density functional theory (DFT) geometry optimizations performed with variation in the structural charge deficit and Mg substitution sites. The edge structure of the classical MD simulations agreed well with previous DFT-based MD simulation results. Our MD simulations revealed an extensive H-bond network stabilizing the Na-MMT edge surface, which required an extensive simulation trajectory. Some Na counter ions formed inner-sphere complexes at two edge sites. The stronger edge site coincided with the exposed vacancy in the dioctahedral sheet; a weaker site was associated with the cleaved hexagonal cavity of the tetrahedral sheet. The six-coordinate Na complexes were not directly associated with the Mg edge site. Our simulations have demonstrated the heterogeneous surface structures, the distribution of edge surface groups, and the reactivity of the MMT edge.

58 GEOSCIENCES↗

SPONTANEOUS FORMATION OF SURFACE MAGNETIC STRUCTURE FROM LARGE-SCALE DYNAMO IN STRONGLY STRATIFIED CONVECTION

We report the first successful simulation of spontaneous formation of surface magnetic structures from a large-scale dynamo by strongly stratified thermal convection in Cartesian geometry. The large-scale dynamo observed in our strongly stratified model has physical properties similar to those in earlier weakly stratified convective dynamo simulations, indicating that the α {sup 2}-type mechanism is responsible for the dynamo. In addition to the large-scale dynamo, we find that large-scale structures of the vertical magnetic field are spontaneously formed in the convection zone (CZ) surface only in cases with a strongly stratified atmosphere. The organization of the vertical magnetic field proceeds in the upper CZ within tens of convective turnover time and band-like bipolar structures recurrently appear in the dynamo-saturated stage. We consider several candidates to be possibly be the origin of the surface magnetic structure formation, and then suggest the existence of an as-yet-unknown mechanism for the self-organization of the large-scale magnetic structure, which should be inherent in the strongly stratified convective atmosphere.

79 ASTRONOMY AND ASTROPHYSICS↗

Adsorption of aromatics on the (111) surface of PtM and PtM 3 (M = Fe, Ni) alloys

The adsorption of benzene and phenol was studied on PtM and PtM3 (111) surfaces, with M being either Ni or Fe. Under vacuum, the most favorable near surface structures showed an enrichment in Pt over the M species. An analysis of the electronic structure of the metal species in the clean surfaces with different near surface structures was done with the d-band model and showed that the Pt's d-states are significantly shifted away from the Fermi level due to the Pt-M interactions while the M species' d-states were less affected, with Ni's d-band shifting closer to the Fermi level and Fe's d-band shifting away from the Fermi level. The adsorption of aromatics, benzene and phenol, on several near surface structures for the PtM and PtM3 (111) surfaces showed that higher surface M concentrations resulted in a stronger adsorption due to the larger amount of charge transferred between the adsorbate and surface. However, compared to the adsorption of benzene and phenol on monometallic surfaces, the adsorption of these species on the PtM and PtM3 (111) surfaces was significantly weakened. Overall, our results show that the observed behavior of these Pt/Fe and Pt/Ni alloys is similar to that seen for the previously studied Pd/Fe surfaces. Furthermore, balancing the weakly adsorbing Pt surface species with the more strongly interacting Fe or Ni species can lead to the tailored adsorption of aromatics with applications in both hydrodeoxygenation and hydrogenation reactions by increasing the desorption rate of wanted aromatic products.

Hensley, Alyssa J. R.↗

A Study of Support Effects for CH 4 and CO Oxidation over Pd Catalysts on ALD-Modified Al 2 O 3

Interactions between a metal and its oxide support can influence CO and CH 4 oxidation, but promotion by the support can be difficult to study because oxides can have different surface structures and surface areas. To focus on the chemical aspects of support promotion for CO and CH 4 oxidation, this study investigated the effect of support composition on Pd catalysts by preparing uniform films of NiO, Co 3 O 4 , Fe 2 O 3 , MnO 2 , CeO 2 , and ZrO 2 on γ-Al 2 O 3 using Atomic Layer Deposition (ALD). The structure of the films was characterized by XRD and STEM, and catalysts with ~ 1-wt% Pd were examined for CO and CH 4 oxidation. CeO 2 /γ-Al 2 O 3 was unique among the supports in greatly stabilizing the Pd dispersion to 1173 K. Rates for CO oxidation were enhanced by the presence of CeO 2 , Fe 2 O 3 , and MnO 2 , while the other oxides had no promotional effect. For CH 4 oxidation, only NiO and Co 3 O 4 were modest promoters, while the other reducible oxides even showed a negative effect on rates. Finally, possible reasons for the differences between CH 4 and CO oxidation activities are discussed.

42 ENGINEERING↗

A Bayesian Monte Carlo inversion of spatial auto-correlation (SPAC) for near-surface Vs structure applied to both broad-band and geophone data

SUMMARY We propose a new Bayesian method to reveal the Vs structure of the near surface of the earth using spatial autocorrelation (SPAC) functions and apply this new method to synthetic, broad-band and geophone data sets. The principle of SPAC is introduced, and an implementation of the Bayesian Monte Carlo inversion (BMCI) for modelling SPAC coherency functions is described. To demonstrate its effectiveness, BMCI is applied to synthetic tests, data from 14 SPAC array sites in the Salt Lake Valley (SLV), Utah, and two arrays (one broad-band and one geophone) located in south central Utah. The Vs models derived from previous SPAC analysis of the 14 SLV sites differ by 10 per cent at most from those determined by BMCI and lie within uncertainties determined for the BMCI models. These agreements demonstrate the effectiveness of the BMCI method. The synthetic tests and applications to the SLV SPAC data show BMCI has great potential to resolve Vs structure down to at least 400 m. To achieve resolution for deeper Vs structure, longer duration deployments, wider array apertures, and additional seismometers or geophones can be used. Additionally, when the target frequencies are greater than 0.1 Hz, there is no apparent disadvantage in using geophone data for BMCI compared to broad-band data. Most significantly, BMCI places a quantifiable constraint on the uncertainties of the Vs models as well as Vs30.

58 GEOSCIENCES↗

Influence of Process-Induced Anisotropy and Synovial Environment on Wear of EBM Built Ti6Al4V Joint Implants

Additive manufacturing (AM) technology is identified as an ideal solution to overcome challenges in design and manufacturing of complex components. However, the layered fashion of AM process result in directionally solidified microstructures on the system. The anisotropic surface texture will affect wear and corrosion resistance. The current study investigates tribological responses of AM-made Ti6Al4V for joint implant applications during the combined effect from synovial lubrication and process-induced surface structure on surface fatigue damage response. Electron beam melting was used to produce Ti6Al4V specimens and mechanical characterizations were performed using nanoindentation and micro bending tests to determine their mechanical properties. A series of pin-on-disk wear tests were performed to quantify sliding contact fatigue damage in three simulated synovial fluids with variable concentrations of bovine serum albumin and hyaluronic acid in the PBS solution. Physical properties of simulated synovial fluids were measured using a nanoindenter-based technique and correlated to fatigue wear response. The lower wear rate is found in greater protein concentrations. The results presented AM build direction significantly affects sliding fatigue wear resistance on TI6Al4V surface in all synovial environments.

36 MATERIALS SCIENCE↗

Security system

A security system includes a structure having a structural surface. The structure is sized to contain an asset therein and configured to provide a forceful breaching delay. The structure has an opening formed therein to permit predetermined access to the asset contained within the structure. The structure includes intrusion detection features within or associated with the structure that are activated in response to at least a partial breach of the structure.

42 ENGINEERING↗

INTERFACES. A Program for Determining the 3D Structures of Surfaces Sites Using NMR Data

Dynamic nuclear polarization surface enhanced NMR spectroscopy has enabled the determination of high-resolution structures from surface-supported molecules, including singlesite heterogeneous catalysts. Structure determinations have largely mimicked the approaches used in biomolecular NMR spectroscopy, namely, using distance measurements to constrain a conformational search. These early demonstrations made use of purpose-built software, which has limited the adoption of the technique. Herein, we describe the open-source program INTERFACES (Interpret NMR to Elucidate or Reconstruct the Full Atomistic Configurations of External Surfaces) which automates the analysis of RE(SP)DOR data as well as the structure determination for surface sites. Distances, angles, dihedral angles, complex orientation, and distance from the support can all be sampled to find all structures that agree with the experimental data. A χ 2 metric is used to define the error ranges of the REDOR fits and produce structures with an arbitrary level of confidence. Structural solutions are then provided as both overlays and ORTEP-like probability ellipsoids.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Stoichiometry-dependent surface electronic structure of SrTiO3 films grown by hybrid molecular beam epitaxy

We investigate the surface electronic structure of SrTiO3 (STO) films grown by a hybrid molecular beam epitaxy that are both stoichiometric and nonstoichiometric by means of x-ray photoelectron spectroscopy and electron energy loss spectroscopy. Increasing the fraction of the surface that is terminated with an SrO layer is correlated with a decrease in the chemical potential whereby the valence band maximum moves closer to the Fermi level, but without a significant change in the bandgap. Inasmuch as SrO-terminated STO (001) has previously been shown to act as an electron scavenger in which carriers from the bulk are trapped, we argue that the high fraction of SrO in the terminal layer is what lowers the chemical potential in Sr-rich STO. Our experimental results provide important insights into various physical phenomena that can occur on STO (001) surfaces and their effect on bulk electronic properties.

Lee, Dooyong (ORCID:0000000175361677)↗

When does atomic resolution plan view imaging of surfaces work?

We present that surface structures that are different from the corresponding bulk, reconstructions, are exceedingly difficult to characterize with most experimental methods. Scanning tunneling microscopy, the workhorse for imaging complex surface structures of metals and semiconductors, is not as effective for oxides and other insulating materials. This paper details the use of transmission electron microscopy plan view imaging in conjunction with image processing for solving complex surface structures. We address the issue of extracting the surface structure from a weak signal with a large bulk contribution. This method requires the sample to be thin enough for kinematical assumptions to be valid. The analysis was performed on two sets of data, c(6×2) on the (100) surface and (3×3) on the (111) surface of SrTiO 3 , and was unsuccessful in the latter due to the thickness of the sample and a lack of inversion symmetry. In conclusion, the limits and the functionality of this method are discussed.

36 MATERIALS SCIENCE↗

Spallation-induced roughness promoting high spatial frequency nanostructure formation on Cr

Interaction of ultrafast laser pulses with metal surfaces in the spallation regime can result in the formation of anisotropic nanoscale surface morphology commonly referred to as laser-induced periodic surface structures (LIPSS) or ripples. The surface structures generated by a single pulse irradiation of monocrystalline Cr samples are investigated experimentally and computationally for laser fluences that produce high spatial frequency nanostructures in the multi-pulse irradiation regime. Electron microscopy reveals distinct response of samples with different crystallographic surface orientations, with (100) surfaces exhibiting the formation of more refined nanostructure by a single pulse irradiation and a more pronounced LIPSS after two laser pulses as compared to (110) surfaces. A large-scale molecular dynamics simulation of laser interaction with a (100) Cr target provides detailed information on processes responsible for spallation of a liquid layer, redistribution of molten material, and rapid resolidification of the target. The nanoscale roughness of the resolidified surface predicted in the simulation features elongated frozen nanospikes, nanorims and nanocavities with dimensions and surface density similar to those in the surface morphology observed for (100) Cr target with atomic force microscopy. The results of the simulation suggest that the types, sizes and dimensions of the nanoscale surface features are defined by the competition between the evolution of transient liquid structures generated in the spallation process and the rapid resolidification of the surface region of the target. The spallation-induced roughness is likely to play a key role in triggering the generation of high-frequency LIPSS upon irradiation by multiple laser pulses.

Materials Science↗

Evaluating the Potential for Marine and Hydrokinetic Devices to Act as Artificial Reefs or Fish Aggregating Devices. Based on Analysis of Surrogates in Tropical, Subtropical, and Temperate U.S. West Coast and Hawaiian Coastal Waters

Wave energy converters (WECs) and tidal energy converters (TECs) are only beginning to be deployed along the U.S. West Coast and in Hawai‘i, and a better understanding of their ecological effects on fish, particularly on special-status fish (e.g., threatened and endangered) is needed to facilitate project design and environmental permitting. The structures of WECs and TECs placed on to the seabed, such as anchors and foundations, may function as artificial reefs that attract reef-associated fishes, while the midwater and surface structures, such as mooring lines, buoys, and wave or tidal power devices, may function as fish aggregating devices (FADs), forming the nuclei for groups of fishes. Little is known about the potential for WECs and TECs to function as artificial reefs and FADs in coastal waters of the U.S. West Coast and Hawai‘i. We evaluated these potential ecological interactions by reviewing relevant information about fish associations with surrogate structures, such as artificial reefs, natural reefs, kelps, floating debris, oil and gas platforms, marine debris, anchored FADs deployed to enhance fishing opportunities, net-cages used for mariculture, and piers and docks. Based on our review, we postulate that the structures of WECs and TECs placed on or near the seabed in coastal waters of the U.S. West Coast and Hawai‘i likely will function as small-scale artificial reefs and attract potentially high densities of reef-associated fishes (including special-status rockfish species [Sebastes spp.] along the mainland), and that the midwater and surface structures of WECs placed in the tropical waters of Hawai‘i likely will function as de facto FADs with species assemblages varying by distance from shore and deployment depth. Along the U.S. West Coast, frequent associations with midwater and surface structures may be less likely: juvenile, semipelagic, kelp-associated rockfishes may occur at midwater and surface structures of WECs in coastal waters of southern California to Washington, and occasional, seasonal, or transitory associations of coastal pelagic fishes such as jack mackerel (Trachurus symmetricus) may also occur at WECs in these waters. Importantly, our review indicated that negative effects of WEC structures on special-status fish species, such as increased predation of juvenile salmonids or rockfishes, are not likely. In addition, WECs installed in coastal California, especially in southern California waters, have the potential to attract high densities of reef-associated fishes and may even contribute to rockfish productivity, if fish respond to the WECs similarly to oil and gas platforms, which have some of the highest secondary production per unit area of seafloor of any marine habitat studied globally (Claisse et al. 2014). We encountered some information gaps, owing to the paucity or lack, in key locations, of comparable surrogate structures in which fish assemblages and ecological interactions were studied. TECs are most likely to be used in the Puget Sound area, but suitable surrogates are lacking there. However, in similarly cold-temperate waters of Europe and Maine, benthopelagic fish occurred around tidal turbines during lower tidal velocities, and this type of interaction may be expected by similar species at TECs in Puget Sound. To address information gaps in the near term, such as whether WECs would function as FADs in temperate waters, studies of navigation buoys using hydroacoustics are recommended.

59 BASIC BIOLOGICAL SCIENCES↗

Adsorption of methylene blue by bismuth impregnated biochar of different biomass materials: pore structure and surface chemistry characteristics

Abstract In this study, three different types of biochar (biomass materials were beech wood, corncob, and bamboo) were loaded with bismuth to form bismuth impregnated biochars (named respectively as Bi@WBC, Bi@CBC, and Bi@BBC) to investigate their properties (pore structure and surface chemistry characteristics) on methylene blue (MB) removal capacities. Three bismuth impregnated biochars made from different biomass materials were ranked for their adsorption capacity of MB as follows: Bi@WBC > Bi@CBC > Bi@BBC, in which Bi@WBC showed the largest Langmuir adsorption capacity of 178.59 mg g −1 . While the specific surface area (SSA) and pore volume of Bi@WBC were the largest (accounting for 477.74 m 2 g −1 and 0.15 cm 3 g −1 , respectively), according to the FTIR and XPS results, Bi@WBC (72.3%) exhibited a higher proportion of BiO bonds than the Bi@CBC (52.3%) and Bi@BBC (48.4%) did. Conclusively, the rich porous structure and surface functional groups of Bi@WBC affected the adsorption capacity of MB, and the chemical adsorption provided the main contribution. © 2022 Society of Chemical Industry (SCI).

Li, Peiyi↗

Model of evolution of surface grain structure under ion bombardment

Diffusion and chemical reactions in multicomponent systems play an important role in numerous technology applications. For example, surface treatment of materials and coatings by particle beam leads to chemical composition and grain structure change. To investigate the thermal-diffusion and chemical processes affecting the evolution of surface structure, the mathematical modeling is efficient addition to experiment. In this paper two-dimensional model is discussed to describe the evolution of titanium nitride coating on the iron substrate under implantation of boron and carbon. The equation for diffusion fluxes and reaction rate are obtained using Gibbs energy expansion into series with respect to concentration and their gradients.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Pauling's rules for oxide surfaces

Determination of surface structures currently requires careful measurement and computationally expensive methods since, unlike bulk crystals, guiding principles for generating surface structural hypotheses are frequently lacking. In this work, we discuss the applicability of Pauling's rules as a set of guidelines for surface structures. The wealth of solved reconstructions on SrTiO 3 (100), (110), and (111) are considered, as well as nanostructures on these surfaces and a few other ABO 3 oxide materials. These rules are found to explain atomic arrangements for reconstructions and thin films just as they apply to bulk oxide materials. Lastly, using this data and Pauling's rules, the fundamental structural units of reconstructions and their arrangement are discussed.

36 MATERIALS SCIENCE↗

Enable High-Energy LiNi0.5Co0.2Mn0.3O2 by Ultra-Thin Coating through Wet Impregnation

A high cut-off voltage is required for nickel-rich layered oxide LiNixCoyMnzO2 (NCM) to meet the high energy density requirement of lithium-ion batteries in electric vehicles. However, such a high voltage application leads to an unstable interface between NCM and liquid electrolytes. To stabilize the interface, the facile wet impregnation method has been developed to apply an ultra-thin Al2O3 coating layer on the NCM particles. This coating layer was found to have a strong interaction with the NCM and resulted in Al-doped NCM at the surface structure of NCM. The change of surface structure can not only reduce the surface resistance of lithium diffusion of LiNi0.5Co0.2Mn0.3O2 (NCM523), but also stabilize the solid electrolyte interface between NCM523 and the electrolyte with the cut-off voltage of 4.5 V vs. Li/Li+. Compared to other coating methods, wet impregnation coating can provide an ultra-thin and uniform coating with surface doping on NCM particles. Furthermore, this scalable coating method can be applied to various electrode materials without adding much additional cost.

25 ENERGY STORAGE↗

Chemical reactivity of twin-modified copper nanowire surfaces

Effect of twin boundary (TB) spacing on atomic surface structure and chemical reactivity of nanotwinned Cu nanowires (NWs) is investigated. Post-etching surface structure and wire diameter of Cu NWs were examined by transmission electron microscopy. When TB spacing is less than 10 nm, the Cu NWs remain almost intact after chemical attack and show faceted surface structures with low atomic step density. A mechanism based on surface tension torque acting on TB/surface triple junctions is proposed to explain the faceted structure formation and enhanced corrosion resistance of nanotwinned Cu NWs.

36 MATERIALS SCIENCE↗