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At least 145 records · Page 8

Multiscale Richtmyer-Meshkov instability experiments to isolate the strain rate dependence of strength

Theoretical analysis of Richtmyer-Meshkov instability (RMI) experiments for solid strength shows that the strain rate for a given shock should be inversely proportional to the length scale of the sine wave perturbations when η 0 k , the nondimensional amplitude to wavelength ratio, is held fixed. To isolate the effect of strain rate on strength, free-surface RMI specimens of annealed copper were prepared with three perturbation regions with the same η 0 k but different length scales, characterized by the wavelength λ varying by a factor of 4.9 from 65 to 130 to 320 µ m . Three such targets with different fixed η 0 k ′ s were impacted to a shock pressure of 25 GPa, and the instability evolution was measured with photon Doppler velocimetry. Strengths estimated by comparing hydrocode simulation to the data increased from 700 to 1200 MPa as λ decreased. The different η 0 k targets exercised increasing amounts of plastic strain yet showed no evidence of strain hardening. Physical regime sensitivity analysis determined that for 320 − 65 µ m wavelength perturbations, the effective strain rates increased from 8.7 × 10 6 to 3.3 × 10 7 s − 1 , a factor of 3.8. Thus, the predicted strain rate scaling was mostly achieved but slightly suppressed by increased strength at higher rates. The RMI strength estimates were plotted against constitutive testing data on copper from the literature to show striking evidence of the strength upturn at higher strain rates. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗

Epitaxial stabilization of thin films of the frustrated Ge-based spinels

Frustrated magnets can host numerous exotic many-body quantum and topological phenomena. GeNi 2 O 4 is a three-dimensional S=1 frustrated magnet with an unusual two-stage transition to the two-dimensional antiferromagnetic ground state, while GeCu 2 O 4 is a high-pressure phase with a strongly tetragonally elongated spinel structure and magnetic lattice formed by S=1/2 CuO 2 linear chains with frustrated interchain exchange interactions and exotic magnetic behavior. Here, we report on the thin-film epitaxial stabilization of these two compounds. The developed growth mode, surface morphology, crystal structure, and copper valence state were characterized by in situ reflection high-energy electron diffraction, atomic force microscopy, x-ray reflectivity, x-ray diffraction, x-ray photoelectron spectroscopy, and resonant x-ray absorption spectroscopy. Our results pave an alternative route to the comprehensive investigation of the puzzling magnetic properties of these compounds and the exploration of emergent features driven by strain.

36 MATERIALS SCIENCE↗

Construction of Cryogen-Free 4.3T Superconducting Wiggler for NSLS-II Ring

With the 3 GeV electron beam energy for the National Synchrotron Light Source II (NSLS-II) ring, only superconducting wigglers (SCW) producing greater than 4T peak field can cover the photon energy range of 20 keV and 200 keV with sufficient number of photons. The High energy Engineering X-ray (HEX) Diffraction beamline, which is primarily funded by the New York State Energy Research and Development Authority (NYSERDA) and NSLS-II, will be equipped with a 1.2m-long SCW with 70 mm period length and 4.3 T on-axis field. This SCW is free from the use of liquid Helium and is cooled only with cryo-coolers. The Electron Beam Chamber (EBC) with vertical aperture of 8 mm is made from 316LN stainless steel and copper plating is applied both surface and +-12.5mm wide from the center in the inner surface. The expected heat load from the electron beam of the NSLS-II ring is estimated to be 10 W/m. Here, we describe the design principles and engineering challenges for the device.

36 MATERIALS SCIENCE↗

Intercalative Redox Tuning for Cu/Li x Mn 2 O 4 -Catalyzed Oxidative Alkyne Coupling

Modulation of heterogeneous catalyst structure is ubiquitous within efforts to improve catalytic activity and selectivity at the molecular level. Herein, manganese oxide (MnO 2 ) is employed as a continuously tunable catalyst support through increasing extent of lithium intercalation and reduced surface potential. Oxidative grafting of an organocopper complex onto various lithium manganese oxides (Li x Mn 2 O 4 , x = 0-2.1) produced divalent and monovalent copper species on the partially reduced (0 ≤ x ≤ 1.2) and fully reduced (x = 2.1) surfaces, respectively, as determined by X-ray absorption fine structure (XAFS) analysis. In this study, the resultant materials are catalytically active for the oxidative coupling of terminal alkynes, with steady-state reaction rate data of oxidative propyne dimerization (200 °C, 0.6-2.4 kPa propyne, 2.4-9.9 kPa O 2 ) indicating that complete support lithiation (Li 2.1 Mn 2 O 4 ) provides increased catalytic performance and renders reoxidation steps less kinetically demanding compared to the unreduced parent material. Enacting a dual site (Cu and MnO x ) kinetic model can account for dimerization rates measured over Cu/Li 2.1 Mn 2 O 4 under various reactant concentrations, copper loadings, and surface coverages, providing supporting evidence for the synergistic role of the metal and support in facilitating the coupling reaction. Overall, results presented here provide an extension for general strategies of systematically controlling catalytic structure and function through lithium reduction of bulk oxides and subsequent electronic modulation of the metals supported thereon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DEMONSTRATION OF TWICE REDUCED LORENTZ FORCE DETUNING IN SRF CAVITY BY COPPER COLD SPRAYING

Superconducting RF (SRF) cavities usually are made of thin-wall high RRR Niobium that is susceptible to Lorentz Force Detuning (LFD) ? cavity deformation phenomena caused by high magnitude RF fields. This type of deformation can be mitigated by using an additional copper layer deposited on the outer surface of the cavity. In this paper, we present both modeling results and experimental data of high gradient test of an SRF cavity at cryogenic temperatures. It was demonstrated that LFD can be significantly reduced (factor of two) by the copper cold spray reinforcement without sacrificing cavity flexibility for tuning. We also present a finite-element model that allows us to confirm our experimental results and optimize the cavity geometry for LFD reduction with incorporated coupled RF, structural and thermal modules.

Kostin, R.↗

Operando Surface-Enhanced Infrared Spectroscopy Connects Interfacial Dynamics with Reaction Kinetics During Electrochemical CO 2 Reduction on Copper

The reaction microenvironment plays a key role in dictating the selectivity of electrochemical CO 2 reduction. However, understanding the chemical nature of this microenvironment under operating conditions remains a substantial challenge. For this study, we employed attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) in operando for simultaneous measurements of reaction kinetics and concentrations of reactants and intermediates at the reaction interface, all under controlled mass transport conditions. These operando measurements enable direct correlations between the reaction microenvironment, mass transport, and kinetics for a Cu electrocatalyst, such as higher local concentrations of CO 2 under faster mass transport corresponding to higher rates of CO 2 reduction. We observed that faster mass transport decreased the *CO coverage at less negative potentials (-0.6 V RHE ) and increased the *CO coverage at more negative potentials (-1.1 V RHE ). We developed a transport-coupled kinetic model that captures these spectroscopic observations and provides insight into the processes controlling interfacial concentrations of reactants and intermediates, aiding future efforts toward tailoring reaction microenvironments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Above-threshold multiphoton photoemission from noble metal surfaces

Exciting solids with intense femtosecond laser pulses prompts electrons of the interrogated material to respond in a highly nonlinear manner, as is evident in the emission of high-order harmonic radiation and photoelectrons with kinetic energies well above that of the driving photons. Such high-field interactions can be resolved, for example, in above-threshold multiphoton photoemission (ATP) spectroscopy. In this work, we interrogate the nonlinear photoelectric responses of the pristine copper, silver, and gold noble metal surfaces in (111) and (100) crystal orientations in the perturbative regime. Using multiphoton photoemission spectroscopy (mPP) excited by finely tuned optical fields, we characterize enhancement of the mPP and ATP yields from (111) surfaces in selected k||-momentum ranges when the occupied Shockley surface (SS) states are (near-)resonantly coupled by multiphoton transitions to image potential (IP) intermediate states in the excitation process. The ATP signal from the IP states of (111) surfaces is largely defined by their formation through polarization of SS electrons; this observation is contrasted with ATP experiments from the Ag(100) surface, for which the SS becomes an unoccupied resonance and the IP states can only be excited from bands with significantly more bulk character. In addition, based on the optical power and nonlinear order-dependent mPP spectra, we provide evidence for ATP being a one-step, rather than a sequential process, as previously postulated.

74 ATOMIC AND MOLECULAR PHYSICS↗

Decoupling the effects of substrate hardness and roughness upon particle adhesion in cold spray

There are two stages of particle adhesion relevant to cold spray: adhesion of the first layer to the substrate, followed by inter-particle adhesion during subsequent deposition. In this work we study the second of these, in which particles strike a previously-deposited layer that is roughened and hardened by prior particle impacts. Specifically, we decouple the effects of surface roughness and hardness on particle adhesion for copper-on-copper impacts. We measure changes to the critical velocity, V cr , in single particle impacts produced by the Laser Induced Particle Impact Test on several surfaces including a cold sprayed surface and a polished version of that surface. We find that increases in both substrate roughness and hardness suppress particle adhesion to higher velocities, indeed in rather equal proportion by ∼10–15% each. This suggests that there is a higher V cr associated with coating build-up (particle-particle bonding) that is overall ∼30% higher than V cr for particle-substrate adhesion.

36 MATERIALS SCIENCE↗

Measurement and analysis of the Doppler broadened energy spectra of gamma radiation originating from the annihilation of positrons incident on clean and adsorbate-covered surfaces

We present measurements and theoretical modeling demonstrating the capability of coincidence Doppler broadened (CDB) annihilation gamma spectroscopy to provide element-specific information from the topmost atomic layer of surfaces. Our measurements show that the energy spectra of Doppler-shifted annihilation gamma photons emitted following the annihilation of positrons from the topmost atomic layers of clean and adsorbate covered surfaces of gold (Au), silver (Ag) and copper (Cu) differ significantly. The shape of the Doppler-broadened gamma spectrum, as analyzed using ratio curves, indicates that the elemental composition of the surface can still be identified despite contributions from positronium annihilation and a significant reduction in core electron annihilation. We estimate the chemical composition of the various probed surfaces by modeling the ratios of the measured Doppler spectra with respect to the Doppler spectra from a clean Cu surface using a linear combination of calculated ratio curves. The fitting of the experimental ratio curves was used to obtain an estimate of the elemental composition of Cu surfaces with sulfur segregation, oxygen adsorption, a thin film of Selenium (Se), and a single layer of graphene (SLG). A similar analysis was performed on the Ag surface with environmental adsorbates, the same surface after argon ion sputtering, as well as a sputter cleaned Au surface. The surface compositions obtained from the analysis of the CDB data were compared to the compositions obtained using positron annihilation induced Auger electron spectroscopy (PAES). Our results show that CDB can detect, identify, and quantify, sub-monolayer adsorbates and a single atomic layer deposited on metal substrates.

Lotfimarangloo, Sima [Univ. of Texas, Arlington, T↗

Mesoporous CuFe 2 O 4 Photoanodes for Solar Water Oxidation: Impact of Surface Morphology on the Photoelectrochemical Properties**

Abstract Metal oxide‐based photoelectrodes for solar water splitting often utilize nanostructures to increase the solid‐liquid interface area. This reduces charge transport distances and increases the photocurrent for materials with short minority charge carrier diffusion lengths. While the merits of nanostructuring are well established, the effect of surface order on the photocurrent and carrier recombination has not yet received much attention in the literature. To evaluate the impact of pore ordering on the photoelectrochemical properties, mesoporous CuFe 2 O 4 (CFO) thin film photoanodes were prepared by dip‐coating and soft‐templating. Here, the pore order and geometry can be controlled by addition of copolymer surfactants poly(ethylene oxide)‐ block ‐poly(propylene oxide)‐ block ‐poly(ethylene oxide) (Pluronic® F‐127), polyisobutylene‐ block ‐poly(ethylene oxide) (PIB‐PEO) and poly(ethylene‐ co ‐butylene)‐ block ‐poly(ethylene oxide) (Kraton liquid™‐PEO, KLE). The non‐ordered CFO showed the highest photocurrent density of 0.2 mA/cm 2 at 1.3 V vs. RHE for sulfite oxidation, but the least photocurrent density for water oxidation. Conversely, the ordered CFO presented the best photoelectrochemical water oxidation performance. These differences can be understood on the basis of the high surface area, which promotes hole transfer to sulfite (a fast hole acceptor), but retards oxidation of water (a slow hole acceptor) due to electron‐hole recombination at the defective surface. This interpretation is confirmed by intensity‐modulated photocurrent (IMPS) and vibrating Kelvin probe surface photovoltage spectroscopy (VKP‐SPS). The lowest surface recombination rate was observed for the ordered KLE‐based mesoporous CFO, which retains spherical pore shapes at the surface resulting in fewer surface defects. Overall, this work shows that the photoelectrochemical energy conversion efficiency of copper ferrite thin films is not just controlled by the surface area, but also by surface order.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intermittent oxidation kinetics and metal/oxide interfacial undulation

The phenomenon of oxygen-adsorption-induced surface restructuring is widespread across various metal-oxygen systems, yet its impact on initiating bulk oxide formation remains largely unexplored. In this study, through in-situ atomic-resolution electron microscopy observations of surface oxidation of Cu(110) and Cu 85 Au 15 (110), we unveil intermittent oxide-film growth modulated by oxygen-induced surface restructuring. This modulation is evidenced by repeated pinning of Cu 2 O growth front at isolated Cu columns of the c(6×2)-O reconstruction, owing to required long-range diffusion of Cu and O atoms to the Cu 2 O growth front. We reveal that Cu vacancies, generated at the Cu 2 O growth front, are injected into the Cu 2 O/Cu interface, inducing hill-and-valley undulation of the Cu 2 O film. In contrast, atomic vacancies produced during the Cu 85 Au 15 (110) oxidation preferentially migrate into interfaces between Au-rich and Au-poor regions in the bulk, resulting in a flat and adherent Cu 2 O film. These findings demonstrate the critical role of oxygen-induced surface restructuring in modulating oxide-film-growth kinetics and manipulability of the fate of injected vacancies by alloying, thereby offering insights applicable to a broader range of metal-oxygen systems for fine-tuning oxidation kinetics and enhancing oxide/metal interfacial adhesion.

25 ENERGY STORAGE↗

Metal fluxes at the sediment–water interface in a free water surface constructed wetland

Metal biogeochemistry in the sediment, water, and the sediment–water interface (SWI) was studied in a free water surface constructed wetland. Concentrations of labile copper (Cu), zinc (Zn), sulfate, chloride, and dissolved organic carbon (DOC) were measured with the diffusive gradients in thin film (DGT) and peeper. A good agreement between peeper- and DGT-measured metals was observed for Cu (regression r 2 = 0.3, 95% CI of the slopes > 0), but not for Zn (95% CI of the slopes overlapped with 0), which was attributed to the different complexed compounds between Cu and Zn in porewater. The depth profile of labile metals in sediment porewater varied with time and was consistent with the solid-phase metal deposition, showing higher concentrations in the surface layer (3 to –3 cm) than in the bottom layer (–4 to –13 cm). The depth-averaged labile Cu and Zn concentrations measured by DGT were 1.0 and 3.1 µg/L, and labile sulfate, chloride, and DOC concentrations measured by peeper were 1.8, 3.6, and 2.1 mg/L, respectively. A sharp decrease in sulfate occurred in September when sulfate concentrations became the lowest among sampling months. This was caused by the seasonal sulfur cycles in the wetland, where the dominant sulfur reaction is sulfate reduction in warm seasons and sulfide oxidation in cold seasons. Different metal-removal mechanisms were observed in the two wetland cells; sulfur dynamics controlled the removal processes in the cell without frequent disturbance but failed to influence metal removal in the cell with frequent disturbance due to the interruption of anoxic layers. The flux ratios that compare labile element concentrations between the water column and the SWI (R-Cu, R-Zn, R-DOC, R-sulfate, and R-chloride) were generated to determine metal diffusive fluxes at the interface. Labile Zn was mostly transported from the water to the SWI during all seasons (R-Zn < 1 for all months except January). Labile Cu moved from the SWI to the water during the warm months (R-Cu < 1), which was explained by the bioturbation-induced transport of organic matter based on the positive correlations between R-Cu and R-DOC. In general, sediment can serve either as a sink or a source depending on the environmental conditions, metal speciation, and presence of living organisms. Here, metal flux at the SWI is a key component in the biogeochemical cycling of a constructed wetland.

54 ENVIRONMENTAL SCIENCES↗

Brazing characteristics, microstructure, and wettability of laser powder bed fusion additive manufactured GRCop-84 compared to CuCrZr and OFC, and brazing to titanium-zirconium-molybdenum alloy limiters

Laser Powder Bed Fusion (L-PBF) of Glenn Research Copper 84 (GRCop-84), a Cr 2 Nb (8 at. % Cr, 4 at. % Nb) precipitation hardened alloy, produces a fully dense, high conductivity alloy with a yield strength of 500 MPa and ultimate tensile strength (UTS) of 740 MPa with 20% elongation; superior to other competing copper alloys. Braze wetting characteristics of GRCop-84 with Ag-Cu-X, and Au-Cu brazes were similar to CuCrZr, but less than oxygen free copper. No difference in wetting was observed between infill and surface contour areas in L-PBF GRCop-84. Wet sanding to 240 grit (R a =0.24 µm) was considered the optimal surface condition. Silver diffusing through GRCop-84 depleted Cr 2 Nb precipitates from the copper grain and deposited agglomerations of coarsened precipitates within silver-rich regions of intergranular diffusion once a density threshold was reached. Microstructure modification was minimized with 50Au-50Cu braze implying that silver caused precipitate coarsening and agglomeration, and not high temperature exposure. Coarsened precipitates were observed on the surface within braze pools implying a contribution to braze wetting. Palcusil-25, Ticusil, CuSil-ABA, and 50Au-50Cu brazes were suitable for brazing to unplated Titanium-Zirconium-Molybdenum (TZM), while sulfamate nickel plating to allows wetting with CuSil or other non-active brazes. Additionally, vacuum brazing techniques were developed to join a 1 mm thick layer of TZM to the front of additive manufactured GRCop-84 waveguides considering the brazing characteristics of both GRCop-84, TZM, and internal stress from the difference in coefficient in thermal expansion.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Hole‐Carrier‐Dominant Transport in 2D Single‐Crystal Copper

Abstract In 2D noble metals like copper, the carrier scattering at grain boundaries has obscured the intrinsic nature of electronic transport. However, it is demonstrated that the intrinsic nature of transport by hole carriers in 2D copper can be revealed by growing thin films without grain boundaries. As even a slight deviation from the twin boundary is perceived as grain boundaries by electrons, it is only through the thorough elimination of grain boundaries that the hidden hole‐like attribute of 2D single‐crystal copper can be unmasked. Two types of Fermi surfaces, a large hexagonal Fermi surface centered at the zone center and the triangular Fermi surface around the zone corner, tightly matching to the calculated Fermi surface topology, confirmed by angle‐resolved photoemission spectroscopy (ARPES) measurements and vivid nonlinear Hall effects of the 2D single‐crystal copper account for the presence of hole carriers experimentally. This breakthrough suggests the potential to manipulate the majority carrier polarity in metals by means of grain boundary engineering in a 2D geometry.

36 MATERIALS SCIENCE↗

Sink or source? Insights into the behavior of copper and zinc in the sediment porewater of a constructed wetland by peepers

The H-02 free water surface constructed wetland has been applied to remove heavy metals, mainly copper (Cu) and zinc (Zn), from wastewater on the Savannah River Site (Aiken, SC, USA). More and more studies focus on the metal behavior between the sediment and the overlying water, which directly reflects the stability of metals after sedimentation in constructed wetlands. This study focused on the biogeochemical pathways in metal bioavailability and remobilization in the sediment after metals were removed from the overlying water. The dialysis sampling devices (peepers) were used to collect porewater samples from eight depths in the sediment for the measurement of Cu, Zn, dissolved organic carbon (DOC), and major anions (sulfate and chloride). Surface water samples were also collected for the measurement of Cu, Zn, DOC, and anions. Different temporal trends were observed for dissolved Cu between the surface and bottom waters, but not for dissolved Zn. There were no obvious changes in porewater metal concentrations with increasing depths in the sediment. Sediment served as a sink for Cu as only 3% of porewater samples showed higher labile Cu concentrations than the surface water during the entire year. Furthermore, sediment served as a source for Zn in summer and winter as 32% of porewater samples showed higher labile Zn concentrations than the surface water, and these samples were collected at all sediment depths. We think the seasonal changes in the behaviors of Cu and Zn were primarily controlled by the sulfur dynamics and the metal removal processes in the constructed wetland, as well as the different complexing chemistry between Cu and Zn. Also, our study supports that peeper is a powerful tool for studying the biogeochemistry of metals in the sediment.

54 ENVIRONMENTAL SCIENCES↗

Metal-Insulation REBCO Pancake Coil With Solder Surface Shunt: Testing and Modeling

Rare-earth barium copper oxide (REBCO) high-temperature superconducting (HTS) magnets can generate very high magnetic fields with superior engineering current density and robust mechanical integrity. The no-insulation (NI) winding technique, including its metal-insulation (MI) variant, enables “self-protection” against localized overheating through inter-turn current sharing, improving defect tolerance and allowing temporary current overloads. In REBCO pancake coils, the current-sharing path is predominantly confined to the edges of the REBCO tapes due to insulating buffer layers. Applying a surface shunt using solder can effectively enhance current sharing in NI/MI coils via the REBCO tape edges. Here, in this paper, we present both experimental and numerical research on the current distribution in surface-shunt metal-insulation (SSMI) REBCO pancake coils. We tested a stainless steel co-wound MI REBCO double-pancake coil, before and after applying a soldered surface shunt, in a saturated liquid nitrogen bath. The SSMI coil was modeled using the H-formulation and rotated anisotropic resistivity to study its dynamic behavior, including inter-turn current sharing and intra-turn screening currents. Benchmarked by experimental data, the numerical model is able to study the defect tolerance of the SSMI coil during energization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

In Situ Studies of Copper-Zirconia-Zinc Oxide Model Catalysts for CO 2 Hydrogenation

A combination of in situ X-ray photoelectron spectroscopy (XPS) and infrared reflection absorption spectroscopy (IRAS) was used to investigate the formation of surface intermediates from CO 2 hydrogenation on copper-zirconia-zinc oxide model catalysts under reaction conditions. Copper clusters with different numbers of atoms (n = 1, 4, 13) were deposited onto bare and ZrO 2 -modified ZnO powder supports to systematically examine the effects of Cu cluster size and the synergy between metal and metal-oxide components. Under low pressure CO 2 hydrogenation conditions (CO 2 :H 2 = 1:9, 0.4 mbar, 300–600 K), XPS and IRAS identify the most prominent intermediates as carbonate (CO 3 *), formate (HCOO*) and methoxy (CH 3 O*), which is the final surface-bound intermediate leading to methanol. The temperature profiles are consistent with a mechanism in which CO 2 is adsorbed as carbonate species (HCO 3 *, CO 3 *) followed by hydrogenation reactions to formate (HCOO*) and methoxy (CH 3 O*), but the relative yields strongly depend on surface composition. Specifically, the presence of ZrO 2 promotes CO 2 adsorption and activation and improves the thermal stability of the Cu clusters against loss of surface area. Moreover, the ternary Cu 4 /ZrO 2 /ZnO surface is significantly more active than Cu 4 /ZnO and ZrO 2 /ZnO surfaces for the formation of methoxy (CH 3 O*), indicating that Cu–ZrO 2 interfaces promote the formation of key intermediates leading to methanol. Finally, the yields of intermediates are similar for all Cu cluster sizes (Cu 1 , Cu 4 and Cu 13 ), indicating that the primary role of Cu is to provide H atoms via H 2 dissociation and spillover. In conclusion, these molecular-level insights provide a fundamental understanding of the enhanced efficiency of ternary Cu–ZrO 2 –ZnO catalysts and establish design principles for developing improved catalysts for CO 2 conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗