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At least 667 records · Page 37

Laser‐Induced Nanodroplet Injection and Reconfigurable Double Emulsions with Designed Inner Structures

Abstract Microfabrication of complex double emulsion droplets with controlled substructures, which resemble biological cells, is an important but a highly challenging subject. Here, a new approach is proposed based on laser‐induced injection of water nanodroplets into a liquid crystal (LC) drop. In contrast to the conventional top‐down microfluidic fabrication, this method employs a series of bottom‐up strategies such as nanodroplet injection, spontaneous and assisted coalescence, elastically driven actuation, and self‐assembly. Each step is controlled precisely by adjusting the laser beam, interfacial tension, and its gradients, surface anchoring, and elasticity of the LC. Whispering gallery mode illumination is used to monitor the injection of droplets. A broad spectrum of double emulsions with a predesigned hierarchical architecture is fabricated and reconfigured by temperature, laser‐induced coalescence, and injection. The proposed bottom‐up method to produce customized microemulsions that are responsive to environmental cues can be used in the development of drug delivery systems, biosensors, and functional soft matter microstructures.

42 ENGINEERING↗

Newton-Krylov method in solving drift-flux two-phase flow problems for both pre-CHF and post-CHF conditions at steady state

Furthermore, this paper presents numerical simulations of two-phase flow heat transfer for both pre-CHF and post-CHF conditions typical in light water nuclear reactors. The conjugate heat transfer problem is modeled with one-dimensional drift-flux two-phase flow model for coolant flow and two-dimensional heat conduction equation in solid walls. Fully implicit time integration schemes were employed, and the resulted non-linear equations were solved with a Newton-Krylov method. For the drift-flux two-phase flow model, the EPRI drift-flux closure correlation is used to model the relative motion between the two phases. Additional closure correlations were adopted from REALP5-3D to determine two-phase flow regime, wall boiling heat and mass transfer, interfacial heat and mass transfer, and two-phase flow frictional pressure drop. Three sets of experiments were used for code validation, including Bartolomei subcooled flow boiling in vertical pipes, FRIGG boiling tests in vertical bundles, and Bennett heated tube tests. RELAP5-3D simulation results were also provided to perform code-to-code benchmark. Overall, numerical results of this work showed good agreements with both experimental data and RELAP5-3D simulation results. Discrepancy between them were also identified in post-CHF region, which suggests necessary further improvement.

42 ENGINEERING↗

Reduced recombination via tunable surface fields in perovskite thin films

Here, the ability to reduce energy loss at semiconductor surfaces through passivation or surface field engineering is an essential step in the manufacturing of efficient photovoltaic (PV) and optoelectronic devices. Similarly, surface modification of emerging halide perovskites with quasi-two-dimensional (2D) heterostructures is now ubiquitous to achieve PV power conversion efficiencies (PCEs) >25%, yet a fundamental understanding to how these treatments function is still generally lacking. Here we use a unique combination of depth-sensitive nanoscale characterization techniques to uncover a tunable passivation strategy and mechanism found in perovskite PV devices that were the first to reach the >25% PCE milestone. Namely, treatment with hexylammonium bromide leads to the simultaneous formation of an iodide-rich 2D layer along with a Br halide gradient that extends from defective surfaces and grain boundaries into the bulk three-dimensional (3D) layer. This interface can be optimized to extend the charge carrier lifetime to record values >30 μs and to reduce interfacial recombination velocities to values as low as <7 cm s −1 .

Devices for energy harvesting↗

Infusible thermoplastic resin based sandwich structures for wind blade applications and the influence of scrim on facesheet to core interface debonding

Infusible thermoplastic Elium® family of resins from Arkema have garnered much attention in recent years as a possible replacement for thermoset resins in laminate and sandwich composite manufacturing for wind blade applications due to its ease of recyclability and the ability to utilize existing manufacturing processes without imposing complicated variations. However, physical and mechanical properties of the proposed Elium® based thermoplastic composites must be comparable to existing epoxy (thermoset) based composites using manufacturing processes relevant for large wind turbine blades. A 13-meter-long demonstration blade was manufactured for that purpose and sandwich samples were obtained from that project for a detailed study. This paper details three-point flexural properties of unidirectional E-glass fiber reinforced acrylic and epoxy based sandwich panels with identical balsa wood core materials. In addition, to evaluate the relative merit considering debond failure mode, the interfacial critical strain energy release rate, predominantly in mode-1, was compared via single cantilever beam testing. In sandwich composites constructed with balsa wood core material, resin uptake by the balsa core is traditionally impeded via the insertion of a scrim material at the facesheet to core interface. Results revealed that inclusion of scrim mesh layer at the facesheet to core interface reduced flexural properties and strain energy release rates in panels infused with acrylic resin but did not significantly reduce these properties in epoxy infused facesheets.

Engineering↗

Heteroepitaxial control of thickness, strain, and domain architecture in few-layer ferroelectric tin monochalcogenides

Thin-film epitaxy and epitaxial strain have been widely exploited to tune domain configurations, switching behavior, and ferroic properties in conventional three-dimensional ferroelectric thin films; however, its application to controlling the properties of two-dimensional (2D) ferroelectrics has remained largely unexplored. Here, using SnX (X = Se, S) as a model system, we demonstrate heteroepitaxial control of thickness, strain state, and domain architecture in few-layer ferroelectric SnX via growth on monolayer MoS2 van der Waals (vdW) templates. Compared with conventional growth, MoS2-templated heteroepitaxy promotes epitaxial alignment, yielding ultrathin SnSe films with improved crystalline quality, full areal coverage, and enlarged lateral dimensions. Strong interfacial epitaxial coupling induces pronounced in-plane strain and stabilizes a hierarchical ferroelastic domain architecture, in which long-range 90° stripe domains are further subdivided into nanoscale rotational variants, as revealed by scanning transmission electron microscopy and synchrotron X-ray microscopy. Piezoresponse force microscopy and second-harmonic polarimetry confirm robust in-plane polarization, while ferroelectricity in SnSe is established through polarization-electric field hysteresis and nonvolatile ferroelectric resistive switching with on/off ratios approaching 1000. A nonvolatile, switchable ferroelectric diode effect further evidences direct coupling between polarization and charge transport. Notably, ferroelectric switchability exhibits a strong thickness dependence and is preserved only below ∼10 layers. This vdW heteroepitaxial strategy is further extended to ferroelectric SnS. The seamless heteroepitaxial integration of 2D ferroelectrics with CMOS-compatible, wafer-scale MoS2 templates provides a general and scalable route for strain-enabled structural and ferroelectric engineering in emerging memory and low-power optoelectronic applications.

Wang, Yueyin↗

Giant Orbital Anisotropy with Strong Spin–Orbit Coupling Established at the Pseudomorphic Interface of the Co/Pd Superlattice

Orbital anisotropy at interfaces in magnetic heterostructures has been key to pioneering spin–orbit-related phenomena. However, modulating the interface’s electronic structure to make it abnormally asymmetric has been challenging because of lack of appropriate methods. Here, the authors report that low-energy proton irradiation achieves a strong level of inversion asymmetry and unusual strain at interfaces in [Co/Pd] superlattices through nondestructive, selective removal of oxygen from Co3O4/Pd superlattices during irradiation. Structural investigations corroborate that progressive reduction of Co3O4into Co establishes pseudomorphic growth with sharp interfaces and atypically large tensile stress. The normal component of orbital to spin magnetic moment at the interface is the largest among those observed in layered Co systems, which is associated with giant orbital anisotropy theoretically confirmed, and resulting very large interfacial magnetic anisotropy is observed. All results attribute not only to giant orbital anisotropy but to enhanced interfacial spin–orbit coupling owing to the pseudomorphic nature at the interface. They are strongly supported by the observation of reversal of polarity of temperature-dependent Anomalous Hall signal, a signature of Berry phase. This work suggests that establishing both giant orbital anisotropy and strong spin–orbit coupling at the interface is key to exploring spintronic devices with new functionalities.

42 ENGINEERING↗

Coupled Interfacial Kinetics and Transport Resistances Govern High-Current Behavior in Bipolar Membranes

Bipolar membranes (BPMs) enable electrochemical systems that operate across large pH gradients; however, high-current operation is often limited by voltage losses whose origins remain difficult to resolve in membrane−electrode assemblies. Here, we combine electrochemical impedance spectroscopy with distribution of relaxation times (EIS–DRT) analysis and operando synchrotron X-ray diffraction to examine interfacial polarization, membrane hydration, and transport in commercial and synthesized BPMs. EIS–DRT isolates the BPM-associated interfacial contribution and shows that the commercial BPM exhibits larger water-dissociation-associated overpotentials than the synthesized BPM. Operando hydration mapping shows that both membranes retain water at the bipolar junction during high-current operation, while anode-adjacent hydration gradients are more pronounced in the commercial membrane. These results indicate that high-current voltage losses are not governed by junction water starvation alone but by coupled interfacial polarization and transport resistances.

36 MATERIALS SCIENCE↗

Implementation of a Pressure Correction Term in the CTF Subchannel Code

CTF is a modernized and improved version of the legacy subchannel code COBRA-TF, being jointly developed and maintained by Oak Ridge National Laboratory (ORNL) and North Carolina State University. The code was adopted by ORNL for use in the Consortium for Advanced Simulation of Light Water Reactors (CASL) in 2012 to help address CASL challenge problems. Since that time, activities related to CTF have included implementing software quality assurance measures, implementing new features and models, performing validation and verification testing, establishing and supporting a CTF user group, and developing the code for use in coupled applications. CTF is applicable to single- and two-phase flows in light water reactor geometries at normal and accident operating conditions. The two-phase flow model consists of the six-equation two-phase flow model augmented by equations for the droplet field, and it also includes appropriate source terms. This work focuses on the numerical stability of the six-equation two-phase flow model and is part of a recent effort to improve CTF capabilities for simulating flows in boiling water reactors (BWRs). The six-equation two-phase flow model is not strongly hyperbolic, meaning that some of its eigenvalues are either not real or not distinct. In a Cauchy sense, and for an initial-value problem, strong hyperbolicity was found to be equivalent to well-posedness, which ensures the uniqueness of the solution in the space-time used. This concept is also of importance when designing high-order numerical methods and also when implementing boundary conditions that rely on real eigenvalues such as Riemann solvers. A tremendous amount of research is available in the literature on how to hyperbolize the six-equation two-phase flow model by adding ad hoc terms to the system of equations. Such terms are often referred to as virtual mass or interfacial pressure correction terms. From a mathematical perspective, this approach adds terms to the phasic momentum equation containing first-order partial derivatives of the unknowns to modify the Jacobian matrix, thus the imaginary part of the eigenvalues. For this work, an interfacial pressure correction (IPC) term on the same model as what was used for the CATHARE system code, is implemented in CTF. This allows for recovery of a two-pressure formulation. In the following, the six-equation two-phase flow model is recalled, along with the IPC term and its influence on the eigenvalues. Then, numerical results and convergence studies are presented for a water-faucet problem at a pressure of 10 bar. Finally, conclusions and future work are addressed.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Robust Interfacial Effect in Multi-interface Environment through Hybrid Reconstruction Chemistry for Enhanced Energy Storage

Electrochemical-oxidation-driven reconstruction has emerged as an efficient approach for developing advanced materials, but the reconstructed microstructure still faces challenges including inferior conductivity, unsatisfying intrinsic activity, and active-species dissolution. In this report we present hybrid reconstruction chemistry that synergistically couples electrochemical oxidation with electrochemical polymerization (EOEP) to overcome these constraints. During the EOEP process, the metal hydroxides undergo rapid reconstruction and dynamically couple with polypyrrole (PPy), resulting in an interface-enriched microenvironment. We observe that the interaction between PPy and the reconstructed metal center (i.e., Mn > Ni, Co) is strongly correlated. Theoretical calculation results demonstrate that the strong interaction between Mn sites and PPy breaks the intrinsic limitation of MnO 2 , rendering MnO 2 with a metallic property for fast charge transfer and enhancing the ion-adsorption dynamics. Operando Raman measurement confirms the promise of EOEP-treated Mn(OH) 2 (E-MO/PPy) to stably work under a 1.2 V potential window. The tailored E-MO/PPy exhibits a high capacitance of 296 F g –1 at a large current density of 100 A g –1 . Here our strategy presents breakthroughs in upgrading the electrochemical reconstruction technique, which enables both activity and kinetics engineering of electrode materials for better performance in energy-related fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemistry and Interfacial Structure Promoting Quasi-van der Waals Epitaxial Growth of WS 2 Nanosheets on Sapphire for Prospective Application in Field-Effect Transistors

How do chemical and structural modifications to the supporting crystal surface affect the subsequent van der Waals (vdW) or quasi(Q)-vdW epitaxial growth of 2D nanocrystals? Developing an atomic-scale picture of such an interfacial system is crucial for understanding its impact on the physical and chemical properties of the supported 2D materials. The elucidation of the interfacial structure and chemistry needed to promote the Q-vdW epitaxial growth of 2D tungsten disulfide (WS 2 ) nanocrystals contributes to the growth mechanism understanding, thus pushing forward the integration of such atomically thin semiconductors toward real field-effect transistor applications. In addition to an atomic-force microscopy top view, we showcase a combination of X-ray techniques for a top-to-bottom investigation of the complexities of the buried interface structures. Furthermore, this approach uses X-ray photoelectron spectroscopy, X-ray standing wave excited X-ray fluorescence, and crystal truncation rod scattering to produce a highly resolved chemical-state-specific 3D atomic map for the extended interface structure of WS 2 /α-Al 2 O 3 (001). Employing these detailed analysis methods, along with density functional theory to further refine the picoscale structure, we demonstrate how two different types of interface engineering during the pregrowth stage lead to significant differences in the chemical and structural modifications to the terminal surface of c-face sapphire, which in turn leads to substantial differences in the submonolayer growth of supported WS 2 2D nanocrystals in terms of lateral domain sizes, epitaxial registry, vdW gaps, and stability.

36 MATERIALS SCIENCE↗

The chemical reactivity of the Martian soil and implications for future missions

Possible interpretations of the results of the Viking Biology Experiments suggest that greater than 1 ppm of a thermally labile oxidant, perhaps H2O2, and about 10 ppm of a thermally stable oxidant are present in the martian soil. We reexamine these results and discuss implications for future missions, the search for organics on Mars, and the possible health and engineering effects for human exploration. We conclude that further characterization of the reactivity of the martian regolith materials is warrented-although if our present understanding is correct the oxidant does not pose a hazard to humans. There are difficulties in explaining the reactivity of the Martian soil by oxidants. Most bulk phase compounds that are capable of oxidizing H2O to O2 per the Gas Exchange Experiment (GEx) are thermally labile or unstable against reduction by atmospheric CO2. Models invoking trapped O2 or peroxynitrates (NOO2(-)) require an unlikely geologic history for the Viking Lander 2 site. Most suggested oxidants, including H2O2, are expected to decompose rapidly under martian UV. Nonetheless, we conclude that the best model for the martian soil contains oxidants produced by heterogeneous chemical reactions with a photochemically produced atmospheric oxidant. The GEx results may be due to catalytic decomposition of an unstable oxidizing material by H2O. We show that interfacial reaction sites covering less than 1% of the available soil surfaces could explain the Viking Biology Experiments results.

Zent, Aaron P.↗

Microwave Heating-Induced Temperature Gradients in Liquid–Liquid Biphasic Systems

Microwaves (MWs) can enable the electrification and intensification of chemical manufacturing. They have been applied to various unit separations, such as drying, distillation, and extraction, entailing gas–liquid and solid–liquid systems. However, a limited quantitative understanding of MW-heated liquid–liquid biphasic systems related to extraction exists. This work measures the temporal and spatial temperature difference between an aqueous and an organic phase in batch and continuous microfluidic modes. We demonstrate permanent temperature differences between phases over 35 °C and spatiotemporal periodic and quasiperiodic oscillations modulated by the flow patterns. The temperature differences are primarily driven by the faster absorption rate of MW irradiation by the aqueous phase versus the slower heat transfer from the aqueous phase to the organic phase. These are amplified by low specific interfacial area and modifications of the electromagnetic field. We employ a multiphysics model to predict the temperature difference in a batch system. The model is in good agreement with the experiments. We demonstrate a strong effect of input power, dielectric properties of organic solvents, the volume of solvents, and the volume ratio between phases on the temperature difference. A simple analytical model describes the temperature difference and provides design principles. Furthermore, the combined approach offers new insights into the design and optimization of the MW-heated biphasic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Membrane peptides and their role in protobiological evolution

How simple membrane peptides performed such essential protocellular functions as transport of ions and organic matter across membranes separating the interior of the cell from the environment, capture and utilization of energy, and transduction of environmental signals, is a key question in protobiological evolution. On the basis of detailed, molecular-level computer simulations we explain how these peptides fold at water-membrane interfaces, insert into membranes, self-assemble into higher-order structures and acquire functions. We have investigated the interfacial behavior and folding of several peptides built of leucine and glutamine residues and have demonstrated that many of them tend to adopt ordered structures. Further, we have studied the insertion of an alpha-helical peptide containing leucine (L) and serine (S) of the form (LSLLLSL)3 into a model membrane. The transmembrane state is metastable, and approximately 15 kcal mol(-1) is required to insert the peptide into the membrane. Investigations of dimers formed by (LSLLLSL)3 and glycophorin A demonstrate how the favorable free energy of helix association can offset the unfavorable free energy of insertion, leading to self-assembly of peptide helices in the membrane. An example of a self-assembled structure is the tetrameric transmembrane pore of the influenza virus M2 protein, which is an efficient and selective voltage-gated proton channel. Our simulations explain the gating mechanism and provide guidelines how to re-engineer the channel to act as a simple proton pump. In general, emergence of integral membrane proteins appears to be quite feasible and may be easier to envision than the emergence of water-soluble proteins.

Models, Chemical↗

Self-healing Growth of LaNiO 3 on a Mixed-Terminated Perovskite Surface

Developing atomic-scale synthesis control is a prerequisite for understanding and engineering the exotic physics inherent to transition-metal oxide heterostructures. Thus, far, however, the number of materials systems explored has been extremely limited, particularly with regard to the crystalline substrate, which is routinely SrTiO 3 . Here, we investigate the growth of a rare-earth nickelate-LaNiO 3 -on (LaAlO 3 )(Sr 2 AlTaO 6 ) (LSAT) (001) by oxide molecular beam epitaxy (MBE). Whereas the LSAT substrates are smooth, they do not exhibit the single surface termination usually assumed necessary for control over the interface structure. Performing both nonresonant and resonant anomalous in situ synchrotron surface X-ray scattering during MBE growth, we show that reproducible heterostructures can be achieved regardless of both the mixed surface termination and the layer-by-layer deposition sequence. The rearrangement of the layers occurs dynamically during growth, resulting in the fabrication of high-quality LaNiO 3 /LSAT heterostructures with a sharp and consistent interfacial structure. This is due to the thermodynamics of the deposition window as well as the nature of the chemical species at interfaces-here, the flexible charge state of nickel at the oxide surface. This has important implications regarding the use of a wider variety of substrates for fundamental studies on complex oxide synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Processing Methodology for Double Sensor Probe in a Bubbly Flow

Bubbly flow phenomenon is the most common flow pattern in nuclear plant system. In this paper, according to Hibiki and Bartel, the experiment was designed to observe the fluid conditions surrounding nuclear rod. In recent years, double sensor probe is one of the measuring techniques for the bubbly flow. It can measure local void fraction and bubble velocity. After mathematical statistical calculation, interfacial area concentration is obtained by Kataoka. The double sensor probe method, with the advantage for measuring local interfacial area concentration, has become widely used in many measurement methods. The paper of Liu and Zhao were referred to establish the post-processing for the raw data obtained from measuring instrument. After drawing the signal of the probe, it is important to analyze the raw data for the elimination of unnecessary noise signal and highlight the characteristic signal. Based on the same experimental condition, the different filtering methods, Simple Moving Average (SMA) and Gaussian average, were compared and discussed by the double sensor probe.

42 ENGINEERING↗

Predictive Engineering of Interfaces and Cathodes for High-Performance All Solid-State Lithium-Sulfur Batteries

The primary goal of this project is to leverage data-driven methods and machine learning strategies to develop accurate multi-physics models for all-solid-state Li-S battery (ASLSB) materials that can capture electrochemical and transport phenomena over atomic to mesoscopic length/timescales. These models will be rigorously validated by synthesis and advanced characterization experiments. The team will leverage the predictive power of these models, alongside synthesis/characterization experiments and battery fabrication to address longstanding issues at the electrode/electrolyte interfaces in ASLSBs. The project’s proposed technology involves the following: (1) halide-doped solid sulfide electrolytes that can concurrently provide high Li + ion conductivity and suppress dendrite growth; (2) novel mesoporous cathode composed of super-P and carbon nanotubes co-infiltrated with sulfur and sulfide electrolyte, which hold potential to allow high sulfur loading and optimal ion/electron pathways; and (3) functionalization of sulfide electrolyte with ionic liquids to improve physical contact and minimize impedance at the cathode/electrolyte interface. Successful development of proposed predictive models (at multiple scales) will bridge this knowledge gap and will advance fundamental understanding of reaction chemistry, kinetics, charge transfer, and dendrite growth at electrified SSIs. This will enable predictive design of effective strategies to mitigate interfacial problems in ASSLSBs, including poor interfacial contact, interfacial impedance to Li + ion transport, and poor electron/ion conduction within cathodes. Ultimately, the fundamental knowledge gained will lead to development of high-performance ASSLSBs.

25 ENERGY STORAGE↗

High-Pressure Lightweight Thrusters

Returning samples of Martian soil and rock to Earth is of great interest to scientists. There were numerous studies to evaluate Mars Sample Return (MSR) mission architectures, technology needs, development plans, and requirements. The largest propulsion risk element of the MSR mission is the Mars Ascent Vehicle (MAV). Along with the baseline solid-propellant vehicle, liquid propellants have been considered. Similar requirements apply to other lander ascent engines and reaction control systems. The performance of current state-ofthe- art liquid propellant engines can be significantly improved by increasing both combustion temperature and pressure. Pump-fed propulsion is suggested for a single-stage bipropellant MAV. Achieving a 90-percent stage propellant fraction is thought to be possible on a 100-kg scale, including sufficient thrust for lifting off Mars. To increase the performance of storable bipropellant rocket engines, a high-pressure, lightweight combustion chamber was designed. Iridium liner electrodeposition was investigated on complex-shaped thrust chamber mandrels. Dense, uniform iridium liners were produced on chamber and cylindrical mandrels. Carbon/carbon composite (C/C) structures were braided over iridium-lined mandrels and densified by chemical vapor infiltration. Niobium deposition was evaluated for forming a metallic attachment flange on the carbon/ carbon structure. The new thrust chamber was designed to exceed state-of-the-art performance, and was manufactured with an 83-percent weight savings. High-performance C/Cs possess a unique set of properties that make them desirable materials for high-temperature structures used in rocket propulsion components, hypersonic vehicles, and aircraft brakes. In particular, more attention is focused on 3D braided C/Cs due to their mesh-work structure. Research on the properties of C/Cs has shown that the strength of composites is strongly affected by the fiber-matrix interfacial bonding, and that weakening interface realizes pseudo-plastic behavior with significant increase in the tensile strength. The investigation of high-temperature strength of C/Cs under high-rate heating (critical for thrust chambers) shows that tensile and compression strength increases from 70 MPa at room temperature to 110 MPa at 1,773 K, and up to 125 MPa at 2,473 K. Despite these unique properties, the use of C/Cs is limited by its high oxidation rate at elevated temperatures. Lining carbon/carbon chambers with a thin layer of iridium or iridium and rhenium is an innovative way to use proven refractory metals and provide the oxidation barrier necessary to enable the use of carbon/ carbon composites. Due to the lower density of C/Cs as compared to SiC/SiC composites, an iridium liner can be added to the C/C structure and still be below the overall thruster weight. Weight calculations show that C/C, C/C with 50 microns of Ir, and C/C with 100 microns of Ir are of less weight than alternative materials for the same construction.

Holmes, Richard↗