Precise Control Of Composition Research Articles

Unveiling the Dynamic Electrocatalytic Activity of Online Synthesized Bimetallic Nanocatalysts via Electrochemiluminescence Microscopy.

Effective bimetallic nanoelectrocatalysis demands precise control of composition, structure, and understanding catalytic mechanisms. To address these challenges, we employ a two-in-one approach, integrating online synthesis with real-time imaging of bimetallic Au@Metal core-shell nanoparticles (Au@M NPs) via electrochemiluminescence microscopy (ECLM). Within 120 s, online electrodeposition and in situ catalytic activity screening alternate. ECLM captures transient faradaic processes during potential switches, visualizes electrochemical processes in real-time, and tracks catalytic activity dynamics at the single-particle level. Analysis using ECL photon flux density eliminates size effects and yields quantitative electrocatalytic activity results. Notably, a nonlinear activity trend corresponding to the shell metal to Au surface atomic ratio is discerned, quantifying the optimal surface component ratio of Au@M NPs. This approach offers a comprehensive understanding of catalytic behavior during the deposition process with high spatiotemporal resolution, which is crucial for tailoring efficient bimetallic nanocatalysts for diverse applications.

Utilizing Constant Energy Difference between sp-Peak and C 1s Core Level in Photoelectron Spectra for Unambiguous Identification and Quantification of Diamond Phase in Nanodiamonds.

The modification of nanodiamond (ND) surfaces has significant applications in sensing devices, drug delivery, bioimaging, and tissue engineering. Precise control of the diamond phase composition and bond configurations during ND processing and surface finalization is crucial. In this study, we conducted a comparative analysis of the graphitization process in various types of hydrogenated NDs, considering differences in ND size and quality. We prepared three types of hydrogenated NDs: high-pressure high-temperature NDs (HPHT ND-H; 0-30 nm), conventional detonation nanodiamonds (DND-H; ~5 nm), and size- and nitrogen-reduced hydrogenated nanodiamonds (snr-DND-H; 2-3 nm). The samples underwent annealing in an ultra-high vacuum and sputtering by Ar cluster ion beam (ArCIB). Samples were investigated by in situ X-ray photoelectron spectroscopy (XPS), in situ ultraviolet photoelectron spectroscopy (UPS), and Raman spectroscopy (RS). Our investigation revealed that the graphitization temperature of NDs ranges from 600 °C to 700 °C and depends on the size and crystallinity of the NDs. Smaller DND particles with a high density of defects exhibit a lower graphitization temperature. We revealed a constant energy difference of 271.3 eV between the sp-peak in the valence band spectra (at around 13.7 eV) and the sp3 component in the C 1s core level spectra (at 285.0 eV). The identification of this energy difference helps in calibrating charge shifts and serves the unambiguous identification of the sp3 bond contribution in the C 1s spectra obtained from ND samples. Results were validated through reference measurements on hydrogenated single crystal C(111)-H and highly-ordered pyrolytic graphite (HOPG).

Silicon solar cell efficiency improvement employing electrostatically assembled polyelectrolyte–quantum dot multilayers

Down-shifting (DS) has proven to be an effective technique to address thermalization losses in photovoltaic devices. It involves the modification of the incident solar spectrum by luminescent species to better suit solar cell’s optimal absorption regions. Despite the number of favorable characteristics of quantum dots (QDs) as DS materials, their incorporation into highly ordered close-packed films remains the major drawback of QD-based DS applications. This limitation can be overcome by the sequential integration of QDs into a multilayered film via the layer-by-layer assembly technique, that allows the precise control of composition and thickness. The experimental results discussed herein indicate that upon optimization employing a model-assisted design approach, the spectral response of a silicon solar cell benefits from the down-shifting and antireflection capabilities of the QD film, as evinced by their quantum efficiency. For the optimum design, the incorporation of QDs triggered an increment of 26.1% in the power conversion efficiency driven by an increase of 29.2% in the short circuit current density. The controlled assembly of QD multilayers offers unique opportunities in light harvesting for new hybrid photovoltaic technologies.

Coordinated regulation of phosphatidylinositol 4-phosphate and phosphatidylserine levels by Osh4p and Osh5p is an essential regulatory mechanism in autophagy

Macroautophagy (hereafter autophagy) is an intracellular degradative pathway in budding yeast cells. Certain lipid types play essential roles in autophagy; yet the precise mechanisms regulating lipid composition during autophagy remain unknown. Here, we explored the role of the Osh family proteins in the modulating lipid composition during autophagy in budding yeast. Our results showed that osh1-osh7∆ deletions lead to autophagic dysfunction, with impaired GFP-Atg8 processing and the absence of autophagosomes and autophagic bodies in the cytosol and vacuole, respectively. Freeze-fracture electron microscopy (EM) revealed elevated phosphatidylinositol 4-phosphate (PtdIns(4)P) levels in cytoplasmic and luminal leaflets of autophagic bodies and vacuolar membranes in all deletion mutants. Phosphatidylserine (PtdSer) levels were significantly decreased in the autophagic bodies and vacuolar membranes in osh4∆ and osh5∆ mutants, whereas no significant changes were observed in other osh deletion mutants. Furthermore, we identified defects in autophagic processes in the osh4∆ and osh5∆ mutants, including rare autophagosome formation in the osh5∆ mutant and accumulation of autophagic bodies in the vacuole in the osh4∆ mutant, even in the absence of the proteinase inhibitor PMSF. These findings suggest that Osh4p and Osh5p play crucial roles in the transport of PtdSer to autophagic bodies and autophagosome membranes, respectively. The precise control of lipid composition in the membranes of autophagosomes and autophagic bodies by Osh4p and Osh5p represents an important regulatory mechanism in autophagy.

Gas-phase self-assembly: Converting 2D graphitic carbon nitride into 1D nanotubes for improved photocatalytic tetracycline degradation

Achieving precise control and optimization of structure and composition is paramount for advancing photocatalyst performance. In this study, we successfully synthesized nitrogen-defect and boron-doped one-dimensional g-C3N4 nanotubes (BCNNT) with a tube diameter of approximately 100 nm using a one-step gas-phase self-assembly strategy. Intriguingly, the introduction of boric acid induced a transformation from a two-dimensional g-C3N4 structure to a one-dimensional tubular form. The physicochemical properties and photocatalytic performance of BCNNT were found to be influenced by the quantity of boric acid employed. The as-synthesized BCNNT exhibited notable advantages, including enhanced visible light absorption, a 0.1 eV reduction in the band gap, 5.1 times increase in photocurrent density, effective suppression of electron-hole recombination, and significant improvement in mass transfer compared to pure g-C3N4. Consequently, the first-order kinetic constant of BCNNT increased by 73.7 %, resulting in nearly 80 % degradation of tetracycline (TC) within half an hour. The boron doping played a crucial role in reducing the surface energy required for nanotube formation during synthesis, a key factor in their structural development. Both density functional theory (DFT) calculations and experimental studies confirmed that the Lewis acid site B enhanced tetracycline adsorption, while nitrogen-deficient sites suppressed electron-hole recombination, thus accelerating photocatalytic degradation rate. This research provides a novel perspective on fabricating tubular g-C3N4 structures and compositions, offering insights for improving the kinetics of photocatalytic reactions.

Electrochemical Redox Conversion of Formate to CO via Coupling Fe-Co Layered Double Hydroxides and Au Catalysts.

Formate has been considered an inactive molecule and thus cannot be further reduced under CO2 reduction conditions, which limits its widespread application as feedstock. Here we present an electrochemical redox conversion of formate to CO through the potential-dependent generation of carbon dioxide radical anions (CO2 ⋅- ) on Fe-Co layered double hydroxides (Fe-Co LDHs) and the subsequent reduction of CO2 ⋅- to CO on Au catalysts. We present an electrodeposition protocol for the synthesis of Fe-Co LDHs with precise composition control and find that Fe1 Co4 exhibits a promising potential window for CO2 ⋅- formation between 1.14 and 1.4 V and an optimized potential at 1.24 V at a neutral pH condition. We further determined the formation of CO2 ⋅- at 1.24 V via electron paramagnetic resonance and CO2 at >1.4 V through differential electrochemical mass spectrometry. This work provides a redox chemistry route for converting formate into CO through a coupled slit parallel-plate electrode system.

Electrochemical Additive Manufacturing of Binary and Ternary Alloys at the Mircon Scale by Electrohydrodynamic Redox 3D Printing

The need for miniaturisation throughout many different industries brings classical subtractive manufacturing techniques to their limits. Additive manufacturing is able to overcome these limits which has made it a topic of interest in many scientific fields. This additional geometric freedom becomes increasingly important if feature sizes on the micron- or even nano-scale are desired. Multiple different techniques to fabricate device-grade metals at such length-scales have been reported [1]. As one of these techniques, electrohydrodynamic redox printing (EHD-RP) has shown promise to be a versatile fabrication tool [2, 3, 4] depositing dense, pure metallic structures at high deposition rates.In this contribution, we present our work on additively manufactured alloys. First, we introduce a novel EHD-RP approach using aqueous metal salt electrolytes instead of sacrificial anodes as ion sources. The use of metal salts not only expands the range of manufacturable metals, but also enables the fabrication of metal alloys with precise compositional control without the need for additives or a surplus of the less noble metal. We demonstrate this control by fabricating binary and ternary Cu-Ag, Cu-Zn and Cu-Ag-Zn alloys. The composition of the fabricated alloy exactly mirrors the composition of the aqueous metal salt solutions. These systems were chosen as a representative immiscible and miscible system, in order to study different growth mechanisms. Microstructural analysis of Cu-Ag alloys reveals the formation of a metastable mixed phase. Cu-Ag alloys were successively dealloyed to produce nano-porous Ag structures. The compositional control over the Cu-Ag alloy enables precise control of porosity in the dealloyed structures. These nano-porous Ag structures have also been tested as substrates for surface enhanced Raman spectroscopy.(1) L. Hirt, A. Reiser, R. Spolenak & T. Zambelli, Adv. Mater 2017, 29, 1604211(2) A. Reiser, M. Lindén, P. Rohner, A. Marchand, H. Galinski, A. S. Sologubenko, J. M. Wheeler, R. Zenobi, D. Poulikakos & R. Spolenak, Nat. Comm. 2019, 10, 1853(3) M. Nydegger, A. Pruška, H. Galinski, R. Zenobi, A. Reiser & R. Spolenak, Nanoscale 2022, 14, 17418(4) M. Menétrey, L. Koch, A. Sologubenko, S. Gerstl, R. Spolenak & A. Reiser, Small 2022, 18, 2205302

Metal-Assisted Chemical etching for the direct synthesis of bimetallic Cu-Pd nanoparticles on silicon

An original study is presented for the synthesis of Cu100-xPdx nanoparticles directly on silicon by Metal Assisted Chemical Etching (MACE). CuPd is chosen as a representative bimetallic system on account of its interest and potential applications in catalysis and electrocatalysis, among others. The proposed methodology allows precise control of the nanoparticle bimetallic composition and structure. Thus, we demonstrate that Cu100-xPdx solid solutions and phase-separated nanoparticles can be synthesized at will by simply changing the deposition conditions. In-depth physical characterization of the synthesized material (structure, morphology, composition, oxidation state and d-band center position) is carried out by XRD, SEM-EDX and XPS. Finally, band bending simulations at the nanoscale in combination with electrochemical measurements help to interpret some of the peculiarities of the Pd, Cu and Cu100-xPdx deposits. The new method can be easily implemented, used for various silicon substrate geometries and extended to any bimetallic system whose metals are suitable for MACE of silicon.

Recent Developments in Atomic Layer Deposition of Functional Overlayers in Perovskite Solar Cells.

Over the last decade, research in organic-inorganic lead halide perovskite solar cells (PSCs) has gathered unprecedented momentum, putting the technology on the brink of full-scale commercialization. A wide range of strategies have been implemented for enhancing the power conversion efficiency of devices and modules, as well as improving stability toward high levels of irradiation, temperature, and humidity. Another key element in the path to commercialization is the scalability of device manufacturing, which requires large-scale deposition of conformal layers without compromising the delicate structure of the perovskite film. In this context, atomic layer deposition (ALD) tools excel in depositing high-quality conformal films with precise control of film composition and thickness over large areas at relatively low processing temperatures. In this commentary, we will briefly outline recent progress in PSC technology enabled by ALD tools, focusing on layers deposited above the absorber layer. These interlayers include charge transport layers, passivation layers, buffer layers, and encapsulation techniques. Additionally, we will discuss some of the challenges and potential avenues for research in PSC technology underpinned by ALD tools.

Ex Vivo Peptide Decoration Strategies on Stem Cell Surfaces for Augmenting Endothelium Interaction.

Ischemic vascular diseases remain leading causes of disability and death. Although various clinical therapies have been tried, reperfusion injury is a major issue, occurring when blood recirculates at the damaged lesion. As an alternative approach, cell-based therapy has emerged. Mesenchymal stem cells (MSCs) are attractive cellular candidates due to their therapeutic capacities, including differentiation, safety, angiogenesis, and tissue repair. However, low levels of receptors/ligands limit targeted migration of stem cells. Thus, it is important to improve homing efficacy of transplanted MSCs toward damaged endothelium. Among various MSC modulations, ex vivo cell surface engineering could effectively augment homing efficiency by decorating MSC surfaces with alternative receptors/ligands, thereby facilitating intercellular interactions with the endothelium. Especially, exogenous decoration of peptides onto stem cell surfaces could provide appropriate functional signaling moieties to achieve sufficient MSC homing. Based on their protein-like functionalities, high modularity in molecular design, and high specific affinities and multivalency to target receptors, peptides could be representative surface-presentable moieties. Moreover, peptides feature a mild synthetic process, enabling precise control of amino acid composition and sequence. Such ex vivo stem cell surface engineering could be achieved primarily by hydrophobic interactions of the cellular bilayer with peptide-conjugated anchor modules and by covalent conjugation between peptides and available compartments in membranes. To this end, this review provides an overview of currently available peptide-mediated, ex vivo stem cell surface engineering strategies for enhancing MSC homing efficiency by facilitating interactions with endothelial cells. Stem cell surface engineering techniques using peptide-based bioconjugates have the potential to revolutionize current vascular disease treatments while addressing their technical limitations.

Interfacial excess of solutes across phase boundaries using atom probe microscopy

Three-dimensional elemental mapping in atom probe microscopy provides invaluable insights into the structure and composition of interfaces in materials. Quasi-atomic resolution facilitates access to the solute decoration of grain boundaries, advancing the knowledge on local segregation and depletion phenomena. More recent developments unlocked three-dimensional mapping of the interfacial excess across grain boundaries. Such detailed understanding of the local structure and composition of these interfaces enabled advancements in processing methods and material development. However, many engineering alloys, such as Ni-based superalloys, have much more complex microstructures with various solutes and precipitates in close proximity to grain boundaries. The complex interaction of grain boundary segregation and grain boundary precipitates requires precise compositional control. However, abrupt changes in solute solubility across phase boundaries obscure the interfacial excess in proximity to grain boundaries.Therefore, this study provides a methodological framework of the quantitative characterization of phase boundaries in proximity to grain boundaries using atom probe microscopy. The detailed mass spectrum ranging of MC, M23C6, and M6C carbides is explored in order to achieve satisfactory compositional information. Proximity histograms and correlating concentration difference profiles determine the interface location, where a Gibbs dividing surface is not accessible. This enables reliable direct calculation of the interfacial excess across phase boundaries. Intuitively interpretable and quantitative ‘interface plots’ are introduced, and showcased for phase boundaries between γ-matrix, γ' precipitates, GB-γ', MC, M23C6, and M6C carbides. The presented framework advances access to the local composition in proximity to grain boundaries and may be applicable to other engineering alloys or materials with functional properties.

Modeling the impact of incomplete conformality during atomic layer processing

Atomic layer processing (ALP) is a modern fabrication technique for the deposition or etching of materials, which provides precise control of film thickness, composition, and conformality on a nanometer scale. This makes it crucial for the fabrication of high aspect ratio (HAR) structures, such as 3D NAND memory stacks, as its self-limiting nature provides enhanced conformality compared to traditional processes. However, as the number of NAND stacks grows and the aspect ratio continues to increase, deviations from full conformality can often occur due to precursor desorption from the surface. In this regard, a model for surface coverage during ALD in the presence of desorption, leading to incomplete conformality, has been developed and implemented in process simulation frameworks. This work is an extension of our previous research which concentrated on developing an accurate modeling approach for ALD in HAR structures (L.Aguinsky et al., Solid State Electron. 201, 2023). The model combines existing Knudsen diffusion and Langmuir kinetics methods and includes the Bosanquet formula for gas-phase diffusivity and reaction reversibility. It has been incorporated into academic and commercial level-set-based topography simulators. The parameters for the model have been calibrated using published results for the ALD of Al2O3 from trimethylaluminum (TMA) and H2O in HAR geometries. The temperature dependence of the H2O step is likewise analyzed, revealing an activation energy of 0.178eV, which is consistent with recent experiments. In the TMA step, the Bosanquet formula leads to improved accuracy, and the same parameter set is able to reproduce multiple experiments, demonstrating that the model parameters accurately capture reactor conditions. Finally, the developed model is combined with atomic layer etching (ALE) to simulate the controlled, conformal deposition of HfO2 inside HAR 3D NAND structures.

Relationship among intrinsic magnetic parameters and structure and crucial effect of metastable Fe3B phase in Fe-metalloid amorphous alloys

The intrinsic heterogeneity of an amorphous structure originates from composition, and the structure determines the magnetic properties and crystallization models of amorphous magnets. Based on classical Fe–B binary magnetic amorphous alloys, the relationship between the structure and magnetic properties was extensively studied. The stacking structure of Fe–B binary amorphous alloys exhibit discontinuous changes within the range of 74–87 at.% Fe. The structural feature can be expressed as Amor. Fe3B matrix + Fe atoms are transforming into Amor. Fe matrix + B atoms with the increase of Fe content. The solute atoms are uniformly distributed in the amorphous matrix holes, similar to a single-phase solid solution structure. The transition point corresponds to the eutectic crystallization model composition (Fe82B18 to Fe83B17). A high Fe content will amplify magnetic moment sensitivity to temperature. Under a given service temperature, the disturbance effect of magnetic moment self-spinning will offset the beneficial effect of increasing Fe content and induce the saturation magnetization (Ms) value to decrease. Binary amorphous Fe–B alloys obtain the maximum Curie temperature near 75 at.% Fe, which is slightly smaller than that of the corresponding metastable Fe3B phase, i.e., the amorphous short-range order structure maintains the highest similarity to the Fe3B phase. The chemical short-range ordering (SRO) structure of amorphous alloys exhibits heredity to corresponding (meta)stable crystal phases. The unique spatial orientation structure of the metastable Fe3B phase is the structural origin of the amorphous nature. This study can guide the composition design of Fe-metalloid magnetic amorphous alloys. The design of materials with excellent magnetic properties originates from a deep understanding of precise composition control and temperature disturbance mechanism.

Co-precipitation of M2B on ZrO2 in a Ni-base superalloy with B & Zr additions

Polycrystalline superalloys are high-performance materials with complex microstructures often affected by micro-alloying elements B, C, or Zr added to control mechanical properties during manufacturing and in-service. This requires precise compositional control and makes increasing recycling rates challenging. One example is Zr in scrap used for making René 41. Zr is incorporated due to comparably higher concentration in Waspaloy commonly mixed with René 41 scrap. Increasing recycling rates therefore requires a detailed understanding of the impact of Zr on the microstructure of superalloys. High B and High B&Zr variants of the Ni-based superalloy René 41 are compared using analytical electron microscopy, focused ion beam, and transmission electron microscopy techniques. We show that morphology and dispersion of C16-M2B borides are affected by Zr. C16-M2B, TiC, (Ti,Zr)C, and γ′ Ni3(Al,Ti) co-precipitate on m-ZrO2. The lattice mismatch between C16-M2B and m-ZrO2 is mitigated with an (012)ZrO2 || (200)M2B orientation relationship allowing epitaxial growth. This demonstrates how the C16-M2B morphology and dispersion is affected by Zr additions in polycrystalline superalloys.

Sol-gel synthesis control of iron-cobalt alloy/ferrite core/shell nanoparticles supported by a carbon medium with semi-hard magnetic features

We explore a simple and optimized approach for obtaining magnetic nanoparticle-carbon composites by a novel one-pot sol-gel method. In them, various metal cations ratios of Fe3+ and Co2+ are evaluated. The ratio of Fe:Co is a critical parameter that governs the presence of different crystalline phases with tailored magnetic properties. Interestingly, the smallest introduction of Co into the synthesis (19Fe:1Co) provides an abrupt emergence of the body-centered cubic (bcc) Fe-Co alloy, instead of the orthorhombic Pnma structure characteristic of the Fe3C intermetallic compound (1Fe:0Co). Advanced structural and electronic characterizations reveal the formation of Fe-Co/Co-ferrite core/shell nanoparticle structures embedded in a carbon matrix. The sphere-like nanoparticles range from 10 to 45 nm and the shells show a spinel structure with a thickness of 2–3 nm. In addition, X-ray absorption spectroscopy unveils that the oxidation state of Fe and Co cations is close to zero, demonstrating their predominant metallic character. The magnetic properties can be modulated by a precise control of the alloy composition varying the Co content, displaying saturation magnetization values close to ∼137 emu/g. The nanoparticles are mainly single magnetic domain with a considerable coercive field (∼450 Oe), higher than those reported in the literature for Fe-Co nanoparticles. This semi-hard character is due to a notable spring exchange effect emerged by passivating the surface of Fe-Co-bcc cores with a thin Co-ferrite-like shell.

Plasma-Enhanced Atomic Layer Deposition of Molybdenum Oxide Thin Films at Low Temperatures for Hydrogen Gas Sensing.

Molybdenum oxide thin films are very appealing for gas sensing applications due to their tunable material characteristics. Particularly, the growing demand for developing hydrogen sensors has triggered the exploration of functional materials such as molybdenum oxides (MoOx). Strategies to enhance the performance of MoOx-based gas sensors include nanostructured growth accompanied by precise control of composition and crystallinity. These features can be delivered by using atomic layer deposition (ALD) processing of thin films, where precursor chemistry plays an important role. Herein, we report a new plasma-enhanced ALD process for molybdenum oxide employing the molybdenum precursor [Mo(NtBu)2(tBu2DAD)] (DAD = diazadienyl) and oxygen plasma. Analysis of the film thickness reveals typical ALD characteristics such as linearity and surface saturation with a growth rate of 0.75 Å/cycle in a broad temperature window between 100 and 240 °C. While the films are amorphous at 100 °C, crystalline β-MoO3 is obtained at 240 °C. Compositional analysis reveals nearly stoichiometric and pure MoO3 films with oxygen vacancies present at the surface. Subsequently, hydrogen gas sensitivity of the molybdenum oxide thin films is demonstrated in a laboratory-scale chemiresistive hydrogen sensor setup at an operation temperature of 120 °C. Sensitivities of up to 18% are achieved for the film deposited at 240 °C, showing a strong correlation between crystallinity, oxygen vacancies at the surface, and hydrogen gas sensitivity.

Strongly Confined CsPbBr3 Quantum Dots as Quantum Emitters and Building Blocks for Rhombic Superlattices.

The success of the colloidal semiconductor quantum dots (QDs) field is rooted in the precise synthetic control of QD size, shape, and composition, enabling electronically well-defined functional nanomaterials that foster fundamental science and motivate diverse fields of applications. While the exploitation of the strong confinement regime has been driving commercial and scientific interest in InP or CdSe QDs, such a regime has still not been thoroughly explored and exploited for lead-halide perovskite QDs, mainly due to a so far insufficient chemical stability and size monodispersity of perovskite QDs smaller than about 7 nm. Here, we demonstrate chemically stable strongly confined 5 nm CsPbBr3 colloidal QDs via a postsynthetic treatment employing didodecyldimethylammonium bromide ligands. The achieved high size monodispersity (7.5% ± 2.0%) and shape-uniformity enables the self-assembly of QD superlattices with exceptional long-range order, uniform thickness, an unusual rhombic packing with an obtuse angle of 104°, and narrow-band cyan emission. The enhanced chemical stability indicates the promise of strongly confined perovskite QDs for solution-processed single-photon sources, with single QDs showcasing a high single-photon purity of 73% and minimal blinking (78% "on" fraction), both at room temperature.

Nanoscale membrane curvature sorts lipid phases and alters lipid diffusion

The precise spatiotemporal control of nanoscale membrane shape and composition is the result of a complex interplay of individual and collective molecular behaviors. Here, we employed single-molecule localization microscopy and computational simulations to observe single-lipid diffusion and sorting in model membranes with varying compositions, phases, temperatures, and curvatures. Supported lipid bilayers were created over 50-nm-radius nanoparticles to mimic the size of naturally occurring membrane buds, such as endocytic pits and the formation of viral envelopes. The curved membranes recruited liquid-disordered lipid phases while altering the diffusion and sorting of tracer lipids. Disorder-preferring fluorescent lipids sorted to and experienced faster diffusion on the nanoscale curvature only when embedded in a membrane capable of sustaining lipid phase separation at low temperatures. The curvature-induced sorting and faster diffusion even occurred when the sample temperature was above the miscibility temperature of the planar membrane, implying that the nanoscale curvature could induce phase separation in otherwise homogeneous membranes. Further confirmation and understanding of these results are provided by continuum and coarse-grained molecular dynamics simulations with explicit and spontaneous curvature-phase coupling, respectively. The curvature-induced membrane compositional heterogeneity and altered dynamics were achieved only with a coupling of the curvature with a lipid phase separation. These cross-validating results demonstrate the complex interplay of lipid phases, molecular diffusion, and nanoscale membrane curvature that are critical for membrane functionality.

Exploring the Formation Mechanism, Evolution Law, and Precise Composition Control of Interstitial Oxygen in Body-Centered Cubic Mo

Interstitial oxygen (O) on the formation mechanism and enrichment distribution of body-centered cubic (BCC) molybdenum (Mo) has rarely been reported, and the O usually can cause serious brittle fracture in Mo. In this paper, we studied the formation mechanism and evolution of oxygen (O) when it was precisely controlled in the range of 3700–8600 parts per million (wppm). It was found that, with an increase in O concentration, O element not only existed in the form of solid solution but generated O element with different valence states in Mo metal. Large amounts of MoO2, MoO3, and Mo4O11 intermediate oxides were identified by electron probe micro-analyzer (EPMA) and X-ray photoelectron spectroscopy (XPS). Thermodynamic calculations revealed the formation process of oxides, and authenticity of the presence of O was verified by XPS. Enrichment and distribution of O element were analyzed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and EPMA. Moreover, the compressive yield strength and hardness of Mo were greatly affected by O content range of 4500–8600 wppm. Our study is helpful to understand the behavior of interstitial impurity O in refractory Mo metals and provides important guidance for development of high-purity rare Mo metals.

Numerical modelling of in-situ alloying of Al and Cu using the laser powder bed fusion process: A study on the effect of energy density and remelting on deposited track homogeneity

In-situ alloying using laser powder bed fusion (LPBF) allows for formation of new alloys and complicated components with spatially controlled characteristics. A major issue in in-situ alloying is the macro-segregation of alloying elements, that results in chemical inhomogeneity. The precise control of composition is one of the most important steps in any effective in-situ alloying process. In this study, a mesoscale computational fluid dynamics (CFD) model for simulating single-tracks is developed to advance the in-depth understanding of in-situ alloying of dissimilar metals. Surface tension and recoil pressure driven flows at the free surface, rapid phase change, laser reflections, and other physical phenomena affecting the LPBF process have all been examined. Species conservation is used to trace the mixing of different metals. Simulations are performed by melting a layer of Al powder on a Cu substrate, and the impact of recoil pressure and Marangoni convection driven flows on Al-Cu mixing was addressed. The homogeneity of the simulated track is quantified by defining a mixing index. The effect of different laser energy densities and remelting on the homogeneity of the deposited track is investigated. Numerically, it was observed that the high thermal conductivity of both metals results in a sharp and short melt pool, and rapid solidification of such a melt pool generates a heterogeneous concentration dispersion. At high energy density, a low mixing index value is observed, indicating improved homogeneity in the deposited track. Furthermore, remelted tracks have a low mixing index value, indicating that remelting is an effective strategy for improving homogeneity. This study provides fundamental insights on the mixing of dissimilar metals and aims to support future research activities on the design and development of new alloys using LPBF process.