Effects during the cathode polarization of porous silicon.

The large inner surface of porous silicon (pSi) not only provides unique opportunities for introducing various foreign materials into the open pores, but is also responsible for a lot of processes during the pSi cathode polarization. PSi surface and contact effects are considered in the article. The space charge layer induced by both the surface states and the double electrical layer in the solution is shown to have a decisive influence on the electrical conductivity of the silicon skeleton in the pSi layer. Depending on the depletion degree of the pSi skeleton, the electrochemical deposition of metals is possible either on the entire pSi surface or pore filling from the bottom. The erbium hydroxide formation in the process of the cathode polarization of pSi in the solution of erbium salt is shown to have a chemical nature and is stimulated by the alkalization of the cathode space. The formation of erbium-containing deposits occurs by the following mechanism. First, hydrogen is electrochemically reduced at the cathode. This causes the ion imbalance and leads to the alkalinization in the space near the cathode. The alkaline medium creates conditions for the chemical process of the erbium hydroxide formation. Formed as a gel, erbium hydroxide is physically adsorbed on the cathode surface as a film. The components of the solution are necessarily included in the deposit composition. The accompanying oxidation and dehydrogenation effects during the cathode pSi polarization are considered. Moreover, during the pSi oxidation, the solid phase extends in the pore increases the steric factor, which is essential for the formation of internal oxygen bonds. These effects are characteristic features of any pSi cathode treatment. These formation rules are true for any lanthanide. The obtained results open wide prospects for practical application of Er-filled pSi as a promising material for practical biomedical application as prospective electrodes.

Triple Effects of the Physicochemical Interaction between Water and Copper and Their Influence on Microcutting.

Water has been recognized in promoting material removal, traditionally ascribed to friction reduction and thermal dissipation. However, the physicochemical interactions between water and the workpiece have often been overlooked. This work sheds light on how the physicochemical interactions that occur between water (H2O) and copper (Cu) workpiece influence material deformations during the cutting process. ReaxFF molecular dynamics simulations were employed as the primary method to study the atomistic physical and chemical interactions between the applied medium and the workpiece. Upon contact with the Cu surface, H2O dissociated into OH- ions, H+ ions, and traces of O2- ions. The OH- and O2- ions chemically reacted with Cu to form bonds that weakened the Cu-Cu bonds by elongation, while the H+ ions gained electrons and diffused into the Cu lattice as H- ions. The weakening of surface Cu bonds promoted plastic deformation and reduced the difficulty of material removal. Meanwhile, further addition of H2O molecules saw a plateau in hydrolysis and more dominance of H2O physical adsorption on Cu, which weakens the elongation of Cu-Cu bonds. While the ideal case for atomic-scale material removal was found with an optimal number of 240 H2O molecules, the presented Cu material state with more H2O molecules could account for the observations in microcutting. The constricted nature of physical adsorption and hydrogen ion diffusion in the surface layer prevented the propagation of dislocations through the surface, which subsequently caused pinning points to be closer together during chip formation as observed by smaller chip fold widths on the microscale. Theoretical and experimental analysis identified the importance of accounting for physicochemical interactions between surface media and the workpiece when considering material deformations at micronanoscale.

Size and Surface Properties of Functionalized Organosilica Particles Impact Cell-Particle Interactions Including Mitochondrial Activity.

Understanding of the interactions between macrophages and multifunctional nanoparticles is important for development of novel macrophage-based immunotherapies. Here, we investigated the effects of fluorescent thiol-organosilica particle size and surface properties on cell-particle interactions, including mitochondrial activity, using the mouse macrophage cell line J774A.1. Three different sizes of thiol-organosilica particles (150, 400, and 680 nm in diameter) containing fluorescein (OS/F150, OS/F400, and OS/F680) and particles surface functionalized with polyethylenimine (PEI) (OS/F150PEI, OS/F400PEI, and OS/F680PEI) were prepared. Flow cytometric analysis, time-lapse imaging, and single-cell analysis of particle uptake and mitochondrial activity of J774A.1 cells demonstrated variations in uptake and kinetics depending on the particle size and surface as well as on each individual cell. Cells treated with OS/F150 and OS/F150PEI showed higher uptake and mitochondrial activity than those treated with other particles. The interaction between endosomes and mitochondria was observed using 3D fluorescent imaging and was characterized by the involvement of iron transport into mitochondria by iron-containing proteins adsorbed on the particle surface. Scanning electron microscopy of the cells treated with the particles revealed alterations in cell membrane morphology, depending on particle size and surface. We performed correlative light and electron microscopy combined with time-lapse and 3D imaging to develop an integrated correlation analysis of particle uptake, mitochondrial activity, and cell membrane morphology in single macrophages. These cell-specific characteristics of macrophages against functional particles and their evaluation methods are crucial for understanding the immunological functions of individual macrophages and developing novel immunotherapies.

Dynamic stability of the euler nanobeam subjected to inertial moving nanoparticles based on the nonlocal strain gradient theory.

This research studied the dynamic stability of the Euler-Bernoulli nanobeam considering the nonlocal strain gradient theory (NSGT) and surface effects. The nanobeam rests on the Pasternak foundation and a sequence of inertial nanoparticles passes above the nanobeam continuously at a fixed velocity. Surface effects have been utilized using the Gurtin-Murdoch theory. Final governing equations have been gathered implementing the energy method and Hamilton's principle alongside NSGT. Dynamic instability regions (DIRs) are drawn in the plane of mass-velocity coordinates of nanoparticles based on the incremental harmonic balance method (IHBM). A parametric study shows the effects of NSGT parameters and Pasternak foundation constants on the nanobeam's DIRs. In addition, the results exhibit the importance of 2T-period DIRs in comparison to T-period ones. According to the results, the Winkler spring constant is more effective than the Pasternak shear constant on the DIR movement of nanobeam. So, a 4 times increase of Winkler and Pasternak constants results in 102 % and 10 % of DIR movement towards higher velocity regions, respectively. Furthermore, the effect of increasing nonlocal and material length scale parameters on the DIR movement are in the same order regarding the magnitude but opposite considering the motion direction. Unlike nonlocal parameter, an increase in material length scale parameter shifts the DIR to the more stable region.

Ligand-induced hollow binary metal-organic framework derived Fe-doped cobalt-carbon nanomaterials for oxygen evolution.

There is significant anticipation for high-efficiency and cost-effective non-precious metal-based catalysts to advance the industrial application of the anodic oxygen evolution reaction (OER) for hydrogen production. This study introduces an efficient strategy that utilizes ligand-induced metal-organic framework (MOF) building blocks for the synthesis of hollow binary zeolitic imidazolate frameworks 67 (ZIF-67) and Prussian blue analogues (PBAs) (ZIF-67@PBA) heterostructures through a hybrid MOF-on-MOF approach. Manipulating the Co2+/Zn2+ ratio in the precursor ZIF-67 allows for the convenient synthesis of the final product, denoted as CoxFe-ZP, after pyrolysis, where the inclusion of Zn effectively modulates the distribution of Co in the catalyst. The resulting CoxFe-ZP catalysts exhibit a positive synergistic effect between hollow graphitic carbon nanomaterials and Fe-doped Co nanoparticles. The optimal Co0.3Fe-ZP catalyst demonstrates satisfactory OER performance, achieving an overpotential of 302 mV at 10 mA cm-2 and a small Tafel slope of 60.0 mV dec-1. Further analysis of the activation energy confirms that the enhanced OER activity of Co0.3Fe-ZP can be reasonably attributed to the combined influence of its morphology and composition. This study demonstrates a ligand-induced method for examining the morphology and electrochemical properties of grown binary MOF-on-MOF heterostructures for OER applications.

Effective oxidation and adsorption of As(III) in water by nanoconfined Ce-Mn binary oxides with excellent reusability.

Herein, a highly efficient As(III) purifier Ce-Mn@N201 with excellent reusability was developed by stepwise precipitating hydrated cerium(IV) oxides (HCO) and hydrated manganese(IV) oxides (HMO) inside N201, a widely-used gel-type anion exchange resin. Owing to confinement of unique nanopores in N201, the in-situ generated nanoparticles (NPs) inside Ce-Mn@N201 were highly dispersed with ultra-small sizes of around 2.6 nm. Results demonstrated that HMO NPs effectively oxidized As(III) to As(V) with the conversion of Mn(IV) to Mn(II), while the generated Mn2+ was mostly re-adsorbed onto the negatively-charged surface of HMO NPs. During the regeneration process by simple alkaline treatment, the re-adsorbed Mn2+ was firstly precipitated as (hydr)oxides of Mn(II) and then oxidized to HMO NPs by dissolved oxygen to fully refresh its oxidation capacity. Though HCO NPs mainly served as adsorbent for arsenic, they could partially oxidize As(III) to As(V) at the beginning, while the oxidation capacities continuously diminished with the irreversible conversion of Ce(IV) to Ce(III). In 10 consecutive adsorption-regeneration cycle, Ce-Mn@N201 efficiently decontaminated As(III) from 500 µg/L to below 5 µg/L with Mn2+ leaching less than 0.3% per batch. During 3 cyclic fixed-bed adsorptions, Ce-Mn@N201 steadily produced 8500-9150 bed volume (BV) and 3150-3350 BV drinkable water from the synthesized and real groundwater, respectively, with Mn leaching in effluent constantly < 100 µg/L.

High Breakthrough Pressure in Hydrogels Enabled Ultrastable Treatment of Hypersaline Wastewaters.

Surface effects of low-surface-tension contaminants accumulating at the evaporation surface easily induce wetting in membrane distillation, especially in hypersaline scenarios. Herein, we propose a novel strategy to eliminate the surface effect and redistribute contaminants at the evaporation interface simply by incorporating a layer of hydrogel. The as-fabricated composite membrane exhibits remarkable stability, even when exposed to solution with salt concentration of 5 M and surfactant concentration of 8 mM. Breakthrough pressure of the membrane reaches 20 bar in the presence of surfactants, surpassing commercial hydrophobic membranes by one to two magnitudes. Density functional theory and molecular dynamics simulations reveal the important role of the hydrogel-surfactant interaction in suppressing the surface effect. As a proof of concept, we demonstrate the membrane in stably processing synthetic wastewater containing 144 mg L-1 surfactants, 1 g L-1 mineral oils, and 192 g L-1 NaCl, showing its potential in addressing challenges of hypersaline water treatment.

Interfacial and intrinsic molecular effects on the phase separation/transition of heteroprotein condensates.

Liquid-liquid phase separation (LLPS) and droplet formation by LLPS are key concepts used to explain compartmentalization in living cells. Protein contact to a membrane surface is considered an important process for protein organization in a liquid phase or during transition to a solid or liquid dispersion state. The direct experimental comprehensive investigation is; however, not performed on the surface-droplet interaction and phase transition. In the present study, we constructed simple and reproducible experiments to analyze the structural transition of aggregates and droplets in an ovalbumin (OVA) and lysozyme (LYZ) complex on glass slides with various coatings. The difference in droplet-surface interaction may only be important in the boundary region between aggregates and droplets of a protein mixture, as shown in the phase diagram. Co-aggregates of OVA-LYZ changed to droplet-like circular forms during incubation. In contrast, free l-lysine resulted in the uniform droplet-to-solid phase separation at lower concentrations and dissolved any structures at higher concentrations. These results represent the first phase-diagram-based analysis of the phase transition of droplets in a protein mixture and a comparison of surface-surface and small molecular-droplet structure interactions.

Surface Effect of Thickness-Dependent Polarization and Domain Evolution in BiFeO3 Epitaxial Ultrathin Films.

With the trend of device miniaturization, ultrathin ferroelectric films are gaining more and more attention. However, understanding ferroelectricity in this nanoscale context remains a formidable challenge, primarily due to the heightened relevance of surface effects, which often leads to the loss of net polarization. Here, the influence of surface effects on the polarization as a function of thickness in ultrathin BiFeO3 films is investigated using phase-field simulations. The findings reveal a notable increase in ferroelectric polarization with increasing thickness, with a particularly discernible change occurring below the 10 nm threshold. Upon accounting for surface effects, the polarization is marginally lower than the case without such considerations, with the disparity becoming more pronounced at smaller thicknesses. Moreover, the hysteresis loop and butterfly loop of the ultrathin film were simulated, demonstrating that the ferroelectric properties of films remain robust even down to a thickness of 5 nm. Our investigations provide valuable insights into the significance of ferroelectric thin films in device miniaturization.

Soft Carbon as Cathode with High Rate Performance for Dual-Ion Batteries via Fast PF6 - Intercalation Improved by Surface Effect.

Dual-ion battery is a new type of battery in which both anions and cations participate in the energy storage process. However, this unique battery configuration imposes high requirements on the cathode, which typically presents a poor rate performance due to the sluggish diffusion dynamics and intercalation reaction kinetics of anions. Herein, we report petroleum coke-based soft carbon as the cathode for dual-ion batteries, exhibiting a superior rate performance with a specific capacity of 96 mAh g-1 at a rate of 2 C and 72 mAh g-1 remained even at 50 C. In situ XRD and Raman demonstrate that the anions can directly form lower-stage graphite intercalation compounds during the charge process owing to the surface effect, skipping the long evolutionary process from higher to lower stage, thus significantly improving the rate performance. This study highlights the impact of the surface effect and provides a promising perspective for dual-ion batteries.

Characterization and biofouling potential analysis of two cyanobacterial strains isolated from Cape Verde and Morocco.

Cyanobacteria are new sources of value-added compounds but also ubiquitous and harmful microfoulers on marine biofouling. In this work, the isolation and identification of two cyanobacterial strains isolated from Cape Verde and Morocco, as well as their biofilm-forming ability on glass and Perspex under controlled hydrodynamic conditions, were performed. Phylogenetic analysis revealed that cyanobacterial strains isolated belong to Leptothoe and Jaaginema genera (Leptothoe sp. LEGE 181153 and Jaaginema sp. LEGE 191154). From quantitative and qualitative data of wet weight, chlorophyll a content and biofilm thickness obtained by optical coherence tomography, no significant differences were found in biofilms developed by the same cyanobacterial strain on different surfaces (glass and Perspex). However, the biofilm-forming potential of Leptothoe sp. LEGE 181153 proved to be higher compared with Jaaginema sp. LEGE 191154, particularly at the maturation stage of biofilm development. Three-dimensional biofilm images obtained from confocal laser scanning microscopy showed different patterns between both cyanobacterial strains and also among the two surfaces. Because standard methodologies to evaluate cyanobacterial biofilm formation, as well as two different optical imaging techniques, were used, this work also highlights the possibility of integrating different techniques to evaluate a complex phenomenon like cyanobacterial biofilm development.

Effects on the Titanium Implant Surface by Different Hygiene Instrumentations: A Narrative Review.

Peri-implant disease is usually caused by the accumulation of dental biofilm around the implant, and this biofilm can irradiate the gingiva tissue, which leads to inflammation and, more severely, to a deterioration of the bone structure. There is a concern regarding the removal of biofilm from the implant surface by using different hygiene instruments. Some hygiene instruments may have some effect on the dental implant surface, resulting in roughening or damage to the implant surfaces. This study reviewed the effects of titanium implant surfaces on different hygiene instruments. A literature search was conducted from PubMed, ScienceDirect, and Scopus databases for articles published from 1992 to 2021. A total of 19 full-text papers with keywords of interest that met all the eligibility criteria were selected. Surface roughness was evaluated with a scanning electron microscope and also using a profilometer, laser scanning, scanning probe, and atomic force microscopes. A metal curette produced a roughened surface on the titanium implant, but a plastic curette did not alter the surface. Instrumentation with rubber cups left the surface unchanged and appeared to smoothen the surface, whereas the air-powder abrasive instrumentation altered the surface with the presence of micro pits and pores. A conventional metal ultrasonic scaler showed significant surface topographical changes and scratches on both titanium surfaces, as a diode laser, light-emitting diode (LED), and laser treatment did not show any alteration on the rough and smooth titanium surfaces. Thus, a non-metallic instrument such as a plastic curette, rubber cups, and novel technology including diode laser, LED, and laser treatment is appropriate and can be used for debridement on smooth and machined titanium implant surfaces as well as sandblasted and acid-etched (SLA), titanium plasma-sprayed (TPS), and resorbable blasted media (RBM) surfaces. The use of metallic instruments should be avoided, and it is not recommended.

Shear Horizontal Surface Waves in a Layered Piezoelectric Nanostructure with Surface Effects.

This work aims to provide a fundamental understanding on the dispersive behaviors of shear horizontal (SH) surface waves propagating in a layered piezoelectric nanostructure consisting of an elastic substrate and a piezoelectric nanofilm by considering the surface effects. Theoretical derivation based on the surface piezoelectricity model was conducted for this purpose, and analytic expressions of the dispersion equation under the nonclassical mechanical and electrical boundary conditions were obtained. Numerical solutions were given to investigate the influencing mechanism of surface elasticity, surface piezoelectricity, surface dielectricity, as well as the surface density upon the propagation characteristics of SH surface waves, respectively. The results also reveal the size-dependence of dispersive behaviors, which indicates that the surface effects make a difference only when the thickness of the piezoelectric nanofilm stays in a certain range.

Nonsingular Stress Distribution of Edge Dislocations near Zero-Traction Boundary.

Among many types of defects present in crystalline materials, dislocations are the most influential in determining the deformation process and various physical properties of the materials. However, the mathematical description of the elastic field generated around dislocations is challenging because of various theoretical difficulties, such as physically irrelevant singularities near the dislocation-core and nontrivial modulation in the spatial distribution near the material interface. As a theoretical solution to this problem, in the present study, we develop an explicit formulation for the nonsingular stress field generated by an edge dislocation near the zero-traction surface of an elastic medium. The obtained stress field is free from nonphysical divergence near the dislocation-core, as compared to classical solutions. Because of the nonsingular property, our results allow the accurate estimation of the effect of the zero-traction surface on the near-surface stress distribution, as well as its dependence on the orientation of the Burgers vector. Finally, the degree of surface-induced modulation in the stress field is evaluated using the concept of the L2-norm for function spaces and the comparison with the stress field in an infinitely large system without any surface.

Analytic formulation of elastic field around edge dislocation adjacent to slanted free surface.

Explicit and tractable formulation of the internal stress field around edge dislocations is indispensable for considering the mechanics of fine crystalline solids, because the motion of edge dislocations in a slanted direction with respect to the free surface often plays a vital role in the plastic deformation of the solids under loading. In this study, we formulated an analytical solution for the stress distribution that occurs around edge dislocations embedded in a semi-infinite elastic medium. This formulation is based on the image force method and the Airy stress function method; it describes the variation in the stress distribution with changes in the slanted angle between the traction-free flat surface of the medium and the Burgers vector of the edge dislocation. Furthermore, our analytical solution shows that the attractive force acting on the edge dislocation due to the presence of the free surface is always perpendicular to the surface, regardless of the relative angle of the Burgers vector with the surface.

Carbon fibre-supported hierarchical NiCo layered double hydroxide nanosheets as non-enzymatic glucose sensors for sport drinks and serum.

We report a systematic study of carbon fibre (CF)-supported NiCo layered double hydroxide nanosheets (LDHNs) with and without heat treatment at 200 and 400 °C (CF-NiCo LDHN200 and CF-NiCo oxide nanoparticles (NPs), respectively) as catalysts and sensors for glucose oxidation reactions (GORs). Tafel measurements for the GORs showed that the exchange current density of CF-NiCo LDHN was 1.91 × 10-3 mA·cm-2 at an early rest potential of -0.422 V. This was markedly higher than those of CF-NiCo LDHN200 (1.22 × 10-3 mA·cm-2 at - 0.352 V) and CF-NiCo oxide NP (1.18 × 10-3 mA·cm-2 at -0.327 V). The electron transfer number and Tafel slopes suggested that the glucose dehydrogenation step and one-electron release occurred first in the GORs. Amperometric measurements revealed high recoveries (101.92% and 98.92%) and low relative standard deviations (1.98% and 2.34%) for the determination of glucose using the CF-NiCo LDHN in sports drink samples and human serum.

Operando surface science methodology reveals surface effect in charge storage electrodes.

Surface and interface play critical roles in energy storage devices, calling for operando characterization techniques to probe the electrified surfaces/interfaces. In this work, surface science methodology, including electron spectroscopy and scanning probe microscopy, has been successfully applied to visualize electrochemical processes at operating electrode surfaces in an Al/graphite model battery. Intercalation of anions together with cations is directly observed in the surface region of a graphite electrode with tens of nanometers thickness, the concentration of which is one order higher than that in bulk. An intercalation pseudocapacitance mechanism and a double specific capacity in the electrode surface region are expected based on the super-dense intercalants and anion/cation co-intercalation, which are in sharp contrast to the battery-like mechanism in the electrode bulk. The distinct electrochemical mechanism at the electrode surface is verified by performance tests of real battery devices, showing that a surface-dominant, nanometer-thick graphite cathode outperforms a bulk-dominant, micrometer-thick graphite cathode. Our findings highlight the important surface effect of working electrodes in charge storage systems.

Effect of Nanopores on Mechanical Properties of the Shape Memory Alloy.

Nanoporous Shape Memory Alloys (SMA) are widely used in aerospace, military industry, medical and health and other fields. More and more attention has been paid to its mechanical properties. In particular, when the size of the pores is reduced to the nanometer level, the effect of the surface effect of the nanoporous material on the mechanical properties of the SMA will increase sharply, and the residual strain of the SMA material will change with the nanoporosity. In this work, the expression of Young's modulus of nanopore SMA considering surface effects is first derived, which is a function of nanoporosity and nanopore size. Based on the obtained Young's modulus, a constitutive model of nanoporous SMA considering residual strain is established. Then, the stress-strain curve of dense SMA based on the new constitutive model is drawn by numerical method. The results are in good agreement with the simulation results in the published literature. Finally, the stress-strain curves of SMA with different nanoporosities are drawn, and it is concluded that the Young's modulus and strength limit decrease with the increase of nanoporosity.

Photoluminescence of Fully Inorganic Colloidal Gold Nanocluster and Their Manipulation Using Surface Charge Effects.

Fully inorganic, colloidal gold nanoclusters (NCs) constitute a new class of nanomaterials that are clearly distinguishable from their commonly studied metal-organic ligand-capped counterparts. As their synthesis by chemical methods is challenging, details about their optical properties remain widely unknown. In this work, laser fragmentation in liquids is performed to produce fully inorganic and size-controlled colloidal gold NCs with monomodal particle size distributions and an fcc-like structure. Results reveal that these NCs exhibit highly pronounced photoluminescence with quantum yields of 2%. The emission behavior of small (2-2.5 nm) and ultrasmall (<1 nm) NCs is significantly different and dominated by either core- or surface-based emission states. It is further verified that emission intensities are a function of the surface charge density, which is easily controllable by the pH of the surrounding medium. This experimentally observed correlation between surface charge and photoluminescence emission intensity is confirmed by density functional theoretical simulations, demonstrating that fully inorganic NCs provide an appropriate material to bridge the gap between experimental and computational studies of NCs. The presented study deepens the understanding of electronic structures in fully inorganic colloidal gold NCs and how to systematically tune their optical properties via surface charge density and particle size.

Neutron and X-ray Diffraction Analysis of Macro and Phase-Specific Micro Residual Stresses in Deep Rolled Duplex Stainless Steels.

Experimental analyses of depth distributions of phase-specific residual stresses after deep rolling were carried out by means of laboratory X-ray diffraction and neutron diffraction for the two duplex steels X2CrNiMoN22-5-3 and X3CrNiMoN27-5-2, which differ significantly in their ferrite to austenite ratios. The aim of the investigation was to elucidate to which extent comparable results can be achieved with the destructive and the non-destructive approach and how the process induced phase-specific micro residual stresses influence the determination of the phase- and {hkl}-specific reference value d0, required for evaluation of neutron strain scanning experiments. A further focus of the work was the applicability of correction approaches that were developed originally for single-phase materials for accounting for spurious strains during through surface neutron scanning experiments on coarse two-phase materials. The depth distributions of macro residual stresses were separated from the phase-specific micro residual stresses. In this regard, complementary residual stress analysis was carried out by means of incremental hole drilling. The results indicate that meaningful macro residual stress depth distributions can be determined non-destructively by means of neutron diffraction for depths starting at about 150-200 µm. Furthermore, it was shown that the correction of the instrumental surface effects, which are intrinsic for surface neutron strain scanning, through neutron ray-tracing simulation is applicable to multiphase materials and yields reliable results. However, phase-specific micro residual stresses determined by means of neutron diffraction show significant deviations to data determined by means of lab X-ray stress analysis according to the well-known sin2ψ-method.