Surface Gradient Research Articles

Clickable Plastic Surfaces with Controllable Azide Surface Density

AbstractThis study investigates the surface functionalization of plastic substrates through dip‐coating in azide‐functionalized polymer solutions, followed by a click reaction (i.e., strain‐promoted azide–alkyne cycloaddition). Acrylic, poly(ethylene terephthalate) (PET), and nylon substrates are dip‐coated with a series of polymers containing various azide groups grafted onto the poly(methyl methacrylate‐co‐hydroxyethyl methacrylate) backbone to examine structural effects on the surface density of clickable azide groups. X‐ray photoelectron spectroscopy and fluorescence spectroscopy confirm the subsequent click‐immobilization of cycloalkyne‐tagged fluorescein, which is quantified to calculate the surface density of clickable azide groups. Further investigations demonstrate that the surface density of azide groups can be controlled by manipulating the polymer ratio during dip‐coating, thus enabling the preparation of a linear surface gradient in terms of azide group density. Finally, the microcontact printing (µCP) method is employed to pattern the functionalized surfaces and quantify the functional molecules immobilized on the surface by µCP. This study highlights the adaptability of click chemistry and polymer coating techniques for the advanced functionalization of plastic surfaces for materials science and engineering applications.

Exploring mechanisms of asymmetric droplet impact dynamics on roughness gradient surface

Droplet impact on surfaces with varying roughness and wettability is a common phenomenon in both natural and industrial environments. While previous studies have primarily examined asymmetric droplet rebound driven by impact velocity or Weber number, the influence of surface structure and associated impact mode transitions has received less attention. In this study, molecular dynamics simulations and detailed analyses are employed to investigate the mechanisms governing droplet rebound on nanopillar arrays with gradient distributions. Results reveal that nanopillar height significantly influences rebound direction, with two distinct directional transitions occurring as the height increases. Additionally, the effects of surface structure and Weber number on impact patterns, rebound velocity, and contact time are systematically evaluated, with contact angle calculations shedding light on the underlying force mechanisms. A phase diagram is developed to illustrate the relationship between rebound direction, Weber number, and nanopillar height. The study further extends the analysis to substrates with bidirectional gradient distributions, demonstrating consistency with single-directional gradient results and validating the broader applicability of the findings. This research provides critical insights into droplet dynamics on roughness gradient surfaces, emphasizing the role of nanopillar height and impact mode in controlling droplet behavior and highlighting potential applications in the design of structured array surfaces.

Synthesis, Crystal Structure, Intermolecular Interactions, HOMO-LUMO, MEP, NLO Properties, and DFT/TD-DFT Investigation of (Z)-5-(4-Nitrobenzylidene)-3-N(3-Chlorophenyl)-2-Thioxothiazolidin-4-One

A novel heterocyclic compound named (Z)-5-(4-nitrobenzylidene)-3-N(3-chlorophenyl)-2-thioxothiazolidin-4-one (NCTh) was synthesized and analyzed using various techniques, including single crystal X-ray diffraction, FT-IR, UV-Vis, NMR spectroscopy, and mass spectral data methods. NCTh was observed to crystallize in the triclinic crystal system P-1 space group. To validate the experimental findings, density functional theory (DFT) calculations were performed using the B3LYP functional with the 6-311 G(d,p) basis set. The results indicated good agreement in geometrical parameters between the experimental and theoretical outcomes. The study also calculated HOMO-LUMO energies, molecular electrostatic potential (MEP), and global chemical reactivity descriptors to evaluate the compound’s reactivity. Additionally, the study conducted reduced density gradient and Hirshfeld surface analyses to reveal attractive, repulsive, and van der Waals strong and weak interactions. The calculation of thermodynamic parameters was also included. The study focused on investigating the nonlinear optical (NLO) properties of NCTh, which were characterized through key parameters such as the electric dipole moment (µ), polarizability (α), first-order hyperpolarizability (β), and second-order hyperpolarizability (γ). These properties provide insights into the material’s potential applications in optical and photonic technologies. Additionally, a molecular docking study was performed to further explore the structure-activity relationship, particularly in a biological context. The docking results revealed a strong ligand-protein interaction, with a binding energy of −10.3 kcal/mol, indicating significant affinity. Moreover, the inhibition constant (Ki) was calculated to be 0.0281 μM, suggesting a highly potent interaction, which could be relevant for drug design or biochemical applications.

Shape optimization for high efficiency metasurfaces: theory and implementation

Complex non-local behavior makes designing high efficiency and multifunctional metasurfaces a significant challenge. While using libraries of meta-atoms provide a simple and fast implementation methodology, pillar to pillar interaction often imposes performance limitations. On the other extreme, inverse design based on topology optimization leverages non-local coupling to achieve high efficiency, but leads to complex and difficult to fabricate structures. In this paper, we demonstrate numerically and experimentally a shape optimization method that enables high efficiency metasurfaces while providing direct control of the structure complexity through a Fourier decomposition of the surface gradient. The proposed method provides a path towards manufacturability of inverse-designed high efficiency metasurfaces.

Investigation of Mechanical Properties and Microstructural Evolution in Pure Copper with Dual Heterostructures Produced by Surface Mechanical Attrition Treatment

Heterostructured materials consist of heterogeneous zones with dramatic variations in mechanical properties, and have attracted extensive attention due to their superior performance. Various heterostructured materials have been widely investigated in recent years. In the present study, a combination of two different types of heterogeneous structures, a surface bimodal structure and gradient structure, was designed using the traditional surface mechanical attrition treatment (SMAT) method in pure copper, and the mechanical properties and microstructural evolution of dual-heterostructure Cu were studied in depth. In total, 100 stainless steel balls with a diameter of 6 mm were utilized to impact the specimen surface at room temperature for a short period of time. In this work, the sample surface was divided into hard areas and soft areas, along with a roughly 90 μm gradient structure in the cross-sectional direction after 30 s of SMAT processing. After the partial SMAT processing, lasting 30 s, the strength increased to 158.0 MPa and a considerable ductility of 25.7% was sustained, which overcomes the strength–ductility trade-off. The loading–unloading–reloading (LUR) test was utilized to measure the HDI stress, and the result showed that the HDI stress of the partial SMAT sample was much higher than the annealed one, especially for the Cu-SMAT-30S specimen, the strength of which increased from 80.4 MPa to 153.8 MPa during the tensile test. An in situ digital image correlation (DIC) investigation demonstrated that the strain developed stably in the Cu-SMAT-10S specimen. Furthermore, electron backscatter diffraction (EBSD) was carried out to study the microstructural evolution after partial SMAT processing; the KAM value increased to 0.34 for the Cu-SMAT-10S specimen. This research provides insights for the effective combination of superior strength and good ductility in dual-heterostructure materials.

High-Efficiency Microwave Wireless Power Transmission via Reflective Phase Gradient Metasurfaces and Surface Wave Aggregation.

Microwave Wireless Power Transfer (MWPT) technology is crucial for emergency power supply during natural disasters and powering off-grid equipment. Traditional antenna arrays, however, suffer from low energy capture efficiency, difficult impedance matching, complex synthetic networks, and intricate manufacturing processes. This paper introduces a microwave energy receiver design utilizing Reflective Phase Gradient Metasurfaces (R-PGMs) and surface wave energy convergence technology. The design leverages the effective plane wave-to-surface wave conversion capability of R-PGMs to transform incident microwave energy into a surface wave mode, which is then efficiently harvested using a circular energy convergence array before being output to a coupling port. By optimizing R-PGM parameters, an ideal 60° phase gradient distribution is achieved, facilitating the focus of surface wave energy via dispersion characteristics. These components are integrated into a hybrid antenna array, complemented by a matched energy output port structure. Numerical simulations show that this array can efficiently convert microwave energy from plane waves to surface waves, achieving a conversion efficiency of 85.32% and a collection efficiency of 68.26%. Experimental results corroborate these findings, with peak energy collection efficiency reaching 64.68% at 5.8 GHz and an RF-DC conversion efficiency of 42%, confirming the design's efficacy. Compared to conventional methods, this design simplifies the system by avoiding complex combining networks and significantly enhances the efficiency of microwave MWPT.

Persistently active El Niño–Southern Oscillation since the Mesozoic

The El Niño-Southern Oscillation (ENSO), originating in the central and eastern equatorial Pacific, is a defining mode of interannual climate variability with profound impact on global climate and ecosystems. However, an understanding of how the ENSO might have evolved over geological timescales is still lacking, despite a well-accepted recognition that such an understanding has direct implications for constraining human-induced future ENSO changes. Here, using climate simulations, we show that ENSO has been a leading mode of tropical sea surface temperature (SST) variability in the past 250 My but with substantial variations in amplitude across geological periods. We show this result by performing and analyzing a series of coupled time-slice climate simulations forced by paleogeography, atmospheric CO2 concentrations, and solar radiation for the past 250 My, in 10-My intervals. The variations in ENSO amplitude across geological periods are little related to mean equatorial zonal SST gradient or global mean surface temperature of the respective periods but are primarily determined by interperiod difference in the background thermocline depth, according to a linear stability analysis. In addition, variations in atmospheric noise serve as an independent contributing factor to ENSO variations across intergeological periods. The two factors together explain about 76% of the interperiod variations in ENSO amplitude over the past 250 My. Our findings support the importance of changing ocean vertical thermal structure and atmospheric noise in influencing projected future ENSO change and its uncertainty.

Coherent turbulent flow structure under plunging breaker on movable grain bed simulated by 3D DEM-MPS method

ABSTRACT Breaking waves transport momentum, gas, and sediment vertically. Recent particle image velocimetry (PIV) measurements have elucidated the coherent vortex and turbulence structures under breaking waves. However, clarifying three-dimensional fluid motion under breaking waves with PIV remains challenging. Although particle methods have performed wave-breaking simulations, they have never been validated through velocity distributions for breaking waves above movable sediment beds. This study simulated the sediment transport process under plunging waves using a 3D Lagrangian fluid-particle mixture model. The investigation focuses on the first wave plunging for a fundamental investigation. Our simulation shows the instantaneous velocity distributions at different wave phases, which agree with the PIV measurement. A physically-based turbulence extraction method is introduced: a numerical filter based on the coherence between the water elevation and horizontal velocity. Visualized three-dimensional vortex and turbulence structures are consistent with previous studies. The transport equation of the kinetic turbulence energy investigates the turbulence budget near the bed surface and emphasizes the negative contribution of the fluid-particle interaction. Our findings show that a contribution of the pressure gradient to offshore sediment transport. The pressure gradient is difficult to correlate to the water surface gradient and is derived from the large vortex induced by the plunging wave.

Evolution of Graded Surface Microstructure and Property of Ti6Al4V Threads Processed by Surface Rolling

The surface rolling process is important for the forming property of titanium alloy bolts. This study systematically investigated the evolution of the surface microstructure and property of Ti6Al4V threads induced by surface rolling processes with different feeding times. Gradient surface microstructure and property, as characterized by the depth-dependent variations of refined and deformed grains and hardness, were revealed. A comparative analysis of the microstructure and property of the topmost and subsurface layers in different characteristic areas (root, flank, and crest) of the thread was specifically carried out. The surface microstructure and properties are highly heterogeneous in different areas of the rolled thread. Meanwhile, a gradient microstructure and hardness along the depth from the surface was revealed in the surface layer. Our results showed that the highly heterogeneous surface microstructure and property can be attributed to the close correlation between the different stress/strain levels at different depths from the surface and the different deformation mechanisms in the characteristic surface areas of the thread. The present study has indicated that the distinctive microstructure and property in the different characteristic areas of the rolled thread should be featured by those of surface layers at different depths.

Optimizing crucible geometry to improve the quality of AlN crystals by the physical vapor transport method

In the conventional crucible structure for AlN crystal growth by physical vapor transport, owing to the long molecular transport path of Al vapor and the disruption of the gas flow by the presence of a deflector, the Al vapor easily forms polycrystals in the growth domain. The result is increased internal stress in the crystals and increased difficulty in growing large-sized crystals. On this basis, with the help of finite element simulations, a novel crucible structure is designed. This crucible not only optimizes the gas transport but also increases the radial gradient of the AlN crystal surface, making the enhanced growth rate in the central region more obvious. The thermal stresses between the deflector and the crystal are also reduced. High-quality AlN crystals with an FWHM of 79 arcsec were successfully grown with this structure, verifying the accuracy of finite element simulation of the growth of AlN crystals. Our work has important guiding significance for the growth of high-quality AlN crystals.

Gradient Functionalization of Poly(lactic acid)-Based Materials with Polylysine for Spatially Controlled Cell Adhesion.

The development of biomaterials with gradient surface modification capable of spatially controlled cell adhesion and migration is of great importance for tissue engineering and regeneration. In this study, we proposed a method for the covalent modification of PLA-based materials with a cationic polypeptide (polylysine, PLys) via a thiol-ene click reaction carried out under a light gradient. With this aim, PLA-based films were fabricated and modified with 2-aminoethyl methacrylate (AEMA) as a double bond source. The latter was introduced by reacting pre-formed and activated surface carboxyl groups with the amino group of AEMA. The success of the modification was confirmed by 1H NMR, Raman and X-ray photoelectron spectroscopy data. A further photoinduced thiol-ene click reaction in the presence of a photosensitive initiator as a radical source was further optimized using cysteine. For grafting of PLys via the thiol-ene click reaction, PLys with a terminal thiol group was synthesized by ring-opening polymerization using Cys(Acm) as an amine initiator. Deprotection of the polypeptide resulted in the formation of free thiol groups of Cys-PLys. Successful gradient grafting of Cys-PLys was evidenced by covalent staining with the fluorescent dye Cy3-NHS. In addition, PLys gradient-dependent adhesion and migration of HEK 293 cells on PLys-PLA-based surfaces was confirmed.

Analytical Evaluation of Ground State Gradients in Quantum Electrodynamics Coupled Cluster Theory.

Analytical gradients of potential energy surfaces play a central role in quantum chemistry, allowing for molecular geometry optimizations and molecular dynamics simulations. In strong coupling conditions, potential energy surfaces can account for strong interactions between matter and the quantized electromagnetic field. In this paper, we derive expressions for the ground state analytical gradients in quantum electrodynamics coupled cluster theory. We also present a Cholesky-based implementation for the coupled cluster singles and doubles model. We report timings to show the performance of the implementation and present optimized geometries to highlight cavity-induced molecular orientation effects in strong coupling conditions.

Long range self-transport of liquid droplets driven by electric field and roughness gradient

It is well known that roughness and charge gradients could be used for droplet self-transport. The key issue is how to synergize the two effects. The uniform density charge can form linearly increasing charge gradient on a roughness gradient surface. Under this condition, the influence on the droplet self-transport under the synergy of these two effects was obtained by statics analysis, and the driving function was presented. An energy equation was constructed to study the conditions for crossing periodic boundaries, and the problem of distance limitation on periodic surfaces due to energy dissipation was solved by converting electric potential into droplet kinetic energy. A periodic roughness gradient surface with K = 0.07 was designed and prepared via 3D printing. Water droplets can be transported over long distances and the maximum velocity increases with charge density up to 46 mm/s. Finally, the effect of different structures on the maximum charge density in the Cassie state was investigated by simulation. The biomimetic structures exhibit great compressive stability, which can increase the surface charge density of droplets in the Cassie state by 3.6 times compared to pillar structures. It can be widely used in the fields of materials science and interface chemistry, etc.

Measurement and Analysis of Surface Temperature Gradients on Magnetron Sputtered Thin Film Growth Studied Using NiCr/NiSi Thin Film Thermocouples.

In the general analysis of thin-film growth processes, it is often assumed that the temperature of the film growth surface is the same as the temperature of the film growth substrate. However, a temperature gradient exists between the film growth surface and film growth substrate. Using the growth surface of TiO2 thin films as an example, the temperature gradient of the film growth surface is tested and analyzed. A NiCr/NiSi thin-film thermocouple is fabricated using the direct-current pulse magnetron sputtering method. A three-layer NiCr/NiSi thin-film thermocouple temperature measurement system is established to measure the temperature gradient of the film growth surface. The growth surface temperature and substrate temperature of the TiO2 thin films are measured. For a sputtering power density of 0.83W cm- 2, the temperature difference between the first and second layers is 104.79°C, while the temperature difference between the second and third layers is 39.92°C. A standard K-type thermocouple is used to measure the substrate temperature, which is recorded to be 132.05°C, consistent with common measurements of substrate temperature. The heat conduction on the film growth surface in the vacuum chamber is examined and a model for the temperature measurement device during film growth is constructed.

A unified structure-preserving parametric finite element method for anisotropic surface diffusion

We propose and analyze a unified structure-preserving parametric finite element method (SP-PFEM) for the anisotropic surface diffusion of curves in two dimensions ( d = 2 ) (d=2) and surfaces in three dimensions ( d = 3 ) (d=3) with an arbitrary anisotropic surface energy density γ ( n ) \gamma (\boldsymbol {n}) , where n ∈ S d − 1 \boldsymbol {n}\in \mathbb {S}^{d-1} represents the outward unit vector. By introducing a novel unified surface energy matrix G k ( n ) \boldsymbol {G}_k(\boldsymbol {n}) depending on γ ( n ) \gamma (\boldsymbol {n}) , the Cahn-Hoffman ξ \boldsymbol {\xi } -vector and a stabilizing function k ( n ) : S d − 1 → R k(\boldsymbol {n}):\ \mathbb {S}^{d-1}\to {\mathbb R} , we obtain a unified and conservative variational formulation for the anisotropic surface diffusion via different surface differential operators, including the surface gradient operator, the surface divergence operator and the surface Laplace-Beltrami operator. A SP-PFEM discretization is presented for the variational problem. In order to establish the unconditional energy stability of the proposed SP-PFEM under a very mild condition on γ ( n ) \gamma (\boldsymbol {n}) , we propose a new framework via local energy estimate for proving energy stability/structure-preserving properties of the parametric finite element method for the anisotropic surface diffusion. This framework sheds light on how to prove unconditional energy stability of other numerical methods for geometric partial differential equations. Extensive numerical results are reported to demonstrate the efficiency and accuracy as well as structure-preserving properties of the proposed SP-PFEM for the anisotropic surface diffusion with arbitrary anisotropic surface energy density γ ( n ) \gamma (\boldsymbol {n}) arising from different applications.

Vertical heterogeneity enhances network complexity and stability of co-occurrence microbes in the eastern Indian Ocean

Microbes are core to driving biogeochemical cycles and differ between sun-drenched surface and relatively dark deep oceans. However, their distinct contributions to the organization and association of communities are still remaining elusive. Here, their assembly and co-occurrence stability are systematically researched along the surface and vertical gradients in the eastern Indian Ocean. The distribution of surface microbes was grouped tightly with closer phylogenetic distance and broader niche breadth, and separately from those vertical samples. Clear distance-decay of community similarity was observed in surface microbes with lower richness, while more diverse microeukaryotes and prokaryotes were observed in surface and vertical environments, respectively. Co-occurrence microbes along vertical gradients had a more complex network that was dominated by prokaryotes, while exhibited a lower modularity compared to the surface network. Microbial associations along vertical gradients were more stable and resilient, with lower robustness, higher vulnerability, and a relatively consistent fragmentation. Moreover, prokaryotes contribute greatly to the network topology and stability compared to microeukaryotes in surface environments, emphasizing their distinct functions and survival strategies in maintaining community stability across spatial variations. Environmental selection and community differentiation led to the divergence in organization and potential function of microbes. This study shed light on new perspectives on how marine microbes were associated with and influenced by spatial heterogeneity and their distinct roles in community organization in the face of environmental fluctuations.

Downstream Control on the Stability of River Bifurcations

AbstractRiver bifurcations are prevalent features in both gravel‐bed and sand‐bed fluvial systems, including braiding networks, anabranches and deltas. Therefore, gaining insight into their morphological evolution is important to understand the impact they have on the adjoining environment. While previous investigations have primarily focused on the influence on bifurcation morphodynamics by upstream channels, recent research has highlighted the importance of downstream controls. In particular, in the case of rivers, current linear stability analyses for a simple bifurcation are unable to capture the stabilizing effect of branches length unless a confluence is added downstream. In this work, we introduce a novel theoretical model that effectively accounts for the effects of downstream branch length in a single bifurcation. To substantiate our findings, a series of fully 2D numerical simulations are carried out to test different branches lengths. Results from linear stability analysis show that bifurcation stability increases as the branches length decreases. These results are confirmed by the numerical simulations, which also show that, as the branch length tends to vanish, bifurcations are invariably stable. Finally, our results interestingly reveal that when a source of asymmetry, such as a free surface gradient or channel area advantage, is present at the node, there are scenarios in which the less‐favored branch becomes dominant over the hydraulically favored branch.

Facilitating water droplet removal from surfaces using air flow and wettability gradients

A new method is proposed to mitigate ice accretions on wind turbine blades via the creation of a microstructural gradient surface geometry that facilitates spontaneous water droplet motion along the surface. The wettability gradients are formed by laser etching 35 μm wide, 35 μm deep channels into aluminum to form a surface with a gradually increasing solid area fraction. Different design variations are then proposed and systematically evaluated on the merits of their performance. An analytical model is also derived based on a balance of hysteresis and drag forces to predict the critical airspeed necessary for droplet movement as a function of the droplet size and surface contact angle. Experimentation has shown good agreement with the model for both the baseline and fixed-pitch channel surfaces and has also demonstrated that, in certain cases, up to 70 % lower critical airspeeds are needed to initiate droplet motion on these microstructured surfaces.

Plasma Etching Constructs Step Gradient Surface Conductivity to Improve the Insulation Properties of Epoxy Resin

Plasma Etching Constructs Step Gradient Surface Conductivity to Improve the Insulation Properties of Epoxy Resin

Disentangling the Impacts of Environmental Factors on Evaporative Fraction Across Climate Regimes

AbstractEvaporative fraction (EF) is a useful measure for quantifying land surface energy partitioning processes and determining evaporative regimes; however, its influencing factors remain highly uncertain. Here, global data sets were compiled to disentangle the effects of environmental variables on EF variations along climate and land surface gradients. We found that (a) at annual timescales, ecosystem‐level EF could be expressed as a power law function of aridity index. The relationships of mean annual soil water content (SWC) and leaf area index (LAI) with mean annual EF resembled the traditional evaporative regime theory; (b) at daily timescales, the boosted regression tree method quantitatively revealed that the impacts of environmental variables (including meteorological variables) on EF showed equal importance, especially at humid sites, primarily due to the different response direction and magnitude of latent heat (LE) and sensible heat (H) fluxes to environmental changes. Particularly, the contrasting responses of LE (positive) and H (negative) to SWC, LAI, and relative humidity enhanced the positive effects of those influencing variables on EF; whereas, the correlations between EF and energy‐related factors (i.e., net radiation‐Rn and air temperature‐Ta) deteriorated as both LE and H showed positive response patterns to those variables; (c) meteorological factors were also found to have nonlinear effects on daily EF, further modified by climatic conditions. Rn near 150 W/m2 and Ta near 15°C appeared to be important energy‐partitioning thresholds at drier and humid sites, respectively. Moreover, changing interactions among environmental variables with climates were demonstrated to be important for better explaining EF variations.