Metal Substrate Research Articles

Interface Effects in the Stability of 2D Silica, Silicide, and Silicene on Pt(111) and Rh(111).

Ultrathin two-dimensional silica films have been suggested as highly defined conductive models for fundamental studies on silica-supported catalyst particles. Key requirements in this context are closed silica films that isolate the gas phase from the underlying metal substrate and stability under reaction conditions. Here, we present silica bilayer films grown on Pt(111) and Rh(111) and characterize them by scanning tunneling microscopy and X-ray photoelectron spectroscopy. We provide the first report of silica bilayer films on Rh(111) and have further successfully prepared fully closed films on Pt(111). Interestingly, surface and interface silicide phases play a decisive role in both cases: On platinum, closed films can be stabilized only when silicon is deposited in excess, which results in an interfacial silicide or silicate layer. We show that these silica films can also be grown directly from a surface silicide phase. In the case of rhodium, the silica phase is less stable and can be reduced to a silicide in reductive environments. Though similar in appearance to the "silicene" phases that have been controversially discussed on Ag(111), we conclude that an interpretation of the phase as a surface silicide is more consistent with our data. Finally, we show that the silica film on platinum is stable in 0.8 mbar CO but unstable at elevated temperatures. We thus conclude that these systems are only suitable as model catalyst supports to a limited extent.

Development of a Janus radiative cooler using a versatile fabrication process

Radiative cooling is a passive heat dissipation technique that emits thermal radiation to outer space through the atmosphere window. A radiative cooler has one side facing the sky, and the other side extracts heat from hot targets. Excellent cooling performance of a cooler can be archived via broadband absorption on one side and wavelength-selective emission on the other side like a Janus structure. However, Janus radiative coolers are usually constructed with complicated structures that take tremendous effort and costly facility. This work thus proposes an alternative Janus radiative cooler, which can be fabricated using a versatile and cost-effective fabrication technique, the electrophoretic deposition. The same setup and procedure can deposit chitosan and carbon black thin films on each side of a metallic substrate to achieve dual functionality. Five measurement units were constructed, and fabricated samples were placed on the top surface of each. The cooler successfully lowered the heater temperature inside the unit. Temperature reduction of 5.6 °C and 0.2 °C can be achieved respectively during daytime and nighttime with the proposed cooler compared to the case without thin film depositions. The repeatability of results was validated, and numerical modeling was conducted to exhibit thermal fields. The proposed cooler is promising in diminishing energy demand as well as carbon emissions while taking cost-effectiveness, feasibility, and simplicity into consideration.

Investigation of structure, morphology, and corrosion behavior of carboxylic acids/hydroxyapatite/chitosan coatings on Ti discs for implants

Titanium (Ti) and its alloys are widely used in bone defect repair owing to their advantages, including high strength, corrosion resistance, and biocompatibility. The formation of a stable oxide layer on Ti implants enhances the osseointegration process. Nevertheless, additional progress is required to improve the incorporation of these implants at the microscopic and nanoscopic levels to achieve a biocompatible interface. The main objective of this study was to enhance the morphology of hydroxyapatite and the corrosion resistance of Ti implants by applying hydroxyapatite/chitosan (HA/Cs) nanocomposite coatings embedded with carboxylic acids. The coatings were fabricated by electrodeposition, wherein various acid concentrations (acrylic and acetic acids) were employed as Cs electrolyte solvents to enhance the adhesion and bond strength with the titanium metal substrate. The microstructures of the HA/Cs coatings were analyzed using X-ray diffraction. The results demonstrated that the structure of HA was affected by the type of acid used and its concentration as the crystallinity increased with a high concentration of acrylic acid. Additionally, the morphology of HA/Cs was analyzed using a transmission electron microscope. The results showed that the morphology of HA/Cs changed from a hexagonal rod-like shape with acrylic acid samples into a needle-like shape in acetic acid samples. The corrosion behavior was investigated using electrochemical impedance spectroscopy (EIS) in a simulated body fluid (SBF) at 37±2ºC. The EIS results showed a high corrosion resistance with phase angles close to −80° and high impedance values of 80.5 kΩ cm2 with a high concentration of acrylic acid. These results indicated the formation of a highly adhesive and stable film on the implants in the test solution. In conclusion, based on this study and our previous work, the corrosion resistance, good biocompatibility, and biomineralization properties of the prepared HA/Cs-coated Ti recommend it as an alternative implant for clinical applications.

Surface engineering of aerospace aluminium alloys: Understanding alloying effects on chemical pre-treatment and sol-gel coating adhesion

The sol–gel process is a chemical surface preparation method based on hydrolysis and polycondensation reactions for enhanced adhesion for metallic substrates in adhesive bonding and coating applications. This paper describes an investigation into the effect of the microstructural complexity of two commonly used aerospace aluminium alloys (AAs) 2024-T3 and 7075-T6, on the response to different surface pre-treatments before deposition of the sol-gel coating and subsequent adhesive bonding.Different surface pre-treatments, including two abrasive treatments and three chemical surface pre-treatments were used, and their effect on surface chemistry, wettability and roughness was assessed. Surfaces were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry and static contact angles. A hybrid silane sol-gel film was deposited on the differently pre-treated aluminium alloys, an epoxy adhesive was applied and the adhesion properties were evaluated using pull-off testing. The role of the altered physicochemical properties of the pre-treated surfaces was related to the adhesion strength of the sol–gel reinforced epoxy/aluminium interfaces.The microstructural complexity of the aerospace alloys caused non-uniform responses to the pre-treatments, proving the importance of compatibility between material and treatment conditions. Statistical analysis revealed that, despite that overall higher adhesion values were obtained on rougher surfaces, only a strong correlation exists between the surface hydroxyl fraction and adhesion strength. The relation of roughness and water contact angle to interfacial adhesion was found to be non-significant.The findings of this study underscore the critical role of surface pre-treatments and their impact on adhesion strength in aerospace aluminium alloys, providing valuable insights for the effective utilization of sol-gel coatings in adhesive bonding and coating processes.

Enhancement of laser ablation via high-frequency electromagnetic induction heating

The efficiency of pulsed laser ablation has always been the focus point of research. A novel high-frequency electromagnetic induction heating-assisted laser ablation scheme is proposed and investigated to enhance the efficiency and improve the surface processing quality during the nanosecond laser ablation of metal substrates. To reduce laser energy required to reach the ablation threshold of metal, this method utilizes the electromagnetic induction to rapidly elevate substrate temperature, making the metal easier to be ablated. The results show that ablation width increases 16% and ablation depth increases 31% with the assistance of electromagnetic induction heating at a laser fluence of 1.32 J/cm2, which increases 90% of the laser-ablated volume. Meanwhile, the surface ablation quality is significantly improved due to the smaller temperature gradient around the ablation region. This new method has great potentials in the laser micromachining at a higher processing efficiency and better laser-processed surface quality.

Self-healing and corrosion-sensing multifunctional coatings containing pH-sensitive TiO2-based composites

Polyelectrolyte-encapsulated nanocontainers can effectively respond to changes of pH and thus control the on-demand release of corrosion inhibitors. A pH-responsive release system (Phen-Tpp@MTNs-PDDA) was developed based on the cationic polyelectrolyte poly dimethyl diallyl ammonium chloride (PDDA) encapsulated mesoporous TiO2 nanocontainers (MTNs) loaded with 1,10-phenanthroline (Phen) and tripolyphosphate ions (Tpp) corrosion inhibitors. The epoxy coating (EP) embedded with Phen-Tpp@MTNs-PDDA (Phen-Tpp@MTNs-PDDA/EP) demonstrates superior self-healing properties and confers long-term protection on the metal substrate through the cooperative effect of Phen and Tpp. Simultaneously, this hybrid coating is endowed with corrosion sensing capability based on the color development originating from the interaction of Phen and carbon steel. This self-healing and corrosion-sensing multifunctional coating provides an effective strategy for the corrosion protection of metals.

Peristome‐mimetic Surfaces Fabricated by Nanosecond Laser for Uni‐directional Liquid Spreading

Unidirectional liquid transport, which operates without external energy input, has garnered remarkable interests in the global energy sector. A crucial breakthrough in this field involves understanding how liquids spread on the peristome surface of Nepenthes alata. This study, inspired by the microstructural traits of the Nepenthes peristome, has brought about the development of a biomimetic surface on metal substrates using nanosecond laser processing on inclined bases. This process replicates the natural peristome’s microstructure, which allows for controlled liquid spread on the surface. The research also examines how wettability influences unidirectional liquid spread. Additionally, it involves adjusting the microstructure parameters on the biomimetic surface, which leads to variations in edge curvature and microcavity wedge angles. More importantly, this study comprehensively investigates the relationship between these structural changes and the phenomenon of unidirectional liquid transport. The findings suggest that altering edge curvature and micro‐cavity wedge angles can manage the directional spread of liquids. The optimized surface, with ideal curvature and wedge angles, achieves liquid movement speeds up to 12.03mm/s. This represents a notable improvement, 2.2 and 2.7 times faster than the original structure, respectively. These findings provides valuable insight into the design of energy‐independent unidirectional liquid spreading surfaces on metal substrates.This article is protected by copyright. All rights reserved.

Novel Penetrated Nucleation Mechanism for Controlled Synthesis of 2D Materials on Metal Substrates

Abstract2D materials have attracted considerable attention in the past decades for their unique properties, making the understanding of their nucleation process key to effective synthesis. Traditional explanations of thin‐film growth, focusing on the competition between atom interactions at the interface and within layers, often fall short of explaining real experimental results. Herein, a penetrated nucleation mechanism is proposed for 2D materials growth on metal substrates, taking into account the role of metal substrate atoms. This approach leads to a better understanding of how the surface shape evolves in two specific ways during growth in real experimental findings. Supported by detailed first‐principles simulations of boron on metal substrates and thermodynamic analyses of other studies involving metals and nonmetals, the above‐proposed mechanism is validated. Moreover, a broad strategy for growing large‐scale 2D materials on metal surfaces without creating undesired alloy layers is also presented, by adjusting the interfacial interactions by surface passivation, validated by existing experiments.

Growth of Single Crystalline 2D Materials beyond Graphene on Non-metallic Substrates.

The advent of 2D materials has ushered in the exploration of their synthesis, characterization and application. While plenty of 2D materials have been synthesized on various metallic substrates, interfacial interaction significantly affects their intrinsic electronic properties. Additionally, the complex transfer process presents further challenges. In this context, experimental efforts are devoted to the direct growth on technologically important semiconductor/insulator substrates. This review aims to uncover the effects of substrate on the growth of 2D materials. The focus is on non-metallic substrate used for epitaxial growth and how this highlights the necessity for phase engineering and advanced characterization at atomic scale. Special attention is paid to monoelemental 2D structures with topological properties. The conclusion is drawn through a discussion of the requirements for integrating 2D materials with current semiconductor-based technology and the unique properties of heterostructures based on 2D materials. Overall, this review describes how 2D materials can be fabricated directly on non-metallic substrates and the exploration of growth mechanism at atomic scale.

Effect of metallic substrate and rubber elastic materials over passive constrained layer damping on tool vibration during boring process

Tool vibration is a key factor that affects surface finish, generates noise, and reduces the tool life during conventional boring because of the excessive overhanging length of the tool holder. The interaction between the dynamics of the machine tool and the boring process led to progressive vibration. The creation of appropriate mechanisms in reducing tool vibration will help manufacturing industries to become more productive. In this research, in order to control vibration in the overhanging boring bar, a passive vibration control method was employed. Constrained layer dampers consist of boring bar, substrate, and elastic materials and it is used to minimize tool vibration produced during boring operation. The investigation utilized computational analysis through the ANSYS Workbench platform, employing key parameters such as the overhanging length of the tool holder (100, 150, and 200 mm), substrate material (aluminum, brass, and copper), and elastic material (Nitrile rubber, Natural rubber, and polyurethane). A comprehensive series of 27-run boring experiments were conducted to assess the impact of the constrained layer damper on tool vibration and cutting properties. The results of the study revealed remarkable improvements in various performance metrics. The constrained layer damper demonstrated an impressive 98% reduction in tool vibration, signifying its efficacy in dampening vibrational forces during the boring operation. Furthermore, a substantial 83% decrease in surface roughness was observed, indicating enhanced machining precision and surface finish. The constrained layer damper also exhibited a noteworthy 97.5% reduction in tool wear, highlighting its ability to significantly prolong tool life under challenging machining conditions.

Toward the Production of Super Graphene.

The quality requirements of graphene depend on the applications. Some have a high tolerance for graphene quality and even require some defects, while others require graphene as perfect as possible to achieve good performance. So far, synthesis of large-area graphene films by chemical vapor deposition of carbon precursors on metal substrates, especially on Cu, remains the main way to produce high-quality graphene, which has been significantly developed in the past 15 years. However, although many prototypes are demonstrated, their performance is still more or less far from the theoretical property limit of graphene. This review focuses on how to make super graphene, namely graphene with a perfect structure and free of contaminations. More specially, this study focuses on graphene synthesis on Cu substrates. Typical defects in graphene are first discussed together with the formation mechanisms and how they are characterized normally, followed with a brief review of graphene properties and the effects of defects. Then, the synthesis progress of super graphene from the aspects of substrate, grain size, wrinkles, contamination, adlayers, and point defects are reviewed. Graphene transfer is briefly discussed as well. Finally, the challenges to make super graphene are discussed and a strategy is proposed.

Ferromagnetic Order in 2D Layers of Transition Metal Dichlorides.

Magnetism in two dimensions is traditionally considered an exotic phase mediated by spin fluctuations, but far from collinearly ordered in the ground state. Recently, 2D magnetic states have been discovered in layered van der Waals compounds. Their robust and tunable magnetic state by material composition, combined with reduced dimensionality, foresee a strong potential as a key element in magnetic devices. Here, a class of 2D magnets based on metallic chlorides is presented. The magnetic order survives on top of a metallic substrate, even down to the monolayer limit, and can be switched from perpendicular to in-plane by substituting the metal ion from iron to nickel. Using functionalized STM tips as magnetic sensors, local exchange fields are identified, even in the absence of an external magnetic field. Since the compounds are processable by molecular beam epitaxy techniques, they provide a platform with large potential for incorporation into current devicetechnologies.

Ca/P in situ introduction for enhancing coating biocompatibility via plasma electrolytic oxidation in low-temperature molten salt

Plasma electrolytic oxidation (PEO) is one of the most promising methods for synthesizing ceramic coatings on metallic substrates. Recently, PEO in molten salt electrolytes was found to be advantageous due to overcoming system heating and the formation of contaminants. However, the PEO in molten salt was conducted at a high temperature (Tm∼220 °C), limiting the introduction of different components such as Ca and P. This study realizes the employment of a low-temperature electrolyte based on a ternary eutectic system of Ca(NO3)2–NaNO3–KNO3 (Tm∼130 °C) jointly with the in situ introduction of Ca/P in the form of ammonium dihydrogen phosphate (ADP). The surface morphology, phase and chemical composition, wettability, and anti-corrosion performance were examined. The results indicate improved surface performance with the addition of 1 wt% ADP to the electrolyte. This surface preferably comprises the anatase phase of TiO2 and exhibits enhanced biocompatibility and corrosion resistance in a biological environment.

Hemocompatibility and Preangiogenic Attributes of SiBxCyNzOm Coatings for Biomedical Applications.

In current clinical practices related to orthopedics, dental, and cardiovascular surgeries, a number of biomaterial coatings, such as hydroxyapatite (HAp), diamond-like carbon (DLC), have been used in combination with metallic substrates (stainless steel, Ti6Al4V alloy, etc.). Although SiBCN coatings are widely explored in material science for diverse applications, their potential remains largely unexplored for biomedical applications. With this motivation, the present work reports the development of SiBxCyNzOm coatings on a Ti6Al4V substrate, employing a reactive radiofrequency (RF) magnetron sputtering technique. Three different coating compositions (Si0.27B0.10C0.31N0.07O0.24, Si0.23B0.06C0.21N0.22O0.27, and Si0.20B0.05C0.19N0.20O0.35) were obtained using a Si2BC2N target and varying nitrogen flow rates. The hydrophilic properties of the as-synthesized coatings were rationalized in terms of an increase in the number of oxygen-containing functional groups (OH and NO) on the surface, as probed using XPS and FTIR analyses. Furthermore, the cellular monoculture of SVEC4-10 endothelial cells and L929 fibroblasts established good cytocompatibility. More importantly, the coculture system of SVEC4-10 and L929, in the absence of growth factors, demonstrated clear cellular phenotypical changes, with extensive sprouting leading to tube-like morphologies on the coating surfaces, when stimulated using a customized cell stimulator (StimuCell) with 1.15 V/cm direct current (DC) electric field strength for 1 h. In addition, the hemocompatibility assessment using human blood samples revealed clinically acceptable hemolysis, less erythrocyte adhesion, shorter plasma recalcification, and reduced risk for thrombosis on the SiBxCyNzOm coatings, when compared to uncoated Ti6Al4V. Taken together, the present study unambiguously establishes excellent cytocompatibility, hemocompatibility, and defines the preangiogenic properties of SiBxCyNzOm bioceramic coatings for potential biomedical applications.

Effects of Oxygen Content on Low-Temperature Bonding Using Organic-Free Silver Nanostructured Film with Different Types of Substrate Metallization

Effects of Oxygen Content on Low-Temperature Bonding Using Organic-Free Silver Nanostructured Film with Different Types of Substrate Metallization

Heteroepitaxial GaAs thin-films on flexible, large-area, single-crystal-like substrates for wide-ranging optoelectronic applications

Recent advances in semiconductor based electronic devices can be attributed to the technological demands of ever increasing, application specific markets. These rapidly evolving markets for devices such as displays, wireless communication, photovoltaics, medical devices, etc. are demanding electronic devices that are increasingly thinner, smaller, lighter and flexible. High-quality, III-V epitaxial thin-films deposited on single-crystal substrates have yielded extremely high-performance, but are extremely expensive and rigid. Here we demonstrate heteroepitaxial deposition of GaAs thin-films on large-grained, single-crystal-like, biaxially-aligned, flexible, metallic substrates. We use molecular beam epitaxy (MBE) for the controlled growth of high quality GaAs layers on lattice matched Ge capped, flexible metal substrates. The structural, optical, interfacial and electrical characteristics and properties of the heteroepitaxial GaAs layers are analyzed and discussed. The results show that heteroepitaxial GaAs layers with good crystalline and optoelectronic properties can be realized for flexible, III-V based semiconductor devices. III-V materials integrated on large-grained, single-crystal-like, flexible, metallic substrates offer a potential route towards fabrication of large-area, high-performance electronic devices.

Frequency-Selective Radar-Absorbing Composites Using Hybrid Core-Shell Spheres.

Radar-absorbing materials (RAMs) covering the exterior surfaces of installed parts and assembled devices are crucial in absorbing most incident electromagnetic (EM) waves. This absorption minimizes reflected energy, thereby enhancing pilot safety and the stability of operating electronic devices without interference. Particularly, active stealth aircraft require effective protection from near- and far-field EM radiation across a wide spectrum of frequencies from both highly integrated electronic components and advanced enemy radars. Studies of RAMs often prioritize absorption over crucial tunability in frequency selectivity, revealing a research gap. In this study, we propose smart RAMs with frequency-selective absorption capabilities. Our approach involves incorporating two types of core-shell spheres in a polymer matrix, which feature shells of either wave-diffuse reflecting metal or wave-absorbing graphene. The key innovation lies in the ability to tailor absorption frequencies in the X-band range (8.2-12.4 GHz) by adjusting the interstitial spaces between the metallic spheres while the scattered waves are efficiently attenuated by graphene networks in the composites. On a metal substrate, a 2 mm-thick composite with an optimized structural composition and ratio of the two types of spheres exhibits a maximum absorption efficiency of 99.3%, effectively trapping and extinguishing incident waves. Combined with the structural tunability and frequency-selective properties of spherical fillers, our approach provides a scalable and effective method for creating functional isotropic coverings on various metallic surfaces.

Electroplated Copper Additives for Advanced Packaging: A Review.

Acid copper electroplating stands as a core technology in advanced packaging processes, facilitating the realization of metal interconnects, bumps, vias, and substrate wiring between transistors. The deposition quality of copper interconnect materials has a crucial impact on the final performance of chips, directly influencing their yield, reliability, and stability. In this intricate process, additives play a pivotal role in regulating the deposition quality and behavior of metal copper. This mini-review comprehensively summarizes the recent research progress in the field of electroplating copper additives for advanced packaging, both domestically and internationally, delving into the types and mechanisms of various additive molecules, including accelerators, inhibitors, and leveling agents. Through in-depth research on these additives, we gain a profound understanding of their specific roles in the electroplating process and the intricate interaction mechanisms among them, providing theoretical support for optimizing the electroplating process. Furthermore, this mini-review also delves into a thorough analysis of the current issues and challenges facing acid copper electroplating, exploring the key factors that constrain the further development of electroplating copper technology. Based on this analysis, we propose several potential solutions and research directions, offering crucial references for the development and application of electroplating copper additives in advanced packaging. In conclusion, this mini-review aims to provide a comprehensive perspective and profound understanding of the development and application of electroplating copper additives through a review and analysis of recent research progress, ultimately aiming to promote the further advancement of advanced packaging technology.

Polyaniline-wrapped h-boron nitride nanosheets as anticorrosive filler in epoxy coatings for substantially enhanced protection of mild steel

Excellent impermeability, electronic insulation, thermal stability, and high surface area of hexagonal boron nitride nanosheets (h-BNNS) promise immense potential for corrosion inhibition when coated on the metal substrate. However, the interfacial incompatibility of h-BNNS with polymeric coating matrix has been a major challenge to utilize h-BNNS for metal protection against corrosive environments. In the present work, surface-functionalities-enriched h-BNNS prepared by alkali hydroxides molten salt-induced exfoliation of h-BN powder is used for in-situ growth of polyaniline-emeraldine salt (PANI-ES) by oxidative polymerization of aniline to prepare the h-BNNS-PANI-ES nanocomposites. The excellent compatibility of nitrogen functionalities of h-BNNS-PANI-ES nanocomposites with highly polar epoxy matrix strengthened the coating by enhancement of elastic modulus and hardness. The thoroughly dispersed h-BNNS-PANI-ES nanocomposites into epoxy coating notably enhanced the corrosion inhibition properties in an accelerated corrosive environment (3.5 % saline water). The electrochemical measurements showed eleven-fold rise in total impedance by h-BNNS-PANI-ES nanocomposites compared to PANI-ES-based epoxy coating, highlighting the role of h-BNNS as a structural barrier to protect the underlying mild steel substrate against corrosion. Moreover, mild steel coated with h-BNNS-PANI-ES nanocomposites remained intact even after ten days of exposure to salty fog, demonstrating the potential of such coatings for industrial applications.

Surface-enhanced optical absorption and induced heating in tapered silicon nanoprobes

Subject of study. This study investigates the correlation between the heating temperature and the mesoscopic shape of the Si probe of an atomic force microscope subjected to medium-intensity laser irradiation (5mW/cm2) in the presence of a rough metal substrate. Aim of study. This study aims to quantitatively assess the dependence of optical-field enhancement and induced heating of the tip of a tapered Si nanoprobe, under laser irradiation, on the radius of curvature and cone angle of the probe tip, the distance between the tip and substrate, and the surface roughness of an Au substrate. Method. The localization of the electromagnetic field in the gap between a Si nanoantenna and a defect on the surface of an Au substrate was simulated using the finite-difference time-domain method. A thin Au coating (thickness up to 50 nm) on a glass substrate was used as a plasmonic surface. Owing to the excitation of surface plasmon resonance, such a coating enhances the absorption of light and increases the heating temperature of the Si optical antenna. Main results. The influence of the polarization angle of the incident laser radiation on the distribution of the electric field near the tip of the probe was examined. Only the component of the incident light field along the direction of the probe axis was enhanced near the tip of the Si cantilever. The influence of various parameters, including the radius of curvature, cone angle of the tip of the Si nanoantenna, distance between the probe and substrate, and surface roughness of the Au substrate, on the maximum temperature in the tip region of the Si probe was investigated. The probe temperature was found to decrease with decreasing cone angle of the probe, whereas the temperature of the cantilever tip decreased as the cone angle of the probe tip increased. The dependence of temperature on the radius of curvature of the Si nanoantenna tip in the presence of an Au substrate was evaluated. With an increase in the surface roughness of the Au film, the temperature of the Si antenna tip increased, gradually approaching a limit value. Practical significance. The results of this study are useful for selecting the optimal parameters of an experiment in which a heated probe is used. Controlled heating of a Si probe can facilitate the study of phase transitions in various nanomaterials and that of local thermochemical nanocatalysis for creating new structural materials with specific properties.