An in-situ small angle x ray scattering analysis of nanopore formation during thermally induced chemical dealloying of brass thin foils.
ABSTRACT: The development of non-noble nano-porous metal materials is hindered by surface oxidation reactions and from the difficulty to generate long range order pore arrays. Dealloying is a promising route to generate such materials by selective chemical etching of metal alloy materials. This process can generate nano-metal materials with superior plasmonic, catalytic and adsorptive surface properties. Here, the impact of properties of the etching solution on the dealloying process to generate nano-pores across thin film alloys was investigated by in-situ SAXS dealloying experiments. Single phase CuZn alloys were used as model materials to evaluate the influence of the solution temperature on the pore formation kinetics. This novel analysis allowed to visualize the change in surface properties of the materials over time, including their surface area as well as their pore and ligament sizes. The dealloying kinetics at the very early stage of the process were found to be critical to both stable pore formation and stabilization. SAXS in-situ data were correlated to the morphological properties of the materials obtained from ex-situ samples by Rutherford back scattering and scanning electron microscopy.
Project description:Three-dimensional bicontinuous open (3DBO) nanoporosity has been recognized as an important nanoarchitecture for catalysis, sensing, and energy storage. Dealloying, i.e., selectively removing a component from an alloy, is an efficient way to fabricate nanoporous materials. However, current electrochemical and liquid-metal dealloying methods can only be applied to a limited number of alloys and usually require an etching process with chemical waste. Here, we report a green and universal approach, vapor-phase dealloying, to fabricate nanoporous materials by utilizing the vapor pressure difference between constituent elements in an alloy to selectively remove a component with a high partial vapor pressure for 3DBO nanoporosity. We demonstrate that extensive elements, regardless of chemical activity, can be fabricated as nanoporous materials with tunable pore sizes. Importantly, the evaporated components can be fully recovered. This environmentally friendly dealloying method paves a way to fabricate 3DBO nanoporous materials for a wide range of structural and functional applications.
Project description:Three-dimensional bicontinuous porous materials formed by dealloying contribute significantly to various applications including catalysis, sensor development and energy storage. This work studies a method of molten salt dealloying via real-time in situ synchrotron three-dimensional X-ray nano-tomography. Quantification of morphological parameters determined that long-range diffusion is the rate-determining step for the dealloying process. The subsequent coarsening rate was primarily surface diffusion controlled, with Rayleigh instability leading to ligament pinch-off and creating isolated bubbles in ligaments, while bulk diffusion leads to a slight densification. Chemical environments characterized by X-ray absorption near edge structure spectroscopic imaging show that molten salt dealloying prevents surface oxidation of the metal. In this work, gaining a fundamental mechanistic understanding of the molten salt dealloying process in forming porous structures provides a nontoxic, tunable dealloying technique and has important implications for molten salt corrosion processes, which is one of the major challenges in molten salt reactors and concentrated solar power plants.
Project description:Although Raney nickel made by dealloying has been used as a heterogeneous catalyst in a variety of organic syntheses for more than 80 years, only recently scientists have begun to realize that dealloying can generate nanoporous alloys with extraordinary structural characteristics. Herein, we achieved successful synthesis of a variety of monodisperse alloy nanoporous nanoparticles via a facile chemical dealloying process using nanocrystalline alloys as precursors. The as-prepared alloy nanoporous nanoparticles with large surface area and small pores show superior catalytic properties compared with alloyed nanoparticles. It is believed that these novel alloy nanoporous nanoparticles would open up new opportunities for catalytic applications.
Project description:Nano-textured porous metal materials present unique surface properties due to their enhanced surface energy with potential applications in sensing, molecular separation and catalysis. In this paper, commercial alloy foils, including brass (Cu<sub>85</sub>Zn<sub>15</sub> and Cu<sub>70</sub>Zn<sub>30</sub>) and white gold (Au<sub>50</sub>Ag<sub>50</sub>) foils have been chemically de-alloyed to form nano-porous thin films. The impact of the initial alloy micro-structure and number of phases, as well as chemical de-alloying (DA) parameters, including etchant concentration, time and solution temperature on the final nano-porous thin film morphology and properties were investigated by electron microscopy (EM). Furthermore, the penetration depth of the pores across the alloys were evaluated through the preparation of cross sections by focus ion beam (FIB) milling. It is demonstrated that ordered pores ranging between 100 nm and 600 nm in diameter and 2-5 ?m in depth can be successfully formed for the range of materials tested. The microstructure of the foils were obtained by electron back-scattered diffraction (EBSD) and linked to development of pits across the material thickness and surface during DA. The role of selective etching of both noble and sacrificial metal phases of the alloy were discussed in light of the competitive surface etching across the range of microstructures and materials tested.
Project description:Nano-scale surface roughening of metallic bio-implants plays an important role in the clinical success of hard tissue reconstruction and replacement. In this study, the nano-topographical features of titanium-niobium-zirconium (TNZ) alloy surfaces were controlled by using the target-ion induced plasma sputtering (TIPS) technique to improve the in vitro osteoblastic response. The TIPS technique is a novel strategy for etching the surface of metallic bio-implants using bombardment of target metal cations, which were accelerated by an extremely high negative bias voltage applied to the substrates. The nano-topography of the TNZ surfaces was successfully controlled by modulating experimental variables (such as the ion etching energy and the type of substrate or target materials) of TIPS. As a result, various nanopatterns (size: 10-210 nm) were fabricated on the surface of the TNZ alloys. Compared with the control group, experimental groups with nanopattern widths of ≥130 nm (130 and 210 nm groups) exhibited superior cell adhesion, proliferation, and differentiation. Our findings demonstrate that TIPS is a promising technology that can impart excellent biological functions to the surface of metallic bio-implants.
Project description:A versatile, compact heater designed at National Synchrotron Light Source-II for in situ X-ray nano-imaging in a full-field transmission X-ray microscope is presented. Heater design for nano-imaging is challenging, combining tight spatial constraints with stringent design requirements for the temperature range and stability. Finite-element modeling and analytical calculations were used to determine the heater design parameters. Performance tests demonstrated reliable and stable performance, including maintaining the exterior casing close to room temperature while the heater is operating at above 1100°C, a homogenous heating zone and small temperature fluctuations. Two scientific experiments are presented to demonstrate the heater capabilities: (i) in situ 3D nano-tomography including a study of metal dealloying in a liquid molten salt extreme environment, and (ii) a study of pore formation in icosahedral quasicrystals. The progression of structural changes in both studies were clearly resolved in 3D, showing that the new heater enables powerful capabilities to directly visualize and quantify 3D morphological evolution of materials under real conditions by X-ray nano-imaging at elevated temperature during synthesis, fabrication and operation processes. This heater design concept can be applied to other applications where a precise, compact heater design is required.
Project description:We present a two-step surface modification process to tailor the micro and nano morphology of niobium oxide layers. Niobium was firstly anodized in spark regime in a Ca- and P-containing solution and subsequently treated by acid etching. The effects of anodizing time and applied potential on the surface morphology is investigated with SEM and AFM, complemented by XPS compositional analysis. Anodizing with a limiting potential of 250 V results in the fast growth of oxide layers with a homogeneous distribution of micro-sized pores. Cracks are, however, observed on 250 V grown layers. Limiting the anodizing potential to 200 V slows down the oxide growth, increasing the anodizing time needed to achieve a uniform pore coverage but produces fracture-free oxide layers. The surface nano morphology is further tuned by a subsequent acid etching process that leads to the formation of nano-sized pits on the anodically grown oxide surface. In vitro tests show that the etching-induced nanostructure effectively promotes cell adhesion and spreading onto the niobium oxide surface.
Project description:The surface of dental implants plays a vital role in early and more predictable osseointegration. SLA (sandblasted large grit and acid-etched) represents the most widely accepted, long-term clinically proven surface. Primarily, dental implants are manufactured by either commercially pure titanium (CP-Ti) or Ti6Al4V ELI alloy. The acid etch behavior of CP-Ti is well known and its effects on the surface microstructure and physicochemical properties have been studied by various researchers in the past. However, there is a lack of studies showing the effect of acid etching parameters on the Ti6Al4V alloy surface. The requirement of the narrow diameter implants necessitates implant manufacturing from alloys due to their high mechanical properties. Hence, it is necessary to have an insight on the behavior of acid etching of the alloy surface as it might be different due to changed compositions and microstructure, which can further influence the osseointegration process. The present research was carried out to study the effect of acid etching parameters on Ti6Al4V ELI alloy surface properties and the optimization of process parameters to produce micro- and nanotopography on the dental implant surface. This study shows that the Ti6Al4V ELI alloy depicts an entirely different surface topography compared to CP-Ti. Moreover, the surface topography of the Ti6Al4V ELI alloy was also different when etching was done at room temperature compared to high temperature, which in turn affected the behavior of the cell on these surfaces. Both microns and nano-level topography were achieved through the optimized parameters of acid etching on Ti6Al4V ELI alloy dental implant surface along with improved roughness, hydrophilicity, and enhanced cytocompatibility.
Project description:Hollow alloyed nanoparticles (NPs) represent one kind of promising fuel cell electrocatalyst. However, the formation of single-cavity hollow structures by a dealloying process is quite challenging owing to the random leaching/dissolution of transition metals, surface passivation and the limited diffusion distance of the noble metals. Here we present a facile method to prepare hollow PtPdCu NPs derived from monodisperse alloy NPs by an acetic acid-assisted dealloying process. Here, acetic acid not only acts as a chemical etching agent but also plays an important role in the removal of the residual surfactants for colloidal NPs. Our findings rectify the current knowledge that hollow alloyed NPs cannot be prepared by a dealloying strategy and provide further understanding of the dealloying process in a ternary system. Such unique hollow ternary PtPdCu NPs exhibit outstanding durability and improved catalytic activity toward the oxygen reduction reaction.
Project description:Meso-porous metal materials have enhanced surface energies offering unique surface properties with potential applications in chemical catalysis, molecular sensing and selective separation. In this paper, commercial 20 nm diameter metal nano-particles, including silver and copper were blended with 7 nm silica nano-particles by shear mixing. The resulted powders were cold-sintered to form dense, hybrid thin films. The sacrificial silica template was then removed by selective etching in 12 wt% hydrofluoric acid solutions for 15 min to reveal a purely metallic meso-porous thin film material. The impact of the initial silica nano-particle diameter (7-20 nm) as well as the sintering pressure (5-20 ton·m<sup>-2</sup>) and etching conditions on the morphology and properties of the final nano-porous thin films were investigated by porometry, pyknometery, gas and liquid permeation and electron microscopy. Furthermore, the morphology of the pores and particle aggregation during shear mixing were assessed through cross-sectioning by focus ion beam milling. It is demonstrated that meso-pores ranging between 50 and 320 nm in average diameter and porosities up to 47% can be successfully formed for the range of materials tested.