Nanoporous Metals Research Articles

Oxidation Driven Thin‐Film Solid‐State Metal Dealloying Forming Bicontinuous Nanostructures

AbstractSolid‐state metal dealloying (SSMD) is a promising method for fabricating nanoscale metallic composites and nanoporous metals across a range of materials. Thin‐film SSMD is particularly attractive due to its ability to create fine features via solid‐state interfacial reactions within a thin‐film geometry, which can be integrated into devices for various applications. This work examines a new dealloying couple, namely the Nb–Al alloy with the dealloying agent Sc, as previously predicted in the machine‐learning (ML) models. Prior ML predictions aimed to guide the design of nanoarchitectured materials through dealloying, relying on intuition‐driven discovery within a large parameter space. However, this work reveals that at the nanoscale, the involvement of oxygen in thin film processing may instead drive the dealloying process, resulting in the formation of bicontinuous nanostructures similar to those formed by metal‐agent dealloying. The phase evolution, as well as chemical and morphological changes, are closely analyzed using a combination of X‐ray absorption spectroscopy, diffraction, and scanning transmission electron microscopy to understand the mechanisms behind nanostructure formation. The findings suggest a potential pathway for utilizing oxygen to drive the formation of bicontinuous metal–metal oxide nanocomposites, paving the way for further development of functional nanoporous materials in diverse fields.

Nanoporous Metals Based on Metallic Glasses: Synthesis, Structure and Functional Applications

Nanoporous Metals Based on Metallic Glasses: Synthesis, Structure and Functional Applications

Liquid-Metal Solvents for Designing Hierarchical Nanoporous Metals at Low Temperatures.

Metallic nanoarchitectures hold immense value as functional materials across diverse applications. However, major challenges lie in effectively engineering their hierarchical porosity while achieving scalable fabrication at low processing temperatures. Here we present a liquid-metal solvent-based method for the nanoarchitecting and transformation of solid metals. This was achieved by reacting liquid gallium with solid metals to form crystalline entities. Nanoporous features were then created by selectively removing the less noble and comparatively softer gallium from the intermetallic crystals. By controlling the crystal growth and dealloying conditions, we realized the effective tuning of the micro-/nanoscale porosities. Proof-of-concept examples were shown by applying liquid gallium to solid copper, silver, gold, palladium, and platinum, while the strategy can be extended to a wider range of metals. This metallic-solvent-based route enables low-temperature fabrication of metallic nanoarchitectures with tailored porosity. By demonstrating large-surface-area and scalable hierarchical nanoporous metals, our work addresses the pressing demand for these materials in various sectors.

Imbibition and rheology of polymer-matrix nanoporous metal composites: Towards extrusion-based 3D printing

When combined with additive manufacturing, nanoporous metals can be shaped into multifunctional and interdigitated 3D circuits with hierarchical diffusional pathways, critical for optimizing electrochemical storage devices. In an attempt to develop a method for extrusion-based additive manufacturing of nanoporous metals and their composites, this paper examines a new polymer matrix composite reinforced with spherical nanoporous copper powders (PMC-NP-Cu) synthesized by dealloying at high fill fractions (>45 vol%), that can be integrated with fused filament fabrication (FFF). The role of capillary imbibition of the polymer into the metal's nanopores was investigated by examining their wettability, rheology, and density as a function of polymer's molecular weight (MW) particularly for a range of radius of gyration (Rg) between 2 and 20 nm comparable to its average pore size (22 nm). It was found that the melt viscosity of PMC-NP-Cu with the shortest Mw departed from classical viscosity scaling (i.e., η ∞ MW1) which is attributed to the polymer imbibition into nanopores and composite densification. For molecular weights equal to 5 and 200 kg/mol, it was found that the volume fraction of the reinforcing phase was 16% and 8% higher respectively when imbibition was accounted for, resulting in an increase of two orders of magnitude in its zero-shear viscosity. These results correlated to the extrudability tests of PMC-NP-Cu filaments at higher packing factors (i.e., 47 vol%) for FFF. The insight of this study might be beneficial to integrate nanoporous metals into binder-based 3D printing technology to fabricate interdigitated battery electrodes and multifunctional 3D printed electronics.

Synthesizing Nanoporous Stainless Steel Films via Vacuum Thermal Dealloying

Vacuum thermal dealloying is a recently developed technique and was newly introduced to produce nanoporous metals, due to its intriguing advantages, i.e., preventing oxidation and producing no chemical waste, etc. Here, we report on the fabrication of nanoporous stainless steel films by vacuum thermal dealloying of sputtered stainless steel–magnesium precursor films. It was found that crack-free nanoporous stainless steel films can be successfully attained under a broad temperature range of 450–600 °C, with a dealloying time of 0.5–2 h. The resulting structure and ligaments were temperature- and time-dependent, and moreover, the condition of “600 °C + 2 h” generated the most homogeneous structure. Moreover, small amounts of residual Mg were found at pore sites in the resultant structures, suggesting that the dealloying was not fully complete.

Data-driven modelling of the multiaxial yield behaviour of nanoporous metals

Nanoporous metals, built out of complex ligament networks, can be produced with an additional level of hierarchy. The resulting complexity of the structure makes modelling of the mechanical behaviour computationally expensive and time consuming. In addition, multiaxial stresses occur in the higher hierarchy ligaments. Therefore, knowledge of the multiaxial material behaviour, including the 6D yield surface, is required. Surrogate models, predicting the mechanical behaviour of the lower level of hierarchy, represented by finite element beam models, are a promising approach to overcome such challenges, when existing analytical models are not able to describe the material behaviour. Therefore, as a first step, we studied the elastic behaviour and the yield surfaces of representative volume elements with idealised diamond and Kelvin structure in finite element simulations. The yield surfaces showed pronounced anisotropy and could not be described by the Deshpande-Fleck model for isotropic solid foams. Instead, we used data-driven and hybrid artificial neural networks, as well as data-driven support vector machines and compared them regarding their potential for the prediction of yield surfaces. All considered methods were well suited and resulted in relative errors <4.5%. Support vector machines showed the best generalisation and accuracy in 6D stress space and are suitable for extrapolation outside the range of training data.

Electro-Chemical Actuation of Nanoporous Metal Materials Induced by Surface Stress

Similar to biological muscles, the actuator materials can function as artificial muscles by directly converting an external stimulus in the form of electrical or chemical energy into a mechanical response through the reversible changes in material dimensions. As a new type of high surface-area actuator materials, nanoporous metals represent a novel class of smart electrodes that undergo reversible dimensional changes when applying an electronic voltage on the surface. The dimensional changes in nanoporous metal/polymer composite still originate from the surface stress of nanoporous metal. Additionally, this surface stress can be modulated by the co-adsorbed sulfate counter-ions that are present in the doped polymer chains coating matrix upon the application of an external potential. Nanoporous metals fabricated by dealloying have received extensive attention in many areas, such as catalysis/electrocatalysis, energy conversion/storage, and sensing/biosensing. In this review, we focus on the recent developments of dealloyed nanoporous metals in the application of actuation. In particular, we summarize the experimental strategies in the studies and highlight the recent advances in the actuator materials. Finally, we conclude with outlook and perspectives with respect to future research on dealloyed nanoporous metals in applications of actuation in electrochemical or chemical environment.

Salt-Mediated Coarsening in Conversion-Reaction-Synthesized Nanoporous Metals and Nanocomposites Resolved through In Situ Synchrotron Diffraction Studies

High-energy synchrotron X-rays were used to probe the structural and microstructural evolution in Fe, Co, and Cu nanoporous metals (NPMs) and metal/salt nanocomposites (NCs) produced by recently developed conversion reaction synthesis (CRS) methods. Microstructure analysis of as-synthesized samples via whole pattern fitting showed that the NPMs exhibit domain sizes that increase as Co < Fe < Cu, with both Fe and Co having crystallite sizes below 3.0 nm. The as-synthesized metal/salt NCs had similar metal sizes, and additionally, the salt in the composite had unusually large lattice microstrain whose origin is attributed to chemical substitution of metal ions into the salt (e.g., Li1–3xFexCl for Fe3+). When thermal annealing is used to modify crystallite size, pore collapse often occurs in NPMs but NCs can be effectively tuned without this problem. While the NC coarsening occurs slowly at low temperatures, it was found that there is a drastic acceleration of the reaction rate at a specific onset temperature that results in the crystallite size increasing by an order of magnitude in about a minute. Curiously, there was no evidence in the diffraction data for salt melting at this onset temperature. However, there was a sharp reduction in the salt chemical lattice strain at the onset temperature, indicating that rapid metal coarsening is facilitated by the salt. This behavior indicates an unexpectedly coupled reaction mechanism by which the metal ions needed for grain growth are supplied by the salt in a rate-limiting fashion.

Hybrid homogenization theory with surface effects: Application to columnar nanoporous materials

Nanocomposites, including nanoporous ceramics, metals and polymers, are being widely used in various engineering applications. At the nanoscale, surface/interface effects have significant influence on the homogenized properties and local stresses. To account for these nanoscale effects, the well-established Gurtin–Murdoch theory of surface elasticity is typically incorporated into classical elasticity-based micromechanics schemes and numerical approaches based on the finite-element and most recently finite-volume methods. Whereas the classical micromechanics models either neglect the interactions of adjacent fibers/pores or account for the interactions in an average sense, the finite-element and finite-volume based approaches require high discretization to capture the large stress/strain gradients around the interface/surface. In contrast, the recently proposed hybrid homogenization theory (HHT) combines elements of locally-exact elasticity and finite-volume approaches and is both accurate and efficient, enabling rapid generation and analysis of ordered and quasi-random fiber or pore arrays. Herein, a continuous bulk matrix layer of arbitrary size endowed with a two-dimensional energetic surface is introduced between fiber/pore and discretized matrix region that enables exact calculation of stress jump conditions in the Young–Laplace equations of the Gurtin–Murdoch model. The enhanced HHT with interface/surface effects is validated by comparison with the stress concentration factors obtained using a classical elasticity solution and point-wise stress fields predicted by the locally-exact and finite-volume homogenization theories, exhibiting stable solutions even for very thin bulk matrix layers. The enhanced theory is then employed to study the influence of random nanopore microstructures with random pore radii on the complete set of homogenized moduli of porous silicon used in the electronics industry.

Simulated annealing framework for generating representative volume elements of materials with complex ligamentous microstructures

At the microscale, various materials from biological tissues to nanoporous metals are formed by networks of ligaments. Here we propose a highly efficient simulated annealing (SA) framework for generating synthetic representative volume elements (RVE) of such materials. It can produce RVE where the microstructural characteristics both on the network level (e.g., node valency and ligament length) and on the level of individual ligaments (e.g., curvature) can be predefined by the user via probability distributions. As an application example of our framework, we generate a large variety of RVEs, analyze their mechanical properties by the finite element method, and establish through this approach links between microstructural descriptors and macromechanical properties of materials with ligamentous microstructures.

Atomistic simulation of the effect of porosity on shock response of nanoporous gold.

Nanoporous metals (NPMs) have a three-dimensional bicontinuous porous network structure that consists of interconnected nanoligaments. NPMs have the potential to effectively attenuate and dissipate the effects of impacts and blasts. Previous studies do not provide data on the possible effects of porosity at the nanoscale. Molecular dynamics simulations based on the embedded-atom method potential were performed using the open-source code LAMMPS (Large-scale Atomic/Molecular Massively Parallel Simulator). Nanoporous gold (NPG) absorbs shock energy first through the elastic-plastic deformation of ligaments and then through the collapse of ligaments. After the shock loading is relaxed, NPG with lower porosity has a higher amount of springback, and new voids tend to nucleate and grow at collapsed ligaments where the packing is looser. NPG with higher porosity has a better ability to resist the propagation of a shock wave and is subjected to a smaller stress effect.

Enhanced compressive mechanical properties in stochastic bicontinuous porous structures

Inspired by the morphology of dealloyed nanoporous metals, we derive a novel open-celled porous structure with stochastic bicontinuous cell. The polymeric porous specimens are fabricated by additive manufacturing (AM), and the compressive mechanical properties and energy absorption capacity are explored experimentally. Results show that Young’s modulus, yield stress, plateau stress, and energy absorption characteristics are monotonically increasing with the relative density, obeying the Gibson-Ashby power correlation. Due to more defects generated in the specimen with smaller ligament diameter during AM, there is a significant decrease in Young’s modulus and a slight decrease in yield stress with the decrease of ligament diameter, which is opposite to the size effect in nanomaterials. Attributing to the bending and yielding deformation of ligaments, the stochastic bicontinuous porous solids show an enhanced energy absorption capacity. The ligament morphological structure has shown to be an additional factor affecting the mechanical responses of porous solids, and might magnify its sensitivity to structural characteristics. This study provides valuable idea and guidance for designing efficient open-celled porous structures in the promising application of energy absorption.

Development of Bicontinuous Nanoporous and Heterostructured Metals by Liquid Metal Dealloying

Development of Bicontinuous Nanoporous and Heterostructured Metals by Liquid Metal Dealloying

Dry Synthesis of Pure and Ultrathin Nanoporous Metallic Films.

Nanoporous metals possess unique properties attributed to their high surface area and interconnected nanoscale ligaments. They are mostly fabricated by wet synthetic methods that are not universal to various metals and not free from impurities due to solution-based etching processes. Here, we demonstrate that the plasma treatment of metal nanoparticles formed by physical vapor deposition is a general route to form such films with many metals including the non-noble ones. The resultant nanoporous metallic films are free of impurities and possess highly curved ligaments and nanopores. The metal films are ultrathin, yet remarkably robust and very well connected, and thus are highly promising for various applications such as transparent conducting electrodes.

Three-dimensional nanoporous Ag fabricated by a reduction-induced approach for sensitive surface-enhanced Raman scattering

Nanoporous metals with high specific surface area, excellent conductivity, and unique surface structure have attracted attention in a variety of applications such as catalysis, energy storage, and sensing. However, there is a significant challenge for the fabrication of uniform nanoporous architectures in metals through a simple and cost-effective process. In this study, we report a facile approach to create monolithic nanoporous Ag (MNPA) from the direct reduction of insoluble Ag2O precursor in an aqueous solution, fundamentally avoiding the introduction of secondary components and complex preparation of precursors. The formation of porous structures is attributed not only to the volume shrinkage but also to the spontaneous reconstruction of reserved Ag atoms during the reduction process. Furthermore, for a typical application, the optimized MNPA with a small grain size (∼113 nm) is used as a surface-enhanced Raman scattering (SERS) substrate, which exhibits ultrahigh SERS sensitivity with an enhancement factor of ∼109.

Boosting the H2–D2 Exchange Activity of Dilute Nanoporous Ti–Cu Catalysts through Oxidation–Reduction Cycle–Induced Restructuring

The use of nanoporous metals as catalysts has attracted significant interest in recent years. Their high‐curvature, nanoscale ligaments provide not only high surface area but also a high density of undercoordinated step edge and kink sites. However, their long‐term stability, especially at higher temperatures, is often limited by thermal coarsening and the associated loss of surface area. Herein, it is demonstrated that the nanoscale morphology of nanoporous Cu can be regenerated by applying oxidation/reduction cycles at 250 °C. Specifically, the morphological evolution and H2 dissociation activity of hierarchical nanoporous Cu catalysts doped with Ti during structural rearrangement triggered by oxidative and reductive atmospheres at elevated temperatures are studied. In addition to coarsening of the structure at elevated temperatures, oxidation at 400 °C causes an expansion of the ligaments. Subsequent reduction at 400 °C leads to the formation of particles and a drop in the H2 dissociation activity compared the fresh catalyst. However, performing the redox cycle at 250 °C reverses coarsening and boosts the H2 dissociation activity for the hydrogen–deuterium (H2–D2) reaction. Herein, the possibility to reverse coarsening is demonstrated, thereby mitigating the loss of activity frequently observed in nanoporous catalysts.

Densification of nanoporous metals during nanoindentation: The role of structural and mechanical properties

The analysis of the densification behavior of nanoporous metals in nanoindentation is challenging in simulations and experiments. A deeper understanding of the densification behavior provides valuable information about the different deformation mechanisms in nanoindentation and compression experiments. The developed two-scale model allows for predicting the densification field for variable microstructure and elastic–plastic behavior. It could be shown that the penetration depth of the densification field is mainly controlled by the ratio of the macroscopic work hardening rate to yield stress. The shape as well as the value at characteristic isolines of densification depend mainly on the macroscopic plastic response of the nanoporous material. This could be confirmed by nanoindentation experiments, where the densification under the indenter was measured for ligament sizes from 35 to 150 nm. Although the depth of the densification field was underpredicted by the simulations, the experiments confirmed the predicted trends.Graphical abstract

Surface Defects Improved SERS Activity of Nanoporous Gold Prepared by Electrochemical Dealloying.

Nanoporous metals possess excellent catalytic and optical properties that are related with surface morphology. Here, we modulated the ligament surface of nanoporous gold (NPG) by controlling electrochemical dealloying and obtained NPG with an improved enhancement of its surface-enhanced Raman scattering (SERS) property. We found that both high-density atomic steps and kinks on the curved surfaces and high-content silver atoms close to the ligament surface contributed to the high SERS ability. The presented strategy will be useful for the fabrication of nanoporous metal with an excellent surface that is needed for sensing, conversion, and catalytic.

Incipience of Plastic Flow in Aluminum with Nanopores: Molecular Dynamics and Machine-Learning-Based Description

Incipience of plastic flow in nanoporous metals under tension is an important point for the development of mechanical models of dynamic (spall) fracture. Here we study axisymmetric deformation with tension of nanoporous aluminum with different shapes and sizes of nanopores by means of molecular dynamics (MD) simulations. Random deformation paths explore a sector of tensile loading in the deformation space. The obtained MD data are used to train an artificial neural network (ANN), which approximates both an elastic stress–strain relationship in the form of tensor equation of state and a nucleation strain distance function. This ANN allows us to describe the elastic stage of deformation and the transition to the plastic flow, while the following plastic deformation and growth of pores are described by means of a kinetic model of plasticity and fracture. The parameters of this plasticity and fracture model are identified by the statistical Bayesian approach, using MD curves as the training data set. The present research uses a machine-learning-based approximation of MD data to propose a possible framework for construction of mechanical models of spall fracture in metals.

Crystal plane-orientation dependent phase evolution from precursor to porous intermediate phase in the vapor phase dealloying of a Co-Zn alloy

Understanding phase transitions and pore formation during vapor phase dealloying (VPD) is essential to optimize the microstructure and composition of nanoporous metals for versatile applications. Nevertheless, the underlying atomic mechanisms of phase formation and pore evolution during VPD are unknown. Using a binary γ-CoZn precursor alloy as a prototype system, we found a two-step dealloying process. The microsized porous β-CoZn intermediate phase that formed at the dealloying front facilitated the subsequent growth of completely dealloyed hierarchical nanoporous α-Co with the micropore structure of the intermediate phase. Combining aberration-corrected scanning transmission electron microscopy with energy dispersion X-ray spectrometry, we found that the intermediate phase preferentially formed on specific crystal planes of the precursor, and the vacancies generated by sublimation of Zn atoms diffused dominantly on the {110} planes of the precursor close to the intermediate phase. Theoretical calculations indicated that the energy barrier to the diffusion of Zn vacancies on the low-index {110} plane was lower than on other planes. The atomic-scale phase evolution play a key role in the subsequent evolution of the porous structure and provide deep insight into the phase transition during VPD. This insight may provide a new approach to tune the pore structure and composition of nanoporous metals by designing and regulating their intermediate phases.