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The practical application of electrochemical water splitting has been plagued by the sluggish kinetics of bubble generation and the slow escape of bubbles which block reaction surfaces at high current densities. Here, 3D-printed Ni (3DP Ni) electrodes with a rationally designed periodic structure and surface chemistry are reported, where the macroscopic ordered pores allow fast bubble evolution and emission, while the microporosity ensures a high electrochemically active surface area (ECSA). When they are further loaded with MoNi4 and NiFe layered double hydroxide active materials, the 3D electrodes deliver 500 mA cm-2 at an overpotential of 104 mV for the hydrogen evolution reaction (HER) and 310 mV for the oxygen evolution reaction (OER), respectively. An all-3D-printed alkaline electrolyzer (including electrodes, membrane, and cell) delivers 500 mA cm-2 at a remarkable voltage of 1.63 V with no noticeable performance decay after 1000 h. Such a tailored bubble trajectory demonstrates feasible solutions for future large-scale clean energy production.
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It was found that nanodomains existed in the ionic liquid (IL)-based ternary system containing IL 1-ethyl-3-methylimidazole tetrafluoroborate (EmimBF4 ), IL 1-decyl-3-methylimidazole nitrate (DmimNO3 ) and water, and the size distribution of the domains varied continuously with the composition of the solution. A strategy to synthesize hierarchical porous metals using IL-based media as solvent and template is proposed, and the hierarchical porous Ru and Pt metals were prepared by the assembly of metal clusters of about 1.5â nm using this new method. It is demonstrated that the metals have micropores and mesopores, and the size distribution is tuned by controlling the composition of the solution. Porous Ru was used for a series of hydrogenation reactions. It has an outstanding catalytic performance owing to its special morphology and structure.
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The atomic redistribution processes occurring in multiparticle nanostructures are hardly understood. To obtain a more detailed insight, we applied high-resolution microscopic, diffraction and spectroscopic characterization techniques to investigate the fine structure and elemental distribution of various bimetallic aerogels with 1:1 compositions, prepared by self-assembly of single monometallic nanoparticles. The system Au-Ag exhibited a complete alloy formation, whereas Pt-Pd aerogels formed a Pd-based network with embedded Pt particles. The assembly of Au and Pd nanoparticles resulted in a Pd-shell formation around the Au particles. This work confirms that bimetallic aerogels are subject to reorganization processes during their gel formation.
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Metal nanoparticles have drawn great interest due to their unique properties for applications in the fields of catalysis, biomedicine and environmental science depending on the architecture of the metal nanoparticle composites. Amongst different designing routes, the chemical template deposition offers great flexibility in terms of the template selection and interfacial interactions, giving rise to controllable designs. In order to control over nanoparticle size distribution and deposition efficiency, a sonochemical approach has been systematically followed in this study. Key parameters of the ultrasound-assisted deposition procedures during the seeding step to synthesise gold nanoparticle-coated poly(styrene) beads were investigated. The impact of the solution pH and the ultrasonic frequency on the template deposition was examined at 139, 300, 500 and 1000 kHz. The results, monitored by transmission electron spectroscopic imaging, show that the highest gold deposition was achieved at 300 kHz, revealing the mechanistic details of the nucleation-crystal growth behaviour as a function of ultrasonic frequency and reaction time. In addition, the concentration ratio between gold ions and poly(styrene) beads was varied. The highest deposition coverage and smallest particle size were reached at 0.05 mM and 2.5 mg, respectively. The proposed mechanism of the MNPs formation and deposition behaviour were then discussed based on the tested parameters.
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Porous metal has been introduced to obtain biological fixation and improve longevity of orthopedic implants. The new generation of porous metal has intriguing characteristics that allows bone healing and high osteointegration of the metallic implants. This article gives an overview about biomaterials properties of the contemporary class of highly porous metals and about the clinical use in orthopaedic surgery.
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Powder-based methods that are used to make porous metals are relatively simple and scalable, and porosity can be controlled by interparticle spacing as well as the addition of a sacrificial template. A relatively new process based on reducing oxides in a metal matrix has been demonstrated to produce microscale porosity within individual powder particles and thereby may be used to enhance other powder metal techniques. Templating methods require relatively large quantities of powder, but oxide-reduction feedstock powders have only been produced by small-batch ball milling processes (e.g., 10 s of grams). Planetary ball milling is capable of processing larger quantities of powder (e.g., 100 s of grams) but has significantly different milling characteristics. To successfully apply this technique, it was systematically studied in terms of composition, milling conditions, and the addition of stearic acid to control powder size and morphology along with final porosity. It was found that by controlling basic parameters, such as oxide levels and milling time, a relatively high porosity (25%) and powder percentage (99%) can be achieved in Cu-2 mol% CuO with only 0.035 wt% stearic acid and only 90 min of milling.
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Porous and functionally graded materials have seen extensive applications in modern biomedical devices-allowing for improved site-specific performance; their appreciable mechanical, corrosive, and biocompatible properties are highly sought after for lightweight and high-strength load-bearing orthopedic and dental implants. Examples of such porous materials are metals, ceramics, and polymers. Although, easy to manufacture and lightweight, porous polymers do not inherently exhibit the required mechanical strength for hard tissue repair or replacement. Alternatively, porous ceramics are brittle and do not possess the required fatigue resistance. On the other hand, porous biocompatible metals have shown tailorable strength, fatigue resistance, and toughness. Thereby, a significant interest in investigating the manufacturing challenges of porous metals has taken place in recent years. Past research has shown that once the advantages of porous metallic structures in the orthopedic implant industry have been realized, their biological and biomechanical compatibility-with the host bone-has been followed up with extensive methodical research. Various manufacturing methods for porous or functionally graded metals are discussed and compared in this review, specifically, how the manufacturing process influences microstructure, graded composition, porosity, biocompatibility, and mechanical properties. Most of the studies discussed in this review are related to porous structures for bone implant applications; however, the understanding of these investigations may also be extended to other devices beyond the biomedical field.
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Stress shielding remains a challenge in orthopaedic implants, including total hip arthroplasty. Recent development in printable porous implants offers improved patient-specific solutions by providing adequate stability and reducing stress shielding possibilities. This work presents an approach for designing patient-specific implants with inhomogeneous porosity. A novel group of orthotropic auxetic structures is introduced, and their mechanical properties are computed. These auxetic structure units were distributed at different locations on the implant along with optimized pore distribution to achieve optimum performance. A computer tomography (CT) based finite element (FE) model was used to evaluate the performance of the proposed implant. The optimized implant and the auxetic structures were manufactured using laser powder bed-based laser metal additive manufacturing. Validation was done by comparing FE results with experimentally measured directional stiffness and Poisson's ratio of the auxetic structures and strain on the optimized implant. The correlation coefficient for the strain values was within a range of 0.9633-0.9844. Stress shielding was mainly observed in Gruen zones 1, 2, 6, and 7. The average stress shielding on the solid implant model was 56%, reduced to 18% when the optimized implant was used. This significant reduction in stress shielding can decrease the risk of implant loosening and create an osseointegration-friendly mechanical environment on the surrounding bone. The proposed approach can be effectively applied to the design of other orthopaedic implants to minimize stress shielding.
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Ligas , Próteses e Implantes , Humanos , Porosidade , Titânio/químicaRESUMO
Additive manufacturing allows for the production of porous metallic implants for use in orthopaedics, providing excellent mechanical stability and osseointegration. However, the increased surface area of such porous implants also renders them susceptible to bacterial colonization. In this work, two trabecular porous Ti6Al4V alloys produced by electron beam melting were investigated for their osteocompatibility and antimicrobial effects, comparing samples with a silver-coated surface to uncoated samples. Dense grit-blasted Ti samples were used for comparison. The porous samples had pore sizes of 500-600 µm and 5 to 10 µm surface roughness, the silver-coated samples contained 7 at.% Ag, resulting in a cumulative Ag release of 3.5 ppm up to 28 days. Silver reduced the adhesion of Staphylococcus aureus to porous samples and inhibited 72 h biofilm formation by Staphylococcus epidermidis but not that of S. aureus. Primary human osteoblast adhesion, proliferation and differentiation were not impaired in the presence of silver, and expression of osteogenic genes as well as production of mineralized matrix were similar on silver-coated and uncoated samples. Our findings indicate that silver coating of porous titanium implants can achieve antimicrobial effects without compromising osteocompatibility, but higher silver contents may be needed to yield a sustained protection against fast-growing bacteria.
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Antibacterianos , Próteses e Implantes , Prata , Titânio , Ligas/farmacologia , Antibacterianos/farmacologia , Humanos , Porosidade , Impressão Tridimensional , Prata/farmacologia , Staphylococcus aureus , Titânio/farmacologiaRESUMO
We study some mathematical properties of a novel implicit constitutive relation wherein the stress and the linearized strain appear linearly that has been recently put into place to describe elastic response of porous metals as well as materials such as rocks and concrete. In the corresponding mixed variational formulation the displacement, the deviatoric and spherical stress are three independent fields. To treat well-posedness of the quasi-linear elliptic problem, we rely on the one-parameter dependence, regularization of the linear-fractional singularity by thresholding, and applying the Browder-Minty existence theorem for the regularized problem. An analytical solution to the nonlinear problem under constant compression/extension is presented.
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Lamellar pores have superior biocompatibility due to their similarity to the lamellar structure of natural bones. In the present work, porous Ti6Al4V alloys with lamellar pores were successfully fabricated by directionally freeze casting. The lamellar structure/processing relationships were systematically studied through analyzing the interaction between ice front and alloy powders. The structural feature of translamella bridges is observed in the lamellar structure. The volume shrinkage of porous Ti6Al4V alloys is in the range of 44-60%. This is much higher compared with that of the porous ceramics. The solid content in the slurry exerts a strong influence on the porosity, while the freezing ice front velocity affects the structural wavelength and pore width. With the increase in ice front velocity, the structural wavelength decreases by an exponential function. The lamella formation mechanism and porosity gradient along the freezing direction were discussed. Young's modulus and yield stress of porous Ti6Al4V alloys fall in the range of 2-12â¯GPa and 40-300â¯MPa, respectively. The dominant compressive deformation mode is lamella buckling and splitting. The fabricated porous Ti6Al4V alloys possess higher relative yield stress.
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Ligas/química , Congelamento , Titânio/química , Força Compressiva , Testes Mecânicos , Porosidade , Estresse MecânicoRESUMO
Bone defects during acetabular revision of total hip arthroplasty raise a problem of primary fixation and of durable reconstruction. Bone graft with direct cemented fixation or in a reinforcement cage was long considered to be the gold standard; however, failures were reported after 10 years' follow-up, especially in segmental defect of the roof or pelvic discontinuity. In such cases, metallic materials were proposed, to ensure primary fixation by a roughness effect with added screws, and especially to avoid failure due to bone resorption in the medium term. We report a systematic literature analysis, addressing the following questions: (1) What materials are available and can be used with dual mobility (DM) designs? Apart from Trabecular Metal™ (TM), in which a DM cup can be cemented for sizes≥56mm, 4 other porous metals are available (Tritanium™, Trabecular Titanium™, Conceloc™, Regenerex™ and Gription™) although only the first 3 can be associated to DM. (2) Can the cost of these materials be estimated and compared to allograft with reinforcement cage? Considering simply the cost of the implant itself, compared to reconstruction by graft+cage+cemented cup (2100), TM incurs an extra cost of 534, but with 1434 not covered by the French healthcare insurance. The cost of custom implants (apart from hemi-pelvis) ranges between 4200 and 8500, with only 4749 cover. (3) Do metallic materials ensure better survival than allograft+cage, according to severity of bone loss? Metallic reconstruction is claimed (with a low level of evidence) to reduce the risk of iterative loosening, but with a higher rate of dislocation, probably due to the lack of DM in many series. (4) What are the advantages and drawbacks of modular and custom metallic reconstructions? Modular reconstructions do not require 3D preoperative planning, but incur the risks of complications inherent to modularity. Custom implants can deal with more extensive defects, but require 5 to 8 weeks' production and are difficult to implant for the larger ones and/or when revision is limited to the acetabulum. (5) In what indications are these materials irreplaceable? Prior failure of allograft+cage in Paprosky type III defect with or without pelvic discontinuity shows the greatest benefit from metallic reconstruction, conditional on certain technical tricks. Only reconstructions using TM have more than 10 years' follow-up; other materials will need close monitoring. Failures in allograft with reinforcement cages occurred after about 10 years, and TM will need longer follow-up to prove its effectiveness. The high risk of dislocation should enable DM to be used, especially for small-diameter metallic reconstructions.
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Acetábulo/cirurgia , Artroplastia de Quadril , Prótese de Quadril , Desenho de Prótese , Aloenxertos , Transplante Ósseo , Humanos , Porosidade , Reoperação , Tantálio , TitânioRESUMO
Cu50Zr45Al5 bulk metallic glass (BMG) presents high fracture strength. For improving its plasticity and controlling its mechanical properties, superficial dealloying of the BMG was performed. A composite structure containing an inner rod-shaped Cu-Zr-Al amorphous core with high strength and an outer dealloyed nanoporous layer with high energy absorption capacity was obtained. The microstructures and mechanical properties of the composites were studied in detail. It was found, for the first time, that the mechanical properties of Cu50Zr45Al5 BMG can be controlled by adjusting the width of the buffer deformation zone in the dealloyed layer, which can be easily manipulated with different dealloying times. As a result, the compressive strength, compressive strain, and energy absorption capacity of the BMGs can be effectively modulated from 0.9 to 1.5 GPa, from 2.9% to 4.7%, and from 29.1 to 40.2 MJ/m³, respectively. The paper may open a door for developing important engineering materials with regulable and comprehensive performances.
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One of the critical issues in orthopaedic regenerative medicine is the design of bone scaffolds and implants that replicate the biomechanical properties of the host bones. Porous metals have found themselves to be suitable candidates for repairing or replacing the damaged bones since their stiffness and porosity can be adjusted on demands. Another advantage of porous metals lies in their open space for the in-growth of bone tissue, hence accelerating the osseointegration process. The fabrication of porous metals has been extensively explored over decades, however only limited controls over the internal architecture can be achieved by the conventional processes. Recent advances in additive manufacturing have provided unprecedented opportunities for producing complex structures to meet the increasing demands for implants with customized mechanical performance. At the same time, topology optimization techniques have been developed to enable the internal architecture of porous metals to be designed to achieve specified mechanical properties at will. Thus implants designed via the topology optimization approach and produced by additive manufacturing are of great interest. This paper reviews the state-of-the-art of topological design and manufacturing processes of various types of porous metals, in particular for titanium alloys, biodegradable metals and shape memory alloys. This review also identifies the limitations of current techniques and addresses the directions for future investigations.
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Osso e Ossos/fisiologia , Metais/química , Metais/farmacologia , Ortopedia , Próteses e Implantes , Alicerces Teciduais/química , Animais , Osso e Ossos/efeitos dos fármacos , Humanos , PorosidadeRESUMO
Highly porous metal nanowire aerosponges are produced by direct assembly of the Cu nanowire in situ during their synthesis. Such a method offers not only great simplicity, but also excellent properties such as extremely low densities, high electrical conductivities, and remarkable mechanical properties. Furthermore, these Cu aerosponges exhibit excellent wicking behavior, suggesting their potential for heat-exchange applications in heat pipes.
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We report a universal platform for the synthesis of monolithic porous gold materials with hierarchical bicontinuous morphology and combined macro- and mesoporosity using a synergistic combination of nanocasting and chemical dealloying. This robust and accessible approach offers a new design paradigm for the parallel optimization of active surface area and mass transport in porous metal electrodes.