Uniaxial compression testing of bulk nanoporous gold

Abstract

The mechanical properties of bulk nanoporous gold (np–Au) with a relative density of 0.35 were investigated by compression testing of millimetre-scale specimens. Young’s modulus, Poisson’s ratio and yield strength values were determined from uniaxial, quasi-static experiments using a custom-built mechanical testing system. The cuboid-shaped specimens were fabricated following a specific, controlled process (including cutting and grinding) that guaranteed a precise and repeatable geometry. The np–Au structure was created from a silver–gold alloy by electrochemical dealloying in nitric acid. Mechanical properties obtained from compression testing are compared to values reported in the literature and to scaling relations. Values are found to agree with a recently proposed scaling relation for the yield strength of np–Au that incorporates a ligament size effect and a modified scaling exponent.     

Effects of pores and temperature on mechanics of gold nanowires using molecular dynamics

The deformation mechanisms of gold nanowires with different nanopores under tension were simulated by molecular dynamics (MD). The stress–strain curves varied from different porous defects, and the tension caused dislocations to take place and slip along plane (1 1 1). Moreover, the tensile strength of the nanoporous monocrystalline gold was decreased when the simulated temperature increased. The stress concentrations factors of porous nanowires were calculated, and it was found that there was a great influence of size and model effects on the stress concentration factors.     

Mechanical properties of bulk single crystalline nanoporous gold investigated by millimetre-scale tension and compression testing

In this work, the mechanical behaviour of millimetre-scale, bulk single crystalline, nanoporous gold at room temperature is reported for the first time. Tension and compression tests were performed with a custom-designed test system that accommodates small-scale samples. The absence of grain boundaries in the specimens allowed measurement of the inherent strength of millimetre-scale nanoporous gold in tension. The elastic modulus and strength values in tension and compression were found to be significantly lower than values measured with nanoindentation-based techniques and previously reported in the literature, but close to those reported for millimetre-scale polycrystalline samples tested using traditional compression techniques. Fracture toughness was found to be very low, in agreement with the macroscopic brittleness of nanoporous gold, but this is due to the localization of deformation to a narrow zone of ligaments, which individually exhibit significant plasticity and necking.     

Hybrid Nanoparticle Film Material

A new hybrid material consisting of a nanoparticle film on a flexible, porous substrate is formed. The hybrid nanoparticle films are non-redispersable in solvents, yet remain porous and flexible. Visually, the hybrid films are highly reflective and metallic gold in appearance. However, the electronic properties of the films are characteristic for materials made from separate, non-sintered nanoparticles. Films of large area (several tens of cm²) and several microns in thickness can be formed. The method of formation is based on cross-linking gold nanoparticles using alkane-dithiols followed by filtration onto nanoporous supports. The films were characterized by transmission electron microscopy, atomic force microscopy and resistance measurements. The effect of the ratio of alkane-dithiol cross-linker to gold nanoparticles on the resistance of the nanoparticle films was also studied.     

纳米多孔银力学性能表征分子动力学模拟

纳米多孔金属拥有优异的物理、化学性能,在众多领域中极具应用前景.相关力学性能的认知是实现其功能化应用的重要基础之一.基于分子动力学模拟,以三种拓扑结构(立方体结构、金刚石结构、螺旋体结构)的纳米多孔银为对象,研究了单轴拉伸下的力学响应,探讨了拓扑结构和相对密度与其力学性能的内在联系.仿真结果表明,纳米多孔银的极限强度和杨氏模量随相对密度增大而增大的同时,还紧密地依赖于拓扑结构.其中,金刚石结构与螺旋体结构的模量随相对密度的变化趋势较为相近,而螺旋体结构中螺旋形式的孔棱在受力拉直的过程中抵抗变形,表现出相对较好的塑性.立方体结构中,孔棱分布形式单一,抵抗变形的能力较弱,模量值较低.同一相对密度下,金刚石结构的强度最大,立方体结构次之,螺旋体结构最小.金刚石结构中,交错的孔棱间形成三角骨架结构,具有一定的稳定性,表现出相对较高的强度.     

自支撑纳米多孔金薄膜制备研究

采用磁控溅射镀金银膜,长时间热处理合金化制备前驱体合金,以渐进浓度的硝酸自由腐蚀去合金化成功制备出具有自支撑结构的纳米多孔金薄膜。采用扫描电镜和X射线能谱仪对去合金腐蚀前后样品的形貌和成分进行了分析,结果表明:400℃,36h的热处理使得薄膜样品完全合金化,获得了结晶致密的Au42Ag58合金膜;渐进浓度的自由腐蚀避免了薄膜的完全开裂,获得了样品尺寸大于15mm×15mm、厚度400~500nm、孔隙率约56%、具有自支撑结构的纳米多孔金薄膜,其微观结构为连续的三维多孔结构,系带尺寸40~140nm,80~100nm的系带达58%。     

Controlled ligament coarsening in nanoporous gold by annealing in vacuum versus nitrogen

The structural evolution of nanoporous gold during thermal treatment was studied by annealing samples in vacuum and in flowing nitrogen. As expected, ligament thickness generally increased in both environments. However, ligaments annealed at high temperature in vacuum remained relatively narrow, undergoing much less coarsening than nitrogen-annealed samples, albeit with some ligament agglomeration. When annealed in flowing nitrogen, gold ligaments coarsened significantly at temperatures above 300?°C. This discrepancy is attributed to different surface diffusion rates of gold in the two annealing environments. The current results suggest that diffusion on the surfaces of nanoporous gold ligaments proceeds more quickly in nitrogen than in vacuum.     

Nanoporous gold: 3D structural analyses of representative volumes and their implications on scaling relations of mechanical behaviour

We present a quantitative study of the salient structural parameters identified from so-called ‘representative volumes’ of the bicontinuous nanoporous gold (NPG) network, and examine the validity of self-similarity in describing its evolution. The approach is based on 3D-focused ion beam tomography applied to as-dealloyed and isothermally annealed NPG samples. After identifying sufficiently large representative volumes, we show that the ligament width distributions coarsen in a sufficiently self-similar, time-invariant manner, while the scaled connectivity density shows a self-similar ligament network topology. Using these critical parameters, namely mean ligament diameter and connectivity density, the Gibson–Ashby scaling laws for the mechanical response of cellular materials are revisited. The inappropriateness of directly applying the Gibson–Ashby model to NPG is demonstrated by comparing finite element method compression simulations of both the NPG reconstruction and that of the Gibson–Ashby solid model; rather than the solid volume fraction, we show that an effective load-bearing ring structure governs mechanical behaviour.     

Strengthening Porous PVA with TiO_2 Structure by an Ice-Templating Method

A poly vinyl alcohol(PVA) scaffold with aligned porous is strengthened by in-situ combining with TiO_2. The increased freezing rate can be used to further increase the strength of aligned porous materials. The strengthened porous PVA exhibits aligned interconnected porous structures and shows a significant enhancement in tensile testing and compression strength testing.     

Mechanism of coarsening and bubble formation in high-genus nanoporous metals

Coarsening of crystalline nanoporous metals involves complex changes in topology associated with the reduction of genus via both ligament pinch-off and void bubble formation. Although void bubbles in metals are often associated with vacancy agglomeration, we use large-scale kinetic Monte Carlo simulations to show that both bubble formation and ligament pinch-off are natural results of a surface-diffusion-controlled solid-state Rayleigh instability that controls changes in the topology of the porous material during coarsening. This result is used to find an effective activation energy for coarsening in nanoporous metals that is associated with the reduction of topological genus, and not the reduction of local surface roughness.     

去合金化工艺对纳米多孔铜纯度的影响

采用腐蚀去合金化方法制备纳米多孔铜材料。研究了固溶时间、腐蚀时间及腐蚀温度对纳米多孔铜表面形貌及残余Mn含量的影响。研究表明:由于固溶时间的延长，合金成分越来越均匀化，去合金化后所得纳米多孔铜的残余Mn原子分数降低。固溶95 h的前驱体合金，随着腐蚀时间的延长，其残余Mn含量降低不明显；随着温度的升高，其残余Mn原子分数由25 ℃的3.54%降至60℃的1.14%，但是60 ℃腐蚀后的孔隙与丝径尺寸明显粗化，样品易碎。通过调整去合金化参数，实验所制备的纳米多孔铜呈现均匀的海绵状纳米多孔结构，残余Mn原子分数1.23%, 平均丝径尺寸40 nm。     

金纳米管力学性能的分子动力学模拟

采用分子动力学模拟方法, 研究了金纳米管沿不同晶向拉伸与压缩载荷下的力学性能, 并分析了金纳米管的半径对其力学行为的影响. 在模拟计算中, 采用镶嵌原子势描述金原子之间的相互作用. 模拟结果表明, 在拉伸及压缩过程中, 不同晶向的金纳米管力学性能相差较大, 在拉伸和压缩载荷下金纳米管<110>向的屈服强度最大; 在三个晶向<100>, <110>, <111>的金纳米管中, <100>晶向的金纳米管其屈服强度和杨氏模量都远远小于其他晶向. 研究结果还发现, 当纳米管的半径小于3.0 nm时, 金纳米管的屈服强度没有大的变化, 而当半径大于3.0 nm后, 随着半径的增大, 其屈服强度明显降低. 关键词： 分子动力学模拟 金纳米管 力学性能     

High‐Pressure Evaporation‐Based Nanoporous Black Sn for Enhanced Performance of Lithium‐Ion Battery Anodes

Increasing the surface area to improve chemical activity is an unending task from conventional catalysis to recently emerging electrochemical energy conversion and storage. Here, a simple, vacuum‐deposition‐based method to form nanoporous structures of metals is reported. By utilizing thermal evaporation at a high pressure, fractal‐like nanoporous structures of Sn with porosity exceeding 98% are synthesized. The obtained nanostructure consists of nanoparticle aggregates, and the morphology can be controlled by adjusting the working pressure. The formation of the nanoporous structure is explained by homogeneous nucleation and diffusion‐limited aggregation, where nanoparticles produced by the repeated collisions of evaporated atoms adhere to the substrate without diffusion, forming porous aggregates. Due to the easy oxidation of Sn, the constituent nanoparticles are covered with amorphous SnO_x and crystalline SnO phases. When the nanoporous Sn/SnO_x aggregates are applied to a lithium‐ion battery anode through direct deposition on a Cu foil current collector without binders or conducting additives, the nanoporous Sn/SnO_x anode shows greatly enhanced cyclability and exceptional rate performance compared to those of a dense Sn thin film anode. The approach investigated in this work is expected to provide a new platform to other fields that require highly porous structures.     

Nanoporous Nanocomposite Hydrogels Composed of Polyvinyl Alcohol and Na-montmorillonite

Polyvinyl alcohol nanoporous nanocomposite hydrogels containing various levels of Na-montmorillonite were prepared by a cyclic freezing–thawing technique. An exfoliated morphology of silicate layers was observed for the nanocomposite hydrogels. The uniaxial tensile test indicated that the tensile modulus and tensile strength of the nanocomposite hydrogels increased with increasing Na-montmorillonite content, while their elongation-at-break values decreased. The results showed that by adding 15 wt% of montmorillonite to polyvinyl alcohol hydrogels, the molecular weight of polymer chains between two adjacent cross-links decreased to 56% and the effective cross-linking density increased up to 353%. It is also indicated that all nanocomposite hydrogel samples had nanoscale pore diameters and network mesh sizes less than 30 nm. The nanoporous structure of the nanocomposite hydrogels was confirmed by transmission electron microscopy observations and mercury intrusion porosimetry tests.     

Improved surface-enhanced Raman scattering of patterned gold nanoparticles deposited on silicon nanoporous pillar arrays

Large-area silicon nanoporous pillar arrays (Si-NPA) uniformly coated with gold nanoparticles was synthesized, and surface-enhanced Raman scattering of rhodamine 6G adsorbed on these gold nanoparticles were studied and compared. It's found that Au/Si-NPA substrate has a significantly high Raman signal sensitivity and good homogeneity. These are attributed to gold nanoparticles with narrow particle-size distribution uniformly coated on the surface and to the enlarged specific surface area for adsorption of target molecules brought by the porous silicon pillars.     

Effects of interstitial oxygen and nitrogen on the mechanical properties of niobium-titanium alloys

The effects were studied of the clustering of substitutional titanium with interstitial oxygen or nitrogen on the strength of the niobium −1 at.-% titanium alloy. The observed values of the yield parameters and flow stress were resolved into a sum of contributions due to the solution strengthening and intrinsic strength components. From the obtained relation the substitutional-interstitial complex hardening coefficients for oxygen and nitrogen in the alloy were determined and compared with the respective solution hardening coefficients for unalloyed niobium. It was also found that the strengthening contribution due to atomic size mismatch and modulus differences introduced by unassociated titanium is small in comparison with that due to substitutional-interstitial complexing. In addition, the alloy displays both higher strength and elongation with respect to the base material. Strain-ageing experiments were carried out on the same alloy and the results were combined with the information obtained from the stress-strain tests and the internal friction measurements reported in a previous work.     

On the role of vacancies in pore formation in the course of anodizing of silicon carbide

Experimental data on the preparation of stoichiometric nanoporous silicon carbide are analyzed. Theoretical calculations are performed under the assumption that nanopores are formed through the vacancy diffusion mechanism. The results obtained confirm the hypothesis that the formation of pores with a steadystate radius of several tens of nanometers in silicon carbide can be associated with the diffusion and clustering of vacancies. The experimental data indicating that the proposed mechanism of formation of nanoporous silicon carbide correlates with the existing model of formation of porous silicon carbide with a fiber structure are discussed. This correlation can be revealed by assuming that nanopores are formed at the first stage with subsequent transformation of the nanoporous structure into a fiber structure due to the dissolution of the material in an electrolyte.     

Effects of microgeometry on the permittivity of impregnated porous media

We propose a new approximative relation for the low-frequency dielectric permittivity of liquid-filled porous materials. In this formulation, effects of microgeometry are included through the so-called [Formula: see text] parameter. Our measurements on salt-water-impregnated artificial sandstones support the new relation. We also show that the high permittivities at low frequencies reported earlier for brine-impregnated sintered glass spheres (N?st et al 1992 Phys. Scr. T 44 67) may be due to effects at the solid - liquid interface in the `bulk' porous material. The latter results are also in agreement with our proposed relation.     

Enhancing the interfacial strength of glass/epoxy composites using ZnO nanowires

This paper investigated the application of ZnO nanowires (ZnO NW) to enhance the interfacial strength of glass/epoxy composites. ZnO NW were grown on glass fibers by hydrothermal method, tensile properties of bare and ZnO NW coated fibers were measured by single fiber tensile testing, wettability of fiber with resin was studied by contact angle measurements and finally the interfacial strength and mechanisms were determined by single fiber fragmentation testing of glass/epoxy composites. The surface coverage of ZnO NW on glass fibers was fairly uniform without formation of major clusters. The coating of ZnO NW slightly reduced the tensile strength and improved the tensile modulus of fibers. Wettability tests showed reduction in contact angles for ZnO NW coated fibers because of enhanced wetting and infiltration of epoxy resin into nanowires. In fragmentation testing of microcomposites, smaller and concentrated interfacial debonding zones for ZnO NW coated fibers indicated good stress transfer and strong interfacial adhesion. A new form of crossed and closely spaced stress patterns were observed for nanowires of high aspect ratios. The interfacial strength of ZnO NW coated fibers increased by at least 109% and by 430% on average, which was attributed to the increased surface area and mechanical interlocking provided by ZnO NW.     

Microstructure, bonding strength and thermal shock resistance of ceramic coatings on steels prepared by plasma electrolytic oxidation

Ceramic coatings were successfully prepared on steel by plasma electrolytic oxidation (PEO) in aluminate electrolyte and silicate electrolyte, respectively. The microstructure of the coatings including surface morphology, phase and element composition were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The bonding strength between the ceramic coating and the substrate was tested using different methods including tensile tests and shearing tests. The thermal shock resistance of the coatings was also evaluated. The results indicated that coatings obtained in both electrolytes were porous and coarse. The average diameters of the pores were below 10 μm. PEO coatings obtained in aluminate electrolyte were composed of Fe₃O₄ and FeAl₂O₄, while those obtained in silicate electrolyte were in a noncrystal state. PEO coatings obtained in aluminate electrolyte showed similar change trend of tensile strength and shearing strength with increasing treating time, namely, a relatively high values with middle time treating and low value with short and long time treating. The best coating was the samples treated with 30 min, whose tensile strength was 20.6 MPa and shearing strength was 16 MPa. The tensile strength and shearing strength of coatings obtained in silicate electrolyte were not strongly influenced by the treating time, the values of which were range in 14 ± 2 MPa and 11 ± 2 MPa, respectively. Coatings obtained in both electrolytes showed the best thermal shock resistance with middle time treating. Coatings obtained in silicate electrolyte show a little better thermal shock resistance than those obtained in aluminate electrolyte.