Additively manufactured hierarchical stainless steels with high strength and ductility.

Many traditional approaches for strengthening steels typically come at the expense of useful ductility, a dilemma known as strength-ductility trade-off. New metallurgical processing might offer the possibility of overcoming this. Here we report that austenitic 316L stainless steels additively manufactured via a laser powder-bed-fusion technique exhibit a combination of yield strength and tensile ductility that surpasses that of conventional 316L steels. High strength is attributed to solidification-enabled cellular structures, low-angle grain boundaries, and dislocations formed during manufacturing, while high uniform elongation correlates to a steady and progressive work-hardening mechanism regulated by a hierarchically heterogeneous microstructure, with length scales spanning nearly six orders of magnitude. In addition, solute segregation along cellular walls and low-angle grain boundaries can enhance dislocation pinning and promote twinning. This work demonstrates the potential of additive manufacturing to create alloys with unique microstructures and high performance for structural applications.

Synthesis of Nanostructured/Macroscopic Low-Density Copper Foams Based on Metal-Coated Polymer Core-Shell Particles.

A robust, millimeter-sized low-density Cu foam with ∼90% (v/v) porosity, ∼30 nm thick walls, and ∼1 µm diameter spherical pores is prepared by the slip-casting of metal-coated polymer core-shell particles followed by a thermal removal of the polymer. In this paper, we report our key findings that enable the development of the low-density Cu foams. First, we need to synthesize polystyrene (PS) particles coated with a very thin Cu layer (in the range of tens of nanometers). A simple reduction in the amount of Cu deposited onto the PS was not sufficient to form such a low-density Cu foams due to issues related to foam collapse and densification upon the subsequent polymer removal step. Precise control over the morphology of the Cu coating on the particles is essential for the synthesis of a lower density of foams. Second, improving the dispersion of PS-Cu particles in a suspension used for the casting as well as careful optimization of a baking condition minimize the formation of irregular large voids, leading to Cu foams with a more uniform packing and a better connectivity of neighboring Cu hollow shells. Finally, we analyzed mechanical properties of the Cu foams with a depth-sensing indentation test. The uniform Cu foams show a significant improvement in mechanical properties (∼1.5× modulus and ∼3× hardness) compared to those of uncontrolled foam samples with a similar foam density but irregular large voids. Higher surface areas and a good electric conductivity of the Cu foams present a great potential to future applications.

In Situ Real-Time Radiographic Study of Thin Film Formation Inside Rotating Hollow Spheres.

Hollow spheres with uniform coatings on the inner surface have applications in optical devices, time- or site-controlled drug release, heat storage devices, and target fabrication for inertial confinement fusion experiments. The fabrication of uniform coatings, which is often critical for the application performance, requires precise understanding and control over the coating process and its parameters. Here, we report on in situ real-time radiography experiments that provide critical spatiotemporal information about the distribution of fluids inside hollow spheres during uniaxial rotation. Image analysis and computer fluid dynamics simulations were used to explore the effect of liquid viscosity and rotational velocity on the film uniformity. The data were then used to demonstrate the fabrication of uniform sol-gel chemistry derived porous polymer films inside 2 mm inner diameter diamond shells.

Ultra-strong and low-density nanotubular bulk materials with tunable feature sizes.

The synthesis of ultralow-density (>5 mg/cm(3) ) bulk materials with interconnected nanotubular morphology and deterministic, fully tunable feature size, composition, and density is presented. A thin-walled nanotubular design realized by employing templating based on atomic layer deposition makes the material about 10 times stronger and stiffer than aerogels of the same density.

Atomic layer deposition-derived ultra-low-density composite bulk materials with deterministic density and composition.

A universal approach for on-demand development of monolithic metal oxide composite bulk materials with air-like densities (<5 mg/cm(3)) is reported. The materials are fabricated by atomic layer deposition of titania (TiO2) or zinc oxide (ZnO) using the nanoscale architecture of 1 mg/cm(3) SiO2 aerogels formed by self-organization as a blueprint. This approach provides deterministic control over density and composition without affecting the nanoscale architecture of the composite material that is otherwise very difficult to achieve. We found that these materials provide laser-to-X-ray conversion efficiencies of up to 5.3%, which is the highest conversion efficiency yet obtained from any foam-based target, thus opening the door to a new generation of highly efficient laser-induced nanosecond scale multi-keV X-ray sources.

Deterministic control over high-Z doping of polydicyclopentadiene-based aerogel coatings.

We report on simple and efficient routes to dope polydicyclopentadiene (PDCPD)-based aerogels and their coatings with high-Z tracer elements. Initially, direct halogenation of PDCPD wet gels and aerogels with elemental iodine or bromine was studied. Although several pathways were identified that allowed doping of PDCPD aerogels by direct addition of bromine or iodine to the unsaturated polymer backbone, they all provided limited control over the amount and uniformity of doping, especially at very low dopant concentrations. Deterministic control over the doping level in polymeric aerogels and aerogel coatings was then achieved by developing a copolymerization approach with iodine and tin containing comonomers. Our results highlight the versatility of the ring-opening metathesis polymerization (ROMP)-based copolymerization approach in terms of functionalization and doping of low density polymeric aerogels and their coatings.

Defective twin boundaries in nanotwinned metals.

Coherent twin boundaries (CTBs) are widely described, both theoretically and experimentally, as perfect interfaces that play a significant role in a variety of materials. Although the ability of CTBs in strengthening, maintaining the ductility and minimizing the electron scattering is well documented, most of our understanding of the origin of these properties relies on perfect-interface assumptions. Here we report experiments and simulations demonstrating that as-grown CTBs in nanotwinned copper are inherently defective with kink-like steps and curvature, and that these imperfections consist of incoherent segments and partial dislocations. We further show that these defects play a crucial role in the deformation mechanisms and mechanical behaviour of nanotwinned copper. Our findings offer a view of the structure of CTBs that is largely different from that in the literature, and underscore the significance of imperfections in nanotwin-strengthened materials.

ALD functionalized nanoporous gold: thermal stability, mechanical properties, and catalytic activity.

Nanoporous metals have many technologically promising applications, but their tendency to coarsen limits their long-term stability and excludes high temperature applications. Here, we demonstrate that atomic layer deposition (ALD) can be used to stabilize and functionalize nanoporous metals. Specifically, we studied the effect of nanometer-thick alumina and titania ALD films on thermal stability, mechanical properties, and catalytic activity of nanoporous gold (np-Au). Our results demonstrate that even only 1 nm thick oxide films can stabilize the nanoscale morphology of np-Au up to 1,000°C, while simultaneously making the material stronger and stiffer. The catalytic activity of np-Au can be drastically increased by TiO(2) ALD coatings. Our results open the door to high-temperature sensor, actuator, and catalysis applications and functionalized electrodes for energy storage and harvesting applications.

Matrix-assisted energy conversion in nanostructured piezoelectric arrays.

We demonstrate an organic/inorganic hybrid energy-harvesting platform, based on nanostructured piezolelectric arrays embedded in an environmental-responsive polymer matrix, which can self-generate electrical power by scavenging energy from the environment. A proof of principle device is designed, fabricated, and tested using vertically aligned ZnO nanowires and heat as the local energy source. The device layout takes advantage of the collective stretching motion of piezoelectric ZnO NWs, induced by the shape-change of the matrix polymer, to convert the thermal energy into direct current with output power densities of ∼20 nW/cm(2) at a heating temperature of ∼65 °C. The responsive nature of polymeric matrices to various stimuli makes this nanostructured piezoelectric architecture a highly versatile approach to scavenging energy from a multitude of environments including fluid-based and chemical-rich systems.

Effect of surface chemistry on the stability of gold nanostructures.

Understanding the role of surface chemistry in the stability of nanostructured noble-metal materials is important for many technological applications but experimentally difficult to access and thus little understood. To develop a fundamental understanding of the effect of surface chemistry on both the formation and stabilization of self-organized gold nanostructures, we performed a series of controlled-environment annealing experiments on nanoporous gold (np-Au) and ion-bombarded Au(111) single-crystal surfaces. The annealing experiments on np-Au in ambient ozone were carried out to study the effect of adsorbed oxygen under dynamic conditions, whereas the ion-bombarded Au single-crystal surfaces were used as a model system to obtain atomic-scale information. Our results show that adsorbed oxygen stabilizes nanoscale gold structures at low temperatures whereas oxygen-induced mobilization of Au surface atoms seems to accelerate the coarsening under dynamic equilibrium conditions at higher temperatures.

Electrocapillary maximum and potential of zero charge of carbon aerogel.

We present an electrochemical study of carbon aerogel (CA) in aqueous sodium fluoride solutions, focusing on the comparison of two quantities that are related to the potential of zero charge (pzc): the capacitance minimum and the 'electrocapillary maximum' of the surface forces. Capacitance minima are well resolved in our samples. Their potential emerges reproducibly as around 90 mV (vs. Ag/AgCl in KCl), similar to the value, 70 mV, of bulk glassy carbon which we use for comparison, and similar to previous reported pzc values for carbon materials. Significantly, no electrocapillary maximum is found in this potential range. This demonstrates that the pzc does not necessarily coincide with the potential of the maximum of surface stress. We also determined the area-specific capacitances, c(a) = 2.8 microF cm(-2), which agrees well with reports for the basal-plane of graphite single crystals. Our experiments yield large reversible strain amplitudes, up to 0.45%.

Ultralow loading Pt nanocatalysts prepared by atomic layer deposition on carbon aerogels.

Using atomic layer deposition (ALD), we show that Pt nanoparticles can be deposited on the inner surfaces of carbon aerogels (CA). The resultant Pt-loaded materials exhibit high catalytic activity for the oxidation of CO even at loading levels as low as approximately 0.05 mg Pt/cm2. We observe a conversion efficiency of nearly 100% in the 150-250 degrees C temperatures range, and the total conversion rate seems to be limited only by the thermal stability of the CA support in ambient oxygen. The ALD approach described here is universal in nature, and can be applied to the design of new catalytic materials for a variety of applications, including fuel cells, hydrogen storage, pollution control, green chemistry, and liquid fuel production.

Three-dimensional nanofabrication with elastomeric phase masks.

This Feature Article reviews recent work on an optical technique for fabricating, in a single exposure step, three-dimensional (3D) nanostructures with diverse structural layouts. The approach, which we refer to as proximity field nanopatterning, uses conformable, elastomeric phase masks to pattern thick layers of transparent, photosensitive materials in a conformal contact mode geometry. Aspects of the optics, the materials, and the physical chemistry associated with this method are outlined. A range of 3D structures illustrate its capabilities, and several application examples demonstrate possible areas of use in technologies ranging from microfluidics to photonic materials to density gradient structures for chemical release and high-energy density science.

Thick, three-dimensional nanoporous density-graded materials formed by optical exposures of photopolymers with controlled levels of absorption.

Three-dimensional (3D) intensity distributions generated by light passing through conformal phase masks can be modulated by the absorption property of photosensitive materials. The intensity distributions have extremely long depth of focus, which is proportional to the size of the phase masks, and this enables one to pattern thick (approximately 100 microm), nanoporous structures with precise control of grade density. Various density-graded 3D structures that result from computational modeling are demonstrated. Results of x-ray radiograph and the controlled absorption coefficient prove the dominant mechanism of the generated graded density is absorption of the photosensitive materials. The graded-density structures can be applied to a chemical reservoir for controlled release of chemicals and laser target reservoirs useful to shape shockless wave compression.

Ductile crystalline-amorphous nanolaminates.

It is known that the room-temperature plastic deformation of bulk metallic glasses is compromised by strain softening and shear localization, resulting in near-zero tensile ductility. The incorporation of metallic glasses into engineering materials, therefore, is often accompanied by complete brittleness or an apparent loss of useful tensile ductility. Here we report the observation of an exceptional tensile ductility in crystalline copper/copper-zirconium glass nanolaminates. These nanocrystalline-amorphous nanolaminates exhibit a high flow stress of 1.09 +/- 0.02 GPa, a nearly elastic-perfectly plastic behavior without necking, and a tensile elongation to failure of 13.8 +/- 1.7%, which is six to eight times higher than that typically observed in conventional crystalline-crystalline nanolaminates (<2%) and most other nanocrystalline materials. Transmission electron microscopy and atomistic simulations demonstrate that shear banding instability no longer afflicts the 5- to 10-nm-thick nanolaminate glassy layers during tensile deformation, which also act as high-capacity sinks for dislocations, enabling absorption of free volume and free energy transported by the dislocations; the amorphous-crystal interfaces exhibit unique inelastic shear (slip) transfer characteristics, fundamentally different from those of grain boundaries. Nanoscale metallic glass layers therefore may offer great benefits in engineering the plasticity of crystalline materials and opening new avenues for improving their strength and ductility.

Structure of low-density nanoporous dielectrics revealed by low-vacuum electron microscopy and small-angle X-ray scattering.

Aerogels (AGs) are ultralow-density nanoporous solids that have numerous potential applications. However, as most AGs are strong insulators with poor mechanical properties, direct studies of the complex nanoporous structure of AGs by methods such as atomic force and conventional scanning electron microscopy (SEM) have not proven feasible. Here, we use low-vacuum SEM to image directly the ligament and pore size and shape distributions of representative AGs over a wide range of length scales (approximately 100-105 nm). The structural information obtained is used for unambiguous, real-space interpretation of small-angle X-ray scattering curves for these complex nanoporous systems. Low-vacuum SEM permits imaging of both cross-sections and skin layers of AG monoliths. Images of skin layers reveal the presence of microcracks, which alter the properties of cast monolithic AGs.

Size effects on the mechanical behavior of nanoporous Au.

Recent nanomechanical tests on submicron metal columns and wires have revealed a dramatic increase in yield strength with decreasing sample size. Here, we demonstrate that nanoporous metal foams can be envisioned as a three-dimensional network of ultrahigh-strength nanowires, thus bringing together two seemingly conflicting properties: high strength and high porosity. Specifically, we characterized the size-dependent mechanical properties of nanoporous gold using a combination of nanoindentation, column microcompression, and molecular dynamics simulations. We find that nanoporous gold can be as strong as bulk Au, despite being a highly porous material, and that the ligaments in nanoporous gold approach the theoretical yield strength of Au.