Scalable Fabrication of High-Performance Thin-Shell Oxide Nanoarchitected Materials via Proximity-Field Nanopatterning.

Nanoarchitected materials are considered as a promising research field, deriving distinctive mechanical properties by combining nanomechanical size effects with conventional structural engineering. Despite the successful demonstration of the superiority and feasibility of nanoarchitected materials, scalable and facile fabrication techniques capable of macroscopically producing such materials at a low cost are required to take advantage of the nanoarchitected materials for specific applications. Unlike conventional techniques, proximity-field nanopatterning (PnP) is capable of simultaneously obtaining high spatial resolution and mass producibility in synthesizing such nanoarchitected materials in the form of an inch-scale film. Herein, we focus on the feasibility of using PnP as a scalable fabrication technique for three-dimensional nanostructures and the superiority of the resultant thin-shell oxide nanoarchitected materials for specific applications, such as lightweight structural materials, mechanically robust nanocomposites, and high-performance piezoelectric materials. This review will discuss and summarize the relevant results obtained for nanoarchitected materials synthesized by PnP and provide suggestions for future research directions for scalable manufacturing and application.

Friction Control by Deformation Mode in Nanopatterned Amorphous Carbon.

Traditionally, the manipulation of contact mechanisms has been adopted as the primary strategy to tailor the friction properties of surfaces. On the contrary, the detaching process involving the local deformation and failure at the interface has been considered relatively less important. Here, we present a new approach toward the friction control of amorphous carbon through the plasticity and resultant transition of deformation mode on nanopatterned surfaces. Depending on the topography of the nanopatterns, the mechanical responses of the surfaces alter from elastic fracture to plastic flow, through which the friction coefficient changes by a factor of 5 without manipulation of the intrinsic structure of the material.

Stabilized Amorphous Calcium Carbonate as a Precursor of Microcoating on Calcite.

Highly controlled biomineralization of calcium carbonate is via non-classical mesocrystallization of amorphous precursors. In the present study, a simple in vitro assay was developed to mimic the biological process, which involved stabilized amorphous calcium carbonate and a single crystal substrate of calcite. The microcoating layer formed on the calcite substrate displayed mesocrystalline characteristics, and the layers near the substrate were strongly influenced by the epitaxy to the substrate. This behavior was preserved even when the morphology of the coating layer was modified with poly(acrylic acid), a model anionic macromolecule. Interestingly, the extent of the epitaxy increased substantially with poly(ethylene imine), which barely affected the crystal morphology. The in vitro assay in the present study will be useful in the investigations of the biomineralization and bioinspired crystallization of calcium carbonate in general.

Microstructural Evolution of Al-Zn-Mg-Cu Alloys in Accordance with Homogenization Time.

The microstructural evolution of Al-Zn-Mg-Cu alloys has been investigated for the homogenization time effect on the texture, grain orientation and dislocation density. The Al-Zn-Mg-Cu alloys were casted and homogenized for 4, 8, 16 and 24 hours. Electron backscatter diffraction (EBSD) analysis was conducted to characterize the microstructural behavior. Micropillars were fabricated using focused ion beam (FIB) milling in grains of specific crystallographic orientations. Coarse precipitations in the grain boundaries are S (Al2CuMg) and T (Al2Mg3Zn3) phases verified by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) observation. With increasing homogenization time, equiaxed cell sizes increased. The volume fraction of S and T phases decreased with the diffusion of atomic elements into matrix. The Vickers hardness and tensile strength values decreased with homogenization temperature. The micropillar compression analysis was compared to macro tensile test results to understand the size effect and strain burst phenomenon on the mechanical properties of Al-Zn-Mg-Cu alloys.

Ductilization of Nanoporous Ceramics by Crystallinity Control.

Synthesizing ceramic materials with a significant amount of deformability is one of the most important engineering pursuits. In this study, we demonstrate the emergence of metal-like plasticity through the crystallinity control in the monolithic zirconia with the vertically aligned honeycomb-like periodic nanopore structures fabricated using the anodizing technique. The crystalline orders of the nanoporous zirconia films vary between monoclinic, tetragonal, and amorphous phases after the heat treatment and/or proton irradiation, whereas the vertical pore structures are maintained. The micropillar compression tests on those samples reveal a large amount of plasticity, more than 20% of total stains, in the as-anodized and proton-irradiated samples, both of which contain the amorphous phase. In contrast, the fully crystallized zirconia that resulted from annealing at 500 °C shows the brittle failure, the typical characteristic of conventional ceramic foams. These results offer a new opportunity for the nanoporous ceramic materials to be used in various applications, benefited from the tunable structural stability.

Transparent Urethane-Siloxane Hybrid Materials for Flexible Cover Windows with Ceramic-Like Strength, yet Polymer-Like Modulus.

Any transition toward an era of flexible electronics will have to overcome the mechanical limitations of materials. Specifically, the attainment of both strength and flexibility, which are generally mutually exclusive, is required including glass-like wear resistance, plastic-like compliance, and a high level of strain. Here, we fabricate a urethane-methacrylate-siloxane hybrid (UMSH) material. It is found that UMSH, with molecule-level hybridization of urethane linkage and methacrylate-siloxane conetworks, demonstrates ceramic-like high strength (574 MPa), yet polymer-like low modulus (8.42 GPa), and even high strain (6.3%) at fracture with excellent optical transparency. This combination of high strength, flexibility, and optical transparency indicates that this is a suitable material for glass substitution and can be used as a transparent flexible cover window for foldable display.

Emergence of New Density-Strength Scaling Law in 3D Hollow Ceramic Nanoarchitectures.

Density-strength tradeoff appears to be an inherent limitation for most materials and therefore design of cell topology that mitigates strength decrease with density reduction has been a long-lasting engineering pursue for porous materials. Continuum-mechanics-based analyses of mechanical responses of conventional porous materials with bending-dominated structures often give the density-strength scaling law following the power-law relationship with an exponent of 1.5 or higher, which consequentially determines the upper bound of the specific strength for a material to reach. In this work, a new design criterion capable of significantly abating strength degradation in lightweight materials is presented, by successfully combining the size-induced strengthening effect in nanomaterials with the architectural design of cellular porous materials. Hollow-tube-based 3D ceramic nanoarchitectures satisfying such criterion are fabricated in large area using proximity field nano-patterning and atomic layer deposition. Experimental data from micropillar compression confirm that the strengths of these nanoarchitectural materials scale with relative densities with a power-law exponent of 0.93, a hardly observable value in conventional bending-dominated porous materials. This discovery of a new density-strength scaling law in nanoarchitectured materials will contribute to creating new lightweight structural materials attaining unprecedented specific strengths overcoming the conventional limit.

Multifunctional Polymer Nanocomposites Reinforced by 3D Continuous Ceramic Nanofillers.

Polymer nanocomposites with inclusion of ceramic nanofillers have relatively high yield strength, elastic moduli, and toughness that therefore are widely used as functional coating and films for optoelectronic applications. Although the mechanical properties are enhanced with increasing the fraction of nanofiller inclusion, there generally is an upper limit on the amount of nanofiller inclusion because the aggregation of the fillers in the polymer matrix, which typically occurs, degrades the mechanical and/or optical performances above 5 vol % of inclusions. Here, we demonstrate an unconventional polymer nanocomposite composed of a uniformly distributed three-dimensional (3D) continuous ceramic nanofillers, which allows for extremely high loading (∼19 vol %) in the polymer matrix without any concern of aggregation and loss in transparency. The fabrication strategy involves conformal deposition of Al2O3 nanolayer with a precise control in thickness that ranges from 12 to 84 nm on a 3D nanostructured porous polymer matrix followed by filling the pores with the same type of polymer. The 3D continuous Al2O3 nanolayers embedded in the matrix with extremely high filler rate of 19.17 vol % improve compressive strength by 142% compared to the pure epoxy without Al2O3 filler, and this value is in agreement with theoretically predicted strength through the rule of mixture. These 3D nanocomposites show superb transparency in the visible (>85% at 600 nm) and near-IR (>90% at 1 µm) regions and improved heat dissipation beyond that of conventional Al2O3 dispersed nanocomposites with similar filler loading of 15.11 vol % due to the existence of a continuous thermal conduction path through the oxide network.

Flexible Hard Coating: Glass-Like Wear Resistant, Yet Plastic-Like Compliant, Transparent Protective Coating for Foldable Displays.

A flexible hard coating for foldable displays is realized by the highly cross-linked siloxane hybrid using structure-property relationships in organic-inorganic hybridization. Glass-like wear resistance, plastic-like flexibility, and highly elastic resilience are demonstrated together with outstanding optical transparency. It provides a framework for the application of siloxane hybrids in protective hard coatings with high scratch resistance and flexibility for foldable displays.

Delocalized Plastic Flow in Proton-Irradiated Monolithic Metallic Glasses.

Creating new materials with novel properties through structural modification is the Holy Grail of materials science. The range of targetable structures for amplification of mechanical properties in metallic glasses would include types of atomic short range orders at the smallest scale through compositions or morphologies of phases in composites. Even though the usefulness of the latter approach has been successfully demonstrated in the past decades, the feasibility of the former has been incompletely proved with only marginal property improvements reported within experimentally-accessible atomic-level structural changes. Here, we report the significant enhancement of deformability in Zr-based monolithic metallic glass only through the atomic disordering by proton irradiation without altering any other structural traits. Metallic glass nanopillars that originally failed catastrophically without any notable plasticity become capable of attaining more than 30% uniaxial plastic strain accommodated by homogeneous deformation when irradiated to ~1 displacement per atom (DPA). We discuss the atomistic origin of this improved plasticity in terms of density and spatial distributions of icosahedral short range order influenced by irradiation.

Grain boundary sliding in aluminum nano-bi-crystals deformed at room temperature.

Room-temperature uniaxial compressions of 900-nm-diameter aluminum bi-crystals, each containing a high-angle grain boundary with a plane normal inclined at 24° to the loading direction, revealed frictional sliding along the boundary plane to be the dominant deformation mechanism. The top crystallite sheared off as a single unit in the course of compression instead of crystallographic slip and extensive dislocation activity, as would be expected. Compressive stress strain data of deforming nano bicrystals was continuous, in contrast to single crystalline nano structures that show a stochastic stress strain signature, and displayed a peak in stress at the elastic limit of ~ 176 MPa followed by gradual softening and a plateau centered around ~ 125 MPa. An energetics-based physical model, which may explain observed room-temperature grain boundary sliding, in presented, and observations are discussed within the framework of crystalline nano-plasticity and defect microstructure evolution.

Fabrication and deformation of three-dimensional hollow ceramic nanostructures.

Creating lightweight, mechanically robust materials has long been an engineering pursuit. Many siliceous skeleton species--such as diatoms, sea sponges and radiolarians--have remarkably high strengths when compared with man-made materials of the same composition, yet are able to remain lightweight and porous. It has been suggested that these properties arise from the hierarchical arrangement of different structural elements at their relevant length scales. Here, we report the fabrication of hollow ceramic scaffolds that mimic the length scales and hierarchy of biological materials. The constituent solids attain tensile strengths of 1.75 GPa without failure even after multiple deformation cycles, as revealed by in situ nanomechanical experiments and finite-element analysis. We discuss the high strength and lack of failure in terms of stress concentrators at surface imperfections and of local stresses within the microstructural landscape. Our findings suggest that the hierarchical design principles offered by hard biological organisms can be applied to create damage-tolerant lightweight engineering materials.

Deformation mechanisms in nanotwinned metal nanopillars.

Nanotwinned metals are attractive in many applications because they simultaneously demonstrate high strength and high ductility, characteristics that are usually thought to be mutually exclusive. However, most nanotwinned metals are produced in polycrystalline forms and therefore contain randomly oriented twin and grain boundaries making it difficult to determine the origins of their useful mechanical properties. Here, we report the fabrication of arrays of vertically aligned copper nanopillars that contain a very high density of periodic twin boundaries and no grain boundaries or other microstructural features. We use tension experiments, transmission electron microscopy and atomistic simulations to investigate the influence of diameter, twin-boundary spacing and twin-boundary orientation on the mechanical responses of individual nanopillars. We observe a brittle-to-ductile transition in samples with orthogonally oriented twin boundaries as the twin-boundary spacing decreases below a critical value (∼3-4 nm for copper). We also find that nanopillars with slanted twin boundaries deform via shear offsets and significant detwinning. The ability to decouple nanotwins from other microstructural features should lead to an improved understanding of the mechanical properties of nanotwinned metals.

Catastrophic vs gradual collapse of thin-walled nanocrystalline Ni hollow cylinders as building blocks of microlattice structures.

Lightweight yet stiff and strong lattice structures are attractive for various engineering applications, such as cores of sandwich shells and components designed for impact mitigation. Recent breakthroughs in manufacturing enable efficient fabrication of hierarchically architected microlattices, with dimensional control spanning seven orders of magnitude in length scale. These materials have the potential to exploit desirable nanoscale-size effects in a macroscopic structure, as long as their mechanical behavior at each appropriate scale - nano, micro, and macro levels - is properly understood. In this letter, we report the nanomechanical response of individual microlattice members. We show that hollow nanocrystalline Ni cylinders differing only in wall thicknesses, 500 and 150 nm, exhibit strikingly different collapse modes: the 500 nm sample collapses in a brittle manner, via a single strain burst, while the 150 nm sample shows a gradual collapse, via a series of small and discrete strain bursts. Further, compressive strength in 150 nm sample is 99.2% lower than predicted by shell buckling theory, likely due to localized buckling and fracture events observed during in situ compression experiments. We attribute this difference to the size-induced transition in deformation behavior, unique to nanoscale, and discuss it in the framework of "size effects" in crystalline strength.

Influence of homogeneous interfaces on the strength of 500 nm diameter Cu nanopillars.

Interfaces play an important role in crystalline plasticity as they affect strength and often serve as obstacles to dislocation motion. Here we investigate effects of grain and nanotwin boundaries on uniaxial strength of 500 nm diameter Cu nanopillars fabricated by e-beam lithography and electroplating. Uniaxial compression experiments reveal that strength is lowered by introducing grain boundaries and significantly rises when twin boundaries are present. Weakening is likely due to the activation of grain-boundary-mediated processes, while impeding dislocation glide can be responsible for strengthening by twin boundaries.

Transition from a strong-yet-brittle to a stronger-and-ductile state by size reduction of metallic glasses.

Amorphous metallic alloys, or metallic glasses, are lucrative engineering materials owing to their superior mechanical properties such as high strength and large elastic strain. However, their main drawback is their propensity for highly catastrophic failure through rapid shear banding, significantly undercutting their structural applications. Here, we show that when reduced to 100 nm, Zr-based metallic glass nanopillars attain ceramic-like strengths (2.25 GPa) and metal-like ductility (25%) simultaneously. We report separate and distinct critical sizes for maximum strength and for the brittle-to-ductile transition, thereby demonstrating that strength and ability to carry plasticity are decoupled at the nanoscale. A phenomenological model for size dependence and brittle-to-homogeneous deformation is provided.