Microstructural design for mechanical-optical multifunctionality in the exoskeleton of the flower beetle Torynorrhina flammea.

Biological systems have a remarkable capability of synthesizing multifunctional materials that are adapted for specific physiological and ecological needs. When exploring structure-function relationships related to multifunctionality in nature, it can be a challenging task to address performance synergies, trade-offs, and the relative importance of different functions in biological materials, which, in turn, can hinder our ability to successfully develop their synthetic bioinspired counterparts. Here, we investigate such relationships between the mechanical and optical properties in a multifunctional biological material found in the highly protective yet conspicuously colored exoskeleton of the flower beetle, Torynorrhina flammea Combining experimental, computational, and theoretical approaches, we demonstrate that a micropillar-reinforced photonic multilayer in the beetle's exoskeleton simultaneously enhances mechanical robustness and optical appearance, giving rise to optical damage tolerance. Compared with plain multilayer structures, stiffer vertical micropillars increase stiffness and elastic recovery, restrain the formation of shear bands, and enhance delamination resistance. The micropillars also scatter the reflected light at larger polar angles, enhancing the first optical diffraction order, which makes the reflected color visible from a wider range of viewing angles. The synergistic effect of the improved angular reflectivity and damage localization capability contributes to the optical damage tolerance. Our systematic structural analysis of T. flammea's different color polymorphs and parametric optical and mechanical modeling further suggest that the beetle's microarchitecture is optimized toward maximizing the first-order optical diffraction rather than its mechanical stiffness. These findings shed light on material-level design strategies utilized in biological systems for achieving multifunctionality and could thus inform bioinspired material innovations.

Seeded laser-induced cavitation for studying high-strain-rate irreversible deformation of soft materials.

Characterizing the high-strain-rate and high-strain mechanics of soft materials is critical to understanding the complex behavior of polymers and various dynamic injury mechanisms, including traumatic brain injury. However, their dynamic mechanical deformation under extreme conditions is technically difficult to quantify and often includes irreversible damage. To address such challenges, we investigate an experimental method, which allows quantification of the extreme mechanical properties of soft materials using ultrafast stroboscopic imaging of highly reproducible laser-induced cavitation events. As a reference material, we characterize variably cross-linked polydimethylsiloxane specimens using this method. The consistency of the laser-induced cavitation is achieved through the introduction of laser absorbing seed microspheres. Based on a simplified viscoelastic model, representative high-strain-rate shear moduli and viscosities of the soft specimens are quantified across different degrees of crosslinking. The quantified rheological parameters align well with the time-temperature superposition prediction of dynamic mechanical analysis. The presented method offers significant advantages with regard to quantifying high-strain rate, irreversible mechanical properties of soft materials and tissues, compared to other methods that rely upon the cyclic dynamics of cavitation. These advances are anticipated to aid in the understanding of how damage and injury develop in soft materials and tissues.

Phytoavailability-based threshold values for cadmium in soil for safer crop production.

The phytoavailability of heavy metals in soils is important for both food safety and environmental management. Hence soil metal phytoavailability threshold values need to be established based on a firm scientific basis. In this study, optimal Cd phytoavailability threshold values, were determined for bean, rice and sesame cultivated in 100 soils varying widely in soil chemical characteristics by comparing the soil Cd phytoavailability obtained using three commonly used extraction procedures. Subsequently, the transfer functions derived in this study, were used to establish soil Cd phytoavailability threshold value standard limits for each specific crop. In addition, independent experimental data were used to supplement the obtained soil phytoavailable Cd threshold value for rice. Soil phytoavailable Cd concentrations extracted by 1 M NH4NO3, 0.05 M EDTA and Mehlich3 solutions were each more significantly correlated with plant Cd concentrations than total soil Cd concentrations. Thus, the soil Cd phytoavailability threshold values proposed in this study provide a more effective means of ensuring safer agricultural food production. Therefore, it is recommended that current agricultural soil heavy metal management policy; which is based on total concentrations; should be changed to embrace soil metal phytoavailability for safer agricultural food production.

Dynamic Strengthening of Carbon Nanotube Fibers under Extreme Mechanical Impulses.

A monofilament fiber spun from individual carbon nanotubes is an arbitrarily long ensemble of weakly interacting, aligned, discrete nanoparticles. Despite the structural resemblance of carbon nanotube monofilament fibers to crystalline polymeric fibers, very little is known about their dynamic collective mechanics, which arise from van der Waals interactions among the individual carbon nanotubes. Using ultrafast stroboscopic microscopy, we study the collective dynamics of carbon nanotube fibers and compare them directly with nylon, Kevlar, and aluminum monofilament fibers under the same supersonic impact conditions. The in situ dynamics and kinetic parameters of the fibers show that the kinetic energy absorption characteristics of the carbon nanotube fibers surpass all other fibers. This study provides insight into the strain-rate-dependent strengthening mechanics of an ensemble of nanomaterials for the development of high-performance fibers used in body armor and other protective nanomaterials possessing exceptional stability in various harsh environments.

Extreme Mechanical Behavior of Nacre-Mimetic Graphene-Oxide and Silk Nanocomposites.

Biological materials have the ability to withstand extreme mechanical forces due to their unique multilevel hierarchical structure. Here, we fabricated a nacre-mimetic nanocomposite comprised of silk fibroin and graphene oxide that exhibits hybridized dynamic responses arising from alternating high-contrast mechanical properties of the components at the nanoscale. Dynamic mechanical behavior of these nanocomposites is assessed through a microscale ballistic characterization using a 7.6 µm diameter silica sphere moving at a speed of approximately 400 m/s. The volume fraction of graphene oxide in these composites is systematically varied from 0 to 32 vol % to quantify the dynamic effects correlating with the structural morphologies of the graphene oxide flakes. Specific penetration energy of the films rapidly increases as the distribution of graphene oxide flakes evolves from noninteracting, isolated sheets to a partially overlapping continuous sheet. The specific penetration energy of the nanocomposite at the highest graphene oxide content tested here is found to be significantly higher than that of Kevlar fabrics and close to that of pure multilayer graphene. This study evidently demonstrates that the morphologies of nanoscale constituents and their interactions are critical to realize scalable high-performance nanocomposites using typical nanomaterial constituents having finite dimensions.

A DOC coagulant, gypsum treatment can simultaneously reduce As, Cd and Pb uptake by medicinal plants grown in contaminated soil.

The efficiency of gypsum, as a dissolved organic carbon (DOC) coagulator, for the simultaneous immobilization of two heavy metals (Cd and Pb) and one metalloid (As) in agricultural soils near an abandoned mining site was examined. The agricultural soil was defined as long-term contaminated as As (1540mgkg-1), Cd (55mgkg-1) and Pb (1283mgkg-1) concentrations exceeded the Korean guideline values for As (25mgkg-1), Cd (4mgkg-1), and Pb (200mgkg-1). Gypsum was incorporated into the contaminated soil at 3% (w/w). In comparison two commonly using immobilizing agents (lime and compost), together with a mixture (lime+gypsum) were also included in the pot trial for the cultivation of two medical plants (A. gigas and A. macrocephala) and to evaluate the effectiveness of gypsum on As, Cd and Pb immobilization. The results showed that even though pH change-induced immobilizing agents such as lime were more effective than gypsum at immobilizing Cd and Pb, addition of gypsum also effectively reduced heavy metal phytoavailability as indicated by decreases in the concentration of Cd and Pb in medicinal plants. Furthermore, gypsum and gypsum+ lime were also most effective in reducing As concentrations in both plants studied. This was mainly attributed to significant decreases in soil DOC (48-64%) when gypsum and gypsum+lime were applied to the soil. Consequently, it was concluded that enhanced DOC coagulation with gypsum, could be considered as a promising technique for the immobilization of both metals (Cd and Pb) and metalloids (As) in agricultural soils.

Three-Dimensional Networked Nanoporous Ta2O(5-x) Memory System for Ultrahigh Density Storage.

Oxide-based resistive memory systems have high near-term promise for use in nonvolatile memory. Here we introduce a memory system employing a three-dimensional (3D) networked nanoporous (NP) Ta2O5-x structure and graphene for ultrahigh density storage. The devices exhibit a self-embedded highly nonlinear I-V switching behavior with an extremely low leakage current (on the order of pA) and good endurance. Calculations indicated that this memory architecture could be scaled up to a ∼162 Gbit crossbar array without the need for selectors or diodes normally used in crossbar arrays. In addition, we demonstrate that the voltage point for a minimum current is systematically controlled by the applied set voltage, thereby offering a broad range of switching characteristics. The potential switching mechanism is suggested based upon the transformation from Schottky to Ohmic-like contacts, and vice versa, depending on the movement of oxygen vacancies at the interfaces induced by the voltage polarity, and the formation of oxygen ions in the pores by the electric field.

Large-Volume Self-Organization of Polymer/Nanoparticle Hybrids with Millimeter-Scale Grain Sizes Using Brush Block Copolymers.

We report that an exceptionally large volume of highly ordered arrays (single grains) on the order of millimeters in scale can be rapidly created through a unique innate guiding mechanism of brush block copolymers (BBCPs). The grain volume is over 10(9) times larger than that of typical self-assembled linear BCPs (LBCPs). The use of strong interactions between nanoparticles (NPs) and BBCPs enables high loadings of functional materials, up to 76 wt % (46 vol %) in the target domain, while maintaining excellent long-range order. Overall, this work provides a simple method to precisely control the spatial orientation of functionalities at nanometer length scales over macroscopic volumes, thereby enabling the production of hybrid materials for many important applications.

Nanoporous silicon oxide memory.

Oxide-based two-terminal resistive random access memory (RRAM) is considered one of the most promising candidates for next-generation nonvolatile memory. We introduce here a new RRAM memory structure employing a nanoporous (NP) silicon oxide (SiOx) material which enables unipolar switching through its internal vertical nanogap. Through the control of the stochastic filament formation at low voltage, the NP SiOx memory exhibited an extremely low electroforming voltage (∼ 1.6 V) and outstanding performance metrics. These include multibit storage ability (up to 9-bits), a high ON-OFF ratio (up to 10(7) A), a long high-temperature lifetime (≥ 10(4) s at 100 °C), excellent cycling endurance (≥ 10(5)), sub-50 ns switching speeds, and low power consumption (∼ 6 × 10(-5) W/bit). Also provided is the room temperature processability for versatile fabrication without any compliance current being needed during electroforming or switching operations. Taken together, these metrics in NP SiOx RRAM provide a route toward easily accessed nonvolatile memory applications.

Periodic bicontinuous composites for high specific energy absorption.

We report on the mechanical behavior of an interpenetrating carbon/epoxy periodic submicrometer-scale bicontinuous composite material fabricated following the design principles deduced from biological composites. Using microscopic uniaxial compressive tests, the specific energy absorption is quantitatively evaluated and compared with the epoxy/air and carbon/air precursors. The carbon/epoxy material demonstrates extremely high specific energy absorption up to 720 kJ/kg and shear-dominant interphase interactions from the interlocked hard (carbon) and soft (epoxy) phases. Such bicontinuous nanocomposites are a new type of structural metamaterial with designed cell topology and mechanical anisotropy. Their inherent small length scale can play a critical role in prohibiting segregated mechanical responses leading to flaw tolerance.

Molecular Weight Controls Interactions between Plastic Deformation and Fracture in Cold Spray of Glassy Polymers.

Polymer cold spray has gained considerable attention as a novel manufacturing process. A promising aspect of this technology involves the ability to deposit uniform polymer coatings without the requirements of solvent and/or high-temperature conditions. The present study investigates the interplay between shear instability, often considered to be the primary mechanism for bond formation, and fracture, as a secondary energy dissipation mechanism, collectively governing the deposition of glassy thermoplastics on similar and dissimilar substrates. A hybrid experimental-computational approach is utilized to explore the simultaneous effects of several interconnected phenomena, namely the particle-substrate relative deformability, molecular weights, and the resultant yielding versus fracture of polystyrene particles, examined herein as a model material system. The computational investigations are based on constitutive plasticity and damage equations determined and calibrated based on a statistical data mining approach applied to a wide collection of previously reported stress-strain and failure data. Results obtained herein demonstrate that the underlying adhesion mechanisms depend strongly on the molecular weight of the sprayed particles. It is also shown that although the plastic deformation and shear instability are still the primary bond formation mechanisms, the molecular-weight-dependent fracture of the sprayed glassy polymers is also a considerable phenomenon capable of significantly affecting the deposition process, especially in cases involving the cold spray of soft thermoplastics on hard substrates. The strong interplay between molecular-weight-dependent plastic yielding and fracture in the examined system emphasizes the importance of molecular weight as a critical variable in the cold spray of glassy polymers, also highlighting the possibility of process optimization by proper feedstock selection.

Rapid fabrication of 3D terahertz split ring resonator arrays by novel single-shot direct write focused proximity field nanopatterning.

For the next generation of phoXonic, plasmonic, opto-mechanical and microfluidic devices, the capability to create 3D microstructures is highly desirable. Fabrication of such structures by conventional top-down techniques generally requires multiple time-consuming steps and is limited in the ability to define features spanning multiple layers at prescribed angles. 3D direct write lithography (3DDW) has the capability to draw nearly arbitrary structures, but is an inherently slow serial writing process. Here we present a method, denoted focused proximity field nanopatterning (FPnP), that combines 3DDW with single or multiphoton interference lithography (IL). By exposing a thick photoresist layer having a phase mask pattern imprinted on its surface with a tightly focused laser beam, we produce locally unique complex structures. The morphology can be varied based on beam and mask parameters. Patterns may be written rapidly in a single shot mode with arbitrary positions defined by the direct write, thus exploiting the control of 3DDW with the enhanced speed of phase mask IL. Here we show the ability for this technique to rapidly produce arrays of "stand-up" far IR resonators.

Molecular-Weight-Dependent Interplay of Brittle-to-Ductile Transition in High-Strain-Rate Cold Spray Deposition of Glassy Polymers.

Based on the cold spray technique, the solvent-free and solid-state deposition of glassy polymers is envisioned. Adiabatic inelastic deformation mechanisms in the cold spray technique are studied through high-velocity collisions (<1000 m/s) of polystyrene microparticles against stationary target substrates of polystyrene and silicon. During extreme collisions, a brittle-to-ductile transition occurs, leading to either fracture- or shear-dominant inelastic deformation of the colliding microparticles. Due to the nonlinear interplay between the adiabatic shearing and the thermal softening of polystyrene, the plastic shear flow becomes the dominant deformation channel over brittle fragmentation when increasing the rigidity of the target substrate. High molecular weights (>20 kDa) are essential to hinder the evolution of brittle fracture and promote shear-induced heating beyond the glass transition temperature of polystyrene. However, an excessively high molecular weight (∼100 kDa) reduces the adhesion of the microparticles to the substrate due to insufficient wetting of the softened polystyrene. Due to the two competing viscoelastic effects, proper selection of molecular weight becomes critical for the cold spray technique of glassy polymers.

Mechanics of nanoindentation on a monolayer of colloidal hollow nanoparticles.

We explore the collective mechanical behavior of monolayer assemblies composed of close-packed arrays of hollow silica nanoparticles using a spherical nanoindentor. Seven types of well-defined hollow nanoparticles are studied with their radii ranging from 100 to 300 nm and shell thickness ranging from 14 to 44 nm. Micromechanical models reveal the underlying deformation mechanisms during indentation, where the consecutive contacting of the indentor with an increasing number of nanoparticles results in a nonlinear increase in the indentation force with penetration depth. Each contacted hollow nanoparticle successively locally bends, flattens, and then locally buckles. The effective indentation modulus of the monolayer film, which is obtained by a Hertzian fit to the experimental data, is found to be proportional to the elastic modulus of the nanoparticle shell material and scales exponentially with the ratio of particle shell thickness t to radius R to the power of 2.3. Furthermore, we find that for a constant film density with the same (t)/(R) of the constituent nanoparticles, smaller particles with a thinner shell can provide a higher effective indentation modulus, compared to their larger diameter and thicker shell counterparts. This study provides useful insights and guidance for constructing high-performance lightweight nanoparticle films and coatings with potential applications in tailoring stiffness and mechanical energy absorption.

Enhanced energy dissipation in periodic epoxy nanoframes.

Periodic nanostructures fabricated by interference lithography can be precisely designed to have a specific cell geometry, topology, and porosity in contrast to typical stochastic cellular materials. We use nanoindentation to elucidate the mechanical characteristics of the nanoframe as a function of its relative density and model the deformation behavior via numerical simulations. The nanoframe exhibits a scaling exponent of relative modulus versus relative density of 1.26, which is less sensitive than for conventional foams. Moreover, the nanoframe shows large mechanical energy dissipation/volume (up to 4.5 MJ/m(3)), comparable to the highest values achieved in the conventional polymer foams but at a far smaller strain. Counterintuitively, a nanoframe of smaller relative density can dissipate more energy per volume because the geometry of the nanoframe evolves during deformation to engage more of the material in plastic deformation. The results demonstrate how geometrical control at the nano- and microstructural scale can tailor modulus and energy dissipation and suggest means for engineering of mechanically superior materials in the future.

Epoxy Resin-Encapsulated Polymer Microparticles for Room-Temperature Cold Sprayable Coatings.

We designed and synthesized epoxy-encapsulated microparticles with core-shell structures via suspension polymerization to enable high-efficiency, room-temperature cold spray processing. The soft core of the microparticles was comprised of a thermoset resin, diglycidyl ether of bisphenol A (DGEBA), which was optionally blended with the thermoplastic, poly(butyl acrylate); the protective shell was formed using polyurea. The composition, morphology, and thermal behavior of the microparticles were investigated. An inverse relationship between deposition efficiency and particle size was demonstrated by varying the surfactant concentration that was used during particle synthesis. We also determined that the microparticles that had pure resin as the core had the lowest viscosity, exhibited a decrease in the critical impact velocity required for adhesion, had the best flowability, and yielded a dramatic increase in deposition efficiency (56%). We have demonstrated that our in-house synthesized particles can form homogeneous, smooth, and fully coalesced coatings using room-temperature cold spray.

Entanglement Density-Dependent Energy Absorption of Polycarbonate Films via Supersonic Fracture.

The fracture behavior of glassy polymers is strongly coupled to molecular parameters such as entanglement density as well as extrinsic parameters such as strain rate and test temperature. Here we use laser-induced projectile impact testing (LIPIT) to study the extreme strain rate (≈107 s-1) puncture behavior of free-standing polycarbonate (PC) thin films. We demonstrate that changes to the PC molecular mass and the degree of plasticization can lead to substantial changes in the specific puncture energy. We relate these changes to the alteration of the entanglement density of the polymer that determines the underlying failure mechanism as well as the size of the deformation zone.

Polymer Particles with a Low Glass Transition Temperature Containing Thermoset Resin Enable Powder Coatings at Room Temperature.

Epoxy-based powder coatings are an attractive alternative to solvent-borne coatings. Here, in-house synthesized low glass transition temperature (Tg) particles containing epoxy resin and polymethyl methacrylate formed coatings at room temperature upon impact with a surface. Suspension polymerization was used to prepare particles as a function of diglycidyl ether of bisphenol A (DGEBA) and methyl methacrylate ratios. Higher incorporation of DGEBA decreased the Tg to below ~20°C and eliminated the need to heat the particles and/or aluminum substrates to form coatings. Using an electrostatic powder coating apparatus, a ~70% particle deposition efficiency was achieved on aluminum substrates heated to 200°C. Whereas, at room temperature, high-speed single particle impact experiments proved that particle bonding occurred at a critical velocity of 438 m/s, comparable to commercial cold spray technologies. The in-house synthesized particles used in this study hold potential in traditional and emerging additive manufacturing applications.

Polarized thermal radiation by layer-by-layer metallic emitters with sub-wavelength grating.

Metallic thermal emitters consisting of two layers of differently structured nickel gratings on a homogeneous nickel layer are fabricated by soft lithography and studied for polarized thermal radiation. A thermal emitter in combination with a sub-wavelength grating shows a high extinction ratio, with a maximum value close to 5, in a wide mid-infrared range from 3.2 to 7.8 mum, as well as high emissivity up to 0.65 at a wavelength of 3.7 microm. All measurements show good agreement with theoretical predictions. Numerical simulations reveal that a high electric field exists within the localized air space surrounded by the gratings and the intensified electric-field is only observed for the polarizations perpendicular to the top sub-wavelength grating. This result suggests how the emissivity of a metal can be selectively enhanced at a certain range of wavelengths for a given polarization.