Oxidation-induced superelasticity in metallic glass nanotubes.

Although metallic nanostructures have been attracting tremendous research interest in nanoscience and nanotechnologies, it is known that environmental attacks, such as surface oxidation, can easily initiate cracking on the surface of metals, thus deteriorating their overall functional/structural properties1-3. In sharp contrast, here we report that severely oxidized metallic glass nanotubes can attain an ultrahigh recoverable elastic strain of up to ~14% at room temperature, which outperform bulk metallic glasses, metallic glass nanowires and many other superelastic metals hitherto reported. Through in situ experiments and atomistic simulations, we reveal that the physical mechanisms underpinning the observed superelasticity can be attributed to the formation of a percolating oxide network in metallic glass nanotubes, which not only restricts atomic-scale plastic events during loading but also leads to the recovery of elastic rigidity on unloading. Our discovery implies that oxidation in low-dimensional metallic glasses can result in unique properties for applications in nanodevices.

Co-Assembly of Soft and Hard Nanoparticles into Macroscopic Colloidal Composites with Tailored Mechanical Property and Processability.

Colloidal composites, translating the great potential of nanoscale building bricks into macroscopic dimensions, have emerged as an appealing candidate for new materials with applications in optics, energy storage, and biomedicines. However, it remains a key challenge to bridge the size regimes from nanoscopic colloidal particles to macroscale composites possessing mechanical robustness. Herein, a bottom-up approach is demonstrated to manufacture colloidal composites with customized macroscopic forms by virtue of the co-assembly of nanosized soft polymeric micelles and hard inorganic nanoparticles. Upon association, the hairy micellar corona can bind with the hard nanoparticles, linking individual hard constituents together in a soft-hard alternating manner to form a collective entity. This permits the integration of block copolymer micelles with controlled amounts of hard nanoparticles into macroscopic colloidal composites featuring diverse internal microstructures. The resultant composites showed tunable microscale mechanical strength in a range of 90-270 MPa and macroscale mechanical strength in a range of 7-42 MPa for compression and 2-24 MPa for bending. Notably, the incorporation of soft polymeric micelles also imparts time- and temperature-dependent dynamic deformability and versatile capacity to the resulting composites, allowing their application in the low-temperature plastic processing for functional fused silica glass.

Promotion of the Nucleation of Ultrafine Ni-Rich Layered Oxide Primary Particles by an Atomic Layer-Deposited Thin Film for Enhanced Mechanical Stability.

Understanding the atomistic mechanisms of non-equilibrium processes during solid-state synthesis, such as nucleation and grain structure formation of a layered oxide phase, is a critical challenge for developing promising cathode materials such as Ni-rich layered oxide for Li-ion batteries. In this study, we found that the aluminum oxide coating layer transforms into lithium aluminate as an intermediate, which has favorable low interfacial energies with the layered oxide to promote the nucleation of the latter. The fast and uniform nucleation and formation of the layered oxide phase at relatively low temperatures were evidenced using solid-state nuclear magnetic resonance and in situ synchrotron X-ray diffraction. The resulting Ni-rich layered oxide cathode has fine primary particles, as visualized by three-dimensional tomography constructed using a focused-ion beam and scanning electron microscopy. The densely packed fine primary particles enable the excellent mechanical strength of the secondary particles, as demonstrated by in situ compression tests. This strategy provides a new approach for developing next-generation, high-strength battery materials.

Exploration of Hierarchical Metal-Organic Framework as Ultralight, High-Strength Mechanical Metamaterials.

Due to the extraordinarily high surface to volume ratio and enormous structural and chemical diversities, metal-organic frameworks (MOFs) have drawn much attention in applications such as heterogeneous catalysis, gas storage separation, and drug delivery, and so on. However, the potential of MOF materials as mechanical metamaterials has not been investigated. In this work, we demonstrated that through the concerted effort of molecular construct and mesoscopic structural design, hierarchical MOFs can exhibit superb mechanical properties. With the cutting-edge in situ transmission and scanning electron microscope (TEM and SEM) techniques, the mechanical properties of hollow UiO-66 octahedron particles were quantitatively studied by compression on individual specimens. Results showed that the yield strength and Young's modulus of the hierarchical porous framework material presented a distinct "smaller is stronger and stiffer" size dependency, and the maximum yield strength and Young's modulus reached 580 ± 55 MPa and 4.3 ± 0.5 GPa, respectively. The specific strengths were measured as 0.15 ± 0.03 to 0.68 ± 0.11 GPa g-1 cm3, which is comparable to the previously reported state-of-the-art mechanical metamaterials like glassy carbon nanolattices and pyrolytic carbon nanolattices. This work revealed that MOF materials can be made into a new class of low-density, high-strength mechanical metamaterials and provided insight into the mechanical stability of nanoscale MOFs for practical applications.

High Strength and Deformation Mechanisms of Al0.3CoCrFeNi High-Entropy Alloy Thin Films Fabricated by Magnetron Sputtering.

Recently, high-entropy alloy thin films (HEATFs) with nanocrystalline structures and high hardness were developed by magnetron sputtering technique and have exciting potential to make small structure devices and precision instruments with sizes ranging from nanometers to micrometers. However, the strength and deformation mechanisms are still unclear. In this work, nanocrystalline Al0.3CoCrFeNi HEATFs with a thickness of ~4 µm were prepared. The microstructures of the thin films were comprehensively characterized, and the mechanical properties were systematically studied. It was found that the thin film was smooth, with a roughness of less than 5 nm. The chemical composition of the high entropy alloy thin film was homogeneous with a main single face-centered cubic (FCC) structure. Furthermore, it was observed that the hardness and the yield strength of the high-entropy alloy thin film was about three times that of the bulk samples, and the plastic deformation was inhomogeneous. Our results could provide an in-depth understanding of the mechanics and deformation mechanism for future design of nanocrystalline HEATFs with desired properties.

Size-dependent fracture behavior of silver nanowires.

Silver (Ag) nanowires have great potential to be used in the flexible electronics industry for their applications in flexible, transparent conductors due to high conductivity and light reflectivity. Those applications always involve mechanical loading and deformations, which requires an in-depth understanding of their mechanical behavior and performance under loadings. However, current understanding on the mechanical properties of Ag nanowires is limited, especially on their size-dependent fracture behavior. In this work, mechanical properties of Ag nanowires with diameters ranging from 50 to 300 nm were systematically studied by in situ TEM tensile testing for the first time. The size effect was clearly found, with the increasing of the diameter of Ag nanowires, the ultimate tensile stress decreased. More importantly, the fracture behavior of Ag nanowire was studied and a brittle-to-ductile transition in fracture behavior was observed at the diameters around 100 nm which could be attributed to the dislocation activities within the geometry confinement. This work could give insights for understanding nanosized Ag wires and the design of Ag nanowire-based flexible devices and touchable panels.

Piezoelectrically enhanced photocatalysis of KxNa1-xNbO3 (KNN) microstructures for efficient water purification.

As a kind of excellent multifunctional metal oxide semiconductor, KxNa1-xNbO3 (KNN) has been widely applied in a variety of fields such as photocatalysis and energy harvesting due to its excellent piezoelectric, dielectric and photovoltaic properties in recent decades. In this report, octahedron-shaped K0.4Na0.6NbO3 (KNN-6) microstructures assembled by cubic nanoparticles with {010} exposed facets were synthesized via a one-pot hydrothermal reaction. Due to the accumulation of electrons on the exposed facets, which was conducive to the separation of photo-generated electron-hole pairs, the microstructures could achieve a highly efficient photocatalytic performance for wastewater degradation. In addition, owing to the piezoelectric effect of KNN crystals, the degradation efficiency could be further enhanced by introducing ultrasonic vibration. Using methylene blue (MB) as the organic dye to evaluate their wastewater degradation efficiency, the KNN microstructures achieved their best catalytic performance when the atomic ratio of KOH to NaOH in the reactant was set at 4 : 6 (KNN-6). Under the synergistic effect of light irradiation and ultrasonic vibration, MB could almost be completely (99%) degraded within 40 minutes by KNN-6 microstructures, which was several times more efficient than that of pure NaNbO3 or KNbO3 in previous reports. This work demonstrated that the K0.4Na0.6NbO3 (KNN-6) microstructure could be a prominent candidate for wastewater purification. The formation mechanism of KNN crystals and the role of the piezoelectric effect in the photocatalytic process were also discussed.

Nanohybrid of Co3O4 Nanoparticles and Polyphosphazene-Decorated Ultra-Thin Boron Nitride Nanosheets for Simultaneous Enhancement in Fire Safety and Smoke Suppression of Thermoplastic Polyurethane.

Thermoplastic polyurethane (TPU) is widely used in daily life due to its characteristics of light weight, high impact strength, and compression resistance. However, TPU products are extremely flammable and will generate toxic fumes under fire attack, threatening human life and safety. In this article, a nanohybrid flame retardant was designed for the fire safety of TPU. Herein, Co3O4 was anchored on the surface of exfoliated ultra-thin boron nitride nanosheets (BNNO@Co3O4) via coprecipitation and subsequent calcination. Then, a polyphosphazene (PPZ) layer was coated onto BNNO@Co3O4 by high temperature polymerization to generate a nanohybrid flame retardant named BNNO@Co3O4@PPZ. The cone calorimeter results exhibited that the heat release and smoke production during TPU combustion were remarkably restrained after the incorporation of the nanohybrid flame retardant. Compared with pure TPU, the peak heat release rate (PHRR) decreased by 44.1%, the peak smoke production rate (PSPR) decreased by 51.2%, and the peak CO production rate (PCOPR) decreased by 72.5%. Based on the analysis of carbon residues after combustion, the significant improvement in fire resistance of TPU by BNNO@Co3O4@PPZ was attributed to the combination of quenching effect, catalytic carbonization effect, and barrier effect. In addition, the intrinsic mechanical properties of TPU were well maintained due to the existence of the PPZ organic layer.

Facile Synthesis of BiVO4@ZIF-8 Composite with Heterojunction Structure for Photocatalytic Wastewater Treatment.

Water pollution has always been a serious problem across the world; therefore, facile pollutant degradation via light irradiation has been an attractive issue in the field of environmental protection. In this study, a type of Zn-based metal-organic framework (ZIF-8)-wrapped BiVO4 nanorod (BiVO4@ZIF-8) with high efficiency for photocatalytic wastewater treatment was synthesized through a two-step hydrothermal method. The heterojunction structure of BiVO4@ZIF-8 was confirmed by morphology characterization. Due to the introduction of mesoporous ZIF-8, the specific surface area reached up to 304.5 m2/g, which was hundreds of times larger than that of pure BiVO4 nanorods. Furthermore, the band gap of BiVO4@ZIF-8 was narrowed down to 2.35 eV, which enabled its more efficient utilization of visible light. After irradiation under visible light for about 40 min, about 80% of rhodamine B (RhB) was degraded, which was much faster than using pure BiVO4 or other BiVO4-based photocatalysts. The synergistic photocatalysis mechanism of BiVO4@ZIF-8 is also discussed. This study might offer new pathways for effective degradation of wastewater through facile design of novel photocatalysts.

Elastic Properties of High-Symmetry Sb4O6 Cage-Molecular Crystal.

The cubic-phase antimony trioxide (α-Sb2O3) is a room-temperature stable molecular crystal, composed of cage-like tetraantimony hexoxide (Sb4O6) molecules. Despite its versatile functionality, the van der Waals (vdW) bond-dominated nanomechanics is still unclear. Here, the bending plate-like linear behaviors of high-quality α-Sb2O3 nanoflakes were observed using the nanoindentation method. It is found that the cage-molecular crystal owns a very low in-plane Young's modulus of 14.9 ± 0.8 GPa and a remarkable maximum tensile strain of 6.0-8.8%, corresponding to a rupture strength of 0.89-1.31 GPa. Elucidated by the atomistic simulations, the compliant elastic modulus and the unexpectedly strong rupture strain are associated with the high-symmetry vdW bonding structure. The vdW nanomechanics is of fundamental and technological relevance to nanoelectronics.

Mechanically stable ternary heterogeneous electrodes for energy storage and conversion.

Recently, solid asymmetric supercapacitor (ASC) has been deemed as an emerging portable power storage or backup device for harvesting natural resources. Here we rationally engineered a hierarchical, mechanically stable heterostructured FeCo@NiCo layered double hydroxide (LDH) with superior capacitive performance by a simple two-step electrodeposition route for energy storage and conversion. In situ scanning electron microscope (SEM) nanoindentation and electrochemical tests demonstrated the mechanical robustness and good conductivity of FeCo-LDH. This serves as a reliable backbone for supporting the NiCo-LDH nanosheets. When employed as the positive electrode in the solid ASC, the assembly presents high energy density of 36.6 W h kg-1 at a corresponding power density of 783 W kg-1 and durable cycling stability (87.3% after 5000 cycles) as well as robust mechanical stability without obvious capacitance fading when subjected to bending deformation. To demonstrate its promising capability for practical energy storage applications, the ASC has been employed as a portable energy source to power a commercially available digital watch, mini motor car, or household lamp bulb as well as an energy storage reservoir, coupled with a wind energy harvester to power patterned light-emitting diodes (LEDs).

Ultralarge elastic deformation of nanoscale diamond.

Diamonds have substantial hardness and durability, but attempting to deform diamonds usually results in brittle fracture. We demonstrate ultralarge, fully reversible elastic deformation of nanoscale (~300 nanometers) single-crystalline and polycrystalline diamond needles. For single-crystalline diamond, the maximum tensile strains (up to 9%) approached the theoretical elastic limit, and the corresponding maximum tensile stress reached ~89 to 98 gigapascals. After combining systematic computational simulations and characterization of pre- and postdeformation structural features, we ascribe the concurrent high strength and large elastic strain to the paucity of defects in the small-volume diamond nanoneedles and to the relatively smooth surfaces compared with those of microscale and larger specimens. The discovery offers the potential for new applications through optimized design of diamond nanostructure, geometry, elastic strains, and physical properties.

Recent Advances on In Situ SEM Mechanical and Electrical Characterization of Low-Dimensional Nanomaterials.

In the past decades, in situ scanning electron microscopy (SEM) has become a powerful technique for the experimental study of low-dimensional (1D/2D) nanomaterials, since it can provide unprecedented details for individual nanostructures upon mechanical and electrical stimulus and thus uncover the fundamental deformation and failure mechanisms for their device applications. In this overview, we summarized recent developments on in situ SEM-based mechanical and electrical characterization techniques including tensile, compression, bending, and electrical property probing on individual nanostructures, as well as the state-of-the-art electromechanical coupling analysis. In addition, the advantages and disadvantages of in situ SEM tests were also discussed with some possible solutions to address the challenges. Furthermore, critical challenges were also discussed for the development and design of robust in situ SEM characterization platform with higher resolution and wider range of samples. These experimental efforts have offered in-depth understanding on the mechanical and electrical properties of low-dimensional nanomaterial components and given guidelines for their further structural and functional applications.

Flexible Fiber-Shaped Supercapacitor Based on Nickel-Cobalt Double Hydroxide and Pen Ink Electrodes on Metallized Carbon Fiber.

Flexible fiber-shaped supercapacitors (FSSCs) are recently of extensive interest for portable and wearable electronic gadgets. Yet the lack of industrial-scale flexible fibers with high conductivity and capacitance and low cost greatly limits its practical engineering applications. To this end, we here present pristine twisted carbon fibers (CFs) coated with a thin metallic layer via electroless deposition route, which exhibits exceptional conductivity with ∼300% enhancement and superior mechanical strength (∼1.8 GPa). Subsequently, the commercially available conductive pen ink modified high conductive composite fibers, on which uniformly covered ultrathin nickel-cobalt double hydroxides (Ni-Co DHs) were introduced to fabricate flexible FSSCs. The synthesized functionalized hierarchical flexible fibers exhibit high specific capacitance up to 1.39 F·cm-2 in KOH aqueous electrolyte. The asymmetric solid-state FSSCs show maximum specific capacitance of 28.67 mF·cm-2 and energy density of 9.57 µWh·cm-2 at corresponding power density as high as 492.17 µW·cm-2 in PVA/KOH gel electrolyte, with demonstrated high flexibility during stretching, demonstrating their potential in flexible electronic devices and wearable energy systems.

Approaching the ideal elastic strain limit in silicon nanowires.

Achieving high elasticity for silicon (Si) nanowires, one of the most important and versatile building blocks in nanoelectronics, would enable their application in flexible electronics and bio-nano interfaces. We show that vapor-liquid-solid-grown single-crystalline Si nanowires with diameters of ~100 nm can be repeatedly stretched above 10% elastic strain at room temperature, approaching the theoretical elastic limit of silicon (17 to 20%). A few samples even reached ~16% tensile strain, with estimated fracture stress up to ~20 GPa. The deformations were fully reversible and hysteresis-free under loading-unloading tests with varied strain rates, and the failures still occurred in brittle fracture, with no visible sign of plasticity. The ability to achieve this "deep ultra-strength" for Si nanowires can be attributed mainly to their pristine, defect-scarce, nanosized single-crystalline structure and atomically smooth surfaces. This result indicates that semiconductor nanowires could have ultra-large elasticity with tunable band structures for promising "elastic strain engineering" applications.

Recent developments in testing techniques for elastic mechanical properties of 1-D nanomaterials.

One-dimensional (1-D) nanomaterials exhibit great potentials in their applications to functional materials, nano-devices and systems owing to their excellent properties. In the past decade, considerable studies have been done, with new patents being developed, on these 1-D building blocks for for their mechanical properties, especially elastic properties, which provide a solid foundation for the design of nanoelectromechanical systems (NEMS) and predictions of reliability and longevity for their devices. This paper reviews some of the recent investigations on techniques as well as patents available for the quantitative characterization of the elastic behaviors of various 1-D nanomaterials, with particular focus on on-chip testing system. The review begins with an overview of major testing methods for 1-D nanostructures' elastic properties, including nanoindentation testing, AFM (atomic force microscopy) testing, in situ SEM (scanning electron microscopy) testing, in situ TEM (transmission electron microscopy) testing and the testing system on the basis of MEMS (micro-electro-mechanical systems) technology, followed by advantages and challenges of each testing approach. This review also focuses on the MEMS-based testing apparatus, which can be actuated and measured inside SEM and TEM with ease, allowing users to highly magnify the continuous images of the specimen while measuring load electronically and independently. The combination of on-chip technologies and the in situ electron microscopy is expected to be a potential testing technique for nanomechanics. Finally, details are presented on the key challenges and possible solutions in the implementation of the testing techniques referred above.

A glucose-responsive controlled release of insulin system based on enzyme multilayers-coated mesoporous silica particles.

A novel glucose-responsive controlled release of insulin system is constructed through coating enzyme multilayers on mesoporous silica particles (MSPs). The MSPs serve as the drug reservoir, and the enzyme multilayers cross-linked with glutaraldehyde act as a valve to control the release of insulin in response to the external glucose level.