Ultra-low-density digitally architected carbon with a strutted tube-in-tube structure.

Porous materials with engineered stretching-dominated lattice designs, which offer attractive mechanical properties with ultra-light weight and large surface area for wide-ranging applications, have recently achieved near-ideal linear scaling between stiffness and density. Here, rather than optimizing the microlattice topology, we explore a different approach to strengthen low-density structural materials by designing tube-in-tube beam structures. We develop a process to transform fully dense, three-dimensional printed polymeric beams into graphitic carbon hollow tube-in-tube sandwich morphologies, where, similar to grass stems, the inner and outer tubes are connected through a network of struts. Compression tests and computational modelling show that this change in beam morphology dramatically slows down the decrease in stiffness with decreasing density. In situ pillar compression experiments further demonstrate large deformation recovery after 30-50% compression and high specific damping merit index. Our strutted tube-in-tube design opens up the space and realizes highly desirable high modulus-low density and high modulus-high damping material structures.

A natural impact-resistant bicontinuous composite nanoparticle coating.

Nature utilizes the available resources to construct lightweight, strong and tough materials under constrained environmental conditions. The impact surface of the fast-striking dactyl club from the mantis shrimp is an example of one such composite material; the shrimp has evolved the capability to localize damage and avoid catastrophic failure from high-speed collisions during its feeding activities. Here we report that the dactyl club of mantis shrimps contains an impact-resistant coating composed of densely packed (about 88 per cent by volume) ~65-nm bicontinuous nanoparticles of hydroxyapatite integrated within an organic matrix. These mesocrystalline hydroxyapatite nanoparticles are assembled from small, highly aligned nanocrystals. Under impacts of high strain rates (around 104 s-1), particles rotate and translate, whereas the nanocrystalline networks fracture at low-angle grain boundaries, form dislocations and undergo amorphization. The interpenetrating organic network provides additional toughening, as well as substantial damping, with a loss coefficient of around 0.02. An unusual combination of stiffness and damping is therefore achieved, outperforming many engineered materials.

Processing and properties of magnesium containing a dense uniform dispersion of nanoparticles.

Magnesium is a light metal, with a density two-thirds that of aluminium, is abundant on Earth and is biocompatible; it thus has the potential to improve energy efficiency and system performance in aerospace, automobile, defence, mobile electronics and biomedical applications. However, conventional synthesis and processing methods (alloying and thermomechanical processing) have reached certain limits in further improving the properties of magnesium and other metals. Ceramic particles have been introduced into metal matrices to improve the strength of the metals, but unfortunately, ceramic microparticles severely degrade the plasticity and machinability of metals, and nanoparticles, although they have the potential to improve strength while maintaining or even improving the plasticity of metals, are difficult to disperse uniformly in metal matrices. Here we show that a dense uniform dispersion of silicon carbide nanoparticles (14 per cent by volume) in magnesium can be achieved through a nanoparticle self-stabilization mechanism in molten metal. An enhancement of strength, stiffness, plasticity and high-temperature stability is simultaneously achieved, delivering a higher specific yield strength and higher specific modulus than almost all structural metals.

Small-Scale Plastic Deformation of Nanocrystalline High Entropy Alloy.

High entropy alloys (HEAs) have attracted widespread interest due to their unique properties at many different length-scales. Here, we report the fabrication of nanocrystalline (NC) Al0.1CoCrFeNi high entropy alloy and subsequent small-scale plastic deformation behavior via nano-pillar compression tests. Exceptional strength was realized for the NC HEA compared to pure Ni of similar grain sizes. Grain boundary mediated deformation mechanisms led to high strain rate sensitivity of flow stress in the nanocrystalline HEA.

Indentation Tests Reveal Geometry-Regulated Stiffening of Nanotube Junctions.

Here we report a unique method to locally determine the mechanical response of individual covalent junctions between carbon nanotubes (CNTs), in various configurations such as "X", "Y", and "Λ"-like. The setup is based on in situ indentation using a picoindenter integrated within a scanning electron microscope. This allows for precise mapping between junction geometry and mechanical behavior and uncovers geometry-regulated junction stiffening. Molecular dynamics simulations reveal that the dominant contribution to the nanoindentation response is due to the CNT walls stretching at the junction. Targeted synthesis of desired junction geometries can therefore provide a "structural alphabet" for construction of macroscopic CNT networks with tunable mechanical response.

Interconnecting Bone Nanoparticles by Ovalbumin Molecules to Build a Three-Dimensional Low-Density and Tough Material.

Natural building blocks like proteins and hydroxyapatite (HA) are found in abundance. However, their effective utilization to fabricate environment-friendly, strong, stiff, and tough materials remains a challenge. This work reports on the synthesis of a layered material from entirely natural building blocks. A simple process to extract HA from bones, while keeping collagen intact, is presented. These HA nanocrystals have a high aspect ratio as a result of the extraction method that largely retains the pristine nature of the HA. To fabricate the materials, polymerized egg white is used to induce toughness to the crystals where it acts like a load transfer entity between the crystals. As shown by atomic force microscope modulus mapping, the result is a layered material with a modulus that ranges from 3 to 180 GPa. Furthermore, the material exhibits self-stiffening behavior. Hydrogen and ionic bonds are likely to regulate the chemical interactions at the egg white/HA interface and are likely to be responsible for the observed high toughness and stiffness, respectively. The use of the HA/egg white composite as printed scaffolds is also demonstrated together with their biocompatibility.

Atomically thin gallium layers from solid-melt exfoliation.

Among the large number of promising two-dimensional (2D) atomic layer crystals, true metallic layers are rare. Using combined theoretical and experimental approaches, we report on the stability and successful exfoliation of atomically thin "gallenene" sheets on a silicon substrate, which has two distinct atomic arrangements along crystallographic twin directions of the parent α-gallium. With a weak interface between solid and molten phases of gallium, a solid-melt interface exfoliation technique is developed to extract these layers. Phonon dispersion calculations show that gallenene can be stabilized with bulk gallium lattice parameters. The electronic band structure of gallenene shows a combination of partially filled Dirac cone and the nonlinear dispersive band near the Fermi level, suggesting that gallenene should behave as a metallic layer. Furthermore, it is observed that the strong interaction of gallenene with other 2D semiconductors induces semiconducting to metallic phase transitions in the latter, paving the way for using gallenene as promising metallic contacts in 2D devices.

Design maps for failure of all-ceramic layer structures in concentrated cyclic loading.

A study is made of the competition between failure modes in ceramic-based bilayer structures joined to polymer-based substrates, in simulation of dental crown-like structures with a functional but weak "veneer" layer bonded onto a strong "core" layer. Cyclic contact fatigue tests are conducted in water on model flat systems consisting of glass plates joined to glass, sapphire, alumina or zirconia support layers glued onto polycarbonate bases. Critical numbers of cycles to take each crack mode to failure are plotted as a function of peak contact load on failure maps showing regions in which each fracture mode dominates. In low-cycle conditions, radial and outer cone cracks are competitive in specimens with alumina cores, and outer cone cracks prevail in specimens with zirconia cores; in high-cycle conditions, inner cone cracks prevail in all cases. The roles of other factors, e.g. substrate modulus, layer thickness, indenter radius and residual stresses from specimen preparation, are briefly considered.

Role of core support material in veneer failure of brittle layer structures.

A study is made of veneer failure by cracking in all-ceramic crown-like layer structures. Model trilayers consisting of a 1 mm thick external glass layer (veneer) joined to a 0.5 mm thick inner stiff and hard ceramic support layer (core) by epoxy bonding or by fusion are fabricated for testing. The resulting bilayers are then glued to a thick compliant polycarbonate slab to simulate a dentin base. The specimens are subjected to cyclic contact (occlusal) loading with spherical indenters in an aqueous environment. Video cameras are used to record the fracture evolution in the transparent glass layer in situ during testing. The dominant failure mode is cone cracking in the glass veneer by traditional outer (Hertzian) cone cracks at higher contact loads and by inner (hydraulically pumped) cone cracks at lower loads. Failure is deemed to occur when one of these cracks reaches the veneer/core interface. The advantages and disadvantages of the alumina and zirconia core materials are discussed in terms of mechanical properties-strength and toughness, as well as stiffness. Consideration is also given to the roles of interface strength and residual thermal expansion mismatch stresses in relation to the different joining methods.

Role of substrate material in failure of crown-like layer structures.

The role of substrate modulus on critical loads to initiate and propagate radial cracks to failure in curved brittle glass shells on compliant polymeric substrates is investigated. Flat glass disks are used to drive the crack system. This configuration is representative of dental crown structures on dentin support in occlusal contact. Specimens are fabricated by truncating glass tubes and filling with epoxy-based substrate materials, with or without alumina filler for modulus control. Moduli ranging from 3 to 15 GPa are produced in this way. Critical loads for both initiation and propagation to failure increase monotonically with substrate modulus, by a factor of two over the data range. Fracture mechanics relations provide a fit to the data, within the scatter bands. Finite element analysis is used to determine stress distributions pertinent to the observed fracture modes. It is suggested that stiffer substrate materials offer potential for improved crown lifetime in dental practice.

Role of indenter material and size in veneer failure of brittle layer structures.

The roles of indenter material and size in the failure of brittle veneer layers in all-ceramic crown-like structures are studied. Glass veneer layers 1 mm thick bonded to alumina layers 0.5 mm thick on polycarbonate bases (representative of porcelain/ceramic-core/dentin) are subject to cyclic contact loading with spherical indenters in water (representative of occlusal biting environment). Two indenter materials-glass and tungsten carbide-and three indenter radii-1.6, 5.0, and 12.5 mm-are investigated in the tests. A video camera is used to follow the near-contact initiation and subsequent downward propagation of cone cracks through the veneer layer to the core interface, at which point the specimen is considered to have failed. Both indenter material and indenter radius have some effect on the critical loads to initiate cracks within the local Hertzian contact field, but the influence of modulus is weaker. The critical loads to take the veneer to failure are relatively insensitive to either of these indenter variables, since the bulk of the cone crack propagation takes place in the contact far field. Clinical implications of the results are considered, including the issue of single-cycle overload versus low-load cyclic fatigue and changes in fracture mode with loading conditions.

Piezoresistive Response of Quasi-One-Dimensional ZnO Nanowires Using an in Situ Electromechanical Device.

Quasi-one-dimensional structures from metal oxides have shown remarkable potentials with regard to their applicability in advanced technologies ranging from ultraresponsive nanoelectronic devices to advanced healthcare tools. Particularly due to the piezoresistive effects, zinc oxide (ZnO)-based nanowires showed outstanding performance in a large number of applications, including energy harvesting, flexible electronics, smart sensors, etc. In the present work, we demonstrate the versatile crystal engineering of ZnO nano- and microwires (up to centimeter length scales) by a simple flame transport process. To investigate the piezoresistive properties, particular ZnO nanowires were integrated on an electrical push-to-pull device, which enables the application of tensile strain and measurement of in situ electrical properties. The results from ZnO nanowires revealed a periodic variation in stress with respect to the applied periodic potential, which has been discussed in terms of defect relaxations.

Magnetic field controlled graphene oxide-based origami with enhanced surface area and mechanical properties.

One can utilize the folding of paper to build fascinating 3D origami architectures with extraordinary mechanical properties and surface area. Inspired by the same, the morphology of 2D graphene can be tuned by addition of magnetite (Fe3O4) nanoparticles in the presence of a magnetic field. The innovative 3D architecture with enhanced mechanical properties also shows a high surface area (∼2500 m2 g-1) which is utilized for oil absorption. Detailed microscopy and spectroscopy reveal rolling of graphene oxide (GO) sheets due to the magnetic field driven action of magnetite particles, which is further supported by molecular dynamics (MD) simulations. The macroscopic and local deformation resulting from in situ mechanical loading inside a scanning electron microscope reveals a change in the mechanical response due to a change internal morphology, which is further supported by MD simulation.

Role of Atomic Layer Functionalization in Building Scalable Bottom-Up Assembly of Ultra-Low Density Multifunctional Three-Dimensional Nanostructures.

Building three-dimensional (3D) structures from their constituent zero-, one-, and two-dimensional nanoscale building blocks in a bottom-up assembly is considered the holey grail of nanotechnology. However, fabricating such 3D nanostructures at ambient conditions still remains a challenge. Here, we demonstrate an easily scalable facile method to fabricate 3D nanostructures made up of entirely zero-dimensional silicon dioxide (SiO2) nanoparticles. By combining functional groups and vacuum filtration, we fabricate lightweight and highly structural stable 3D SiO2 materials. Further synergistic effect of material is shown by addition of a 2D material, graphene oxide (GO) as reinforcement which results in 15-fold increase in stiffness. Molecular dynamics (MD) simulations are used to understand the interaction between silane functional groups (3-aminopropyl triethoxysilane) and SiO2 nanoparticles thus confirming the reinforcement capability of GO. In addition, the material is stable under high temperature and offers a cost-effective alternative to both fire-retardant and oil absorption materials.

Velcro-Inspired SiC Fuzzy Fibers for Aerospace Applications.

The most recent and innovative silicon carbide (SiC) fiber ceramic matrix composites, used for lightweight high-heat engine parts in aerospace applications, are woven, layered, and then surrounded by a SiC ceramic matrix composite (CMC). To further improve both the mechanical properties and thermal and oxidative resistance abilities of this material, SiC nanotubes and nanowires (SiCNT/NWs) are grown on the surface of the SiC fiber via carbon nanotube conversion. This conversion utilizes the shape memory synthesis (SMS) method, starting with carbon nanotube (CNT) growth on the SiC fiber surface, to capitalize on the ease of dense surface morphology optimization and the ability to effectively engineer the CNT-SiC fiber interface to create a secure nanotube-fiber attachment. Then, by converting the CNTs to SiCNT/NWs, the relative morphology, advantageous mechanical properties, and secure connection of the initial CNT-SiC fiber architecture are retained, with the addition of high temperature and oxidation resistance. The resultant SiCNT/NW-SiC fiber can be used inside the SiC ceramic matrix composite for a high-heat turbo engine part with longer fatigue life and higher temperature resistance. The differing sides of the woven SiCNT/NWs act as the "hook and loop" mechanism of Velcro but in much smaller scale.

Transverse fracture of brittle bilayers: relevance to failure of all-ceramic dental crowns.

This study examines the behavior of cracks approaching interfaces in all-ceramic dental crown-like bilayers. Flat specimens are fabricated by fusing porcelain veneers onto yttria-tetragonal-zirconia-polycrystal (Y-TZP) and alumina core ceramic plates, with veneer/core matching to minimize residual thermal expansion mismatch stresses. Vickers indentations are placed on either side of the interfaces, at systematically decreasing distances, so that the lead corner cracks approach and intersect the interfaces in a normal orientation. Cracks originating in the porcelain arrest at the boundaries and, after further diminution in indentation distance, deflect along the interface without penetration into the tough core ceramic. Cracks initiating in the core ceramic pass unimpeded into the weaker porcelain without deflection, and with abrupt increase in crack size. These latter cracks, because of their lack of containment within the core layer, are regarded as especially dangerous. Implications concerning the design of optimal dental crowns in relation to materials optimization are considered.

A Sinusoidally Architected Helicoidal Biocomposite.

A fibrous herringbone-modified helicoidal architecture is identified within the exocuticle of an impact-resistant crustacean appendage. This previously unreported composite microstructure, which features highly textured apatite mineral templated by an alpha-chitin matrix, provides enhanced stress redistribution and energy absorption over the traditional helicoidal design under compressive loading. Nanoscale toughening mechanisms are also identified using high-load nanoindentation and in situ transmission electron microscopy picoindentation.

3D Porous Graphene by Low-Temperature Plasma Welding for Bone Implants.

3D scaffolds of graphene, possessing ultra-low density, macroporous microstructure, and high yield strength and stiffness can be developed by a novel plasma welding process. The bonding between adjacent graphene sheets is investigated by molecular dynamics simulations. The high degree of biocompatibility along with high porosity and good mechanical properties makes graphene an ideal material for use as body implants.