Electrically assisted 3D printing of nacre-inspired structures with self-sensing capability.
ABSTRACT: Lightweight and strong structural materials attract much attention due to their strategic applications in sports, transportation, aerospace, and biomedical industries. Nacre exhibits high strength and toughness from the brick-and-mortar-like structure. Here, we present a route to build nacre-inspired hierarchical structures with complex three-dimensional (3D) shapes by electrically assisted 3D printing. Graphene nanoplatelets (GNs) are aligned by the electric field (433 V/cm) during 3D printing and act as bricks with the polymer matrix in between as mortar. The 3D-printed nacre with aligned GNs (2 weight %) shows lightweight property (1.06 g/cm3) while exhibiting comparable specific toughness and strength to the natural nacre. In addition, the 3D-printed lightweight smart armor with aligned GNs can sense its damage with a hesitated resistance change. This study highlights interesting possibilities for bioinspired structures, with integrated mechanical reinforcement and electrical self-sensing capabilities for biomedical applications, aerospace engineering, as well as military and sports armors.
Project description:Mollusk nacre is a prototypical biological inorganic-organic composite that combines high toughness, stiffness, and strength by its brick-and-mortar microstructure, which has inspired several synthetic mimics. Its remarkable fracture toughness relies on inelastic deformations at the process zone at the crack tip that dissolve stress concentrations and stop cracks. The micrometer-scale structure allows resolving the size and shape of the process zone to understand the fracture processes. However, for better scalability, nacre-mimetic nanocomposites with aligned inorganic or graphene nanosheets are extensively pursued, to avoid the packing problems of mesoscale sheets like in nacre or slow in situ biomineralization. This calls for novel methods to explore the process zone of biomimetic nanocomposites. Here the fracture of nacre and nacre-inspired clay/polymer nanocomposite is explored using laser speckle imaging that reveals the process zone even in absence of changes in optical scattering. To demonstrate the diagnostic value, compared to nacre, the nacre-inspired nanocomposite develops a process zone more abruptly with macroscopic crack deflection shown by a flattened process zone. In situ scanning electron microscopy suggests similar toughening mechanisms in nanocomposite and nacre. These new insights guide the design of nacre-inspired nanocomposites toward better mechanical properties to reach the level of synergy of their biological model.
Project description:Nature's wisdom resides in achieving a joint enhancement of strength and toughness by constructing intelligent, hierarchical architectures from extremely limited resources. A representative example is nacre, in which a brick-and-mortar structure enables a confluence of toughening mechanisms on multiple length scales. The result is an outstanding combination of strength and toughness which is hardly achieved by engineering materials. Here, a bioinspired Ni/Ni3C composite with nacre-like, brick-and-mortar structure was constructed from Ni powders and graphene sheets. This composite achieved a 73% increase in strength with only a 28% compromise on ductility, leading to a notable improvement in toughness. The graphene-derived Ni-Ti-Al/Ni3C composite retained high hardness up to 1000°C. The present study unveiled a method to smartly use 2D materials to fabricate high-performance metal matrix composites with brick-and-mortar structure through interfacial reactions and, furthermore, created an opportunity of developing advanced Ni-C-based alloys for high-temperature environments.
Project description:The nacreous layer of mollusk shells holds design concepts that can effectively enhance the fracture resistance of lightweight brittle materials. Mineral bridges are known to increase the fracture resistance of nacre-inspired materials, but their role is difficult to quantify due to the lack of experimental systems where only this parameter is controllably varied. In this study, we fabricate tunable nacre-like composites that are used as a model to experimentally quantify the influence of the density of mineral bridges alone on the fracture properties of nacre-like architectures. The composites exhibit a brick-and-mortar architecture comprising highly aligned alumina platelets that are interconnected by titania mineral bridges and infiltrated by an epoxy organic phase. By combining experimental mechanical data with image analysis of such composite microstructures, an analytical model is put forward based on a simple balance of forces acting on an individual bridged platelet. Based on this model, we predict the flexural strength of the nacre-like composite to scale linearly with the density of mineral bridges, as long as the mineral interconnectivity is low enough to keep fracture in a platelet pullout mode. Increasing the mineral interconnectivity beyond this limit leads to platelet fracture and catastrophic failure of the composite. This structure-property correlation provides powerful quantitative guidelines for the design of lightweight brittle materials with enhanced fracture resistance. We illustrate this potential by fabricating nacre-like bulk composites with unparalleled flexural strength combined with noncatastrophic failure.
Project description:Nacre-like composites have been investigated typically in the form of coatings or free-standing sheets. They demonstrated remarkable mechanical properties and are used as ultrastrong materials but macroscale fibres with nacre-like organization can improve mechanical properties even further. The fiber form or nacre can, simplify manufacturing and offer new functional properties unknown yet for other forms of biomimetic materials. Here we demonstrate that nacre-like fibres can be produced by shear-induced self-assembly of nanoplatelets. The synergy between two structural motifs--nanoscale brick-and-mortar stacking of platelets and microscale twisting of the fibres--gives rise to high stretchability (>400%) and gravimetric toughness (640?J?g(-1)). These unique mechanical properties originate from the multiscale deformation regime involving solid-state self-organization processes that lead to efficient energy dissipation. Incorporating luminescent CdTe nanowires into these fibres imparts the new property of mechanically tunable circularly polarized luminescence. The nacre-like fibres open a novel technological space for optomechanics of biomimetic composites, while their continuous spinning methodology makes scalable production realistic.
Project description:The prospect of developing multifunctional flexible three-dimensional (3D) architectures based on integrative chemistry for lightweight, foldable, yet robust, electronic components that can turn the many promises of graphene-based devices into reality is an exciting direction that has yet to be explored. Herein, inspired by nature, we demonstrate that through a simple, yet novel solvophobic self-assembly processing approach, nacre-mimicking, layer-by-layer grown, hybrid composite materials (consisting of graphene oxide, carbon nanotubes, and conducting polymers) can be made that can incorporate many of the exciting attributes of graphene into real world materials. The as-produced, self-assembled 3D multifunctional architectures were found to be flexible, yet mechanically robust and tough (Young's modulus in excess of 26.1 GPa, tensile strength of around 252 MPa, and toughness of 7.3 MJ m(-3)), and exhibited high native electrical conductivity (38700 S m(-1)) and unrivalled volumetric capacitance values (761 F cm(-3)) with excellent cyclability and rate performance.
Project description:Nacre realizes strength and toughness through hierarchical designs with primary "brick and mortar" structures of alternative arrangement of nanoplatelets and biomacromolecules, and these have inspired the fabrication of nanocomposites for decades. However, to simultaneously solve the three critical problems of phase separation, low interfacial strength and random orientation of nanofillers for nanocomposites is a great challenge yet. Here we demonstrate that polymer-grafted graphene oxide sheets are exceptional building blocks for nanocomposites. Their liquid crystalline dispersions can be wet-spun into continuous fibres. Because of well-ordering and efficient load transfer, the composites show remarkable tensile strength (500?MPa), three to four times higher than nacre. The uniform layered microstructures and strong interlayer interactions also endow the fibres good resistance to chemicals including 98% sulfuric acid. We studied the enhancing effect of nanofillers with fraction in a whole range (0-100%), and proposed an equation to depict the relationship.
Project description:Shape memory polymers (SMPs) are attractive materials due to their unique mechanical properties, including high deformation capacity and shape recovery. SMPs are easier to process, lightweight, and inexpensive compared to their metallic counterparts, shape memory alloys. However, SMPs are limited to relatively small form factors due to their low recovery stresses. Lightweight, micro-architected composite SMPs may overcome these size limitations and offer the ability to combine functional properties (e.g., electrical conductivity) with shape memory behavior. Fabrication of 3D SMP thermoset structures via traditional manufacturing methods is challenging, especially for designs that are composed of multiple materials within porous microarchitectures designed for specific shape change strategies, e.g. sequential shape recovery. We report thermoset SMP composite inks containing some materials from renewable resources that can be 3D printed into complex, multi-material architectures that exhibit programmable shape changes with temperature and time. Through addition of fiber-based fillers, we demonstrate printing of electrically conductive SMPs where multiple shape states may induce functional changes in a device and that shape changes can be actuated via heating of printed composites. The ability of SMPs to recover their original shapes will be advantageous for a broad range of applications, including medical, aerospace, and robotic devices.
Project description:A synthetic technique inspired by the biomineralisation process in nacre has been previously reported to be effective in replicating the nanostructural elements of nacre in 2D chitosan hydrogel films. Here we evaluate the applicability of this synthetic biomineralisation technique, herein called the McGrath method, in replicating the flat tabular morphology of calcium carbonate and other nanostructural elements obtained when 2D chitosan hydrogel films were used, on a 3D porous chitosan hydrogel-based scaffold, hence developing 3D chitosan-calcium carbonate composites. Nozzle extrusion-based 3D printing technology was used to develop 3D porous scaffolds using chitosan hydrogel as the printing ink in a custom-designed 3D printer. The rheology of the printing ink and print parameters were optimised in order to fabricate 3D cylindrical structures with a cubic lattice-based internal structure. The effects of various dehydration techniques, including air-drying, critical point-drying and freeze-drying, on the structural integrity of the as-printed scaffolds from the nano to macroscale, were evaluated. The final 3D composite materials were characterised using scanning electron microscopy, X-ray diffraction and energy dispersive X-ray spectroscopy. The study has shown that McGrath method can be used to develop chitosan-calcium carbonate composites wherein the mineral and matrix are in intimate association with each other at the nanoscale. This process can be successfully integrated with 3D printing technology to develop 3D compartmentalised polymer-mineral composites.
Project description:With the emerging of drug-resistant bacterial and fungal pathogens, there raise the interest of utilizing versatile antimicrobial biomaterials to treat the acute wound. Herein, we report the spraying mediated assembly of a bio-inspired Ag@reduced graphene-sodium alginate (AGSA) composite film for effective wound healing. The obtained film displayed lamellar microstructures similar to the typical "brick-and-mortar" structure in nacre. In this nacre-mimic structure, there are abundant interfacial interactions between nanosheets and polymeric matrix, leading to remarkable reinforcement. As a result, the tensile strength, toughness and Young's modulus have been improved 2.8, 2.3 and 2.7 times compared with pure sodium alginate film, respectively. In the wound healing study, the AGSA film showed effective antimicrobial activities towards Pseudomonas aeruginosa, Escherichia coli and Candida albicans, demonstrating the ability of protecting wound from pathogenic microbial infections. Furthermore, in vivo experiments on rats suggested the effect of AGSA film in promoting the recovery of wound sites. According to MTT assays, heamolysis evaluation and in vivo toxicity assessment, the composite film could be applied as a bio-compatible material in vitro and in vivo. Results from this work indicated such AGSA film has promising performance for wound healing and suggested great potential for nacre-mimic biomaterials in tissue engineering applications.
Project description:Discontinuous fibre composites represent a class of materials that are strong, lightweight and have remarkable fracture toughness. These advantages partially explain the abundance and variety of discontinuous fibre composites that have evolved in the natural world. Many natural structures out-perform the conventional synthetic counterparts due, in part, to the more elaborate reinforcement architectures that occur in natural composites. Here we present an additive manufacturing approach that combines real-time colloidal assembly with existing additive manufacturing technologies to create highly programmable discontinuous fibre composites. This technology, termed as '3D magnetic printing', has enabled us to recreate complex bioinspired reinforcement architectures that deliver enhanced material performance compared with monolithic structures. Further, we demonstrate that we can now design and evolve elaborate reinforcement architectures that are not found in nature, demonstrating a high level of possible customization in discontinuous fibre composites with arbitrary geometries.