Nacre (mother-of-pearl), made of inorganic and organic constituents (95 vol% aragonite calcium carbonate (CaCO(3)) platelets and 5 vol% elastic biopolymers), possesses a unique combination of remarkable strength and toughness, which is compatible for conventional high performance materials. The excellent mechanical properties are related to its hierarchical structure and precisely designed organic-inorganic interface. The rational design of aragonite platelet strength, aspect ratio of aragonite platelets, and interface strength ensures that the strength of nacre is maximized under platelet pull-out failure mode. At the same time, the synergy of strain hardening mechanisms acting over multiple scales results in platelets sliding on one another, and thus maximizes the energy dissipation of viscoplastic biopolymers. The excellent integrated mechanical properties with hierarchical structure have inspired chemists and materials scientists to develop biomimetic strategies for artificial nacre materials. This critical review presents a broad overview of the state-of-the-art work on the preparation of layered organic-inorganic nanocomposites inspired by nacre, in particular, the advantages and disadvantages of various biomimetic strategies. Discussion is focused on the effect of the layered structure, interface, and component loading on strength and toughness of nacre-mimic layered nanocomposites (148 references).
Demands of the strong integrated materials have substantially increased across various industries. Inspired by the relationship of excellent integration of mechanical properties and hierarchical nano/microscale structure of the natural nacre, we have developed a strategy for fabricating the strong integrated artificial nacre based on graphene oxide (GO) sheets by dopamine cross-linking via evaporation-induced assembly process. The tensile strength and toughness simultaneously show 1.5 and 2 times higher than that of natural nacre. Meanwhile, the artificial nacre shows high electrical conductivity. This type of strong integrated artificial nacre has great potential applications in aerospace, flexible supercapacitor electrodes, artificial muscle, and tissue engineering.
Multi‐walled carbon nanotube (MWNT)‐sheet‐reinforced bismaleimide (BMI) resin nanocomposites with high concentrations (∼60 wt%) of aligned MWNTs are successfully fabricated. Applying simple mechanical stretching and prepregging (pre‐resin impregnation) processes on initially randomly dispersed, commercially available sheets of millimeter‐long MWNTs leads to substantial alignment enhancement, good dispersion, and high packing density of nanotubes in the resultant nanocomposites. The tensile strength and Young's modulus of the nanocomposites reaches 2 088 MPa and 169 GPa, respectively, which are very high experimental results and comparable to the state‐of‐the‐art unidirectional IM7 carbon‐fiber‐reinforced composites for high‐performance structural applications. The nanocomposites demonstrate unprecedentedly high electrical conductivity of 5 500 S cm−1 along the alignment direction. Such unique integration of high mechanical properties and electrical conductance opens the door for developing polymeric composite conductors and eventually structural composites with multifunctionalities. New fracture morphology and failure modes due to self‐assembly and spreading of MWNT bundles are also observed.
Densification via bridging layers MXenes are a family of layered two-dimensional metal carbides and nitrides with interesting properties that can be lost if voids are formed during synthesis. By using a sequential combination of hydrogen and covalent bonding agents, Wan et al . were able to densify the layered structure and remove voids. This procedure leads to improvements in the mechanical strength and toughness, electrical conductivity, and shielding from electromagnetic interference. —MSL
Flexible reduced graphene oxide (rGO) sheets are being considered for applications in portable electrical devices and flexible energy storage systems. However, the poor mechanical properties and electrical conductivities of rGO sheets are limiting factors for the development of such devices. Here we use MXene (M) nanosheets to functionalize graphene oxide platelets through Ti-O-C covalent bonding to obtain MrGO sheets. A MrGO sheet was crosslinked by a conjugated molecule (1-aminopyrene-disuccinimidyl suberate, AD). The incorporation of MXene nanosheets and AD molecules reduces the voids within the graphene sheet and improves the alignment of graphene platelets, resulting in much higher compactness and high toughness. In situ Raman spectroscopy and molecular dynamics simulations reveal the synergistic interfacial interaction mechanisms of Ti-O-C covalent bonding, sliding of MXene nanosheets, and π-π bridging. Furthermore, a supercapacitor based on our super-tough MXene-functionalized graphene sheets provides a combination of energy and power densities that are high for flexible supercapacitors.
Nature has inspired researchers to construct structures with ordered layers as candidates for new materials with high mechanical performance. As a prominent example, nacre, also known as mother of pearl, consists of a combination of inorganic plates (aragonite calcium carbonate, 95% by volume) and organic macromolecules (elastic biopolymer, 5% by volume) and shows a unique combination of strength and toughness. Investigations of its structure reveal that the hexagonal platelets of calcium carbonate and the amorphous biopolymer are alternatively assembled into the orderly layered structure. The delicate interface between the calcium carbonate and the biopolymer is well defined. Both the building blocks that make up these assembled layers and the interfaces between the inorganic and organic components contribute to the excellent mechanical property of natural nacre. In this Account, we summarize recent research from our group and from others on the design of bioinspired materials composed by layering various primitive materials. We focus particular attention on nanoscale carbon materials. Using several examples, we describe how the use of different combinations of layered materials leads to particular properties. Flattened double-walled carbon nanotubes (FDWCNTs) covalently cross-linked in a thermoset three-dimensional (3D) network produced the materials with the highest strength. The stiffest layered materials were generated from borate orthoester covalent bonding between adjacent graphene oxide (GO) nanosheets, and the toughest layered materials were fabricated with Al2O3 platelets and chitosan via hydrogen bonding. These new building blocks, such as FDWCNTs and GO, and the replication of the elaborate micro-/nanoscale interface of natural nacre have provided many options for developing new high performance artificial materials. The interface designs for bioinspired layered materials are generally categorized into (1) hydrogen bonding, (2) ionic bonding, and (3) covalent bonding. Using these different strategies, we can tune the materials to have specific mechanical characteristics such as high strength, excellent strain resistance, or remarkable toughness. Among these design strategies, hydrogen bonding affords soft interfaces between the inorganic plates and the organic matrix. Covalent cross-linking forms chemical bonds between the inorganic plates and the organic matrix, leading to much stronger interfaces. The interfaces formed by ionic bonding are stronger than those formed by hydrogen bonding but weaker than those formed by covalent bonding.
Inspired by the layered aragonite platelet/nanofibrillar chitin/protein ternary structure and integration of extraordinary strength and toughness of natural nacre, artificial nacre based on clay platelet/nanofibrillar cellulose/poly(vinyl alcohol) is constructed through an evaporation-induced self-assembly technique. The synergistic toughening effect from clay platelets and nanofibrillar cellulose is successfully demonstrated. The artificial nacre achieves an excellent balance of strength and toughness and a fatigue-resistant property, superior to natural nacre and other conventional layered clay/polymer binary composites.
Natural nacre, which consists of almost 95 vol % inorganic content (calcium carbonate) and 5 vol % elastic biopolymers, possesses a unique combination of remarkable strength and toughness, [1] which is attributed to its hierarchical nano-/ microscale structure and precise inorganic-organic interface. [2] Inspired by the intrinsic relationship between the structures and the mechanical properties lying in the natural nacre, different types of nacre-like layered nanocomposites have been fabricated with two-dimensional (2D) inorganic additives, including glass flake, [3] alumina flake, [4] graphene oxide, [5] layered double hydroxides, [6] nanoclay, [7] and flattened double-walled carbon nanotubes. [8] Although great progress has been achieved in tensile mechanical properties, [7b,c, 8, 9] in only very rare cases are artificial layered composites with excellent toughness are obtained. [6,10] One of the most important causes is the relatively low interfacial strength between interlayers of artificial nacre. Recently, 2D graphene has attracted much research interest owing to its outstanding electrical, thermal, and mechanical properties, [11] and many graphene-based devices have been fabricated, [12] such as bulk composites, [13] one-dimensional fibers, [14] supercapacitors. [15] As the water-soluble derivative of graphene,
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