Exceptionally Ductile and Tough Biomimetic Artificial Nacre with Gas Barrier Function

Synthetic mimics of natural high‐performance structural materials have shown great and partly unforeseen opportunities for the design of multifunctional materials. For nacre‐mimetic nanocomposites, it has remained extraordinarily challenging to make ductile materials with high stretchability at high fractions of reinforcements, which is however of crucial importance for flexible barrier materials. Here, highly ductile and tough nacre‐mimetic nanocomposites are presented, by implementing weak, but many hydrogen bonds in a ternary nacre‐mimetic system consisting of two polymers (poly(vinyl amine) and poly(vinyl alcohol)) and natural nanoclay (montmorillonite) to provide efficient energy dissipation and slippage at high nanoclay content (50 wt%). Tailored interactions enable exceptional combinations of ductility (close to 50% strain) and toughness (up to 27.5 MJ m^?3). Extensive stress whitening, a clear sign of high internal dynamics at high internal cohesion, can be observed during mechanical deformation, and the materials can be folded like paper into origami planes without fracture. Overall, the new levels of ductility and toughness are unprecedented in highly reinforced bioinspired nanocomposites and are of critical importance to future applications, e.g., as barrier materials needed for encapsulation and as a printing substrate for flexible organic electronics.     

Bioinspired Nacre‐Like Alumina with a Metallic Nickel Compliant Phase Fabricated by Spark‐Plasma Sintering

Many natural materials present an ideal “recipe” for the development of future damage‐tolerant lightweight structural materials. One notable example is the brick‐and‐mortar structure of nacre, found in mollusk shells, which produces high‐toughness, bioinspired ceramics using polymeric mortars as a compliant phase. Theoretical modeling has predicted that use of metallic mortars could lead to even higher damage‐tolerance in these materials, although it is difficult to melt‐infiltrate metals into ceramic scaffolds as they cannot readily wet ceramics. To avoid this problem, an alternative (“bottom‐up”) approach to synthesize “nacre‐like” ceramics containing a small fraction of nickel mortar is developed. These materials are fabricated using nickel‐coated alumina platelets that are aligned using slip‐casting and rapidly sintered using spark‐plasma sintering. Dewetting of the nickel mortar during sintering is prevented by using NiO‐coated as well as Ni‐coated platelets. As a result, a “nacre‐like” alumina ceramic displaying a resistance‐curve toughness up to ≈16 MPa m^½ with a flexural strength of ≈300 MPa is produced.     

冷冻铸造技术制备仿贝壳层状结构陶瓷复合材料研究进展

贝壳珍珠层是一种天然的层状结构复合材料,类似"砖和泥"的软硬相交替的层状分级组装结构赋予其优良的力学性能。通过对贝壳的珍珠层进行仿生研究,人们已利用不同技术如冷冻铸造技术等,制备了一系列仿生高强超韧层状复合材料,并且这些材料在航空航天、军事、民用及机械工程等领域表现出广阔的应用前景。首先介绍了贝壳珍珠层的结构性能,并对其断裂机制进行了阐述;然后综合介绍了冷冻铸造技术的发展历程、作用机理、控制因素、装置设计和总体工艺流程。在此基础上,对制备仿贝壳层状结构陶瓷复合材料的表观密度、多孔陶瓷的孔隙率进行介绍,综述了多孔陶瓷的性能、陶瓷/金属层状结构复合材料以及陶瓷/聚合物层状结构复合材料的特点和应用,最后分析和总结了在研究仿贝壳层状结构陶瓷复合材料过程中出现的问题,并对该复合材料的未来发展趋势做了一定的预测。     

25th Anniversary Article: Artificial Carbonate Nanocrystals and Layered Structural Nanocomposites Inspired by Nacre: Synthesis,Fabrication and Applications

Rigid biological systems are increasingly becoming a source of inspiration for the fabrication of next generation advanced functional materials due to their diverse hierarchical structures and remarkable engineering properties. Among these rigid biomaterials, nacre, as the main constituent of the armor system of seashells, exhibiting a well‐defined ‘brick‐and‐mortar’ architecture, excellent mechanical properties, and interesting iridescence, has become one of the most attractive models for novel artificial materials design. In this review, recent advances in nacre‐inspired artificial carbonate nanocrystals and layered structural nanocomposites are presented. To clearly illustrate the inspiration of nacre, the basic principles relating to plate‐like aragonite single‐crystal growth and the contribution of hierarchical structure to outstanding properties in nacre are discussed. The inspiration of nacre for the synthesis of carbonate nanocrystals and the fabrication of layered structural nanocomposites is also discussed. Furthermore, the broad applications of these nacre inspired materials are emphasized. Finally, a brief summary of present nacre‐inspired materials and challenges for the next generation of nacre‐inspired materials is given.     

A Hydrogel‐Film Casting to Fabricate Platelet‐Reinforced Polymer Composite Films Exhibiting Superior Mechanical Properties

The fabrication of mechanically superior polymer composite films with controllable shapes on various scales is difficult. Despite recent research on polymer composites consisting of organic matrices and inorganic materials with layered structures, these films suffer from complex preparations and limited mechanical properties that do not have even integration of high strength, stiffness, and toughness. Herein, a hydrogel‐film casting approach to achieve fabrication of simultaneously strong, stiff, and tough polymer composite films with well‐defined microstructure, inspired from a layer‐by‐layer structure of nacre is reported. Ca²⁺‐crosslinked alginate hydrogels incorporated with platelet‐like alumina particles are dried to form composite films composed of horizontally aligned alumina platelets and alginate matrix with uniformly layered microstructure. Alumina platelets are evenly distributed parallel without precipitations and contribute to synergistic enhancements of strength, stiffness and toughness in the resultant film. Consequentially, Ca²⁺‐crosslinked alginate/alumina (Ca²⁺‐Alg/Alu) films show exceptional tensile strength (267 MPa), modulus (17.9 GPa), and toughness (3.60 MJ m⁻³). Furthermore, the hydrogel‐film casting allows facile preparation of polymer composite films with controllable shapes and various scales. The results suggest an alternative approach to design and prepare polymer composites with the layer‐by‐layer structure for superior mechanical properties.     

Biomimetic structure design — a possible approach to change the brittleness of ceramics in nature

Based on the analysis on structure of natural biomaterials, two kinds of ceramic composites with high toughness have been designed and prepared: one is fibrous monolithic Si₃N₄/BN composite imitating bamboos or trees in structure, the other is laminated Si₃N₄/BN composite imitating nacre in structure. Plastic forming methods, including extrusion and roll compaction, respectively, followed by hot-pressed sintering are used to prepare these two materials with particular structures. Both of the two composites have high values of fracture toughness and work of fracture: fracture toughness are 24 MPa m^1/2 and 28 MPa m^1/2, respectively, for fibrous monolithic and laminated Si₃N₄/BN composites, and works of fracture are both more than 4000 J/m². The load-displacement curves reveal that these two materials with biomimetic structure exhibit non-brittle feature when applied load to fracture. Through analysis on fractographs of the materials, it is revealed that high toughness comes from the synergistic toughening among multi-level toughening mechanisms in different scales: weak interfaces, whiskers and elongated grains toughening in ceramic matrix cells.     

Multiscale Toughening Mechanisms in Biological Materials and Bioinspired Designs

Biological materials found in Nature such as nacre and bone are well recognized as light‐weight, strong, and tough structural materials. The remarkable toughness and damage tolerance of such biological materials are conferred through hierarchical assembly of their multiscale (i.e., atomic‐ to macroscale) architectures and components. Herein, the toughening mechanisms of different organisms at multilength scales are identified and summarized: macromolecular deformation, chemical bond breakage, and biomineral crystal imperfections at the atomic scale; biopolymer fibril reconfiguration/deformation and biomineral nanoparticle/nanoplatelet/nanorod translation, and crack reorientation at the nanoscale; crack deflection and twisting by characteristic features such as tubules and lamellae at the microscale; and structure and morphology optimization at the macroscale. In addition, the actual loading conditions of the natural organisms are different, leading to energy dissipation occurring at different time scales. These toughening mechanisms are further illustrated by comparing the experimental results with computational modeling. Modeling methods at different length and time scales are reviewed. Examples of biomimetic designs that realize the multiscale toughening mechanisms in engineering materials are introduced. Indeed, there is still plenty of room mimicking the strong and tough biological designs at the multilength and time scale in Nature.     

New classes of tough composite materials—Lessons from natural rigid biological systems

The structures and properties of a new class of composite materials, containing a predominantly high volume fraction ceramic or glass phase, combined with minor organic (adhesive) phases, have been studied. These composites have unusual combinations of mechanical properties, such as stiffness, strength, and toughness. They are based on the architecture of a rigid natural material, the nacre structure, such as those found in the shells of the abalone Haliotis rufescens, and those of other mollusk shells. The mechanisms underlying these properties have also been studied. Analogs (utilizing high-performance engineering materials), that mimic many of the mechanisms underlying those superior combinations of properties, have been built. The results of the foregoing investigations are discussed. It was found that the toughness of segmented composite beams which have high volume fractions of ceramic (89 v / o) exceeded those of continuous layered beams, as well as the monolithic ceramic (alumina) on which they are based.     

Toughening mechanisms in bioinspired multilayered materials

Outstanding mechanical properties of biological multilayered materials are strongly influenced by nanoscale features in their structure. In this study, mechanical behaviour and toughening mechanisms of abalone nacre-inspired multilayered materials are explored. In nacre''s structure, the organic matrix, pillars and the roughness of the aragonite platelets play important roles in its overall mechanical performance. A micromechanical model for multilayered biological materials is proposed to simulate their mechanical deformation and toughening mechanisms. The fundamental hypothesis of the model is the inclusion of nanoscale pillars with near theoretical strength (σ_th ~ E/30). It is also assumed that pillars and asperities confine the organic matrix to the proximity of the platelets, and, hence, increase their stiffness, since it has been previously shown that the organic matrix behaves more stiffly in the proximity of mineral platelets. The modelling results are in excellent agreement with the available experimental data for abalone nacre. The results demonstrate that the aragonite platelets, pillars and organic matrix synergistically affect the stiffness of nacre, and the pillars significantly contribute to the mechanical performance of nacre. It is also shown that the roughness induced interactions between the organic matrix and aragonite platelet, represented in the model by asperity elements, play a key role in strength and toughness of abalone nacre. The highly nonlinear behaviour of the proposed multilayered material is the result of distributed deformation in the nacre-like structure due to the existence of nano-asperities and nanopillars with near theoretical strength. Finally, tensile toughness is studied as a function of the components in the microstructure of nacre.     

Bio-inspired laminate design exhibiting pseudo-ductile (graceful) failure during flexural loading

Discontinuous reinforcement phases are often observed in high toughness natural materials, for example, nacre. The aim of this study is to introduce a degree of ‘pseudo-ductility’ to fibre reinforced polymer materials by exploiting such discontinuities. The work presented aims to take a simple concept of discrete material sections and apply it in the form of ply cuts in a carbon fibre reinforced polymer. A variety of specimen types which encompass the principles inspired by the architecture of nacre were tested in four point bend flexure and the failure processes investigated. Finite element analysis was also carried out to understand stress conditions around ply cuts and their role in the observed failure. It was observed that ply cut spacing and ply cut density were important parameters in achieving ‘pseudo-ductile’ failure.     

A strong,lightweight, and damping cermet material with a nacre-like ultrafine 3D interpenetrated architecture

While materials that are light, strong, tough and simultaneously damping are highly attractive for a range of applications, it remains a challenge to achieve a combination of all these properties in a single material as these properties are often mutually exclusive. Here we present a cermet material comprising an ultrafine-grained Mg-Al-Zn magnesium alloy with ultrafine Ti₃AlC₂ ceramic platelets, where the two phases are bi-continuous and interpenetrated in 3D space yet are alternately arranged in a layered fashion as in natural nacre. Such an architecture was constructed by infiltrating the alloy into the porous ceramic scaffold where the Ti₃AlC₂ platelets were preferentially aligned by vacuum filtration and partially sintered. The resulting cermet exhibits a high flexural strength exceeding 1 GPa and a high specific flexural strength (strength normalized by density) of over 350 MPa/(g cm⁻³) – both exceeding those of most other bulk magnesium (and magnesium alloys), ceramics, and their composite materials – as well as high damping capacities and good fracture toughness. The architectural design strategy and the robust fabrication approach may prove to be effective for developing new high-performance cermet materials.     

Bioinspired Flexible and Tough Layered Peptide Crystals

One major challenge of functional material fabrication is combining flexibility, strength, and toughness. In several biological and artificial systems, these desired mechanical properties are achieved by hierarchical architectures and various forms of anisotropy, as found in bones and nacre. Here, it is reported that crystals of N‐capped diphenylalanine, one of the most studied self‐assembling systems in nanotechnology, exhibit well‐ordered packing and diffraction of sub‐Å resolution, yet display an exceptionally flexible nature. To explore this flexibility, the mechanical properties of individual crystals are evaluated, assisted by density functional theory calculations. High‐resolution scanning electron microscopy reveals that the crystals are composed of layered self‐assembled structures. The observed combination of strength, toughness, and flexibility can therefore be explained in terms of weak interactions between rigid layers. These crystals represent a novel class of self‐assembled layered materials, which can be utilized for various technological applications, where a combination of usually contradictory mechanical properties is desired.     

Nano/Micro‐Manufacturing of Bioinspired Materials: a Review of Methods to Mimic Natural Structures

Through billions of years of evolution and natural selection, biological systems have developed strategies to achieve advantageous unification between structure and bulk properties. The discovery of these fascinating properties and phenomena has triggered increasing interest in identifying characteristics of biological materials, through modern characterization and modeling techniques. In an effort to produce better engineered materials, scientists and engineers have developed new methods and approaches to construct artificial advanced materials that resemble natural architecture and function. A brief review of typical naturally occurring materials is presented here, with a focus on chemical composition, nano‐structure, and architecture. The critical mechanisms underlying their properties are summarized, with a particular emphasis on the role of material architecture. A review of recent progress on the nano/micro‐manufacturing of bio‐inspired hybrid materials is then presented in detail. In this case, the focus is on nacre and bone‐inspired structural materials, petals and gecko foot‐inspired adhesive films, lotus and mosquito eye inspired superhydrophobic materials, brittlestar and Morpho butterfly‐inspired photonic structured coatings. Finally, some applications, current challenges and future directions with regard to manufacturing bio‐inspired hybrid materials are provided.     

Molecular origin of the sawtooth behavior and the toughness of nacre

We present in this paper a method to build a computer model that mimic the mineral–protein composite structure of a nacre tablet. Motivated by the interesting observations in AFM experiments of nacre, protein chains stretching out from grain boundaries are simulated by steered molecular dynamics (SMD) to gain an insight into the effect of protein–aragonite interaction on the mechanical properties of nacre and the molecular mechanisms of the sawtooth behavior. Force-extension curves are obtained and the key characteristics of sawtooth behavior are observed in SMD simulations in agreement with existing AFM experiments of nacre. The effect of water on protein–mineral interaction is investigated through including and excluding water molecules in the grain boundaries of the models. Different from the existing belief that protein unfolding is the origin of the “sawtooth” behavior, we have found that the electrostatic interactions between the protein and aragonite mineral are responsible for the sawtooth behavior and hence the high toughness of nacre.     

On the Fracture Toughness of Advanced Materials

Few engineering materials are limited by their strength; rather they are limited by their resistance to fracture or fracture toughness. It is not by accident that most critical structures, such as bridges, ships, nuclear pressure vessels and so forth, are manufactured from materials that are comparatively low in strength but high in toughness. Indeed, in many classes of materials, strength and toughness are almost mutually exclusive. From a fracture‐mechanics perspective, the ability of a microstructure to develop toughening mechanisms acting either ahead or behind the crack tip can result in resistance‐curve (R‐curve) behavior where the fracture resistance actually increases with crack extension; the implication here is that toughness is often developed primarily during crack growth and not for crack initiation. Biological materials are perfect examples of this; moreover, they offer microstructural design strategies for the development of new materials for structural applications demanding combinations of both strength and toughness.     

A Strong,Tough, and Scalable Structural Material from Fast-Growing Bamboo

Lightweight structural materials with high strength are desirable for advanced applications in transportation, construction, automotive, and aerospace. Bamboo is one of the fastest growing plants with a peak growth rate up to 100 cm per day. Here, a simple and effective top-down approach is designed for processing natural bamboo into a lightweight yet strong bulk structural material with a record high tensile strength of ≈1 GPa and toughness of 9.74 MJ m⁻³. More specifically, bamboo is densified by the partial removal of its lignin and hemicellulose, followed by hot-pressing. Long, aligned cellulose nanofibrils with dramatically increased hydrogen bonds and largely reduced structural defects in the densified bamboo structure contribute to its high mechanical tensile strength, flexural strength, and toughness. The low density of lignocellulose in the densified bamboo leads to a specific strength of 777 MPa cm³ g⁻¹, which is significantly greater than other reported bamboo materials and most structural materials (e.g., natural polymers, plastics, steels, and alloys). This work demonstrates a potential large-scale production of lightweight, strong bulk structural materials from abundant, fast-growing, and sustainable bamboo.     

Water‐Rich Biomimetic Composites with Abiotic Self‐Organizing Nanofiber Network

Load‐bearing soft tissues, e.g., cartilage, ligaments, and blood vessels, are made predominantly from water (65–90%) which is essential for nutrient transport to cells. Yet, they display amazing stiffness, toughness, strength, and deformability attributed to the reconfigurable 3D network from stiff collagen nanofibers and flexible proteoglycans. Existing hydrogels and composites partially achieve some of the mechanical properties of natural soft tissues, but at the expense of water content. Concurrently, water‐rich biomedical polymers are elastic but weak. Here, biomimetic composites from aramid nanofibers interlaced with poly(vinyl alcohol), with water contents of as high as 70–92%, are reported. With tensile moduli of ≈9.1 MPa, ultimate tensile strains of ≈325%, compressive strengths of ≈26 MPa, and fracture toughness of as high as ≈9200 J m^?2, their mechanical properties match or exceed those of prototype tissues, e.g., cartilage. Furthermore, with reconfigurable, noncovalent interactions at nanomaterial interfaces, the composite nanofiber network can adapt itself under stress, enabling abiotic soft tissue with multiscale self‐organization for effective load bearing and energy dissipation.     

仿生材料的研究现状

简要地介绍了贝壳珍珠层天然生物材料的结构特征，进而综述了仿生材料的研究现状。     

The toughening mechanism of nacre and structural materials inspired by nacre

Abstract

The structure and the toughening mechanism of nacre have been the subject of intensive research over the last 30 years. This interest originates from nacre’s excellent combination of strength, stiffness and toughness, despite its high, for a biological material, volume fraction of inorganic phase, typically 95%. Owing to the improvement of nanoscale measurement and observation techniques, significant progress has been made during the last decade in understanding the mechanical properties of nacre. The structure, microscopic deformation behavior and toughening mechanism on the order of nanometers have been investigated, and the importance of hierarchical structure in nacre has been recognized. This research has led to the fabrication of multilayer composites and films inspired by nacre with a layer thickness below 1 μm. Some of these materials reproduce the inorganic/organic interaction and hierarchical structure beyond mere morphology mimicking. In the first part of this review, we focus on the hierarchical architecture, macroscopic and microscopic deformation and fracture behavior, as well as toughening mechanisms in nacre. Then we summarize recent progress in the fabrication of materials inspired by nacre taking into consideration its mechanical properties.     

Merger of structure and material in nacre and bone – Perspectives on de novo biomimetic materials

In contrast to synthetic materials, evolutionary developments in biology have resulted in materials with remarkable structural properties, made out of relatively weak constituents, arranged in complex hierarchical patterns. For instance, nacre from seashells is primarily made of a fragile ceramic, yet it exhibits superior levels of strength and toughness. Structural features leading to this performance consist of a microstructure organized in a hierarchical fashion, and the addition of a small volume fraction of biopolymers. A key to this mechanical performance is the cohesion and sliding of wavy ceramic tablets. Another example is bone, a structural biological material made of a collagen protein phase and nanoscopic mineral platelets, reaching high levels of toughness and strength per weight. The design and fabrication of de novo synthetic materials that aim to utilize the deformation and hardening mechanism of biological materials such as bone or nacre is an active area of research in mechanics of materials. In this review, our current knowledge on microstructure and mechanics of nacre and bone are described, and a review of the fabrication of nacre-inspired artificial and related materials is presented. Both experimental and simulation approaches are discussed, along with specific examples that illustrate the various approaches. We conclude with a broader discussion of the interplay of size effects and hierarchies in defining mechanical properties of biological materials.