Crustacean‐Derived Biomimetic Components and Nanostructured Composites

Over millions of years, the crustacean exoskeleton has evolved into a rigid, tough, and complex cuticle that is used for structural support, mobility, protection of vital organs, and defense against predation. The crustacean cuticle is characterized by a hierarchically arranged chitin fiber scaffold, mineralized predominately by calcium carbonate and/or calcium phosphate. The structural organization of the mineral and organic within the cuticle occurs over multiple length scales, resulting in a strong and tough biological composite. Here, the ultrastructural details observed in three species of crustacean are reviewed: the American lobster (Homarus americanus), the edible crab (Cancer pagurus), and the peacock mantis shrimp (Odontodactylus scyllarus). The Review concludes with a discussion of recent advances in the development of biomimetics with controlled organic scaffolding, mineralization, and the construction of nanoscale composites, inspired by the organization and formation of the crustacean cuticle.     

Application of Fracture Mechanics Concepts to Hierarchical Biomechanics of Bone and Bone-like Materials

Fracture mechanics concepts are applied to gain some understanding of the hierarchical nanocomposite structures of hard biological tissues such as bone, tooth and shells. At the most elementary level of structural hierarchy, bone and bone-like materials exhibit a generic structure on the nanometer length scale consisting of hard mineral platelets arranged in a parallel staggered pattern in a soft protein matrix. The discussions in this paper are organized around the following questions: (1) The length scale question: why is nanoscale important to biological materials? (2) The stiffness question: how does nature create a stiff composite containing a high volume fraction of a soft material? (3) The toughness question: how does nature build a tough composite containing a high volume fraction of a brittle material? (4) The strength question: how does nature balance the widely different strengths of protein and mineral? (5) The optimization question: Can the generic nanostructure of bone and bone-like materials be understood from a structural optimization point of view? If so, what is being optimized? What is the objective function? (6) The buckling question: how does nature prevent the slender mineral platelets in bone from buckling under compression? (7) The hierarchy question: why does nature always design hierarchical structures? What is the role of structural hierarchy? A complete analysis of these questions taking into account the full biological complexities is far beyond the scope of this paper. The intention here is only to illustrate some of the basic mechanical design principles of bone-like materials using simple analytical and numerical models. With this objective in mind, the length scale question is addressed based on the principle of flaw tolerance which, in analogy with related concepts in fracture mechanics, indicates that the nanometer size makes the normally brittle mineral crystals insensitive to cracks-like flaws. Below a critical size on the nanometer length scale, the mineral crystals fail no longer by propagation of pre-existing cracks, but by uniform rupture near their limiting strength. The robust design of bone-like materials against brittle fracture provides an interesting analogy between Darwinian competition for survivability and engineering design for notch insensitivity. The follow-up analysis with respect to the questions on stiffness, strength, toughness, stability and optimization of the biological nanostructure provides further insights into the basic design principles of bone and bone-like materials. The staggered nanostructure is shown to be an optimized structure with the hard mineral crystals providing structural rigidity and the soft protein matrix dissipating fracture energy. Finally, the question on structural hierarchy is discussed via a model hierarchical material consisting of multiple levels of self-similar composite structures mimicking the nanostructure of bone. We show that the resulting “fractal bone”, a model hierarchical material with different properties at different length scales, can be designed to tolerate crack-like flaws of multiple length scales.     

Multiscale Experimental Mechanics of Hierarchical Carbon‐Based Materials

Investigation of the mechanics of natural materials, such as spider silk, abalone shells, and bone, has provided great insight into the design of materials that can simultaneously achieve high specific strength and toughness. Research has shown that their emergent mechanical properties are owed in part to their specific self‐organization in hierarchical molecular structures, from nanoscale to macroscale, as well as their mixing and bonding. To apply these findings to manmade materials, researchers have devoted significant efforts in developing a fundamental understanding of multiscale mechanics of materials and its application to the design of novel materials with superior mechanical performance. These efforts included the utilization of some of the most promising carbon‐based nanomaterials, such as carbon nanotubes, carbon nanofibers, and graphene, together with a variety of matrix materials. At the core of these efforts lies the need to characterize material mechanical behavior across multiple length scales starting from nanoscale characterization of constituents and their interactions to emerging micro‐ and macroscale properties. In this report, progress made in experimental tools and methods currently used for material characterization across multiple length scales is reviewed, as well as a discussion of how they have impacted our current understanding of the mechanics of hierarchical carbon‐based materials. In addition, insight is provided into strategies for bridging experiments across length scales, which are essential in establishing a multiscale characterization approach. While the focus of this progress report is in experimental methods, their concerted use with theoretical‐computational approaches towards the establishment of a robust material by design methodology is also discussed, which can pave the way for the development of novel materials possessing unprecedented mechanical properties.     

Modulating the Mechanical Performance of Macroscale Fibers through Shear‐Induced Alignment and Assembly of Protein Nanofibrils

Protein‐based fibers are used by nature as high‐performance materials in a wide range of applications, including providing structural support, creating thermal insulation, and generating underwater adhesives. Such fibers are commonly generated through a hierarchical self‐assembly process, where the molecular building blocks are geometrically confined and aligned along the fiber axis to provide a high level of structural robustness. Here, this approach is mimicked by using a microfluidic spinning method to enable precise control over multiscale order during the assembly process of nanoscale protein nanofibrils into micro‐ and macroscale fibers. By varying the flow rates on chip, the degree of nanofibril alignment can be tuned, leading to an orientation index comparable to that of native silk. It is found that the Young's modulus of the resulting fibers increases with an increasing level of nanoscale alignment of the building blocks, suggesting that the mechanical properties of macroscopic fibers can be controlled through varying the level of ordering of the nanoscale building blocks. Capitalizing on strategies evolved by nature, the fabrication method allows for the controlled formation of macroscopic fibers and offers the potential to be applied for the generation of further novel bioinspired materials.     

3D Printing of Ultralight Biomimetic Hierarchical Graphene Materials with Exceptional Stiffness and Resilience

Biological materials with hierarchical architectures (e.g., a macroscopic hollow structure and a microscopic cellular structure) offer unique inspiration for designing and manufacturing advanced biomimetic materials with outstanding mechanical performance and low density. Most conventional biomimetic materials only benefit from bioinspired architecture at a single length scale (e.g., microscopic material structure), which largely limits the mechanical performance of the resulting materials. There exists great potential to maxime the mechanical performance of biomimetic materials by leveraging a bioinspired hierarchical structure. An ink‐based three‐dimensional (3D) printing strategy to manufacture an ultralight biomimetic hierarchical graphene material (BHGMs) with exceptionally high stiffness and resilience is demonstrated. By simultaneously engineering 3D‐printed macroscopic hollow structures and constructing an ice‐crystal‐induced cellular microstructure, BHGMs can achieve ultrahigh elasticity and stability at compressive strains up to 95%. Multiscale finite element analyses indicate that the hierarchical structures of BHGMs effectively reduce the macroscopic strain and transform the microscopic compressive deformation into the rotation and bending of the interconnected graphene flakes. This 3D printing strategy demonstrates the great potential that exists for the assembly of other functional materials into hierarchical cellular structures for various applications where high stiffness and resilience at low density are simultaneously required.     

Combining Bottom‐Up Self‐Assembly with Top‐Down Microfabrication to Create Hierarchical Inverse Opals with High Structural Order

Colloidal particles can assemble into ordered crystals, creating periodically structured materials at the nanoscale without relying on expensive equipment. The combination of small size and high order leads to strong interaction with visible light, which induces macroscopic, iridescent structural coloration. To increase the complexity and functionality, it is important to control the organization of such materials in hierarchical structures with high degrees of order spanning multiple length scales. Here, a bottom‐up assembly of polystyrene particles in the presence of a silica sol–gel precursor material (tetraethylorthosilicate, TEOS), which creates crack‐free inverse opal films with high positional order and uniform crystal alignment along the (110) crystal plane, is combined with top‐down microfabrication techniques. Micrometer scale hierarchical superstructures having a highly regular internal nanostructure with precisely controlled crystal orientation and wall profiles are produced. The ability to combine structural order at the nano‐ and microscale enables the fabrication of materials with complex optical properties resulting from light–matter interactions at different length scales. As an example, a hierarchical diffraction grating, which combines Bragg reflection arising from the nanoscale periodicity of the inverse opal crystal with grating diffraction resulting from a micrometer scale periodicity, is demonstrated.     

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.     

Multiscale mechanical and structural characterizations of Palmetto wood for bio-inspired hierarchically structured polymer composites

There has been a great deal of effort focused on engineering polymer composites with hierarchical microstructures consisting of one or more ingredients that can be organized differently across multiple length scales. However, there are hierarchical microstructures that have evolved over eons in biological materials. These unique structure–property relationships may serve as templates for engineering hierarchically structured polymer composites with tailored properties. One such biological material is the Palmetto wood of South Carolina, which was successfully used as a protective structure during the Revolutionary and Civil Wars to absorb cannon shot. Through an assembly of microfibers into macrofibers embedded in a cellulose matrix, the Palmetto wood has optimized its ability to resist failure when subjected to extreme dynamic loading events, such as hurricanes. Understanding of the dynamic and static structure–property relationship in Palmetto wood can facilitate the development of new hierarchically structured polymer composites with increased resistance to failure. Therefore, the structure–property relationship in Palmetto wood has been studied using novel multiscale microstructural and mechanical characterization techniques. Models have been developed that indicate that the hierarchical structure of Palmetto wood obeys the linear Rule-of-Mixtures across multiple length scales. This understanding has led to the development of new polymer composite structures that exhibit properties similar to Palmetto wood using conventional laminated carbon fiber–epoxy composites and new polymer nanocomposites consisting of carbon nanofibers. The use of the nanofibers appears to enhance the interaction between the composite components in a manner similar to the interaction between fibers in the Palmetto wood that enables the laminated composite to behave more like the individual layers by resisting the tendency to delaminate and increasing the Weibull statistical parameters closer to those observed in Palmetto wood.     

From Wood to Textiles: Top‐Down Assembly of Aligned Cellulose Nanofibers

Advanced textiles made of macroscopic fibers are usually prepared from synthetic fibers, which have changed lives over the past century. The shortage of petrochemical resources, however, greatly limits the development of the textile industry. Here, a facile top‐down approach for fabricating macroscopic wood fibers for textile applications (wood‐textile fibers) comprising aligned cellulose nanofibers directly from natural wood via delignification and subsequent twisting is demonstrated. Inherently aligned cellulose nanofibers are well retained, while the microchannels in the delignified wood are squeezed and totally removed by twisting, resulting in a dense structure with approximately two times higher mechanical strength (106.5 vs 54.9 MPa) and ≈20 times higher toughness (7.70 vs 0.36 MJ m^?3) than natural wood. Dramatically different from natural wood, which is brittle in nature, the resultant wood‐textile fibers are highly flexible and bendable, likely due to the twisted structures. The wood‐textile fibers also exhibit excellent knitting properties and dyeability, which are critical for textile applications. Furthermore, functional wood‐textile fibers can be achieved by preinfiltrating functional materials in the delignified wood film before twisting. This top‐down approach of fabricating aligned macrofibers is simple, scalable, and cost‐effective, representing a promising direction for the development of smart textiles and wearable electronics.     

Phase Stability in Nanostructures

Nanostructured materials provide access to tailor‐made materials properties by microstructural design. Excellent mechanical properties such as high strength or wear resistance are often found in nanocrystalline materials. For magnetic materials, the design of nanostructured composites offers advantages if the structural scales match the intrinsic magnetic length scales. In some cases, as in the new nanocrystalline soft magnetic alloys, the combination of amorphous and nanocrystalline phases is necessary to obtain the desired properties. This rises the question of the limiting size for a stable crystalline structure, especially in contact with an amorphous phase. These considerations, which have been of interest for basic research in the context of the microcrystalline model for amorphous materials, are of technical importance for the optimization of nanostructured composites. Recent model experiments about the stability of thin Fe‐based glass forming alloy films are reviewed. A relationship between phase stability, composition, and interface density has been established. The implications of the results for the design of nanostructured alloy systems are discussed.     

Nanolattices: An Emerging Class of Mechanical Metamaterials

In 1903, Alexander Graham Bell developed a design principle to generate lightweight, mechanically robust lattice structures based on triangular cells; this has since found broad application in lightweight design. Over one hundred years later, the same principle is being used in the fabrication of nanolattice materials, namely lattice structures composed of nanoscale constituents. Taking advantage of the size‐dependent properties typical of nanoparticles, nanowires, and thin films, nanolattices redefine the limits of the accessible material‐property space throughout different disciplines. Herein, the exceptional mechanical performance of nanolattices, including their ultrahigh strength, damage tolerance, and stiffness, are reviewed, and their potential for multifunctional applications beyond mechanics is examined. The efficient integration of architecture and size‐affected properties is key to further develop nanolattices. The introduction of a hierarchical architecture is an effective tool in enhancing mechanical properties, and the eventual goal of nanolattice design may be to replicate the intricate hierarchies and functionalities observed in biological materials. Additive manufacturing and self‐assembly techniques enable lattice design at the nanoscale; the scaling‐up of nanolattice fabrication is currently the major challenge to their widespread use in technological applications.     

Strong Anisotropy and Ultralow Percolation Threshold in Multiscale Composites Modified by Carbon Nanotubes Coated Hollow Glass Fiber

Inspired by biological materials, the use of combined fillers of different types and sizes has led to multiscale, hierarchical composites which are considered to be the multifunctional materials of the next generation. However, the effects of hierarchical architecture on the electrical properties and percolation behavior remain poorly understood. Here, a multiscale polymer‐based micro‐/nano‐composite with hollow glass fibers coated by carbon nanotubes (CNTs) has been produced based on a simple dip‐coating approach. Besides a significant increase in electrical performance, the composites exhibit a very strong anisotropy of electrical properties with the difference of 2–5 orders of magnitude in different directions. In the longitudinal direction of composites, an ultralow percolation threshold is found. These unique properties are shown to be related to the hierarchical morphology, which gives rise to the existence of two percolation levels with different thresholds: a local threshold in the nanoscale 2D CNT networks at the fiber‐polymer interfaces and a global threshold in 3D network formed by the fibers. This study helps to deeper understand the macroscopic electrical performance of the hierarchical composites, potentially opening up new ways for designing novel materials via flexible tailoring the orientation of fiber and the morphology of interfaces.

     

Theoretical and computational hierarchical nanomechanics of protein materials: Deformation and fracture

Proteins constitute the building blocks of biological materials such as tendon, bone, skin, spider silk or cells. An important trait of these materials is that they display highly characteristic hierarchical structures, across multiple scales, from nano to macro. Protein materials are intriguing examples of materials that balance multiple tasks, representing some of the most sustainable material solutions that integrate structure and function. Here we review progress in understanding the deformation and fracture mechanisms of hierarchical protein materials by using a materials science approach to develop structure-process-property relations, an effort defined as materiomics. Deformation processes begin with an erratic motion of individual atoms around flaws or defects that quickly evolve into formation of macroscopic fractures as chemical bonds rupture rapidly, eventually compromising the integrity of the structure or the biological system leading to failure. The combination of large-scale atomistic simulation, multi-scale modeling methods, theoretical analyses combined with experimental validation provides a powerful approach in studying deformation and failure phenomena in protein materials. Here we review studies focused on the molecular origin of deformation and fracture processes of three types of protein materials. The review includes studies of collagen - Nature’s super-glue; beta-sheet rich protein structures as found in spider silk - a natural fiber that can reach the strength of a steel cable; as well as intermediate filaments - a class of alpha-helix based structural proteins responsible for the mechanical integrity of eukaryotic cells. The article concludes with a discussion of the significance of universally found structural patterns such as the staggered collagen fibril architecture or the alpha-helical protein motif.     

天然和仿生柔性生物结构的设计

自然界中生物材料表现出的力学性能与其结构设计形式紧密相关。柔性生物材料多为多级结构设计,其独特的功能梯度特征使其具备优异的变形能力及良好的断裂韧性。本文借鉴工程结构设计基本单元的思想提出柔性结构仿生元素理念,根据几何形态将结构仿生元素分为：线元素、梁元素、柱元素、板壳元素、薄膜元素及组合元素。根据系统论的观点建立仿生柔性结构设计体系,归纳总结出柔性仿生结构的设计准则,并基于鱼鳞梯度结构设计新型仿生功能梯度板。通过有限元的方法对功能梯度板归一化自然频率进行分析。结果表明,类鱼鳞功能梯度板具有柔韧性及刚度软化特性。阐述了仿生柔性结构的设计方法,包括模仿设计、组合设计及选择匹配设计。     

Patterning Porous Oxides within Microchannel Networks

A continuing challenge for materials chemists and engineers is the ability to create multifunctional composite structures with well‐defined superimposed structural order from nanometer to micrometer length scales. Materials with three‐dimensional structures ordered over multiple length scales can be prepared by carrying out colloidal crystallization and inorganic/organic cooperative self‐assembly within microchannel networks. The resulting materials show hierarchical ordering over several discrete and tunable length scales ranging from several nanometers to micrometers. These patterned porous materials hold promise for use as advanced catalysts, sensors, low‐k dielectrics, optoelectronic and integrated photonic crystal devices.     

Hierarchical Structure of Silk Materials Versus Mechanical Performance and Mesoscopic Engineering Principles

A comprehensive review on the five levels of hierarchical structures of silk materials and the correlation with macroscopic properties/performance of the silk materials, that is, the toughness, strain‐stiffening, etc., is presented. It follows that the crystalline binding force turns out to be very important in the stabilization of silk materials, while the β‐crystallite networks or nanofibrils and the interactions among helical nanofibrils are two of the most essential structural elements, which to a large extent determine the macroscopic performance of various forms of silk materials. In this context, the characteristic structural factors such as the orientation, size, and density of β‐crystallites are very crucial. It is revealed that the formation of these structural elements is mainly controlled by the intermolecular nucleation of β‐crystallites. Consequently, the rational design and reconstruction of silk materials can be implemented by controlling the molecular nucleation via applying sheering force and seeding (i.e., with carbon nanotubes). In general, the knowledge of the correlation between hierarchical structures and performance provides an understanding of the structural reasons behind the fascinating behaviors of silk materials.     

Nanoconfinement of spider silk fibrils begets superior strength, extensibility, and toughness

Silk is an exceptionally strong, extensible, and tough material made from simple protein building blocks. The molecular structure of dragline spider silk repeat units consists of semiamorphous and nanocrystalline β-sheet protein domains. Here we show by a series of computational experiments how the nanoscale properties of silk repeat units are scaled up to create macroscopic silk fibers with outstanding mechanical properties despite the presence of cavities, tears, and cracks. We demonstrate that the geometric confinement of silk fibrils to diameters of 50 ± 30 nm is critical to facilitate a powerful mechanism by which hundreds of thousands of protein domains synergistically resist deformation and failure to provide enhanced strength, extensibility, and toughness at the macroscale, closely matching experimentally measured mechanical properties. Through this mechanism silk fibers exploit the full potential of the nanoscale building blocks, regardless of the details of microscopic loading conditions and despite the presence of large defects. Experimental results confirm that silk fibers are composed of silk fibril bundles with diameters in the range of 20-150 nm, in agreement with our predicted length scale. Our study reveals a general mechanism to map nanoscale properties to the macroscale and provides a potent design strategy toward novel fiber and bulk nanomaterials through hierarchical structures.     

Hierarchical and Heterogeneous Bioinspired Composites—Merging Molecular Self‐Assembly with Additive Manufacturing

Biological composites display exceptional mechanical properties owing to a highly organized, heterogeneous architecture spanning several length scales. It is challenging to translate this ordered and multiscale structural organization in synthetic, bulk composites. Herein, a combination of top‐down and bottom‐up approach is demonstrated, to form a polymer‐ceramic composite by macroscopically aligning the self‐assembled nanostructure of polymerizable lyotropic liquid crystals via 3D printing. The polymer matrix is then uniformly reinforced with bone‐like apatite via in situ biomimetic mineralization. The combinatorial method enables the formation of macrosized, heterogeneous composites where the nanostructure and chemical composition is locally tuned over microscopic distances. This enables precise control over the mechanics in specific directions and regions, with a unique intrinsic–extrinsic toughening mechanism. As a proof‐of‐concept, the method is used to form large‐scale composites mimicking the local nanostructure, compositional gradients and directional mechanical properties of heterogeneous tissues like the bone‐cartilage interface, for mechanically stable osteochondral plugs. This work demonstrates the possibility to create hierarchical and complex structured composites using weak starting components, thus opening new routes for efficient synthesis of high‐performance materials ranging from biomaterials to structural nanocomposites.     

Biological materials: Structure and mechanical properties

Most natural (or biological) materials are complex composites whose mechanical properties are often outstanding, considering the weak constituents from which they are assembled. These complex structures, which have risen from hundreds of million years of evolution, are inspiring Materials Scientists in the design of novel materials.Their defining characteristics, hierarchy, multifunctionality, and self-healing capability, are illustrated. Self-organization is also a fundamental feature of many biological materials and the manner by which the structures are assembled from the molecular level up. The basic building blocks are described, starting with the 20 amino acids and proceeding to polypeptides, polysaccharides, and polypeptides-saccharides. These, on their turn, compose the basic proteins, which are the primary constituents of ‘soft tissues’ and are also present in most biominerals. There are over 1000 proteins, and we describe only the principal ones, with emphasis on collagen, chitin, keratin, and elastin. The ‘hard’ phases are primarily strengthened by minerals, which nucleate and grow in a biomediated environment that determines the size, shape and distribution of individual crystals. The most important mineral phases are discussed: hydroxyapatite, silica, and aragonite.Using the classification of Wegst and Ashby, the principal mechanical characteristics and structures of biological ceramics, polymer composites, elastomers, and cellular materials are presented. Selected systems in each class are described with emphasis on the relationship between their structure and mechanical response. A fifth class is added to this: functional biological materials, which have a structure developed for a specific function: adhesion, optical properties, etc.An outgrowth of this effort is the search for bioinspired materials and structures. Traditional approaches focus on design methodologies of biological materials using conventional synthetic materials. The new frontiers reside in the synthesis of bioinspired materials through processes that are characteristic of biological systems; these involve nanoscale self-assembly of the components and the development of hierarchical structures. Although this approach is still in its infancy, it will eventually lead to a plethora of new materials systems as we elucidate the fundamental mechanisms of growth and the structure of biological systems.