3D Direct Laser Writing of Nano‐ and Microstructured Hierarchical Gecko‐Mimicking Surfaces

Applying 3D direct laser writing, artificial hierarchical gecko‐type structures are designed and fabricated down to nanometer dimensions. In this way, the elastic modulus and the length scale of the gecko's setae are very closely matched. Direct laser writing is a very flexible rapid prototyping method allowing the fabrication of arbitrary nanostructures. Since the parameters of the structures can be easily changed, this technique is perfect for design studies of dry adhesives. Measuring the adhesional forces by atomic force microscopy, the influence of several design parameters like density, aspect ratio, and tip‐shape on dry adhesion performance are systematically examined. In this way, it is revealed that hierarchy is favorable for artificial gecko‐inspired dry adhesives made of stiff materials on the nanometer scale.     

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.     

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。     

Analytical solutions of the displacement and stress fields of the nanocomposite structure of biological materials

Biological materials, such as bone and nacre, are nanocomposites of protein and mineral with superior mechanical properties. The basic building blocks of these materials feature a generic nanocomposite structure with staggered alignment of mineral platelets in protein matrix. Because of the structural complexity of the generic structure, its displacement and stress fields are currently still unknown. In this study, a perturbation method was applied for analytically solving the displacement and stress fields of the nanocomposite structure under uniaxial tension. The effect of the elastic modulus, aspect ratio and volume fraction of mineral and protein on the displacement and stress fields in the nanocomposite structure was studied. A non-dimensional parameter γ was then suggested for characterizing the stress and strain fields in this nanostructure. We showed that the assumption of uniform shear stress distribution at the mineral-protein interface in the TSC model is valid when γ is less than 4 which is broadly applicable to most biological materials. The analytical solutions of displacement and stress fields obtained in this study provide a solid basis for further analyses of mechanical properties, such as the buckling and the fracture behaviors of biological materials.     

The predominant role of collagen in the nucleation, growth, structure and orientation of bone apatite

The involvement of collagen in bone biomineralization is commonly admitted, yet its role remains unclear. Here we show that type I collagen in?vitro can initiate and orientate the growth of carbonated apatite mineral in the absence of any other vertebrate extracellular matrix molecules of calcifying tissues. We also show that the collagen matrix influences the structural characteristics on the atomic scale, and controls the size and the three-dimensional distribution of apatite at larger length scales. These results call into question recent consensus in the literature on the need for Ca-rich non-collagenous proteins for collagen mineralization to occur in vivo. Our model is based on a collagen/apatite self-assembly process that combines the ability to mimic the in vivo extracellular fluid with three major features inherent to living bone tissue, that is, high fibrillar density, monodispersed fibrils and long-range hierarchical organization.     

The quest for stiff,strong and tough hybrid materials: an exhaustive exploration

How to arrange soft materials with strong but brittle reinforcements to achieve attractive combinations of stiffness, strength and toughness is an ongoing and fascinating question in engineering and biological materials science. Recent advances in topology optimization and bioinspiration have brought interesting answers to this question, but they provide only small windows into the vast design space associated with this problem. Here, we take a more global approach in which we assess the mechanical performance of thousands of possible microstructures. This exhaustive exploration gives a global picture of structure–property relationships and guarantees that global optima can be found. Landscapes of optimum solutions for different combinations of desired properties can also be created, revealing the robustness of each of the solutions. Interestingly, while some of the major hybrid designs used in engineering are absent from the set of solutions, the microstructures emerging from this process are reminiscent of materials, such as bone, nacre or spider silk.     

Hierarchical flexural strength of enamel: transition from brittle to damage-tolerant behaviour

Hard, biological materials are generally hierarchically structured from the nano- to the macro-scale in a somewhat self-similar manner consisting of mineral units surrounded by a soft protein shell. Considerable efforts are underway to mimic such materials because of their structurally optimized mechanical functionality of being hard and stiff as well as damage-tolerant. However, it is unclear how different hierarchical levels interact to achieve this performance. In this study, we consider dental enamel as a representative, biological hierarchical structure and determine its flexural strength and elastic modulus at three levels of hierarchy using focused ion beam (FIB) prepared cantilevers of micrometre size. The results are compared and analysed using a theoretical model proposed by Jäger and Fratzl and developed by Gao and co-workers. Both properties decrease with increasing hierarchical dimension along with a switch in mechanical behaviour from linear-elastic to elastic-inelastic. We found Gao''s model matched the results very well.     

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.     

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.     

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.     

Influence of Structural Principles on the Mechanics of a Biological Fiber‐Based Composite Material with Hierarchical Organization: The Exoskeleton of the Lobster Homarus americanus

The cuticle of the lobster Homarus americanus is a nanocomposite, such as most structural biological materials. It consists of a matrix of chitin‐protein fibers associated with various amounts of crystalline and amorphous calcium carbonate in the rigid parts of the body, and is organized hierarchically at all length scales. One prominent design principle found in the hierarchical structure of such biological fibrous composite materials is the twisted plywood structure. In the lobster cuticle, it is formed by superimposing and gradually rotating planes of parallel aligned chitin‐protein fibers. To adjust the mechanical properties to the requirements on the macroscopic level, the spatial arrangement and the grade of mineralization of the fibers can be modified. A second design principle of lobster cuticle is its honeycomb‐like structure, generated by the well‐developed pore canal system, whose twisted ribbon‐shaped canals penetrate the cuticle perpendicular to its surface. Due to the hierarchical structure, the mechanical properties of the lobster cuticle have to be investigated at different length scales, which is essential for the understanding of the structure–mechanical function relations of mineralized tissues (e.g., potentially also bone and teeth). In order to investigate the influence of the structural principles on the mechanical properties on the macroscopic scale miniaturized tensile, compression, and shear tests were carried out to obtain integral mechanical data. Characterization of the microstructure included scanning electron microscopy (SEM) combined with energy dispersive X‐ray (EDX) measurements.     

Hierarchy of Bone Microdamage at Multiple Length Scales

Microdamage formation is a critical determinant of bone fracture and the nature and type of damage formed in bone depends on the interaction of its extracellular matrix (ECM) with the applied loading. More importantly, because bone is a hierarchical composite with multiple length scales linked to each other, the nature and type of damage in bone could also be hierarchical. In this review article, based on new unpublished data and a reanalysis of literature reports on in vivo and in vitro observations of microdamage, three length scales including mineralized collagen fibrils, lamellar and osteonal levels have been identified as the key contributors to microdamage hierarchy and energy dissipation in bone. Inherent hierarchy in bone's ECM therefore has specific microstructural features and energy dissipation mechanisms at different length scales that allow the bone to effectively resist the different components of the applied physiological loading. Furthermore, because human bones experience multiaxial cyclic loading and its ECM is subjected to variation with aging and disease, additional emphasis is placed on investigating how the nature of applied loading and the quality of ECM affect the hierarchy of microdamage formation with age.     

Ordered Arrays of Nanostructures and Applications in High‐Efficient Nano‐Generators

Large‐scale ordered nanostructure arrays on substrates, including nanowires, nanotubes, nanodots, and nano‐holes, can be fabricated using template fabrication processes. The controllable structural parameters and properties of the ordered nanostructure arrays make them quite suitable to be used in many device‐related application areas. It is shown that large‐scale nanowire arrays are good candidates for the realization of a nano‐generator based on the piezoelectric effect of ZnO nanowires. The mechanism of a proposed high‐efficient nano‐generator based on an assembled nanowire/nanohole embedded structure shows high application potentials for biological and nanometer‐sized devices.     

Microarchitected Stretching‐Dominated Mechanical Metamaterials with Minimal Surface Topologies

Historically, the creation of lightweight, yet mechanically robust, materials have been the most sought‐after engineering pursuit. For that purpose, research efforts are dedicated to finding pathways to emulate and mimic the resilience offered by natural biological systems (i.e., bone and wood). These natural systems evolved over time to provide the most attainable structural efficiency through their architectural characteristics that can span over multiple length scales. Nature‐inspired man‐made cellular metamaterials have effective properties that depend largely on their topology rather than composition and are hence remarkable candidates for a wide range of application. Despite their geometrical complexity, the fabrication of such metamaterials is made possible by the emergence of advanced fabrication techniques that permit the fabrication of complex architectures down to the nanometer scale. In this work, we report the fabrication and mechanical testing of nature‐inspired, mathematically created, micro‐architected, cellular metamaterials with topologies based on triply periodic minimal surfaces (TPMS) with cubic symmetries fabricated through direct laser writing two‐photon lithography. These TPMS‐based microlattices are sheet/shell‐ and strut‐based metamaterials with high geometrical complexity. Interestingly, results show that TPMS sheet‐based microlattices follow a stretching‐dominated mode of deformation, and further illustrate their mechanical superiority over the traditional and well‐known strut‐based microlattices and microlattice composites. The TPMS sheet‐based polymeric microlattices exhibited mechanical properties superior to other micrloattices comprising metal‐ and ceramic‐coated polymeric substrates and, interestingly, are less affected by the change in density, which opens the door for fabricating ultralightweight materials without much sacrificing mechanical properties.

     

Enzyme Directed Templating of Artificial Bone Mineral

Bone is one of Nature's most remarkable materials, not only for its mechanical properties but also for its ability to repair fractures and remodel its microstructure in response to stress. At the nanoscale bone is a supramolecular matrix of collagen fibers reinforced by hydroxyapatite crystals with a high degree of order. Emulating elements of the biological synthesis of this composite could help develop strategies for advanced materials. Previous work has demonstrated the use of functionalized peptide amphiphile nanofibers in a two-dimensional system to emulate hydroxyapatite mineralization in natural bone. We describe here an artificial, in vitro biomineralization process that allows a similar process to occur in three dimensions. The system employs the natural enzyme alkaline phosphatase and a phosphorylated, anionic nanofiber gel matrix to template hydroxyapatite nanocrystals with size, shape, and crystallographic orientation resembling natural bone mineral. The formation of this biomimetic mineral in three dimensions results from the synergy of fiber-induced nucleation and the temporal control of phosphate ion harvesting by the enzyme. Gradual enzymatic harvesting of ions for crystal growth and the strong nucleating ability of the phosphorylated fibers suppresses uncontrolled precipitation of mineral. The strategy could lead to biomimetic materials to promote bone regeneration or the synthesis of hybrid materials with crystallographically defined structures.     

仿生功能化骨修复材料研究

由肿瘤、炎症及各类创伤而导致的骨组织坏死、病变、缺失及骨折是临床多发病症,自体骨移植虽然是临床治疗的“金标准”,但由于供体受限而很难满足需求。通过对天然骨本身的成分、结构特性及矿化过程的模仿,应用先进材料制备技术,特别是纳米技术,对材料的组成、结构进行设计与凋控,获得仿生型骨修复材料或者对传统材料进行仿生功能化修饰,以满足临床对痫损或缺失的骨组织进行有效修复和功能重建具有重要意义。阐述了仿生功能化骨修复材料的相关研究,主要包括类骨钙磷纳米矿物的合成,有机分子摸板对纳米矿物尺寸和形貌的调控,以及仿生多孔结构支架的构建等。     

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.     

The role of nanoscale architecture in supramolecular templating of biomimetic hydroxyapatite mineralization

Understanding and mimicking the hierarchical structure of mineralized tissue is a challenge in the field of biomineralization and is important for the development of scaffolds to guide bone regeneration. Bone is a remarkable tissue with an organic matrix comprised of aligned collagen bundles embedded with nanometer-sized inorganic hydroxyapatite (HAP) crystals that exhibit orientation on the macroscale. Hybrid organic-inorganic structures mimic the composition of mineralized tissue for functional bone scaffolds, but the relationship between morphology of the organic matrix and orientation of mineral is poorly understood. Herein the mineralization of supramolecular peptide amphiphile templates, that are designed to vary in nanoscale morphology by altering the amino acid sequence, is reported. It is found that 1D cylindrical nanostructures direct the growth of oriented HAP crystals, while flatter nanostructures fail to guide the orientation found in biological systems. The geometric constraints associated with the morphology of the nanostructures may effectively control HAP nucleation and growth. Additionally, the mineralization of macroscopically aligned bundles of the nanoscale assemblies to create hierarchically ordered scaffolds is explored. Again, it is found that only aligned gel templates of cylindrical nanostructures lead to hierarchical control over hydroxyapatite orientation across multiple length scales as found in bone.     

Bioinspired Materials with Self-Adaptable Mechanical Properties

Natural structural materials, such as bone, can autonomously modulate their mechanical properties in response to external loading to prevent failure. These material systems smartly control the addition/removal of material in locations of high/low mechanical stress by utilizing local resources guided by biological signals. On the contrary, synthetic structural materials have unchanging mechanical properties limiting their mechanical performance and service life. Inspired by the mineralization process of bone, a material system that adapts its mechanical properties in response to external mechanical loading is reported. It is found that charges from piezoelectric scaffolds can induce mineralization from surrounding media. It is shown that the material system can adapt to external mechanical loading by inducing mineral deposition in proportion to the magnitude of the stress and the resulting piezoelectric charges. Moreover, the mineralization mechanism allows a simple one-step route for fabricating functionally graded materials by controlling the stress distribution along the scaffold. The findings can pave the way for a new class of self-regenerating materials that reinforce regions of high stress or induce deposition of minerals on the damaged areas from the increase in mechanical stress to prevent/mitigate failure. It is envisioned that the findings can contribute to addressing the current challenges of synthetic materials for load-bearing applications from self-adaptive capabilities.     

Role of hydroxyapatite crystal shape in nanoscale mechanical behavior of model tropocollagen–hydroxyapatite hard biomaterials

Shape of mineral (e.g. hydroxyapatite (HAP) or aragonite) crystals can be a strong determinant of the nanoscale strength of hard biological materials such as bone, dentin, and nacre. This work presents an understanding of the effect of HAP shape variation on nanoscale strength of model TC-HAP biomaterials. For this purpose, 3-dimensional molecular dynamics analyses of direction dependent tensile deformation in two structurally distinct TC-HAP cells with HAP crystals in needle shaped configuration and plate shaped configuration are performed. Analyses point out that the peak interfacial strength for failure is the highest for supercells with plate shaped HAP crystals. In addition, the plate shaped HAP crystals result in the localization of peak stress over a larger length scale indicating higher fracture strength. Peak strength during transverse loading is always found to be lower than that during the longitudinal loading. However, interfacial strength shows a reverse trend. Overall, analyses point out that HAP crystal shape along with the optimal direction of applied loading with respect to the TC-HAP orientation strongly influence biomaterial strength at the nanoscale.