Francois Barthelat

Biomimetics for next generation materials

Billions of years of evolution have produced extremely efficient natural materials, which are increasingly becoming a source of inspiration for engineers. Biomimetics—the science of imitating nature—is a growing multidisciplinary field which is now leading to the fabrication of novel materials with remarkable mechanical properties. This article discusses the mechanics of hard biological materials, and more specifically of nacre and bone. These high-performance natural composites are made up of relatively weak components (brittle minerals and soft proteins) arranged in intricate ways to achieve specific combinations of stiffness, strength and toughness (resistance to cracking). Determining which features control the performance of these materials is the first step in biomimetics. These ‘key features’ can then be implemented into artificial bio-inspired synthetic materials, using innovative techniques such as layer-by-layer assembly or ice-templated crystallization. The most promising approaches, however, are self-assembly and biomineralization because they will enable tight control of structures at the nanoscale. In this ‘bottom-up’ fabrication, also inspired from nature, molecular structures and crystals are assembled with a little or no external intervention. The resulting materials will offer new combinations of low weight, stiffness and toughness, with added functionalities such as self-healing. Only tight collaborations between engineers, chemists, materials scientists and biologists will make these ‘next-generation’ materials a reality.

A novel biomimetic material duplicating the structure and mechanics of natural nacre

Nacre from mollusk shell is a high-performance natural composite composed of microscopic mineral tablets bonded by a tough biopolymer. Under tensile stress, the tablets slide on one another in a highly controlled fashion, which makes nacre 3000 times tougher than the mineral it is made of. Significant efforts have led to nacre-like materials, but none can yet match this amount of toughness amplification. This article presents the first synthetic material that successfully duplicates the mechanism of tablet sliding observed in nacre. Made of millimeter-size wavy poly-methylmethacrylate tablets held by fasteners, this “model material” undergoes massive tablet sliding under tensile loading, accompanied by strain hardening. Analytical and finite element models successfully captured the salient deformation mechanisms in this material, enabling further design refinements and optimization. In addition, two new mechanisms were identified: the effect of free surfaces and “unzipping.” Both mechanisms may be relevant to natural materials such as nacre or bone.

The weak interfaces within tough natural composites: Experiments on three types of nacre

Mineralization is a typical strategy used in natural materials to achieve high stiffness and hardness for structural functions such as skeletal support, protection or predation. High mineral content generally leads to brittleness, yet natural materials such as bone, mollusk shells or glass sponge achieve relatively high toughness considering the weakness of their constituents through intricate microstructures. In particular, nanometers thick organic interfaces organized in micro-architectures play a key role in providing toughness by various processes including crack deflection, crack bridging or energy dissipation. While these interfaces are critical in these materials, their composition, structure and mechanics is often poorly understood. In this work we focus on nacre, one of the most impressive hard biological materials in terms of toughness. We performed interfacial fracture tests on chevron notched nacre samples from three different species: red abalone, top shell and pearl oyster. We found that the intrinsic toughness of the interfaces is indeed found to be extremely low, in the order of the toughness of the mineral inclusions themselves. Such low toughness is required for the cracks to follow the interfaces, and to deflect and circumvent the mineral tablets. This result highlights the efficacy of toughening mechanisms in natural materials, turning low-toughness inclusions and interfaces into high-performance composites. We found that top shell nacre displayed the highest interfacial toughness, because of higher surface roughness and a more resilient organic material, and also through extrinsic toughening mechanisms including crack deflection, crack bridging and process zone. In the context of biomimetics, the main implication of this finding is that the interface in nacre-like composite does not need to be tough; the extensibility or ductility of the interfaces may be more important than their strength and toughness to produce toughness at the macroscale.

A Review on the Structure and Mechanical Properties of Mollusk Shells – Perspectives on Synthetic Biomimetic Materials

Natural materials can exhibit remarkable combinations of stiffness, low weight, strength, and toughness which are in some cases unmatched by manmade materials. In the past two decades significant efforts were therefore undertaken in the materials research community to elucidate the microstructure and mechanisms behind these mechanical performances, in order to duplicate them in artificial materials [1, 2]. This approach to design, called biomimetics, has now started to yield materials with remarkable properties. The first step in this biomimetic approach is the identification of materials performances in natural materials, together with a fundamental understanding of the mechanisms behind these performances (which has been greatly accelerated by recent techniques such as scanning probe microscopy). The mechanical performance of natural materials is illustrated in Fig. 19.1, a material properties map for a selection of natural ceramics, biopolymer, and their composites [3]. The upper left corner of the map shows soft and tough materials such as skin, with a mechanical behavior similar to elastomers. The lower right corner of the chart shows stiff but brittle minerals such as hydroxyapatite or calcite. Most hard biological materials incorporate minerals into soft matrices, mostly to achieve the stiffness required for structural support or armored protection [4]. These materials are seen in the upper right part of the map and show how natural materials achieve high stiffness by incorporating minerals while retaining an exceptional toughness. Alternatively, one can consider how natural materials turn brittle minerals into much tougher materials, in some cases only with a few percent additions of biopolymers. These materials have in general relatively complex structures organized over several length scales (hierarchical structures [1, 2]) with mechanisms operating over several length scales, down to the nanoscale [5, 6]. Mollusk shells, the topic of this chapter, are an excellent example of such highperformance natural materials. Mollusks are composed to at least 95% of minerals

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.

Effects of dehydration on the viscoelastic properties of vocal folds in large deformations.

Dehydration may alter vocal fold viscoelastic properties, thereby hampering phonation. The effects of water loss induced by an osmotic pressure potential on vocal fold tissue viscoelastic properties were investigated. Porcine vocal folds were dehydrated by immersion in a hypertonic solution, and quasi-static and low-frequency dynamic traction tests were performed for elongations of up to 50%. Digital image correlation was used to determine local strains from surface deformations. The elastic modulus and the loss factor were then determined for normal and dehydrated tissues. An eight-chain hyperelastic model was used to describe the observed nonlinear stress-stretch behavior. Contrary to the expectations, the mass history indicated that the tissue absorbed water during cyclic extension when submerged in a hypertonic solution. During loading history, the elastic modulus was increased for dehydrated tissues as a function of strain. The response of dehydrated tissues was much less affected when the load was released. This observation suggests that hydration should be considered in micromechanical models of the vocal folds. The internal hysteresis, which is often linked to phonation effort, increased significantly with water loss. The effects of dehydration on the viscoelastic properties of vocal fold tissue were quantified in a systematic way. A better understanding of the role of hydration on the mechanical properties of vocal fold tissue may help to establish objective dehydration and phonotrauma criteria.

Teleost fish scales amongst the toughest collagenous materials

Fish scales from modern teleost fish are high-performance materials made of cross-plies of collagen type I fibrils reinforced with hydroxyapatite. Recent studies on this material have demonstrated the remarkable performance of this material in tension and against sharp puncture. Although it is known that teleost fish scales are extremely tough, actual measurements of fracture toughness have so far not been reported because it is simply not possible to propagate a crack in this material using standard fracture testing configurations. Here we present a new fracture test setup where the scale is clamped between two pairs of miniature steel plates. The plates transmit the load uniformly, prevent warping of the scale and ensure a controlled crack propagation. We report a toughness of 15 to 18kJm(-2) (depending on the direction of crack propagation), which confirms teleost fish scales as one of the toughest biological material known. We also tested the individual bony layers, which we found was about four times less tough than the collagen layer because of its higher mineralization. The mechanical response of the scales also depends on the cohesion between fibrils and plies. Delamination tests show that the interface between the collagen fibrils is three orders of magnitude weaker than the scale, which explains the massive delamination and defibrillation observed experimentally. Finally, simple fracture mechanics models showed that process zone toughening is the principal source of toughening for the scales, followed by bridging by delaminated fibrils. These findings can guide the design of cross-ply composites and engineering textiles for high-end applications. This study also hints on the fracture mechanics and performance of collagenous materials with similar microstructures: fish skin, lamellar bone or tendons.

Dynamic torsion testing of nanocrystalline coatings using high-speed photography and digital image correlation

The strength and ductility of microcrystalline and nanocrystalline tungstsen carbide-cobalt (WC-Co) cermets have been evaluated by employing a stored energy Kolsky bar apparatus, high-speed photography and digital image correlation. The test specimens were thin-walled tubular AI7075-T6 substrates 250 μm thick, coated with a 300 μm thick microcrystalline or nanocrystalline WC-Co layer with an average grain size of about 3 μm and 100 nm, respectively. Dynamic torsion experiments reported in this paper reveal a shear modulus of 50 GPa and a shear strength of about 50 MPa for both microcrystalline and nanocrystalline WC-Co coatings.The use of high-speed photography along with digital image correlation has shown that damage to the coating coincides with a significant softening on the stress-strain curve. The coating failed in mode III, and strong interactions between the crack faces were probably responsible for the increase in load after failure of the coating. The overall failure of the coating-substrate system was not brittle but rather progressive and controlled by the ductility of the aluminum substrate.A methodology for investigating damage kinetics and failure has been established. This methodology can be applied to examine the behavior of other advanced materials that can be manufactured as coatings on ductile substrates. Manufacturing coatings free of initial microcracks remains a significant challenge. Research on optimization of the spray deposition parameters should be pursued to produce high-quality nanostructured coatings that can fully exploit the benefits of nano-size grains.

Architectured materials in engineering and biology: fabrication, structure, mechanics and performance

Ever-increasing requirements for structural performance drive the research and the development of stronger, tougher and lighter materials. Specific microstructures, heterogeneities or hybrid compositions are now used in modern materials to generate high performance structures. Pushed to the extreme, these concepts lead to architectured materials, which contain highly controlled structures at length scales which are intermediate between the microscale and the size of the component. This review focuses on dense architectured materials made of building blocks of well-defined size and shape, arranged in two or three dimensions. These building blocks are stiff so their deformation remains small and within elastic limits, but their interfaces can channel cracks and undergo large deformations. These basic principles lead to building blocks which can slide, rotate, separate or interlock collectively, providing a wealth of tunable mechanisms. Nature is well ahead of engineers in making use of architectured materials. Materials such as bone, teeth or mollusc shells are made of stiff building blocks of well-defined sizes and shapes, bonded together by deformable bio-adhesives. These natural materials demonstrate how the interplay between building block properties, shape, size and arrangement together with non-linear behaviour at the interfaces generate unusual combinations of stiffness, strength and toughness. In this review we discuss the general principles underlying the structure and mechanics of engineering architectured materials and of biological and bio-inspired architectured materials. Recent progress and remaining issues in the modelling, design optimisation and fabrication of these materials are also presented. The discussion draws from examples in the engineering and natural worlds, emphasising not only how natural materials can help us improve existing architectured materials, but also how they can inspire entirely new structural materials with unusual and highly attractive combinations of properties.

An improved failure criterion for biological and engineered staggered composites

High-performance biological materials such as nacre, spider silk or bone have evolved a staggered microstructure consisting of stiff and strong elongated inclusions aligned with the direction of loading. This structure leads to useful combinations of stiffness, strength and toughness, and it is therefore increasingly mimicked in bio-inspired composites. The performance of staggered composites can be tuned; for example, their mechanical properties increase when the overlap between the inclusions is increased. However, larger overlaps may lead to excessive tensile stress and fracture of the inclusions themselves, a highly detrimental failure mode. Fracture of the inclusions has so far only been predicted using highly simplified models, which hinder our ability to properly design and optimize engineered staggered composites. In this work, we develop a new failure criterion that takes into account the complex stress field within the inclusions as well as initial defects. The model leads to an ‘optimum criterion’ for cases where the shear tractions on the inclusions is uniform, and a ‘conservative’ criterion for which the tractions are modelled as point forces at the ends of the overlap regions. The criterion can therefore be applied for a wide array of material behaviour at the interface, even if the details of the shear load transfer is not known. The new criterion is validated with experiments on staggered structures made of millimetre-thick alumina tablets, and by comparison with data on nacre. Formulated in a non-dimensional form, our new criterion can be applied on a wide variety of engineered staggered composites at any length scale. It also reveals new design guidelines, for example high aspect ratio inclusions with weak interfaces are preferable over inclusions with low aspect ratio and stronger interfaces. Together with existing models, this new criterion will lead to optimal designs that harness the full potential of bio-inspired staggered composites.