Bioinspired Bouligand-Structured Cellulose Nanocrystals/Poly(vinyl alcohol) Composite Hydrogel for Enhanced Impact Resistance.

Impact-protective materials are gaining importance because of the widespread occurrence of impact damage. Hydrogels have emerged as promising candidates owing to their lightweight and flexible nature. However, achieving soft impact-resistant hydrogels with exceptional stiffness, strength, and toughness remains a challenge. Inspired by the Bouligand structure found in the smasher dactyl club of stomatopods, we propose a straightforward multiscale hierarchical structural design strategy. This strategy integrates self-assembly and salting-out techniques to enhance the impact resistance of soft hydrogels. Rigid cellulose nanocrystals (CNCs) self-assemble into Bouligand-like structures within soft poly(vinyl alcohol) (PVA) matrix via supramolecular interactions. This rational structural design combines the CNC Bouligand structure with a cross-linked network of soft PVA crystalline domains, resulting in a composite hydrogel with impressive mechanical properties: high tensile fracture strength (30.2 MPa), elastic modulus (62.7 MPa), and fracture energy (75.6 kJ m-2), surpassing those of other tough hydrogels. Moreover, the multiscale hierarchical structure facilitates various energy dissipation mechanisms, including crack twisting, tortuous crack paths, and PVA chain orientation, resulting in notable force attenuation (80.4%) in the composite hydrogel. This biomimetic design strategy opens new avenues for developing soft and lightweight impact-resistant materials.

A multiscale fracture model to reveal the toughening mechanism in bioinspired Bouligand structures.

The Bouligand structure has been observed in a variety of biological materials, such as lamellar bone and exoskeleton of lobsters. It is a hierarchical and non-homogeneous architecture that exhibits excellent damage-resistant performance. This paper presents a multiscale fracture model considering the material inhomogeneity, the multiscale property, and the anisotropy to reveal the toughening mechanisms in the Bouligand structure. Firstly, the macro and micro constitutive properties of this composite are derived. Then, a multiscale fracture model is developed to characterize the local stress intensity factors and the energy release rates at the crack front of twisted cracks. Our results demonstrate that the decrease in the local energy release rate can be attributed to two-step mechanisms. The first mechanism is that the multiscale structure and the material inhomogeneity cause a release of stress near the initial crack tip. The second mechanism is that the twisted crack leads to the transformation from single-mode loading to mixed-mode loading, which enhances the fracture toughness. These results can not only reveal the toughening mechanism of the Bouligand structure but also provide guidelines for the design of high-performance composites. STATEMENT OF SIGNIFICANCE: Biological materials in nature often possess excellent mechanical properties that have not been achieved by synthetic materials. Bioinspired Bouligand structures provide prototypes for designing high-performance materials. In this study, we propose a multiscale theoretical fracture model to investigate the fracture properties of Bouligand structures with twisted cracks. We systematically consider the roles of material inhomogeneity, anisotropy, and multiscale properties. Our analysis demonstrates that the remarkable toughness of Bouligand structures results from the combined effects of material inhomogeneity and twisted cracks. This research contributes to unveiling the secret behind the outstanding toughness of Bouligand structures and provides inspiration for the development of novel designs for man-made composites.

Optimization Design and Nonlinear Bending of Bio-Inspired Helicoidal Composite Laminated Plates.

Inspired by the bionic Bouligand structure, helicoidal carbon fiber-reinforced polymer composite (CFRPC) laminates have been proven to own outstanding out-of-plane mechanical properties. This work aims to further explore the excellent bending characteristics of helicoidal CFRPC laminated plates and find out the optimal helicoidal layup patterns. The optimization design of laminated plates stacked with single-form and combination-form helicoidal layup sequences are carried out by using the finite element method (FEM) and adaptive simulated annealing (ASA) optimization algorithm on the Isight platform. Then, the nonlinear bending responses of optimal helicoidal CFRPC laminated plates are investigated via the FEM for the first time. The helicoidal CFRPC laminated plates under three different types of boundary conditions subjected to transverse uniformly distributed load are considered. The numerical results reveal that the combination-form helicoidal layup sequences can decrease the dimensionless bending deflection of laminated plates by more than 5% compared with the quasi-isotropic plate and enhance the out-of-plane bending characteristics of CFRPC laminated plates effectively. The boundary conditions can significantly influence the nonlinear bending responses of helicoidal CFRPC laminated plates.

Biomimetic Gradient Bouligand Structure Enhances Impact Resistance of Ceramic-Polymer Composites.

Biological materials relied on multiple synergistic structural design elements typically exhibit excellent comprehensive mechanical properties. Hierarchical incorporation of different biostructural elements into a single artificial material is a promising approach to enhance mechanical properties, but remains challenging. Herein, a biomimetic structural design strategy is proposed by coupling gradient structure with twisted plywood Bouligand structure, attempting to improve the impact resistance of ceramic-polymer composites. Via robocasting and sintering, kaolin ceramic filaments reinforced by coaxially aligned alumina nanoplatelets are arranged into Bouligand structure with a gradual transition in filament spacing along the thickness direction. After the following polymer infiltration, biomimetic ceramic-polymer composites with a gradient Bouligand (GB) structure are eventually fabricated. Experimental investigations reveal that the incorporation of gradient structure into Bouligand structure improves both the peak force and total energy absorption of the obtained ceramic-polymer composites. Computational modeling further suggests the substantial improvement in impact resistance by adopting GB structure, and clarifies the underlying deformation behavior of the biomimetic GB structured composites under impact. This biomimetic design strategy may provide valuable insights for developing lightweight and impact-resistant structural materials in the future.

Analysis and simulation of fracture behavior in naturally occurring Bouligand structures.

Through natural selection processes, refined biological materials could be created that adapt to various environments and exhibit specific functions. Such materials include typical Bouligand structures that can be widely observed in marine creatures that have hard shells. Consisting of a helicoidal arrangement of aligned fibrils, layered single-twisted Bouligand-type structures (SBS) display exceptional fracture and damage resistance. A much more primitive and rarer type of this formation, the double-twisted Bouligand-type structures (DBS), has been discovered in ancient fish scales, and this architecture could provide added rigidity and significantly contribute to toughness when facing fracture risk. In this work, we describe a computational modeling approach to investigating fracture behaviors and toughening mechanisms in Bouligand structures. To achieve qualitative insights into the fracture behaviors of DBS and SBS, we applied these two configurations, which were identified from corresponding biological materials, to analyze load-displacement responses during single edge notched (SEN) tensile testing; the toughening mechanism is also discussed further. The results clearly show that the arrangement of helix fibrils and interlaminar properties play a major role in the resulting fracture behaviors of Bouligand architectures. This is of interest for the future design of engineering materials and structures that require composites with enhanced toughness, and could deepen our understanding of the structure-property relationship of Bouligand-type structures in bionic design. STATEMENT OF SIGNIFICANCE: In this work, a novel numerical modeling approach based on the extended finite element method (XFEM) has been established to evaluate the fracture behavior of a naturally-occurring Bouligand-type helicoidal structure subjected to the single edge notched (SEN) tensile loading. The roles of the biological features (i.e., layered arrangement of collagen fibrils and interbundle fibrils) on the fracture resistance and toughening mechanism of the Bouligand-type structures have been uncovered and analyzed quantitatively. This is of interest for future design of engineering materials and structures that require composites with enhanced toughness, and can deepen the understanding of the structure-property relationship of the Bouligand-type structure in bionic design.

Microstructure and nanomechanical properties of the exoskeleton of an ironclad beetle (Zopherus haldemani).

This study examined natural composite structures within the remarkably strong exoskeleton of the southwestern ironclad beetle (Z. haldemani). Structural and nanomechanical analyses revealed that the exoskeleton's extraordinary resistance to external forces is provided by its exceptional thickness and multi-layered structure, in which each layer performed a distinct function. In detail, the epicuticle, the outmost layer, comprised 3%-5% of the overall thickness with reduced Young's moduli of 2.2-3.2 GPa, in which polygonal-shaped walls (2-3µm in diameter) were observed on the surface. The next layer, the exocuticle, consisted of 17%-20% of the total thickness and exhibited the greatest Young's moduli (∼15 GPa) and hardness (∼800 MPa) values. As such, this layer provided the bulk of the mechanical strength for the exoskeleton. While the endocuticle spanned 70%-75% of the total thickness, it contained lower moduli (∼8-10 GPa) and hardness (∼400 MPa) values than the exocuticle. Instead, this layer may provide flexibility through its specifically organized chitin fiber layers, known as Bouligand structures. Nanoindentation testing further reiterated that the various fibrous layer orientations resulted in different elastic moduli throughout the endocuticle's cross-section. Additionally, this exoskeleton prevented delamination within the composite materials by overlapping approximately 5%-19% of each fibrous stack with neighboring layers. Finally, the innermost layer, the epidermis contributing 5%-7 % of the total thickness, contains attachment sites for muscle and soft tissue that connect the exoskeleton to the beetle. As such, it is the softest region with reduced Young's modulus of ∼2-3 GPa and hardness values of ∼290 MPa. These findings can be applied to the development of innovative, fiber-reinforced composite materials.

Experimental degradation of helicoidal photonic nanostructures in scarab beetles (Coleoptera: Scarabaeidae): implications for the identification of circularly polarizing cuticle in the fossil record.

Scarab beetles (Coleoptera: Scarabaeidae) can exhibit striking colours produced by pigments and/or nanostructures. The latter include helicoidal (Bouligand) structures that can generate circularly polarized light. These have a cryptic evolutionary history in part because fossil examples are unknown. This suggests either a real biological signal, i.e. that Bouligand structures did not evolve until recently, or a taphonomic signal, i.e. that conditions during the fossilization process were not conducive to their preservation. We address this issue by experimentally degrading circularly polarizing cuticle of modern scarab beetles to test the relative roles of decay, maturation and taxonomy in controlling preservation. The results reveal that Bouligand structures have the potential to survive fossilization, but preservation is controlled by taxonomy and the diagenetic history of specimens. Further, cuticle of specific genus (Chrysina) is particularly decay-prone in alkaline conditions; this may relate to the presence of certain compounds, e.g. uric acid, in the cuticle of these taxa.

Circularly polarized reflection from the scarab beetle Chalcothea smaragdina: light scattering by a dual photonic structure.

Helicoidal architectures comprising various polysaccharides, such as chitin and cellulose, have been reported in biological systems. In some cases, these architectures exhibit stunning optical properties analogous to ordered cholesteric liquid crystal phases. In this work, we characterize the circularly polarized reflectance and optical scattering from the cuticle of the beetle Chalcothea smaragdina (Coleoptera: Scarabaeidae: Cetoniinae) using optical experiments, simulations and structural analysis. The selective reflection of left-handed circularly polarized light is attributed to a Bouligand-type helicoidal morphology within the beetle's exocuticle. Using electron microscopy to inform electromagnetic simulations of this anisotropic stratified medium, the inextricable connection between the colour appearance of C. smaragdina and the periodicity of its helicoidal rotation is shown. A close agreement between the model and the measured reflectance spectra is obtained. In addition, the elytral surface of C. smaragdina possesses a blazed diffraction grating-like surface structure, which affects the diffuse appearance of the beetle's reflected colour, and therefore potentially enhances crypsis among the dense foliage of its rainforest habitat.