Biomaterials and Chitin composites

Microtexture and chitin/calcite orientation relationship in the mineralized exoskeleton of the American lobster

Local orientation analysis using X-ray microdiffraction reveals that the crystalline calcium carbonate fraction in lobster cuticle is associated with the chitin/protein fibers oriented perpendicular to the surface. The calcite crystallites show a fiber texture with the crystallographic c-axis pointing perpendicular to the cuticle surface, suggesting an orientation relationship between calcite and the organic chitin/protein fibers.
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Exoskeletons of two crustaceans were analysed with respect to their chemical and mineralogical composition

The exoskeletons of the American lobster Homarus americanus and of the edible crab Cancer pagurus were analysed with structural and chemical methods. The exoskeletons consist of crystalline magnesian-calcite in the form of nanocrystals (domain size about 20 nm), amorphous calcium phosphate (ACP), and a-chitin. The composition is different at different parts of the skeleton and also between these two species. This can be related to the mechanical requirements and also to the biological escape behaviour of these animals upon attack of predators. The finger and the claw are used for cutting and therefore strongly mineralized and very hard. The shell of the body (the carapace) is less mineralized and therefore more elastic. The lobster as mobile, fast-swimming animal typically escapes from a predator's attack whereas the crab clings to the ground and buries into the sand. Consequently, the shell of the lobster is less mineralized (and therefore lighter and less hard) than the shell of the crab.
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The role of extrafibrillar mineralization in the hierarchical mechanical properties of bone

In this project we model the elastic properties of bone at the level of mineralized collagen fibrils via step-by-step homogenization from the staggered arrangement of collagen molecules up to an array of parallel mineralized fibrils. A new model for extrafibrillar mineralization is proposed, assuming that the extrafibrillar minerals are mechanically equivalent to reinforcing rings coating each individual fibril. Our modeling suggests that no more than 30% of the total mineral content is extrafibrillar and the fraction of extrafibrillar minerals grows linearly with the degree of mineralization. It is shown that the extrafibrillar mineralization considerably reinforces the fibrils properties in the transverse directions and the fibrils shear moduli. The model predictions for the elastic moduli and constants are found to be in a good agreement with the experimental data reported in the literature.
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Using digital image correlation for the investigation of the elastic-plastic deformation behavior of mineralized lobster cuticle

This study presents a novel experimental approach to the characterization of the deformation of a mineralized biological composite using arthropod cuticle as a model material. By performing tensile tests combined with a detailed strain analysis via digital image correlation, the elastic-plastic deformation behavior of the endocuticle of the American lobster Homarus americanus is examined. The test specimens originate from the pincher and crusher claws. For evaluating the effect of moisture on the deformation behavior, the samples are tested both in dry and in wet state. Sample characterization using the digital image correlation method requires a stochastic spot pattern on the sample surface. Digital images are then taken at subsequent deformation stages during the mechanical test. These images are used to calculate the displacement, the displacement gradient, and the strain fields via pattern correlation. The method is applied both, at a global scale to measure with high precision the stress-strain behavior of the bulk cuticle and at a microscopic scale to reveal strain heterogeneity, strain patterning, and strain localization phenomena.
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The influence of sterilization processes on the micromechanical properties of carbon fiber reinforced PEEK composites for bone-implant applications

The effect of sterilization on the structural integrity of the thermoplastic matrix composite polyetheretherketone (PEEK) reinforced with carbon fibers (CF) is investigated by nanoindentation and nanoscratch tests. The use of the material as a medical implant grade requires a detailed understanding of its micromechanical properties which primarily define the in-vivo behavior. Sterilization is a mandatory process for such materials used in medical applications like bone-implants. The steam and gamma radiation sterilization processes employed in this study are at sufficient levels to affect the micromechanical properties of some polymer materials, particularly in the interphase region between the polymer matrix and the reinforcing fibers. Nanoindentation and nanoscratch tests are used in this work to reveal local gradients in the hardness and the elastic properties of the interphase regions. Both methods help to explore microscopic changes in the hardness, reduced stiffness, and scratch resistance in the interphase region and in the bulk polymer matrix due to the different sterilization processes employed. The results reveal that steam and gamma radiation sterilization do both not entail significant changes of the reduced elastic modulus, hardness, or coefficient of friction in the bulk polymer matrix. However, minor material changes of the PEEK matrix were observed in the interphase region. Of the two sterilization methods used, the steam treatment has a more significant influence on these small changes in this region and appears to increase slightly the thickness of the interphase zone.
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Texture and Smart Anisotropy of the Exoskeleton Tissue of Lobster

Electron microscopy and synchrotron diffraction were used for the investigation of the crystallographic texture and structure of the exoskeleton of lobster. The study reveals a pronounced microstructure hierarchy and a strong crystallographic and topological texture of the α-chitin-protein network underlying the twisted plywood structure.
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Mesostructure of the exoskeleton of the lobster Homarus americanus

The exoskeleton of the lobster Homarus americanus is a multiphase bio-composite which consists of a fibrous organic matrix (crystalline α-chitin and various types of non-crystalline proteins) and embedded biominerals (mainly calcite). In this study we present experimental data about the microscopic and mesoscopic structure of this material.
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Mechanical Properties of the Lobster Cuticle

We present experiments on the mechanical and structural gradients through the cuticle of homarus americanus (lobster). The exocuticle (outer layer) is characterized by a very fine woven structure of the chitin-protein matrix (Bouligand structure) and by a high stiffness (8.5–9.5 GPa). The hardness increases within the exocuticle between the surface region (130 MPa) and the region close to the interface to the endocuticle (270 MPa). In the endocuticle which is characterized by a much coarser twisted plywood (Bouligand) structure both, the stiffness (3–4.5 GPa) and hardness (30–55 MPa) are much smaller than in the exocuticle. The transition in mechanical properties and structure between the exo- and endocuticle is abrupt.
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The exoskeleton of the lobster Homarus americanus as an example of a smart anisotropic biological material

Many biological materials are composed of fibrils arranged according to well defined three-dimensional patterns. These materials often show a strong anisotropy in their properties. Their composite microstructure, comprising soft organic and sometimes also hard inorganic materials, plays a key role in enhancing the toughness, strength, and hardness of materials like arthropod cuticles by restricting crack growth and delocalizing deformation fields. An essential characteristic of biological materials is their hierarchical organization from the nanometer- to the millimeter scale. Lobster cuticle is a good example for this and a suitable model for studying these properties.
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Structural building principles and mechanics of chitin-based biological composite material with hierarchical organization: example of the lobster Homarus americanus

The cuticle of the lobster Homarus americanus is a nano-composite like 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 mechanical properties on the macroscopic scale miniaturized tensile, compression and shear tests were carried out to obtain integral mechanical data. At the microscopic scale the local mechanical properties were investigated by nanoindentation. Characterization of the microstructure included scanning electron microscopy (SEM) combined with energy dispersive X-ray (EDX) measurements.
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Effect of microstructure on anisotropy of mineralized cuticle from the lobster Homarus americanus

The exoskeleton of the American lobster Homarus americanus is a hierarchically organized nano-composite material consisting of organic chitin-protein fibers associated with inorganic calcium carbonate. The presence of a well developed and periodically arranged pore canal system leads to a honeycomb-like structure. The concomitant presence of the twisted plywood arrangement of the mineralized chitin-protein fibers alters the elastic properties, the deformation and fracture behavior compared to classical honeycomb structures. By performing compression tests in various directions of the cuticle we examined the anisotropic elastic-plastic deformation and fracture behavior of the mineralized cuticle. By applying digital image correlation during compression testing, the evolution of the elastic-plastic deformation at the microscopic scale was observed with high resolution and simultaneously global stress and strain data were acquired. Shear tests were performed in order to determine the fracture energy for different shear planes and directions. The investigation of the microstructure after plastic deformation revealed the underlying deformation mechanisms of lobster endocuticle under different loading conditions. For evaluating the effect of hydration the samples were tested both in the dry and in the wet state.
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