Keratin is a highly multifunctional biopolymer serving various roles in nature due to its diverse material properties, wide spectrum of structural designs, and impressive performance. Keratin-based materials are mechanically robust, thermally insulating, lightweight, capable of undergoing reversible adhesion through van der Waals forces, and exhibit structural coloration and hydrophobic surfaces. Thus, they have become templates for bioinspired designs and have even been applied as a functional material for biomedical applications and environmentally sustainable fiber-reinforced composites. This review aims to highlight keratin's remarkable capabilities as a biological component, a source of design inspiration, and an engineering material. We conclude with future directions for the exploration of keratinous materials.

The horse hoof wall exhibits exceptional impact resistance and fracture control due to its unique hierarchical structure which contains tubular, lamellar, and gradient configurations. In this study, structural characterization of the hoof wall was performed revealing features previously unknown. Prominent among them are tubule bridges, which are imaged and quantified. The hydration-dependent viscoelasticity of the hoof wall is described by a simplified Maxwell-Weichert model with two characteristic relaxation times corresponding to nanoscale and mesoscale features. Creep and relaxation tests reveal that the specific hydration gradient in the hoof keratin likely leads to reduced internal stresses that arise from spatial stiffness variations. To better understand realistic impact modes for the hoof wall in-vivo, drop tower tests were executed on hoof wall samples. Fractography revealed that the hoof wall's reinforced tubular structure dominates at lower impact energies while the intertubular lamellae are dominant at higher impact energies. Broken fibers were observed on the surface of the tubules after failure, suggesting that the physically intertwined nature of the tubule reinforcement and intertubular matrix improves the toughness of this natural fiber reinforced composite. The augmented understanding of the structure-mechanical property relationship in dynamic loading led to the design of additively manufactured bioinspired structures, which were evaluated in quasistatic and dynamic loadings. The inclusion of gradient structures and lamellae significantly reduced the damage sustained in drop tower tests, while tubules increased the energy absorption of samples tested in compact tension. The samples most similar to the hoof wall displayed remarkably consistent fracture control properties.

The jackfruit is the largest fruit on the Earth, reaching upwards of 35 kg and falling from heights of 25 m. To survive such high energy impacts, it has evolved a unique layered configuration with a thorny exterior and porous tubular underlayer. During compression, these layers exhibit a progressive collapse mechanism where the tubules are first to deform, followed by the thorny exterior, and finally the mesocarp layer in between. The thorns are composed of lignified bundles which run longitudinally from the base of the thorn to the tip and are embedded in softer parenchymal cells, forming a fiber reinforced composite. The mesocarp contains more lignin than any of the other layers while the core appears to contain more pectin giving rise to variations in compressive and viscoelastic properties between the layers. The surface thorns provide a compelling impact-resistant feature for bioinspiration, with a cellular structure that can withstand large deformation without failing and wavy surface features which densify during compression without fracturing. Even the conical shape of the thorns is valuable, presenting a gradually increasing surface area during axial collapse. A simplified model of this mechanism is put forward to describe the force response of these features. The thorns also distribute damage laterally during impact and deflect cracks along their interstitial valleys. These phenomena were observed in 3D printed, jackfruit-inspired designs which performed markedly better than control prints with the same mass. STATEMENT OF SIGNIFICANCE: Many biological materials have evolved remarkable structures that enhance their mechanical performance and serve as sources of inspiration for engineers. Plants are often overlooked in this regard yet certain botanical components, like nuts and fruit, have shown incredible potential as blueprints for improved impact resistant designs. The jackfruit is the largest fruit on Earth and generates significant falling impact energies. Here, we explore the jackfruit's structure and its mechanical capabilities for the first time. The progressive failure imparted by its multilayered design and the unique collapse mode of the surface thorns are identified as key mechanisms for improving the fruit's impact resistance. 3D printing is used to show that these structure-property benefits can be successfully transferred to engineering materials.

Peroxide has been considered a chemical agent that can be used to tune the properties of polymeric materials. This research evaluated the influence of different concentrations of dialkyl peroxides on the mechanical, thermal, and morphological properties of linear low-density polyethylene (LLDPE) and ultra-high molecular weight polyethylene (UHMWPE). The neat polymer, as well as those with the addition of 1% and 2% by mass of dialkyl peroxides, were subjected to compression molding and immersion in water for 1 h, under controlled temperatures of 90 °C. The values of the gel content found in the samples indicated that the addition of peroxide to the LLDPE and to the UHMWPE promoted the formation of a reticulated network. The structure obtained by the crosslinking led to less reorganization of the chains during the crystallization process, resulting in the formation of imperfect crystals and, consequently, in the reduction in melting temperatures, crystallization and enthalpy. The mechanical properties were altered with the presence of the crosslinker. The polymers presented had predominant characteristics of a ductile material, with the occurrence of crazing with an increased peroxide content.

The equine hoof wall has a unique hierarchical structure that allows it to survive high‐impact scenarios. Previous authors have explored the compressive, viscoelastic, and fracture control properties of the hoof wall and suggested that this complex structure plays a vital role in the hoof's behavior. However, the link between the structure and the behavior of the hoof wall has been made primarily with the use of post‐fracture analysis. Here, periodic microcomputed tomography scans are used to observe the temporal behavior of the hoof's meso and microstructures during compression, fracture, and relaxation. These results shed light on the structural anisotropy of the hoof wall and how its hollow tubules behave when compressed in different directions, at different hydration levels, and in various locations within the hoof wall. The behavior of tubule bridges during compression is also reported for the first time. This study elucidates several fracture phenomena, including the way cracks are deflected at tubule interfaces and tubule bridging, tubule arresting, and fiber bridging. Finally, relaxation tests are used to show how the tubule cavities can regain their shape after compression.