From Basic Principles of Protein-Polysaccharide Association to the Rational Design of Thermally Sensitive Materials.

Biology resolves design requirements toward functional materials by creating nanostructured composites, where individual components are combined to maximize the macroscale material performance. A major challenge in utilizing such design principles is the trade-off between the preservation of individual component properties and emerging composite functionalities. Here, polysaccharide pectin and silk fibroin were investigated in their composite form with pectin as a thermal-responsive ion conductor and fibroin with exceptional mechanical strength. We show that segregative phase separation occurs upon mixing, and within a limited compositional range, domains ∼50 nm in size are formed and distributed homogeneously so that decent matrix collective properties are established. The composite is characterized by slight conformational changes in the silk domains, sequestering the hydrogen-bonded ß-sheets as well as the emergence of randomized pectin orientations. However, most dominant in the composite's properties is the introduction of dense domain interfaces, leading to increased hydration, surface hydrophilicity, and increased strain of the composite material. Using controlled surface charging in X-ray photoelectron spectroscopy, we further demonstrate Ca ions (Ca2+) diffusion in the pectin domains, with which the fingerprints of interactions at domain interfaces are revealed. Both the thermal response and the electrical conductance were found to be strongly dependent on the degree of composite hydration. Our results provide a fundamental understanding of the role of interfacial interactions and their potential applications in the design of material properties, polysaccharide-protein composites in particular.

Fragmentation of Beaded Fibres in a Composite.

The fibre-matrix interface plays an important role in the overall mechanical behaviour of a fibre-reinforced composite, but the classical approach to improving the interface through chemical sizing is bounded by the materials' properties. By contrast, structural and/or geometrical modification of the interface may provide mechanical interlocking and have wider possibilities and benefits. Here we investigate the introduction of polymer beads along the interface of a fibre and validate their contribution by a single fibre fragmentation test. Using glass fibres and the same epoxy system for both matrix and beads, an increase of 17.5% is observed in the interfacial shear strength of the beaded fibres compared to fibres with no polymer beads. This increase should lead to a similar improvement in the strength and toughness of a beaded fibre composite when short fibres are used. The beads were also seen to stabilise the fragmentation process of a fibre by reducing the scatter in fragment density at a given strain. A case could also be made for a critical beads number-4 beads in our experimental system-to describe interfacial shear strength, analogous to a critical length used in fibre composites.

Hierarchical Interfaces as Fracture Propagation Traps in Natural Layered Composites.

Compared with their monolithic version, layered structures are known to be beneficial in the design of materials, especially ceramics, providing enhanced fracture toughness, mechanical strength, and overall reliability. This was proposed in recent decades and extensively studied in the engineering literature. The source of the property enhancement is the ability of layered structures to deflect and often arrest propagating cracks along internal interfaces between layers. Similar crack-stopping abilities are found in nature for a broad range of fibrillary layered biological structures. Such abilities are largely governed by complex architectural design solutions and geometries, which all appear to involve the presence of various types of internal interfaces at different structural levels. The simultaneous occurrence at several scales of different types of interfaces, designated here as hierarchical interfaces, within judiciously designed layered composite materials, is a powerful approach that constrains cracks to bifurcate and stop. This is concisely described here using selected biological examples, potentially serving as inspiration for alternative designs of engineering composites.

Efficient Toughening of Short-Fiber Composites Using Weak Magnetic Fields.

Short fibers may serve as toughening agents of composite materials because of the high energy dissipated during fracture, associated with numerous fiber pullouts. An ongoing challenge is to improve their toughness even further, by directing and concentrating fibers near highly stressed structural regions. Weak magnetic fields are utilized to increase the fracture toughness of an epoxy matrix reinforced by short magnetized glass fibers by directing and concentrating fibers near highly stressed structural regions. The orientation and local concentration of the fibers are controlled by the vector components of the magnetic field, and by the gradient in field intensity, respectively. Optimized fracture toughness was achieved by using two pairs of permanent magnets, combining enhanced concentration of fibers in the crack-tip vicinity with alignment of the fibers along the load direction. This optimized value was well above the reference fracture-toughness measured for composites with the same filler content in the absence of a magnetic field, as well as above the value achieved by exploiting unidirectional alignment, without fiber translation, using a solenoid. The method suggested in this study-localized reinforcement using magnetic translation of fillers through the formation of magnetic gradients-enables efficient and controllable improvement in the composite's overall resistance to fracture, without the involvement of additional phases or material.

Ultra-Tough Inverse Artificial Nacre Based on Epoxy-Graphene by Freeze-Casting.

Epoxy nanocomposites combining high toughness with advantageous functional properties are needed in many fields. However, fabricating high-performance homogeneous epoxy nanocomposites with traditional methods remains a great challenge. Nacre with outstanding fracture toughness presents an ideal blueprint for the development of future epoxy nanocomposites. Now, high-performance epoxy-graphene layered nanocomposites were demonstrated with ultrahigh toughness and temperature-sensing properties. These nanocomposites are composed of ca. 99 wt % organic epoxy, which is in contrast to the composition of natural nacre (ca. 96 wt % inorganic aragonite). These nanocomposites are named an inverse artificial nacre. The fracture toughness reaches about 4.2 times higher than that of pure epoxy. The electrical resistance is temperature-sensitive and stable under various humidity conditions. This strategy opens an avenue for fabricating high-performance epoxy nanocomposites with functional properties.

Sensitivity of carbon nanotubes to the storage of stress in polymers.

Residual stress in polymers arises from the freezing of unstable molecular conformations. Residual stress is critical because its relaxation can cause shrinkage, defects, and fractures of polymer materials. The storage of stress is purposely enhanced to develop shape memory materials. Unfortunately, the storage of mechanical stress is still poorly controlled and understood. An approach to sense the storage of stress based on the spectroscopic response of carbon nanotubes is explored. The Raman response of nanotubes exhibits a variable sensitivity to strain when embedded in polymers that have experienced different thermal and mechanical treatments. This unique feature opens up new possibilities for the use of carbon nanotubes as mechanical nanosensors.