Molecular-level dispersion of graphene into epoxidized natural rubber: Morphology, interfacial interaction and mechanical reinforcement

The interfacial interaction of composites dominates the properties of polymeric/inorganic nanocomposites. Herein, epoxy and hydroxyl groups are introduced into the natural rubber (NR) molecular chains to anchor oxygenous functional groups on the surface of graphene oxide (GO) sheets and therefore enhance the interfacial interaction between GO and rubber. From the morphological observation and interaction analysis, it is found that epoxidized natural rubber (ENR) latex particles are assembled onto the surfaces of GO sheets by employing hydrogen bonding interaction as driving force. This self-assembly depresses restacking and agglomeration of GO sheets and leads to homogenous dispersion of GO within ENR matrix. The formation of hydrogen bonding interface between ENR and GO demonstrates a significant reinforcement for the ENR host. Compared with those of pure ENR, the composite with 0.7 wt% GO loading receives 87% increase in tensile strength and 8.7 fold increase in modulus at 200% elongation after static in-situ vulcanization.

A novel approach to functionalise pristine unsized carbon fibre using in situ generated diazonium species to enhance interfacial shear strength

Complex molecules have been successfully grafted onto the surface of unsized carbon fibre, a heterogeneous material which is a challenge to functionalise. The in situ generation of highly reactive phenyldiazo-species from their corresponding anilines was employed to achieve this task. The success of an initial proof-of-concept study (bearing a nitro moiety) supported by X-ray Photoelectron Spectroscopy (XPS) and physical characterisation, led to the design and synthesis of a more complex compound possessing a pendant amine moiety which could theoretically react with an epoxide based resin. After attachment to unsized oxidised fibres, analysis by XPS of the resulting fibres (fluorine used as an XPS tag) indicated a marked difference in functionalisation success which was attributed to steric factors, shown to be critical in influencing the attachment of the phenyldiazo-intermediate to the carbon fibre surface. Analysis of key fibre performance parameters of these fibres showed no change in elastic modulus, strength, surface topography or microscopic roughness when compared to the control unsized oxidised fibres. The functionalised fibres did however show a large increase in coefficient of friction. Single fibre fragmentation tests indicated a marked increase in interfacial shear strength, which was attributed to the pendent amine functionalities interacting with the epoxy resin.

A systematic study of carbon fibre surface grafting via in situ diazonium generation for improved interfacial shear strength in epoxy matrix composites

A recently established means of surface functionalization of unsized carbon fibres for enhanced compatibility with epoxy resins was optimised and evaluated using interfacial shear stress measurements. Interfacial adhesion has a strong influence on the bulk mechanical properties of composite materials. In this work we report on the optimisation of our aryl diazo-grafting methodology via a series of reagent concentration studies. The fibres functionalised at each concentration are characterised physically (tensile strength, modulus, coefficient of friction, and via AFM), and chemically (XPS). The interfacial shear strength (IFSS) of all treated fibres was determined via the single fibre fragmentation test, using the Kelly-Tyson model. Large increases in IFSS for all concentrations (28-47%) relative to control fibres were observed. We show that halving the reagent concentration increased the coefficient of friction of the fibre and the interfacial shear strength of the composite while resulting in no loss of the key performance characteristics in the treated fibre.

Facet selectivity in gold binding peptides: exploiting interfacial water structure

Peptide sequences that can discriminate between gold facets under aqueous conditions offer a promising route to control the growth and organisation of biomimetically-synthesised gold nanoparticles. Knowledge of the interplay between sequence, conformations and interfacial properties is essential for predictable manipulation of these biointerfaces, but the structural connections between a given peptide sequence and its binding affinity remain unclear, impeding practical advances in the field. These structural insights, at atomic-scale resolution, are not easily accessed with experimental approaches, but can be delivered via molecular simulation. A current unmet challenge lies in forging links between predicted adsorption free energies derived from enhanced sampling simulations with the conformational ensemble of the peptide and the water structure at the surface. To meet this challenge, here we use an in situ combination of Replica Exchange with Solute Tempering with Metadynamics simulations to predict the adsorption free energy of a gold-binding peptide sequence, AuBP1, at the aqueous Au(111), Au(100)(1 × 1) and Au(100)(5 × 1) interfaces. We find adsorption to the Au(111) surface is stronger than to Au(100), irrespective of the reconstruction status of the latter. Our predicted free energies agree with experiment, and correlate with trends in interfacial water structuring. For gold, surface hydration is predicted as a chief determining factor in peptide-surface recognition. Our findings can be used to suggest how shaped seed-nanocrystals of Au, in partnership with AuBP1, could be used to control AuNP nanoparticle morphology.

Interfacial adhesion in natural fiber-reinforced polymer composites

Concerns about the environment and increasing awareness about sustainability issues are driving the push for developing new materials that incorporate renewable sustainable resources. Th is has resulted in the use of natural fi bers for developing natural fi ber-reinforced polymer composites (NFRPCs). A fundamental understanding of the fi ber-fi ber and fi ber-matrix interface is critical to the design and manufacture of polymer composite materials because stress transfer between load-bearing fi bers can occur at the both of these interfaces. Effi cient stress transfer from the matrix to the fi ber will result in polymer composites exhibiting suitable mechanical and thermal performance. Th e development of new techniques has facilitated a better understanding of the governing forces that occur at the interface between matrix and natural fi ber. Th e use of surfacemodification is seen as a critical processing parameter for developing new materials, and plasma-based modifi cation techniques are gaining more prominence from an environmental point of view, as well as a practical approach.

Improvement of coating durability, interfacial adhesion and compressive strength of UHMWPE fiber/epoxy composites through plasma pre-treatment and polypyrrole coating

Ultra-high-molecular-weight polyethylene (UHMWPE) fibers have exceptionally higher specific strength and stiffness compared with other high-performance fibers. However, the interfacial adhesion and compressive performance of UHMWPE fiber-reinforced polymer composites (FPCs) are extremely low. The challenges are to achieve load transfer at the interface between the fiber and matrix at a molecular level. Here, we show that plasma pre-treatment of UHMWPE fibers followed by coating with polypyrrole (PPy) results in an 848% improvement in the interfacial adhesion and 54% enhancement in compressive performance. This method takes advantage of a toughening mechanism observed in spider silk and collagen, which the hydrogen bond power the load transfer. The results showed that these improvements of interfacial adhesion and compressive strength were attributed to hydrogen-bonding interactions between the plasma pre-treated UHMWPE and PPy, which improves the fiber-matrix-fiber load transfer process. In addition, the hydrogen-bonded PPy coatings also endowed durability electrical conductivity properties of the UHMWPE fiber.

Enhanced homogeneity and interfacial compatibility in melt-extruded cellulose nano-fibers reinforced polyethylene via surface adsorption of poly(ethylene glycol)-block-poly(ethylene) amphiphiles

In this paper, we demonstrate that an amphiphilic block copolymer such as polyethylene glycol-b-polyethylene can be used as both dispersing and interfacial compatibilizing agent for the melt compounding of LLDPE with cellulose nano-fibers. A simple and effective spray drying methodology was first used for the first time for the preparation of a powdered cellulose nano-fibers extrusion feedstock. Surface adsorption of the amphiphilic PEG-b-PE was carried out directly in solution during this process. These various dry cellulosic feedstock were subsequently combined with LLDPE via extrusion to produce a range of nano-composites. The collective outcomes of this research are several folds. Firstly we show that presence of surface adsorbed PEG-b-PE effectively hindered the aggregation of the cellulose nano-fibers during the extrusion, affording clear homogenous materials with minimum aggregation even at the highest loading of cellulose nano-fibers (∼23 vol.%). Secondly, the tailored LLDPE/cellulose interface arising from intra- and inter-molecular hydrogen and Van der Waals bonds yielded significant levels of mechanical improvements in terms of storage and tensile modulus. We believe this study provides a simple technological template to produce high quality and performant polyolefins cellulose-based nano-composites.

Elucidating the influence of polymorph-dependent interfacial solvent structuring at chitin surfaces

Interfacial solvent structuring is thought to be influential in mediating the adsorption of biomolecules at aqueous materials interfaces. However, despite the enormous potential for exploitation of aqueous chitin interfaces in industrial, medical and drug-delivery applications, little is known at the molecular-level about such interfacial solvent structuring for chitin. Here we use molecular simulation to predict the structure of the [100] and [010] interfaces of α-chitin and β-chitin dihydrate in contact with liquid water and saline solution. We find the α-chitin [100] interface supports lateral high-density regions in the first water layer at the interface, which are also present, but not as pronounced, for β-chitin. The lateral structuring of interfacial ions at the saline/chitin interface is also more pronounced for α-chitin compared with β-chitin. Our findings provide a foundation for the systematic design of biomolecules with selective binding affinity for different chitin polymorphs.

Interfacial characterization and reinforcing mechanism of novel carbon nanotube – carbon fibre hybrid composites

Carbon nanotube (CNT) deposition onto carbon fibre resulting in hybrid surface structures with various morphologies were successfully carried out using electrospray technique. In terms of tensile testing and Weibull analysis this process did not degrade fibre mechanical properties. When incorporated into composites, the interfacial shear strength (IFSS), as measured by single fibre fragmentation testing, increased by up to 124%. Experimental work was carried out to develop a deeper understanding of the interfacial reinforcing mechanism. Contact angle measurements demonstrated that the CNT deposition resulted in good wettability by the resin. Significant increases in roughness, friction and surface area were also found after CNT deposition, especially for the sample prepared using the parameter of 20 kV/10 cm at 100 °C. Surface energy analysis revealed that an increase in the dispersive surface energy due to the CNTs likely contributed to the improvement of interaction between fibre and matrix. Fractographic analysis revealed that the length of fibre pull-out and the size of cracks between the fibre and matrix were markedly decreased in the hybrid CNT surface structure, indicating that the stress transfer and interfacial shear strength have been improved. Finally, the potential for further improvement in interfacial composite properties by this approach was assessed.