Historically, the irreversible reduction of aryldiazonium salts has provided a reliable method to modify surfaces, demonstrating a catalogue of suitable diazonium salts for targeted applications. This work expands the knowledge of diazonium salt chemistry to participate in surface electroinitiated emulsion polymerization (SEEP). The influence of concentration, electronic effects, and steric hindrance/regiochemistry of the diazonium salt initiator on the production of polymeric films is examined. The objective of this work is to determine if a polymer film can be tailored, controlling the thickness, density, and surface homogeneity using specific diazonium chemistry. The data presented herein demonstrate a significant difference in polymer films that can be achieved when selecting a variety of diazonium salts and vinylic monomers. A clear trend aligns with the electron-rich diazonium salt substitution providing the thickest films (up to 70.9 ± 17.8 nm) with increasing diazonium concentration and electron-withdrawing substitution achieving optimal homogeneity for the surface of the film at a 5 mM diazonium concentration.

Silk fibroin is an excellent biopolymer for application in a variety of areas, such as textiles, medicine, composites and as a novel material for additive manufacturing. In this work, silk membranes were surface modified by in situ polymerization of aqueous acrylic acid, initiated by the reduction of various aryldiazonium salts with vitamin C. Treatment times of 20 min gave membranes which possessed increased tensile strength, tensile modulus, and showed significant increased resistance to needle puncture (+131%), relative to ‘untreated’ standards. Most interestingly, the treated silk membranes were able to be reversibly formed into various shapes via the hydration and plasticizing of the surface bound poly(acrylic acid), by simply steaming the modified membranes. These membranes and their unique properties have potential applications in advanced textiles, and as medical materials.

Bonding dissimilar materials has been a persistent challenge for decades. This paper presents a method to modify a stainless steel surface (316 L), routinely used in medical applications to enable the significant adhesion of a biopolymer (silk fibroin). The metallic surface was first covalently grafting with polyacrylamide, to enable a hydrogen bonding compatible surface. The polymerisation was initiated via the irreversible electrochemical reduction of a 4-nitrobenzene diazonium salt (20 mM), in the presence of an acrylamide monomer (1 M) at progressively faster scan rates (0.01 V/s to 1 V/s). Examination of the modified samples by FT-IR was consistent with successful surface modification, via observations of the acrylamide carbonyl (1600-1650 cm À 1 ) was observed, with more intense peaks correlating to slower scan rates. Similar observations were made with respect to increasing surface polarity, assessed by water contact angle. Reductions of > 60°were observed for the grafted surfaces, relative to the unmodified control materials, indicating a surface able to undergo significant hydrogen bonding. The adhesion of silk to the metallic surface was quantified using a lap shear test, effectively using silk fibroin as an adhesive. Adhesion improvements of 5-7-fold, from 4.1 MPa to 29.3 MPa per gram of silk fibroin, were observed for the treated samples, highlighting the beneficial effect of this surface treatment. The methods developed in this work can be transferred to any metallic (or conductive) surface and can be tailored to complement any desired interface.

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