Using Nitroxides to Enhance Carbon Fiber Interfacial Adhesion and as an Anchor for "Graft to" Surface Modification Strategies.

Nitroxide groups covalently grafted to carbon fibers are used as anchoring sites for TEMPO-terminated polymers (poly-n-butylacrylate and polystyrene) in a "graft to" surface modification strategy. All surface-modified fibers are evaluated for their physical properties, showing that several treatments have enhanced the tensile strength and Young's modulus compared to the control fibers. Up to an 18% increase in tensile strength and 12% in Young's modulus are observed. Similarly, the evaluation of interfacial shear strength in an epoxy polymer shows improvements of up to 144% relative to the control sample. Interestingly, the polymer-grafted surfaces show smaller increases in interfacial shear strength compared to surfaces modified with a small molecule only. This counterintuitive result is attributed to the incompatibility, both chemical and physical, of the grafted polymers to the surrounding epoxy matrix. Molecular dynamics simulations of the interface suggest that the diminished increase in mechanical shear strength observed for the polymer grafted surfaces may be due to the lack of exposed chain ends, whereas the small molecule grafted interface exclusively presents chain ends to the resin interface, resulting in good improvements in mechanical properties.

Accelerated lithium-ion diffusion via a ligand 'hopping' mechanism in lithium enriched solvate ionic liquids.

Solvate ionic liquids (SILs), equimolar amounts of lithium salts and polyether glymes, are well studied highly customisable "designer solvents". Herein the physical, thermal and ion mobility properties of SILs with increased LiTFSI (LiTFSA) concentration, with ligand 1 : >1 LiTFSI stoichiometric ratios, are presented. It was found that between 60-80 °C, the lithium cation diffuses up to 4 times faster than the corresponding anion or ligand (glyme). These systems varied from viscous liquids to self-supporting gels, though were found to thin exponentially when heated to mild temperatures (50-60 °C). They were also found to be thermally stable, up to 200 °C, well in excess of normal operating temperatures. Ion mobility, assessed under an electric potential via ionic conductivity, showed the benefit of SIL optimisation for attaining greater concentrations of Li+ cations to store charge during supercapacitor charging and discharging. Molecular dynamics simulations interrogate the mechanism of enhanced diffusion at high temperatures, revealing a lithium hopping mechanism that implicates the glyme in bridging two lithiums through changes in the denticity.

From stress to charge: investigating the piezoelectric response of solvate ionic liquid in structural energy storage composites.

Solvate ionic liquids (SILs) are a class of ionic liquids where the liquid-state salt is chelated by a coordinating solvent, and of interest due to their advantageous properties such as low vapour pressure and superb thermal and chemical stability for energy storage applications. The electromechanical and piezoelectric effect were studied in lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) solvated by triethylene glycol dimethyl ether (triglyme, G3), forming [Li-G3]TFSI. These effects were also investigated in full solid polymer electrolyte (SPE) used in energy storage devices, consisting of [Li-G3]TFSI paired with an epoxy-based resin system. The SIL's electromechanical response was first established in isolation, as well as within the SPE. Experimental data demonstrates the effect of a major part of the SPE contributing to the electrical potential generation during application of force and subsequent pressurisation as well as depressurisation, underlined by a direct piezoelectric effect. SPE response to applied load is explored after the recent discovery of liquid-to-crystalline phase transition following pressurisation in pure ionic liquids. This finding has the potential to ameliorate the performance of energy storage composites via additional effects of charging such a device by subjecting it to stress, leading to increased efficiency. Results to date show a bulk potential difference across the SIL of up to 150 mV, while the SPE potential response is scaled down due to a significantly lower volume of SIL at the interface (∼30 mV). Nevertheless, such findings can still significantly affect the performance of carbon fibre (CF)-based structural supercapacitors and batteries that are able to store and release electrical energy whilst simultaneously contributing to load-bearing performance.

Carbon fibre surface modification facilitated by silver-catalysed radical decarboxylation.

A silver catalysed radical decarboxylation process was used to graft a copolymer (4 : 1; methylacrylate/acrylic acid) onto short carbon fibres. Surface grafting was confirmed by XPS, SEM and TGA, suggesting that the polymer accounted for 10% of the modified materials mass. Incorporation of these surface enhanced carbon fibres into an epoxy resin gave composites demonstrating an increase in ductility and a clear change in failure mode from adhesive, at the fibre-matrix interface, to cohesive, within the matrix polymer itself.

Promoting Silk Fibroin Adhesion to Stainless Steel Surfaces by Interface Tailoring.

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-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.

Biomedical Applications of Electro-Initiated Polymerisation on Ti6Al4†V Titanium Alloy using Silk Fibroin Coatings for Antibiotic Delivery and Improved Cell Metabolism.

Silk fibroin interactions with metallic surfaces can provide utility for medical materials and devices. Toward this goal, titanium alloy (Ti6Al4 V) was covalently grafted with polyacrylamide via electrochemically reducing 4-nitrobenzene diazonium salt in the presence of acrylamide. Analysis of the modified surfaces with FT-IR spectra, SEM and AFM were consistent with surface grafting. Functionalised titanium samples with a silk fibroin membrane, with and without impregnated therapeutics, were used to assess cytocompatibility and drug delivery. Initial cytocompatibility experiments using fibroblasts showed that the functionalised samples, both with and without silk fibroin coatings, supported significant increases between 72-136 % in cell metabolism, compared to the controls after 7 days. A 7-days release profiling showed consistent bacterial inhibition through gentamicin release with average inhibition zones of 239 mm2 . Over a 5-week period, silk fibroin coated samples, both with and without growth factors, supported better human mesenchymal stem cell metabolism with increases reaching 1031 % and 388 %, respectively, compared to samples without the silk fibroin coating with.