CHARACTERIZATION OF FILLING MATERIALS FOR EASEL PAINTINGS

Developing appropriate treatments for easel paintings can be complex, as many works are composed of various materials that respond in different ways. When selecting a filling material for these artworks, several properties are investigated including: the need for the infill to react to environmental conditions in a similar manner as the original material; the need for the infill to have good handling properties, adhesion to the original support, and cohesion within the filling material; the ability for the infill to withstand the stress of the surrounding material and; be as flexible as the original material to not cause further damage. Also, changes in colour or mechanical properties should not occur as part of the ageing process. Studies are needed on acrylic-based materials used as infills in conservation treatments. This research examines some of the chemical, physical, and optical changes of eleven filling materials before and after ageing, with the aim to evaluate the overall appropriateness of these materials as infills for easel paintings. The materials examined were three rabbit skin glue (RSG) gessoes, and seven commercially prepared acrylic materials, all easily acquired in North America. Chemical analysis was carried out with Fourier transform infrared (FTIR) spectroscopy and X-ray fluorescence (XRF), pyrolysis gas chromatography-mass spectroscopy (Py-GC/MS), and differential scanning calorimetry (DSC). Overall the compositions of the various materials examined were found to be in agreement with the available literature and previous research. This study also examined characteristics of these materials not described in previous works and, additionally, presented the compositions and behaviour of several commonly used materials with little literature description. After application of an ageing regimen, most naturally aged and artificially aged samples displayed small changes in gloss, colour, thickness, and diffusive behaviour; however, to evaluate these materials fully mechanical testing and environmental studies should be carried out.

THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.