Timber has been used as a construction material in civil infrastructure throughout the world for several millennia and it is still a popular construction material to this day. Degradation of timber due to mechanical and environmental actions, as well as possible higher loads, can necessitate the need for strengthening or repair. The external bonding of fibre-reinforced polymer (FRP) composites offers a viable solution. A lack of understanding of the strength and behaviour of FRP-to-timber bonded interfaces is, however, hindering the safe and rational design of FRP strengthening measures for timber structures. The aim of this research project is to enhance understanding of the strength and behaviour of the bonded interface between timber and FRP. Important tangible outcomes of the project include the development of effective bonding systems as well as bond stress-slip models and bond strength model which quantify the bonded interface. In order to achieve these outcomes, an extensive experimental and analytical investigation is conducted. Tests are performed and reported on FRP-to-timber joints as well as FRP-strengthened beams. For the former, softwood (Pine), hardwood (Camphorwood) and glulam timber products have been tested. Variables include (i) externally bonded (EB) plates and near-surface mounted (NSM) plates, (ii) FRP plates formed in a wet lay-up procedure and pultrusion, (iii) bonded length of FRP, (iv) adhesive type, (v) adhesive thickness, (vi) timber species, and (vii) natural growth characteristics of the timber such as annual growth rings and knots. The concept of an effective bond length has been verified from the tests as well as effective procedures and materials for bonding FRP to softwoods and hardwoods. Models are also proposed and validated to quantify the bond strength and bond stress-slip relationships of the joint tests. The strengthening methods are then applied to glulam beams in order to observe the behaviour and strength of the bonding systems on a larger scale as well as on a system that bends. The bond strength model proposed from the joint tests is then assessed against the beam tests. Finally, conclusions are made on the entire program of study. Then, recommendations for future research are proposed. / published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

Palladium is one of the most common and versatile transition metals used in modern organometallic chemistry. The chemistry of palladium in its 0, +II, and +IV oxidation states is well-known; by comparison, the chemistry of palladium in its +III oxidation state is in its infancy. The work in this thesis involves the study of previously unknown Pd(III) complexes, including applications in materials chemistry and catalysis. / Chemistry and Chemical Biology

published_or_final_version / Mechanical Engineering / Master / Master of Philosophy

Ongoing efforts to improve the efficiency of organic photovoltaic cells emphasize the significance of the architecture of molecular assemblies in thin films, at nanometer and micron length scales, to enhance both exciton diffusion and charge transport, in donor and acceptor layers. Controlled growth of molecules via self-assembly techniques presents new opportunities to develop nano-structured organic thin films for electronic devices. This thesis is focused on controlling the orientation of phthalocyanine molecular assemblies in thin films in order to demonstrate the impact of microscopic control of molecular order on electrical properties and organic solar cell device performance.The studies performed here provide insights into the self-assembling behavior, film morphology, nanoscale electrical conductivity, and photovoltaic properties of a disk-shaped peripherally substituted phthalocyanine (Pc) molecule possessing amide functional groups in the side chains. Amide functionality was integrated in the side chains of this phthalocyanine molecule with the purpose of increasing the intra-columnar interaction through formation of a hydrogen bonding network between molecules, and to guide columnar orientation in a preferred direction via specific surface-molecule interactions. It is realized that molecule-substrate interactions must dominate over molecule-molecule interactions to achieve control over the deposition of molecules in a preferred direction for organic solar cell applications. Microscopic imaging and spectroscopic studies confirm the formation of flat-lying, well ordered, layered phthalocyanine films as anticipated.The remarkable electrical conductivity of the flat-lying phthalocyanine molecules, as studied by Conducting tip Atomic Force Microscopy (C-AFM) provide the impetus for the formation of organic solar cells based on layers of these hydrogen bonding phthalocyanine molecules. The photocurrent from devices that are made with the ordered Pc molecules and disordered Pc molecules as the primary photoactive donor layer, and vacuum deposited C60 as the acceptor material, were evaluated. The results presented here demonstrate the feasibility of increasing the photogenerated current by controlling the molecular organization in the photo active layer.

Self-assembly is an efficient method for generating large numbers of structurally diverse catalysts for screening. In this work, the method of self-assembly was explored in the construction of bifunctional catalysts, from a chiral aminophosphine, 2-formylphenylboronic acid, and a (thio)urea-containing diol. These catalysts were evaluated by their effect on the asymmetric aza-Morita-Baylis-Hillman reaction. In the second half of this thesis, the hydrogen bonding abilities of different dithiosquaramides were analyzed. As thioureas have been shown to be stronger hydrogen bond donors than ureas, it was hypothesized that dithiosquaramides may also follow a similar trend. Affinities of corresponding squaramides and dithiosquaramides to chloride, sulfate, and tosylate were compared, as well as their abilities to catalyze the Freidel-Crafts alkylation between indole and trans-β-nitrostyrene.

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No description available.

Transient Liquid Phase bonding under Temperature Gradient (TG-TLP bonding) is a relatively new process of TLP diffusion bonding family for joining difficult-to-weld aerospace materials. Earlier studies have suggested that in contrast to the conventional TLP bonding process, liquid state diffusion drives joint solidification in TG-TLP bonding process. In the present work, a mass conservative numerical model that considers asymmetry in joint solidification is developed using finite element method to properly study the TG-TLP bonding process. The numerical results, which are experimentally verified, show that unlike what has been previously reported, solid state diffusion plays a major role in controlling the solidification behavior during TG-TLP bonding process. The newly developed model provides a vital tool for further elucidation of the TG-TLP bonding process.

This thesis reports theoretical and experimental investigations carried out to better understand the effect of process parameters on the microstructure of transient liquid phase (TLP) joint. The theoretical investigations were carried out using analytical and numerical models to simulate base metal dissolution and isothermal solidification stages of the TLP bonding process. The experimental investigation was carried out by using standard metallographic technique to study the microstructure of bonded materials using optical and Scanning Electron Microscopes. Deviation from parabolic relationship between solid/liquid interface migration and holding time during TLP bonding is suggested as a new alternate phenomenon responsible for the anomalous increase in processing time required to produce eutectic microconstituent free joint with increase in bonding temperature. The results of TLP joining of commercial pure nickel using a Ni-P filler alloy showed that an increase in bonding temperature would be beneficial provided that sufficient holding time is allowed for complete isothermal solidification of liquated insert. Otherwise, an increase in bonding temperature may result in formation of thicker deleterious eutectic along the TLP joint. Furthermore, it was observed that the joint centerline eutectic product and interface second phase particles that form during TLP bonding of Inconel 738 using Ni-P filler can be significantly reduced by post bond heat treatment. The effectiveness of this approach, however, requires proper selection of heat treatment temperature above Ni-P binary eutectic temperature.

Self-assembly is an efficient method for generating large numbers of structurally diverse catalysts for screening. In this work, the method of self-assembly was explored in the construction of bifunctional catalysts, from a chiral aminophosphine, 2-formylphenylboronic acid, and a (thio)urea-containing diol. These catalysts were evaluated by their effect on the asymmetric aza-Morita-Baylis-Hillman reaction. In the second half of this thesis, the hydrogen bonding abilities of different dithiosquaramides were analyzed. As thioureas have been shown to be stronger hydrogen bond donors than ureas, it was hypothesized that dithiosquaramides may also follow a similar trend. Affinities of corresponding squaramides and dithiosquaramides to chloride, sulfate, and tosylate were compared, as well as their abilities to catalyze the Freidel-Crafts alkylation between indole and trans-β-nitrostyrene.