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Wood is often combined with other materials such as thermoplastics, adhesives and coatings. In general, combinations of wood and polymers especially in outdoor exposure have poor long-term durability. This behaviour can be related to an insufficient wood-polymer adhesion due to the low intrinsic compatibility between the wood substance and the polymers used. Another source for woodpolymer de-bonding is the high hygroscopicity of wood and great difference in hygro-thermal properties between the components. The basic conceptual idea related to this work is to reduce the hygrosensitivity of wood by applying different wood modification methods, in particular, acetylation, furfurylation and heat treatment. The effects of such chemical modifications of wood, also accompanied with ageing effects, on its adhesion properties with commonly used synthetic polymers are, however, not well understood. In this context, the over-all purpose of this thesis is to achieve a better understanding of wood-polymer adhesion and interfacial forces which also may guide us to tailor the interaction between modified wood and e.g. thermoplastics and adhesives. The main focus of this thesis is therefore to apply contact angle analysis based on the Chang-Qin-Chen (CQC) Lewis acid-base model in order to estimate the work of adhesion (Wa) between the wood, modified wood and certain polymers. Contact angle measurements on wood samples were performed based on the Wilhelm plate principle. Related to this, an effort was also made to characterize the studied modified wood surfaces according to morphology and chemical composition. The methods that have been used are low vacuum scanning electron microscopy (LV-SEM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Results show that so-called interaction parameters can be successfully estimated for prediction of Wa between wood and polymers using the applied CQC model. Furthermore, such wetting analysis was successfully related to spectroscopic findings of the chemical composition of the wood samples surface. Ageing effects, i.e. the time after preparation of the wood surface, play a central role for the surface characteristics. In most cases, ageing resulted in a significant decrease of Wa between wood and water and a moderate decrease between wood and thermoplastics. The surface characteristics of acetylated wood were, however, more stable over time compared to unmodified, furfurylated and heat treated wood. The predicted Wa with the adhesives for heat treated and acetylated wood was increased due to ageing. Future work is planned to involve studies in order to relate such predicted adhesion properties with the actual performance of various wood-polymer systems. / QC 20101108

Industries’ interest in nanomaterials is tremendous and catalysis is one of their applications. Catalysts allow reactions to occur under milder conditions, avoiding committing excessive heat or pressure to foster reactions. The discovery of Frustrated Lewis Pairs (FLP) in 2006 led to a new concept of homogeneous catalysis: metal-free acids and bases preventing from forming an Lewis adduct because their bulkiness create an active clamp that is able to cleave dihydrogen and other small molecules at room temperature. Transferring the FLP concept to the “nano”-world which is more relevant for industrial applications, requires well-designed nanoparticles and rationalization of their interaction with ligands aiming at forming a FLP between nanoparticles and ligands. The following project conducted at LCMCP (Laboratoire de Chimie de la Matière Condensée de Paris) under the supervision of Sophie Carenco aimed at studying the insertion of phosphorus in metallic nanoparticles in order to tune their catalytic activity and demonstrate Frustrated-Lewis Pair catalytic behaviours. To that end, copper nanoparticles and bimetallic core-shell nickel-cobalt nanoparticles were synthesized in colloidal solution. The phosphidation of both nanoparticles was investigated with trioctylphosphine (TOP) as the phosphorous source. Nanoparticles were characterized by X-Ray Diffraction, Transmission Electron Microscopy and X-ray Photoelectron Spectroscopy. Starting from the failure to reproduce a published procedure of copper phosphide nanoparticles synthesis, conditions of the reaction and the washing procedure were successively improved aiming the obtention of copper phosphide nanoparticles. The one-pot synthesis with hot-injection of TOP at the second step (320°C, 1h), allowed to isolate copper phosphide nanoparticles but a longer reaction time did not result in enhanced phosphorus doping. Further work would need to examine the reproducibility problems faced and investigate harsher reaction conditions (eg. higher temperature). Cu3P nanoparticles would be interesting to test as catalysts for hydrosilylation of benzaldehyde or CO2, a model reaction for CO2 hydrogenation. The synthesis of core-shell nickel-cobalt nanoparticles has been previously rationalized by Sophie Carenco’s team. Phosphidation was attempted from this optimized procedure. We started with harsh conditions (> 250°C, > 1h30) which caused reconstruction of the nanoparticles after leaching of the cobalt shell. In such conditions, the core-shell structure is not retained and a NiCoP alloy is obtained. Milder conditions allowed to retain the structure but further studies are required to characterize and locate the phosphorus insertion in the core-shell nanoparticles. NiCoP alloy and phosphidized core-shell Ni@Co will be of great interest to apply in catalysis for water splitting and hydrogenation of nitriles, respectively.

My thesis draws connections between today's network society and the workings of gothic literature in the late eighteenth- and early nineteenth-century. Just as our society is formed and affected by the flow of information, the eighteenth-century culture of sensibility was formed by the merging and flow of scientific "technology" (or new scientific discoveries) and societal norms and rules. Gothic literature was born out of this science-society network, and in many ways embodies the ruptures implicit in it. Although gothic literature is not a network in the same sense as informationalism and the culture of sensibility are, gothic literature works according to the logic of networks on both a microscopic and macroscopic level. These correlations between networks and the gothic potentially illuminate two of gothic literature's strange and signature qualities: the subversive nature of the gothic convention, as well as the incredible—and almost inexplicable, considering its libeled and unpopular reputation—staying power of the genre. In Chapter One, I compare the society of informationalism and the eighteenth-century society of sensibility in order to extrapolate a three-pronged logic of networks: networks are subversive, networks are exclusive, and networks are based on codes. In Chapter Two I trace this logic through eighteenth-century gothic conventions as they are portrayed in Ann Radcliffe's The Italian and Matthew Lewis's The Monk. This shows how the gothic, like network society, depends on the paradox of containing the ideology that it subverts. In Chapter Three I investigate this paradox on a macroscopic level by examining the connections between "tales of terror" in Blackwood's Magazine and gothic literature in both the pre-Romantic and Victorian literature. By both adopting and subverting the conventions of Radcliffean gothic, these tales are a key node in the web of the gothic stretching backwards to into the eighteenth century, forwards into the nineteenth century, and beyond.

Computational chemistry is a branch of modern chemistry that utilizes the computers to solve chemical problems. The fundamental of computational chemistry is Schrödinger equation. To solve the equation, researchers developed many methods based on BornOppenheimer Approximation, such as Hartree-Fock method and DFT method, etc. Computational chemistry is now widely used on reaction mechanism study and new chemical designing. In the first project described in Chapter 3, we designed phosphine oxide modified Ag3, Au3 and Cu3 nanocluster catalysts with DFT method. We found that these catalysts were able to catalyze the activation of H2 by cleaving the H-H bond asymmetrically. The activated catalyst-2H complex can be further used as reducing agent to hydrogenate CO molecule to afford HCHO. The mechanism study of these catalysts showed that the electron transfer from electron-rich metal clusters to O atom on the phosphine oxide ligand is the major driving force for H2 activation. In addition, different substituent groups on phosphine oxide ligand were tested. Both H affinity of metal and the substituent groups on ligand can both affect the activation energy. Another project described in Chapter 4 is the modelling of catalyst with DFT. We chose borane/NHC frustrated Lewis pair (FLP) catalyzed methane activation reaction as example to establish a relationship between activation energy and catalysts’ physical properties. After performing simulation, we further proved the well-accepted theory that the electron transfer is the main driving force of catalysis. Furthermore, we were able to establish a linear relationship for each borane between activation energy and the geometrical mean value of HOMO/LUMO energy gap (ΔEMO). Based on that, we introduced the formation energy of borane/NHC complex (ΔEF) and successfully established a generalized relationship between Ea and geometrical mean value of ΔEMO and ΔEF. This model can be used to predict reactivity of catalysts.

Experimental studies on the coupled effects of transport properties and unsteady fluid dynamics have been conducted on laminar, acoustically forced, hydrogen jet diffusion flames diluted by argon and helium. The primary purpose of this research is to determine how the fuel Lewis number and the flow unsteadiness play a combined role in maximum flame temperature and affect NOx emission from jet diffusion flame. The fuel Lewis number is varied by increasing/decreasing the mole fraction of diluents in the fuel stream. Therefore, maximum flame temperatures and then NOx emission levels were expected to differ for Ar- and He-diluted flames. In an investigation of unsteady flames, two different frequencies (10 and 100 Hz) were applied to observe a behavior of NOx emission levels and flame lengths by changes of unsteady fluid dynamics and transport properties.

The purpose of this thesis is to determine how guilt and shame act as engines of social control in two Gothic narratives of the 1790s, how they tie into the terror and horror modes of the genre, and how they give rise to two distinct narrative models, one centered on punishment and the other on rehabilitation. The premise of the paper is that both Matthew G. Lewis's The Monk and Ann Radcliffe's The Italian harness radically different emotional responses, one that demands the punishment of the aberrant individual and the other that reveres the reformative power of domestic felicity. The purposes of both responses are to civilize readers and their respective representations of the Holy Office of the Inquisition are central to this process. I examine the role of the Inquisition in The Monk and contrast it with the depiction of the same institution in The Italian. Lewis's book subordinates the ecclesiastical world to the authority of the aristocracy and uses graphic scenes of torture to support conservative forms of social control based on shame. The Italian, on the other hand, depicted the Inquisition as a conspiratorial body that causes Radcliffe's protagonists, and by extension her readers, to question their complicity in oppressive systems of social control and look for alternative means to punishment. The result is a push toward rehabilitation that is socially progressive but questions the English Enlightenment's promotion of the carceral.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.