Modelling Cutting States in Rough Turning of 34CrNiMo6 Steel

Rough turning is an important form of manufacturing cylinder-symmetric parts. Thus far, increasing the level of automation in rough turning has included process monitoring methods or adaptive turning control methods that aim to keep the process conditions constant. However, in order to improve process safety, quality and efficiency, an adaptive turning control should be transformed into an intelligent machining system optimizing cutting values to match process conditions or to actively seek to improve process conditions. In this study, primary and secondary chatter and chip formation are studied to understand how to measure the effect of these phenomena to the process conditions and how to avoid undesired cutting conditions. The concept of cutting state is used to address the combination of these phenomena and the current use of the power capacity of the lathe. The measures to the phenomena are not developed based on physical measures, but instead, the severity of the measures is modelled against expert opinion. Based on the concept of cutting state, an expert system style fuzzy control system capable of optimizing the cutting process was created. Important aspects of the system include the capability to adapt to several cutting phenomena appearing at once, even if the said phenomena would potentially require conflicting control action.

Towards the enantioselective synthesis of lycoricidine alkaloids /

Two efficient, regio- and stereo controlled synthetic approaches to the synthesis of racemic analogs of pancratistatin have been accomplished and they serve as the model systems for the total synthesis of optically active 7-deoxy-pancratistatin. In the Diels-Alder approach, an efficient [4+2] cycloaddition of 3,4-methylenedioxyco- nitrostyrene with Danishefsky's diene to selectively form an exo-nitro adduct has been developed as the key step in the construction of the C-ring of the target molecule. In the Michael addition approach, the key step was a conjugate addition of an organic zinc-cuprate to the 3,4-methylenedioxy-(B-nitrostyrene, followed by a diastereocontroUed closure to form the cyclohexane C-ring of the target molecule via an intramolecular nitro-aldol cyclization on a neutral alumina surface. A chair-like transition state for such a cyclization has been established and such a chelation controlled transition state can be useful in the prediction of diastereoselectivity in other related 6-exo-trig nitroaldol reactions. Cyclization of the above products fi^om both approaches by using a Bischler-Napieralski type reaction afforded two lycoricidine derivatives 38 and 50 in good yields. The initial results from the above modeling studies as well as the analysis of the synthetic strategy were directed to a chiral pool approach to the total synthesis of optically active 7-deoxy-pancratistatin. Selective monsilylation and iodination of Ltartaric acid provided a chiral precursor for the proposed key Michael transformation. The outlook for the total synthesis of 7-deoxy-pancratistatin by this approach is very promising.A concise synthesis of novel designed, optically pure, Cz-symmetrical disulfonylamide chiral ligands starting from L-tartaric acid has also been achieved. This sequence employs the metallation of indole followed by Sfj2 replacement of a dimesylate as the key step. The activity for this Cz-symmetric chiral disulfonamide ligand in the catalytic enantioselective reaction has been confirmed by nucleophilic addition to benzaldehyde in the disulfonamide-Ti (0-i-Pr)4-diethylzinc system with a 48% yield and a 33% e.e. value. Such a ligand tethered with a suitable metal complex should be also applicable towards the total synthesis of 7-deoxy-pancratistatin.

Using stimulus equivalence to teach monetary skills to school-age children with autism

The present study evaluated the use of stimulus equivalence in teaching monetary skills to school aged children with autism. An AB within-subject design with periodic probes was used. At pretest, three participants demonstrated relation DA, an auditory-visual relation (matching dictated coin values to printed coin prices). Using a three-choice match-to-sample procedure, with a multi-component intervention package, these participants were taught two trained relations, BA (matching coins to printed prices) and CA (matching coin combinations to printed prices). Two participants achieved positive tests of equivalence, and the third participant demonstrated emergent performances with a symmetric and transitive relation. In addition, two participants were able to show generalization of learned skills with a parent, in a second naturalistic setting. The present research replicates and extends the results of previous studies by demonstrating that stimulus equivalence can be used to teach an adaptive skill to children with autism.

Investigation of molecular polarizabilities and derivatives in halomethanes

The research undertaken was to obtain absolute Raman intensities for the symmetric stretching vibrations of the methyl halides, CH3X with (X=F, CI, Br), by experiment and theory. The intensities were experimentally measured using the Ar+ ion gas laser as excitation source, a Spex 14018 double monochromator and a RCA C-31034 photomultiplier tube as detector. These intensities arise from changes in the derivative of the polarizability (8 a'), with respect to vibration along a normal coordinate (8qi). It was intended that these derivatives obtained with respect to normal coordinates would be converted to derivatives with respect to internal coordinates, for a quantitative comparison with theory. Theoretical numerical polarizability derivatives for the stretching vibrations are obtained using the following procedure. A vibration was simulated in the molecule by increasi.ng and decreasing the respective bond by the amount ±o.oosA for the C-H bonds and ±o.oIA for the C-X (X=F, CI, Br) bond. The derivative was obtained by taking the difference in the polarizability for the equilibrium geometry and the geometry when a particular bond is changed. This difference, when divided by the amount of change in each bond and the number of bonds present results in the derivative of the polarizability with respect to internal coordinate i.e., !1u/!1r. These derivatives were obtained by two methods: I} ab initio molecular orbital calculation and 2} theory of atoms in molecules (AIM) analysis. Due to errors in the experimental setup only a qualitative analysis of the results was undertaken relative to the theory. Theoretically it is predicted that the symmetric carbonhalogen stretch vibrations are more intense than the respective carbon-hydrogen stretch, but only for the methyl chloride and bromide. The carbon fluorine stretch is less intense than the carbon-hydrogen stretch, a fact which is attributed to the small size and high electronegativity of the fluorine atom. The experimental observations are seen to agree qualitatively with the theory results. It is hoped that when the experiment is repeated, a quantitative comparison can be made. The analysis by the theory of atoms in molecules, along with providing polarizabilities and polarizability derivatives, gives additional information outlined below. The theory provides a pictorial description of the main factors contributing to the molecular polarizability and polarizability derivative. These contributions are from the charge transfer and atomic dipole terms i.e., transfer of charge from one atom to another and the reorganization of atomic electronic charge distribution due to presence of an electric field. The linear relationship between polarizability and molecular volume was also observed.

Solid state NMR chemical shifts as an alternative to diffraction data in the determination of SIC polytypic structures

Silicon carbide, which has many polytypic modifications of a very simple and very symmetric structure, is an excellent model system for exploring, the relationship between chemical shift, long-range dipolar shielding, and crystal structure in network solids. A simple McConnell equation treatment of bond anisotropy effects in a poly type predicts chemical shifts for silicon and carbon sites which agree well with the experiment, provided that contributions from bonds up to 100 A are included in the calculation. The calculated chemical shifts depend on three factors: the layer stacking sequence, electrical centre of gravity, and the spacings between silicon and carbon layers. The assignment of peaks to lattice sites is proved possible for three polytypes (6H, 15R, and 3C). The fact that the calculated chemical shifts are very sensitive to layer spacings provides us a potential way to detennine and refine a crystal structure. In this work, the layer spacings of 6H SiC have been calculated and are within X-ray standard deviations. Under this premise, the layer spacings of 15R have been detennined. 29Si and 13C single crystal nmr studies of 6H SiC polytype indicate that all silicons and carbons are magnetically anisotropic. The relationship between a magnetic shielding tensor component and layer spacings has been derived. The comparisons between experimental and semi-empirical chemical shielding tensor components indicate that the paramagnetic shielding of silicon should be included in the single crystal chemical shift calculation.

Generating finite integral relation algebras

Relation algebras and categories of relations in particular have proven to be extremely useful as a fundamental tool in mathematics and computer science. Since relation algebras are Boolean algebras with some well-behaved operations, every such algebra provides an atom structure, i.e., a relational structure on its set of atoms. In the case of complete and atomic structure (e.g. finite algebras), the original algebra can be recovered from its atom structure by using the complex algebra construction. This gives a representation of relation algebras as the complex algebra of a certain relational structure. This property is of particular interest because storing the atom structure requires less space than the entire algebra. In this thesis I want to introduce and implement three structures representing atom structures of integral heterogeneous relation algebras, i.e., categorical versions of relation algebras. The first structure will simply embed a homogeneous atom structure of a relation algebra into the heterogeneous context. The second structure is obtained by splitting all symmetric idempotent relations. This new algebra is in almost all cases an heterogeneous structure having more objects than the original one. Finally, I will define two different union operations to combine two algebras into a single one.

Market reactions to changes in the Nasdaq-100 Index membership

We examine stock market reactions around the Nasdaq-100 Index reconstitutions. We find a symmetric and transitory price response accompanied by a significant increase in trading volume on the effective date. Firms added to the Nasdaq-100 Index experience significant increases in institutional ownership, the number of market makers, and the number of shareholders. In contrast, firms removed from the index show significant decreases in the number of institutional shareholders. Additions to the Nasdaq-100 Index also show significant increases in four liquidity measures, whereas deletions demonstrate significant decreases in two liquidity measures. These changes in liquidity are related to the abnormal return on the announcement day. Taken together, the results suggest support for the price pressure, liquidity, and investor awareness hypotheses.

Region Connection Calculus: Composition Tables and Constraint Satisfaction Problems

Qualitative spatial reasoning (QSR) is an important field of AI that deals with qualitative aspects of spatial entities. Regions and their relationships are described in qualitative terms instead of numerical values. This approach models human based reasoning about such entities closer than other approaches. Any relationships between regions that we encounter in our daily life situations are normally formulated in natural language. For example, one can outline one's room plan to an expert by indicating which rooms should be connected to each other. Mereotopology as an area of QSR combines mereology, topology and algebraic methods. As mereotopology plays an important role in region based theories of space, our focus is on one of the most widely referenced formalisms for QSR, the region connection calculus (RCC). RCC is a first order theory based on a primitive connectedness relation, which is a binary symmetric relation satisfying some additional properties. By using this relation we can define a set of basic binary relations which have the property of being jointly exhaustive and pairwise disjoint (JEPD), which means that between any two spatial entities exactly one of the basic relations hold. Basic reasoning can now be done by using the composition operation on relations whose results are stored in a composition table. Relation algebras (RAs) have become a main entity for spatial reasoning in the area of QSR. These algebras are based on equational reasoning which can be used to derive further relations between regions in a certain situation. Any of those algebras describe the relation between regions up to a certain degree of detail. In this thesis we will use the method of splitting atoms in a RA in order to reproduce known algebras such as RCC15 and RCC25 systematically and to generate new algebras, and hence a more detailed description of regions, beyond RCC25.

Uncovering Financial Markets Beliefs About Inflation Targets

This paper exploits the term structure of interest rates to develop testable economic restrictions on the joint process of long-term interest rates and inflation when the latter is subject to a targeting policy by the Central Bank. Two competing models that econometrically describe agents’ inferences about inflation targets are developed and shown to generate distinct predictions on the behavior of interest rates. In an empirical application to the Canadian inflation target zone, results indicate that agents perceive the band to be substantially narrower than officially announced and asymmetric around the stated mid-point. The latter result (i) suggests that the monetary authority attaches different weights to positive and negative deviations from the central target, and (ii) challenges on empirical grounds the assumption, frequently made in the literature, that the policy maker’s loss function is symmetric (usually a quadratic function) around a desired inflation value.

Aggregations and Marginalization of GARCH and Stochastic Volatility Models

The GARCH and Stochastic Volatility paradigms are often brought into conflict as two competitive views of the appropriate conditional variance concept : conditional variance given past values of the same series or conditional variance given a larger past information (including possibly unobservable state variables). The main thesis of this paper is that, since in general the econometrician has no idea about something like a structural level of disaggregation, a well-written volatility model should be specified in such a way that one is always allowed to reduce the information set without invalidating the model. To this respect, the debate between observable past information (in the GARCH spirit) versus unobservable conditioning information (in the state-space spirit) is irrelevant. In this paper, we stress a square-root autoregressive stochastic volatility (SR-SARV) model which remains true to the GARCH paradigm of ARMA dynamics for squared innovations but weakens the GARCH structure in order to obtain required robustness properties with respect to various kinds of aggregation. It is shown that the lack of robustness of the usual GARCH setting is due to two very restrictive assumptions : perfect linear correlation between squared innovations and conditional variance on the one hand and linear relationship between the conditional variance of the future conditional variance and the squared conditional variance on the other hand. By relaxing these assumptions, thanks to a state-space setting, we obtain aggregation results without renouncing to the conditional variance concept (and related leverage effects), as it is the case for the recently suggested weak GARCH model which gets aggregation results by replacing conditional expectations by linear projections on symmetric past innovations. Moreover, unlike the weak GARCH literature, we are able to define multivariate models, including higher order dynamics and risk premiums (in the spirit of GARCH (p,p) and GARCH in mean) and to derive conditional moment restrictions well suited for statistical inference. Finally, we are able to characterize the exact relationships between our SR-SARV models (including higher order dynamics, leverage effect and in-mean effect), usual GARCH models and continuous time stochastic volatility models, so that previous results about aggregation of weak GARCH and continuous time GARCH modeling can be recovered in our framework.

Responsibility and Cross-Subsidization in Cost Sharing

We propose two axiomatic theories of cost sharing with the common premise that agents demand comparable -though perhaps different- commodities and are responsible for their own demand. Under partial responsibility the agents are not responsible for the asymmetries of the cost function: two agents consuming the same amount of output always pay the same price; this holds true under full responsibility only if the cost function is symmetric in all individual demands. If the cost function is additively separable, each agent pays her stand alone cost under full responsibility; this holds true under partial responsibility only if, in addition, the cost function is symmetric. By generalizing Moulin and Shenker’s (1999) Distributivity axiom to cost-sharing methods for heterogeneous goods, we identify in each of our two theories a different serial method. The subsidy-free serial method (Moulin, 1995) is essentially the only distributive method meeting Ranking and Dummy. The cross-subsidizing serial method (Sprumont, 1998) is the only distributive method satisfying Separability and Strong Ranking. Finally, we propose an alternative characterization of the latter method based on a strengthening of Distributivity.

Solidarity in Choosing a Location on a Cycle

We study the implications of two solidarity conditions on the efficient location of a public good on a cycle, when agents have single-peaked, symmetric preferences. Both conditions require that when circumstances change, the agents not responsible for the change should all be affected in the same direction: either they all gain or they all loose. The first condition, population-monotonicity, applies to arrival or departure of one agent. The second, replacement-domination, applies to changes in the preferences of one agent. Unfortunately, no Pareto-efficient solution satisfies any of these properties. However, if agents’ preferred points are restricted to the vertices of a small regular polygon inscribed in the circle, solutions exist. We characterize them as a class of efficient priority rules.

iVici: Interrelational Visualization and Correlation Interface

Affiliation: Département de Biochimie, Faculté de médecine, Université de Montréal

Étude de réactivité et de sélectivité de nouveaux catalyseurs à base de ruthénium

Ce projet de recherche consiste en l’étude de la réactivité et de la sélectivité de nouveaux catalyseurs de métathèse d’oléfines à base de ruthénium lors de réaction de fermeture de cycle par métathèse d’oléfines (RCM). L’emphase de cette étude repose sur l’évaluation de nouveaux catalyseurs possédant un ligand NHC (carbène N-hétérocyclique) C1-symétrique développés par le laboratoire Collins pour des réactions de désymétrisations asymétriques de méso-triènes par ARCM. Le projet a été séparé en deux sections distinctes. La première section concerne la formation d’oléfines trisubstituées par ARCM de méso-triènes. La seconde section consiste en la formation d’oléfines tétrasubstituées par le biais de la RCM de diènes et de la ARCM de méso-triènes. Il est à noter qu’il n’y a aucun précédent dans la littérature concernant la formation d’oléfines tétrasubstituées suite à une désymétrisation par ARCM. Lors de l’étude concernant la formation d’oléfines trisubstituées, une étude de cinétique a été entreprise dans le but de mieux comprendre la réactivité des différents catalyseurs. Il a été possible d’observer que le groupement N-alkyle a une grande influence sur la réactivité du catalyseur. Une étude de sélectivité a ensuite été entreprise pour déterminer si le groupement N-alkyle génère aussi un effet sur la sélectivité des catalyseurs. Cette étude a été effectuée par l’entremise de réactions de désymétrisation d’une variété de méso-triènes. En ce qui a trait à la formation d’oléfines tétrasubstituées, une étude de la réactivité des différents catalyseurs a été effectuée par l’intermédiaire de malonates de diéthyldiméthallyle. Il a encore une fois a été possible d’observer que le groupement N-alkyle possède un effet important sur la réactivité du catalyseur. Une étude de sélectivité a ensuite été entreprise pour déterminer si le groupement iv N-alkyle génère aussi un effet sur la sélectivité des catalyseurs. Cette étude a été effectuée par l’entremise de réactions de désymétrisation de différents mésotriènes.

Découverte et application de nouveaux motifs d'association propres à l'hexaphénylbenzène et à ses dérivés

Les propriétés des matériaux moléculaires proviennent à la fois de la structure des composantes individuelles et de la façon dont elles s’associent. Ce dernier aspect reste difficile à contrôler, malgré de grandes avancées en science des matériaux. Pour mieux comprendre la relation structure-propriétés, nous avons entrepris une étude systématique de l'hexaphénylbenzène et de ses dérivés, qui offrent une charpente symétrique et rigide. En premier lieu, nous avons attaché six groupements diaminotriazinyles sur l’hexaphénylbenzène afin de produire des réseaux tridimensionnels hautement poreux maintenus par des ponts hydrogène. En modifiant systématiquement le coeur moléculaire, nous avons excisé près du tiers de la molécule-mère, générant des réseaux supramoléculaires dont la porosité s’est élevée graduellement jusqu’à 75%, équivalant ainsi le record pour ce type de matériaux. Ensuite, nous avons étudié le comportement de l’hexakis(4-nitrophényl)benzène. Dans les structures cristallines obtenues, des interactions non-covalentes entre groupements nitro démontrent leur potentiel en chimie supramoléculaire. Le coeur moléculaire ne joue qu’un rôle secondaire dans l’empilement des molécules : seules quelques interactions C-H•••π impliquant le cycle aromatique central de l’hexaphénylbenzène sont évidentes. Cette dernière observation nous a poussés à étudier le comportement à l’état cristallin de l’hexaphénylbenzène et ses dérivés. En scrutant attentivement neuf structures cristallines de ces composés, nous avons décerné la présence récurrente d’interactions C-H•••π impliquant le cycle aromatique central. Cette association caractéristique a été exploitée pour créer des réseaux supramoléculaires maintenus par des interactions C-H•••π sélectives entre un groupement éthynyle et le cycle aromatique central de l’hexaphénylbenzène. Finalement, nous avons joint le côté sombre de l’ingénierie cristalline en utilisant nos connaissances dans le but d’empêcher la formation d’interactions directionnelles. En protégeant le cycle aromatique central de l’hexaphénylbenzène à l’aide de groupements alkyles, les interactions C-H•••π ont été pratiquement éliminées. Ces résultats offrent la possibilité de créer de nouveaux matériaux amorphes. Dans ces études, focalisées sur le système hexaphénylbenzène, nous avons mis en relief des phénomènes qui sont obscurcis dans d'autres familles de molécules. De plus, ce système a grandement facilité l’utilisation d’une approche méthodique pour explorer la relation structure-propriétés. Nos travaux nous ont amenés à des conclusions de valeur universelle en science des matériaux moléculaires.