Polymerization of Ethene and Branched α-olefins with Group IV Metal Complexes Bearing Nitrogen- and Oxygen-Based Ligands

The commodity plastics that are used in our everyday lives are based on polyolefin resins and they find wide variety of applications in several areas. Most of the production is carried out in catalyzed low pressure processes. As a consequence polymerization of ethene and α-olefins has been one of the focus areas for catalyst research both in industry and academia. Enormous amount of effort have been dedicated to fine tune the processes and to obtain better control of the polymerization and to produce tailored polymer structures The literature review of the thesis concentrates on the use of Group IV metal complexes as catalysts for polymerization of ethene and branched α-olefins. More precisely the review is focused on the use of complexes bearing [O,O] and [O,N] type ligands which have gained considerable interest. Effects of the ligand framework as well as mechanical and fluxional behaviour of the complexes are discussed. The experimental part consists mainly of development of new Group IV metal complexes bearing [O,O] and [O,N] ligands and their use as catalysts precursors in ethene polymerization. Part of the experimental work deals with usage of high-throughput techniques in tailoring properties of new polymer materials which are synthesized using Group IV complexes as catalysts. It is known that the by changing the steric and electronic properties of the ligand framework it is possible to fine tune the catalyst and to gain control over the polymerization reaction. This is why in this thesis the complex structures were designed so that the ligand frameworks could be fairly easily modified. All together 14 complexes were synthesised and used as catalysts in ethene polymerizations. It was found that the ligand framework did have an impact within the studied catalyst families. The activities of the catalysts were affected by the changes in complex structure and also effects on the produced polymers were observed: molecular weights and molecular weight distributions were depended on the used catalyst structure. Some catalysts also produced bi- or multi-modal polymers. During last decade high-throughput techniques developed in pharmaceutical industries have been adopted into polyolefin research in order to speed-up and optimize the catalyst candidates. These methods can now be regarded as established method suitable for both academia and industry alike. These high-throughput techniques were used in tailoring poly(4-methyl-1-pentene) polymers which were synthesized using Group IV metal complexes as catalysts. This work done in this thesis represents the first successful example where the high-throughput synthesis techniques are combined with high-throughput mechanical testing techniques to speed-up the discovery process for new polymer materials.

A simple method of estimating the detonation velocity from chemical composition of organic explosives

A simple yet fairly accurate method of calculating the ideal detonation velocity of an organic explosive from a knowledge of the chemical composition alone is proposed. The method is based on the concept that the energetics of a stoichiometrically balanced fuel-oxidizer system is a function of the total oxidizing or reducing valences of the composition. A combination of the valences in the form of Image , where R and P are, respectively, the reducing and oxidizing valences and MW is the molecular weight, has been found to be linearly related to the detonation velocity of the expolosive. The predicting capacity of the method has been found to be superior to other methods in the literature.

Stress-optical dispersion in rubidium chloride and rubidium bromide crystals

The stress-optical coefficients C = (n3/2) (q11−q12) and C′ = (n3/2)q44 of RbCl and RbBr crystals have been measured at room temperature (26°C) over the wave length range 5750-2500 A.

Gauging the conformal group

It is demonstrated that Kibble’s method of gauging the Poincaré group can be applied to the gauging of the conformal group. The action of the gauge transformations is the action of general spacetime diffeomorphisms (or coordinate transformations) combined with a local action of an 11-parameter subgroup of SO(4,2). Because the translational subgroup is not an invariant subgroup of the conformal group the appropriate generalisation of the derivative of a physical field is not a covariant derivative in the usual sense, but this does not lead to any inconsistencies.

Resting sites, edge effects and dispersion of a polyphagous Bactrocera fruit fly within crops of different architecture

The spot or strip application of poisoned protein bait is a lure-and-kill technique used for the management of fruit flies. Knowledge of where flies occur in the crop environment is an important part of maximizing the efficacy of this tool. Bactrocera tryoni is a polyphagous pest of horticulture for which very little is known about its distribution within crops. With particular reference to edge effects, we monitored the abundance of B. tryoni in two crops of different architecture; strawberry and apple. In strawberries, we found more flies on the crop edge early in the fruiting season, which lessened gradually and eventually disappeared as the season progressed. In apple orchards, no such edge effect was observed and flies were found equally throughout the orchard. We postulated these differences may be due to differences in crop height (high vs. short) and/or crop canopy architecture (opened and branched in apple, dense and closed in strawberry). In a field cage trial, we tested these predictions using artificial plants of different height and canopy condition. Height and canopy structure type had no significant effects on fly oviposition and protein feeding, but the 'apple' type canopy significantly influenced resting. We thus postulate that there was an edge effect in strawberry because the crop was not providing resting sites and flies were doing so in vegetation around the field margins. The finding that B. tryoni shows different resting site preferences based on plant architecture offers the potential for strategic manipulation of the fly through specific border or inter-row plantings. © 2013 Blackwell Verlag GmbH.

Hydration numbers of some metal acetates, monochloroacetates and trichloroacetates in solution from ultrasonic velocity and conpressibility measurements

Ultrasonic velocities in aqueous solutions of some metal acetates, monochloroacelates and trichloroacetates, and the respective acids have been measured at 1 MHz frequency using the pulse technique. The ultrsonic velocity, adiabatic compressibility and apperent molal compressibility were measured as a function of concentration. The apparent molal compressibility values at infinite dilution were calculated and used to determine the hydration numbers.

Velocity ratio in the analysis of linear dynamical systems

The transfer matrix method is known to be well suited for a complete analysis of a lumped as well as distributed element, one-dimensional, linear dynamical system with a marked chain topology. However, general subroutines of the type available for classical matrix methods are not available in the current literature on transfer matrix methods. In the present article, general expressions for various aspects of analysis-viz., natural frequency equation, modal vectors, forced response and filter performance—have been evaluated in terms of a single parameter, referred to as velocity ratio. Subprograms have been developed for use with the transfer matrix method for the evaluation of velocity ratio and related parameters. It is shown that a given system, branched or straight-through, can be completely analysed in terms of these basic subprograms, on a stored program digital computer. It is observed that the transfer matrix method with the velocity ratio approach has certain advantages over the existing general matrix methods in the analysis of one-dimensional systems.

Energy losses at pipe trifurcations

In the case of pipe trifurcation, previous observations report negative energy losses in the centre branch. This causes an anomaly, because there should not be any negative energy loss due to conservation of energy principle. Earlier investigators have suggested that this may be due to the non-inclusion of kinetic energy coefficient (a) in the computations of energy losses without any experimental evidence. In the present work, through experimentally determined velocity profiles, energy loss coefficients have been evaluated. It has been found that with the inclusion of a in the computations of energy loss, there is no negative energy loss in the centre branch.

Fungus-feeding Thysanoptera: Phlaeothripinae of the Idiothrips genus-group in Australia, with nine new species

In a group of fungus-feeding Phlaeothripinae characterized by complex body sculpture, identification keys are provided to three genera and 15 species from Australia, including nine new species. In the genus Azaleothrips one new species is described, and one Asian species is newly recorded from Australia. The genus Stictothrips is recorded from Australia for the first time, with two new species. Within the genus Strepterothrips considerable structural diversity is recorded including three new species in which antennal segment III is greatly reduced and bears no sense cones. Some species in this genus exhibit the unusual condition of having several setae on the pelta, the first abdominal tergite. Problems in the production of generic diagnoses within the Phlaeothripinae are discussed.

A note on the evaluation of dielectric dispersion parameters of non-debije type liquids

A simple method for evaluating dielectric relaxation parameters ie given whioh can be used for analyeing the arelaxation times of a liquid into two absorptions.

A note on the analysis of the dispersion equation for surface magnetoplasmons in the Faraday configuration

The analysis of the dispersion equation for surface magnetoplasmons in the Faraday configuration for the degenerate case of decaying constants being equal is given from the point of view of understanding the non-existence of the “degenerate modes”. This analysis also shows that there exist well defined “degenerate points” on the dispersion curve with electromagnetic fields varying linearly over small distances taken away from the interface.

The neuroscience of inspirational leadership: the importance of collective-oriented language and shared group membership

Effective leaders are believed to inspire followers by providing inclusive visions of the future that followers can identify with. In the present study, we examined the neural mechanisms underlying this process, testing key hypotheses derived from transformational and social identity approaches to leadership. While undergoing functional MRI, supporters from the two major Australian political parties (Liberal vs. Labor) were presented with inspirational collective-oriented and noninspirational personal-oriented statements made by in-group and out-group leaders. Imaging data revealed that inspirational (rather than noninspirational) statements from in-group leaders were associated with increased activation in the bilateral rostral inferior parietal lobule, pars opercularis, and posterior midcingulate cortex: brain areas that are typically implicated in controlling semantic information processing. In contrast, for out-group leaders, greater activation in these areas was associated with noninspirational statements. In addition, noninspirational statements by in-group (but not out-group) leaders resulted in increased activation in the medial prefrontal cortex, an area typically associated with reasoning about a person’s mental state. These results show that followers processed identical statements qualitatively differently as a function of leaders’ group membership, thus demonstrating that shared identity acts as an amplifier for inspirational leadership communication.

Dispersion of the stress-optic coefficient in glasses

The stress-optic coefficient (n3/2)(q11-q12) has been determined for a series of 18 optical glasses of different compositions in the wavelength range 5700-3200 Å. The coefficients are negative for all the glasses except for a high-lead-content glass of density 6·7 and refractive index 1·89. The numerical value of the coefficient decreases as one proceeds to the ultraviolet. This behaviour is just the opposite of what is observed in fused silica. By applying Mueller's theory, the strain polarizability constant and its dispersion have been evaluated.

Velocity Distribution in Smooth Rectangular Open Channels-Closure

Abstract is not available.