Tailoring polyolefin properties by metallocene catalysis

This doctoral thesis deals with the syntheses of olefin homo- and copolymers using different kind of metallocene catalyst. Ethene, propene, 1-hexene, 1-hexadecene, vinylcyclohexane and phenylnorbornene were homo- or copolymerized with the catalysts. The unbridged benzyl substituted zirconium dichloride catalysts (1-4), ansa- bridged acenaphtyl substituted zirconium dichloride catalysts, ( 5, 6), rac- and meso-ethylene-bis(1-indenyl)zirconium dichlorides, (rac- and meso-8), rac-ethylene-bis(1-indenyl)hafnium dichloride, ( 12), bis(9-fluorenyl)hafnium dichloride (14 ) enantiomerically pure (R)- phenylethyl[(9-fluorenyl-1-indenyl)]ZrCl2, (11), 14 and asymmetric dimethylsilyl[(3-benzylindenyl-(2-methylbenzen[e]indenyl)] zirconium dichloride, (13), were prepared in our laboratory. Dimethylsilyl-bis(1-indenyl)zirconium dichloride, (9), isopropylidene(9-fluorenyl-cyclopentadienyl)zirconium dichloride, (10), and were obtained commercially. The solid-state structures of the catalysts rac- and meso-1 were determined by X-ray crystallography. Computational methods were used for the structure optimization of the catalyst rac- and meso-1 in order to compare the theoretical calculations with the experimental results. Polymerization experiments were conducted in a highly purified autoclave system using low pressures (< 5 bar) of gaseous monomers. The experiments were designed to attain the optimal catalytic activity and a uniform copolymer composition. The prepared homo- and copolymers were characterized by the gel permeation chromatography, GPC, differential scanning calorimetry, DSC, nuclear magnetic resonance, NMR, and Fourier transform infrared spectrometry, FTIR . Molar mass (Mw, Mn), molar mass distribution (Mw/Mn), tacticity, comonomer content, melting temperature, glass transition temperature, and end group structures and content were determined. A special attention was paid on the correlation of the polymer properties with the catalyst structures and polymerization conditions. An intramolecular phenyl coordination was found in phenyl substituted benzyl zirconocenes 1-3 explaining the decreased activity of the catalysts. Novel copolymers poly(propene-co-phenylnorbornene) and poly(propene co-vinylcyclohexane), were synthesized and high molar mass poly(ethene-co-1-hexene) and poly(ethene-co-1-hexadecene) copolymers with elastic properties were prepared. Activation of a hafnocene catalyst was studied with UV-Vis spectrometry and activation process for the synthesis of ultra high molar mass poly(1-hexene) was found out.

TlBr raw material purification, crystal growth, annealing, detector fabrication and characterisation for gamma-ray detector applications

The research reported in this thesis dealt with single crystals of thallium bromide grown for gamma-ray detector applications. The crystals were used to fabricate room temperature gamma-ray detectors. Routinely produced TlBr detectors often are poor quality. Therefore, this study concentrated on developing the manufacturing processes for TlBr detectors and methods of characterisation that can be used for optimisation of TlBr purity and crystal quality. The processes under concern were TlBr raw material purification, crystal growth, annealing and detector fabrication. The study focused on single crystals of TlBr grown from material purified by a hydrothermal recrystallisation method. In addition, hydrothermal conditions for synthesis, recrystallisation, crystal growth and annealing of TlBr crystals were examined. The final manufacturing process presented in this thesis deals with TlBr material purified by the Bridgman method. Then, material is hydrothermally recrystallised in pure water. A travelling molten zone (TMZ) method is used for additional purification of the recrystallised product and then for the final crystal growth. Subsequent processing is similar to that described in the literature. In this thesis, literature on improving quality of TlBr material/crystal and detector performance is reviewed. Aging aspects as well as the influence of different factors (temperature, time, electrode material and so on) on detector stability are considered and examined. The results of the process development are summarised and discussed. This thesis shows the considerable improvement in the charge carrier properties of a detector due to additional purification by hydrothermal recrystallisation. As an example, a thick (4 mm) TlBr detector produced by the process was fabricated and found to operate successfully in gamma-ray detection, confirming the validity of the proposed purification and technological steps. However, for the complete improvement of detector performance, further developments in crystal growth are required. The detector manufacturing process was optimized by characterisation of material and crystals using methods such as X-ray diffraction (XRD), polarisation microscopy, high-resolution inductively coupled plasma mass (HR-ICPM), Fourier transform infrared (FTIR), ultraviolet and visual (UV-Vis) spectroscopy, field emission scanning electron microscope (FESEM) and energy-dispersive X-ray spectroscopy (EDS), current-voltage (I-V) and capacity voltage (CV) characterisation, and photoconductivity, as well direct detector examination.

Wear resistance of cast graphitic aluminium alloys

Wear rates of several cast aluminium base alloys have been measured for lubricated rubbing against a rotating hardened steel disk. Wear rates of cast graphitic aluminium-silicon-nickel alloys were lower than those of pure Al, Al-Si and Al-Si-Ni alloys especially above pressures of 0.02 kg/mm2. The high wear resistance is attributed to the presence of graphite particles in the matrix which act as a solid lubricant. Additions of nickel alone to Al-Si alloys decrease the wear resistance. Graphitic aluminium-silicon-nickel alloys containing above 2% graphite can be mated unlubricated against the rotating steel disk after a one minute lubricated run-in period. Graphite particles may be potentially suitable to replace part of all of the tin in aluminium-tin bearing alloys.

Isotopic records of terrestrial ice age environments in mammoth bioapatite

Palaeoenvironments of the latter half of the Weichselian ice age and the transition to the Holocene, from ca. 52 to 4 ka, were investigated using isotopic analysis of oxygen, carbon and strontium in mammal skeletal apatite. The study material consisted predominantly of subfossil bones and teeth of the woolly mammoth (Mammuthus primigenius Blumenbach), collected from Europe and Wrangel Island, northeastern Siberia. All samples have been radiocarbon dated, and their ages range from >52 ka to 4 ka. Altogether, 100 specimens were sampled for the isotopic work. In Europe, the studies focused on the glacial palaeoclimate and habitat palaeoecology. To minimise the influence of possible diagenetic effects, the palaeoclimatological and ecological reconstructions were based on the enamel samples only. The results of the oxygen isotope analysis of mammoth enamel phosphate from Finland and adjacent nortwestern Russia, Estonia, Latvia, Lithuania, Poland, Denmark and Sweden provide the first estimate of oxygen isotope values in glacial precipitation in northern Europe. The glacial precipitation oxygen isotope values range from ca. -9.2±1.5 in western Denmark to -15.3 in Kirillov, northwestern Russia. These values are 0.6-4.1 lower than those in present-day precipitation, with the largest changes recorded in the currently marine influenced southern Sweden and the Baltic region. The new enamel-derived oxygen isotope data from this study, combined with oxygen isotope records from earlier investigations on mammoth tooth enamel and palaeogroundwaters, facilitate a reconstruction of the spatial patterns of the oxygen isotope values of precipitation and palaeotemperatures over much of Europe. The reconstructed geographic pattern of oxygen isotope levels in precipitation during 52-24 ka reflects the progressive isotopic depletion of air masses moving northeast, consistent with a westerly source of moisture for the entire region, and a circulation pattern similar to that of the present-day. The application of regionally varied δ/T-slopes, estimated from palaeogroundwater data and modern spatial correlations, yield reasonable estimates of glacial surface temperatures in Europe and imply 2-9°C lower long-term mean annual surface temperatures during the glacial period. The isotopic composition of carbon in the enamel samples indicates a pure C3 diet for the European mammoths, in agreement with previous investigations of mammoth ecology. A faint geographical gradient in the carbon isotope values of enamel is discernible, with more negative values in the northeast. The spatial trend is consistent with the climatic implications of the enamel oxygen isotope data, but may also suggest regional differences in habitat openness. The palaeogeographical changes caused by the eustatic rise of global sea level at the end of the Weichselian ice age was investigated on Wrangel Island, using the strontium isotope (Sr-87/Sr-86) ratios in the skeletal apatite of the local mammoth fauna. The diagenetic evaluations suggest good preservation of the original Sr isotope ratios, even in the bone specimens included in the study material. To estimate present-day environmental Sr isotope values on Wrangel Island, bioapatite samples from modern reindeer and muskoxen, as well as surface waters from rivers and ice wedges were analysed. A significant shift towards more radiogenic bioapatite Sr isotope ratios, from 0.71218 ± 0.00103 to 0.71491 ± 0.00138, marks the beginning of the Holocene. This implies a change in the migration patterns of the mammals, ultimately reflecting the inundation of the mainland connection and isolation of the population. The bioapatite Sr isotope data supports published coastline reconstructions placing the time of separation from the mainland to ca. 10-10.5 ka ago. The shift towards more radiogenic Sr isotope values in mid-Holocene subfossil remains after 8 ka ago reflects the rapid rise of the sea level from 10 to 8 ka, resulting in a considerable reduction of the accessible range area on the early Wrangel Island.

Pressure and alloying effects on the metal to insulator transition in NiS2-xSex studied by infrared spectroscopy

The metal to insulator transition in the charge-transfer NiS2-xSex compound has been investigated through infrared reflectivity. Measurements performed by applying pressure to pure NiS2 (lattice contraction) and by Se alloying (lattice expansion) reveal that in both cases an anomalous metallic state is obtained. We find that optical results are not compatible with the linear Se-alloying vs pressure-scaling relation previously established through transport, thus pointing out the substantially different microscopic origin of the two transitions.

Determination of the optically equivalent model in three-dimensional photoelasticity

Any stressed photoelastic medium can be reduced to an optically equivalent model consisting of a linear retarder, with retardation 1 and principal axis at azimuth 1, and a pure rotator of power 2. The paper describes two simple methods to determine these quantities experimentally. Further, a method is described to overcome the problem of rotational effects in scattered-light investigations. This new method makes use of the experimentally determined characteristic parameters

Conformal Field Theory Methods for Variants of Schramm-Loewner Evolutions

This thesis consists of an introduction, four research articles and an appendix. The thesis studies relations between two different approaches to continuum limit of models of two dimensional statistical mechanics at criticality. The approach of conformal field theory (CFT) could be thought of as the algebraic classification of some basic objects in these models. It has been succesfully used by physicists since 1980's. The other approach, Schramm-Loewner evolutions (SLEs), is a recently introduced set of mathematical methods to study random curves or interfaces occurring in the continuum limit of the models. The first and second included articles argue on basis of statistical mechanics what would be a plausible relation between SLEs and conformal field theory. The first article studies multiple SLEs, several random curves simultaneously in a domain. The proposed definition is compatible with a natural commutation requirement suggested by Dubédat. The curves of multiple SLE may form different topological configurations, ``pure geometries''. We conjecture a relation between the topological configurations and CFT concepts of conformal blocks and operator product expansions. Example applications of multiple SLEs include crossing probabilities for percolation and Ising model. The second article studies SLE variants that represent models with boundary conditions implemented by primary fields. The most well known of these, SLE(kappa, rho), is shown to be simple in terms of the Coulomb gas formalism of CFT. In the third article the space of local martingales for variants of SLE is shown to carry a representation of Virasoro algebra. Finding this structure is guided by the relation of SLEs and CFTs in general, but the result is established in a straightforward fashion. This article, too, emphasizes multiple SLEs and proposes a possible way of treating pure geometries in terms of Coulomb gas. The fourth article states results of applications of the Virasoro structure to the open questions of SLE reversibility and duality. Proofs of the stated results are provided in the appendix. The objective is an indirect computation of certain polynomial expected values. Provided that these expected values exist, in generic cases they are shown to possess the desired properties, thus giving support for both reversibility and duality.

Mathematical Aspects of Financial Markets with Frictions

Frictions are factors that hinder trading of securities in financial markets. Typical frictions include limited market depth, transaction costs, lack of infinite divisibility of securities, and taxes. Conventional models used in mathematical finance often gloss over these issues, which affect almost all financial markets, by arguing that the impact of frictions is negligible and, consequently, the frictionless models are valid approximations. This dissertation consists of three research papers, which are related to the study of the validity of such approximations in two distinct modeling problems. Models of price dynamics that are based on diffusion processes, i.e., continuous strong Markov processes, are widely used in the frictionless scenario. The first paper establishes that diffusion models can indeed be understood as approximations of price dynamics in markets with frictions. This is achieved by introducing an agent-based model of a financial market where finitely many agents trade a financial security, the price of which evolves according to price impacts generated by trades. It is shown that, if the number of agents is large, then under certain assumptions the price process of security, which is a pure-jump process, can be approximated by a one-dimensional diffusion process. In a slightly extended model, in which agents may exhibit herd behavior, the approximating diffusion model turns out to be a stochastic volatility model. Finally, it is shown that when agents' tendency to herd is strong, logarithmic returns in the approximating stochastic volatility model are heavy-tailed. The remaining papers are related to no-arbitrage criteria and superhedging in continuous-time option pricing models under small-transaction-cost asymptotics. Guasoni, Rásonyi, and Schachermayer have recently shown that, in such a setting, any financial security admits no arbitrage opportunities and there exist no feasible superhedging strategies for European call and put options written on it, as long as its price process is continuous and has the so-called conditional full support (CFS) property. Motivated by this result, CFS is established for certain stochastic integrals and a subclass of Brownian semistationary processes in the two papers. As a consequence, a wide range of possibly non-Markovian local and stochastic volatility models have the CFS property.

Tannakian Formalism Applied to the Category of Mixed Hodge Structures

Many problems in analysis have been solved using the theory of Hodge structures. P. Deligne started to treat these structures in a categorical way. Following him, we introduce the categories of mixed real and complex Hodge structures. Category of mixed Hodge structures over the field of real or complex numbers is a rigid abelian tensor category, and in fact, a neutral Tannakian category. Therefore it is equivalent to the category of representations of an affine group scheme. The direct sums of pure Hodge structures of different weights over real or complex numbers can be realized as a representation of the torus group, whose complex points is the Cartesian product of two punctured complex planes. Mixed Hodge structures turn out to consist of information of a direct sum of pure Hodge structures of different weights and a nilpotent automorphism. Therefore mixed Hodge structures correspond to the representations of certain semidirect product of a nilpotent group and the torus group acting on it.

A Decentralized Session Management Framework for Heterogeneous Ad-Hoc and Fixed Networks

Wireless technologies are continuously evolving. Second generation cellular networks have gained worldwide acceptance. Wireless LANs are commonly deployed in corporations or university campuses, and their diffusion in public hotspots is growing. Third generation cellular systems are yet to affirm everywhere; still, there is an impressive amount of research ongoing for deploying beyond 3G systems. These new wireless technologies combine the characteristics of WLAN based and cellular networks to provide increased bandwidth. The common direction where all the efforts in wireless technologies are headed is towards an IP-based communication. Telephony services have been the killer application for cellular systems; their evolution to packet-switched networks is a natural path. Effective IP telephony signaling protocols, such as the Session Initiation Protocol (SIP) and the H 323 protocol are needed to establish IP-based telephony sessions. However, IP telephony is just one service example of IP-based communication. IP-based multimedia sessions are expected to become popular and offer a wider range of communication capabilities than pure telephony. In order to conjoin the advances of the future wireless technologies with the potential of IP-based multimedia communication, the next step would be to obtain ubiquitous communication capabilities. According to this vision, people must be able to communicate also when no support from an infrastructured network is available, needed or desired. In order to achieve ubiquitous communication, end devices must integrate all the capabilities necessary for IP-based distributed and decentralized communication. Such capabilities are currently missing. For example, it is not possible to utilize native IP telephony signaling protocols in a totally decentralized way. This dissertation presents a solution for deploying the SIP protocol in a decentralized fashion without support of infrastructure servers. The proposed solution is mainly designed to fit the needs of decentralized mobile environments, and can be applied to small scale ad-hoc networks or also bigger networks with hundreds of nodes. A framework allowing discovery of SIP users in ad-hoc networks and the establishment of SIP sessions among them, in a fully distributed and secure way, is described and evaluated. Security support allows ad-hoc users to authenticate the sender of a message, and to verify the integrity of a received message. The distributed session management framework has been extended in order to achieve interoperability with the Internet, and the native Internet applications. With limited extensions to the SIP protocol, we have designed and experimentally validated a SIP gateway allowing SIP signaling between ad-hoc networks with private addressing space and native SIP applications in the Internet. The design is completed by an application level relay that permits instant messaging sessions to be established in heterogeneous environments. The resulting framework constitutes a flexible and effective approach for the pervasive deployment of real time applications.

Ratio of Diffusion Coefficient to Mobility for Electrons in SF6-Air and Freon-Nitrogen Mixtures

The ratio of diffusion coefficient to mobility (D/¿) for electrons has been measured in SF6-air and freon-nitrogen mixtures for various concentrations of SF6 and freon in the mixtures over the range 140¿ E/p¿ 220 V.cm-1 - torr-1. In SF6-air mixtures, the values of D/¿ were always observed to lie intermediate between the values for the pure gases. However, in freon-nitrogen mixtures, with a small concentration (10 percent) of freon in the mixture, the values of D/¿ are found to lie above the boundaries determined by the pure gases. In this mixture, over the lower E/p range (140 to 190) the electrons appear to lose a large fraction of their energy by the excitation of the complex freon molecules, while at higher E/p values (200 to 240), the excitation and consequent deexcitation of nitrogen molecules and its metastables seem to cause an increased rate of ionization of freon molecules.

Generalised quaternion methods in conformal geometry

A new approach to Penrose's twistor algebra is given. It is based on the use of a generalised quaternion algebra for the translation of statements in projective five-space into equivalent statements in twistor (conformal spinor) space. The formalism leads toSO(4, 2)-covariant formulations of the Pauli-Kofink and Fierz relations among Dirac bilinears, and generalisations of these relations.

Investigations on the preparation, oxidation and reduction reactions of thiophosphoryl fluoride

Pure thiophosphoryl fluoride has been prepared by the fluorination of thiophosphoryl chloride by sodium fluoride in acetonitrile medium. Oxidation of this phosphoryl fluoride by acidified chloramine-T ruptures the phosphorus-sulphur bond and oxidises the sulphur present to the hexavalent state. Anhydrous hydrogen iodide reduces the sulphur to hydrogen sulphide and phosphorus to the trivalent state.