Free-radical polymerisation (FRP) has been one of the most important techniques for producing materials used in a very wide variety of applications and has enhanced the lives of millions of people around the world. However, for many years a number of fundamental questions regarding the key kinetic processes involved in FRP have remained unresolved. In particular, an accurate description of the mechanism for diffusion-controlled bimolecular termination has proven elusive. As a result, conventional modelling tools for FRP have often proven unreliable. The aim of this thesis, therefore, was to accurately study the evolution of the bimolecular termination rate coefficient during free radical polymerisation using a new and more accurate methodology based on ‘controlled/living’ reversible addition-fragmentation chain transfer (RAFT) polymerisation. This was undertaken in order to develop a more precise understanding of bimolecular termination and thereby develop a more reliable modeling approach capable of predicting the rates of reaction and evolution of molecular weight distributions for a wide range of experimental conditions and a wide range of functional monomers. The RAFT-CLD-T (RAFT Chain-Length-Dependent Termination) Method was used to determine accurate values for the conversion and chain-length-dependent termination rate coefficient, kti,i(x), as a function of various parameters. These parameters included the chain size, i, polymer concentration (or conversion, x), chain length size distribution and chain architecture/structure. The accuracy of the RAFT-CLD-T Method was crucial to this work, therefore, an important part of this thesis was devoted to evaluating the reliability of this technique. Below 5 % conversion and above 80 % conversion the method was found to be unreliable due to the effects of chain-length-dependent propagation, high PDI’s and short-long termination. However, between 5 % and 80 % conversion it was found that the method is extremely robust and a series of easy-to-use experimental guidelines were determined for accurately applying the RAFT-CLD-T Method. The effects of chain size, chain size distribution, solution polymer concentration, and matrix architecture were examined for the RAFT-mediated polymerisations of methyl methacrylate (MMA), styrene (STY) and methyl acrylate (MA). It was found that four distinct scaling regimes of termination are observed: (1) a ‘short’ chain dilute solution regime, (2) a ‘long’ chain dilute solution regime, (3) a semi-dilute solution regime and (4) a concentrated solution regime. In dilute polymer solutions, chain-length-dependent power law exponents, ’s, determined during the polymerisation of MMA, STY and MA (where kti,i(x)  i-) indicated that termination follows two major scaling regimes with exponents of approximately ~0.5 to 0.6 for ‘short’ chains and and ~0.12 to 0.16 for ‘long’ chains. Importantly, these exponents are in excellent agreement with theoretical predictions for translational and segmental diffusion-controlled termination, respectively. At increasing polymer concentrations, kti,i(x) falls rapidly coinciding with the onset of the gel effect. By comparing results from the RAFT-mediated polymerisations of MMA, STY, MA, and vinyl acetate (VAc) with theoretical models, we found that the onset of the gel effect coincided closely with the theoretical onset of chain overlap. Considerable uncertainty has plagued the evaluation of this phenomenon, but using a difunctional RAFT agent we showed this uncertainty arises from the influence of broad MWD’s on chain overlap and short-long termination. Finally, critical tests of this theory involving the bimolecular termination of linear radicals in solutions of star polymer confirmed that the gel effect coincided with chain overlap. Beyond the gel effect termination slows enormously, passing through the ‘semi-dilute solution’ regime and into the ‘concentrated solution’. In semi-dilute solution, theoretical predictions based on scaling theory (i.e. the ‘blob’ model) were in excellent agreement with results for the polymerisation of PSTY in linear and star polymer solutions, indicating that the solvent quality diminished both with increasing chain length and through the addition of a star polymer matrix. In concentrated solutions, the chain-length-dependent power law exponent increased linearly with conversion. For example, for MMA the chain length dependence of kt in the gel regime scaled as gel = 1.8x + 0.056, suggesting that reptation alone does not describe termination in the concentrated solution. Values of gel for PSTY, MA, and VAc were in similar agreement, indicating that a mechanism intermediate between unentangled and entangled semi-dilute scaling laws applies in the concentrated solution regime. Interestingly, gel values for these monomers were found to decrease with increasing chain flexibility in the order gel(MMA)> gel(STY)> gel(VAc)> gel(MA), suggesting matrix mobility is rate determining in concentrated solutions. Similarly, gel values were also larger in star polymer solutions, coinciding with decreasing matrix mobility. Thus, although it has been commonly believed that polymer chains diffuse via reptation above the gel effect, these results show that this only occurs for solutions containing rigid and/or highly immobile macromolecules and in very high concentrations. To describe these behaviours, a semi-empirical ‘composite kt model’ was also developed to describe kti,i(x) as a function of i and x up to high conversions. We showed that the model is very simple to implement and accurate for modelling a wide range of functional monomers and experimental conditions. In particular, we showed the method was accurate for modelling RAFT-mediated polymerisations of a very wide range of monomers (MA, MMA, and PSTY) and was even accurate for modelling conventional FRP’s. Thus, the model provides a simple, flexible and accurate method for predicting the rate of reaction and evolution of molecular weight distributions across a range of experimental conditions based on accurate kti,i(x) values.

Free-radical polymerisation (FRP) has been one of the most important techniques for producing materials used in a very wide variety of applications and has enhanced the lives of millions of people around the world. However, for many years a number of fundamental questions regarding the key kinetic processes involved in FRP have remained unresolved. In particular, an accurate description of the mechanism for diffusion-controlled bimolecular termination has proven elusive. As a result, conventional modelling tools for FRP have often proven unreliable. The aim of this thesis, therefore, was to accurately study the evolution of the bimolecular termination rate coefficient during free radical polymerisation using a new and more accurate methodology based on ‘controlled/living’ reversible addition-fragmentation chain transfer (RAFT) polymerisation. This was undertaken in order to develop a more precise understanding of bimolecular termination and thereby develop a more reliable modeling approach capable of predicting the rates of reaction and evolution of molecular weight distributions for a wide range of experimental conditions and a wide range of functional monomers. The RAFT-CLD-T (RAFT Chain-Length-Dependent Termination) Method was used to determine accurate values for the conversion and chain-length-dependent termination rate coefficient, kti,i(x), as a function of various parameters. These parameters included the chain size, i, polymer concentration (or conversion, x), chain length size distribution and chain architecture/structure. The accuracy of the RAFT-CLD-T Method was crucial to this work, therefore, an important part of this thesis was devoted to evaluating the reliability of this technique. Below 5 % conversion and above 80 % conversion the method was found to be unreliable due to the effects of chain-length-dependent propagation, high PDI’s and short-long termination. However, between 5 % and 80 % conversion it was found that the method is extremely robust and a series of easy-to-use experimental guidelines were determined for accurately applying the RAFT-CLD-T Method. The effects of chain size, chain size distribution, solution polymer concentration, and matrix architecture were examined for the RAFT-mediated polymerisations of methyl methacrylate (MMA), styrene (STY) and methyl acrylate (MA). It was found that four distinct scaling regimes of termination are observed: (1) a ‘short’ chain dilute solution regime, (2) a ‘long’ chain dilute solution regime, (3) a semi-dilute solution regime and (4) a concentrated solution regime. In dilute polymer solutions, chain-length-dependent power law exponents, ’s, determined during the polymerisation of MMA, STY and MA (where kti,i(x)  i-) indicated that termination follows two major scaling regimes with exponents of approximately ~0.5 to 0.6 for ‘short’ chains and and ~0.12 to 0.16 for ‘long’ chains. Importantly, these exponents are in excellent agreement with theoretical predictions for translational and segmental diffusion-controlled termination, respectively. At increasing polymer concentrations, kti,i(x) falls rapidly coinciding with the onset of the gel effect. By comparing results from the RAFT-mediated polymerisations of MMA, STY, MA, and vinyl acetate (VAc) with theoretical models, we found that the onset of the gel effect coincided closely with the theoretical onset of chain overlap. Considerable uncertainty has plagued the evaluation of this phenomenon, but using a difunctional RAFT agent we showed this uncertainty arises from the influence of broad MWD’s on chain overlap and short-long termination. Finally, critical tests of this theory involving the bimolecular termination of linear radicals in solutions of star polymer confirmed that the gel effect coincided with chain overlap. Beyond the gel effect termination slows enormously, passing through the ‘semi-dilute solution’ regime and into the ‘concentrated solution’. In semi-dilute solution, theoretical predictions based on scaling theory (i.e. the ‘blob’ model) were in excellent agreement with results for the polymerisation of PSTY in linear and star polymer solutions, indicating that the solvent quality diminished both with increasing chain length and through the addition of a star polymer matrix. In concentrated solutions, the chain-length-dependent power law exponent increased linearly with conversion. For example, for MMA the chain length dependence of kt in the gel regime scaled as gel = 1.8x + 0.056, suggesting that reptation alone does not describe termination in the concentrated solution. Values of gel for PSTY, MA, and VAc were in similar agreement, indicating that a mechanism intermediate between unentangled and entangled semi-dilute scaling laws applies in the concentrated solution regime. Interestingly, gel values for these monomers were found to decrease with increasing chain flexibility in the order gel(MMA)> gel(STY)> gel(VAc)> gel(MA), suggesting matrix mobility is rate determining in concentrated solutions. Similarly, gel values were also larger in star polymer solutions, coinciding with decreasing matrix mobility. Thus, although it has been commonly believed that polymer chains diffuse via reptation above the gel effect, these results show that this only occurs for solutions containing rigid and/or highly immobile macromolecules and in very high concentrations. To describe these behaviours, a semi-empirical ‘composite kt model’ was also developed to describe kti,i(x) as a function of i and x up to high conversions. We showed that the model is very simple to implement and accurate for modelling a wide range of functional monomers and experimental conditions. In particular, we showed the method was accurate for modelling RAFT-mediated polymerisations of a very wide range of monomers (MA, MMA, and PSTY) and was even accurate for modelling conventional FRP’s. Thus, the model provides a simple, flexible and accurate method for predicting the rate of reaction and evolution of molecular weight distributions across a range of experimental conditions based on accurate kti,i(x) values.

The aim of this work was to successfully prepare polymers of N-(2-hydroxypropyl)methacrylamide, (PHPMA) using controlled/"living" free-radical polymerisation technique. For this purpose, atom transfer radical polymerisation (ATRP) and reversible addition-fragmentation (chain) transfer (RAFT) polymerisation were used in preparation of a number of base polymers with the intention of quantitatively converting them into PHPMA. Both methods were applied under varying polymerisation conditions, and the kinetics of the systems investigated. Various rate constants were measured, while computer modelling of the experimental data allowed estimation of other kinetic parameters of interest. Investigations into solvent and ligand effects on the kinetics of ATRP of the activated ester methacryloyloxy succinimide (MAOS) and one of the archetypal methacrylate monomers, methyl methacrylate (MMA) were carried out. The method of RAFT was also employed in polymerisation of MAOS and a number of other monomers in the hope of finding the best synthetic precursor of PHPMA. Polymers of methacryloyl chloride (MAC) and p-nitrophenyl methacrylate (NPMA) were prepared, as well as the polymers of HPMA itself and N-isopropyl methacrylamide. Polymerisation of MMA by RAFT was also attempted in view of adding to current knowledge on the monomer's behaviour and the kinetic characteristics of its RAFT polymerisation. Preparation of PHPMA from PMAOS, PMAC and PNPMA was attempted. Successful preparation of PHPMA from the polymer of the acid chloride was achieved under mild reaction conditions, while displacement of N-hydroxysuccinimide groups of PMAOS resulted in unexpected modification of the polymer under the conditions used. Conversion of PNPMA into PHPMA was not achieved. At this stage these results suggest inadequacy of both PMAOS and PNPMA as reactive polymeric precursors.

The mechanisms by which magnetisation changes occur in magnetic materials may be investigated by a variety of hysteresis measurements. During this study both alternating and rotational hysteresis measurements were used to characterise the mechanisms of magnetisation change in a number of permanent magnet materials. Studies of the time dependence of magnetisation, remanent magnetisations and the dependence of the reversible magnetisation on the irreversible magnetisation were undertaken. These studies revealed that in sintered rare-earth iron magnets the magnetisation change is predominately controlled by domain nucleation, with a lesser contribution from domain wall pinning within the boundary regions of the grains. Similar mechanisms control the magnetisation change in the larger grains of melt-quenched rare-earth iron magnets. In the single domain grains of the melt-quenched materials incoherent rotation mechanisms control the changes of magnetisation. Magnetisation change in MnAlC and sintered AlNiCo was found to be controlled by domain wall pinning within the interior of the grains of the materials. Two devices were constructed for the measurement of rotational hysteresis. The first measures the angular acceleration of a sample set spinning in a magnetic field, from which the rotational hysteresis loss may be determined. The second employs rotating search coils to make direct measurements of the component of magnetisation that contributes to rotational hysteresis loss during the rotation of a sample in a field. Both devices were found to produce data consistent with that in the literature and to be useful for the characterisation of rotational hysteresis in permanent magnet materials. A simple model was used to examine the dependence of rotational hysteresis loss on various material parameters. It was found that the value of the rotational hysteresis integral is dependent on interactions and to a lesser extent distributions in anisotropy. This is contrary to assumptions commonly made in the literature but consistent with published experimental data, which has been reinterpreted. Measurements of rotational hysteresis losses in the materials studied were found to be effected by geometric demagnetisation effects. A method by which such data may be corrected for these effects is proposed. Following correction and consideration of the interactions within the materials, the rotational hysteresis data was found to be consistent with the characterisations performed in linearly alternating fields.

Made available in DSpace on 2014-06-11T19:26:56Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-02Bitstream added on 2014-06-13T18:55:32Z : No. of bitstreams: 1 alves_mo_me_sjrp.pdf: 609574 bytes, checksum: 7280f95db92aacc87fc1116bf82914da (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Neste trabalho apresentamos um estudo dos campos de vetores lineares reversíveis e equivariantes. Tal estudo tem como base a Teoria de Representações de grupos de Lie compactos. Usaremos o fato de que a ascensão de um grupo de Lie compacto pode ser decomposta como soma direta de representações irredutíveis e de acordo com o Lema de Schur tais representações poderão ser de três tipos: R; C ou H. Daremos uma classificação das possíveis estruturas dos sistemas lineares reversíveis equivariantes baseado na teoria de representações citada acima e faremos um estudo dos autovalores para uma classe particular de funções Lreversíveis. Dessa forma temos um cenário bem claro da dinâmica de tais sistemas em cada uma dessas classes. / In this work we present a study of the linear equivariant reversible vector fields. This study is based on the Theory of Representation of compact Lie groups. We use the fact that an action of a compact Lie group can be decomposed as a direct sum of irreducible representations, and according to Schur's Lemma these representations can be only of three types: R; C ou H. We give a classification of the possible structures of the linear equivariant reversible systems based on the Theory of Representations mentioned above and we study of the eigenvalues for a particular classes of Lreversible maps. In this way we have a very clear scenario about the dynamics of such systems in each one of these classes.

BACKGROUND: One in ten sexually active adolescents in the United States become pregnant each year. Significant differences in unintended pregnancy and use of long-acting reversible contraceptive (LARC) methods: the sub-dermal implant, the copper intrauterine device (IUD) and hormonal IUDs, exist between socioeconomic strata as well as ethnic and racial groups. Women using LARC are 20 times less likely to experience a pregnancy than women using short-acting reversible methods. Thus, LARCs present a major opportunity for the prevention of unintended pregnancy. PURPOSE: Characterize contraceptive use, demographics, and behavioral characteristics of a novel population: young women presenting to an urban Pediatric Emergency Department (PED) in order to better understand the contraceptive needs of this population. METHODS: We characterized the current LARC usage. Using an anonymous paper-based questionnaire, we surveyed women ages 16-21 years regardless of chief complaint presenting to our PED regarding their demographics, health care access, sexual history, and history of contraceptive use. We conducted a cross-sectional analysis of demographic characteristics for current LARC and non-LARC users (n=331) using chi-squared for categorical variables and student's t-test for continuous variables. RESULTS: No significant differences were found between women currently using LARC and those not using LARC, however current LARC usage in our population was 15.8%, about three times that documented in the most recent national studies conducted in 2013. CONCLUSION: Current LARC use is particularly high in our urban PED setting. More research is necessary to determine if this is part of a larger national trend or if the early implementation of no-cost contraception in Massachusetts and changes in provider or patient attitudes towards LARC may explain the large observed difference in LARC usage.

Muitas são as características quantitativas que são, significativamente, influenciadas por fatores genéticos, em geral, existem vários genes que colaboram para a variação de uma ou mais características quantitativas. As informações ausentes a respeito dos genótipos nos marcadores moleculares é um problema comum em estudo de mapeamento genético e, por conseguinte, no mapeamento dos locus que controlam estas características fenotípicas (QTL). Os dados que não foram observados ocorrem, principalmente, devido a erros de genotipagem e de marcadores não informativos. Para solucionar este problema foi utilizado o método do modelo oculto de Markov para inferir estes dados. Os métodos de acurácias evidenciaram o sucesso da aplicação desta técnica de imputa- ção. Uma vez imputado, na inferência bayesiana estes dados não serão mais tratados como uma variável aleatória resultando assim, numa redução no espaço paramétrico do modelo. Outra grande dificuldade no mapeamento de QTL se deve ao fato de que não se conhece ao certo a quantidade destes que influenciam uma dada característica, fazendo com que surjam diversos problemas, um deles é a dimensão do espaço paramétrico e, consequentemente, a obtenção da amostra a posteriori. Assim, com o objetivo de contornar este problema foi proposta a utilização do método Monte Carlo via cadeia de Markov com Saltos Reversíveis, uma vez que este permite flutuar, entre cada iteração, modelos com diferentes quantidades de parâmetros. A utilização da abordagem bayesiana permitiu detectar cinco QTL para a característica estudada. Todas as análises foram implementadas no programa estatístico R. / There are many quantitative characteristics which are significantly influenced by genetic factors, in general, there are several genes that contribute to the variation of one or more quantitative trait. The missing information about the genotypes in molecular markers is a common problem in studying genetic mapping and therefore the mapping of loci that control these phenotypic traits (QTL). The data were not observed occur mainly due to errors in genotyping and uninformative markers. To solve this problem the method of occult Markov model to infer this information was used. Techniques accuracies demonstrated the successful application of this technique of imputation. Once allocated, in the Bayesian inference this data will no longer be treated as a random variable thus resulting in a reduction in the parameter space of the model. Another great difficulty in mapping QTL is due to the fact that no one knows exactly the amount of these which influence a given characteristic, so that several problems arise, one of them is dimension of the parameter space and, consequently, obtaining the sample a posterior. Thus, in order to solve this problem using the method via Monte Carlo Markov chain Reversible Jump was proposed, since this allows fluctuate between each iteration, models with different numbers of parameters. The use of the Bayesian approach allowed five QTL detected for the studied trait. All analyzes were implemented in the statistical software R.

This systematic review consolidates and discusses all the advantages and disadvantages of each contraceptive method, organized by mammalian species, with emphasis on reversible immune-contraception, obtained from the international scientific literature. The objective is to deepen the knowledge and elucidate adequate solutions to a serious global problem of wildlife population control. Furthermore, serving as pre-project to the next stage of development of a contraceptive method, economically viable, with better attributes, high effectiveness of the action, better and safer techniques of application, and more importantly, ensure overall health and population genetics. Finalizing this review by offering in a brief and concise manner, an updated understanding of reversible contraceptive methods, organized by methods, taxon, drugs, and associated risks / Esta revisão sistemática, consolida e discuti todas as vantagens e desvantagens de cada método contraceptivo, organizada por espécies de mamíferos, com ênfase em imunocontracepção reversível, obtidos em literatura científica internacional. O objetivo é aprofundar os conhecimentos e elucidar soluções adequadas para o grande problema mundial do controle das populações de animais silvestres. Além disto, pode servir como pré-projeto para a próxima fase de desenvolvimento de um método contraceptivo economicamente viável, com melhores atributos, alta eficácia da ação, técnicas de aplicação melhores e mais seguras, e mais importante, garantir saúde geral e genética das populações. Finalizando, esta revisão oferecer de forma breve e concisa, uma atualização sobre o conhecimento de métodos contraceptivos reversíveis, organizada por métodos, táxon, fármacos, e riscos associados

The reversible logic has promising applications in emerging computing paradigms, such as quantum computing, quantum dot cellular automata, optical computing, etc. In reversible logic gates, there is a unique one-to-one mapping between the inputs and outputs. To generate a useful gate function, the reversible gates require some constant ancillary inputs called ancilla inputs. Also to maintain the reversibility of the circuits some additional unused outputs are required that are referred to as the garbage outputs. The number of ancilla inputs, the number of garbage outputs and quantum cost plays an important role in the evaluation of reversible circuits. Thus minimizing these parameters are important for designing an efficient reversible circuit. Reversible circuits are of highest interest in optical computing, quantum dot cellular automata and quantum computing. The quantum gates perform an elementary unitary operation on one, two or more two-state quantum systems called qubits. Any unitary operation is reversible in nature, and hence, quantum networks are also reversible, to conclude the quantum computers must be built from reversible logic components. The main contribution of this dissertation is the design exploration and application of reversible circuits in emerging nanotechnologies. The emerging technologies explored in this work are 1) Optical quantum computing 2) Quantum computing. The first contribution of this dissertation is Mach-Zehnder interferometer based design of all optical reversible binary adder. The all optical reversible adder design is based on two new optical reversible gates referred as optical reversible gate I (ORG-I) and optical reversible gate II (ORG-II) and the existing all optical Feynman gate. The two new reversible gates ORG-I and ORGI-II have been proposed and can implement a reversible adder with a reduced optical cost which is equal to the number of MZI switches required, less propagation delay, and with zero overhead in terms of number of ancilla inputs and the garbage outputs. The proposed all optical reversible adder design based on the ORG-I and ORG-II reversible gates are compared and shown to be better than the other existing designs of reversible adder proposed in the non-optical domain in terms of number of MZI switches, delay, the number of ancilla inputs and the garbage outputs. The proposed all optical reversible adder will be a key component of an all optical reversible arithmetic logical unit (ALU), that is a quite essential component in a wide variety of optical signal processing applications. In the existing literature, the NAND logic based implementation is the only known implementation available for reversible gates and its functions. There is a lack of research in the direction of NOR logic based implementation of reversible gates and functions. The second contribution of this dissertation is the design of NOR logic based n-input and n-output reversible gates, one of which can be efficiently mapped into optical computing using the Mach-Zehnder interferometer (MZI), while the other can be mapped efficiently in optical computing using the linear optical quantum gates. The proposed reversible NOR gates work as a corresponding NOR counterpart of NAND logic based Toffoli gates. The proposed optical reversible NOR logic gates can implement the reversible boolean logic functions with less number of linear optical quantum logic gates with reduced optical cost and propagation delay compared to the implementation using existing optical reversible NAND gates. It is illustrated that an optical reversible gate library having both optical Toffoli gate and the proposed optical reversible NOR gate is superior compared to the library containing only the optical Toffoli gate: (i) in terms of number of linear optical quantum gates when implemented using linear optical quantum computing (LOQC), (ii) in terms of optical cost and delay when implemented using the Mach-Zehnder interferometer. The third contribution of this dissertation is a binary tree-based design methodology for a NxN reversible multiplier. The proposed binary tree-based design methodology for a NxN reversible multiplier performs the addition of partial products in parallel using the reversible ripple adders with zero ancilla bit and zero garbage bit; thereby, minimizing the number of ancilla and garbage bits used in the design. The proposed design methodology shows improvements in terms of number of ancilla inputs and garbage outputs compared to all the existing reversible multiplier designs. The methodology is also extended to the design of NxN reversible signed multiplier based on modified Baugh-Wooley multiplication methodology.

This diploma thesis is dedicated to a design of a reversing turbo-compressor. The thesis is divided into several parts. The introductory part includes the relevant theory and categorization of turbomachines. The second part describes the storage system the machine is designed for. A separate chapter is devoted to other examples of possible use of this machine. The next chapter provides a detail description of modes and individual parts of the machine. The most comprehensive chapter is then devoted to the design of the compressor, turbine calculation and design of integrated gearbox. The thesis also includes an annex, which contains the technical documentation.