Magma-crust interaction in magma reservoirs and conduits is a crucial process during magma evolution and ascent. This interaction is recorded by crustal xenoliths that frequently show partial melting, inflation and disintegration textures. Frothy xenoliths are widespread in volcanic deposits from all types of geological settings and indicate crustal gas liberation. To unravel the observed phenomena of frothy xenolith formation we experimentally simulated the behaviour of crustal lithologies in volcanic conduits. We subjected various sedimentary lithologies to elevated temperature (maximum 916 °C) and pressure (maximum 160 MPa) in closed-system autoclaves. Experimental conditions were held constant between 24h and 5 days. Controlled decompression to atmospheric pressure then simulated xenolith ascent. Pressure release was a function of temperature decline in our setup. Temperature lapse rate proceeded exponentially; the mean rate during the first 30 minutes was 17.8 ˚C/min and the mean decompression rate during the same interval was 3.0 MPa/min, eventually reaching room temperature after approximately 5.5 hours of slow cooling. The experimental products have been analysed for internal textures by synchrotron X-ray μ-CT at a resolution of 3.4 – 9 microns/pixel. This method permits visualisation and quantification of vesicle volumes, -networks and-connectivity in 3D without destroying the sample. Experimental products closely reproduced textures of natural frothy xenoliths in 3D and define anevolutionary sequence from partial melting to gas exsolution and bubble nucleation that eventually leads to the development of three-dimensional bubble networks. Experimental P-T-t conditions and especially rock lithology proved decisive for degassing behaviour and ensuing bubble nucleation during decompression. Progressive bubble nucleation leads to subsequent bubble coalescence to form interconnected bubble networks. This, in turn, enables efficient gas liberation and release. Our results attest to significant potential of even very common crustal rock types to release volatiles and develop interconnected bubble networks upon heating and decompression in magmatic systems. Crustal volatile input from xenoliths affects magma rheology and may drive magmas to sudden explosive eruptions. Our experiments offer insight into the mechanism of how such crustal volatile liberation is accomplished.

GSR ou Gunshot Residues são partículas microscópicas de resíduos provenientes da descarga de uma arma de fogo e que, em geral, ficam depositadas pelo corpo do atirador e aos arredores da cena do crime. Este trabalho tem como objetivo empregar as técnicas de PIXE (Particle-Induced X-ray Emission) convencional e -PIXE na análise da munição e GSR gerados por disparo de arma de fogo, utilizando munição de fabricação brasileira. O estudo foi dividido em duas etapas, sendo que na primeira etapa foi utilizada a técnica PIXE no estudo da composição elementar de todos os componentes (estojo, espoleta, pólvora, projétil e camisa) de dois cartuchos distintos virgens, ou seja, antes do disparo com a arma de fogo. Na segunda etapa foram efetuados os ensaios de disparo com arma de fogo, utilizando os mesmos tipos de cartuchos analisados na primeira etapa. As partículas foram coletadas e analisadas por μ-PIXE. As amostras foram irradiadas com feixes de prótons, empregando diferentes parâmetros (energia e corrente), o que depende das amostras em estudo e da técnica utilizada. Para tal fim, foi utilizado o acelerador Tandetron (modelo TN-4130-HC) disponível no Laboratório de Implantação Iônica (IF-UFRGS). Dois diferentes tipos de munição foram analisadas: CHOG e EXPO +P+. Os elementos presentes nas amostras de espoleta de ambos os tipos de munição são o alumínio, antimônio, bário e chumbo, e em menores quantidades cobre, zinco e ferro (invólucro), além de níquel no caso da munição EXPO +P+. Ambos os estojos são constituídos por cobre e zinco, apresentando adicionalmente uma grande quantidade de níquel e um pouco de ferro na munição EXPO +P+. No projétil da munição CHOG os elementos predominantes são chumbo e antimônio, além de apresentar alumínio e ferro em menores quantidades. Na munição EXPO +P+ o projétil também é constituído por chumbo, antimônio e alumínio, mas o ferro é substituído pelo cobre. As amostras de pólvora de ambos os tipos são compostas por alumínio, silício, enxofre, potássio, cálcio, titânio, cromo, níquel, ferro, cobre e zinco, e essas quantidades foram diferentes para cada tipo de munição. A pólvora CHOG apresentou bário e chumbo adicionalmente. Por último, a camisa do projétil da munição EXPO +P+ apresentou cobre, zinco, níquel, chumbo e ferro. Estes resultados são em maioria condizentes com as especificações do fabricante, a Companhia Brasileira de Cartuchos – CBC. Para a coleta das amostras de GSR, foram efetuados disparos em um anteparo de papel, onde foi fixada uma fita microporosa da marca Missner. Neste estudo, foram utilizados os dois tipos de munição analisados por PIXE. Nos dois tipos de partículas coletadas, foi possível correlacionar a presença de Ba, Pb e Sb na mesma partícula, sendo inequivocamente caracterizadas como partículas de GSR. No entanto, os resíduos apresentaram diferentes características e particularidades. Em partículas do tipo CHOG as principais características observadas foram a diferença de tamanhos, homogeneidade (exceto em alguns pontos) e ausência de formato característico. Nas partículas do tipo EXPO +P+ as características se repetem, exceto no formato que, em geral, se apresentou esférico. Comparando os resultados de PIXE e μ-PIXE, observou-se que há relação entre a munição utilizada e os resíduos de disparo produzidos, mas, no entanto as quantidades dos elementos na munição antes e depois do disparo não possuem correlação, o que pode ser explicado pela distância entre o atirador e o anteparo. Os elementos bário, chumbo e antimônio precisam de altas temperaturas para vaporizar, e não alcançariam efetivamente o anteparo a uma distância de um metro, causando grande variabilidade de concentrações entre as partículas. / GSR stands for Gunshot Residues wich are microscopic particles stemming from the discharge of a firearm. These particles are deposited on the body of the shooter and on the vicinity of the crime scene. The aim of this work is to characterize two Brazilian ammunitions and their respective GSRs using PIXE (Particle-Induced X-ray Emission) and -PIXE. Initially, the components (case, primer, gunpowder, projectile and jacket) of two pristine cartridges were analyzed by PIXE technique. Then, shooting sessions were carried out with the same cartridges. In this case, the GSR were collected for -PIXE analysis. The samples were irradiated with protons with different energies and beam currents depending on the sample under study and the technique used for analysis. To that end, a Tandetron accelerator (model TN-4130-HC) from the Ion Implantation Laboratory (IF-UFRGS) was used. The elements present in the primer for both ammunitions were aluminum, antimony, barium and lead. Other trace elements like copper, zinc and iron were present as well. Nickel was also detected in EXPO +P+ samples. The cases were made of copper and zinc. For the EXPO +P+, other elements like nickel and, to a lesser degree, iron were present as well. The bullet from CHOG ammunition was mainly composed by lead and antimony with traces of iron and aluminum. On the other hand, bullets from EXPO +P+ were characterized by lead, antimony and aluminum while iron is replaced by copper. The gunpowder from both ammunitions were characterized by aluminum, silicon, sulfur, potassium, calcium, titanium, chromium, nickel, iron, copper and zinc, and their amounts were different for each type of ammunition. In addition, the CHOG type gunpowder presented barium and lead. Finally, the jacket of the EXPO +P+ bullet has considerable amounts of copper, zinc, nickel, lead and iron. These results are compatible with the datasheet provided by the Companhia Brasileira de Cartuchos. For the study of the GSR, shootings were performed using the afore mentioned ammunitions on a paper screen with Missner tape for the collection of the ejected particles. Elements like Ba, Pb and Sb were found in the particles, thus characterizing the GSR. The CHOG particles were characterized by a large distribution of sizes and distinct shapes. On the other hand, EXPO +P+ particles were distinct due to its round shape. Comparing the results of PIXE and μ-PIXE, it was observed that there is a correlation between ammunition used and the GSR produced, but nevertheless the amounts of the elements before and after the ammunition shot does not have correlation, which can be explained the distance between the shooter and the target. The elements barium, lead and antimony require high temperatures to vaporize and not effectively reach the target at a distance of one meter, causing large variability in concentrations between particles.

GSR ou Gunshot Residues são partículas microscópicas de resíduos provenientes da descarga de uma arma de fogo e que, em geral, ficam depositadas pelo corpo do atirador e aos arredores da cena do crime. Este trabalho tem como objetivo empregar as técnicas de PIXE (Particle-Induced X-ray Emission) convencional e -PIXE na análise da munição e GSR gerados por disparo de arma de fogo, utilizando munição de fabricação brasileira. O estudo foi dividido em duas etapas, sendo que na primeira etapa foi utilizada a técnica PIXE no estudo da composição elementar de todos os componentes (estojo, espoleta, pólvora, projétil e camisa) de dois cartuchos distintos virgens, ou seja, antes do disparo com a arma de fogo. Na segunda etapa foram efetuados os ensaios de disparo com arma de fogo, utilizando os mesmos tipos de cartuchos analisados na primeira etapa. As partículas foram coletadas e analisadas por μ-PIXE. As amostras foram irradiadas com feixes de prótons, empregando diferentes parâmetros (energia e corrente), o que depende das amostras em estudo e da técnica utilizada. Para tal fim, foi utilizado o acelerador Tandetron (modelo TN-4130-HC) disponível no Laboratório de Implantação Iônica (IF-UFRGS). Dois diferentes tipos de munição foram analisadas: CHOG e EXPO +P+. Os elementos presentes nas amostras de espoleta de ambos os tipos de munição são o alumínio, antimônio, bário e chumbo, e em menores quantidades cobre, zinco e ferro (invólucro), além de níquel no caso da munição EXPO +P+. Ambos os estojos são constituídos por cobre e zinco, apresentando adicionalmente uma grande quantidade de níquel e um pouco de ferro na munição EXPO +P+. No projétil da munição CHOG os elementos predominantes são chumbo e antimônio, além de apresentar alumínio e ferro em menores quantidades. Na munição EXPO +P+ o projétil também é constituído por chumbo, antimônio e alumínio, mas o ferro é substituído pelo cobre. As amostras de pólvora de ambos os tipos são compostas por alumínio, silício, enxofre, potássio, cálcio, titânio, cromo, níquel, ferro, cobre e zinco, e essas quantidades foram diferentes para cada tipo de munição. A pólvora CHOG apresentou bário e chumbo adicionalmente. Por último, a camisa do projétil da munição EXPO +P+ apresentou cobre, zinco, níquel, chumbo e ferro. Estes resultados são em maioria condizentes com as especificações do fabricante, a Companhia Brasileira de Cartuchos – CBC. Para a coleta das amostras de GSR, foram efetuados disparos em um anteparo de papel, onde foi fixada uma fita microporosa da marca Missner. Neste estudo, foram utilizados os dois tipos de munição analisados por PIXE. Nos dois tipos de partículas coletadas, foi possível correlacionar a presença de Ba, Pb e Sb na mesma partícula, sendo inequivocamente caracterizadas como partículas de GSR. No entanto, os resíduos apresentaram diferentes características e particularidades. Em partículas do tipo CHOG as principais características observadas foram a diferença de tamanhos, homogeneidade (exceto em alguns pontos) e ausência de formato característico. Nas partículas do tipo EXPO +P+ as características se repetem, exceto no formato que, em geral, se apresentou esférico. Comparando os resultados de PIXE e μ-PIXE, observou-se que há relação entre a munição utilizada e os resíduos de disparo produzidos, mas, no entanto as quantidades dos elementos na munição antes e depois do disparo não possuem correlação, o que pode ser explicado pela distância entre o atirador e o anteparo. Os elementos bário, chumbo e antimônio precisam de altas temperaturas para vaporizar, e não alcançariam efetivamente o anteparo a uma distância de um metro, causando grande variabilidade de concentrações entre as partículas. / GSR stands for Gunshot Residues wich are microscopic particles stemming from the discharge of a firearm. These particles are deposited on the body of the shooter and on the vicinity of the crime scene. The aim of this work is to characterize two Brazilian ammunitions and their respective GSRs using PIXE (Particle-Induced X-ray Emission) and -PIXE. Initially, the components (case, primer, gunpowder, projectile and jacket) of two pristine cartridges were analyzed by PIXE technique. Then, shooting sessions were carried out with the same cartridges. In this case, the GSR were collected for -PIXE analysis. The samples were irradiated with protons with different energies and beam currents depending on the sample under study and the technique used for analysis. To that end, a Tandetron accelerator (model TN-4130-HC) from the Ion Implantation Laboratory (IF-UFRGS) was used. The elements present in the primer for both ammunitions were aluminum, antimony, barium and lead. Other trace elements like copper, zinc and iron were present as well. Nickel was also detected in EXPO +P+ samples. The cases were made of copper and zinc. For the EXPO +P+, other elements like nickel and, to a lesser degree, iron were present as well. The bullet from CHOG ammunition was mainly composed by lead and antimony with traces of iron and aluminum. On the other hand, bullets from EXPO +P+ were characterized by lead, antimony and aluminum while iron is replaced by copper. The gunpowder from both ammunitions were characterized by aluminum, silicon, sulfur, potassium, calcium, titanium, chromium, nickel, iron, copper and zinc, and their amounts were different for each type of ammunition. In addition, the CHOG type gunpowder presented barium and lead. Finally, the jacket of the EXPO +P+ bullet has considerable amounts of copper, zinc, nickel, lead and iron. These results are compatible with the datasheet provided by the Companhia Brasileira de Cartuchos. For the study of the GSR, shootings were performed using the afore mentioned ammunitions on a paper screen with Missner tape for the collection of the ejected particles. Elements like Ba, Pb and Sb were found in the particles, thus characterizing the GSR. The CHOG particles were characterized by a large distribution of sizes and distinct shapes. On the other hand, EXPO +P+ particles were distinct due to its round shape. Comparing the results of PIXE and μ-PIXE, it was observed that there is a correlation between ammunition used and the GSR produced, but nevertheless the amounts of the elements before and after the ammunition shot does not have correlation, which can be explained the distance between the shooter and the target. The elements barium, lead and antimony require high temperatures to vaporize and not effectively reach the target at a distance of one meter, causing large variability in concentrations between particles.

GSR ou Gunshot Residues são partículas microscópicas de resíduos provenientes da descarga de uma arma de fogo e que, em geral, ficam depositadas pelo corpo do atirador e aos arredores da cena do crime. Este trabalho tem como objetivo empregar as técnicas de PIXE (Particle-Induced X-ray Emission) convencional e -PIXE na análise da munição e GSR gerados por disparo de arma de fogo, utilizando munição de fabricação brasileira. O estudo foi dividido em duas etapas, sendo que na primeira etapa foi utilizada a técnica PIXE no estudo da composição elementar de todos os componentes (estojo, espoleta, pólvora, projétil e camisa) de dois cartuchos distintos virgens, ou seja, antes do disparo com a arma de fogo. Na segunda etapa foram efetuados os ensaios de disparo com arma de fogo, utilizando os mesmos tipos de cartuchos analisados na primeira etapa. As partículas foram coletadas e analisadas por μ-PIXE. As amostras foram irradiadas com feixes de prótons, empregando diferentes parâmetros (energia e corrente), o que depende das amostras em estudo e da técnica utilizada. Para tal fim, foi utilizado o acelerador Tandetron (modelo TN-4130-HC) disponível no Laboratório de Implantação Iônica (IF-UFRGS). Dois diferentes tipos de munição foram analisadas: CHOG e EXPO +P+. Os elementos presentes nas amostras de espoleta de ambos os tipos de munição são o alumínio, antimônio, bário e chumbo, e em menores quantidades cobre, zinco e ferro (invólucro), além de níquel no caso da munição EXPO +P+. Ambos os estojos são constituídos por cobre e zinco, apresentando adicionalmente uma grande quantidade de níquel e um pouco de ferro na munição EXPO +P+. No projétil da munição CHOG os elementos predominantes são chumbo e antimônio, além de apresentar alumínio e ferro em menores quantidades. Na munição EXPO +P+ o projétil também é constituído por chumbo, antimônio e alumínio, mas o ferro é substituído pelo cobre. As amostras de pólvora de ambos os tipos são compostas por alumínio, silício, enxofre, potássio, cálcio, titânio, cromo, níquel, ferro, cobre e zinco, e essas quantidades foram diferentes para cada tipo de munição. A pólvora CHOG apresentou bário e chumbo adicionalmente. Por último, a camisa do projétil da munição EXPO +P+ apresentou cobre, zinco, níquel, chumbo e ferro. Estes resultados são em maioria condizentes com as especificações do fabricante, a Companhia Brasileira de Cartuchos – CBC. Para a coleta das amostras de GSR, foram efetuados disparos em um anteparo de papel, onde foi fixada uma fita microporosa da marca Missner. Neste estudo, foram utilizados os dois tipos de munição analisados por PIXE. Nos dois tipos de partículas coletadas, foi possível correlacionar a presença de Ba, Pb e Sb na mesma partícula, sendo inequivocamente caracterizadas como partículas de GSR. No entanto, os resíduos apresentaram diferentes características e particularidades. Em partículas do tipo CHOG as principais características observadas foram a diferença de tamanhos, homogeneidade (exceto em alguns pontos) e ausência de formato característico. Nas partículas do tipo EXPO +P+ as características se repetem, exceto no formato que, em geral, se apresentou esférico. Comparando os resultados de PIXE e μ-PIXE, observou-se que há relação entre a munição utilizada e os resíduos de disparo produzidos, mas, no entanto as quantidades dos elementos na munição antes e depois do disparo não possuem correlação, o que pode ser explicado pela distância entre o atirador e o anteparo. Os elementos bário, chumbo e antimônio precisam de altas temperaturas para vaporizar, e não alcançariam efetivamente o anteparo a uma distância de um metro, causando grande variabilidade de concentrações entre as partículas. / GSR stands for Gunshot Residues wich are microscopic particles stemming from the discharge of a firearm. These particles are deposited on the body of the shooter and on the vicinity of the crime scene. The aim of this work is to characterize two Brazilian ammunitions and their respective GSRs using PIXE (Particle-Induced X-ray Emission) and -PIXE. Initially, the components (case, primer, gunpowder, projectile and jacket) of two pristine cartridges were analyzed by PIXE technique. Then, shooting sessions were carried out with the same cartridges. In this case, the GSR were collected for -PIXE analysis. The samples were irradiated with protons with different energies and beam currents depending on the sample under study and the technique used for analysis. To that end, a Tandetron accelerator (model TN-4130-HC) from the Ion Implantation Laboratory (IF-UFRGS) was used. The elements present in the primer for both ammunitions were aluminum, antimony, barium and lead. Other trace elements like copper, zinc and iron were present as well. Nickel was also detected in EXPO +P+ samples. The cases were made of copper and zinc. For the EXPO +P+, other elements like nickel and, to a lesser degree, iron were present as well. The bullet from CHOG ammunition was mainly composed by lead and antimony with traces of iron and aluminum. On the other hand, bullets from EXPO +P+ were characterized by lead, antimony and aluminum while iron is replaced by copper. The gunpowder from both ammunitions were characterized by aluminum, silicon, sulfur, potassium, calcium, titanium, chromium, nickel, iron, copper and zinc, and their amounts were different for each type of ammunition. In addition, the CHOG type gunpowder presented barium and lead. Finally, the jacket of the EXPO +P+ bullet has considerable amounts of copper, zinc, nickel, lead and iron. These results are compatible with the datasheet provided by the Companhia Brasileira de Cartuchos. For the study of the GSR, shootings were performed using the afore mentioned ammunitions on a paper screen with Missner tape for the collection of the ejected particles. Elements like Ba, Pb and Sb were found in the particles, thus characterizing the GSR. The CHOG particles were characterized by a large distribution of sizes and distinct shapes. On the other hand, EXPO +P+ particles were distinct due to its round shape. Comparing the results of PIXE and μ-PIXE, it was observed that there is a correlation between ammunition used and the GSR produced, but nevertheless the amounts of the elements before and after the ammunition shot does not have correlation, which can be explained the distance between the shooter and the target. The elements barium, lead and antimony require high temperatures to vaporize and not effectively reach the target at a distance of one meter, causing large variability in concentrations between particles.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17961号 / 工博第3809号 / 新制||工||1583(附属図書館) / 30791 / 京都大学大学院工学研究科マイクロエンジニアリング専攻 / (主査)教授 小寺 秀俊, 教授 中部 主敬, 教授 岩田 博夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Cochlear implants are electronic devices intended for restoring hearing to the profoundly deaf. Unfortunately the degree of restored hearing varies greatly between subjects. To investigate some of the mechanisms that determine this variability, mathematical models of the auditory system are used. The level of detail that these models incorporate varies greatly. The present study describes the development of a method to create high detail, subject specific cochlea models. μ-CT scans and photomicrographs were used to obtain the morphology and histology of a specific guinea pig cochlea. A 3D model was constructed from this data and the finite element method was used to determine the potential distribution inside the cochlea. The potential distribution was calculated for different stimulus protocols applied to different modelled electrodes. A neuron model was then used to obtain neural excitation profiles. The modelled excitation profiles were compared to data from literature and it was found that this model is valid and can be used as a tool in electric hearing research. The model output was also compared to brainstem response data from the specific subject to assess the degree to which this model can predict brain stem data from a specific subject. Possible improvements to the model were also discussed. / Dissertation (MEng)--University of Pretoria, 2009. / Electrical, Electronic and Computer Engineering / unrestricted

The solution of stiff systems of Ordinary Differential Equations (ODEs), that typically arise after spatial discretization of many important evolutionary Partial Differential Equations (PDEs), constitutes a topic of wide interest in numerical analysis. A prominent way to numerically integrate such systems involves using exponential integrators. In general, these kinds of schemes do not require the solution of (non)linear systems but rather the action of the matrix exponential and of some specific exponential-like functions (known in the literature as φ-functions). In this PhD thesis we aim at presenting efficient tensor-based tools to approximate such actions, both from a theoretical and from a practical point of view, when the problem has an underlying Kronecker sum structure. Moreover, we investigate the application of exponential integrators to compute numerical solutions of important equations in various fields, such as plasma physics, mean-field optimal control and computational chemistry. In any case, we provide several numerical examples and we perform extensive simulations, eventually exploiting modern hardware architectures such as multi-core Central Processing Units (CPUs) and Graphic Processing Units (GPUs). The results globally show the effectiveness and the superiority of the different approaches proposed.

High-valent iron-oxo intermediates play central roles as active oxidants in enzymatic and synthetic catalytic oxidations. Many transition metal catalysts are designed for biomimetic studies of the predominant oxidation catalysts in Nature, the cytochrome P450 enzymes. In this work, a new photochemical method to generate high-valent iron-oxo porphyrin models was discovered. As controlled by the electronic nature of porphyrin ligands, iron(IV)-oxo porphyrin radical cations (Compound I model) and iron(IV)-oxo porphyrin derivatives (Compound II model) were produced. These observations indicate that the photochemical reactions involve a heterolytic cleavage of O-Br in precursors to give a putative iron(V)-oxo intermediate, which might relax to Compound I through electron transfer from porphyrin to the iron or undergo rapid comproportionation reaction with residual iron(III) to afford the Compound II derivative. Furthermore, visible light photolysis of bis-porphyrins-dimanganese(III)-μ-oxo complexes, [MnIII(Por)]2O, was studied in three porphyrin systems. Direct conversion of manganese(III)-μ-oxo dimers to manganese(IV)-oxo porphyrins [MnIV(Por)(O)] and manganese(III) products was observed in benzene solution upon light irradiation. The spectral signature of [MnIV(Por)(O)] was further confirmed by production of the same species in the reported reaction of the [MnIII(Por)Cl] with PhI(OAc)2. Continuous irradiation of bis-porphyrins-dimanganese(III)-μ-oxo complexes in the presence of pyridine or triphenylphospine gave rise to the formation of [MnII(Por)(Py)] or [MnII(Por)(PPh3)], which are stable to be detected. A photo-disproportionation mechanism similar to that for bis-porphyrins-diiron(III)-μ-oxo complex was proposed to explain above photochemical behaviors of bis-porphyrins-dimanganese(III)-μ-oxo complexes. With iodobenzene diacetate [PhI(OAc)2] as the oxygen source, manganese(III) porphyrin complexes exhibit remarkable catalytic activity towards the selective oxidation of alkenes and activated hydrocarbons. Conspicuous is the fact that the readily soluble PhI(OAc)2 in the presence of a small amount of water is more efficient oxygen source than the commonly used PhIO under same conditions. High selectivity for epoxides and excellent catalytic efficiency with up to 10,000 Turnovers (TONs) were achieved in alkene epoxidations. A manganese(IV)-oxo porphyrin was observed in the oxidation of the manganese(III) porphyrin and PhI(OAc)2. However, catalytic competition and Hammett studies suggested that the more reactive manganese(V)-oxo intermediate was favored as the premier active oxidant, even it is too short-lived to be detected in the catalytic reaction.

Σκοπός της παρούσας διπλωματικής εργασίας είναι η μελέτη του αντίστροφου καθορισμού πηγής (inverse source localization problem) και του ρυθμού μ (mu). Έχοντας ως δεδομένο το σήμα του ΗΕΓ γίνεται προσπάθεια µέσω της εφαρμογής της μεθόδου Ανάλυσης Ανεξάρτητων συνιστωσών (ICA) να προσδιοριστούν οι συνιστώσες οι οποίες σχετίζονται με τις περιοχές του εγκεφάλου που ενεργοποιούνται από την κίνηση των χεριών. Με βάση τη λειτουργία της αισθητηριοκινητικής περιοχής του εγκεφάλου και τις ιδιότητες του ρυθμού μ, γίνεται μια μελέτη πάνω στις συνιστώσες που προκύπτουν από την ICA τόσο σε δεδομένα από πραγματική κίνηση, όσο και σε δεδομένα από νοερή κίνηση, καθώς και στην εφαρμογή που μπορεί να υπάρχει σε συστήματα Διεπαφής Εγκεφάλου – Υπολογιστή. / The subject of this diploma thesis is the study of the inverse source localization problem and the mu rhythm. Performing Independent Component Analysis (ICA) on EEG data, we try to specify the components that are related to the brain areas activated by hand movement. By focusing on the function of the somatosensory brain area and the properties or mu rhythm, we study the components resulting from Independent Component Analysis on data of both real and imaginary movement, as well as the possible implementations on Brain – Computer Interface systems.

This in vitro study was conducted to evaluate the influence of surface treatments on the bond strength between an yttrium-stabilized tetragonal zirconia polycrystal (Y-TZP) ceramic and resin cement. For this purpose, 120 Y-TZP blocks (IPS e.max® ZirCAD in inLab®) were randomly distributed into 12 experimental groups (n = 10), according to six surface treatment strategies and two storage conditions (24 hours post cementation and after 60 days in water and 10,000 thermocicles): AS (as sintered, no treatment); TBS (tribochemical silica coating followed by silanization); AAP (particle abrasion with 50 μm aluminum oxide followed by application of Monobond®Plus); FS (fusion sputtering); SN (5 nm SiO2 nanofilm deposition and silanization) and FSSN (FS + SN). The Y-TZP blocks were embedded in acrylic resin and cylinders of resin cement (Ø=0.96 mm x 1 mm in height) (RelyX ARC) were built up on the ceramic surface. After the storage, the specimens were submitted to microshear test (μSBS) (1 mm/min) in a universal testing machine. After testing, the surfaces were analyzed with a stereomicroscope and scanning electron microscope (SEM) in order to categorize the failure modes. One additional specimen per surface treatment strategy was analyzed by X-ray diffraction, for phases content, and by SEM for micromorphology observation. Bond strength values were statistically analyzed by Kruskal-Wallis and Mann Whitney tests for surface treatments (p <0.001) and aging factor (p <0.05). In both storage conditions, TBS and AAP provided higher bond strength values, followed by FSSN, FS and SN groups. The aging negatively influenced the results, with one exception for the FS. An increase in the amount of monoclinic phase was observed in the abraded groups. Sandblasting of alumina particles followed by application of a primer with MPA is as effective as the tribochemical treatment combined with silane for pretreatment of the Y-TZP surface, with respect to the bond strength to the composite. / No presente trabalho objetivou-se avaliar, in vitro, o efeito de diferentes tratamentos de superfície na resistência de união de uma cerâmica à base de zircônia policristalina tetragonal estabilizada por ítria (Y-TZP) a um cimento resinoso. Para tanto, 120 blocos de Y-TZP (IPS e.max® ZirCAD for inLab®, Ivoclar-Vivadent, Schaan, Liechtenstein) foram distribuídos randomicamente em 12 grupos experimentais (n=10), conforme 6 estratégias de tratamento de superfície e 2 condições de envelhecimento (24 horas e após o envelhecimento em água e termociclagem): AS (sem tratamento); TBS (jateamento de partículas de alumina revestidas por sílica e silanização); AAP (abrasão com partículas de alumina seguida da aplicação de primer universal); FS (pulverização de micropartículas de zircônia na superfície livre da Y-TZP e após, fusão por sinterização); SN (deposição de nanofilme de sílica com 5 nm) e FSSN (FS seguido de SN). Os blocos de Y-TZP foram embutidos em resina acrílica e microcilindros de cimento resinoso (0,96 mm de diâmetro; 1 mm de altura) (RelyX ARC) foram confeccionados na superfície cerâmica. Após o armazenamento, os testes de microcisalhamento foram conduzidos a uma velocidade de 1 mm/min, em máquina de ensaios universal. Após o teste, as superfícies foram analisadas com estereomicroscópio e microscópio eletrônico de varredura (MEV) para caracterização das falhas. Em um espécime adicional, também foi conduzida análise de fases do material por difração de raios-X e caracterização da micromorfologia de superfície em MEV. Os valores de resistência de união foram submetidos aos testes estatísticos Kruskal-Wallis e Mann Whitney para os tratamentos testados (p<0.001) e para o fator envelhecimento (p<0.05). Em ambas as condições de envelhecimento, TBS e AAP proporcionaram os maiores valores de resistência adesiva, seguidos dos grupos FSSN, FS e SN. O envelhecimento influenciou negativamente os resultados, com única exceção para o FS. A difractometria revelou aumento de conteúdo monoclínico nos grupos jateados. FS não alterou a percentagem de fase monoclínica. O jateamento de partículas de alumina seguido da aplicação de um primer com MPA apresentou-se tão efetivo quanto o tratamento triboquímico aliado ao silano, para o pré-tratamento da superfície da Y-TZP, no que diz respeito à resistência de união ao compósito.