Requirements of high performing engine oil are today necessary since the development of new machinery with modern standardsis a cutting edge technology demanding highly optimized components. One way of increasing the lubricating properties of engineoil is through the addition of antioxidants. Antioxidants included in lubricants have a number of functions, one being buffering theinorganic acids sulphuric acid and nitric acid.A novel method expected to lower the hydrogen ion concentration in acidified engine oil was evaluated in this thesis. Thecapability of four different types of cation exchangers to serve as complements for buffering additives in heavy vehicle engineswas assessed. Two cation exchangers were weak and two were strong. The analysis techniques used to evaluate what effect thecation exchangers have on engine oil were standard test method ASTM D4739, for measurements of the total base number (TBN),and inductively coupled plasma – atomic emission spectroscopy (ICP-AES). With ASTM D4739 it was found that weak cationexchangers give positive results with respect to the ability to decrease the hydrogen ion concentration in acidified engine oil.However, after begin subjected to strong cation exchangers, ASTM D4739 indicated that the hydrogen ion concentration in theacidified engine oil remains the same or increases.With additional literature studies of a variety of cation exchangers currently on the market, further optimization of the cationexchanging material could likely be achieved. In addition, the preparation method used during the evaluation of the cationexchangers should be optimized to give more reliable results.

This thesis establishes methods to locally and effciently detect the fluorescence from photonic crystals (PCs) in dependence on wavelength and direction. These are applied to three dimensional (3D) PCs grown by vertical deposition of polystyrene beads. The experiments allow conclusions about the local 3D structure of a sample, about defects in its volume and about spatial structural variations. They thus provide more information than typical spectroscopy measurements that average over large areas and methods that only image the surface structure like scanning electron microscopy. A focused laser is used to excite emitters in the sample only locally. The fluorescence is then collected by a microscope objective. Every point in this objective’s back focal plane (BFP) corresponds to a certain direction. This property is utilized in two ways. When observing a small spectral range of the emission in the BFP, stop bands appear as intensity minima since they hinder the emission into the corresponding directions. Thus, back focal plane imaging (BFPI) allows to visualize stop bands of many directions at the same time. The detected patterns permit to find the in-plane and out-of-plane orientation of the PC lattice and to conclude on the presence of stacking faults. Spatial variations of the structure are observed on a length scale of a few micrometers. The depth of the stop band is reduced at sample positions, where structural changes occur. In back focal plane spectroscopy (BFPS), a slit selects light from certain points in the BFP, which is spectrally dispersed subsequently. This allows to record spectra from many directions simultaneously. From them, a lattice compression along the sample normal of about 4% is found. Small deformations are also observed for other directions. Scattering at defects redistributes the emission. This increases the detected intensity compared to homogeneous media at some stop band edges in a broad spectral range for samples thicker than the scattering mean free path. Thinner samples show a narrow enhancement due to an increase in the fractional density of optical states and thus in emission. BFPI and BFPS are also used to observe the growth of PCs from drying droplets. The experiments show that the beads initially form a non-close packed lattice. This causes stress as the lattice constant decreases, which is released by cracking of the PCs.

Graphite Furnace Atomic Absorption Spectroscopy (GFAA) and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) are two primary means of analyzing metals at the elemental level. Both techniques are widely accepted as tools for basic research. Each technique is performed differently and has its own distinct advantages as well as disadvantages. The choice of which technique to employ is determined by the needs of the analysis and the limitations of the instrumental technique.The idea to merge the two techniques was originallydeveloped by the research group of Dr. Michael W. Blades of the University of British Columbia, Vancouver, in 1989, who successfully demonstrated a "mini" plasma within a graphite furnace. The goal of the research was to design a device that would combine the advantages of both techniques and hopefully eliminate or minimize the unfavorable characteristics of each technique.The sustaining of a "mini" plasma has been demonstrated by this group. Although the end result was similar to that of Blades' group, the method of achieving the plasma was such that the "new" instrument could easily be mounted onto the furnace via a small Interface/Power Coupling device. The advantages of this system are: existing GFAA instruments can be used; modification of the furnace and RF supply is minimal; RF electronics can be remotely located; removal of the interface device is quickly achieved; and sample introduction, through the use of an autosampler, can be facilitated with small modification.Background spectra were acquired using helium, argon, and a mixture of argon/helium. It was found that all the plasmas have highly structured backgrounds and demonstrate the potential for many analysis regions. Two methods of sample introduction were used in acquiring the line emission of magnesium: injection through the sample inlet port to the furnace and end window injection. Inlet port injection suffers from a loss of sensitivity, when compared to end cap injection, but is more easily performed. / Department of Chemistry

The analysis of metals is now a major application area for ICP-AES, however, the technique suffers from both spectral and non-spectral interferences. This thesis details the application of univariate and multivariate calibration methods for the prediction of Pt, Pd, and Rh in acid-digested and of Au, Ag and Pd in fusion-digested autocatalyst samples. Of all the univariate calibration methods investigated matrix matching proved the most accurate method with relative root mean square errors (RRMSEs) for Pt, Pd and Rh of 2.4, 3.7, and 2.4 % for a series of synihelic lest solutions, and 12.0, 2.4, and 8.0 % for autocatalyst samples. In comparison, the multivariate calibration method (PLSl) yielded average relative errors for Pt, Pd, and RJi of 5.8, 3.0, and 3.5 % in the test solutions, and 32.0, 7.5, and 75.0 % in the autocatalyst samples. A variable selection procedure has been developed enabling multivariate models to be built using large parts of the atomic emission spectrum. The first stage identified and removed wavelengths whose PLS regression coefficients were equal to zero. The second stage ranked the remaining wavelengths according to their PLS regression coefficient and estimated standard error ratio. The algorithms were applied to the emission spectra for the determination of Pt, Pd and Rh in a synthetic matrix. For independent test samples variable selection gave RRMSEs of 5.3, 2.5 and 1.7 % for Pt, Pd and Rh respectively compared with 8.3, 7.0 and 3.1 % when using integrated atomic emission lines. Variable selection was then applied for the prediction of Au, Ag and Pd in independent test fusion digests. This resulted in RRMSEs of 74.2, 8.8 and 12.2 % for Au, Ag and Pd respectively which were comparable to those obtained using a more traditional univariate calibration approach. A preliminary study has shown that calibration drift can be corrected using Piecewise Direct Standardisation (PDS). The application of PDS to synthetic test samples analysed 10 days apart resulted in RRMSEs of 4.14, 3.03 and 1.88%, compared to 73.04, 44.39 and 28.06 % without correction, for Pt, Pd, and Rh respectively.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23883号 / 工博第4970号 / 新制||工||1776(附属図書館) / 京都大学大学院工学研究科機械理工学専攻 / (主査)教授 蓮尾 昌裕, 教授 鈴木 基史, 教授 江利口 浩二 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Στα πλαίσια της παρούσας διπλωματικής εργασίας μελετήθηκε, σχεδιάστηκε και κατασκευάστηκε ένα σύστημα ελέγχου ενός φασματοσκοπίου εκπομπής υψηλής φασματικής ανάλυσης. Η συσκευή αυτή, γνωστή και ως μονοχρωμάτορας, χρησιμοποιήθηκε για την καταγραφή φασμάτων εκπομπής από μία εκκένωση αίγλης σε διάκενο ακίδα-πλάκα σε συνθήκες χαμηλής πίεσης και θερμοκρασίας. Ο μονοχρωμάτορας χρησιμοποιεί ένα διάφραγμα περίθλασης που αναλύει μια πολυχρωματική δέσμη που προσπίπτει σε αυτό, στα επιμέρους μήκη κύματος Ο έλεγχος του συνόλου των λειτουργιών του συστήματος καθώς και η καταγραφή των φασμάτων πραγματοποιείται με τη χρήση λογισμικού που αναπτύχθηκε υπό την πλατφόρμα Labview. Στα πλαίσια αυτής της εργασίας υλοποιήθηκε: Η σύνδεση της συσκευής οδήγησης του βηματικού κινητήρα που περιστρέφει το διάφραγμα με κατάλληλο τροφοδοτικό. Η ενίσχυση των σημάτων ελέγχου της συσκευής οδήγησης. Η ενίσχυση και καταγραφή του ρεύματος του φωτοπολλαπλασιαστή που καταγράφει τη φωτεινή δραστηριότητα. Η βαθμονόμηση του μονοχρωμάτορα. Η ανάπτυξη λογισμικού, φιλικού προς τον χρήστη, με το οποίο ελέγχεται ο μονοχρωμάτορας, καταγράφεται το φάσμα και αποθηκεύεται σε αρχείο για περαιτέρω επεξεργασία. Η συγκέντρωση του φωτός που εκπέμπεται από την εκκένωση και η οδήγησή του στην είσοδο του μονοχρωμάτορα με τη χρήση κατάλληλης οπτικής διάταξης. Η καταγραφή φασμάτων του παραγόμενου πλάσματος της εκκένωσης κατά μήκος του διακένου. Η μελέτη και ανάλυση των καταγεγραμμένων φασμάτων. / The main purpose of this thesis was to construct a control system for a high precision spectrometer. Using this spectrometer, also known as monochromator, spectra was recorded from a low temperature – low pressure, pin to plate, glow discharge. The monochromator uses a diffraction grating to separate spatially a polychromatic beam of light available at its input. The stepper motor control, along with the recording of spectra, is being conducted by suitable software developed under the Labview platform. Among the challenges of the thesis was to: Αssemble a stepper motor controller which rotates the diffraction grating with a suitable power supply. Αmplify the control signals of the controller. Αmplify the photomultiplier signals which records the luminous intensity. Calibrate the monochromator. Develop a user-friendly software which can control the monochromator, record spectra and export a file with the recorded spectra for further use. Concentrate the emitted light of the discharge and guide it to the monochromator's input slit, using a UV lens and an optical fiber. Capture emitted spectra of the produced plasma, at different positions along the pin to plate gap. Analyze the recorded spectra.

Made available in DSpace on 2014-12-17T14:06:56Z (GMT). No. of bitstreams: 1 DaniloCB_DISSERT.pdf: 3100682 bytes, checksum: ca6553081fbf48a3fd486b3f20d01cc2 (MD5) Previous issue date: 2011-06-09 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Discs were grade II cp Ti oxynitride by plasma of Ar - N2 - O2 using different proportions of individual gases. These ratios were established from analysis of optical emission spectroscopy (OES) of plasma species. The proportions that resulted in species whose spectra showed an abrupt change of light intensity were chosen for this study. Nanohardness tests revealed that there was a correlation between the intensity of N2 + species with the hardness, because the treatments where they had a higher intensity, obtained a higher value nanohardness, although the crystalline phases have remained unchanged. With respect to topography, it was observed that in general, the surface roughness is related to the intensities of plasma species, because they may have different values depending on the behavior of the species. Images obtained by optical microscopy revealed a surface with grains of different colors to optical reflectance showed a peak of reflection in the red area. Measures the contact angle and surface tension showed hydrophilic properties and hydrophilic with little variation of polar and dispersive components of surface tension / Discos de tit?nio cp grau II foram oxinitretados por plasma de Ar - N2 - O2 usando diferentes propor??es de gases individuais. Essas propor??es foram estabelecidas a partir de an?lises de espectroscopia de emiss?o ?ptica (OES) das esp?cies do plasma. As propor??es que resultaram em espectros cujas esp?cies apresentaram varia??o abrupta de intensidade luminosa foram escolhidas para o presente trabalho. Os ensaios de nanodureza revelaram que houve uma rela??o entre a intensidade da esp?cie N2 + com a dureza, pois para os tratamentos onde estas apresentaram maior intensidade, obteve-se maior valor de nanodureza, embora as fases cristalinas tenham se mantido inalteradas. Com rela??o ?s topografias, observou-se que de um modo geral, a rugosidade superficial est? relacionada com as intensidades das esp?cies do plasma, pois estas podem apresentar valores diferentes dependendo do comportamento das esp?cies. Imagens obtidas por microscopia ?ptica revelaram uma superf?cie com gr?os de diferentes cores e a reflet?ncia ?ptica mostrou um pico m?ximo de reflex?o na regi?o do vermelho. As medidas de ?ngulo de contato e tens?o mostraram superf?cies com propriedades hidrof?licas e pouco hidrof?licas com varia??o das componentes polar e dispersiva da tens?o superficial

Made available in DSpace on 2014-12-17T14:07:10Z (GMT). No. of bitstreams: 1 IgorON_DISSERT.pdf: 2261728 bytes, checksum: ec2c0dd089b3f051427a0e42ea972424 (MD5) Previous issue date: 2011-12-09 / The technique of surface coating using magnetron sputtering is one of the most widely used in the surface engineering, for its versatility in obtaining different films as well as in the micro / nanometric thickness control. Among the various process parameters, those related to the active species of the plasma are of the most fundamental importance in the mechanism and kinetics of deposition. In order to identify the active species of the plasma, parameters such as gas flow, pressure and density of electric power were varied during titanium coating on glass substrate. By flowing argon gas of 10, 20, 30, 40 and 50 sccm (cubic centimeters per minute) for each gas flow a sequential scan of the electric current of 0.10, 0.20, 0.30, 0.40 , 0.50 A. The maximum value of 0.50 A was chosen based both on literature data and on limitations of the equipment. The monitoring of plasma species present during the deposition was carried out in situ by the technique of optical emission spectroscopy (OES) through the spectrometer Ocean Optics USB2000 Series. For this purpose, an apparatus was developed to adapt the OES inside the plasma reactor to stay positioned closest to the target. The radiations emitted by the species were detected by an optical fiber placed behind the glass substrate and their intensities as a function of wavelength were, displayed on a monitor screen. The acquisition time for each condition of the plain parameters was related to the minima of spectral lines intensities due to the film formed on the substrate. The intensities of different emission lines of argon and titanium were then analyzed as a function of time, to determine the active species and estimate the thickness of the deposited films. After the deposition, the coated glasses thin films were characterized by optical transmittance through an infrared laser. It was found that the thickness and deposition rate determined by in situ analysis were consistent with the results obtained by laser transmittance / t?cnica de revestimento superficial utilizando magnetron sputtering ? uma das mais utilizadas pela engenharia de superf?cie, pela sua versatilidade na obten??o de diferentes filmes bem como no controle micro/nanom?trico de sua espessura. Dentre os v?rios par?metros do processo, aqueles relacionados com as esp?cies ativas do plasma s?o de fundamental import?ncia no mecanismo e cin?tica da deposi??o. Com o objetivo de identificar as esp?cies ativas do plasma, par?metros como fluxo de g?s, press?o de trabalho e densidade de pot?ncia el?trica foram variados durante o revestimento de tit?nio em substrato de vidro. Foi utilizado arg?nio com fluxos de 10; 20; 30; 40 e 50 sccm (cent?metro c?bico por minuto) e para cada fluxo de g?s uma varredura sequencial da corrente el?trica de 0,10; 0,20; 0,30; 0,40; 0,50A (amp?res). O valor de m?ximo de 0,50A foi escolhido com base em dados da literatura e limita??es do equipamento. O monitoramento das esp?cies do plasma presentes durante a deposi??o foi realizado "in situ", pela t?cnica de espectroscopia de emiss?o ?ptica (EEO) atrav?s do espectr?metro USB2000 Series da Ocean Optics. Para isso um aparato foi desenvolvido para adaptar o EEO dentro do reator de plasma de maneira que ficasse posicionado o mais pr?ximo poss?vel do alvo. As radia??es emitidas pelas esp?cies foram detectadas atrav?s de uma fibra ?ptica colocada por tr?s do substrato de vidro e suas intensidades, em fun??o do comprimento de onda, foram exibidas na tela de um monitor. O tempo de aquisi??o para cada condi??o de par?metro do plasma foi aquele em que a intensidade espectral deca?a para zero, devido ao filme formado no substrato. As intensidades de diferentes linhas de emiss?o de arg?nio e de tit?nio foram ent?o analisadas em fun??o do tempo, para determinar as esp?cies ativas e estimar a espessura dos filmes depositados. Ap?s a deposi??o, os filmes finos que revestiram os vidros foram caracterizados por transmit?ncia optica, atrav?s de um laser no infravermelho. Verificou-se que os valores da espessura e da taxa de deposi??o s?o determinada pela an?lise "in situ", foram coerentes com os resultados obtidos atraves da transmit?ncia por laser

Made available in DSpace on 2014-10-09T12:47:21Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:36Z (GMT). No. of bitstreams: 1 08714.pdf: 5593309 bytes, checksum: 07a3421e8c97a3073c8119f90a38d4ac (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Les décharges plasma dans la vapeur d’eau sont d’un grand intérêt pour de nombreuses applications potentielles, telles que le traitement biomédical, la production d’hydrogène ou la combustion assistée par plasma. Cette thèse propose une caractérisation expérimentale détaillée de l’effet thermique et chimique des décharges non-thermique nanosecondes répétitives pulsées (NRP) à la pression atmosphérique dans la vapeur d’eau pure. Un réacteur a été conçu pour fonctionner avec la vapeur d’eau préchauffée à 400-500 K. Les conditions opératoires retenues sont un débit de 300 g/h à 500 K et une décharge avec une énergie moyenne de 20 à 100 W, en régime Spark. Différents diagnostics ont été développés afin de déterminer les produits de cette décharge en termes d’espèces intermédiaires, de densité électronique et des produits stables. La concentration des produits de réaction stables (H2 et O2) et leurs débits respectifs ont été mesurés par chromatographie en phase gazeuse. Une valeur maximale de 0,85 g-H2/kWh a été obtenue. La densité électronique a été mesurée par spectroscopie d’émission optique (OES) résolue en temps grâce à l’élargissement par effet Stark des raies (H, H et O). La densité électronique maximale mesurée est 2X1018 cm-3 pendant l’impulsion. La température du gaz a été mesurée lors de la décharge de 20 ns par OES ainsi que entre deux décharges (100 us) par fluorescence induite par laser du radical OH (OH-PLIF) à deux couleurs. L’élévation maximale de la température est de 950 K après l’impulsion, et la température décroît ensuite de façon exponentielle avec un temps de décroissance caractéristique de 5 us. La densité relative du radical OH a été mesurée par OH-PLIF, révélant la durée de vie relativement longue de OH avec un temps de décroissance d’environ 50 us. En utilisant un modèle cinétique 0-D, la densité absolue OH à la fin de l’impulsion a été estimée à 400 plus ou moins 200 ppm. Les résultats obtenus ont permis d’éclairer les mécanismes sous-jacents à la génération de décharges NRP en régime Spark dans la vapeur d’eau pure à basse température. / Plasma discharges in water vapor are of great interest for a variety of potential applications, such as biomedical treatment, hydrogen production, or plasma assisted combustion. This thesis proposes a detailed experimental characterization of the thermal and chemical effects of non thermal discharge, particularly Nanosecond Repetitively Pulsed (NRP) discharges at atmospheric pressure in pure water vapor. A reactor has been designed to operate with water vapor preheated at 400-500 K. We investigated the various discharge regimes and the operating conditions for each regime. The selected operating conditions are a flow rate of 300 g/h at 500 K. The discharge has an average energy from 20 to 100 W in the spark regime. Various diagnostics have been developed in order to infer the products of this discharge in terms of intermediate species, electrons, and stable products. The concentration of the reaction products (H2 and O2) and their respective flow rates were measured using gas chromatography. A maximal value of 0.85 g- H2/kWh was obtained. The electron number density has been measured using time-resolved optical emission spectroscopy (OES) via Stark-broadened lines (H, H and O). The maximum measured electron density is 2X1018 cm-3 during the pulse, and a slow recombination process was observed. The gas temperature was measured during the 20-ns discharge by OES as well as between two discharges (100 us) by two-color OH-Planar Laser Induced Fluorescence (OH-PLIF). The maximum temperature elevation is 950 K after the pulse ; the temperature then decays exponentially with a characteristic time of 5 us. Between two successive discharges, the relative density of the OH radical was measured by OH-PLIF. An interesting result is the relatively long-lived nature of OH, with a 1/e decay time of about 50 us. Using a 0D-chemical kinetics model, the absolute OH density at the end of the pulse was estimated to 400 more or less 200 ppm. These results provide useful information to better understand the mechanisms underlying the generation of NRP spark discharges in low temperature pure water vapor.