Dissertations / Theses on the topic 'Solid phase content'

The thesis presents the evaluation of polysulfone sorbents for solid phase extraction (SPE) and the development of colorimetric probes for pesticides analysis in water. Through electrospraying and electrospinning techniques, different morphologies of sorbents (particles, beaded fibers and bead-free fibers) were fabricated. The sorbents were morphologically characterized by scanning electron microscopy. Adsorption capacities of sorbents were evaluated by conducting recoveries studies for model pesticides; atrazine, chlorpyrifos and DDT using batch and column SPE modes. Better recovery results were achieved by employing the batch mode of fibers, as values ranged from 98 to 105percent. Further sorbent evaluation was conducted using breakthrough experiments and static experiments. The breakthrough studies indicated that 1700 μL was the sample volume that could be percolated with no breakthrough of the analyte that correspond to a concentration of 150 mg/g of sorbent that can be extracted without any loss of analyte. From static studies, quantities of each model compound adsorbed into the fiber at the equilibrium time were evaluated. The adsorbed atrazine was 65, chlorpyrifos 250 and DDT 400 mg/g of sorbent. Kinetic studies suggested retention mechanism following pseudo first and second order model observed by high correlation coefficients (> 0. 96), demonstrating the fiber affinity to retain both polar and non-polar compounds opening a possibility to be used as sorbent for sample preparation of different classes of pesticides in water. For the second part of the study simple strategies for colorimetric sensing based on silver nanoparticles and polivinylpyrrolidone capped nanoparticles were developed, respectively for atrazine and chlorpyrifos detection. The limits of detection of the methods were 3.32 and 0.88 mg/L for atrazine and chlorpyrifos respectively. The applicability of the probe in real samples was demonstrated by the recoveries studies of tap water varying from 94 to 104 percent. The versatility of the probe was demonstrated by affording a simple, rapid and selective detection of atrazine and chlorpyrifos in the presence of other pesticides by direct analysis without employing any sample handling steps. Attempt to incorporate the probes in a solid support was achieved by using nylon 6 as solid support polymer proving to be fast and useful for on-site detection.

The emission of trace metals (TMs) into boreal forest regions of the northern hemisphere is an important environmental issue due to their potential detrimental impacts on these sensitive ecosystems. One of the foremost factors controlling metal cycling is the chemistry of the overlying organic forest floor of the forest soil. In this thesis we examine the chemistry of forest floor horizons of podzolic soils. Our goal is to improve our ability to predict the partitioning of metals between the soil solid and solution phases.
We developed a standard protocol to produce solutions that resemble lysimeter solutions from podzolic soils using air-dried samples. We hypothesized that the stabilization point of the electrical conductivity (EC) of the soil solution is indicative of the point in which soluble salts and organic material precipitated during sampling and storage are removed from the soil particle surfaces. Solutions produced by leaching the soils, once the EC of wash solutions had stabilized, were comparable to lysimeter solutions from the area where samples were collected with respect to the concentrations of divalent cations, pH, EC and dissolved organic carbon (DOC). The applicability of this procedure to trace metal partitioning in forest floors was explored. Laboratory extractions produced partition coefficients (log Kd) similar to observed lysimeter solutions ranging from 3.4 to 3.9 for Cd, 3.4 to 3.9 for Cu, 3.4 to 4.1 for Ni, 4.1 to 5.2 for Pb and 3.2 to 3.5 for Zn. According to a semi-mechanistic regression model based on observed lysimeter concentrations, the metal concentrations in solution were appropriate relative to known factors that influence metal partitioning in soils: pH, the concentrations of total metals and DOC.
While chemical characteristics of soils have been consistently observed to play important roles in the partitioning and toxicity of metals we wished to place the importance of the chemical characteristics of soil on mobility and toxicity in context. We interpreted field data that had been collected from transects established with distance from two point source emitters in Rouyn PQ, and Sudbury ON. Canada find developed equations that predict dissolved metal concentrations from total metal concentrations, soil pH, soil organic matter (SOM), and DOC contents. We integrated these equations into a simple box model that calculates changes in the concentration of metals in the organic and upper mineral horizons and includes a loop for vegetative return of metals to the forest floor.

is is a study of the relationship between structure, mechanical properties and relaxing behavior of the polypropylene. The structure was evaluated by the quantity the solid phase content (SPC). This was defined as mathematical result of free induction decay (FID) signal from pulsed 1H-NMR. The solid phase content is a quite new structural parameter representing the quantity for description of semi-crystalline polymers. Whereas pulsed 1H-NMR is non-destructive, accurate and repeatable, it becomes a unique tool for a description of mechanical, structural, physical-mechanical changes of polypropylene within the time and temperature. Particularly, this method registers the small changes in the time-dependant shipments during secondary crystallization with small structure changes.

The interaction of a bubble with solid surfaces, hydrophobic and hydrophilic, was investigated. When a bubble approaches towards a solid surface, a thin liquid film forms between them. The liquid in the film drains until an instability forms and film ruptures resulting in a three phase contact (TPC). Following rupture, the TPC line spreads on the solid surface. In the present study, glycerol-water solutions with varying percentages of water were used to investigate the effect of viscosity. Experiments were carried out with varying bubble size. The rupture and TPC line movement were recorded by high-speed digital video camera. The dependence of the TPC line movement on different parameters was investigated. The experimental results were compared with the existing theories for the TPC line movement. An empirical equation was developed to predict the TPC line movement. Formation or rupturing of the intervening film in case of a hydrophilic surfaces, which were glass surface cleaned by six cleaning techniques, was investigated. It was shown that a stable film forms for acid or alkali cleaning.

Les composites Cu-Cr sont couramment utilisés comme matériaux de contact électrique pour ampoules à vide des disjoncteurs de moyenne tension. Pourtant très répandu, le frittage en phase solide de ces matériaux a été relativement peu étudié. L’optimisation du procédé passe par la compréhension des mécanismes de frittage. Cette étude est focalisée sur deux aspects importants du frittage : les processus d’oxydo-réduction liés aux oxydes de surfaces des poudres et la compétition entre mécanismes de densification et de gonflement au cours du frittage.L’oxydo-réduction a été étudiée par analyse thermogravimétrique couplée à différentes techniques de spectroscopie d’abord sur les matériaux purs puis sur les composites. Des analyses des interfaces par des coupes réalisées au FIB ont permis de préciser la localisation de l’oxyde dans les matériaux frittés. Un transfert d’oxygène a lieu entre les poudres de cuivre et de chrome. L’intensité de ce transfert dépend de la nature réductrice de l’atmosphère utilisée.La densification a été analysée par dilatométrie sur les matériaux purs et sur les composites. Ces analyses ont été appuyées par des observations microstructurales, notamment par tomographie des rayons X. L’effet des paramètres du procédé (atmosphère, vitesse de chauffage, poudres…) a été étudié. Les résultats montrent le lien entre la désoxydation des poudres de cuivre et le frittage. Un phénomène de gonflement du cuivre seul s’explique par le dégazage du cuivre à haute température lors de la fermeture des pores. Ce gonflement n’a pas lieu dans les composites Cu-Cr car le chrome retarde la fermeture des pores et piège les gaz émis par le cuivre en formant l’oxyde Cr2O3. L’atmosphère de frittage, la morphologie et la taille des poudres de chrome influent sur la densification. Le frittage sous vide permet de réduire la porosité. Une morphologie sphérique des particules de chrome limite l’effet inhibiteur de celui-ci sur la densification. Pour de faibles tailles de particules, le chrome participe à la densification, ce qui permet de mieux densifier le matériau. Ces résultats ouvrent des voies d’optimisation du procédé de frittage des matériaux.Les matériaux élaborés ont été testés dans leurs conditions d’utilisation, c'est-à-dire lors de coupures sur court-circuit en ampoule à vide. Ces essais ont montré l’intérêt de réduire la quantité d’oxyde de chrome et ont permis de déterminer l’effet des impuretés rencontrées usuellement sur les poudres de cuivre et de chrome
Cu-Cr composites are commonly used as contact materials for medium voltage circuit breakers vacuum bottles. Solid state sintering process of Cu-Cr composites is widespread but has been relatively little studied. Optimizing the process requires understanding the sintering mechanisms. This study was focused on two important aspects of sintering: the redox reactions associated to oxides on the powder surface and the competition between densification and swelling mechanisms during sintering.The redox reactions were studied by thermogravimetric analysis coupled to various spectroscopic techniques, first on isolated Cu and Cr, then on Cu-Cr composites. Interfaces analyses obtained by FIB clarified the location of the oxide inside the sintered materials. Oxygen transfer takes place between copper and chromium powders. This phenomenon strongly depends on the reducing character of the sintering atmosphere.Densification was analyzed by dilatometry on Cu, Cr and Cu-Cr composites. This analysis was supported by microstructural observations, including X-ray tomography .The effect of process parameters (atmosphere, heating rate, powders ...) was studied. The results show the relationship between sintering and copper oxide reduction. The swelling phenomenon of copper compacts is explained by high temperature degassing of copper during pore closure. This swelling does not occur in Cu-Cr composites as chromium delays pore closing and entraps the gases released by copper. Sintering atmosphere, chromium morphology and chromium particle size affect densification. Vacuum sintering reduces porosity. Chromium particles with spherical shape limit its inhibiting effect on densification. For small particle sizes, chromium participates to densification, leading to better densification of the material. These results open the route for optimizing the sintering of Cu-Cr composites.Cu-Cr composites were tested for short circuit performance in vacuum interrupters. The result of these tests showed the importance of reducing the chromium oxide amount. The effect of impurities commonly encountered on the powders copper and chromium powders was also determined

Cette thèse traite de la modélisation du frittage à l’échelle du Volume Élémentaire Représentatif de la pastille de matériau. L’objectif est de développer des outils numériquesde compréhension des phénomènes physiques mis en jeu lors du frittage. Le domaine d’application ciblé est la fabrication du combustible nucléaire. Une approche multi-Échelle a été mise en oeuvre. Dans un premier temps une modélisation à l’échelle d’un empilement, basée sur la méthode des Éléments Discrets, a été adoptée. Différentes études utilisant cette approche ont été proposées dans la littérature ces dernières années. Tous ces travaux utilisent une méthode discrète explicite. Si certains résultats ont pu être validés expérimentalement,une des limites vient de l’utilisation des méthodes explicites dontle pas de temps critique est très petit. Afin d’augmenter le pas de temps, la masse des particules y est augmentée artificiellement de plusieurs ordres de grandeur. Or,il a été démontré que cette pratique conduit, dans certains cas, à une diminution du réarrangement des particules au sein de l’empilement. Dans cette thèse, une méthode Éléments Discrets implicite appelée Dynamique des Contacts a été adaptée au frittage. Elle permet l’utilisation d’un pas de temps très supérieur à celui des méthodes discrètes explicites et ne nécessite pas d’augmenter artificiellement la massedes particules. La comparaison entre la Dynamique des Contacts et la Méthode des Éléments Discrets explicite montre que notre approche conduit à une représentation plus fidèle du réarrangement. Une validation expérimentale par Microtomographie X ainsi qu’une étude paramétrique sur le frittage des poudres bidispersés sont également présentées pour montrer les possibilités de l’approche discrète appliquée au frittage.La seconde partie est consacrée à une modélisation à l’échelle de deux particules parla méthode des Éléments Finis. Ce modèle repose sur une approche mécanique et vise à représenter de façon plus précise le comportement de deux particules en contact. Les diffusions au joint de grains, en surface et en volume peuvent être représentées. Pour le moment, seules les diffusions en surface et au joint de grains ont été étudiées. Si certaines optimisations restent nécessaires pour que le code soit fonctionnel, plusieurs aspects apparaissent déjà déterminants, comme la courbure de la surface à proximité du joint de grains. A l’avenir, le modèle Dynamique des Contacts du frittage pourra être complété etamélioré grâce aux éléments apportés par le modèle mécanique à l’échelle du grain
This thesis deals with the simulation of the sintering of nuclear fuel on a pellet scale. The goal is to develop numerical tools which can contribute to a better understandingof the physical phenomena involved in the sintering process. Hence, a multi scale approach is proposed. First of all, a Discrete Element model is introduced. It aims at modeling the motion of particles on a Representative Elementary Volume scale using an original Discrete Element Method. The latter is a Non Smooth Method called Contact Dynamics. Recently, there have been numerous papers about the simulation of sintering using Discrete Element Method. As far as we know, all these papers use smooth methods. Different studies show that the results match well experimental data. However, some limits come from the fact that smooth methods use an explicit scheme which needsvery small time steps. In order to obtain an acceptable time step, the mass of particles have to be dramatically increased. The Non Smooth Contact Dynamics uses an implicit scheme, thus time steps can be much larger without scaling up the mass of particles. The comparison between smooth and non smooth approaches shows thatour method leads to a more realistic representation of rearrangement. An experimental validation using synchrotron X-Ray microtomography is then presented, followedby a parametric study on the sintering of bimodal powders that aims at showing the capacity of this model.The second part presents a mechanical model on the sub-Granular scale, using a Finite Element method. This targets a better understanding of the behavior of twograins in contact. The model is currently being developped but the first results already show that some parameters like the shape of the surface of the neck are very sensitive.In the future, the Non smooth Contact Dynamics model of sintering may be improvedusing the results obtained by the sub-Granular scale mechanical model

Els aminoàcids biarílics es troben en una àmplia varietat de pèptids naturals amb important activitat biològica. Concretament, les arilhistidines formen part de les aciculitines, pèptids amb activitat citotòxica i antifúngica, La reacció de Suzuki-Miyaura és el mètode més versàtil per obtenir biarils assimètrics, encara que, fins el moment, no s'havia aplicat per a l'arilació de l'imidazole de la histidina. L'objectiu general d'aquesta tesi fou demostrar que es podia arilar l'imidazole de la histidina en fase sòlida mitjançant una reacció de Suzuki-Miyaura. En primer lloc, es sintetitzaren 4(5)-metil-5(4)-fenilimidazole i 4(5)-metil-5(4)-(2-metoxifenil)imidazole a través de l'acoblament creuat entre un N-benzilbromoimidazole i el corresponent àcid arilborònic. Posteriorment, s'arilaren 5-bromohistidines utilitzant diversos àcids arilborònics mitjançant una reacció de Suzuki-Miyaura assistida per irradiació micrones, tant en dissolució com en fase sòlida. I finalment, mitjançant aquesta metodología, es sintetitzaren pèptids antimicrobians contenint 5-arilhistidines actius contra bacteris gram-negatius responsables d'importants malalties en plantes com el foc bacterià.
Biaryl amino acids are present in a great variety of natural peptides which display important biological activities. In particular, arylhistidines naturally occur in cytotoxic and antifungal marine peptides, aciculitins. The Suzuki-Miyaura cross-coupling is the most versatile method to obtain unsymmetrical biaryls. Up to now, it had not been applied to the arylation of the histidine imidazole ring. The main objective of this thesis was to demonstrate that a Suzuki-Miyaura reaction was amenable to solid-phase arylation of the histidine imidazole ring. Firstly, it was synthesized 4(5)-methyl-5(4)-phenylimidazole and 4(5)-methyl-5(4)-(2-methoxyphenyl)imidazole by cross-coupling between N-benzylbromoimidazole and the corresponding arylboronic acid. Secondly, 5-bromohistidines were arylated with several arylboronic acids by a microwave-assisted Suzuki-Miyaura cross-coupling reaction in solution as well as solid-phase leading to the corresponding arylhistidines. Finally, antimicrobial peptides containing 5-arylhistidines were prepared using the previous methodology. They showed activity against gram-negative bacteria responsible of important plant diseases such as fire blight.

Des réacteurs avec solide en suspension (« slurry »), très répandu dans l'industrie chimique, du laboratoire à la production, offrent des bonnes capacités en transfert de matière et de chaleur. Leur flexibilité facilite le changement de la phase solide et permet une régénération en continue des catalyseurs en cas de désactivation. Cependant, ils présentent un fort rétro-mélange, et donc un désavantage pour des réactions ayant des enjeux de sélectivité et/ou de conversion poussées. L'écoulement segmenté dit de Taylor est souvent mis en œuvre dans les réacteurs micro-structurés (RMS), grâce à ses propriétés intéressantes (capacités de transfert, écoulement, piston). Cependant, l'utilisation des solides catalytiques dans ces RMS est le plus souvent résolue par immobilisation du catalyseur nuisant la flexibilité. L'écoulement « slurry Taylor » (EST) qui utilise les recirculations internes dans les segments liquides pour transporter des particules en poudre, peut potentiellement répondre à cet enjeu. L'objet de cette étude est la conception et la caractérisation de ce nouveau mode de contact gaz-liquide-solide (G-L-S) dans des tubes millimétriques horizontaux et verticaux. Des études hydrodynamiques ont révélé différents régimes d'écoulement dépendant de la vitesse et de l'orientation de l'écoulement. Pour étudier le transfert de matière L-S, une résine échangeuse d'ion a été utilisée et une première corrélation pour le nombre de Sherwood est proposée
Slurry reactors, widely encountered in chemical industry (laboratory scale up to manufactaring), offer good mass and heat transfer capacities and their high flexibility ensures the simple changeover of solid phases enables a continuous online fresh catalyst feed for fast deactivating catalysts. However slurry reactors promote a high degree of backmixing which can be a drawback for reactions with selectivity issues or when very high conversions are required. In microreaction technology, Taylor flow is often employed providing excellent heat and mass transfer and almost ideal plug flow behavior. Solid handing in these small structures is often resolved by immobilizing the solid catalyst which impinges on the flexibility. One possible solution to combine beneficial properties of Taylor flow with the operational flexibility of conventional slurry reactors is a “slurry Taylor” flow (STF) where catalyst particles are suspended and kept in motion by the internal circulations present in the liquid slugs. The focus of this work is the design and characterization of this innovative gas-liquid-solid contactor. Particles were transported in millimetric horizontal and vertical tubing without the risk of clogging. Hydrodynamic studies revealed different flow patterns depending mainly on velocity and flow orientation. Ion exchange resin particles were used to study the liquid-solid mass transfer and first correlation for the Sherwood number in STF is proposed

The growing need for fast sampling of explosives in high throughput areas has increased the demand for improved technology for the trace detection of illicit compounds. Detection of the volatiles associated with the presence of the illicit compounds offer a different approach for sensitive trace detection of these compounds without increasing the false positive alarm rate. This study evaluated the performance of non-contact sampling and detection systems using statistical analysis through the construction of Receiver Operating Characteristic (ROC) curves in real-world scenarios for the detection of volatiles in the headspace of smokeless powder, used as the model system for generalizing explosives detection. A novel sorbent coated disk coined planar solid phase microextraction (PSPME) was previously used for rapid, non-contact sampling of the headspace containers. The limits of detection for the PSPME coupled to IMS detection was determined to be 0.5-24 ng for vapor sampling of volatile chemical compounds associated with illicit compounds and demonstrated an extraction efficiency of three times greater than other commercially available substrates, retaining >50% of the analyte after 30 minutes sampling of an analyte spike in comparison to a non-detect for the unmodified filters. Both static and dynamic PSPME sampling was used coupled with two ion mobility spectrometer (IMS) detection systems in which 10-500 mg quantities of smokeless powders were detected within 5-10 minutes of static sampling and 1 minute of dynamic sampling time in 1-45 L closed systems, resulting in faster sampling and analysis times in comparison to conventional solid phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) analysis. Similar real-world scenarios were sampled in low and high clutter environments with zero false positive rates. Excellent PSPME-IMS detection of the volatile analytes were visualized from the ROC curves, resulting with areas under the curves (AUC) of 0.85-1.0 and 0.81-1.0 for portable and bench-top IMS systems, respectively. Construction of ROC curves were also developed for SPME-GC-MS resulting with AUC of 0.95-1.0, comparable with PSPME-IMS detection. The PSPME-IMS technique provides less false positive results for non-contact vapor sampling, cutting the cost and providing an effective sampling and detection needed in high-throughput scenarios, resulting in similar performance in comparison to well-established techniques with the added advantage of fast detection in the field.

Ce mémoire reporte dans une première partie les études menées sur des polymères à empreintes moléculaires (MIP) en extraction solide-liquide (SPE). La nature des interactions polymère-analyte, l’influence de la composition de la matrice de l’échantillon et la sélectivité des MIPs sont étudiés.La première application concerne l’extraction de molécules ciblées dans un extrait de plante. Deux MIPs respectivement préparés à partir de l’acide méthacrylique (MAA) et l’acide itaconique (IA) et avec respectivement la catharanthine et la vindoline comme molécule empreinte ont montré leur sélectivité sur des solutions standards puis sur un extrait de plante. Des expériences de réactivité croisée réalisées sur des molécules analogues à la molécule empreinte (alcaloïdes dimères) montrent la spécificité de reconnaissance des analytes par les MIPs. Le MIP-catharanthine est caractérisé par les isothermes de Scatchard et sa capacité est évaluée en SPE à partir de l’extrait de Catharanthus roseus. Un MIP préparé à partir de MAA avec la vinorelbine comme molécule empreinte a été appliqué à des matrices aqueuses salines pour l’extraction de la vinflunine et de son métabolite dans du plasma bovin et de l’urine. Des rendements d’extraction élevés ont été atteints grâce à une étude de l’impact des sels et au choix de solvants de lavage adaptés à la matrice. Une deuxième partie montre la simplicité d’utilisation et la sensibilité de la détection conductimétrique sans contact à couplage capacitif (C4D) lors de l’analyse du contre-ion et du principe actif dans des composés pharmaceutiques en électrophorèse capillaire (EC). La technique de la double injection a permis l’analyse simultanée des cations et des anions. La méthode EC-C4D développée est appliquée aux alcaloïdes Vinca et à différents médicaments avec des contre-ions anioniques ou cationiques
This thesis reports in a first part results obtained with molecularly imprinted polymers (MIP) during solid liquid extraction. Polymer-analyte interactions, composition of the sample matrix and selectivity of MIPs have been studied.The first application concerned the extraction of molecules in a plant extract. Two MIPs respectively prepared from the methacrylic acid (MAA) and itaconic acid ( IA) and with respectively catharanthine and vindoline as template showed their selectivity on standard solutions then on a plant extract. Experiments of cross reactivity performed with analogue of the template (dimers alkaloids) have proved the specificity of analytes recognition by the MIPs. The MIP-catharanthine is characterized by Scatchard isotherms and its capacity was estimated from the extract of Catharanthus roseus. A MIP prepared from MAA with the vinorelbine as template was applied in salt aqueous matrices for the extraction of vinflunine and its metabolite in bovine plasma and urine. High extraction recoveries were reached with a study of the impact of salts and the choice of washing solvents adapted to the matrix. The second part showed the simplicity of use and the sensibility of capacitively coupled contactless conductivity detection (C4D) for the analysis of counter-ion and active principle in pharmaceutical compounds in capillary electrophoresis (CE). The technique of double injection allowed the simultaneous analysis of cations and anions. The developed method EC-C4D was applied to Vinca alkaloids and various medicines with anionic or cationic counter-ions

During the pyrometallurgical extraction of copper, a significant part of the copper is lost with discard slag, which decreases profits, overall copper recovery, and efficiency of raw material usage. Smelting furnace slag usually has a copper content that is close to or higher than that of copper ores. The investigation of copper losses to slag is thus a task of practical significance, as the ore grades are depleting. Slag cleaning, e.g., a settling furnace, can reduce copper losses to slag as the mechanically suspended copper-containing droplets separate from slag under the action of gravity and can hence be recovered.  An industrial trial was conducted in an electric settling furnace with slag originating from an electric smelting furnace and processed in a zinc fuming furnace. The trial was conducted to increase the understanding of copper losses to slag and how the process parameters temperature and settling time influence the slag copper content. The obtained slag samples were also evaluated to gain better insights as to the settling mechanism and, if any, factors that hinder the copper phases from settling. Slag modification with CaO was also evaluated to investigate how the modification influences the settling of copper phases and, thus, the final slag copper content.  Samples collected during the industrial trial were the basis for the evaluation in the current work. The samples came from batches with varying temperatures, settling times, and CaO content collected at four different sample positions. Instrumental techniques, including XRF, FAAS, ICP-SFMS, and SEM-EDS, were used to analyze the chemical compositions of the samples and the appearance of copper and associated phases.  The results indicated that the copper content of outgoing slag increased with increasing temperature in the evaluated interval. The copper content was also concluded to be more strongly affected by the temperature compared to the settling time. Regulating the temperature to the lower temperature interval in the settling furnace could thus decrease the final slag copper content. During the slag characterization, it was found that suspended copper-containing phases were hindered from settling, due to the attachment to solid phases and gas bubbles in the slag. By controlling and minimizing the presence of the bottom buildup and thus solid phases in the slag, the copper content can be decreased. The results indicated that the CaO slag modification decreased the final slag copper content, and can thus be used as a modifier for increased settling.

The purpose of this thesis work was to develop a headspace solid phase microextraction gas chromatography mass spectrometry (HS-SPME-GC-MS) method to detect volatile organic compounds (VOCs) in board samples and to statistically investigate potential correlation between chromatographic data and flavor data obtained from a trained panel. The developed method would hopefully serve as a complement to the already established routine analyses at Stora Enso and gain an increased understanding of which VOCs in the board influence its flavor properties. The impact of incubation time and adsorption time on the area under curve (AUC) was studied with a Design of Experiment screening using the software MODDE. The screening data showed a correlation between large AUC and low repeatability measured as relative standard deviation (RSD). The data was hard to fit to a model due to the large RSD values for the replicates, AUC for identified compounds as response gave an acceptable fit. The regression coefficients for the model showed that a longer adsorption time gave larger AUC, while incubation time had no significant impact on the response.  Instead of following up the screening with an optimization, the focus was shifted to improving the repeatability of the method, i.e. lowering the RSD. The high RSD was believed to mainly be the result of leakage of analytes and unstable temperature during adsorption, preventing the system from reaching equilibrium. Different heating options and capping options for the vial was tested. Septum in crimp cap ensured a gas tight seal for the vial, giving lower RSD values and larger AUC compared to the other alternatives, showing that there was indeed a leakage. Using oil bath ensured stable temperature during the adsorption and detection of a larger number of VOCs but created a temperature gradient in the vial due to it not being fully submerged in the oil. Oil bath gave larger AUC, but still high RSD due to the temperature gradient making the method sensitive to variance in fiber depth in the vial. The final method was performed with 2 g of board sample in a 20 ml headspace vial sealed with a crimp cap with septa. The incubation and adsorption were performed with the vial immersed in a 90-degree oil bath. 20 min incubation time was chosen based on the time it took to get a stable temperature gradient in the vial, and 20 minutes adsorption time was chosen as a good compromise between large AUC and low RSD. Compared to Stora Ensos routine analysis, the developed SPME method gave chromatograms with an improved signal-to-noise ratio for the base line and several more peaks with larger AUC. For the board sample used during method development, the SPME-method identified 34 VOCs, while the routine analysis only identified 12. The developed method was applied on 11 archived board samples of the same quality that were selected based on their original flavor properties, to get a large diversity of samples. Flavor analysis was performed by letting a trained flavor panel describe the flavor based on intensity and character of the water that had individually been in indirect contact with one of the 11 board sample for 24 h. Potential correlation between chromatographic data obtained with the developed method and the flavor experience described by the flavor panelists was statistically investigated with the multivariate analysis software SIMCA. The correlation study showed that a combination of 12 VOCs with short retention time are most likely the main source of off-flavor which of 5 could only be identified with the developed SPME method. VOCs with long retention time did not contribute to an off-flavor and might have a masking effect on flavor given by other VOCS, however not confirmed in this study. Furthermore, the age of the board samples proved to be a good indicator for prediction of the flavor intensity, whereas the total AUC of the samples was not. Possible correlation between detected VOCs in the samples and flavor character given by the flavor panel were seen, however the variation in the data and the sample set were too small, preventing from making conclusions on individual VOCs impact on the flavor experience. The developed HS-SPME-GC-MS method would serve as a complement to the already established routine analyses at Stora Enso and has slightly increased the understanding of which VOCs in the board influence the flavor properties

Les systèmes cryogéniques sont l’une des technologies les plus prometteuses et toujours en progrès pour valoriser le biogaz, car elles permettent son épuration sans solvants et possiblement à pression atmosphérique. Dans ce travail, un nouveau concept de récupération de froid par sublimation contrôlée est présenté. Un gaz froid est utilisé en tant que gaz de dégivrage. Il sublimera le givre en utilisant le gradient de pressions partielles entre le givre et la teneur de CO2 dans le gaz au lieu de gaspiller le froid par transfert de chaleur par convection. Avant cette étape, les dépôts de CO2 doivent être étudiés. La formation et la croissance de givre de CO2 sont détaillées et un modèle est présenté pour mieux expliquer comment le CO2 est séparé du biogaz et des dépôts sur une surface froide. Une comparaison entre les configurations de plaque plane et de tube a montré que cette dernière était meilleure pour la capture de CO2 dans un système cryogénique en termes de transfert de chaleur et de masse. Cependant, elle pose un problème de colmatage lorsque le givre augmente à l'intérieur du tube. L'étude de la formation de givre le long du tube a montré un décalage de temps pour le dépôt de givre le long du tube. Un processus d’épuration cryogénique du biogaz et de liquéfaction de biométhane a été présenté avec des calculs pour tous les composants inclus dans le système. Les résultats de la simulation montrent que la récupération de froid est possible par sublimation contrôlée et que la température du tube a atteint des valeurs inférieures à la température initiale, ce qui n'est pas possible par le simple transfert de chaleur par convection. Le concept de vaporisation contrôlée fonctionne mieux pour les faibles concentrations de CO2 dans le biogaz si les phases de givrage et de dégivrage doivent être terminées à durée égale. Enfin, une expérience a été menée pour valider le concept de récupération à froid par sublimation contrôlée. Les résultats montrent que cette technique a le potentiel d’éliminer complètement les utilités froides de certains procédés cryogéniques d’élimination de CO2
Cryogenic systems are one of the most promising and still rising technologies for upgrading biogas as it is solvent free and can operate at atmospheric pressure. In this work a new concept for cold recovery by controlled sublimation is presented. A cold gas flow is used as a defrosting gas that will sublimate the frost using the partial pressure gradient between the frost and the gas flow instead of wasting the cold by convective heat transfer. Prior to this step, CO2 deposition should be studied. CO2 frost formation and growth is thoroughly detailed and a model is presented to better explain how CO2 is separated from biogas and deposits on a cold surface. A comparison between the flat plate and the tube configurations showed that the latter was better for CO2 capture in a cryogenic system in terms of heat and mass transfer but it presents a problem of clogging as frost increases inside the tube. The study of frost formation along the tube showed a delay in the starting time of deposition at position further from the biogas inlet. A process for biogas cryogenic upgrading and biomethane liquefaction was presented with calculations for all the components included in the system. Simulation results show that cold recovery is possible by controlled sublimation and the tube temperature reached values lower to the gas flow temperature which is not possible by single convective heat transfer. The concept works best for lower CO2 concentrations in the inlet biogas if the frosting and defrosting phases are to be completed at the same time. Finally, an experiment was conducted to validate the concept of cold recovery by controlled sublimation, for which results have shown the potential to totally avoid cold utilities use in the cryogenic capture of CO2

Ein Großteil der Lebensmittel wird in der heutigen Zeit vor allem aufgrund ihrer langen Haltbarkeit in Konservendosen verpackt. Zur Qualitätserhaltung des Lebensmittels werden Weißblechdosen im Innenbereich in der Regel mit einer Lackierung versehen. Lackrohstoffe sind dabei u. a. Phenol- und Epoxidharze, die als Basis- oder Vernetzerkomponente eingesetzt werden. Bei der Herstellung und Lagerung dieser Lebensmittel kann jedoch nicht ausgeschlossen werden, dass es zur Migration von Bestandteilen aus der Kunststoffinnenbeschichtung in das Füllgut kommt. Toxikologisch und somit auch analytisch sind dabei vor allem die migrierenden Verbindungen unter 1000 Da von Interesse, da Substanzen mit einer Molmasse von über 1000 Da nur zu weniger als 1 % im Gastrointestinaltrakt absorbiert werden. Analytik von phenolischen Verbindungen Bei Untersuchungen zur Migration phenolischer Verbindungen unter Verwendung verschiedener Modellcoatings und Simulanzlösemittel wurden Konzentrationen an migrierenden phenolischen Substanzen in Summe bis 160 µg/dm² bestimmt, womit dieser Gehalt deutlich unter dem gesetzlichen Grenzwert für die Gesamtmigration von 10 mg/dm² liegt. Die Quantifizierung erfolgte dabei über SEC-FLD-Kalibriergeraden der für diese Coatings verwendeten Phenolharze. Tendenziell steigt dabei die Menge an übergehenden Verbindungen mit abnehmender Polarität der verwendeten Simulanzien. Ebenso abhängig vom Lösungsmittel ist die Molekulargewichts¬verteilung der im Migrat enthaltenen Phenole. So zeigte sich eine deutliche Verschiebung der phenolischen Verbindungen zu höheren Molekulargewichten mit abnehmender Polarität der Simulanzlösemittel. Mit wenigen Ausnahmen besitzen jedoch alle migrierenden Substanzen eine Molmasse von unter 1000 Da. Das beobachtete Migrationsverhalten kann u. a. auf die unterschiedliche Reaktivität der phenolischen Basismonomere der Harze zurückgeführt werden, wodurch die Fähigkeit variiert, unter den Einbrennbedingungen ein ausgeprägtes Netzwerk zu bilden. Zur näheren Charakterisierung der Phenolharze wurden einzelne Hauptverbindungen der RP-HPLC-FLD-Chromatogramme identifiziert. Über Derivatisierungsreaktionen mit Picolinsäure, Essigsäureanhydrid sowie Dansylchlorid konnten Informationen zur Anzahl an alkoholischen und phenolischen Hydroxylgruppen im Molekül erhalten werden. Mit dem Wissen um die eingesetzten Phenolmonomere und einer eventuellen Veretherung konnten Strukturvorschläge erstellt werden. Die Quantifizierung der migrierenden phenolischen Verbindungen in Migraten kommerzieller Coatings in Summe wurde über eine universell anwendbare Kalibrierung angestrebt. Dazu wurden 17 verschiedene Phenolharze bezüglich der Steigung der SEC-FLD-Kalibriergeraden, des mittleren Molekulargewichtes, der Hydroxylzahl und dem Verhältnis OH-Gruppen/Molekül charakterisiert. Wie erwartet steigt mit wenigen Ausnahmen die Anzahl der OH-Gruppen im Molekül tendenziell mit dem mittleren Molekulargewicht. Es zeigte sich zudem, dass die verschiedenen Phenolharze in ihren fluorophoren Eigenschaften stark variieren. Die Steigung der SEC-FLD-Kalibriergeraden konnte zudem in keine Korrelation mit einem anderen ermittelten Parameter gebracht werden. Die Anwendung einer universellen Kalibriergerade zur Quantifizierung war deshalb nicht möglich. Die Größenordnungen der Migratkonzentrationen konnten daher nur über die zwei im Anstieg am stärksten variierenden SEC-FLD-Kalibriergeraden abgeschätzt werden. Bei der Analyse kommerzieller Epoxy-Phenol-Coatings war im Gegensatz zu Polyester-Phenol-Coatings die isolierte Detektion der phenolischen Verbindungen im Migrat mittels Fluoreszenz nicht möglich, da sowohl Epoxide als auch Phenole fluorophorer Eigenschaft besitzen. Es wurde daher eine Methode zur Abtrennung der Phenole von anderen im Migrat enthaltenen Subtanzen auf Basis eines Anionenaustauschermaterials entwickelt. Dabei wurde die Eigenschaft der Phenole genutzt, im basischen Milieu Phenolate zu bilden. Diese, aber auch Säuren adsorbieren am Austauschermaterial, während Epoxide oder Polyester nicht retardiert werden. Für zwei kommerzielle Epoxy-Phenol-Coatings konnte somit der Anteil an phenolischen Verbindungen im Migrat zu 7 und 28 % bestimmt werden. Mittels RP-HPLC/ESI-MS war es möglich, einige der phenolischen Verbindungen in diesen Migraten zu identifizieren. Dabei handelt es sich um nichtepoxidierte BPA-Derivate der Epoxidkomponente des Coatings, die aufgrund des BPA-Grundkörpers eine phenolische Hydroxylgruppe besitzen. Phenolische Vernetzungsprodukte beider Basisharze konnten dagegen nicht identifiziert werden. Die Menge an migrierenden phenolischen Verbindungen der beiden Epoxy-Phenol-Coatings konnte über die Kalibration eines niedermolekularen Epoxidharzes zu 0,1 mg/dm² bzw. 0,27 mg/dm² abgeschätzt werden. Während für einzelne phenolische Verbindungen gesetzliche Grenzwerte für die Migration bestehen, gibt es für Oligomere, mit Ausnahme von BPA keine spezifischen Migrationslimits. Ebenso sind in der Literatur kaum toxikologische Untersuchungen zu Phenololigomeren zu finden. Um einen ersten Einblick in die toxikologische Relevanz migrierender phenolischer Verbindungen zu erhalten, wurden mehrere kommerzielle als auch selbst synthetisierte phenolische Standardsubstanzen und verschiedene Molekulargewichtsfraktionen eines Phenolharzes, im Fischembryotest an Eiern des Zebrabärblings (Brachydanio rerio) nach DIN 38415-T647 und/oder Neutralrottest an Hep-G2 und HT-29 Zellen untersucht. Die stärksten Effekte im Fischembryotest bewirkte das Trimer BPM, hier reichte bereits eine Konzentration von etwa 2 mg/l aus, um 50 % der Fischembryonen letal zu schädigen. Im Gegensatz dazu waren beim Dimer 5-Hydroxymethyl-2,4´-dihydroxydiphenylmethan (M 230) mit einem EC50-Wert von 170 mg/l die geringste toxikologische Wirkung zu beobachten. Für alle anderen Subtanzen konnten EC50-Werte im Bereich 20 - 100 mg/l bestimmt werden. Tendenziell zeichnete sich dabei eine Zunahme der EC50-Werte mit steigender Lipophilie, ausgedrückt über den KOW-Wert ab, was auf den Aufbau der Fischeier zurückzuführen ist. So müssen die zu untersuchenden Xenobiotika mehrere lipophile Membranen durchdringen, um am eigentlichen Wirkungsort Einfluss auf die Embryonalentwicklung nehmen zu können. Im Zelltest konnten tendenziell ähnliche Ergebnisse ermittelt werden wie im Fischembryotest, wobei in der Regel die Hep-G2 Zellen empfindlicher reagieren als die HT-29 Zellen. Während für Phenol im untersuchten Konzentrationsbereich keine toxischen Effekte beobachtet werden konnten, liegen die EC50-Werte für das Trimer BPM, analog zum Fischembryotest deutlich unter 10 mg/l. Für die anderen Verbindungen wurden EC50-Werte zwischen 16 und 100 mg/l bestimmt. Analog zu den Untersuchungen der Einzelsubstanzen zeigte sich auch bei den 5 untersuchten Molekulargewichtsfraktionen zwischen 0 und 1000 Da, dass das toxikologische Potential im niedermolekularen Bereich (0 - 200 Da) gegenüber den Fraktionen 200 400 und 400 600 Da vergleichsweise gering ist. Bereits 25,1 mg/l bzw. 17,3 mg/l der Fraktionen 200 400 Da und 400 600 Da waren in den Tests ausreichend, um alle Embryonen letal zu schädigen. Im Molekulargewichtsbereich über 600 Da konnten dagegen lediglich subletale oder gar keine Missbildungen beobachtet werden. Analytik von Epoxiden In der amtlichen Überwachung beschränkt sich die Analytik von Epoxidverbindungen bisher auf die Bestimmung rechtlich geregelter Einzelsubstanzen. Eine Summenmethode zur Erfassung aller in einem Migrat enthaltenen Substanzen mit reaktionsfähigen Oxirangruppen, wodurch das gesamte Reaktionspotential erfasst werden kann, liegt dagegen nicht vor. Zur selektiven Erfassung aller oxirangruppenhaltigen Verbindungen wurde daher mittels statistischer Versuchsplanung eine Derivatisierung mittels Cysteamin entwickelt. Die Reaktion mit Cysteamin erfolgt dabei nach Abtrennung der Substanzen > 1000 Da mittels Größenausschlusschromatographie. Im Anschluss werden die Derivate durch Zugabe eines Kationenaustauschers aus der Lösung entfernt. Durch den Vergleich der RP-HPLC-FLD Chromatogramme vor und nach der Aufarbeitung können Substanzen mit intakten Oxirangruppen somit einfach erkannt werden. Eine quantitative Abschätzung der enthaltenen Epoxidverbindungen ist bei Lacken auf Basis von BPA-Harzen über die BPA-Chromophorkonzentration möglich. Bei der Untersuchung von 5 kommerziellen Coatings wurden in den einzelnen Migraten recht unterschiedliche Gehalte an Substanzen mit intakten Epoxidgruppen ermittelt. Ebenso ist die Anzahl der oxriangruppenhaltigen Verbindungen, auf die sich dieser Gehalt verteilt sehr unterschiedlich, was möglicherweise an unterschiedlichen Einbrennzeiten, -temperaturen aber auch der Menge an Lack pro m² und an der Art und Menge des Reaktionspartners liegt. Für die Konzentration der epoxidischen Verbindungen in den Coatingmigraten wurden Werte zwischen 18,5 und 835 µg/dm² bestimmt. Dies entspricht einem Anteil der reaktionsfähigen Substanzen an der Fraktion unter 1000 Da berechnet über die Flächen im Chromatogramm zwischen 2,6 und 76,3 %. Neben dem Einsatz als Basismaterial für Konservendoseninnenbeschichtungen werden Epoxidharzsysteme auch in Zubereitungen wie Grundierungen, Füllmassen, Lacken oder Klebstoffen für die Bauchemie vielfach in verschiedenen Mischungen (aromatische, aliphatische oder cycloaliphatische Glycidylether bzw. Siloxanglycidylether) eingesetzt. Durch den Kontakt dieser Materialien mit der Haut kann es zu Kontaktekzemen kommen, deren Ursache durch Epikutantests (Patchtests) mit den potentiell auslösenden Substanzen ermittelt werden kann. Der Umfang der in den Standardtestsystemen enthalten Testsubstanzen entspricht dabei jedoch nicht dem Spektrum der in der Industrie verwendeten Materialien. Über die genaue Zusammensetzung der in den Patchtest´s eingesetzten Materialien ist zudem wenig bekannt. Durch die Analyse einer Vielzahl von Patchtestsubstanzen und industriellen Epoxidkomponenten mittels RP-HPLC/UVD bzw. -ELSD Chromatographie und die Identifizierung der enthaltenen Verbindungen über RP-HPLC/ESI-MSD, konnte ein genaueres Bild über den Charakter dieser Materialen gewonnen werden. Bei den BPA- und BPF-Harzen wurden überwiegend Monomere, die entsprechenden Di- und Trimere aber auch dessen hydrolysierte Verbindungen identifiziert. Im Gegensatz dazu liegen bei den analysierten aliphatischen Produkten z. T. die reinen Glycidylether gar nicht oder nur in geringen prozentualen Anteilen vor. Vielmehr wird durch die sauer geführte Reaktion bei den aliphatischen Verbindungen die Bildung von 1,3 Chlorhydrinen als Nebenreaktion zur 1,2 Chlorhydrinbildung gefördert, wodurch eine beträchtliche Menge an Substanzen, die nicht verseifbares Chlor enthalten, in den Materialien vorhanden ist. Um die enthaltenen Verbindungen von aliphatischen und cycloaliphatischen Epoxidzubereitungen quantifizieren zu können, wurde eine Derivatisierung mit einem selbst synthetisierten Fluorophor (5-(Dimethylamino)-N-(2-mercaptoethyl)-1-naphthalen-sulfonamid) entwickelt. Dadurch konnten auch Verbindungen erfasst werden, die aufgrund ihrer Flüchtigkeit mittels ELSD nicht detektierbar waren. Bei der Analyse von Handelsprodukten zeigte sich, dass die einzelnen Komponenten in ihrer Zusammensetzung gut mit den untersuchten aromatischen und aliphatischen Rohmaterialien vergleichbar sind. Bei entsprechend eingesetzten Patchtestsubstanzen spiegeln diese somit die Produkte gut wieder, mit denen die Patienten in Kontakt kommen.

碩士
淡江大學
水資源及環境工程學系
89
Ⅰ. A study on semi-continuous microwave process for removal of heavy metal in fly ash from municipal solid waste (MSW) incinerator The incineration was wildly used in the pretreatment of the municipal solid waste ( MSW ). But the incinerated fly ash contained heavy metals, and considered to be harmful material. The purpose of this study is to extract heavy metal in fly ash from municipal solid waste (MSW) incinerator using microwave. The traditional leaching or shaking method was used to remove the heavy metals in fly ash . The whole processes were time-consuming. In this study, the microwave extraction methods was presented, and the extraction time was decreased to minites. The dilute HCl solution was as an extraction reagent to extract the fly ash, and the experiments were designed to use mix level orthogonal array to find the optimized extracting condition. The optimized conditions were microwave power: 546 W; extract time, 25 sec; extracting solution, 0.3 M HCl; solid / liquid ratio, 1 / 20. The results showed that the removal rate of metals were 89.6% of Pb, 97.2% of Cu, 79.1% of Zn, 92.8 of Cd in fly ash by the microwave extraction treatment. Ⅱ. Preliminary determination of lead content in blood by solid phase microextraction/gas chromatography (SPME-GC) Traditional method for the determination of lead in whole blood was by graphite furnace atomic absorption spectrometry. The purpose of this study was to optimize the extracting procedure for determination of lead in whole blood by SPME-GC with flame ionization detector (FID). The solution 0.1% Triton-X100 was used to release lead from the erythrocytes. Corpuscles and protein were precipitated by adding 10% trichloracetic acid. The four factors of mix level orthogonal array design for SPME were used in this work and found the following conditions to be optimal: sample pH, 4.0 and 1M acetic acid buffer volume, 1 mL (pH 4.0); extraction time,15 mins; 2% sodium tetraethylborate (STEB) solution,0.2ml; with SPME fiber, 100m poly(dimethylsiloxane)(PDMS). The lead ion was first derivatized with STEB to form tetraethyllead, which is then absorbed on SPME fiber in the headspace over the sample. After sampling, the fiber was withdrawn into the needle and the SPME device was transferred to the GC. The needle in the SPME device is introduced into the GC injector which the absorbed analytes are thermally desorbed and delivered to the GC column,5% phenyl 95% dimethyl-polysiloxame (30m×0.25mm I.D×0.25m, DB-5 MS), and finally organic lead was detected by FID. The conecntration of lead blood was found, 5.96 ug / dL

碩士
淡江大學
水資源及環境工程學系
90
Ⅰ. Determination of volatile organic compounds content in soil by solid phase microextraction/ gas chromatography (SPME-GC) Traditional method for the determination of BTEX(Benzene, Toluene, Ethyl benzene, Xylene) in soil or solid waste by purge and trap(P&T). The purpose of this study was to optimize the extracting procedure for determination of BTEX in soil by SPME-GC with flame ionization detector (FID). The four factors of mix level orthogonal array design for SPME were used in this work and found the following conditions to be optimal: extraction temperature:25℃; extraction time:5mins; supersonic oscillate time:1min; desorption time:1min;with SPME fiber, 100mm poly(dimethylsiloxane)(PDMS). BTEX were vaporized and absorbed on SPME fiber in headspace over the sample (0.2g soil) spiked by BTEX in a vial (4mL) . After extraction, the fiber was withdrawn into the needle and the SPME device was transferred to the GC. The needle in the SPME device was introduced into the GC injector where the analytes absorbed were thermally desorbed and delivered to the GC column, 5% phenyl 95% dimethyl-polysiloxame (30m×0.25mm I.D×0.25mm, DB-5 ), and finally BTEX was detected by FID. The results showed that the linear range BTEX was from 1μg/g to 100μg/g, that R2 has 0.999 level. The method detection limits for BTEX in soil was benzene: 7.14ng/g, toluene: 20.49ng/g, ethyl benzene: 17.64ng/g, p,m-xylene: 18.15ng/g, o-xylene: 20.49ng/g respectively. Ⅱ. A study of microwave extraction with acid solution for removal of lead in fly ash from municipal solid waste incineration and the extracts The traditional leaching or shaking method was used to remove the heavy metals in fly ash . The whole processes were time-consuming. In this study, the microwave extraction methods was presented, and the extraction time was decreased to minites. The optimized conditions were microwave power: 546 W; extract time: 25 sec; extracting solution: 0.45 M HCl; solid / liquid ratio: 1 / 20. The residues were collected after extracting fly ash using the optimized conditions, dried and extracted in TCLP(Toxicity characteristic leaching procedure) solution. The concentration of Pb in the extracts was 4.62 mg/L by atomic absorption analysis. The extraction solution which was obtained from microwave extraction were electrolyzed for 7 days. The results showed that the removal of metals were 99.51% for Pb and 97.44% for Cu .

碩士
淡江大學
水資源及環境工程學系
88
Ⅰ. Determination of lead content in wastewater by solid phase microextraction / gas chromatography (SPME-GC) There are several analytical techniques that can be used for determination of lead in water analysis. The purpose of this study was to optimize the extracting procedure for determination of lead by SPME-GC with flame ionization detector (FID). The four factors of mix level orthogonal array design for SPME were used in this work and found the following conditions to be optimal: sample, 10ml aqueous solution containing 1 ml of pH 4 buffer and 1 drop of 1:100 HNO3; absorption time,15 mins; pH value,4.0; after adding 1% sodium tetraethylborate (STEB) solution,0.4ml; with SPME fiber, 100um poly(dimethylsiloxane)(PDMS). The lead ion is first derivatized with STEB to form tetraethyllead, which is then absorbed on SPME fiber from the headspace over the sample. After sampling, the fiber was withdrawn into the needle and the SPME device was transferred to the GC. The needle in the SPME device is introduced into the GC injector which the absorbed analytes are thermally desorbed and delivered to the GC column,5% phenyl 95% dimethyl-polysiloxame (30m×0.25mm I.D×0.25m, DB-5 MS). The detection limit for this method was 0.54ng/ml.Ⅱ. Determination of the organotin compounds in sediments by gas chromatography after microwave-assisted extraction The organotin compounds are known to be toxic to several organisms, including human beings. Their use has been widely extended recently. Thus, several methods for detection of organotin compounds have been developed. A rapid extraction procedure for the organotin compounds in sediments developed in this study was used by the application of open focused low-power microwave technology. The optimized extraction conditions for the tributyltin chloride (TBT) in sediments are (1) extraction time : 2 min (2) microwave power : 60 W (3) the pH of solution after microwave extraction : 3.8. The organotin compounds were derivatized with sodium tetraethylborate (STEB) in the aqueous phase, and simultaneously extracted into isooctane. The detection was carried out by capillary gas chromatography with flame photometric detection (GC-FPD). The recoveries of TBT and DBT in sediments using this method were 98 % and 80 %, respectively.

Non-equilibrium boundary conditions based upon kinetic theory and linear irreversible thermodynamics are applied to the interface kinetics in vapor crystal growth of unitary and binary materials. These are compared to equilibrium boundary conditions in a simple, 1D closed ampoule physical vapor transport model. It is found that in cases where the diffusive impedance is negligible and when system pressure is low, surface kinetics play an important role in limiting the mass transport. In cases where diffusion is the dominant transport impedance, and/or when the pressure in the system is high, the kinetic impedances at the interfaces are negligible, as impedances due to diffusion and latent heat transport at the interfaces become more significant. The non-equilibrium boundary conditions are dependent upon the sticking coefficient of the surface. An experiment to estimate the sticking coefficient on solid surfaces is proposed. The non-equilibrium theory also predicts significant temperature jumps at the interfaces.
Graduate

碩士
高雄師範大學
化學系
97
This research tries to use the Octadecylsilane(ODS) for packing solid phase extraction (SPE)  to have the concentration effect and then the SPE connects with the high performance liquid chromatography(HPLC) to detect the trace catechins in the tea drinks. By using the physical absorption nature of ODS to absorb the catechins and caffeine, the on-line SPE first concentrates the analytes. Then the analytes are desorbed by the gradient elution of mobile phase and analysed by HPLC. The experimental results show that it is effective to separate the catechins and the caffeine (GC, C, EGC, Caf, EC, EGCG, GCG, ECG, CG) by using the on-line SPE-HPLC. The linear correlation coefficient is above 0.998. The detection limits are below 5 μg/L, one tenth of the detection limits with the direct HPLC analysis method. The ODS-solid-phase extraction has the enrichment factors of 49.48, 80.57, 92.87, 81.58, 67.82, 64.79, 104.59, 43.05, and 75.55 correspond to GC, C, EGC, Caf, EC, EGCG, GCG, ECG, and CG, respectively. Finally, we try to determinate the catechins and caffeine content of the real tea drinks by using the on-line SPE-HPLC. The result shows that the recoveries of the real tea drinks are between 100% ± 20% ( except GC, C). So the on-line SPE-HPLC has the advantages for reducing the sample loss, reducing pre-process and having automation for detecting the catechins and caffeine content. It is able to achieve the goal of the lowering the detection limits by the SPE concentration effect.

In this dissertation, physical phenomena relevant to (i) an interface formed between two fluids and a solid phase (wetting line) and (ii) an interface between three fluids (triple contact line) were investigated. In the former case, the wetting line (WL) phenomena, which encompass the wetting line energy (WLE), the wetting line velocity (WLV), and the contact angle hysteresis, were studied using a micropump based on electrowetting on dielectric (EWOD). In the latter case, the air film lubrication effect and the liquid free surface deformation were taken into account to explain the dual equilibrium states of water droplets on liquid free surfaces. A micropump based on droplet/meniscus pressure gradient generated by EWOD was designed and fabricated. By altering the contact angle between liquid and solid using an electric field a pressure gradient was induced and a small droplet was pumped into the channel. The flow rate in the channel was found to be constant in spite of the changes in the droplet's radius. The WL phenomena were studied to unravel the physical concept behind the micropump constant flow rate. The observation and measurement reveal that the shrinking input droplet changes its shape in two modes in time sequence: (i) its contact angle decreases, while its wetting area remains constant, and (ii) its WL starts to move while its contact angle changes. Contact angles were measured for the advancing and receding WLs at different velocities to capture a full picture of contact angle behavior. The effects of the WLE on the static contact angle and the WLV on the dynamic contact angle in the pump operation were investigated. Also the effect of EWOD voltage on the magnitude and uniformity of the micropump flow rate was studied. Dynamic contact angles were used to accurately calculate the pressure gradient between the droplet and the meniscus, and estimate the flow rate. It was shown that neglecting either of these effects not only results in a considerable gap between the predicted and the measured flow rates but also in an unphysical instability in the flow rate analysis. However, when the WLE and WLV effects were fully taken into account, an excellent agreement between the predicted and the experimental flow rates was obtained. For the study of the TCL between three fluids, aqueous droplets were formed at oil-air interface and two stable configurations of (i) non-coalescent droplet and (ii) cap/bead droplet were observed. General solutions for energy and force analysis were obtained and were shown to be in good agreement with the experimental observations. Further the energy barrier obtained for transition from configuration (i) to (ii) was correlated to the droplet release height and the probability of non-coalescent droplet formation. Droplets formed on the solid surfaces and on the free surface of immiscible liquids have various applications in droplet-based microfluidic devices. This research provides an insight into their formation and manipulation.
Ph.D.
Doctorate
Mechanical and Aerospace Engineering
Engineering and Computer Science
Mechanical Engineering

(AJ) Food contact materials pose a risk to human health due to a variety of contaminants which they can release into food. These compounds, migrants, include aromatic hydrocarbons, dialkyl phthalates, bisphenols, printing ink photoinitiators, and perfluoroalkyl compounds. The determination of all these substances can be expensive and time-consuming since universally applicable analytical approaches are not available nowadays. This work attempted to develop methods for the simultaneous determination of migrants from all of the mentioned groups in paper-based food contact materials and fatty food. A total of 68 contaminants were studied in paper products using liquid chromatography and gas chromatography coupled with tandem mass spectrometry detection. All analytes were isolated simultaneously using the modified "QuEChERS" method. This method demonstrated acceptable recovery and repeatability for most analytes in the validation study; LOQs ranged from 1.3 to 220 µg/kg. Analysis of 132 real paper products confirmed the occurrence of almost all studied analytes, which were often present in complex mixtures and at concentrations up to 628 mg/kg. A total of 41 potential contaminants were monitored in fatty foods by liquid chromatography with tandem mass detection. Contamination of the mobile phase by...