This thesis presents experimental studies of low-temperature atmospheric pressure plasma sources with generic ability to effectively treat large-scale three-dimensional (3D) objects. The reported large-scale plasma sources are developed through parallelisation of single plasma jets. This strategy outshines the other reported strategies for treatment of uneven surfaces by being able to produce spatially extended plasma directly onto the surface of heavily three-dimensional objects. Comparable studies of the design of elemental plasma jets bring out a hybrid electrode configuration, the capillary-ring jet, as the best elemental jet to be used in the parallelisation. It is found that the introduction of a ballast resistor to the individual jet circuit or built-in capacitance is important to assure the jet-to-jet synchronism, stability and uniformity. Electrical and optical analyses of one-dimensional (1D) array of atmospheric pressure plasma jets demonstrate robust temporal and spatial jet-to-jet uniformity both for flat and sloped surfaces. Hexagonally-arranged two-dimensional (2D) arrays of atmospheric pressure plasma jets show good level of insusceptibility to variations of the downstream samples in their physical dimensions as well as structural and material properties. The reaction chemistry impact area of a 2D 37-jet array is estimated to be 18.6 cm2. These confirm the plasma jet arrays as a viable option as large-scale atmospheric plasma sources, well suited for many processing applications including plasma medicine. The spatially separated dual-frequency excitation further benefits the plasma jet in that separate control of different important plasma parameters is possible. Enhanced plasma properties achieved by the dual-frequency offer greater potential to the jet arrays.

This thesis presents an experimental study of non-thermal atmospheric pressure gas plasmas in presence of liquid as an efficient source of transient and reactive species to initiate chemical reactions necessary for many important applications. Two types of liquid-containing plasmas are considered: discharges formed between a needle electrode and a liquid electrode, and plasma jets formed in a water vapour flow mixed in helium or argon gas. Two plasma modes (the pulsed and the continuous mode) are observed in the needle-to-liquid plasma. A comparative study of the needle-to-liquid plasma in the continuous mode with DC and AC excitations reveals that the plasmas are glow discharges, and AC excited plasmas have the highest energy efficiency. A study of helium/water vapour plasma jet shows that “plasma bullets” are formed even with water vapour in the gas mixture, but become quenched when the moist helium flow rate is above 300sccm (~1800ppm water concentration). Moderate amount of water vapour (~250ppm water concentration) is beneficial for active species production mainly due to the high electron density. Hydrogen peroxide production in saline solution with three different plasma sources is investigated due to the importance of H2O2 in several important applications. Long lifetime of H2O2 in the liquid after plasma treatment indicates an exciting possibility of plasma pharmacy.

L'objet de cette thèse traite du dépôt de couches minces photocatalytiques de dioxyde de titane par l'utilisation d'un dispositif plasma à la pression atmosphérique. Le dispositif industriel utilisé permet le traitement du substrat en post-décharge à basse température. L'objectif à terme est le développement d'un procédé de dépôt en vue de recouvrir des pièces 3D thermosensibles d'un revêtement autonettoyant à moindre coût. Après avoir mis en évidence les bonnes propriétés photocatalytiques des dépôts effectués dans le cadre de cette thèse, le présent travail s'est focalisé sur la compréhension des mécanismes responsables cette photocatalycité. Pour ce faire, trois séries de dépôts correspondant à trois températures de substrat différentes ont été étudiées selon leur composition chimique, leurs mécanismes de croissance et leur cristallinité. Il ressort de cette étude que la photoactivité des dépôts est essentiellement le fait de leur importante surface spécifique ; la cristallinité, bien que présente à haute température de substrat, semblant avoir une influence moindre. Cette surface spécifique est quant à elle due à la croissance d'agglomérats, dont l'adhésion au dépôt diminue avec leur taille. Formés en phase gaz dans des boucles de recirculation, ceux-ci semblent se développer du fait de multiples phénomènes : croissance CVD à leur surface, « agglomération de surface » et « redépôt ». Aussi, il apparait qu'à débit de précurseur donné, leur nombre et leur taille sont deux facteurs intimement liés. Ainsi, en vue de l'optimisation du procédé de dépôt, la maîtrise de leur formation est nécessaire. Celle-ci passe par la diminution du débit de précurseur, de la puissance incidente et de l'ensemble des débits de gaz, telles sont les perspectives principales de ce travail / This PhD work deals with the deposition of photocatalytic thin films of titanium dioxide at low temperature in the post-discharge of an atmospheric pressure plasma process. The main objective is the development of a low cost route for the deposition of self-cleaning coatings on 3D thermosensitive substrates. The deposited coatings present good photocatalytic properties which origin is firstly investigated. The elemental composition, the growth mechanisms and the crystallinity of three series of coatings corresponding to three different deposition temperatures are studied. The high specific surface of the coatings, due to the growth of agglomerates, appears to be the main parameter responsible for such photocatalytic properties. But these agglomerates are also responsible for the poor mechanical properties of the coatings as their adhesion decreases with their size. These agglomerates are formed in gas phase in recirculation loops and develop through multiple phenomena: CVD growth, agglomeration at the surface of the coating and redeposition due to the influence of the post-discharge on the surface of the coating. Moreover, at a given precursor flow rate, their number and their size are interlocked. Thus, with the aim of optimizing the deposition process, the control of the formation of such structures through the decrease of the precursor flow rate, the power input and the gas flows are mandatory and are a perspective of this PhD work

Orientador: Konstantin Georgiev Kostov / Resumo: Nos últimos anos, tem intensificado o emprego de plasmas em pressão atmosférica para diferentes aplicações. Com o desenvolvimento dos jatos de plasma em pressão atmosférica, alguns tratamentos precisos, como no campo biomédico ou em específicos processamentos de superfícies, tornaram-se mais frequentes. No entanto, a aplicação de plasma à objetos irregulares, dentro de tubos ou mesmo dentro de órgãos ocos é limitada quando se utilizam configurações convencionais de jatos de plasma. Portanto, essas limitações podem ser superadas com o desenvolvimento de jatos de plasma alongados ou gerados remotamente. Neste trabalho, duas configurações de jato de plasma longo visando diferentes campos de aplicação foram aperfeiçoadas e caracterizadas. Inicialmente foi desenvolvido um jato de plasma endoscópico (plasma endoscope) operando em configuração de descarga por barreira dielétrica (DBD) com dimensões milimétricas, versátil ao acoplamento em endoscópios típicos. Este jato de plasma pode operar com hélio ou neônio e conta com um canal externo e concêntrico de gás que permite a introdução de uma cortina de gás eletronegativo ao redor da pluma de plasma. A cortina de proteção a gás preserva a forma do jato de plasma quando operado dentro de cavidades fechadas. As dificuldades advindas do desenvolvimento deste foram investigadas quando diferentes gases foram testados como cortina de proteção dele, dentre estes, o dióxido de carbono se mostrou uma boa opção evitando a formação de descargas ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The use of atmospheric pressure plasmas for different purposes has increased in recent years. With the development of atmospheric pressure plasma jets, some precise treatments such as in the biomedical field or specific surface processing became more often. However, the delivery of plasma to irregular shaped objects, inside tubes or even hollow organs is limited with the use of conventional plasma jet configurations. Therefore, those limitations can be surpassed with the development of elongated or remotely generated plasma jets. In this work, two extended plasma jet configurations aiming at different application fields were further developed and characterized. Firstly, an endoscopic plasma jet (plasma endoscope) operating with a dielectric barrier discharge (DBD) configuration in millimeter dimensions that can be coupled to a typical endoscope was developed. This plasma jet can operate with helium or neon and counts with an external concentric shielding gas channel that provides the introduction of an electronegative gas curtain around the plasma plume. The shielding gas allows the preservation of the plasma jet shape when operated inside closed cavities. The construction difficulties arisen from the use of different feed and shielding gases were explored. Carbon dioxide was proven to be a good option for the curtain gas around the plasma plume avoiding the formation of parasitic discharges inside the shielding gas tube and the endoscopic housing. When operated with neon, th... (Complete abstract click electronic access below) / Doutor

Des études dans le domaine plasma-biologie ont démontré l'effet biocide des jets plasma à pression atmosphérique (JPPAs), faisant de ces dispositifs une alternative aux traitements classiques de décontamination microbiologique. Le gaz (ou mélange de gaz) utilisé et la puissance injectée dans le plasma ont été identifiés comme des paramètres importants influençant l'efficacité biocide des jets plasmas. Récemment, il a été rapporté qu'un autre facteur pouvait influencer l'effet biocide des jets plasmas : la nature de la cible en interaction avec le jet. Cette thèse propose d'étudier l'influence de la nature d'une cible sur les propriétés physiques et biocides des jets plasmas. Dans un premier temps, le jet plasma a été caractérisé en l'absence de cible à l'aide d'outils de diagnostics électriques (sonde de tension, sonde de courant, oscilloscope) et optiques (caméra ICCD, spectromètre optique). Ainsi, la caméra ICCD a permis l'observation de la propagation d'une onde d'ionisation à des vitesses très élevées (de l'ordre du km.s-1). Dans un second temps, la caractérisation a porté sur l'interaction du jet plasma avec d'une part une cible diélectrique (10-10 S.m-1) et d'autre part une cible conductrice (6.0 107 S.m-1). Les résultats montrent que lorsque l'onde d'ionisation atteint la cible diélectrique, celle-ci se propage de manière radiale sur la surface de la cible formant une onde d'ionisation surfacique. Pour la cible conductrice, un canal s'établit entre la source plasma et la surface de la cible, suivi éventuellement par la propagation d'une onde d'ionisation secondaire de la surface de la cible en direction de la sortie de la source plasma. Enfin, afin d'évaluer l'influence de la nature de la cible sur l'efficacité biocide du jet plasma, des suspensions d'endospores de Bacillus atrophaeus et de bactéries Escherichia Coli ont été utilisées comme indicateur biologique. Les endospores et les bactéries ont été inoculées sur la surface des cibles diélectriques et conductrices, puis exposées au jet plasma. Les résultats montrent des modifications différentes sur le manteau des spores et une efficacité biocide plus élevée pour la cible conductrice comparée à la cible diélectrique. En résumé, cette thèse montre que les effets biocides des jets plasmas doivent être évalués dans les conditions expérimentales qui correspondent à l'application envisagée. / Studies in the plasma-biology field have demonstrated the biocidal effect of atmospheric pressure plasma jets (JPPAs), making these devices an alternative to conventional biological decontamination treatments. The gas (or gas mixture) used and the power injected into the plasma were identified as the parameters influencing the biocidal efficacy of plasma jets. Recently, it has been reported that another factor may influence the biocidal effect of plasma jets: the nature of the target in interaction with the jet. This thesis proposes to study the influence of the nature of a target on the biocidal properties of plasma jets. Initially, the plasma jet was characterized in the absence of a target using electrical (voltage probe, current probe, oscilloscope) and optical (ICCD camera, optical spectrometer) diagnostic tools. The ICCD camera allowed the observation of the propagation of an ionization wave at very high velocities (of the order of km.s-1). Secondly, the characterization focused on the interaction of the plasma jet with a dielectric target (10-10 S.m-1) and a conductive target (6.0 107 S.m-1). The results show that when the ionization wave reaches the dielectric target, it propagates radially on the surface of the target forming a surface ionization wave. For the conductive target, a channel is established between the plasma source and the target surface, possibly followed by propagation of a secondary ionization wave from the target surface towards the plasma source outlet. Finally, the influence of the target nature on the biocidal efficacy of the plasma jet was studied. Endospores suspensions of Bacillus atrophaeus and Escherichia coli bacteria were used as biological indicator. Endospores and bacteria were inoculated on the surface of the dielectric and conductive target and exposed to the plasma jet. The results show different changes on the spores coat's and higher biocidal efficiency for the conductive target compared to the dielectric target. In summary, this thesis shows that the biocide effects of plasma jets should be evaluated under the experimental conditions corresponding to the intended applications.

The role of a protein-repelling coating is to limit the interaction between a device and its physiological environment. Plasma-polymerized-PEG (pp-PEG) surfaces are of great interest since they are known to avoid protein adsorption. and cell attachment. However, in all the studies previously published in the literature, the PEG coatings have been prepared using low pressure processes. In this thesis, we synthesize biocompatible pp-PEG coatings using atmospheric pressure plasma. Two original methods are developed to obtain these pp-PEG films. 1. Atmospheric pressure plasma liquid deposition (APPLD) consists in the injection of the precursor, tetra(ethylene glycol)dimethylether (tetraglyme), by means of a liquid spray, directly in the post-discharge of an atmospheric argon plasma torch. 2. In atmospheric pressure plasma-enhanced chemical vapor deposition (APPECVD), tetraglyme vapors are brought in the post-discharge trough a heating sprinkler. The chemical composition, as well as the non-fouling properties of the APPLD and APPECVD films, are compared to those of PEG coatings synthesized by conventional low pressure plasma processes. In the first part of the study, the effect of the power on the chemical composition of the films has been investigated by infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and secondary ions mass spectroscopy (SIMS). The surface analysis reveals that for the APPECVD samples, the fragmentation of the precursor increases as the power of the treatment is increased. In other terms, the lower the plasma power is, the higher the “PEG character” of the resulting films is. Indeed, the C-O component (286.5 eV) of the XPS C 1s peak is decreasing while the hydrocarbon component (285 eV) is increasing as the power of the plasma is increased. The same conclusion can be drawn from the signature ToF-SIMS peaks (m/z = 45 (CH3OCH2+ and +CH2CH2OH), 59 (CH3OCH2CH2+), 103 (CH3(OCH2CH2)2+)) that are decreasing in the case of high power treatments. Accordingly, IRRAS measurements show that the C-O stretching band is decreasing for high power plasma deposition. This is in agreement with the observations made from the analysis of the LP PECVD coatings and from the literature. The films deposited by the APPLD process do not show the same behavior. Indeed, whatever the power injected into the discharge is, we are able to achieve films with a relatively high PEG character (83 %). The second part of this study is dedicated to the evaluation of the non-fouling properties of the coatings by exposing them to proteins (bovine serum albumin and human fibrinogen) and cells (mouse fibroblasts (L929 and MEF)) and controlling the adsorption with XPS (proteins) and SEM (cells). For the APPECVD samples, a low plasma power (30 W) leads to an important reduction of protein adsorption and cell adhesion (over 85%). However, higher-powered treatments tend to reduce the non-fouling ability of the surfaces (around 50% of reduction for a 80 W deposition). The same order of magnitude (over 90% reduction of the adsorption) is obtained for the APPLD surfaces, whatever is the power of the treatment. Those results show an important difference between the two processes in terms of power of the plasma treatment, and a strong relationship between the surface chemistry and the adsorption behavior: the more the PEG character is preserved, the more protein-repellent and cell-repellent is the surface. / Le rôle d’une couche empêchant l’adsorption de protéines est de limiter les interactions entre un implant et le milieu physiologique auquel il est exposé. Les films de poly(éthylène glycol) polymérisés par plasma (pp-PEG) sont d’intérêt majeur car ils sont connus pour empêcher l’adsorption de protéines ainsi que l’attachement cellulaire. Cependant, dans toutes les études publiées précédemment, les couches de type PEG ont été réalisées sous vide. Dans cette thèse de doctorat, nous synthétisons des couches de type pp-PEG biocompatibles par plasmas à pression atmosphérique. A cette fin, deux méthodes originales ont été développées. 1. La première méthode consiste en l’injection du précurseur, le tetra(éthylène glycol) diméthyl éther (tetraglyme), en phase liquide, en nébulisant ce dernier au moyen d’un spray, directement dans la post-décharge d’une torche à plasma atmosphérique fonctionnant à l’argon. En anglais, nous appelons ce procédé « Atmospheric pressure plasma liquid deposition (APPLD) ». 2. Dans la deuxième méthode, appelée en anglais « Atmospheric pressure plasma-enhanced chemical vapor deposition (APPECVD)», le tetraglyme est amené en phase vapeur dans la post-décharge, au moyen d’un diffuseur chauffant. La composition chimique des dépôts de type APPLD et APPECVD, ainsi que leurs propriétés d’anti-adsorption sont évaluées, et comparées aux dépôts pp-PEG obtenus par les méthodes à basse pression conventionnelles. Dans la première partie de cette étude, nous nous focalisons sur la composition chimique des films déposés, et plus particulièrement sur l’influence de la puissance injectée dans le plasma sur cette composition chimique. A cette fin, nous avons fait appel à des techniques d’analyse telles que la spectroscopie de réflexion-absorption infrarouge (IRRAS), la spectroscopie des photoélectrons X (XPS) et la spectrométrie de masse des ions secondaires (SIMS). Il en ressort que les films de type APPECVD perdent progressivement leur « caractère PEG » à mesure que la puissance de la décharge plasma est élevée. Cela serait dû à une plus grande fragmentation du précurseur dans la post-décharge d’un plasma plus énergétique. Cette tendance est cohérente avec ce que nous avons observé pour les dépôts à basse pression ainsi que dans la littérature. Dans le cas des films de type APPLD, un tel comportement n’a pas été mis en évidence : quelle que soit la puissance dissipée dans le plasma, les films présentent un « caractère PEG » relativement élevé. La deuxième partie de cette thèse est dédiée à l’évaluation des propriétés d’anti-adsorption des films synthétisés, en les exposant à des protéines (albumine de sérum bovin et fibrinogène humain) et des cellules (fibroblastes de souris, L929 et MEF). L’adsorption de protéines est contrôlée par XPS tandis que l’attachement cellulaire est contrôlé par imagerie SEM. Pour les échantillons de type APPECVD, un dépôt à faible puissance (30 W) mène à une importante réduction de l’adsorption de protéines et de cellules (> 85%) tandis qu’à de plus hautes puissances (80 W), l’anti-adsorption est sensiblement diminuée (50% de réduction). Dans le cas des dépôts de type APPLD, quelle que soit la puissance du plasma, une forte diminution de l’adsorption de protéines et de cellules est observée (> 90 %). Ces résultats montrent une différence majeure entre les deux procédés quant à l’influence de la puissance du plasma ainsi qu’une forte relation entre la composition chimique de la surface synthétisée et son pouvoir d’anti-adsorption : plus le « caractère PEG » du dépôt est conservé, plus la surface empêchera l’interaction avec les protéines et les cellules.

The research presented in this dissertation involves the development of chiral and achiral analysis using capillary electrochromatography (CEC) and CEC coupled to mass spectrometry (CEC-MS). Chapter 1 briefly reviews CEC fundamentals and latest development on chiral CEC and CEC-MS. The CEC-UV enantioseparations for several acidic compounds are described in Chapter 2. The optimum resolutions for these acidic enantiomers are achieved in ion-suppression mode, i.e. with an acidic mobile phase. One of major drawback in coupling CEC with MS is the bubble formation at the column outlet end, resulting in irreproducible retention time and erratic baseline, or even current breakdown. By introducing internal tapered columns, the aforementioned limitations of CEC-MS are successfully overcome in Chapter 3. The CEC-MS enantioseparation of warfarin and coumachlor is carefully investigated and applied to quantify R- and S-warfarin in human plasma. For individual enantiomers, a concentration of 25 ng/mL is detectable. To further improve the robustness of CEC-MS column, a new procedure of fabricating internal tapered columns is reported in Chapter 4. These internal tapered columns demonstrate excellent ruggedness, low background noise, and good compatibility in reversed-phase and polar organic modes of CEC-MS. In chapter 5, the feasibility of using internal tapered columns packed with vancomycin chiral stationary phase (CSP) is explored for simultaneous enantioseparation of eight â-blockers using CEC-MS. After a careful optimization of the mobile phase composition, sheath liquid and spray chamber parameter, 15 out of 16 enantiomers could be simultaneously resolved with excellent efficiency and detection sensitivity. The synthesis and characterization of sulfated and sulfonated cellulose phenylcarbamate CSPs is described in Chapter 6. The use of these CSPs, especially the sulfonated one, significantly enhances the EOF profile and sample throughput but maintain high enantiomeric resolving power under various modes of CEC and CEC-MS. By combining CEC and atmospheric pressure photo-ionization (APPI) MS, Chapter 7 demonstrates the separation and detection of mono-methylated benzo[a]pyrene (MBAP) isomers with ~100 times enhancement on detection sensitivity than CEC-UV. In Appedix 2, monolithic columns are synthesized through photopolymerized sol-gel approach and utilized for CEC and CEC-APPI-MS of polyaromatic hydrocarbons, and alkyl phenyl ketones.

This dissertation proposed the idea of “plasma-enhanced chemical vapor deposition on living substrates (PECVD on living substrates)” to bridge the gap between the thin film deposition technology and the biological and living substrates. This study focuses on the establishment of the knowledge and techniques necessary to perform “PECVD on living substrates” and contains three main aspects: development, characterization, and biological applications. First, a PECVD tool which can operate in ambient air and at low temperature was developed using a helium dielectric barrier discharge jet (DBD jet). It was demonstrated that various materials, such as polymeric, metallic, and composite films, can be readily synthesized through this technique. Second, the PMMA and copper films deposited using DBD jets were characterized. High-rate (22 nm/s), low-temperature (39 ºC) PMMA deposition was achieved and the film surface morphology can be tailored by altering the discharge power. Conductive copper films with an electrical resistivity lower than 1×10-7 ohm-m were obtained through hydrogen reduction. Both PMMA and copper films can be grown on temperature-sensitive substrates, such as plastics, pork skin, and even fingernail. The electrical, optical, and imaging characterization of the DBD jets was also conducted and several new findings were reported. Multiple short-duration current pulses instead of only one broad pulse per half voltage cycle were observed when a dielectric substrate was employed. Each short-duration current pulse is induced by a leading ionization wave followed by the formation of a plasma channel. Precursor addition further changed the temporal sequence of the pulses. An increase in the power led to a mode change from a diffuse DBD jet to a concentrated one. This mode change showed significant dependence on the precursor type, tube size, and electrode configuration. These findings regarding the discharge characteristics can thus facilitate the development of DBD-jet operation strategies to improve the deposition efficacy. Finally, this technique was used to grow PMMA films onto agar to demonstrate one of its potential biological applications: sterile bandage deposition. The DBD jet with the film depositing ability enabled the surface to be not only efficiently sanitized but also protected by a coating from being reached by bacteria.

No description available.

An enantioselective heart-cut two-dimensional liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry method was developed for the analysis of 25 methylsulfonyl polychlorinated biphenyl metabolites in tissue extracts. Enantioseparation was achieved for 9 out of the 10 chiral analytes in less than 91 minutes, improving upon previous gas chromatography-based methods. Use of a pyrenyl-ethyl silica column in the first dimension enabled separation of all but two pairs of isobaric analytes. Limits of detection of 0.01 to 1.73 ng on-column were achieved. The precision and accuracy were within acceptable limits, but poor sensitivity was achieved for several meta-methylsulfonyl-substituted congeners. Despite this limitation, the method was successfully applied to the analysis of Greenland sledge dog (Canis familiaris) plasma and adipose tissue extracts. Concentration and enantiomer fraction data are presented. None of the target analytes were detected in Norwegian glaucous gull (Larus hyperboreus) plasma extracts.