Le développement dans l'industrie aéronautique des composites à matrices organiques renforcés par des fibres de carbone se justifie entre autres par leur très bonne capacité à transférer les efforts mécaniques élevés en rapport de leur faible masse. Les matrices Poly-EtherEtherCétone (PEEK) sont des candidates idéales pour les applications structurales en raison de leurs bonnes propriétés chimiques, mécaniques, ainsi que d'une stabilité thermique supérieure à d'autres polymères. Cependant celles-ci présentent des inconvénients majeurs pour la phase de mise en peinture, à savoir une faible réactivité de surface et une inertie chimique importante qui impliquent le développement d'un procédé d'activation de surface avant toute étape de revêtement. Ce travail se concentre sur une technologie de plasma froid à la pression atmosphérique développée par la société AcXys Technologie(r) : le module ULS en post-décharge. Cette technologie, choisie sur la base de considérations industrielles et environnementales, vise à garantir une activation de surface efficace, sans détérioration des propriétés intrinsèques de la matrice polymère. L'objectif de ce travail est alors d'améliorer la compréhension des mécanismes d'activation par plasma menant à une meilleure adhésion à l'interface composite PEEK/revêtement industriel. Des caractérisations électriques et optiques de la décharge et de la post-décharge nous permettront de mieux comprendre le fonctionnement intrinsèque de l'équipement. Tandis que la caractérisation des modifications de surface (de nature chimiques, physiques et/ou physico-chimiques), notamment au travers de la mouillabilité et de l'acido-basicité, permet d'appréhender l'influence des paramètres opératoires et du gaz plasmagène utilisé. Dans la perspective de mieux spécifier les conditions optimales d'utilisation industrielles, nous évaluons dans cette étude la pertinence de l'utilisation de la notion de dose plasma pour ce procédé, notion représentative de l'ensemble des paramètres opératoires. Cette notion, communément rencontrée dans d'autres procédés, est revue et développée pour correspondre à notre cas d'étude. Son utilisation permet une juste comparaison entre des configurations d'activation différentes puisqu'elle rend compte à la fois de la puissance dissipée sur le substrat et du temps d'interaction plasma/surface. Afin de valider la dose plasma exprimée pour notre équipement, nous introduisons des mesures d'adhérence effectuées entre le composite activé et le revêtement. Les résultats laissent entrevoir des perspectives d'améliorations dans les procédés industriels d'activation de surface. / Carbon Fiber Reinforced Polymer (CFRP) using thermoplastic polymer matrices as Poly-EtherEtherKetone (PEEK) for example, are increasingly being used in structural engineering due to their light weight coupled with good mechanical properties. In aeronautic industry, the adhesive bonding of these composites is often required. However, their low surface energy motivates the development of robust and reliable surface activation treatments aiming at increasing the surface reactivity before painting. For this reason, we have used an atmospheric pressure plasma torch developed by AcXys Technologies(r). It is a remote plasma, well known to be an effective process to improve surface reactivity without deterioration of the bulk matrix properties. This easily implementable technology attracts many industries looking for a cost-effective and eco-friendly surface activation process. The aim of this work is to contribute to the understanding of plasma activation mechanisms leading to a greater and a more durable adhesion between PEEK matrix and an industrial painting. This study provides some insight into the effects of process parameters (device power, distance between nozzle and substrate, etc) on adhesion improvement. Mechanisms which are attributed to it are investigated by means of three point bending and crosscut adhesion standard tests. Results are discussed with respect to surface properties characterized by wettability measurements including acid-base approach, X-ray Photoelectrons Spectroscopy and Atomic Force Microscopy. In order to facilitate industrialization of atmospheric pressure remote plasma as surface activation technique, this study proposes a new approach aiming at allowing a better and more equitable comparison between atmospheric pressure plasma processes. This comparison is made through the "plasma dose" expression, similar to the one commonly used in Corona process. It is applicable for one plasma gas and accounts for both received energy and interaction time of the post-discharge with the surface. Mechanisms assigned to improvement of adhesion will be more appreciated and their characterization will contribute to a greater definition of industrial surface preparation range by remote plasma.

Negative effects of high temperatures on cattle milk production is a specific problem. Dairy-cows, who produce much more heat than cows that are not milked, are more susceptible to high temperatures of the surrounding environment than other cattle. Changes in temperatures and atmospheric pressure were monitored throughout a year and then its influence on the milk production of cattle has been evaluated. It has been discovered that low temperatures do not have any significant influence on dairy-cows. However, at high temperatures dairy-cows suffer from heat stress and it leads to lower volumes of the daily milk production. The Holstein breed showed a higher sensitivity to temperature fluctuations than the Czech spotted breed; however, the Holstein breed milk production is better balanced in a long run (a year period).

In this thesis I deal with the project of a robotic apparatus that could be used for material treatment by using the gliding arc discharge as well as the appropriate design and choice of materials for the atmospheric pressure discharge jet with regards to a possibility of an industrial use. The input and output parameters were studied, such as the air flow regulation with regards to cooling, the design and choice of materials. Then I observed the temperatures near electrodes depending on the air flow. The applicability of the created atmospheric discharge was taken into account.

La réponse biologique d’un matériau est essentiellement reliée à sa surface : cela souligne l’importance du rôle des techniques de modification de surface dans la réalisation d’une réponse biologique adaptée. Ainsi les surfaces fonctionnalisées par des ‘hydrogels’ minces possèdent un énorme potentiel dans diverses applications. En effet, les hydrogels sensibles au pH et à la température peuvent être utilisés dans le but de libérer de façon contrôlée une molécule dans l’environnement biologique. Ces hydrogels peuvent aussi être utilisés en tant que biocapteur de par leurs fonctions disponibles permettant la reconnaissance spécifique de biomolécules cibles. Différents procédés, choisis principalement en fonction du type de matériau et de la surface à fonctionnaliser, peuvent être utilisés pour l’obtention de ce genre de films. Parmi ces procédés, le choix s’est tourné vers l’utilisation de la polymérisation par plasma dont les propriétés de surfaces peuvent être ajustées en fonction des paramètres de la décharge tel que la puissance électrique, le temps de traitement, la composition et la pression du gaz. / For various industrial applications, there is an urgent need to obtain cost effective coatings having the desired functional groups. Among such methods, dielectric barrier discharge (DBD) at atmospheric pressure makes it possible to modify the physical properties and the chemical composition of various substrates. It is possible to control the chemical nature of the resulting plasma polymer by using appropriate plasma parameters to provide homogeneous and pinhole free films with good surface coverage and preservation of the functional groups present in the used monomers. In this way different articles show the possibility of using plasma deposition to obtain coatings with different chemically reactive moieties widely used for applications in sensor technology and in life science. It has been established that through the control of the plasma parameters it is possible to produce plasma polymers coatings from acrylic acid with a high fraction of carboxylic functionality retained from the monomer. In this way, atmospheric pressure plasma polymerization has been used to create coating able to be used as biosensor as well as drug delivery.

Orientador: Hilary Castle de Menezes / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-04T14:08:09Z (GMT). No. of bitstreams: 1 Torezan_GabrielaAparecidaPompeu_D.pdf: 5215421 bytes, checksum: 2cefe1bcde6d43c19ecb1fdfc1763eac (MD5) Previous issue date: 2005 / Resumo: O desenvolvimento de novos produtos visando o uso de matérias-primas nacionais é de grande interesse para a economia do país, uma vez que agrega valor ao produto e diminui o grande excedente da produção que resulta muitas vezes em perdas. A manga possui apreciação de destaque dentre as frutas tropicais em todo o mundo, é uma matéria-prima barata, presente em abundância em nosso país, mas em contrapartida as perdas da produção chegam a até 30%. Dentro desse contexto e aliando-se o aumento nos últimos tempos da procura por produtos de conveniência, o Departamento de Tecnologia de Alimentos da Unicamp em parceria com o CIRAD (Centre de Coopération International em Recherche Agronomique pour le Développment) ¿ Montpellier/França, implantou uma nova linha de pesquisa que visa expandir a aplicação de fritura em frutas para a produção de chips, da qual faz parte o presente trabalho, tendo como matéria prima a manga. Os estudos foram direcionados a fim de se obter parâmetros otimizados de processos, tipo de pré tratamento (desidratação osmótica), variedade e ponto de maturação da matéria-prima, e caracterização dos produtos finais, quanto aos aspectos químicos, físicos, microscópicos e sensoriais. Primeiramente foram estudadas e estabelecidas algumas condições de processo de fritura, como: razão fruta:óleo (p/p) de 1:4, reutilização do óleo até 15 frituras (3 minutos cada à temperatura de 160°C); espessura das fatias de 3mm, sem descascamento e desidratação osmótica à pressão ambiente com agitação. Em seguida, o pré tratamento de desidratação osmótica foi estudado através da Metodologia de Superfície de Resposta (MSR), verificando-se um aumento das taxas de transferência de massa com aumento do tempo e temperatura; a imersão em banhos consecutivos de solução osmótica com concentração crescente (35, 45 e 65 °Brix; 35 e 65°Brix), empregada a fim de se aumentar o teor de sólidos finais do produto desidratado osmoticamente também foi avaliada; os resultados mostraram no entanto que o aumento dos sólidos obtido pelo uso dos banhos não acarretou em aumento da qualidade final dos chips (aceitação sensorial). Estabelecida a condição de desidratação osmótica (80 minutos, 40°C, agitação de 200rpm, solução sacarose 65°Brix, relação fruta e solução 1:4 (p/p)), o processo de fritura foi estudado através da MSR, sendo analisados os teores de umidade, lipídeos, parâmetros de cor (L*, a*, b*) e aceitação sensorial (aparência, cor, aroma, sabor, textura e intenção de compra). As respostas teor de umidade e aceitação da cor e do sabor foram escolhidas para definição da faixa ótima de tempo (140-180s) e temperatura (155-165°C) de fritura. Estabelecidas as condições do método combinado desidratação osmótica ¿ fritura, foram comparados os chips de manga das cultivares Tommy Atkins e Palmer, nos estágios de maturação verde, ¿de vez¿ e maduro. As análises mostraram que a matéria-prima das duas cultivares, no ponto de maturação verde e ¿de vez¿, foram as de melhor qualidade. As micrografias dos chips de manga apresentaram encolhimento da matriz celular, células plasmolizadas, resultantes da rápida evaporação da água devido à alta temperatura de processo, e glóbulos de óleo aderidos na superfície do tecido ou nos poros criados pela saída da água. As isotermas de sorção dos chips de manga Tommy Atkins e Palmer apresentaram característica do tipo III, e o fenômeno de adsorção começou em atividade de água 0,4, indicando uma boa estabilidade dos produtos. O último trabalho foi conduzido no CIRAD ¿ França, e consistiu na aplicação de pressão reduzida durante o processo de fritura, e os efeitos observados no desenvolvimento de cor dos chips, utilizando uma fruta modelo (maçã Granny Smith). Os resultados revelaram a grande vantagem de aplicação de vácuo, com a obtenção de chips com menor teor de água e praticamente nenhum escurecimento em relação ao material in natura. A aplicação do processo combinado desidratação osmótica ¿ fritura (à pressão atmosférica) para obtenção de chips de manga se mostrou prática, sem a necessidade de equipamentos sofisticados, econômica (uso de materiais abundantes e baratos, como a manga e a sacarose), resultando em um produto de boas características de qualidade, com baixos teores de umidade (2-5%) e de lipídeos (11-13%) e boa aceitação sensorial sensorial (variando entre gostei ligeiramente e gostei moderadamente), mostrando ser uma ótima aplicação de tecnologia para desenvolvimento de um novo produto e agregação de valor à matéria-prima / Abstract: The development of new products using national raw materials is of considerable importance to the national economy, adding value to the product and decreasing surplus production, resulting in increasingly smaller losses. Throughout the World, the mango stands out amongst the tropical fruits, being a cheap raw material, produced in abundance in this country, although currently, production losses reach 30%. In this context and considering the current demand for convenience foods, the Department of Food Technology/UNICAMP/Brazil in partnership with CIRAD (Centre de Coopération International em Recherche Agronomique pour le Développment), Montpellier/France, implanted a new research line aimed at expanding the application of frying to fruits, for the production of chips and this thesis is part of this research line. The studies were directed at optimising the process parameters, defining the type of pre-treatment (osmotic dehydration), raw material variety and maturation and characterising the final products with respect to their chemical, physical, microscopic and sensory aspects. Firstly some of the frying conditions were studied and established, such as: fruit:oil (w/w) ratio of 1:4; re-use of the frying oil up to 15 times without alterations of the oil or the product; 3mm thickness of the mango slices without peeling and osmotic dehydration at atmospheric pressure with agitation. The osmotic dehydration pre-treatment was then studied using Response Surface Methodology (RSM). Immersion in consecutive baths of increasingly concentrated osmotic solution (35, 45 and 65°Brix; 35 and 65°Brix) was also studied, aimed at increasing the final solids content of the osmotically dehydrated product. However, the results showed that this procedure did not result in an improvement in chip quality (sensory acceptance). Having determined the conditions for osmotic dehydration (80 minutes and 40°C), the frying process was studied using RSM, analysing the moisture and lipid contents, colour parameters (L*, a*, b*) and sensory acceptance (appearance, colour, aroma, flavour, texture and intent to buy). The responses of moisture content, colour and taste acceptance were chosen to define the optimal ranges of time (140-180s) and temperature (155-165°C). Having established the conditions for the combined osmotic dehydration ¿ deep fat frying method, mango chips made from the cultivars Tommy Atkins and Palmer were compared, and also the states of maturity (mature green, half ripe and ripe). The analyses showed that for both cultivars, the mature green and the half ripe states of maturity gave the best quality chips. The chip micrographs presented a shrunk cellular matrix, plasmolyzed cells, results of the rapidly evaporated surface water by the high temperature process and oil globules adhered at the surface tissue or at the porous created by the water vaporisation. The sorption isotherms of Tommy Atkins and Palmer mango chips had type III characteristics, and the adsorption phenomenon starts at water activity above 0.4, showing good product stability. The last part of the study was conducted at CIRAD, France, and consisted of the application of reduced pressure during the frying process of a model fruit (Granny Smith apples), and the effects observed on chip colour development. The results showed the great advantage of applying vacuum, obtaining chips with lower moisture content and almost no darkening as compared to the raw material. The application of the combined osmotic dehydration ¿ frying method (at atmospheric pressure) to obtain mango chips was shown to be practical, not requiring sophisticated equipment, economic (use of cheap, abundant raw materials, such as mango and sucrose), resulting in a product with good quality characteristics, low moisture (2 - 5%) and lipid (11 ¿ 13%) contents and good sensory acceptance (6-7), showing itself to be an optimum technological application to develop a new product and add value to the raw material / Doutorado / Tecnologia de Alimentos / Doutor em Tecnologia de Alimentos

Durant la dernière décennie, un nouveau type de décharge hors équilibre thermodynamique à pression atmosphérique a suscité un engouement croissant compte tenu de sa capacité de produire un plasma s'étendant dans l'air ambiant à une température proche de l'ambiante. Ces jets de plasma, souvent basés sur un réacteur de type décharge à barrière diélectrique, sont intéressants du point de vue de leurs propriétés physico-chimiques. De plus, ces jets de plasmas ont l'avantage de permettre des applications des matériaux thermosensibles, ouvrant ainsi un nouveau domaine de recherche, Plasma Médecine. Au GREMI le Plasma Gun, a été développé tant pour l'étude de la physique des jets de plasma que pour les applications biomédicales notamment dans le domaine de la cancérologie. Dans une première étape, des traitements par Plasma Gun in vitro et in vivo, dans le cadre d'un modèle murin du carcinome pancréatique, ont été effectués. L'action anti-tumorale du plasma a été démontrée ainsi que la combinaison bénéfique avec un traitement chimiothérapique. Fondée sur ces résultats encourageants, l'objectif principal de cette étude porte sur l'influence drastique de la cible de l'application sur les propriétés du plasma (propagation et production des espèces réactives) ainsi que l'interaction du gaz et du plasma. Des diagnostiques tels que l'imagerie rapide et filtrée en longueur d'onde, la spectroscopie d'émission optique, l'imagerie Schlieren ainsi que la spectroscopie infrarouge à transformée de Fourier ont été utilisés pour caractériser le jet de plasma. Une étude quantitative de la distribution spatiale et temporelle du radical hydroxyle (densité comprise entre 5.1011 et 1.1014 cm-3) a été réalisée par fluorescence induite par laser. L'étude de l'OH en combinaison avec un modèle numérique a permis une meilleure compréhension de la pénétration de l'air dans le jet de gaz et de l'interaction avec les surfaces humides. L'interaction complexe entre le comportement du gaz, du plasma et la nature de la cible est mise en avant en vue d'optimiser les applications biomédicales. / Over the past decade, a new type of non-equilibrium discharge at atmospheric pressure has attracted growing interest, given the ability to produce a plasma extending in ambient air close to room temperatures. These plasma jets, often based on a dielectric barrier discharge type of reactor, are interesting on their physicochemical property perspectives. In addition, these cold plasma jets have the advantage of allowing applications to heat sensitive materials, creating a new field of research, Plasma Medicine. At GREMI the Plasma Gun, has been developed for both the study of the physics of plasma jets and for biomedical applications particularly in the field of cancerology. In a first step, in vitro and in vivo were performed, within a rodent model of pancreatic carcinoma. The anti-tumor action of the plasma has been demonstrated as well as its benefic combination with a chemotherapeutic treatment. Based on these encouraging biomedical results, the main focus of this study is to report on the drastic influence of the application target on the plasma properties (propagation and production of reactive species) and on the strong coupling between gas jet and plasma discharge. Diagnostics such as fast, wavelength-filtered and Schlieren imaging, optical emission spectroscopy as well as Fourier transform infrared spectroscopy were used to characterize the plasma. A quantitative study on spatial and temporal distribution of hydroxyl radicals (OH density ranging between 5.1011 and 1.1014 cm-3) was performed by laser-induced fluorescence. The study of the OH in combination with a numerical model allowed a better understanding of the moist air penetration into the gas jet and the interaction with wet surfaces. This PhD work enlightened the complex interaction between the gas flow, the plasma and the nature of the target which has to be taken into account for further optimization of biomedical applications.

Gegenstand dieser Arbeit war die Untersuchung antimikrobieller Dünnfilme mit Ag, Cu oder Zn, welche durch Anwendung einer Atmosphärendruck-Plasmatechnologie abgeschieden wurden. Bei der Abscheidung solcher Schichtsysteme ist von Wechselwirkungen zwischen dem Plasma und der Holzoberfläche auszugehen. Um solche Effekte abschätzen zu können wurden Versuche hinsichtlich makroskopischer, mikroskopischer und molekularer Materialeigenschaften durchgeführt. Diese Untersuchungen wurden primär mit dem Ziel durchgeführt, mögliche Wechselwirkungen zwischen dem reaktiven Plasma und Plasmabestandteilen mit der Oberfläche des Holzes besser zu verstehen und in zukünftigen Prozesses gezielt anwenden zu können. Unabhängig von der verwendeten Plasmaquelle und Holzart führten die Behandlungen zu einer verbesserten Benetzbarkeit der Holzoberfläche mit Wasser und zu einer deutlichen Erhöhung der polaren Komponente der Oberflächenenergie. Der Nachweis molekularer Veränderungen wurde durch ATR-FTIR- und XPS-Untersuchungen (einschließlich chemischer Derivatisierung) durchgeführt. Um den Einfluss von Holzinhaltsstoffen und Holzinhomogenitäten zu reduzieren, wurde der Einfluss auf die Holzbestandteile Cellulose und Lignin untersucht. Nach der Plasmabehandlung konnte die Bildung von O-C-Doppelbindungen durch ATR-FTIR für beide Materialien bestätigt werden. Die Bildung von sauerstoffhaltigen, polaren Funktionalitäten auf Cellulose und Lignin konnte auch durch XPSMessungen bestätigt werden. Die chemische Derivatisierung von Cellulose in Kombination mit XPS hat die Bildung von O-C-Doppelbindungen in Verbindung mit dem Abbau von OH-Gruppen aufgezeigt. Ein qualitativ vergleichbarer Behandlungseffekt konnte zwischen Plasma- und Ozonbehandlung nachgewiesen werden; Quantitativ waren die Plasmabehandlungseffekte jedoch deutlich ausgeprägter. Somit kann das vom Plasma gebildete Ozon nicht allein für den Behandlungseffekt verantwortlich sein, und weitere Reaktionsmechanismen müssen in die Interpretation der Ergebnisse einbezogen werden. Untersuchungen zur Abscheidung von SiO2- und TiO2 Schichten haben gezeigt, dass die Prozessparameter exakt angepasst werden müssen. Die Schichtqualität wurde maßgeblich durch die Wahl der chemischen Vorläufer und den Abstand zwischen dem Eintrittspunkt dieser Precursor und dem Substrat bestimmt. REM- und XPS-Untersuchungen bestätigten den Einbau der Elemente Ag, Cu oder Zn in nanopartikulärer Form in die Schichten. Die Abscheidung dieser Schichten auf Holz erzeugte signifikante bakterizide Eigenschaften gegen E. coli. Im Gegensatz dazu war die fungizide Wirkung gering. Durch die Wirkstoffkombination hingegen konnte eine deutliche Steigerung der Schimmelpilz-Mangeleigenschaften erreicht werden. Für mögliche Außenanwendungen und ausreichenden Schutz musste das Eindringen von Wasser in das Holz zusätzlich reduziert werden. Zu diesem Zweck wurden die funktionalisierten Plasmaschichten zusätzlich mit einer Deckschicht versehen. Der Plasmafilm übernahm dabei zwei wesentliche Aufgaben: die Haftung der Deckschicht und die Gewährleistung antimikrobieller Eigenschaften. Insbesondere die Verwendung des SiO2-Films in Verbindung mit einem Primersystem erhöhte die Nassschichthaftung deutlich. Das verwendete Schichtsystem (Plasmafilm + Deckschicht) zeigte sowohl unter künstlicher als auch bei natürlicher Witterung Vorteile gegenüber einem kommerziellen Schichtaufbau (Bläueschutzgrundierung + Decklack). Die Haftung der Deckschicht war nach künstlicher und natürlicher Bewitterung für Plasmaaufbau beständiger. Darüber hinaus zeigte die Plasmagrundierung hinsichtlich der Wirksamkeit des Bläueschutzes unter 11 monatiger natürlicher Bewitterung vergleichbare Eigenschaften im Vergleich zu der kommerziellen Grundierung. Werden die dabei eingesetzten Wirkstoffmengen betrachtet, war die eingebrachte Menge bei der Plasmagrundierung um einen Faktor von schätzungsweise 100-mal geringer als bei der Standardgrundierung. Die im Holzschutz eingesetzten Biozide verursachen hohe Kosten und sind gesundheits- und umweltschädigend. Vom Gesetzgeber wird deshalb gefordert, biozidfreie Alternativen anzuwenden bzw. Maßnahmen zur Minimierung des Biozideinsatzes zur ergreifen. In Folge dessen könnten mit Blick auf eine mögliche Anwendung die hohen Kosten des Einsatzes biozider Stoffe reduziert werden, eine Reduktion der Wirkstoffmenge aber auch zum Umweltschutz und zu einer höheren Akzeptanz bei Verbrauchern beitragen.:Abkürzungsverzeichnis IX Tabellenverzeichnis XI Abbildungsverzeichnis XII 1 Einleitung 1 1.1 Motivation 1 1.2 Zielstellung 2 1.3 Holz und Holzschutz 3 1.3.1 Aufbau und Bestandteile 3 1.3.2 Holzschädigung 4 1.3.3 Mikroorganismen 6 1.3.4 Holzschutz 7 1.4 Plasma 8 1.5 Technische Erzeugung kalter Atmosphärendruckplasmen 9 1.5.1 Atmosphärendruckplasmabehandlung von Holz und Holzbestandteilen 12 1.6 Schichtabscheidung mittels Atmosphärendruckplasma 15 1.6.1 Plasmapolymerisation und Schichtwachstum 16 1.6.2 Funktionelle Beschichtungen 17 1.6.3 Antimikrobielle Oberflächen 19 2 Material und Methoden 22 2.1 Geräte und Verbrauchsmaterial 22 2.2 Plasmaquellen 25 2.2.1 Behandlung 26 2.2.2 APP-CVD und Precursordosierung 27 2.3 Ozonbehandlung 28 2.4 Precursorauswahl 29 2.5 Instrumentelle Analytik 30 2.5.1 Kontaktwinkel und Oberflächenenergie 30 2.5.2 pH-Wert-Messung 32 2.5.3 Schichtdickenmessung 32 2.5.4 Fourier Transform Infrarot Spektroskopie (FT-IR) 33 2.5.5 Rasterelektronenmikroskopie (REM) 34 2.5.6 Röntgen-Photoelektronenspektroskopie (XPS) 35 2.6 Antimikrobielle Untersuchungen 39 2.6.1 BacTiter-Glo® 39 2.6.2 Plattenzählverfahren (KbE-Test) 41 2.6.3 Schimmelpilzbeständigkeit nach DIN EN 60068-2-10 41 2.6.4 Bläuebeständigkeit nach DIN EN 152:2012 42 2.7 Lackhaftung 43 2.7.1 Gitterschnittprüfung nach ISO 2409:2013 43 2.7.2 Künstliche Bewitterung nach EN 927-6 44 2.7.3 Freibewitterung nach EN 927-3 44 2.7.4 Farbveränderung 44 3 Einfluss von Plasma auf Holz 45 3.1 Charakteristika von Plasmaquelle und Material 45 3.2 Makroskopische Veränderungen 47 3.2.1 Kontaktwinkel- und Oberflächenenergiebestimmung 47 3.2.2 Allgemeiner Einfluss durch Atmosphärendruckbehandlung 52 3.2.3 Einfluss Substratmaterial auf Behandlungseffekt 54 3.2.4 Alterung und Extraktstoffeinfluss /Harzanteil 55 3.2.5 Einfluss Plasmasystem 57 3.2.6 Benetzbarkeit nach Ozonbehandlung 60 3.2.7 Einfluss von Plasmabeschichtungen 61 3.3 Änderung pH-Wert 63 3.5 Molekulare Veränderungen 65 3.5.1 ATR-FTIR an Textilzellstoff und Lignin 66 3.5.2 XPS: Sauerstoff/Kohlenstoff-Verhältnis 69 3.5.3 XPS: Nutzung der chemischen Derivatisierung 72 3.5.4 C1s-Detailspektren Textilzellstoff 79 3.5.5 C1s-Detailspektren Lignin 81 3.6 Fazit 86 4 Funktionelle Beschichtungen 87 4.1 Siliziumoxid- und Titanoxidmatrixschichten 87 4.2 Erweiterte Funktionalisierung (Kompositbeschichtungen) 89 4.3 Antimikrobielle Eigenschaften 94 4.4 Plasmagrundierung 103 4.4.1 Lackhaftung 103 4.4.2 Schichtleistung: Wasseraufnahme 107 4.4.3 Schichtleistung: künstliche und natürliche Bewitterung 107 4.4.4 Schichtleistung: antimikrobielle Wirkung 110 4.5 Fazit 112 5 Zusammenfassung 114 6 Ausblick 118 Literaturverzeichnis nach IEEE 119

Vernix caseosa is a natural biofilm which covers the skin of a human fetus from the third trimester of pregnancy. It has hydrating, regenerating and anti-microbial effects. The components responsible for these properties of vernix caseosa could be used in the pharmaceutical and cosmetic industries. For this reason, the total composition is analyzed. The lipid components of vernix caseosa consist of squalene, wax esters, sterol esters, 1,2-diol diesters, triacylglycerides, free fatty acids, fatty alcohols, cholesterol, diacylglycerides, monoacylglyceridesů and phospholipids . This study is focused on structure analysis of the 1,2-diol diesters of vernix caseosa. Conditions were optimized for the HPLC separation. Nova -Pak C18 column was used and a gradient of acetonitrile:ethyl acetate was chosen as a mobile phase. Before entering the APCI source ammonium formate was added; ammonium adducts [M +18]+ were formed. Eight scan events was set in MS method. One for the full scan spectrum, second for MS2 spectrum of the precursor ions and six MS3 data-dependent spectra. The position of the double bonds of unsaturated 1,2-diol diesters was determined by fragmentation of their [M+C3H5N]+ adducts. There were identified over 2200 of 1,2-diol diesters differing in lengths of alcohol and fatty acid chains, and...

Recently there has been a surge in the field of mass spectrometry centered around the concept of rapid analysis of target analytes with minimal or no sample preparation. The target analyte undergoes desorption from its surface of origin and is subsequently ionized under ambient conditions. The technique is termed ambient desorption/ionization mass spectrometry (ADI-MS). Since the introduction of ADI-MS in 2004, there has been an explosion of research based around the development of novel ambient desorption/ionization (ADI) sources with the capability of desorbing and ionizing a variety of target analytes from various sampling surfaces. One type of ADI source uses the properties of an electrical discharge, typically a helium gas plasma, for desorption and ionization. For electrical-discharge-based sources, ionization is the result of an atmospheric pressure chemical ionization (APCI) process. The initiation of the APCI process it generally attributed to the Penning ionization of atmospheric nitrogen (N2) by highly energetic helium metastable species (Hem). In this work, I describe the direct imaging of the densities of helium metastable atoms in atmospheric pressure plasma jet (APPJ) of a helium-based dielectric-barrier discharge (DBD) using collisionally-assisted laser-induced fluorescence. Axial Hem distributions are compared to the emission of excited helium (He*) and nitrogen ion (N2+*) species in the plasma. A correlation is found between Hem densities and the performance of the ionization source in ADI-MS. Fluorescence images also show that Hem densities increase substantially when a glass slide is placed 10 mm from the discharge capillary in a geometry typical for desorption/ionization experiments. Advantage is taken of the time-varying nature of the plasma to produce axial profiles of temporally and spectrally resolved fluorescence images of Hem atoms and ground state nitrogen ions in the plasma jet. The axial distribution and similarities in the temporal behavior of the helium metastable and ground state nitrogen ion species give strong evidence that nitrogen ion species are created via Penning ionization by helium metastable atoms. Although axial distributions of He*,N2+*, and N2* emission support the fluorescence data, temporally-resolved emission measurements show that emission from key plasma species is almost entirely the result of excitation by a temporal energy wave. The effect that hydrogen (H2) has on the helium metastable atom densities is also presented. The addition of hydrogen to the discharge gas severely quenches the metastable state, leaving it virtually undetectable. The addition of 0.9% H2 to the helium in the source provides an order of magnitude increase in ADI-MS signal for target analytes despite the quenching of the Hem population.

Yes / Antioxidant active packaging was prepared by coating a citrus extract on the surface of polyethylene terephthalate (PET) trays which had been either treated with an atmospheric pressure plasma jet or left untreated. The surface characteristics of the packaging were examined, as were its stability and antioxidant efficacy following storage for up to 24 weeks under the following three storage conditions: room temperature, 0 % relative humidity (RH) or 50 °C. Plasma pretreatment increased coating density, thickness and roughness, and oxygenated functional groups at the polymer surface, whereas water contact angle decreased. Trays stored at room temperature did not lose their antioxidant efficacy over 24 weeks and plasma pretreatment enhanced the efficacy from week 8 onwards. Gravimetric analysis of the coating revealed a loss of antioxidant compounds only after 16 weeks. Trays stored at 0 % RH lost coating from week 1 onwards, with lower loss in plasma pretreated trays, while loss of coating was highest at 50 °C, with lower loss in plasma pretreated trays only after 24 weeks. Overall, the surface characteristics of the antioxidant active packaging were modified by plasma pretreatment of the PET surface, with some improvement in antioxidant efficacy, and the efficacy of the packaging in delaying oxidative deterioration in cooked meats was retained during storage at ambient temperature.