Neste trabalho foi investigado o comportamento elétrico dos sistemas poliméricos preparados com o poliestireno, PS, e poli(metacri1ato de metila), PMMA, dopados com o corante vermelho disperso 1, DR1. O processo de polarização dos filmes poliméricos foi realizado usando o triodo de corona operando em duas configurações: i) carregamento com corrente de carga constante, ii) com tensão de grade constante. O processo de polarização por corona foi investigado variando-se os parâmetros do processo, tais como: corrente de carga, tempo, temperatura, campo elétrico de saturação e porcentagem de corante das amostras. As medidas da corrente elétrica no estado estacionário em função campo elétrico permitiram mostrar que o processo de condução elétrica nos dois sistemas obedecem o modelo de Poole-Frenkel. O valor da polarização elétrica induzida foi avaliada através de medidas do coeficiente piroelétrico, o qual é diretamente proporcional a polarização na amostra. No caso do PS(DR1) deu-se ênfase a investigação de medidas de corrente termo estimulada para avaliar a polarização elétrica induzida nas amostras por aplicação de uma ddp. Medidas da constante dielétrica complexa para os dois sistemas poliméricos foram realizadas em função da freqüência para diferentes temperaturas. Os resultados obtidos mostraram que a orientação e relaxação dos corantes nas amostras são associados ao movimento das cadeias poliméricas, i.e., relaxação do tipo &#945. / Some electrical properties of guest-host polymeric systems made with polystyrene, PS, and poly(methyl methacrylate), PMMA, and the disperse red 1 dye, DR1 were investigated. The poling process of films were performed with the corona triode set up operating in two modes: i) charging with constant current, ii) with a constant grid voltage. The influence of parameters such as the charging current, electric field at the s, time, temperature and the percentage of DR1 was investigated. Measurements of the steady state current versus the electric field allowed us to show that the electric conduction process in both polymeric systems follow the Poole-Frenkel model. The electric polarization induced in samples was evaluated measuring the piroelectric coefficient, which is directly proportional to the polarization value. For PS(DR1) samples thermally stimulated current measurements were performed to investigate the electric polarization obtained by application of a dc voltage. Measurements of the complex dielectric constant with the two polymeric systems as function of the frequency for different temperatures were performed. Results showed that orientation and relaxation of DR1 dye in samples are related to the chain movement, i.e., &#945 relaxation process.

A obtenção de compósitos poliméricos condutores de eletricidade tem sido alvo de pesquisa com o objetivo de combinar as propriedades de diferentes materiais poliméricos. Neste trabalho foram preparados compósitos de filmes de poli(tereftalato de etileno) (PET) com camadas superficiais do polímero condutor polianilina (PANI). Para obter a camada condutora o filme de PET foi imerso no meio reacional da síntese da PANI, realizada em solução método este freqüentemente empregado para a produção de PANI. Foram otimizados os parâmetros da síntese (temperatura, concentração dos reagentes, tempo de polimerização, etc..) com o objetivo de se obter uma camada de PANI com espessura adequada, condutividade superficial elevada e com boa adesão no substrato de PET. O processo da reação de polimerização foi monitorada pela medida do potencial de circuito aberto e também diretamente pela camada de PANI depositada no PET, através de medidas de espectrocospia UV-Vis-NIR, condutividade elétrica e adesão da camada de PANI. Em condições otimizadas da síntese, realizada a temperatura ambiente durante o tempo de 20 minutos, pode-se obter camadas de PANI com condutividade da ordem de 10 S/em, boa adesão ao substrato de PET e com razoável transparência óptica. Os compósitos obtidos nas condições otimizadas foram caracterizados usando-se microscopia por SEM, microscopia óptica, microscopia AFM, difratogramas de raios-X, DSC, análise DMTA, análise TGA, correntes termo estimuladas, medidas de ruptura elétrica, medidas de adesão e solubilidade da camada de PANI. Verificou-se também que o tratamento térmico dos compósitos melhora a adesão da camada de PANI ao substrato de PET. Foi descoberto um novo método para dopar as camadas condutoras de PANI no qual o compósito desdopado é tratado por descarga corona. O processo é realizado totalmente a seco e pode-se obter uma condutividade da camada de PANI da ordem de 0,3 S/em com boa adesão. Observou-se que a eficiência do processo é dependente da umidade relativa do ar na câmara de tratamento e que a estabilidade da condutividade elétrica é melhor que nas amostras dopadas em solução / Composites with conductive properties have been proposed as materiais in which different physical properties of polymers are combined. In this work a composite consisting of surface layers of polyaniline, PANI, deposited on films of poly(ethylene terephtalate), PET, were prepared. In order to deposit the PANI the PET film were immersed in the solution in which the synthesis reaction is carried out. The parameters of the synthesis usually optimized in order to obtain a layer of PANI with enough thickness, high electric conductivity and good adhesion to the PET substrate. The synthesis was monitored by means of open circuit potential and also using UV-Vis-NIR spectroscopy and the electric conductivity of the PANI layer on PET. Using the optimized conditions, at room temperature and polymerization time of 20 minutes, a composite with a surface conductivity of the order of 10 S/em, good adhesion and a reasonable optical transparence can be obtained. Such composite were characterized employing electron scanning microscope, atomic force microscope, optic microscope, X-rays diffractometry, differential scanning calorimeter, thermal dynamic analysis, thermogravimetric analysis, thermally stimulated depolarization current, electric thermal stability of the conductivity, electric breakdown measurements, adhesion measurements and solubility of the PANI layer. It was also found that the thermal treatment leads to an improvement of the adhesion properties of the PANllayer. It was found that a corona discharge could be used to dope the PANI layer of a dedoped composite, leading to a new method for doping polymeric materiais. Such process is performed under dry conditions and gave a conductivity of the order 0.3 S/em. The process efficiency is dependent of the relative air humidity of the corona chamber and the thermal stability of the electric conductivity is betler when compared with the composites obtained by doping in solution.

Foram construídas duas montagens experimentais: Com a primeira, mediu-se o decaimento do potencial de superfície em circuito aberto, em função da temperatura; com a segunda mediu-se diretamente a corrente termo-estimulada (derivada do potencial de superfície em circuito aberto) aquecendo-se a amostra a uma taxa constante. Usando essas técnicas estudamos as propriedades de transporte e armazenamento de cargas no Teflon FEP-A, carregado com corona. Usando a segunda técnica, verificou-se que amostras descarregadas, do citado material, podem liberar portadores de cargas positivas que dão origem a uma corrente anômala, que pode interferir nas medidas de corrente termo-estimulada de amostras carregadas positivamente. Estudou-se o comportamento das curvas de corrente em amostras com e sem tratamento térmico, carregadas com corona tanto positiva como negativa. Além disto, é feita uma discussão dos resultados por nós obtidos e os publicados na literatura. / Two experimental systems were constructed: with the first the surface potential could be measured, while with the second, its derivative with respect to the time (the so called open circuit current). In both cases the measurements were performed while heating previously positive or negative corona charged FEP-A Teflon 25&#956m samples. The results gave information about charge storage and transport properties in this material. During the work it was noticed that positive ions maybe emitted from Teflon surface. This unexpected phenomenon was followed in some detail in order to know how far it influences the usual currents. This study led us to carry measurements in previously annealed samples, whose behavior was found to differ from that of virgin samples. Our results were compared with those found in the literature.

Η παρούσα εργασία αναφέρεται στη μελέτη της ηλεκτρικής εκκένωσης τύπου κορώνας και ιδιαίτερα στα ηλεκτρικά και υδροδυναμικά (ηλεκτρικός άνεμος) φαινόμενα που τη συνοδεύουν. Μια εκκένωση κορώνας είναι το φαινόμενο που δημιουργείται σε ένα αέριο διάκενο μεταξύ δύο ηλεκτροδίων διαφορετικής ακτίνας καμπυλότητας, όταν αυτά βρίσκονται υπό την επίδραση διαφοράς δυναμικού μερικών kV. Η εκκένωση κορώνας συνοδεύεται από την εμφάνιση ηλεκτρικών, οπτικών, ακουστικών, χημικών, αεροδυναμικών (ηλεκτρικός άνεμος) και ραδιοηλεκτρικών φαινομένων. Ο ηλεκτρικός άνεμος είναι ένα φαινόμενο το οποίο δημιουργείται από τη μετάδοση της ορμής των ιόντων στα ουδέτερα μόρια του αερίου οπότε παρατηρείται μία κίνηση του αερίου από το ηλεκτρόδιο με μικρή ακτίνα καμπυλότητας, προς το άλλο ηλεκτρόδιο. Το κύριο αντικείμενο της εργασίας αυτής είναι η μελέτη του φαινομένου της θετικής κορώνας, μεταξύ μιας μη συμμετρικής διάταξης ηλεκτροδίων, στον ατμοσφαιρικό αέρα. Στην άνοδο τοποθετήθηκαν μια και δύο ακίδες της ίδιας ακτίνας καμπυλότητας ενώ χρησιμοποιήθηκαν τρεις διαφορετικές κάθοδοι. Οι πειραματικές μετρήσεις είχαν ως στόχο τον προσδιορισμό της χαρακτηριστικής του μέσου ρεύματος της εκκένωσης συναρτήσει της τάσης διακένου, των παλμών του ρεύματος για διάφορες τιμές της τάσης , τον προσδιορισμό της κατανομής και της χαρακτηριστικής της ταχύτητας του ηλεκτρικού ανέμου καθώς και της χαρακτηριστικής της θερμοκρασίας του ηλεκτρικού ανέμου. Πρέπει να αναφέρουμε ότι οι μετρήσεις πραγματοποιήθηκαν για συνεχή και παλμική τάση λειτουργίας. / In this thesis, the effect of the positive corona discharge was studied. Especially, electric and hydrodynamic phenomena (corona wind) were studied. By the term “corona discharge”, one generally refers to the ensemble of phenomena which occur in a gaseous medium in the vicinity of conductors of small radius of curvature, subjected to intense, but not disruptive, electric fields. The main part of this thesis is experimental procedures that were held between a non-symmetrical set-up of electrodes in atmospheric air in order to, initially define the V-I characteristics and study the current impulses for different voltage values. Furthermore, we studied the velocity distribution and velocity characteristics of corona wind. In the last part of this work the temperature characteristics are present. It is important to mention that the experimental measurements were carried out on continuous and pulsed voltage.

Foram construídas duas montagens experimentais: Com a primeira, mediu-se o decaimento do potencial de superfície em circuito aberto, em função da temperatura; com a segunda mediu-se diretamente a corrente termo-estimulada (derivada do potencial de superfície em circuito aberto) aquecendo-se a amostra a uma taxa constante. Usando essas técnicas estudamos as propriedades de transporte e armazenamento de cargas no Teflon FEP-A, carregado com corona. Usando a segunda técnica, verificou-se que amostras descarregadas, do citado material, podem liberar portadores de cargas positivas que dão origem a uma corrente anômala, que pode interferir nas medidas de corrente termo-estimulada de amostras carregadas positivamente. Estudou-se o comportamento das curvas de corrente em amostras com e sem tratamento térmico, carregadas com corona tanto positiva como negativa. Além disto, é feita uma discussão dos resultados por nós obtidos e os publicados na literatura. / Two experimental systems were constructed: with the first the surface potential could be measured, while with the second, its derivative with respect to the time (the so called open circuit current). In both cases the measurements were performed while heating previously positive or negative corona charged FEP-A Teflon 25&#956m samples. The results gave information about charge storage and transport properties in this material. During the work it was noticed that positive ions maybe emitted from Teflon surface. This unexpected phenomenon was followed in some detail in order to know how far it influences the usual currents. This study led us to carry measurements in previously annealed samples, whose behavior was found to differ from that of virgin samples. Our results were compared with those found in the literature.

Neste trabalho foi investigado o comportamento elétrico dos sistemas poliméricos preparados com o poliestireno, PS, e poli(metacri1ato de metila), PMMA, dopados com o corante vermelho disperso 1, DR1. O processo de polarização dos filmes poliméricos foi realizado usando o triodo de corona operando em duas configurações: i) carregamento com corrente de carga constante, ii) com tensão de grade constante. O processo de polarização por corona foi investigado variando-se os parâmetros do processo, tais como: corrente de carga, tempo, temperatura, campo elétrico de saturação e porcentagem de corante das amostras. As medidas da corrente elétrica no estado estacionário em função campo elétrico permitiram mostrar que o processo de condução elétrica nos dois sistemas obedecem o modelo de Poole-Frenkel. O valor da polarização elétrica induzida foi avaliada através de medidas do coeficiente piroelétrico, o qual é diretamente proporcional a polarização na amostra. No caso do PS(DR1) deu-se ênfase a investigação de medidas de corrente termo estimulada para avaliar a polarização elétrica induzida nas amostras por aplicação de uma ddp. Medidas da constante dielétrica complexa para os dois sistemas poliméricos foram realizadas em função da freqüência para diferentes temperaturas. Os resultados obtidos mostraram que a orientação e relaxação dos corantes nas amostras são associados ao movimento das cadeias poliméricas, i.e., relaxação do tipo &#945. / Some electrical properties of guest-host polymeric systems made with polystyrene, PS, and poly(methyl methacrylate), PMMA, and the disperse red 1 dye, DR1 were investigated. The poling process of films were performed with the corona triode set up operating in two modes: i) charging with constant current, ii) with a constant grid voltage. The influence of parameters such as the charging current, electric field at the s, time, temperature and the percentage of DR1 was investigated. Measurements of the steady state current versus the electric field allowed us to show that the electric conduction process in both polymeric systems follow the Poole-Frenkel model. The electric polarization induced in samples was evaluated measuring the piroelectric coefficient, which is directly proportional to the polarization value. For PS(DR1) samples thermally stimulated current measurements were performed to investigate the electric polarization obtained by application of a dc voltage. Measurements of the complex dielectric constant with the two polymeric systems as function of the frequency for different temperatures were performed. Results showed that orientation and relaxation of DR1 dye in samples are related to the chain movement, i.e., &#945 relaxation process.

Orientador: João Sinezio de Carvalho Campos / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-11T18:17:28Z (GMT). No. of bitstreams: 1 Buzeto_FabricioAndre_M.pdf: 5022514 bytes, checksum: da17a266de578a2060bb68a4ba3a873d (MD5) Previous issue date: 2007 / Resumo: Estudos das modificações superficiais de polímeros, causadas por descarga corona, são desenvolvidos com o objetivo de mudar as propriedades hidrofóbicas apresentadas por esses materiais, melhorando suas propriedades superficiais sem alterar suas propriedades mecânicas. No presente estudo, realizou-se, alterações na superfície da borracha natural, por tratamento corona de configuração ponta/plano com potência de 5 kV, visando, num segundo momento, a facilitação da incorporação de cargas com caráter hidrofílico à borracha natural. Um planejamento fatorial 22 foi utilizado para a análise dos resultados obtidos por medidas de ângulo de contato, tendo como objetivo a determinação do tempo e altura ótimos para a diminuição do ângulo de contato medido na superfície do polímero em relação à água destilada. Utilizaram-se técnicas complementares como FTIR/ATR, para a determinação das alterações físico-químicas ocorridas na superfície da borracha, bem como, análises térmicas da borracha natural visando à sustentação da não ocorrência de modificações na estrutura polimérica da borracha natural, tais como, reticulações. Através da técnica de microscopia ótica, foi possível verificar que para alturas menores que 2 mm, a superfície da borracha sofre degradação causada pela intensidade das descargas / Abstract: Studies of the superficial modifications of polymers, caused by corona discharges, are developed with the objective to change the hydrophobic properties presented by these materials, improving their superficial properties without changing their mechanical properties. In the present study, superficial modifications were carried out in the natural rubber, for corona treatment from needles-plane electrode system configuration with power of 5 kV, aiming, on a second moment, the facilitation of the incorporation of fillers with hydrophilic characteristic into the natural rubber. A factorial planning 22 was used on the analysis of the results obtained by contact angle measures, taking as an objective the determination of the best time and height for the reduction of the contact angle measured in the polymer surface regarding the distilled water. Complementary techniques were used, like the FTIR/ATR, to determine the chemical-physic alterations taken place in the rubber surface, as well, thermal studies of the natural rubber aiming for sustenance of not-incident modifications in the internal polymeric structure of the natural rubber, such as, reticulations. Through the optical microscopy technique, it was possible to confirm that, for heights less than 2 mm, the rubber surface suffers degradation caused by the intensity of the applied electric charges. / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

Orientador: João Sinezio de Carvalho Campos / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-02T14:17:27Z (GMT). No. of bitstreams: 1 Sellin_Noeli_D.pdf: 7024979 bytes, checksum: 1a92e73ed7d246d0fa41c67995311407 (MD5) Previous issue date: 2002 / Resumo: Os polímeros, em especial as poliolefinas, apresentam baixa energia livre de superfície, caracterizada pela adesão relativamente fraca a outros materiais. Para resolver este problema, suas superfícies são tratadas por diversas técnicas, destacando-se a descarga corona, amplamente utilizada na indústria. Muitos problemas pós-tratamento surgem por falta de entendimento das propriedades de superfície e sua relação com a adesão. Neste trabalho, estudam-se as modificações causadas na superfície de filmes de polipropileno (PP) isotático tratados por descarga corona. Para isto, os filmes são tratados sob condições ambientes controladas e após o tratamento, parte das amostras é armazenada a diferentes temperaturas, sendo que as armazenadas em temperatura ambiente são retratadas; outra parte é lavada com solventes e também armazenada (temperatura ambiente). As superfícies destes filmes são caracterizadas através de espectroscopia FTIR/ATR, microscopia de força atômica (AFM), ângulo de contato (8), DSC e teste de descolagem Peel. O tratamento por descarga corona induz a formação de grupos polares contendo oxigênio na superfície dos filmes e mudanças na topografia, tais como, o aparecimento de novas estruturas, aumento da rugosidade e dimensão fractal, resultando no aumento da energia livre superficial, molhabilidade e melhoria na adesão. Tratamento estendido promove a formação de material oxidado de baixa massa molar, o qual é facilmente removido pela lavagem com solvente. O envelhecimento ambiente dos filmes tratados e dos tratados/lavados diminui ligeiramente a força de adesão dos filmes em conseqüência da reorientação (lenta) dos grupos formados na superfície e diminuição da energia livre superficial e da molhabilidade. Envelhecimento acima de 60°C acelera os efeitos observados no envelhecimento ambiente. O retratamento dos filmes tratados recupera as propriedades superficiais perdidas após o envelhecimento / Abstract: Many polymer films (polyolefins) present low energy surfaces, characterised by their relatively weak adhesion to other materiais. Numerous methods have been developed to modify polymer surfaces. Among these methods, corona discharge treatment, is widely used in industry. In this work, the surface modification of corona treated polypropylene films (PP) is studied. The films are treated by corona discharge in controlled ambient conditions and after treatment, some samples are aged under different temperatures; other samples are washed by immersion in solvent (acetone and water) and also aged. Their surfaces are characterised by FTIRlATR spectroscopy, atomic force microscopy (AFM), contact angle (8), differential scanning calorimeter (DSC) and peel tests. Discharge treatment introduces oxygen polar groups into the films surface and dramatic change in the topography (new structures, increase in the roughness and fractal dimension), resulting in increased wettability and much enhanced adhesion. Extended oxidation results in the formation of low molecular weight oxidised material (LMWOM), which is easily removed by washing with solvent. For corona treated PP films ageing at ambient temperature, only a slight decrease in adhesion is observed. This decrease is attributed to the reorientation of oxidised functionalities within the surface region and to slight decrease in the surface free energy and wettability. At elevated storage temperatures, migration of oxidised species out of the surface region occurs leading to significant decreases in the wettability and a loss of surface oxidation. The treated films surface properties lost after ageing are restored by re-treatment / Doutorado / Ciencia e Tecnologia de Materiais / Doutor em Engenharia Química

Ever since the discovery of DNA, there has been many pathologies identified effecting mankind. With the development in technology, there are many methods to alleviate these pathologies. One such is gene therapy or gene delivery. It is a process of introducing some foreign material into the body to correct the effected cells. In principle, it is a modern method to cure cells or a method to transfer nucleic acid into a cell to treat specific cells in the body. The process of delivering a genetic material is carried out using vectors, namely, viral vectors and non-viral vectors. In viral vectors, viruses are modified to make it efficient for delivery into the host cells. This method has high transduction rate as compared to non-viral method. Non-viral methods include chemical and physical transfection methods, which are used to deliver the gene of interest into the host cell unlike viral methods. In this study, a physical method using high voltage is used to deliver a genetic material into cells. High voltages are used to permeabilize the cell to allow the foreign material into it and to express it in the host cell. This process is termed as Electroporation. In specific, in this research, studying a process of charging a region that mimics skin and trying to localize the presence of electric fields on the surface where the strongest uptake of genetic material is found. In other words, region where the gene expression is strongest at a specific region if performed on skin is studied by localizing electric fields on the surfaces. My work is to characterize and develop where this effect takes place on the surface based on both positive and negative electric fields. A physical method is useful as it is a non-toxic way to get a DNA/protein into someone’s body without making them sick, unless if not using a virus to deliver. This is all done using high voltages up to 8kV and the electric fields produced due to high voltages are localized, visualized and characterized with both positive and negative polarities of voltages. In this study, experiments with high voltages are performed and the spread of charges at specific regions are collected using a needle. This needle goes into corona, which may be called as a secondary corona. It might be called a secondary corona because the flat conductor is being charged by a metal finger but not directly by the power supply. Here, the conductor is charged by a metal finger of high input voltage, which ionizes the air molecules above the flat conductor to form a conductive region. As the input voltage is increased further, electrons escape from the needle to air or from molecules to needle forming negative or positive ions respectively. The outputs at needle were measured on the oscilloscope. In this study, repeated sets of experiments are carried out to collect consistent and reliable data. Visualizing/characterizing these fields are important as maximum delivery takes place at high voltage regions, with a condition that permeability of the cells should be known for proper transfection to occur, otherwise cells would die due to high voltages or no transfection takes place due to poor permeability of cell membrane.

The thesis is focused on electrical discharge in liquid solutions, in particular in ethanol solutions. In the theoretical section, the plasma is defined along with its important parameters, types of plasma generation and usage of plasma technologies. Main part is focused on the discharges in water solutions. Electric discharges in liquid solutions enable physical processes (shock waves, UV radiaton, electric current) as well as chemical ones (generation of radicals and ions). Both types of the processes are used in many fields – medicine (tool sterilization, destruction of pathogens), consumer technologies (surface adjustemen, processing of the textiles, surface clearing) of environmental protection (clearing water, decomposition of organic compounds). Goal of the thesis was to analyze discharge products on ethanol solution. Multiple samples were measured and concentration od selected products was monitored during the measurement – ethanol, acetone and acetaldehyde. PTR-TOF-MS method was used to collect and analyze the data. This method is well used thanks to quick response and immediate measurement. It produce the reset accurate enough for our purpose. It would be more efficient to use this method in combination with another analytical metohod in the future research, e.g. gas chromatography.