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We present a zero-dimensional plasma kinetics model, including both surface and gas phase kinetics, to determine the role of vibrationally excited states in plasma-catalytic ammonia synthesis. We defined a new method to systematically capture the conditions of dielectric barrier discharges (DBDs), including those found in packed bed DBDs. We included the spatial and temporal nature of such discharges by special consideration of the number of micro-discharges in the model. We introduce a parameter that assigns only a part of the plasma power to the micro-discharges, to scale the model conditions from filamentary to uniform plasma. Because of the spatial and temporal behavior of the micro-discharges, not all micro-discharges occurring in the plasma reactor during a certain gas residence time are affecting the molecules. The fraction of power considered in the model ranges from 0.005%, for filamentary plasma, to 100%, for uniform plasma. If vibrational excitation is included in the plasma chemistry, these different conditions, however, yield an ammonia density that is only varying within one order of magnitude. At only 0.05% of the power put into the uniform plasma component, a model neglecting vibrational excitation clearly does not result in adequate amounts of ammonia. Thus, our new model, which accounts for the concept in which not all the power is deposited by the micro-discharges, but some part may also be distributed in between them, suggests that vibrational kinetic processes are really important in (packed bed) DBDs. Indeed, vibrational excitation takes place in both the uniform plasma between the micro-discharges and in the strong micro-discharges, and is responsible for an increased N2 dissociation rate. This is shown here for plasma-catalytic ammonia synthesis, but might also be valid for other gas conversion applications., SCOPUS: ar.j, info:eu-repo/semantics/published

Submitted by André Bianchi Laraia (andreblaraia@yahoo.com.br) on 2018-08-29T22:49:26Z No. of bitstreams: 1 Dissertacao-Andre-Bianchi-Laraia.pdf: 2142300 bytes, checksum: 9264414d38ac4ce5ec3be46acb98ca44 (MD5) Rejected by Pamella Benevides Gonçalves null (pamella@feg.unesp.br), reason: Solicitamos que realize correções na submissão seguindo as orientações abaixo: • Necessário fazer ajuste no sumario na lateral direita nas numerações. • A palavra APÊNDICE A deve ser centralizada A palavra APÊNDICE A deve ser centralizada • Referências. A palavra Referências deve ser centralizada, As referencias devem ser justificadas, espaço simples com um espaço simples(enter) entre elas. • Sobre a elaboração das referencias e citações favor solicitar orientação para ajuste com a bibliotecária Pâmella - pamella.benevides@unesp.br • A palavra APÊNDICE A deve ser centralizada Mais informações acesse o link: http://www2.feg.unesp.br/Home/Biblioteca21/diretrizes-2016.pdf Agradecemos a compreensão. on 2018-08-30T12:07:55Z (GMT) Submitted by André Bianchi Laraia (andreblaraia@yahoo.com.br) on 2018-09-12T01:58:28Z No. of bitstreams: 1 Tese-Andre-Bianchi-Laraia-v20-converted.pdf: 2144718 bytes, checksum: eef37a1c04c8a387ddbff2e31f67db35 (MD5) Approved for entry into archive by Pamella Benevides Gonçalves null (pamella@feg.unesp.br) on 2018-09-12T17:38:03Z (GMT) No. of bitstreams: 1 laraia_ab_me_guara.pdf: 2144718 bytes, checksum: eef37a1c04c8a387ddbff2e31f67db35 (MD5) Made available in DSpace on 2018-09-12T17:38:03Z (GMT). No. of bitstreams: 1 laraia_ab_me_guara.pdf: 2144718 bytes, checksum: eef37a1c04c8a387ddbff2e31f67db35 (MD5) Previous issue date: 2018-07-31 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Este trabalho apresenta o desenvolvimento de um processo de tratamento com plasma para melhorar ametalização química de placas de circuito impresso (PCI). A pluma de plasma é gerada em argônio a partir da descarga de barreira dielétrica (DBD) promovida entre uma agulha cirúrgica e um cilindro usando capilar de borosilicato como dielétrico. A tensão picoa-pico aplicada foi de 5 kV, com forma de onda senoidal na frequência de 37 kHz e potência de descarga em torno de 765 mW. O substrato é um composto de fibra de vidro e resina epóxi. Com incidência perpendicular da pluma de plasma na superfície, o diâmetro da área tratada circular é de 10 mm. Desta forma, o ângulo de contato reduz de 75 ° a 45 ° com 3 s de interação entre superfície da amostra e a ponta do plasma e o ângulo atinge o mínimo de 33 ° após 180 s de tempo de tratamento. A metalização química foi feita com banhos seqüenciais de solução de paládio e finalizada com banho de solução aquosa de cobre. Testes de adesão padrão mostraram uma forte adesão das camadas de metal nas superfícies previamente tratadas com as plumas de plasma. Esta adesão melhora com o tempo de tratamento. A melhoria na metalização foi observada em superfície plana e também em furos usados para conectar diferentes camadas em PCIs. A área metalizada na superfície dos buracos é maior nos orifícios tratados. Quanto maior o tempo de tratamento, maior é essa área. Todos os resultados indicaram que a técnica de tratamento por plasma de placas de fibra de vidro melhora a sua metalização química pelo cobre, levando a uma adesão mais uniforme e eficaz do metal à superfície com um método ambientalmente amigável This work reports the development of a plasma treatment process to improve the chemical metallization of printed circuit boards (PCB). The plasma plume is generated in argon from a dielectric barrier discharge (DBD) promoted between a surgical needle and a cylinder using a borosilicate capillary as dielectric. The applied peak-to-peak voltage was 5 kV, with sinusoidal waveform at 37 kHz frequency and power in the discharge around 765 mW. The substrate was a composite of fiberglass and epoxy resin. With perpendicular incidence of the plasma plume on the surface the diameter of the circular treated area was 10 mm. In this area the contact angle reduces from 75° to 45° with 3 s of the plasma-surface interaction and the angle reaches the minimum of 33° after 180 s of treatment time. Chemical metallization was made with sequential baths of solution of palladium and finished with bath of aqueous solution of copper. Standard adhesion tests showed a strong adhesion of the metal layer on surfaces previously treated with the plasma plumes. This adhesion improves with the treatment time. The improvement in the metallization was observed on flat surface and also in holes used to connect different layers in PCB’s. The metallized area on the surface of the holes is larger in treated holes. The longer the treatment time the larger is this area. All these results indicated that the technique of plasma treatment of fiberglass boards improves its chemical metallization by copper leading to a more uniform and effective adhesion of the metal to the surface with an environmental friendly method

Microdischarges at moderate to high pressure in argon were investigated. A hole opening diameter of 500 µm direct current (dc) microhollow cathode discharges (MHCD) were characterized by electrical measurements and optical emission spectroscopy (OES) for pressures ranging between 90 and 800 Torr and current from 5 to 20 mA. Current-voltage characteristic curves were obtained as a function of the pressure for this hole diameter. MHCD enables stable dc discharges for molybdenum electrodes material at constant Ar + 2%H2 flow of 0.03 l/min. Optical emission spectroscopy and analysis of the spectral line broadening of plasma line emissions were performed in order to measure gas discharge parameters. Electron number densities were obtained from Hβ Balmer line ( ~ 10(14) cm-3). For the above mentioned discharge conditions, gas temperature was estimated to be 550 - 850 K from OH rotational bands. Excitation temperature was measured based on two lines method (from atomic Mo lines) and from 4p - 4s and 5p - 4s Ar radiative transitions. Hydrogen atom temperature was measured for 800 Torr ( ~ 12000 K).

Non-equilibrium plasmas have been used as one of the principal technologies for development of microelectronics and they are the basis for the development of new generations of nano-electronics devices required for 65 and 40 nm technologies. Microdischarges recently have become more common in everyday life. Technology of plasma etching has enabled us to develop such discharges and the field of microdischarges has grown into the most interesting field of the physics of collisional non-equilibrium plasmas. Recently, an effort to fabricate microplasma sources that can be integrated with other MEMS devices to form larger Microsystems has been made. Plasma-based microsystems can find application in bio-microelectro- mechanical system (bio-MEMS) sterilization, small-scale materials processing and microchemical analysis systems. However, integrability requires not only a size reduction, but also an understanding of the physics governing the new small-scale discharges. In this paper, we have performed modeling of a breakdown voltage by using Particle-in-Cell/Monte Carlo collision (PIC/MCC) code taking into account the secondary electron emission due to a high field.

Le plasma est un gaz ionisé qui possède des caractéristiques physiques intéressantes dans le domaine des hyperfréquences. En simplifiant, on peut le caractériser comme un milieu diélectrique dispersif dont la permittivité est fonction de deux paramètres : la pulsation plasma (wp) et la fréquence de collision électron-neutre (np). En pratique, ces paramètres dépendent principalement de la densité électronique du gaz et de sa pression. Ainsi, en contrôlant les caractéristiques du plasma, on contrôle sa permittivité diélectrique, ce qui permet d’envisager son application dans le domaine de la reconfigurabilité en hyperfréquence. Parmi les topologies pouvant générer une décharge plasma, nous nous sommes focalisés sur l’utilisation de topologies récentes, à savoir les microdécharges plasma. Ces microdécharges sont intéressantes de par leur facilité d’intégration dans un dispositif RF : petite taille, stabilité, température proche de la température ambiante et perspectives d’utilisation à plus haute pression, voire à la pression atmosphérique. Devant la difficulté de modéliser précisément l’effet du plasma sur une onde guidée, une approche expérimentale a été privilégiée. Deux dispositifs de mesure ont ainsi été conçus pour caractériser cette interaction : une ligne de transmission microruban classique et une inversée intégrant une microdécharge en leurs centres. Grâce au protocole expérimental mis en œuvre, les paramètres S de la ligne de transmission sont obtenus et comparés à ceux des lignes sans plasma dans une large gamme paramétrique, qu’il s’agisse de la pression du gaz, de la fréquence ou encore du courant injecté à la décharge. Les résultats obtenus montrent deux phénomènes particulièrement intéressants : un déphasage de l’onde électromagnétique en présence de la décharge plasma et / ou une absorption importante de la puissance par la décharge. Deux dispositifs antennaires ont finalement été conçus en exploitant ces résultats. Le premier est une antenne imprimée accordable en fréquence dans une plage de l’ordre du pourcent, grâce à une décharge plasma contrôlée. Le plasma modifie alors la constante diélectrique entre les deux conducteurs constitutifs de l’antenne. Le second dispositif est une antenne anneau imprimée qui peut protéger son récepteur d’une attaque microondes de forte puissance. Ainsi, lorsqu’un champ incident dépasse un seuil prédéfini, réglable dans une certaine mesure par une tension continue externe, une décharge plasma apparaît au sein de l’élément rayonnant. Elle crée alors de la désadaptation et de l’absorption qui limitent de façon non linéaire la puissance restituée à l’accès. Plasma is an ionized gas with physical characteristics that are of interest to the microwave domain. To simplify, we can characterize it as a dispersive medium whose dielectric permittivity depends on two parameters : the plasma pulsation wp and the electron-neutral collision frequency Vp. These two parameters depend mainly on the electron density of the gas and its pressure. If we can control the characteristics of the plasma, we can also control its dielectric permittivity, which allows us to consider the plasma for applications in the field of microwave reconfigurability. Among the structures that can generate a plasma discharge, we have focused on the use of recent topologies, known as plasma microdischarges. These microdischarges are of interest because of the possibility of easily integrating them into a RF device : small size, stability, temperature near room temperature and potential use at high pressures, including at atmospheric pressure. Given the difficulties in accurately modelling the effects of the plasma on a guided wave, an experimental approachwas preferred. Two measuring devices have been designed to characterize this interaction : a conventional microstrip transmission line and an inverted microstrip transmisison line, both including a microdischarge in their centers. With this experimental characterization, the S-parameters of the transmission line with the plasma are obtained and compared to those without plasma as a function of a wide range of parameters, such as gas pressure, frequency and current injected into the discharge. The results show two particularly interesting phenomena : a phase shift of the electromagnetic wave in presence of the plasma discharge and/or an important absorption of the incident power by the discharge. Two devices have been designed to exploit these results. The first is a frequency tunablemicrostrip patch antenna over a range of the order of one percent. In that case, the plasma changes the dielectric constant between the two conductors of the antenna. The second is a microstrip ring patch antenna that can protect the receiver from a high-power microwave (HPM) attack. When an incident electric field exceeds an adjustable preset threshold (tuned by an external DC voltage source), a plasma discharge appears in the radiating element. The plasma then creates a mismatch and an absorption effect that limits, in a non-linear way, the received power at its input.

We propose a mechanism to explain many features of the multi-filament dielectric barrier discharge: while part of the charge deposited during previous discharge cycles is immobile on the dielectric over time periods of seconds, the larger fraction of the deposited charge must be mobile on time-scales of hundreds of ns. For alumina, we estimate that a sheet resistance of 3 MΩ sq-1 is consistent with the multi-filament discharge; an increase in conductivity of at least 12 orders of magnitude. The existence of this type of plasma-induced surface conductivity could prove relevant in modeling a wide range of plasma devices, in addition to DBD.

Ova doktorska disertacija bavi se proučavanjem fenomena Plazma Elektrolitičke Oksidacije (PEO) ventilnih metala (Al, Mg, Ti, Та) i oksidnih slojeva koji se dobijaju u elektrolitima koji sadrže volfram, pre svega u 12-volframsilicijumskoj kiselini. Primenom metoda optičke emisione spektroskopije i analize procesa u realnom vremenu, omogućeno je određivanje: temperature, elektronske gustine plazme, dimenzionalne distribucije i aktivne površine mikro pražnjenja. Pokazano je da PEO procesi na svim ispitivanim metalima pokazuju tendenciju da se broj mikro pražnjenja smanjuje sa vremenom, a da površine poprečnih preseka mikro pražnjenja rastu. Sa porastom vremena PEO procesa broj kanala za pražnjenje se smanjuje, dok njihov dijametar raste i dolazi do povećanja hrapavosti oksidnih površina. Procenat aktivne površine istovremeno izložen događajima mikro pražnjenja takođe raste u početku PEO procesa, dostiže svoj maksimum, a potom polako opada. Sve spektralne linije detektovane u optičko emisionim spektrima u toku PEO procesa pripadaju ventilnim metalima i jonskim i atomskim elementima prisutnim u elektrolitu. Pored jasno izraženih atomskih i jonskih linija, u optičko emisionom spektru dobijenom tokom PEO procesa na magnezijumu, jasno je vidljiva i vibraciona traka MgO molekula, koja odgovara elektronskom prelazu sa pobuđenog B1Σ+ nivoa na osnovni elektronski nivo X1Σ+. Na sličan način, u spektru dobijenom tokom PEO procesa na aluminijumu opaža se jaka vibraciona traka AlO sistema, koja odgovara elektronskom prelazu sa pobuđenog B2Σ+ nivoa na osnovni elektronski nivo X2Σ+. U slučaju PEO procesa na aluminijumu i magnezijumu, koristeći spektroskopske podatke dobijene za AlO, OH i MgO trake, uz primenu kvantno-mehaničkih proračuna, određene su temperature plazme. Iz vibracionih traka MgO molekula procenjeno je da su temperature plazme (11000 ± 2000) K, dok su u slučaju podataka iz OH trake dobijene nešto niže vrednosti temperature (3500 ± 500) K. Iz analiza vibracione trake AlO molekula u slučaju PEO procesa u limunskoj kiselini procenjena temperatura je (8000 ± 2000) K... This doctoral dissertation is focused on investigation of a relatively new, highvoltage anodization process, called Plasma Electrolytic Oxidation (PEO) on valve metals (such as Al, Mg, Ti and Ta) and their oxide coatings obtained in tungsten containing heteropoly acids. Very useful data concerning temperature, dimensional distribution of the microdischarges, their spatial density, and electron density were obtained using optical emission spectroscopy and real time imaging of PEO events. It is shown that the size of microdischarges becomes larger while their number decreases with increased time of PEO. Spatial density of microdischarges is the highest in the early stage of the PEO process and then slowly decreases. The percentage of oxide coatings’ area simultaneously covered by active discharge sites decreases slowly with extended PEO time. All atomic and ionic lines detected in optical emission spectra originate either from electrolyte or from the metal substrate. During the PEO process on magnesium, wide transition band was also recorded corresponding to the v′−v″=0 band sequence of the B1Σ+ – X1Σ+ emission transition of MgO. During the PEO process on aluminum, visible band of B2Σ+ - X2Σ+ emission of AlO system was also detected. By applying spectroscopic, quantum-chemical and thermodynamical methods to analyze spectra in the range of those bands it was possible to determine the temperature of the microdischarges. In the case of PEO process on magnesium, calculated temperatures are about 11000 K ± 2000 K, while analysis of OH bands in the same sysstem yields sligtly lower value of 3500 K ± 500 K. Analysis of AlO band system gave temperature of 8000 K ± 2000 K. The analysis of hydrogen Balmer Hβ line shape in the case of PEO of tantalum and titanium, indicates the presence of two types of discharges during PEO process and the electron number densities of Ne ≈ 0.8×1015 cm−3 and Ne ≈ 2.1×1016 cm−3 are determined. These two electronic concentrations are similar to those obtained during the PEO process on aluminum...

The multifractal image analysis of Lichtenberg figures has confirrmed a self- similar arrangement of surface streamers belonging to the special case of electrostatic separation discharges propagating along a surface of polymeric dielectrics.

International audience; This paper describes how to light several microdischarges in parallel without having to individually ballast each one. The V-I curve of a microhollow cathode discharge is characterized by a constant voltage in the normal glow regime because the plasma is able to spread over the cathode surface area to provide the additional secondary electrons needed. If one limits the cathode surface area, the V-I characteristic can be forced into an abnormal glow regime in which the operating voltage must increase with the current. It is then possible to light several microdischarges mounted in parallel without ballasting them individually. Microdischarges are nonequilibrium discharges spatially confined to dimensions smaller than 1 mm. They are a promising approach to the generation and maintenance of stable dc glow discharges at atmospheric pressure and they present interesting challenges for plasma science ͑impact of quantum electrodynamics on spontaneous emission rate and quasineu-trality breaking͒. 1 Parallel microplasmas can be created using several kinds of microdevices. 2 Some teams use ballasts to individually initiate the plasma in each microcavity independently. 3,4

We studied statistical behavior of microdischarges of diffuse coplanar surface barrier discharge (DCSBD) operated in nitrogen atmosphere at two input voltage regimes. We measured spectrally unresolved discharge patterns together with discharge electrical parameters using highspeed iCCD camera and digital storage oscilloscope. External synchronization enabled us to measure the discharge pattern during positive and/or negative half-period of input high voltage in the single-shotmode of operation. The comparison of microdischarges behavior during positive, negative and both half periods of input high voltage was performed for two levels of input voltage, i.e. voltage slightly above ignition voltage and high above ignition voltage (“overvoltage”). The number of microchannels crossing discharge gap was counted and compared with number of microdischarge current peaks observed during corresponding half-period of input high voltage. The relations of those incidences was shown and discussed.

Time series of pulsating microdischarges were analysed. The results showed that deterministic chaos is present in these series. The estimated values of the correlation coefficients indicated a strong chaotic discharge behaviour.

Dielectric barrier discharges (DBDs) typically operate in the filamentary regime and thus exhibit great spatial and temporal non-uniformity. In order to optimize DBDs for various applications, such as in plasma catalysis, more fundamental insight is needed. Here, we consider how the millions of microdischarges, characteristic for a DBD, influence individual gas molecules. We use a Monte Carlo approach to determine the number of microdischarges to which a single molecule would be exposed, by means of particle tracing simulations through a full-scale packed bed DBD reactor, as well as an empty DBD reactor. We find that the fraction of microdischarges to which the molecules are exposed can be approximated as the microdischarge volume over the entire reactor gas volume. The use of this concept provides good agreement between a plasma-catalytic kinetics model and experiments for plasma-catalytic NH3 synthesis. We also show that the concept of the fraction of microdischarges indicates the efficiency by which the plasma power is transferred to the gas molecules. This generalised concept is also applicable for other spatially and temporally non-uniform plasmas., SCOPUS: ar.j, info:eu-repo/semantics/published