Barometers and the measurement of atmospheric pressure. A pamphlet of information respecting the theory and construction of barometers in general, with summary of instructions for the care and use of the standard Weather bureau instruments ...

Mode of access: Internet.

Environmental analysis of polar herbicides in complex organic-rich matrices by high performance liquid chromatography atmospheric pressure ionization mass spectrometry (HPLC-API-MS)

A comprehensive forensic investigation of sensitive ecosystems in the Everglades Area is presented. Assessing the background levels of contamination in these ecosystems represents a vital resource to build up forensic evidence required to enforce future environmental crimes within the studied areas. This investigation presents the development and validation of a fractionation and isolation method for two families of herbicides commonly applied in the vicinity of the study area, including phenoxy acids like 2,4-D, MCPA, and silvex; as well as the most common triazine-based herbicides like atrazine, prometyne, simazine and related metabolites like DIA and DEA. Accelerated solvent extraction (ASE) and solid phase extraction (SPE) were used to isolate the analytes from abiotic matrices containing large amounts of organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-), and Chemical Ionization in the positive mode (APCI+) were used to perform the characterization of the herbicides of interest.

Progettazione, realizzazione e caratterizzazione funzionale di sorgenti di plasma atmosferico di non equilibrio per l'idrofobizzazione di fibre tessili

L’attività di tesi ha previsto la progettazione e realizzazione di sorgenti di plasma di non equilibrio a pressione atmosferica e l’individuazione delle condizioni operative ottimali per l’idrofobizzazione di materiali tessili. La prima parte delle attività di tesi hanno riguardato lo studio e l’approfondimento della letteratura scientifica al fine di individuare le sorgenti e i processi plasma assistiti per l’idrofobizzazione dei materiali. Relativamente alle sorgenti di plasma di non-equilibrio a pressione atmosferica, studi di letteratura riportano che sorgenti di tipo APPJ (Atmospheric Pressure Plasma Jet) consentono di effettuare un trattamento localizzato in un punto, mentre sorgenti DBD (Dielectric Barrier Discharge) risultano idonee a trattamenti di materiali large area. Per quanto riguarda i processi plasma assistiti, sulla base di quanto riportato in letteratura il processo di idrofobizzazione può avvenire principalmente mediante polimerizzazione di gas organici contenenti fluoro, introdotti nella regione di plasma, con la conseguente deposizione di coating fluorurati. Le attività sperimentali condotte durante la tesi hanno avuto l’obbiettivo di valutare la possibilità di rendere idrofobico un filato di fibra tessile naturale mediante l’utilizzo di una sorgente plasma jet operante con miscela di argon e gas organoflorurato. Il filato, messo in moto a diverse velocità, è stato fatto transitare attraverso la piuma di plasma. In particolare, si è passati da una velocità di movimentazione di 1 m/min a una di 10 m/min. I risultati ottenuti hanno evidenziato che maggiore è la velocità di movimentazione del filato attraverso la piuma di plasma, minore è il grado di idrofibizzazione raggiungibile sul filato stesso, in quanto minore è il tempo di esposizione del materiale al plasma. Infine, nell’ultima parte dell’attività di tesi, è stata progettata una sorgente DBD, che caratterizzata da una maggiore area di generazione del plasma rispetto alla sorgente plasma jet, consente di incrementare il tempo di esposizione del filato al plasma a parità di velocità di movimentazione del filato.

Guided ionization waves : theory and experiments

This review focuses on one of the fundamental phenomena that occur upon application of sufficiently strong electric fields to gases, namely the formation and propagation of ionization waves-streamers. The dynamics of streamers is controlled by strongly nonlinear coupling, in localized streamer tip regions, between enhanced (due to charge separation) electric field and ionization and transport of charged species in the enhanced field. Streamers appear in nature (as initial stages of sparks and lightning, as huge structures-sprites above thunderclouds), and are also found in numerous technological applications of electrical discharges. Here we discuss the fundamental physics of the guided streamer-like structures-plasma bullets which are produced in cold atmospheric-pressure plasma jets. Plasma bullets are guided ionization waves moving in a thin column of a jet of plasma forming gases (e.g.,He or Ar) expanding into ambient air. In contrast to streamers in a free (unbounded) space that propagate in a stochastic manner and often branch, guided ionization waves are repetitive and highly-reproducible and propagate along the same path-the jet axis. This property of guided streamers, in comparison with streamers in a free space, enables many advanced time-resolved experimental studies of ionization waves with nanosecond precision. In particular, experimental studies on manipulation of streamers by external electric fields and streamer interactions are critically examined. This review also introduces the basic theories and recent advances on the experimental and computational studies of guided streamers, in particular related to the propagation dynamics of ionization waves and the various parameters of relevance to plasma streamers. This knowledge is very useful to optimize the efficacy of applications of plasma streamer discharges in various fields ranging from health care and medicine to materials science and nanotechnology.

Surface chemical modification of carbon nanowalls for wide-range control of surface wettability

Carbon nanowalls (CNWs) are self-assembled, free-standing, few-layered graphenenano-structures with large surface area, and thin graphene edges. For their application to nanobiotechnology, the effects of chemisorbed species on surface wettability were investigated. The surfaces of as-grown CNWs obtained using CH4/H2 mixture were hydrophilic. After Ar atmospheric pressure plasma treatments for up to 30 s, the contact angles of water droplets on the CNWs decreased from 51° to 5°, owing to a result of oxidation only at edges and surface defects. They increased up to 147° by CF4 plasma treatment at low pressure. The wide-range control of surface wettability of CNWs was realized by post-growth plasma treatments. We also demonstrated detection of bovine serum albumin using surface-modified CNWs as electrodes.

Contraction et décontraction des décharges micro-ondes entretenues à la pression atmosphérique

Les colonnes de plasma entretenues par un champ électrique (continu ou alternatif) à haute pression (p > 10 Torr) sont affectées par les phénomènes de contraction (réduction de la section radiale de la décharge) et de filamentation (fragmentation de la section de plasma en plusieurs filaments). La compréhension de ces phénomènes ainsi que le développement d’une méthode pouvant les supprimer demeurent une étape essentielle pour l’optimisation de certains procédés plasma. Dans cette optique, un premier objectif de notre travail était de déterminer les mécanismes à l’origine de la contraction et de la filamentation dans les décharges créées dans des gaz rares. Ainsi, nous avons montré que dans les plasmas micro-ondes contractés la cinétique de la décharge est contrôlée par les ions moléculaires et que la contraction est liée à l’influence du gradient de la température du gaz sur la concentration de ces ions. De plus, nous avons mis en évidence que la filamentation apparaît lorsque l’inhomogénéité radiale du champ électrique devient importante. Dans un second temps, nous avons développé une méthode de décontraction et de défilamentation de la décharge, qui consiste à ajouter à une décharge initiale de gaz rare des traces d’un autre gaz rare de plus faible potentiel d’ionisation. Dans le cas des plasmas décontractés, nous avons démontré que la cinétique de la décharge n’est plus contrôlée par les ions moléculaires, ce qui confirme bien l’importance de ces ions dans la description de la contraction. Pour terminer, nous avons étendu à la pression atmosphérique la technique d’absorption optique de mesure de densité des états métastables et résonnants à l’aide d’une lampe spectrale, ce qui n’avait été réalisé jusqu’ici que pour des pressions inférieures à 10 Torr. Ces états jouent un rôle essentiel dans l’ionisation des décharges contractées alors que dans les décharges décontractées leur désexcitation par les atomes du gaz adjuvant est l’étape fondamentale du processus de changement de cinétique menant à la décontraction.

Characteristics of Dielectric Barrier Discharge Reactor for Material Treatment

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Utilização de plasmas em pressão atmosférica para modificação de polímeros biocompatíveis

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Inmovilización de TiO2 sobre polímeros transparentes en el UV-A para la eliminación fotocatalítica de tricloroetileno en aire

El gran desarrollo industrial y demográfico de las últimas décadas ha dado lugar a un consumo crecientemente insostenible de energía y materias primas, que influye negativamente en el ambiente por la gran cantidad de contaminantes generados. Entre las emisiones tienen gran importancia los compuestos orgánicos volátiles (COV), y entre ellos los compuestos halogenados como el tricloroetileno, debido a su elevada toxicidad y resistencia a la degradación. Las tecnologías generalmente empleadas para la degradación de estos compuestos presentan inconvenientes derivados de la generación de productos tóxicos intermedios o su elevado coste. Dentro de los procesos avanzados de oxidación (Advanced Oxidation Processes AOP), la fotocatálisis resulta una técnica atractiva e innovadora de interés creciente en su aplicación para la eliminación de multitud de compuestos orgánicos e inorgánicos, y se ha revelado como una tecnología efectiva en la eliminación de compuestos orgánicos volátiles clorados como el tricloroetileno. Además, al poder aprovechar la luz solar como fuente de radiación UV permite una reducción significativa de costes energéticos y de operación. Los semiconductores más adecuados para su empleo como fotocatalizadores con aprovechamiento de la luz solar son aquellos que tienen una banda de energía comparable a la de los fotones de luz visible o, en su defecto, de luz ultravioleta A (Eg < 3,5 eV), siendo el más empleado el dióxido de titanio (TiO2). El objetivo principal de este trabajo es el estudio de polímeros orgánicos comerciales como soporte para el TiO2 en fotocatálisis heterogénea y su ensayo para la eliminación de tricloroetileno en aire. Para ello, se han evaluado sus propiedades ópticas y su resistencia a la fotodegradación, y se ha optimizado la fijación del fotocatalizador para conseguir un recubrimiento homogéneo, duradero y con elevada actividad fotocatalítica en diversas condiciones de operación. Los materiales plásticos ensayados fueron el polietileno (PE), copolímero de etil vinil acetato con distintos aditivos (EVA, EVA-H y EVA-SH), polipropileno (PP), polimetil (metacrilato) fabricado en colada y extrusión (PMMA-C y PMMA-E), policarbonato compacto y celular (PC-C y PC-Ce), polivinilo rígido y flexible (PVC-R y PVC-F), poliestireno (PS) y poliésteres (PET y PETG). En base a sus propiedades ópticas se seleccionaron el PP, PS, PMMA-C, EVA-SH y PVC-R, los cuales mostraron un valor de transmitancia superior al 80% en el entorno de la región estudiada (λ=365nm). Para la síntesis del fotocatalizador se empleó la tecnología sol-gel y la impregnación multicapa de los polímeros seleccionados por el método de dip-coating con secado intermedio a temperaturas moderadas. Con el fin de evaluar el envejecimiento de los polímeros bajo la radiación UV, y el efecto sobre éste del recubrimiento fotoactivo, se realizó un estudio en una cámara de exposición a la luz solar durante 150 días, evaluándose la resistencia química y la resistencia mecánica. Los resultados de espectroscopía infrarroja y del test de tracción tras el envejecimiento revelaron una mayor resistencia del PMMA y una degradación mayor en el PS, PVC-R y EVA SH, con una apreciable pérdida del recubrimiento en todos los polímeros. Los fotocatalizadores preparados sobre soportes sin tratamiento y con tres capas de óxido de titanio mostraron mejores resultados de actividad con PMMA-C, PET y PS, con buenos resultados de mineralización. Para conseguir una mayor y mejor fijación de la película al soporte se realizaron tratamientos químicos abrasivos con H2SO4 y NaOH y tratamientos de funcionalización superficial por tecnología de plasma a presión atmosférica (APP) y a baja presión (LPP). Con los tratamientos de plasma se consiguió una excelente mojabilidad de los soportes, que dio lugar a una distribución uniforme y más abundante del fotocatalizador, mientras que con los tratamientos químicos no se obtuvo una mejora significativa. Asimismo, se prepararon fotocatalizadores con una capa previa de dióxido de silicio con la intervención de surfactantes (PDDA-SiO2-3TiO2 y SiO2FC-3TiO2), consiguiéndose buenas propiedades de la película en todos los casos. Los mejores resultados de actividad con tratamiento LPP y tres capas de TiO2 se lograron con PMMA-C (91% de conversión a 30 ppm de TCE y caudal 200 ml·min-1) mejorando significativamente también la actividad fotocatalítica en PVC-R y PS. Sin embargo, el material más activo de todos los ensayados fue el PMMA-C con el recubrimiento SiO2FC-3TiO2, logrando el mejor grado de mineralización, del 45%, y una velocidad de 1,89 x 10-6 mol· m-2 · s-1, que dio lugar a la eliminación del 100 % del tricloroetileno en las condiciones anteriormente descritas. A modo comparativo se realizaron ensayos de actividad con otro contaminante orgánico tipo, el formaldehído, cuya degradación fotocatalítica fue también excelente (100% de conversión y 80% de mineralización con 24 ppm de HCHO en un caudal de aire seco de 200 ml·min-1). Los buenos resultados de actividad obtenidos confirman las enormes posibilidades que ofrecen los polímeros transparentes en el UV-A como soportes del dióxido de titanio para la eliminación fotocatalítica de contaminantes en aire. ABSTRACT The great industrial and demographic development of recent decades has led to an unsustainable increase of energy and raw materials consumption that negatively affects the environment due to the large amount of waste and pollutants generated. Between emissions generated organic compounds (VOCs), specially the halogenated ones such as trichloroethylene, are particularly important due to its high toxicity and resistance to degradation. The technologies generally used for the degradation of these compounds have serious inconveniences due to the generation of toxic intermediates turn creating the problem of disposal besides the high cost. Among the advanced oxidation processes (AOP), photocatalysis is an attractive and innovative technique with growing interest in its application for the removal of many organic and inorganic compounds, and has emerged as an effective technology in eliminating chlorinated organic compounds such as trichloroethylene. In addition, as it allows the use of sunlight as a source of UV radiation there is a significant reduction of energy costs and operation. Semiconductors suitable to be used as photocatalyst activated by sunlight are those having an energy band comparable to that of the visible or UV-A light (Eg <3,5 eV), being titanium dioxide (TiO2), the most widely used. The main objective of this study is the test of commercial organic polymers as supports for TiO2 to be applied in heterogeneous photocatalysis and its assay for removing trichloroethylene in air. To accomplish that, its optical properties and resistance to photooxidation have been evaluated, and different operating conditions have been tested in order to optimize the fixation of the photocatalyst to obtain a homogeneous coating, with durable and high photocatalytic activity. The plastic materials tested were: polyethylene (PE), ethyl vinyl acetace copolymers with different additives (EVA, EVA-H and EVA -SH), polypropylene (PP), poly methyl (methacrylate) manufactured by sheet moulding and extrusion (PMMA-C and PMMA-E), compact and cellular polycarbonates (PC-C PC-Ce), rigid and flexible polyvinyl chloride (PVC-R and PVC-F), polystyrene (PS) and polyesters (PET and PETG). On the basis of their optical properties PP, PS, PMMA-C, EVA-SH and PVC-R were selected, as they showed a transmittance value greater than 80% in the range of the studied region (λ = 365nm). For the synthesis of the photocatalyst sol-gel technology was employed with multilayers impregnation of the polymers selected by dip-coating, with intermediate TiO2 drying at moderate temperatures. To evaluate the polymers aging due to UV radiation, and the effect of photoactive coating thereon, a study in an sunlight exposure chamber for 150 days was performed, evaluating the chemical resistance and the mechanical strength. The results of infrared spectroscopy and tensile stress test after aging showed the PMMA is the most resistant sample, but a greater degradation in PS, PVC-R and EVA SH, with a visible loss of the coating in all the polymers tested. The photocatalysts prepared on the untreated substrates with three layers of TiO2 showed better activity results when PMMA-C, PET and PS where used. To achieve greater and better fixation of the film to the support, chemical abrasive treatments, with H2SO4 and NaOH, as well as surface functionalization treatments with atmospheric pressure plasma (APP) and low pressure plasma (LPP) technologies were performed. The plasma treatment showed the best results, with an excellent wettability of the substrates that lead to a better and uniform distribution of the photocatalyst compared to the chemical treatments tested, in which no significant improvement was obtained. Also photocatalysts were prepared with the a silicon dioxide previous layer with the help of surfactants (SiO2- 3TiO2 PDDA-and-3TiO2 SiO2FC), obtaining good properties of the film in all cases. The best activity results for LPP-treated samples with three layers of TiO2 were achieved with PMMA-C (91% conversion, in conditions of 30 ppm of TCE and 200 ml·min-1 air flow rate), with a significant improvement of the photocatalytic activity in PVC-R and PS samples too. However, among all the materials assayed, PMMA-C with SiO2FC-3TiO2 coating was the most active one, achieving the highest mineralization grade (45%) and a reaction rate of 1,89 x 10-6 mol· m-2 · s-1, with total trichloroethylene elimination in the same conditions. As a comparative assay, an activity test was also performed with another typical organic contaminant, formaldehyde, also with good results (100% conversion with 24 ppm of HCHO and 200 ml·min-1 gas flow rate). The good activity results obtained in this study confirm the great potential of organic polymers which are transparent in the UV-A as supports for titanium dioxide for photocatalytic removal of air organic pollutants.

Length control of He atmospheric plasma jet plumes: Effects of discharge parameters and ambient air

The effects of various discharge parameters and ambient gas on the length of He atmospheric plasma jet plumes expanding into the open air are studied. It is found that the voltage and width of the discharge-sustaining pulses exert significantly stronger effects on the plume length than the pulse frequency, gas flow rate, and nozzle diameter. This result is explained through detailed analysis of the I-V characteristics of the primary and secondary discharges which reveals the major role of the integrated total charges of the primary discharge in the plasma dynamics. The length of the jet plume can be significantly increased by guiding the propagating plume into a glass tube attached to the nozzle. This increase is attributed to elimination of the diffusion of surrounding air into the plasma plume, an absence which facilitates the propagation of the ionization front. These results are important for establishing a good level of understanding of the expansion dynamics and for enabling a high degree of control of atmospheric pressure plasmas in biomedical, materials synthesis and processing, environmental and other existing and emerging industrial applications. © 2009 American Institute of Physics.

On the Purity of Atmospheric Glow-Discharge Plasma

Purity of the glow-discharge plasma at atmospheric pressure for surface modification applications is always debatable, since it works at ambient atmosphere. We have demonstrated on the use of optical emission spectroscopy to test the purity of this kind of plasma. The effect of gas flow pattern, nature of gas, and its flow rate on the plasma chemistry was studied. The importance of proper system design in maintaining a uniform flow of heavy and inert gases as carrier gas in atmospheric glow-discharge plasma was confirmed. The surface of a plasma-treated PET sample was analyzed using X-ray photoelectron spectroscopy to verify the studies on plasma purity done using emission spectrum.

Instabilities in a non-transferred direct current plasma torch operated at reduced pressure

Using an oscilloscope, a high-speed video camera and a double-electrostatic probe system, the periodicity and amplitude of the fluctuations in arc voltage, jet luminance and ion saturation current of a plasma jet were monitored to investigate various sources of instabilities and their effects in a non-transferred dc plasma torch operated at reduced pressure. The results show that besides a 300 Hz main fluctuation inherited from the power supply, arc voltage fluctuation of 3–4 kHz with an amplitude less than 5% of the mean voltage was mainly affected by the total gas flow rate. The arc voltage fluctuation can affect the energy distribution of the plasma jet which is detectable by electrostatic probes and a high-speed video camera. The steadiness of energy transfer is also affected by the laminar or turbulent flow state of the plasma.

Atmospheric plasma treatment of carbon fibers for enhancement of their adhesion properties

Plasma processing of carbon fibers (CFs) is aimed to provide better contact and adhesion between individual plies without decrease in the CF mechanical resistance. This paper deals with surface modification of CFs by an atmospheric pressure dielectric barrier discharge (DBD) for enhancing the adhesion between the CF and the polymeric matrix. The scanning electron microscopy of the treated samples revealed many small particles distributed over entire surface of the fiber. These particles are product of the fiber surface etching during the DBD treatment that removes the epoxy layer covering as-received samples. The alteration of the CF surface morphology was also confirmed by the Atomic force microscopy (AFM), which indicated that the CF roughness increased as a result of the plasma treatment. The analysis of the surface chemical composition provided by X-ray photoelectron spectroscopy showed that oxygen and nitrogen atoms are incorporated onto the surface. The polar oxygen groups formed on the surface lead to the increasing of the CF surface energy. The results of interlaminar shear strength test (short beam) of CFs/polypropylene composites demonstrated a greater shear resistance of the composites made with CFs treated by DBD than the one with untreated fibers. Both the increase in surface roughness and the surface oxidation contribute for the enhancement of CF adhesion properties. © 2012 IEEE.

Sterilizing tissue-materials using pulsed power plasma

This paper investigates the potential of pulsed power to sterilize hard and soft tissues and its impact on their physico-mechanical properties. It hypothesizes that pulsed plasma can sterilize both vascular and avascular tissues and the transitive layers in between without deleterious effects on their functional characteristics. Cartilage/bone laminate was chosen as a model to demonstrate the concept, treated at low temperature, at atmospheric pressure, in short durations and in buffered environment using a purposed-built pulsed power unit. Input voltage and time of exposure were assigned as controlling parameters in a full factorial design of experiment to determine physical and mechanical alteration pre- and post-treatment. The results demonstrated that, discharges of 11 kV sterilized samples in 45 s, reducing intrinsic elastic modules from 1.4 ± 0.9 to 0.9 ± 0.6 MPa. There was a decrease of 14.1 % in stiffness and 27.8 % in elastic-strain energy for the top quartile. Mechanical impairment was directly proportional to input voltage (P value < 0.05). Bacterial inactivation was proportional to treatment time for input voltages above 32 V (P < 0.001; R Sq = 0.98). Thermal analysis revealed that helix-coil transition decelerated with exposure time and collagen fibrils were destabilized as denaturation enthalpy reduced by 200 μV. We concluded by presenting a safe operating threshold for pulsed power plasma as a feasible protocol for effective sterilization of connective tissues with varying level of loss in mechanical robustness which we argue to be acceptable in certain medical and tissue engineering application.