Protection of wind energy systems against the indirect effects of lightning

This paper is concerned with the protection of wind energy systems against the indirect effects of lightning. As wind energy is gaining increasing importance throughout the world, lightning damages involving wind energy systems have come to be regarded with more attention. Nevertheless, there are still very few studies in Portugal regarding lightning protection of wind energy systems using models of the Electro-Magnetic Transients Program (EMTP). Hence, a new case study is presented in this paper, based on a wind turbine with an interconnecting transformer, considering that lightning strikes the soil near the tower at a distance such that galvanic coupling occurs through the grounding electrode. Computer simulations obtained by using EMTP-RV are presented and conclusions are duly drawn. (C) 2011 Elsevier Ltd. All rights reserved.

Assessment of direct radiological risk and indirect associated toxic risks originated by Coal-Fired Power Plants

Over the past few decades there has been some discussion concerning the increase of the natural background radiation originated by coal-fired power plants, due to the uranium and thorium content present in combustion ashes. The radioactive decay products of uranium and thorium, such as radium, radon, polonium, bismuth and lead, are also released in addition to a significant amount of 40K. Since the measurement of radioactive elements released by the gaseous emissions of coal power plants is not compulsory, there is a gap of information concerning this situation. Consequently, the prediction of dispersion and mobility of these elements in the environment, after their release, is based on limited data and the radiological impact from the exposure to these radioactive elements is unknown. This paper describes the methodology that is being developed to assess the radiological impact due to the raise in the natural background radiation level originated by the release and dispersion of the emitted radionuclides. The current investigation is part of a research project that is undergoing in the vicinity of Sines coal-fired power plant (south of Portugal) until 2013. Data from preliminary stages are already available and possible of interpretation.

Indirect hydrogen analysis by gas chromatography coupled to mass spectrometry (GC-MS).

Gas chromatography (GC) is an analytical tool very useful to investigate the composition of gaseous mixtures. The different gases are separated by specific columns but, if hydrogen (H2 ) is present in the sample, its detection can be performed by a thermal conductivity detector or a helium ionization detector. Indeed, coupled to GC, no other detector can perform this detection except the expensive atomic emission detector. Based on the detection and analysis of H2 isotopes by low-pressure chemical ionization mass spectrometry (MS), a new method for H2 detection by GC coupled to MS with an electron ionization ion source and a quadrupole analyser is presented. The presence of H2 in a gaseous mixture could easily be put in evidence by the monitoring of the molecular ion of the protonated carrier gas. Copyright © 2013 John Wiley & Sons, Ltd.

Comparative electron impact and fast atom bombardment mass spectrometric studies of some HMPA adducts of phenyltin and phenyllead halides and studies of strong hydrogen bonding by FAB-MS

The fragmentation patterns and mass spectra of some phenyl tin and -lead halide adducts with hexamethylphosphoramide are compared by subjecting them t~ electron impact and fast atom bombardment ionization in a mass spectrometer. This comparison is restricted to the metal-containing ions. Ligand-exchange mechanisms of some of the metal-containing species are explored by FAB-MS. Several moisturesensitive organo-metallics and H-bonded systems have been examined by FAB for attempted characterization, but without any success. Scavenging and trapping of water molecules by complex aggregates in solutions of quaternary ammonium fluorides and hydroxides are investigated by FAB to complement previous NMR-studies.

Strong hydrogen bonding in organic synthesis

The preparation of phenacyl and para-phenylphenacyl esters, the reactions of carboxylic acids, phenols, 2-nitropropane and alcohols with alkyl halides in the presence of fluoride anion are described. The reactions are thought to be accelerated by the formation of hydrogen bonds between the fluoride anion and the organic electron acceptor. The fluoride ,carboxylic acids, fluoride-phenols and fluoride-2-nitropropane are better reaction systems than the fluoride-alcohol. The source of the fluoride anion and the choice of solvents are also discussed.

The importance of hydrogen bonding in the alkylation of phenols

Hydrogen bond assisted alkylation of phenols is compared with the classical base assisted reactions. The influence of solvents on the fluoride assisted reactions is discussed,· with emphasis on the localization of hydrogen bond charge density. Polar aprotic solvents such as DMF favour a-alkylation, and nonpolar aprotic solvents such as toluene favourC-alkylation of phenol. For more reactive and soluble fluorides, such as tetrabu~ylammoniumfluoride, the polar aprotic solvent favours a-alkylation and nonpolar aprotic solvent favours fluorination. Freeze-dried potassium fluoride is a better catalytic agent in hydrogen bond assisted alkylation reactions of phenol than the oven-dried fluoride. The presence of water in the alkylation reactions reduces the expected yield drastically. The tolerance of the reaction to water has also been studied. The use ofa phase transfer catalyst such as tetrabutylammonium bromide in the alkylation reactions of phenol in the presence of potassium fluoride is very effective under anhydrous conditions. Sterically hindered phenols such as 2,6-ditertiarybutyl-4-methyl phenol could not be alkylated even by using the more reactive fluorides, such as tetrabutylammonium fluoride in either polar or nonpolar aprotic solvents. Attempts were also made to alkylate phenols in the presence of triphenylphosphine oxide.

Mirroring Enzymes: The Role of H-Bonding In HQuin-BAM Catalyzed Asymmetric Aza-Henry Reactions: A DFT Study into the Reactivity, Mechanism, and Origins of Selectivity

The exact mechanistic understanding of various organocatalytic systems in asymmetric reactions such as Henry and aza-Henry transformations is important for developing and designing new synthetic organocatalysts. The focus of this dissertation will be on the use of density functional theory (DFT) for studying the asymmetric aza-Henry reaction. The first part of the thesis is a detailed mechanistic investigation of a poorly understood chiral bis(amidine) (BAM) Brønsted acid catalyzed aza-Henry reaction between nitromethane and N-Boc phenylaldimine. The catalyst, in addition to acting as a Brønsted base, serves to simultaneously activate both the electrophile and the nucleophile through dual H-bonding during C-C bond formation and is thus essential for both reaction rate and selectivity. Analysis of the H-bonding interactions revealed that there was a strong preference for the formation of a homonuclear positive charge-assisted H-bond, which in turn governed the relative orientation of substrate binding. Attracted by this well-defined mechanistic investigation, the other important aspect of my PhD research addressed a detailed theoretical analysis accounting for the observed selectivity in diastereoselective versions of this reaction. A detailed inspection of the stereodetermining C-C bond forming transition states for monoalkylated nitronate addition to a range of electronically different aldimines, revealed that the origins of stereoselectivity were controlled by a delicate balance of different factors such as steric, orbital interactions, and the extent of distortion in the catalyst and substrates. The structural analysis of different substituted transition states established an interesting dependency on matching the shape and size of the catalyst (host molecule) and substrates (guest molecules) upon binding, both being key factors governing selectivity, in essence, offering an analogy to positive cooperative binding effect of catalytic enzymes and substrates in Nature. In addition, both intra-molecular (intra-host) and inter-molecular (host-guest, guest-guest) stabilizing interactions play a key role to the high π-facial selectivity. The application of dispersion-corrected functionals (i.e., ωB97X-D and B3LYP-D3) was essential for accurately modeling these stabilizing interactions, indicating the importance of dispersion effects in enantioselectivity. As a brief prelude to more extensive future studies, the influence of a triflate counterion on both reactivity and selectivity in this reaction was also addressed.

Association entre consommation de drogues illicites et symptomatologie dépressive à l’adolescence : une étude longitudinale auprès de jeunes Québécois fréquentant l’école secondaire en milieu défavorisé

L’usage de drogues illicites et la symptomatologie dépressive sont associés, mais la nature de cette association demeure mal comprise. Une clarification des mécanismes en jeu est nécessaire afin de pouvoir intervenir sur la cooccurrence des deux phénomènes, dont les conséquences individuelles et sociales sont lourdes. Ces efforts de clarification débutent à l’adolescence, moment où sont typiquement initiés la consommation de substances et les problèmes affectifs. L’objectif de cette thèse est de contribuer à clarifier la nature des associations entre l’usage de certaines des drogues illicites les plus fréquemment consommées et les symptômes dépressifs chez les adolescents. Les données utilisées proviennent d’une cohorte de l’échantillon longitudinal de la Stratégie d’Intervention Agir Autrement (SIAA) comprenant plus de 3000 jeunes fréquentant des écoles en milieu défavorisé du Québec, qui ont été suivis pendant leur secondaire (2003-2007). Le premier article empirique de la thèse porte sur la relation entre l’usage de cannabis et la symptomatologie dépressive. Cette étude a examiné l’existence d’associations prospectives bidirectionnelles entre les deux phénomènes du début (13-14 ans) à la fin du secondaire (16-17 ans). Les analyses ont considéré des liens directs, mais également des liens indirects via deux facteurs reflétant des appartenances sociales normatives et non normatives : l’attachement à l’école et l’affiliation à des pairs déviants et consommateurs de drogues. Les résultats indiquent que les symptômes dépressifs et l’usage de cannabis peuvent représenter des facteurs de risque mutuels et suggèrent qu’un mécanisme indirect impliquant une érosion des attaches normatives pourrait jouer un rôle dans des cascades développementales reliant les deux manifestations. Le deuxième article empirique visait à déterminer si l’usage de deux drogues de synthèse, le MDMA (ecstasy) et les méth/amphétamines (speed), à 15-16 ans était associé au développement de symptômes dépressifs élevés un an plus tard, en prenant en considération des facteurs confondants potentiels. Tel qu’attendu, les résultats montrent une prédiction de la symptomatologie dépressive par l’usage de MDMA et de méth/amphetamines, particulièrement lorsque cet usage est concomitant. Ces résultats représentent une des premières évidences d’un risque posé par l’usage de drogues de synthèse par rapport au développement de symptômes affectifs chez les jeunes.

L'évolution des comportements d'agressivité physique de la petite enfance à l'âge scolaire : le rôle des relations d'amitié en début de scolarisation

Cette thèse avait pour objectif d’examiner les liens longitudinaux entre les relations d’amitié et l’évolution des comportements d’agressivité physique en début de scolarisation. Guidé par les principes énoncés par les théoriciens de l’apprentissage social, de l’attachement, du développement de la personnalité et de la théorie du jugement moral, le rôle principal et modérateur de certaines dimensions spécifiques à la qualité de la relation d’amitié, ainsi que des attributs comportementaux des amis et des caractéristiques personnelles de l’enfant a été évalué. Des données provenant de l’Étude Longitudinale du Développement des Enfants du Québec (ELDEQ), de l’Étude des Jumeaux nouveau-nés du Québec (EJNQ) et de l’évaluation des effets d’un programme d’intervention dyadique ont été analysées. Les mesures utilisées dans cette thèse ont été collectées entre la maternelle et la 2e année du primaire, soit de 5 à 8 ans, directement auprès des enfants, de leurs amis, leurs pairs, leurs parents et leurs enseignants par le biais de questionnaires, d’entrevues sociométriques et de mises en situation hypothétiques. En lien avec la perspective de l’apprentissage social, les résultats ont montré que l’association à des amis agressifs en maternelle est liée à une augmentation des comportements d’agressivité physique chez l’enfant. Cependant, en lien avec les théories du développement de la personnalité et la perspective de l’attachement, le fait d’établir une relation d’amitié de bonne qualité est reliée à une diminution des comportements agressifs à travers le temps. De plus, une interaction entre la qualité de la relation et les attributs comportementaux des amis a indiqué que le risque lié à l’association à des amis agressifs est atténué dans le contexte d’une relation d’amitié de bonne qualité. Les résultats indiquent également que chez les garçons, la présence de conflits entre amis à la maternelle est associée de façon linéaire à de plus hauts niveaux de comportements agressifs, indépendamment du risque génétique de l’enfant face à cette problématique. Une interaction triple a par ailleurs révélé que le conflit n’était pas lié à une augmentation de l’agressivité physique dans le contexte d’une relation d’amitié caractérisée par l’affect positif et une bonne capacité à régler les conflits. Enfin, les résultats ont montré un effet indirect d’une intervention dyadique sur la diminution des comportements d’agressivité physique, qui opère à travers l’amélioration de la capacité des amis à régler leurs conflits. Ces résultats appuient le rôle bénéfique de la qualité de la relation d’amitié sur l’évolution des manifestations de comportements d’agressivité physique et suggèrent que cet aspect relationnel soit pris en compte dans les programmes de prévention des conduites agressives. En somme, la mise en évidence d’associations et d’interactions significatives entre la qualité des relations d’amitié, les attributs comportementaux des amis et les manifestations de comportements d’agressivité physique en début de scolarisation suggère que certains aspects et dimensions relationnelles positives peuvent être bénéfiques au développement des enfants agressifs. La prévention du maintien et de l’aggravation des conduites agressives par l’entremise de l’amélioration de la qualité des relations d’amitié représente une avenue prometteuse.

Effect of curing temperature , fibre loading and bonding agent on the equilibrium swelling of isora-natural rubbercomposites

Isora fibre-reinforced natural rubber (NR) composites were cured at 80, 100, 120 and 150°C using a low temperature curing accelerator system. Composites were also prepared using a conventional accelerator system and cured at 150°C. The swelling behavior of these composites at varying fibre loadings was studied in toluene and hexane. Results show that the uptake of solvent and volume fraction of rubber due to swelling was lower for the low temperature cured vulcanizates which is an indication of the better fibre/rubber adhesion. The uptake of aromatic solvent was higher than that of aliphatic solvent, for all the composites. As the fibre content increased, the solvent uptake decreased, due to the superior solvent resistance of the fibre and good fibre-rubber interactions. The bonding agent improved the swelling resistance of the composites due to the strong interfacial adhesion. Due to the improved adhesion between the fibre and rubber, the ratio of the change in volume fraction of rubber due to swelling to the volume fraction of rubber in the dry sample (V,) was found to decrease in the presence of bonding agent. At a fixed fibre loading, the alkali treated fibre composite showed a lower percentage swelling than untreated one for both systems showing superior rubber-fibre interactions.

Mechanical Properties of Short-Isora-Fiber-Reinforced Natural Rubber Composites: Effects of Fiber Length, Orientation, and Loading; Alkali Treatment;and Bonding Agent

A series of short-isora-fiber-reinforced natural rubber composites were prepared by the incorporation of fibers of different lengths (6, 10, and 14 mm) at 15 phr loading and at different concentrations (10, 20, 30, and 40 phr) with a 10 mm fiber length. Mixes were also prepared with 10 mm long fibers treated with a 5% NaOH solution. The vulcanization parameters, processability, and stress-strain properties of these composites were analyzed. Properties such as tensile strength, tear strength, and tensile modulus were found to be at maximum for composites containing longitudinally oriented fibers 10 mm in length. Mixes containing fiber loadings of 30 phr with bonding agent (resorcinol-formaldehyde [RF] resin) showed mechanical properties superior to all other composites. Scanning electron microscopy (SEM) studies were carried out to investigate the fiber surface morphology, fiber pullout, and fiber-rubber interface. SEM studies showed that the bonding between the fiber and rubber was improved with treated fibers and with the use of bonding agent.

The Use of Carboxy Terminated Liquid Natural Rubber (CTNR) as an Adhesive in Bonding Rubber to Rigid and Non-rigid Substrates

Carboxy Terminated Liquid Natural Rubber (CTNR) was prepared by photochemical reaction using maleic anhydride and masticated natural rubber (NR). The use of CTNR as an adhesive in bonding rubber to rubber and rubber to metal was studied. The peel strengths and lap shear strengths of the adherends which were bonded using CTNR were determined. The effect of using a tri isocyanate with CTNR in rubber to metal bonding was also studied. It is found that CTNR can effectively be used in bonding rubber to rubber and rubber to mild steel.

Studies on Rubber-to-Nylon Tire Cord Bonding

ABSTRACT: Nylon tire cord (1680/2) was dipped in different adhesives based on resorcinol formaldehyde resin and latex (RFL) and was bonded to natural rubber-based compounds. The resin-rubber ratio in the RFL adhesive was optimized. The variation of pull-through load was studied by varying the drying and curing temperature of the dipped nylon tire cord. RFL adhesive based on vinylpyridine latex was found to have better rubber-to-nylon tire cord bonding, compared with the one based on natural rubber latex. Addition of a formaldehyde donor into the RFL adhesive/rubber compound improves adhesion.

Rubber Solution Adhesives for Wood-to-Wood Bonding

Rubber solutions were prepared and used for bonding wood pieces. The effect of the variation of chlorinated natural rubber (CNR) and phenolformaldehyde (PF) resin in the adhesive solutions on lap shear strength was determined. Natural rubber and neoprene-based adhesive solutions were compared for their lap shear strength. The storage stability of the adhesive prepared was determined. The change in lap shear strength before and after being placed in cold water, hot water, acid, and alkali was tested. The bonding character of these adhesives was compared with different commercially available solution adhesives. The room-temperature aging resistance of wood joints was also determined. In all the studies, the adhesive prepared in the laboratory was found to be superior compared to the commercial adhesives.

Rheological Characteristics of Short Nylon -6 Fiber Reinforced Styrene Butadiene Rubber Containing Epoxy Resin as Bonding Agent

The rheological characteristics of short Nylon-6 fiber-reinforced Styrene Butadiene rubber (SBR) in the presence of epoxy resin-based bonding agent were studied with respect to the effect of shear rate, fiber concentration , and temperature on shear viscosity and die swell using a capillary rheonzeter. All the composites containing bonding agent showed a pseudoplastic nature, which decreased with increasing temperature. Shear viscosity was increased in the presence of fibers. The temperature sensitivity of the SBR matrices was reduced on introduction of fibers. The temperature sensitivity of the melts was found to be lower at higher shear rates. Die swell was reduced in the presence of fibers. Relative viscosity of the composites increased with shear rate. In the presence of epoxy resin bonding agent the temperature sensitivity of the mixes increased. Die swell was larger in the presence of bonding agent.