Effect of antifoams on oxygen mass transfer in pulp and paper mill effluents

Vaahdonestoaineiden haitallinen vaikutus hapen liukenemisnopeuteen biologisen puhdistamon jätevesissä on yleisesti tunnettua. Aineiden eri vaikutusmekanismien takia on silti vaikea etukäteen arvioida, miten ja kuinka paljon aineensiirto muuttuu. Työn tavoitteena oli saada tietoa vaahdonestoaineiden ja muiden pinta-aktiivisten aineiden vaikutuksesta kuplakokoon, kaasun tilavuusosuuteen ja kaasu-neste aineensiirtoon. Työn teoriaosassa on kuvailtu vaahdon muodostumiseen vaikuttavia tekijöitä sekä eri vaahdonestoaineiden vaikutusmekanismeja sellu- ja paperitehtaan jätevedessä. Edelleen on esitetty useita hapen siirtoa estäviä ja parantavia aineita. Työn kokeellisessa osassa tutkittiin kahdenkymmenenviiden eri pinta-aktiivisen aineen vaikutusta hapen liukenemisnopeuteen yksivaiheisessa kuplakolonnissa. Kokeet tehtiin kahdella pitoisuudella, kahdella eri kaasunjakolaitteella ja kolmella eri kaasun tyhjäputkinopeudella. Aineensiirtokokeiden rinnalla tutkittiin jätevesien laatu- ja fysikaalisiaominaisuuksia, niiden vaikutusta hapen liukenemisnopeuteen sekä testattavien koeaineiden vaikutusta fysikaalisin ominaisuuksiin. Kokeet osoittavat että pinta-aktiivisten aineiden vaikutus hapen aineensiirtoon vaihtelee riippuen kaasunjakolaitteesta ja aineen pitoisuuksista. Testatuista vaahdonestonaineista pienin negatiivinen vaikutus oli aineella AT 35 ja positiivinen vaikutustodettiin olevan vaahdonestoaineiden komponenteilla: P2, S1, F4 ja T9.

Drying of Ink in Inkjet Printing

Tämän diplomityön tavoitteena oli saada perustietoa tekijöistä, jotka vaikuttavat musteen kuivumiseen erilaisilla paperipinnoilla inkjet tulostuksessa. Tavoitteena oli saada tietoa erilaisista musteista, joita käytetään yleisimmissä inkjet tulostustekniikoissa, miten paperit vaikuttavat musteen kuivumiseen ja minkälaisia menetelmiä on olemassa musteen kuivumistekijöiden määrittämiseen. Lisäksi tarkoituksena oli varmistaa, voidaanko inkjetmusteiden absorptioajan määrittämiseen käytettävää DIGAT-laitetta käyttää määrittämään ja ennustamaan erilaisten musteiden kuivumista erilaisilla paperipinnoilla sekä etsiä korrelaatioita musteen absorptioajan ja teknisten paperiominaisuuksien sekä inkjet tulostuksen laadun välillä. Kirjallisuusosassa tarkasteltiin erilaisia inkjet tulostusmenetelmiä, niissä käytettäviä musteita ja musteiden koostumuksia. Tutkittiin myös paperin ja musteen välisiä vuorovaikutuksia sekä inkjet tulostuksen laatua. Kokeellisessa osassa tutkittiin musteenabsorboitumista paperiin DIGAT-laitteen avulla. kuudella eri musteella. Paperinäytteistä määritettiin teknisiä paperiominaisuuksia sekä ominaisuuksia, jotka liittyvät inkjet tulostuksen laatuun. Inkjet tulostuksen laatua tarkasteltiin tulostamalla testikuva kolmella eri tulostimella, jotka olivat Canon Bubble Jet i950, HP DeskJet Cxi970 ja Epson Stylus C46. Havaittiin, että DIGAT-laite ei sovellu määrittämään musteen absorptioaikoja kiiltäville näytteille.Tässä tutkimuksessa näyte, jonka kiilto oli 65 %, oli liian kiiltävä mitattavaksi DIGAT-laitteella. Lisäksi absorptiomäärityksissä havaittiin, että erilaiset musteet asettuvat erilailla paperin pintaan ja että pigmenttipohjaisella musteella asettumisaika oli kaikista pisin. Musteiden absorptioajat olivat nopeimpia erikoisinkjetpaperilla ja hitaimpia päällystetyillä, tiiviillä papereilla. Musteen absorptioajan ja teknisten paperiominaisuuksien ja inkjet tulostuksen laadun välisiä korrelaatioita oli vaikea havaita. Voidaan sanoa, että tulokset olivat muste- ja printterikohtaisia. Havaittiin vain muutamia teknisiä paperiominaisuuksia, jotka korreloivat hyvin musteen absorboitumisen kanssa. Nämäolivat Gurley-Hill huokoisuus, paperin tuhka- sekä kalsiumkarbonaattipitoisuus ja K&N värinabsorptio. Myöskään inkjet tulostuksen laadun ja musteen absorption välisiä korrelaatioita ei löytynyt kuin muutama; densiteetti, mottling sekä bleeding. Tämän tutkimuksen perusteella voidaan todeta DIGAT-laitteen soveltuvan hyvin kuvaamaan inkjet tulostuksen laatuominaisuuksista densiteettia, mottlingia sekä bleedingiä. DIGAT-laitetta voidaan siis käyttää avuksi ennustettaessa kuivumisaikaa ja sen vaikutusta edellä mainittuihin ominaisuuksiin. Läpipainatusominaisuuksia DIGAT-laitteen avulla ei voida tutkia, sillä ne ovat enemmän riippuvaisia paperin neliömassasta, paksuudesta ja huokoisuudesta kuinmusteen absorptioajasta. Teknisistä paperiominaisuuksista Gurley-Hill huokoisuus, paperin tuhka-sekä CaCO3-pitoisuus ja K&N värinabsorptio kuvaavat hyvin musteen imeytymisaikaa paperiin, kun taas ominaisuudet Cobb, HST ja polaari- sekädispersiokomponentit eivät kuvaa. Näyttää siltä, että testikuva, joka on tällä hetkellä käytössä UPM Tutkimus-keskuksessa, ei sovellu suurtehotulostuksen laadun tarkkailuun. Testikuva toimii hyvin pöytätulostimilla ja perinteisillä kopiopapereilla ja inkjetpapereilla, jotka on tarkoitettu tulostettaviksi hitaasti. Tulostusnopeuden ja musteen kuivumisnopeuden välisiä ilmiöitä seei tuo esille, joten se ei sovellu kuvaamaan suurtehotulostusta.

A case of acute retinal pigment epithelitis: spectral domain optical coherence tomography time course and physiopathologic hypothesis.

PURPOSE: To report the time course of retinal morphologic changes in a patient with acute retinal pigment epithelitis (ARPE) using spectral domain optical coherence tomography (SD-OCT). METHODS: A 30-year old man was referred for blurred vision of his right eye after five days that appeared suddenly 15 days after recovery from a flu-like syndrome. SD-OCT was performed immediately, followed by fluorescein and infracyanine angiography at eight days and then at three weeks. RESULTS: At presentation, a bubble of sub-macular deposit was observed on the right macula with central golden micronodules in a honeycomb pattern. SD-OCT showed an "anterior dislocation" of all the retinal layers up to the inner/outer segment (IS/OS) line and irregular deposits at the OS level together with thickening of the retinal pigment epithelial (RPE) layer. As visual acuity increased, eight days later, the OCT showed reduction of the sub-retinal deposits and an abnormal hyperflectivity of the sub-retinal and RPE layers was observed. The patient showed a positive serology for picornavirus. DISCUSSION: The acute SD-OCT sections of this patient with ARPE were compared with histological sections of a 35 day old Royal College of Surgeons rat. Similar findings could be observed, with preservation of the IS/OS line and accumulation of debris at the OS level, suggesting that ARPE symptoms could result from a transient phagocytic dysfunction of the RPE at the fovea, inducing reversible accumulation of undigested OS. Picornaviruses comprising enterovirus and coxsachievirus described as being associated with acute chorioretinitis. In this case, it was responsible for ARPE. CONCLUSION: We hypothesize that ARPE syndrome results from a transient dysfunction of RPE, which can occur as a post viral reaction.

Development of a 3D very high-resolution seismic reflection system for lacustrine settings - a case study over a thrust fault zone in Lake Geneva

Un système efficace de sismique tridimensionnelle (3-D) haute-résolution adapté à des cibles lacustres de petite échelle a été développé. Dans le Lac Léman, près de la ville de Lausanne, en Suisse, des investigations récentes en deux dimension (2-D) ont mis en évidence une zone de faille complexe qui a été choisie pour tester notre système. Les structures observées incluent une couche mince (<40 m) de sédiments quaternaires sub-horizontaux, discordants sur des couches tertiaires de molasse pentées vers le sud-est. On observe aussi la zone de faille de « La Paudèze » qui sépare les unités de la Molasse du Plateau de la Molasse Subalpine. Deux campagnes 3-D complètes, d?environ d?un kilomètre carré, ont été réalisées sur ce site de test. La campagne pilote (campagne I), effectuée en 1999 pendant 8 jours, a couvert 80 profils en utilisant une seule flûte. Pendant la campagne II (9 jours en 2001), le nouveau système trois-flûtes, bien paramétrés pour notre objectif, a permis l?acquisition de données de très haute qualité sur 180 lignes CMP. Les améliorations principales incluent un système de navigation et de déclenchement de tirs grâce à un nouveau logiciel. Celui-ci comprend un contrôle qualité de la navigation du bateau en temps réel utilisant un GPS différentiel (dGPS) à bord et une station de référence près du bord du lac. De cette façon, les tirs peuvent être déclenchés tous les 5 mètres avec une erreur maximale non-cumulative de 25 centimètres. Tandis que pour la campagne I la position des récepteurs de la flûte 48-traces a dû être déduite à partir des positions du bateau, pour la campagne II elle ont pu être calculées précisément (erreur <20 cm) grâce aux trois antennes dGPS supplémentaires placées sur des flotteurs attachés à l?extrémité de chaque flûte 24-traces. Il est maintenant possible de déterminer la dérive éventuelle de l?extrémité des flûtes (75 m) causée par des courants latéraux ou de petites variations de trajet du bateau. De plus, la construction de deux bras télescopiques maintenant les trois flûtes à une distance de 7.5 m les uns des autres, qui est la même distance que celle entre les lignes naviguées de la campagne II. En combinaison avec un espacement de récepteurs de 2.5 m, la dimension de chaque «bin» de données 3-D de la campagne II est de 1.25 m en ligne et 3.75 m latéralement. L?espacement plus grand en direction « in-line » par rapport à la direction «cross-line» est justifié par l?orientation structurale de la zone de faille perpendiculaire à la direction «in-line». L?incertitude sur la navigation et le positionnement pendant la campagne I et le «binning» imprécis qui en résulte, se retrouve dans les données sous forme d?une certaine discontinuité des réflecteurs. L?utilisation d?un canon à air à doublechambre (qui permet d?atténuer l?effet bulle) a pu réduire l?aliasing observé dans les sections migrées en 3-D. Celui-ci était dû à la combinaison du contenu relativement haute fréquence (<2000 Hz) du canon à eau (utilisé à 140 bars et à 0.3 m de profondeur) et d?un pas d?échantillonnage latéral insuffisant. Le Mini G.I 15/15 a été utilisé à 80 bars et à 1 m de profondeur, est mieux adapté à la complexité de la cible, une zone faillée ayant des réflecteurs pentés jusqu?à 30°. Bien que ses fréquences ne dépassent pas les 650 Hz, cette source combine une pénétration du signal non-aliasé jusqu?à 300 m dans le sol (par rapport au 145 m pour le canon à eau) pour une résolution verticale maximale de 1.1 m. Tandis que la campagne I a été acquise par groupes de plusieurs lignes de directions alternées, l?optimisation du temps d?acquisition du nouveau système à trois flûtes permet l?acquisition en géométrie parallèle, ce qui est préférable lorsqu?on utilise une configuration asymétrique (une source et un dispositif de récepteurs). Si on ne procède pas ainsi, les stacks sont différents selon la direction. Toutefois, la configuration de flûtes, plus courtes que pour la compagne I, a réduit la couverture nominale, la ramenant de 12 à 6. Une séquence classique de traitement 3-D a été adaptée à l?échantillonnage à haute fréquence et elle a été complétée par deux programmes qui transforment le format non-conventionnel de nos données de navigation en un format standard de l?industrie. Dans l?ordre, le traitement comprend l?incorporation de la géométrie, suivi de l?édition des traces, de l?harmonisation des «bins» (pour compenser l?inhomogénéité de la couverture due à la dérive du bateau et de la flûte), de la correction de la divergence sphérique, du filtrage passe-bande, de l?analyse de vitesse, de la correction DMO en 3-D, du stack et enfin de la migration 3-D en temps. D?analyses de vitesse détaillées ont été effectuées sur les données de couverture 12, une ligne sur deux et tous les 50 CMP, soit un nombre total de 600 spectres de semblance. Selon cette analyse, les vitesses d?intervalles varient de 1450-1650 m/s dans les sédiments non-consolidés et de 1650-3000 m/s dans les sédiments consolidés. Le fait que l?on puisse interpréter plusieurs horizons et surfaces de faille dans le cube, montre le potentiel de cette technique pour une interprétation tectonique et géologique à petite échelle en trois dimensions. On distingue cinq faciès sismiques principaux et leurs géométries 3-D détaillées sur des sections verticales et horizontales: les sédiments lacustres (Holocène), les sédiments glacio-lacustres (Pléistocène), la Molasse du Plateau, la Molasse Subalpine de la zone de faille (chevauchement) et la Molasse Subalpine au sud de cette zone. Les couches de la Molasse du Plateau et de la Molasse Subalpine ont respectivement un pendage de ~8° et ~20°. La zone de faille comprend de nombreuses structures très déformées de pendage d?environ 30°. Des tests préliminaires avec un algorithme de migration 3-D en profondeur avant sommation et à amplitudes préservées démontrent que la qualité excellente des données de la campagne II permet l?application de telles techniques à des campagnes haute-résolution. La méthode de sismique marine 3-D était utilisée jusqu?à présent quasi-exclusivement par l?industrie pétrolière. Son adaptation à une échelle plus petite géographiquement mais aussi financièrement a ouvert la voie d?appliquer cette technique à des objectifs d?environnement et du génie civil.<br/><br/>An efficient high-resolution three-dimensional (3-D) seismic reflection system for small-scale targets in lacustrine settings was developed. In Lake Geneva, near the city of Lausanne, Switzerland, past high-resolution two-dimensional (2-D) investigations revealed a complex fault zone (the Paudèze thrust zone), which was subsequently chosen for testing our system. Observed structures include a thin (<40 m) layer of subhorizontal Quaternary sediments that unconformably overlie southeast-dipping Tertiary Molasse beds and the Paudèze thrust zone, which separates Plateau and Subalpine Molasse units. Two complete 3-D surveys have been conducted over this same test site, covering an area of about 1 km2. In 1999, a pilot survey (Survey I), comprising 80 profiles, was carried out in 8 days with a single-streamer configuration. In 2001, a second survey (Survey II) used a newly developed three-streamer system with optimized design parameters, which provided an exceptionally high-quality data set of 180 common midpoint (CMP) lines in 9 days. The main improvements include a navigation and shot-triggering system with in-house navigation software that automatically fires the gun in combination with real-time control on navigation quality using differential GPS (dGPS) onboard and a reference base near the lake shore. Shots were triggered at 5-m intervals with a maximum non-cumulative error of 25 cm. Whereas the single 48-channel streamer system of Survey I requires extrapolation of receiver positions from the boat position, for Survey II they could be accurately calculated (error <20 cm) with the aid of three additional dGPS antennas mounted on rafts attached to the end of each of the 24- channel streamers. Towed at a distance of 75 m behind the vessel, they allow the determination of feathering due to cross-line currents or small course variations. Furthermore, two retractable booms hold the three streamers at a distance of 7.5 m from each other, which is the same distance as the sail line interval for Survey I. With a receiver spacing of 2.5 m, the bin dimension of the 3-D data of Survey II is 1.25 m in in-line direction and 3.75 m in cross-line direction. The greater cross-line versus in-line spacing is justified by the known structural trend of the fault zone perpendicular to the in-line direction. The data from Survey I showed some reflection discontinuity as a result of insufficiently accurate navigation and positioning and subsequent binning errors. Observed aliasing in the 3-D migration was due to insufficient lateral sampling combined with the relatively high frequency (<2000 Hz) content of the water gun source (operated at 140 bars and 0.3 m depth). These results motivated the use of a double-chamber bubble-canceling air gun for Survey II. A 15 / 15 Mini G.I air gun operated at 80 bars and 1 m depth, proved to be better adapted for imaging the complexly faulted target area, which has reflectors dipping up to 30°. Although its frequencies do not exceed 650 Hz, this air gun combines a penetration of non-aliased signal to depths of 300 m below the water bottom (versus 145 m for the water gun) with a maximum vertical resolution of 1.1 m. While Survey I was shot in patches of alternating directions, the optimized surveying time of the new threestreamer system allowed acquisition in parallel geometry, which is preferable when using an asymmetric configuration (single source and receiver array). Otherwise, resulting stacks are different for the opposite directions. However, the shorter streamer configuration of Survey II reduced the nominal fold from 12 to 6. A 3-D conventional processing flow was adapted to the high sampling rates and was complemented by two computer programs that format the unconventional navigation data to industry standards. Processing included trace editing, geometry assignment, bin harmonization (to compensate for uneven fold due to boat/streamer drift), spherical divergence correction, bandpass filtering, velocity analysis, 3-D DMO correction, stack and 3-D time migration. A detailed semblance velocity analysis was performed on the 12-fold data set for every second in-line and every 50th CMP, i.e. on a total of 600 spectra. According to this velocity analysis, interval velocities range from 1450-1650 m/s for the unconsolidated sediments and from 1650-3000 m/s for the consolidated sediments. Delineation of several horizons and fault surfaces reveal the potential for small-scale geologic and tectonic interpretation in three dimensions. Five major seismic facies and their detailed 3-D geometries can be distinguished in vertical and horizontal sections: lacustrine sediments (Holocene) , glaciolacustrine sediments (Pleistocene), Plateau Molasse, Subalpine Molasse and its thrust fault zone. Dips of beds within Plateau and Subalpine Molasse are ~8° and ~20°, respectively. Within the fault zone, many highly deformed structures with dips around 30° are visible. Preliminary tests with 3-D preserved-amplitude prestack depth migration demonstrate that the excellent data quality of Survey II allows application of such sophisticated techniques even to high-resolution seismic surveys. In general, the adaptation of the 3-D marine seismic reflection method, which to date has almost exclusively been used by the oil exploration industry, to a smaller geographical as well as financial scale has helped pave the way for applying this technique to environmental and engineering purposes.<br/><br/>La sismique réflexion est une méthode d?investigation du sous-sol avec un très grand pouvoir de résolution. Elle consiste à envoyer des vibrations dans le sol et à recueillir les ondes qui se réfléchissent sur les discontinuités géologiques à différentes profondeurs et remontent ensuite à la surface où elles sont enregistrées. Les signaux ainsi recueillis donnent non seulement des informations sur la nature des couches en présence et leur géométrie, mais ils permettent aussi de faire une interprétation géologique du sous-sol. Par exemple, dans le cas de roches sédimentaires, les profils de sismique réflexion permettent de déterminer leur mode de dépôt, leurs éventuelles déformations ou cassures et donc leur histoire tectonique. La sismique réflexion est la méthode principale de l?exploration pétrolière. Pendant longtemps on a réalisé des profils de sismique réflexion le long de profils qui fournissent une image du sous-sol en deux dimensions. Les images ainsi obtenues ne sont que partiellement exactes, puisqu?elles ne tiennent pas compte de l?aspect tridimensionnel des structures géologiques. Depuis quelques dizaines d?années, la sismique en trois dimensions (3-D) a apporté un souffle nouveau à l?étude du sous-sol. Si elle est aujourd?hui parfaitement maîtrisée pour l?imagerie des grandes structures géologiques tant dans le domaine terrestre que le domaine océanique, son adaptation à l?échelle lacustre ou fluviale n?a encore fait l?objet que de rares études. Ce travail de thèse a consisté à développer un système d?acquisition sismique similaire à celui utilisé pour la prospection pétrolière en mer, mais adapté aux lacs. Il est donc de dimension moindre, de mise en oeuvre plus légère et surtout d?une résolution des images finales beaucoup plus élevée. Alors que l?industrie pétrolière se limite souvent à une résolution de l?ordre de la dizaine de mètres, l?instrument qui a été mis au point dans le cadre de ce travail permet de voir des détails de l?ordre du mètre. Le nouveau système repose sur la possibilité d?enregistrer simultanément les réflexions sismiques sur trois câbles sismiques (ou flûtes) de 24 traces chacun. Pour obtenir des données 3-D, il est essentiel de positionner les instruments sur l?eau (source et récepteurs des ondes sismiques) avec une grande précision. Un logiciel a été spécialement développé pour le contrôle de la navigation et le déclenchement des tirs de la source sismique en utilisant des récepteurs GPS différentiel (dGPS) sur le bateau et à l?extrémité de chaque flûte. Ceci permet de positionner les instruments avec une précision de l?ordre de 20 cm. Pour tester notre système, nous avons choisi une zone sur le Lac Léman, près de la ville de Lausanne, où passe la faille de « La Paudèze » qui sépare les unités de la Molasse du Plateau et de la Molasse Subalpine. Deux campagnes de mesures de sismique 3-D y ont été réalisées sur une zone d?environ 1 km2. Les enregistrements sismiques ont ensuite été traités pour les transformer en images interprétables. Nous avons appliqué une séquence de traitement 3-D spécialement adaptée à nos données, notamment en ce qui concerne le positionnement. Après traitement, les données font apparaître différents faciès sismiques principaux correspondant notamment aux sédiments lacustres (Holocène), aux sédiments glacio-lacustres (Pléistocène), à la Molasse du Plateau, à la Molasse Subalpine de la zone de faille et la Molasse Subalpine au sud de cette zone. La géométrie 3-D détaillée des failles est visible sur les sections sismiques verticales et horizontales. L?excellente qualité des données et l?interprétation de plusieurs horizons et surfaces de faille montrent le potentiel de cette technique pour les investigations à petite échelle en trois dimensions ce qui ouvre des voies à son application dans les domaines de l?environnement et du génie civil.

Development of filter media treatments for liquid filtration

Woven monofilament, multifilament, and spun yarn filter media have long been the standard media in liquid filtration equipment. While the energy for a solid-liquid separation process is determined by the engineering work, it is the interface between the slurry and the equipment - the filter media - that greatly affects the performance characteristics of the unit operation. Those skilled in the art are well aware that a poorly designed filter medium may endanger the whole operation, whereas well-performing filter media can make the operation smooth and economical. As the mineral and pulp producers seek to produce ever finer and more refined fractions of their products, it is becoming increasingly important to be able to dewater slurries with average particle sizes around 1 ¿m using conventional, high-capacity filtration equipment. Furthermore, the surface properties of the media must not allow sticky and adhesive particles to adhere to the media. The aim of this thesis was to test how the dirt-repellency, electrical resistance and highpressure filtration performance of selected woven filter media can be improved by modifying the fabric or yarn with coating, chemical treatment and calendering. The results achieved by chemical surface treatments clearly show that the woven media surface properties can be modified to achieve lower electrical resistance and improved dirt-repellency. The main challenge with the chemical treatments is the abrasion resistance and, while the experimental results indicate that the treatment is sufficiently permanent to resist standard weathering conditions, they may still prove to be inadequately strong in terms of actual use.From the pressure filtration studies in this work, it seems obvious that the conventional woven multifilament fabrics still perform surprisingly well against the coated media in terms of filtrate clarity and cake build-up. Especially in cases where the feed slurry concentration was low and the pressures moderate, the conventional media seemed to outperform the coated media. In the cases where thefeed slurry concentration was high, the tightly woven media performed well against the monofilament reference fabrics, but seemed to do worse than some of the coated media. This result is somewhat surprising in that the high initial specific resistance of the coated media would suggest that the media will blind more easily than the plain woven media. The results indicate, however, that it is actually the woven media that gradually clogs during the coarse of filtration. In conclusion, it seems obvious that there is a pressure limit above which the woven media looses its capacity to keep the solid particles from penetrating the structure. This finding suggests that for extreme pressures the only foreseeable solution is the coated fabrics supported by a strong enough woven fabric to hold thestructure together. Having said that, the high pressure filtration process seems to follow somewhat different laws than the more conventional processes. Based on the results, it may well be that the role of the cloth is most of all to support the cake, and the main performance-determining factor is a long life time. Measuring the pore size distribution with a commercially available porometer gives a fairly accurate picture of the pore size distribution of a fabric, but failsto give insight into which of the pore sizes is the most important in determining the flow through the fabric. Historically air, and sometimes water, permeability measures have been the standard in evaluating media filtration performance including particle retention. Permeability, however, is a function of a multitudeof variables and does not directly allow the estimation of the effective pore size. In this study a new method for estimating the effective pore size and open pore area in a densely woven multifilament fabric was developed. The method combines a simplified equation of the electrical resistance of fabric with the Hagen-Poiseuille flow equation to estimate the effective pore size of a fabric and the total open area of pores. The results are validated by comparison to the measured values of the largest pore size (Bubble point) and the average pore size. The results show good correlation with measured values. However, the measured and estimated values tend to diverge in high weft density fabrics. This phenomenon is thought to be a result of a more tortuous flow path of denser fabrics, and could most probably be cured by using another value for the tortuosity factor.

Kuristettujen isotermisen vesivirtausten kolmidimensionaalinen mallintaminen

Työssä on tutkittu CFX ja Fluent virtauslaskentaohjelmien soveltavuutta kuristet-tujen isotermisten vesivirtausten kolmidimensionaaliseen mallintamiseen. Teoriaosassa on esitelty virtausta hallitsevat perusyhtälöt sekä eri kavitaatioteori-oita kavitaatiokuplan syntymisestä tuhoutumiseen. Laskennallisessa osassa esitellään käytetyt virtauslaskentaohjelmat ja laskentatapaukset sekä verrataan saatuja tuloksia aiemmin suoritettuihin mittauksiin. Työn pääpaino oli tutkia käytettyjen virtauslaskentaohjelmien soveltuvuutta kuris-tettujen virtauksien mallinnukseen.

ADVANCED NUMERICAL METHODS FOR SIMULATING MICROBUBBLE IN AN AERATED MIXING TANK

Fluid mixing in mechanically agitated tanks is one of the major unit operations in many industries. Bubbly flows have been of interest among researchers in physics, medicine, chemistry and technology over the centuries. The aim of this thesis is to use advanced numerical methods for simulating microbubble in an aerated mixing tank. Main components of the mixing tank are a cylindrical vessel, a rotating Rushton turbine and the air nozzle. The objective of Computational Fluid Dynamics (CFD) is to predict fluid flow, heat transfer, mass transfer and chemical reactions. The CFD simulations of a turbulent bubbly flow are carried out in a cylindrical mixing tank using large eddy simulation (LES) and volume of fluid (VOF) method. The Rushton turbine induced flow is modeled by using a sliding mesh method. Numerical results are used to describe the bubbly flows in highly complex liquid flow. Some of the experimental works related to turbulent bubbly flow in a mixing tank are briefly reported. Numerical simulations are needed to complete and interpret the results of the experimental work. Information given by numerical simulations has a major role in designing and scaling-up mixing tanks. The results of this work have been reported in the following scientific articles: ·Honkanen M., Koohestany A., Hatunen T., Saarenrinne P., Zamankhan P., Large eddy simulations and PIV experiments of a two-phase air-water mixer, in Proceedings of ASME Fluids Engineering Summer Conference (2005). ·Honkanen M., Koohestany A., Hatunen T., Saarenrinne P., Zamankhan P., Dynamical States of Bubbling in an Aerated Stirring Tank, submitted to J. Computational Physics.

Mittausmenetelmien kehittaminen kuplakolonnille

Kuplakolonnireaktoreiden CFD-mallinnus on talla hetkella voimakkaasti kehittyva tutkimusalue. Kaksifaasivirtauksen luotettava simulointi ja mallintaminen on haastavaa kuplakolonnireaktorissa tapahtuvien ilmioiden monimutkaisuuden vuoksi. Reaktorin kayttaytymiseen vaikuttavat tekijat, kuten kolonnin hydrodynamiikka ja aineensiirto, tulee tuntea hyvin ennen mallien tekoa. Tassa tyossa on kokeellisesti tutkittu erilaisten mittausmenetelmien soveltuvuutta kuplakolonnin hydrodynamiikan tutkimiseen. Mittausmenetelmissa on keskitytty erityisesti CFD-mallien vaatimiin paikallisiin mittauksiin. Lisaksi tyossa on arvioitu mittausmenetelmien soveltuvuutta j a luotettavuutta CFD-mallien validointiin. Tyon kirjallisuusosassa on perehdytty kuplakolonnireaktorin hydrodynaamiseen kayttaytymiseen ja siihen vaikuttaviin tekijoihin. Naita ovat mm. reaktorityypit, kaasun dispergointi, virtaustyypit ja -alueet, kaasun tilavuusosuus, kaasukuplan koko ja kuplan nousunopeus. Mittauksia tehtiin kahdessa erikokoisessa kuplakolonnissa, joista pienemman halkaisija oli 0,078 m ja suuremman 0,182 m. Molempien kolonnien nestepinnan korkeus oli 4,62 m. Mittaukset tehtiin vesijohtovedella ja epaorgaanisella prosessiliuoksella. Hydrodynaamisista ominaisuuksista mitattiin kaasun tilavuusosuus, kaasukuplan koko seka kaasukuplan nousunopeus. Kaasun tilavuusosuusmittaukset tehtiin paaasiassa paine-eromittauksella ja joissakin tapauksissa pinnanmittausmenetelmalla. Kuplakoko- ja kuplan nousunopeusmittaukset tehtiin suumopeusvideokameralla ja laser Doppler-anemometrilla. Mittauksissa kaytettiin kahdeksaa erilaista kaasunjakolaitetta, joilla selvitettiin kaasunjakolaitteen ominaisuuksien vaikutusta kolonnin hydrodynamiikkaan. Tuloksista havaittiin, etta nestefaasin ominaisuuksilla oli suuri vaikutus kolonnin hydrodynaamiseen kayttaytymiseen. En kaasunjakolaitteilla vesijohtovedella mitatut hydrodynaamiset ominaisuudet eivat poikenneet paljoa toisistaan, kun taas prosessiliuoksella kaasunjakolaitteiden valille saatiin huomattavat erot. Mittausmenetelmista laser Doppler-anemometri ei kaytettavissa olleella optiikalla soveltunut kaasukuplien mittaamiseen. Kuplat olivat menetelmalle liian suuria. Suumopeusvideokamerallaja paine-eromittauksella paastiin hyviin tuloksiin.

Thermodynamic stability of nanosized multicomponent bubbles/droplets: The square gradient theory and the capillary approach

Formation of nanosized droplets/bubbles from a metastable bulk phase is connected to many unresolved scientific questions. We analyze the properties and stability of multicomponent droplets and bubbles in the canonical ensemble, and compare with single-component systems. The bubbles/droplets are described on the mesoscopic level by square gradient theory. Furthermore, we compare the results to a capillary model which gives a macroscopic description. Remarkably, the solutions of the square gradient model, representing bubbles and droplets, are accurately reproduced by the capillary model except in the vicinity of the spinodals. The solutions of the square gradient model form closed loops, which shows the inherent symmetry and connected nature of bubbles and droplets. A thermodynamic stability analysis is carried out, where the second variation of the square gradient description is compared to the eigenvalues of the Hessian matrix in the capillary description. The analysis shows that it is impossible to stabilize arbitrarily small bubbles or droplets in closed systems and gives insight into metastable regions close to the minimum bubble/droplet radii. Despite the large difference in complexity, the square gradient and the capillary model predict the same finite threshold sizes and very similar stability limits for bubbles and droplets, both for single-component and two-component systems.

Abnormal Returns of Dividend Announcements during a Boom and a Recession. Empirical Evidence from U.S. from the years of 2000 - 2002 and 2005 - 2007, including Finnish Extra Dividends

This study examines the short time price effect of dividend announcements during a boom and a recession. The data being used here is gathered from the years of 2000 - 2002 when it was a recession after the techno bubble burst and from the years 2005 - 2007 when investors experienced large capital gains all around the world. The data consists of dividend increases and intact observations. The aim is to find out differences in abnormal returns between a boom and a recession. Second, the study examines differences between different dividend yield brackets. Third, Finnish extra dividends, mainly being delivered to shareholders in 2004 are included to the empirical test. Generally stated, the aim is to find out do investors respect dividends more during a recession than a boom and can this be proved by using dividend yield brackets. The empirical results from U.S shows that the abnormal returns of dividend increase announcements during the recession in the beginning of this decade were larger than during the boom. Thus, investors seem to respect dividend increases more when stock prices are falling. Substantial abnormal returns of dividend increases during the time period of 2005 - 2007 could not be found. The results from the overall samples state that the abnormal returns during the recession were positively slightly higher than during the boom. No clear and strong evidence was found between different dividend yield brackets. In Finland, there were substantial abnormal returns on the announcement day of the extra dividends. Thus, indicating that investors saw the extra dividends as a good thing for shareholders' value. This paper is mostly in line with the theory that investors respect dividends more during bad times than good times.

Abnormal Return of Dividend Announcements during a Boom and a Recession. Empirical evidence from the years of 2002 - 2002 and 2005 - 2007, including the Finnish extra dividends

Tutkimuksen tavoitteena on tutkia epänormaalien tuottojen esiintymistä nousu- ja laskusuhdanteen aikana osingonilmoituspäivän ympärillä. Osinkoilmoitukset ovat kerätty Yhdysvaltojen markkinalta (NYSE) ajanjaksoilta 2000 - 2002, jolloin pörssit laskivat teknokuplan jälkeen ja 2005 - 2007, jolloin sijoittajat kokivat suuria kurssivoittoja. Osinkoilmoitushavainnot koostuvat yhtiöistä, jotka nostivat tai pitivät osinko per osake paikallaan. Tavoitteena on tutkia eroja epänormaaleissa tuotoissa näiden kahden ajanjakson välillä. Toiseksi, tavoitteena on tutkia miten epänormaalit tuotot poikkeavat toisistaan eri osinkotuottoluokissa. Kolmanneksi, tavoitteena on tutkia esiintyikö markkinoilla epänormaaleja tuottoja kun suomalaiset yritykset ilmoittivat ylimääräisistä osingoista, pääasiassa vuonna 2004. Yksinkertaisesti ja lyhyesti sanottuna tavoitteena on tutkia arvostavatko sijoittajat osinkoja enemmän laskukauden vai nousukauden aikana. Rahoitusteorian mukaan sijoittajien tulisi arvostaa laskukauden aikana enemmän yhtiöitä, jotka pystyvät maksamaan huonosta taloustilanteesta huolimatta hyvää osinkoa. Empiiriset testit Yhdysvalloista osoittavat, että osingon nostamisesta johtuvat epänormaalit tuotot olivat suuremmat laskusuhdanteen aikana kuin noususuhdanteen aikana. Tämä on linjassa teorian kanssa. Osingon-nostot aiheuttivat nousukauden aikana vähäisiä epänormaaleja tuottoja. Selviä eroja eri osingontuottoluokkien välillä ei pystytty havaitsemaan. Tulokset yhdistetystä aineistosta osoittavat, että sijoittajat kokivat vähäisiä positiivisia epänormaaleja tuottoja laskukauden aikana. Nousukautena tuotot olivat lähellä nollaa. Suomen markkinoilla havaittiin selvä epänormaalituotto osingonilmoituspäivänä. Tulokset ovat pääpiirteittäin linjassa teorian kanssa. Sijoittajat arvostavat osinkoja hieman enemmän lasku- kuin noususuhdanteen aikana.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Banks, Lies and Bricks: The Determinants of Home Value Inflation in Spain during the Housing Boom

During the first decade of this century, Spain experienced the most important economic and housing boom in its recent history. This situation led the lending industry to dramatically expand through the mortgage market. The high competition among lenders caused a dramatic lowering of credit standards. During this period, lenders operating in the Spanish mortgage market artificially inflated appraised home values in order to draw larger mortgages. By doing this, lenders gave financially constrained households access to mortgage credit. In this paper, we analyze this phenomenon for this first time. To do so, we resort to a unique dataset of matched mortgage-dwelling-borrower characteristics covering the period 2004–2010. Our data allow us to construct an unbiased measure of property’s over-appraisal, since transaction prices in our data also includes any potential side payment in the transactions. Our findings indicate that i) in Spain, appraised home values were inflated on average by around 30% with respect to transaction prices; ii) creditconstrained households were more likely to be involved in mortgages with inflated house values; and iii) a regional indicator of competition in the lending market suggests that inflated appraisal values were also more likely to appear in more competitive regional mortgage markets. Keywords: Housing demand, appraisal values, house prices, housing bubble, credit constraints, mortgage market. JEL Classification: R21, R31

Winner-Loser Performance and Macroeconomic Effects during three last Economic Crises in Finnish Stock Market

The main purpose of this thesis is to investigate winner-loser performance when financial markets are facing crisis. This is examined through the idea that does the prior loser portfolios outperform the prior winner portfolios during the three major crises: The depression of the 1990s, the IT-Bubble and the Subprime -crisis. Firstly, the winner and loser portfolios superiority is counted by using the cumulative excess returns from the examination period. The portfolios were formed by counting the excess returns and locating them in to the order of superiority. The excess returns are counted by using one year pre-data before the actual examination period. The results of this part did not support the results of De Bondt & Thaler’s (1985) paper. Secondly, it is investigated how the Finnish and the US macroeconomic factors are seen to be affecting the stock market valuation in Finnish Stock Markets during economic crises. This is done to explain better the changes in the successes of the winner-loser performance. The crises included different amount of selected macro factors. Two latest crises involved as well few selected US macro factors. Exclusively the IT-Bubble -crisis had the most statistically significant results with the US factors. Two other crises did not receive statistically significant results. An extra research was produced to study do the US macro factors impact more significantly on Finnish stock exchange after lags. The selected lags were three, six, nine and twelve months. Three and six month lagged US macro factors during the IT-Bubble -crisis improved the results. The extra research did not improve the results of the Subprime -crisis.

Surface Modification of Ceramics

Ceramics are widely used in industrial applications due to their advantageous thermal and mechanical stability. Corrosion of ceramics is a great problem resulting in significant costs. Coating is one method of reducing adversities of corrosion. There are several different thin film deposition processes available such as sol-gel, Physical and Chemical Vapour Deposition (PVD and CVD). One of the CVD processes, called Atomic Layer Deposition (ALD) stands out for its excellent controllability, accuracy and wide process capability. The most commonly mentioned disadvantage of this method is its slowness which is partly compensated by its capability of processing large areas at once. Several factors affect the ALD process. Such factors include temperature, the grade of precursors, pulse-purge times and flux of precursors as well as the substrate used. Wrongly chosen process factors may cause loss of self-limiting growth and thus, non-uniformities in the deposited film. Porous substrates require longer pulse times than flat surfaces. The goal of this thesis was to examine the effects of ALD films on surface properties of a porous ceramic material. The analyses applied were for permeability, bubble point pressure and isoelectric point. In addition, effects of the films on corrosion resistance of the substrate in aqueous environment were investigated. After being exposured to different corrosive media the ceramics and liquid samples collected were analysed both mechanically and chemically. Visual and contentual differences between the exposed and coated ceramics versus the untreated and uncoated ones were analysed by scanning electron microscope. Two ALD film materials, dialuminium trioxide and titanium dioxide were deposited on the ceramic substrate using different pulse times. The results of both film materials indicated that surface properties of the ceramic material can be modified to some extent by the ALD method. The effect of the titanium oxide film on the corrosion resistance of the ceramic samples was observed to be fairly small regardless of the pulse time.