A high order model for piezoelectric rods: an asymptotic approach

Preprint submitted to International Journal of Solids and Structures. ISSN 0020-7683

Modelação, simulação e implementação de agitação acústica para aplicações em microfluídica

Tese de Doutoramento (Programa Doutoral em Engenharia Biomédica)

Role of fluid mixing in deep dissolution of carbonates

The presence of cavities filled with new minerals in carbonate rocks is a common feature in oil reservoirs and lead-zinc deposits. Since groundwater equilibrates rapidly with carbonates, the presence of dissolution cavities in deep carbonate host rocks is a paradox. Two alternative geochemical processes have been proposed to dissolve carbonates at depth: hydrogen sulfide oxidation to sulfuric acid, and metal sulfide precipitation. With the aid of geochemical modeling we show that mixing two warm solutions saturated with carbonate results in a new solution that dissolves limestone. Variations in the proportion of the end-member fluids can also form a supersaturated mixture and fill the cavity with a new generation of carbonate. Mixing is in general more effective in dissolving carbonates than the aforementioned processes. Moreover, mixing is consistent with the wide set of textures and mineral proportions observed in cavity infillings.

Formation and Control of Trace Metal Emissions in Co-Firing of Biomass, Peat, and Wastes in Fluidised Bed Combustors

Environmentally harmful consequences of fossil fuel utilisation andthe landfilling of wastes have increased the interest among the energy producers to consider the use of alternative fuels like wood fuels and Refuse-Derived Fuels, RDFs. The fluidised bed technology that allows the flexible use of a variety of different fuels is commonly used at small- and medium-sized power plants ofmunicipalities and industry in Finland. Since there is only one mass-burn plantcurrently in operation in the country and no intention to build new ones, the co-firing of pre-processed wastes in fluidised bed boilers has become the most generally applied waste-to-energy concept in Finland. The recently validated EU Directive on Incineration of Wastes aims to mitigate environmentally harmful pollutants of waste incineration and co-incineration of wastes with conventional fuels. Apart from gaseous flue gas pollutants and dust, the emissions of toxic tracemetals are limited. The implementation of the Directive's restrictions in the Finnish legislation is assumed to limit the co-firing of waste fuels, due to the insufficient reduction of the regulated air pollutants in the existing flue gas cleaning devices. Trace metals emission formation and reduction in the ESP, the condensing wet scrubber, the fabric filter, and the humidification reactor were studied, experimentally, in full- and pilot-scale combustors utilising the bubbling fluidised bed technology, and, theoretically, by means of reactor model calculations. The core of the model is a thermodynamic equilibrium analysis. The experiments were carried out with wood chips, sawdust, and peat, and their refuse-derived fuel, RDF, blends. In all, ten different fuels or fuel blends were tested. Relatively high concentrations of trace metals in RDFs compared to the concentrations of these metals in wood fuels increased the trace metal concentrations in the flue gas after the boiler ten- to hundred-folds, when RDF was co-fired with sawdust in a full-scale BFB boiler. In the case of peat, lesser increase in trace metal concentrations was observed, due to the higher initial trace metal concentrations of peat compared to sawdust. Despite the high removal rate of most of the trace metals in the ESP, the Directive emission limits for trace metals were exceeded in each of the RDF co-firing tests. The dominat trace metals in fluegas after the ESP were Cu, Pb and Mn. In the condensing wet scrubber, the flue gas trace metal emissions were reduced below the Directive emission limits, whenRDF pellet was used as a co-firing fuel together with sawdust and peat. High chlorine content of the RDFs enhanced the mercuric chloride formation and hence the mercury removal in the ESP and scrubber. Mercury emissions were lower than theDirective emission limit for total Hg, 0.05 mg/Nm3, in all full-scale co-firingtests already in the flue gas after the ESP. The pilot-scale experiments with aBFB combustor equipped with a fabric filter revealed that the fabric filter alone is able to reduce the trace metal concentrations, including mercury, in the flue gas during the RDF co-firing approximately to the same level as they are during the wood chip firing. Lower trace metal emissions than the Directive limits were easily reached even with a 40% thermal share of RDF co-firing with sawdust.Enrichment of trace metals in the submicron fly ash particle fraction because of RDF co-firing was not observed in the test runs where sawdust was used as the main fuel. The combustion of RDF pellets with peat caused an enrichment of As, Cd, Co, Pb, Sb, and V in the submicron particle mode. Accumulation and release oftrace metals in the bed material was examined by means of a bed material analysis, mass balance calculations and a reactor model. Lead, zinc and copper were found to have a tendency to be accumulated in the bed material but also to have a tendency to be released from the bed material into the combustion gases, if the combustion conditions were changed. The concentration of the trace metal in the combustion gases of the bubbling fluidised bed boiler was found to be a summary of trace metal fluxes from three main sources. They were (1) the trace metal flux from the burning fuel particle (2) the trace metal flux from the ash in the bed, and (3) the trace metal flux from the active alkali metal layer on the sand (and ash) particles in the bed. The amount of chlorine in the system, the combustion temperature, the fuel ash composition and the saturation state of the bed material in regard to trace metals were discovered to be key factors affecting therelease process. During the co-firing of waste fuels with variable amounts of e.g. ash and chlorine, it is extremely important to consider the possible ongoingaccumulation and/or release of the trace metals in the bed, when determining the flue gas trace metal emissions. If the state of the combustion process in regard to trace metals accumulation and/or release in the bed material is not known,it may happen that emissions from the bed material rather than the combustion of the fuel in question are measured and reported.

Concentrações e associações geoquímicas de Pb e Zn em sedimentos do rio São Francisco impactados por rejeitos da produção industrial de zinco

Surface sediments from the River São Francisco were analyzed to investigate the impact, due to the presence of metals (Cd, Cu, Pb, Zn) in wastes from a metallurgical industry in the city of Três Marias/MG, Brazil. The concentrations and geochemical associations of Pb, Zn and trace metals associated with the minerals employed in zinc production were measured. Sediments close to discharge locations were highly contaminated with Pb (332-512 μg g-1) and Zn (7872-10780 μg g-1), with values decreasing rapidly due to dilution and hydraulic sorting. Evaluation of toxicity according to the Consensus-based Sediment Quality Guidelines indicated for Cd, Pb and Zn a high probability of adverse effects on aquatic biota at these sites.

Kokemäenjoen suiston kehitys, maaperämuodostumat ja niiden kemialliset piirteet

Suurelta osin Natura-alueeseen kuuluvan Kokemäenjoen suistoalueen kuivan maan ja suiston edustan vesialueen erityyppisten maaperäkerrostumien kerrosjärjestys ja alueellinen jakautuminen selvitettiin pintamaaperän kartoituksella, tutkimuskaivannoilla ja kairauksella. Suiston kerrostumat luokiteltiin viiteen maaperämuodostumaan. Vanhimmasta nuorimpaan, Toukari, Vainio-Mattila, Hevosluoto, Lanajuopa ja Säikkä muodostumaan. Nämä edustavat vanhoja Itämeren altaan ja nuorempia merelle päin etenevän suiston eri osien kerrostumisympäristöjä. Eri muodostumien fysikaaliset ja kemialliset ominaisuudet kuvattiin ja ne eroavat luonteeltaan ratkaisevasti toisistaan. Suiston etenemistä edustavat Hevosluoto- ja Säikkä-muodostumat ovat kontaminoituneet 1900-luvun alkupuolelta lähtien yhä voimakkaammin ihmistoiminnasta kertyvistä raskasmetallipitoisuuksista ja orgaanisista haitta-aineista. Tämä näkyy erityisesti elohopean, kadmiumin, arseenin, lyijyn, sinkin, nikkelin, dioksiinien ja furaanien kokonaispitoisuuksien kasvuna näissä muodostumissa. Pitoisuudet ovat suurimpia muodostumien nuorimmissa osissa. Kuivalla maalla raskasmetallipitoisuudet ylittävät paikoin valtioneuvoston pilaantuneelle maaperälle asettamat kynnysarvot, jolloin säädökset on huomioitava suiston maaperää muokattaessa. Vesialueella nämä kynnysarvot ylittyvät myös orgaanisten haitta-aineiden osalta. Tietyin osin ovat esimerkiksi arseenin ja nikkelin osalta taustapitoisuudet suistoalueen vanhimmassa Toukari muodostumassa jo luontaisesti kynnysarvoja suuremmat. Tämä pitää osata ottaa huomioon maansiirtotoimenpiteitä suunniteltaessa. Suistoon kerrostuvan maa-aineksen ja nopean maankohoamisen vuoksi suisto etenee nykyisin 30-40 m vuodessa merialueelle päin. Tämä mataloittaa vääjäämättömästi suiston edustan vesialueita kerrostumisen siirtyessä merelle päin. Näin myös Natura-alueen ainutlaatuiset biotoopit vähitellen siirtyvät merelle päin.

Synthesis and characterization of nanoperforated metal oxide thin films

For advanced devices in the application fields of data storage, solar cell and biosensing, one of the major challenges to achieve high efficiency is the fabrication of nanopatterned metal oxide surfaces. Such surfaces often require both precise structure at the nanometer scale and controllable patterned structure at the macro scale. Nowadays, the dominating candidates to fabricate nanopatterned surfaces are the lithographic technique and block-copolymer masks, most of which are unfortunately costly and inefficient. An alternative bottom-up approach, which involves organic/inorganic self-assembly and dip-coating deposition, has been studied intensively in recent years and has proven to be an effective technique for the fabrication of nanoperforated metal oxide thin films. The overall objective of this work was to optimize the synthesis conditions of nanoperforated TiO2 (NP-TiO2) thin films, especially to be compatible with mixed metal oxide systems. Another goal was to develop fabrication and processing of NP-TiO2 thin films towards largescale production and seek new applications for solar cells and biosensing. Besides the traditional dip-coating and drop-casting methods, inkjet printing was used to prepare thin films of metal oxides, with the advantage of depositing the ink onto target areas, further enabling cost-effective fabrication of micro-patterned nanoperforated metal oxide thin films. The films were characterized by water contact angle determination, Atomic Force Microscopy, Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy and Grazing Incidence XRay Diffraction. In this study, well-ordered zinc titanate nanoperforated thin films with different Zn/Ti ratios were produced successfully with zinc precursor content up to 50 mol%, and the dominating phase was Zn2Ti3O8. NP-TiO2 structures were also obtained by a cost-efficient means, namely inkjet printing, at both ambient temperature and 60 °C. To further explore new biosensing applications of nanoperforated oxide thin films, inkjet printing was used for the fabrication of both continuous and patterned polymeric films onto NP-TiO2 and perfluorinated phosphate functionalized NP-TiO2 substrates, respectively. The NP-TiO2 films can be also functionalized with a fluoroalkylsilane, resulting in hydrophobic surfaces on both titania and silica. The surface energy contrast in the nanoperforations can be tuned by irradiating the films with UV light, which provides ideal model systems for wettability studies.

Jätteiden kemiallisten ominaisuuksien spektrometriset online-mittausmenetelmät

Tässä diplomityössä käsiteltiin spektrometrisia online-mittausmenetelmiä jätteiden kemiallisten ja fysikaalisten ominaisuuksien määrittämiseksi. Tavoitteena oli selvittää, mitä ominaisuuksia menetelmillä voidaan mitata ja kuinka luotettavia tuloksia mittauksilla saadaan. Diplomityössä suoritettiin kirjallisuuskatsaus, jossa käsiteltiin kolmen spektrometrisen menetelmän soveltuvuutta reaaliaikaisiin jätemittauksiin. Työn empiirisessä osassa FPXRFanalysaattorilla mitattiin neljän eri jätenäytteen alkuainepitoisuuksia. Mittauksen tarkoituksena oli selvittää, mitä alkuaineita menetelmällä voidaan mitata. FPXRF-analysaattorilla saatuja tuloksia verrattiin ICP-MS-menetelmällä saatuihin tuloksiin regressioanalyysin avulla. Työssä todettiin, että FPXRF-analysaattori sopii parhaiten kaliumin, kalsiumin, ja raudan pitoisuuksien määrittämiseen. Lisäksi lyijyn, sinkin, kromin, kloorin, kuparin, kadmiumin, arseenin, fosforin, molybdeenin ja vanadiinin määrittäminen on mahdollista, mutta tarkan pitoisuuden saamiseksi laboratoriomenetelmien käyttö voi olla tarpeen. Tutkituista jätenäytteistä menetelmä soveltui parhaiten tuhkalle ja kompostille niiden fyysisten ominaisuuksien, kuten homogeenisuuden ja kosteuspitoisuuden takia. Biojätteelle menetelmä soveltui huonosti. FPXRF-analysaattorin luotettavuuteen vaikuttaa näytteen kosteuspitoisuus, homogeenisuus, partikkelikoko, mittaustapa ja laitteen kalibrointi. Työssä tarkastelluilla menetelmillä ei voida tällä hetkellä täysin korvata laboratorioanalyyseja. FPXRF-analysaattoria voidaan kuitenkin käyttää kvalitatiiviseen tai semikvantitatiiviseen haitta-aineiden analysointiin, millä voidaan vähentää kalliiden laboratorioanalyysien tarvetta.

Postglacial paleoecology and effects of European settlement on the environment of Lake Hunger and Lake Lisgar, Southwestern Ontario /

This investigation has three purposes I to make a comparative chemical study on sediment cores collected for Lake Lisgar (man-made lake in an urban center) and Lake Hunger (natural basin in a rural community) encompassing the time since European settlement I to determine the postglacial chemical history of Lake Hunger, and to determine the vegetational history of the Lake Hunger area from postglacial time to the present. The minus 80 mesh fraction of 108 soil samples and 18 stream sediment samples collected in the vicinity of Lakes' Lisgar and Hunger were analyzed for cold hydrochloric acid soluble lead, zinc, nickel, cobalt, copper, aluminum, sodium, potassium, calcium, magnesium, iron and manganese. Lacustrine sediments from 5 boreholes in the Lake Lisgar basin were collected. Boreholes 1, 2, 3, and 4 were analyzed for palynological and chemical information and Borehole 5 was subjected to pollen and ostracode analysis. Lacustrine sediments from 6 boreholes in the Lake Hunger basin were collected. Palyno- -logical and chemical analysis were performed on Boreholes 1, 2, 3, 4, and 6 and Borehole 5 was analyzed for pollen. In addition, radiocarbon dates were obtained on sediment samples from Boreholes 4 and 5. A total of 8 surface samples were collected from the margins of the Lake Hunger basin and these were chemically analyzed in the laboratory. All of the lacustrine sediments were ashed and analyzed for cold hydrochloric acid soluble lead, zinc, nickel, cobalt, copper, aluminum, sodium, potassium, calcium, magnesium, iron and manganese using a Perkin Elmer 40) Atomic Absorption spectrophotometer. The results . obtained for the 12 elements were expressed as parts per million in dry sediments. It was found that man's influence on the element distribution patterns in the sediments of Lake Lisgar appeared to be related to his urbanizing developments within the lake vicinity, whereas, the rural developments in the vicinity of lake Hunger appeared to have had little effect on the element distribution patterns in the lake sediments. The distribution patterns of lead, zinc, nickel, cobalt, aluminum, magnesium, sodium and potassium are similar to the % ash curve throughout postglacial time indicating that the rate of erosion in the drainage basin is the main factor which controls the concentration of these elements in the sediments of Lake Hunger. The vegetational history, from palynological analysis, of Lake Hunger from postglacial time to the present includes the following stages: tundra, open spruce forest, closed boreal forest, deciduous forest and the trend towards the re-establishment of pine following the clearing of land and the subsequent settlement of the Lake Hunger area by European settlers. The concentrations of some elements (cobalt, nickel, iron, manganese, calcium, magnesium, sodium and potassium) in the sediments of Lake Hunger appears to be higher during pre-cultural compared to post-cultural times. At least one complete postglacial record of the chemical history within a lake basin is necessary in order to accurately assess man's effects on his environment.

Sol-Gel Alumina Nano Composites for Functional Applications

The thesis entitled "Sol-Gel Alumina Nano Composites for Functional Applications" investigate sol-gel methods of synthesis of alumina nanocomposites special reference to alumina-aluminium titanate and alumina-lanthanum phosphate composites. The functional properties such as thermal expansion coefficient and thermal shock resistance, machinability of composites as well as thermal protection are highlighted in addition to novel approach in synthesis of composites.A general introduction of alumina matrix composites materials, followed by brief coverage of alumina-aluminium titanate and alumina-lanthanum phosphate composites is highlight of the first chapter. The second chapter deals with the sol-gel synthesis of aluminium titanate and alumina-aluminium titanate composite. The synthesis of machinable substrate, based on alumina and lanthanum phosphate forms the basis of the third chapter. The fourth chapter describes the sol-gel coating of mullite on SiC substrate for the possible gas filtration application.

Waste Water Treatment Using Low Cost Natural Adsorbents

Heavy metals are major toxic pollutants with severe health effects on humans. They are released into the environment from a variety of industrial activities. Cadmium, lead, zinc, chromium and copper are the most toxic metals of widespread use in industries such as tanning, electroplating, electronic equipment manufacturing and chemical processing plants. Heavy metals contribute to a variety of adverse health environmental effects due to their acute and chronic exposure through air, water and food chain. Conventional treatment methods of metal removal are often limited by their cost and ineffectiveness at low concentrations. Adsorption, the use of inactivated biomass as adsorbents offers an attractive potential alternative to their conventional methods. Mango peel and Alisma plantago aquatica are naturally occurring and abundant biomass can offer an economical solution for metal removal.The Cd(II), Pb(II), Zn(II), Cr(III) and Cu(II) adsorption by milled adsorbents of mango peel and Alisma plantago aquatica were evaluated in batches.

Heavy metal tolerance patterns of total heterotrophic bacteria isolated from the soils of Mahatma Gandhi University campus, Kottayam, Kerala

Industrialization of our society has led to an increased production and discharge of both xenobiotic and natural chemical substances. Many of these chemicals will end up in the soil. Pollution of soils with heavy metals is becoming one of the most severe ecological and human health hazards. Elevated levels of heavy metals decrease soil microbial activity and bacteria need to develop different mechanisms to confer resistances to these heavy metals. Bacteria develop heavy-metal resistance mostly for their survivals, especially a significant portion of the resistant phenomena was found in the environmental strains. Therefore, in the present work, we check the multiple metal tolerance patterns of bacterial strains isolated from the soils of MG University campus, Kottayam. A total of 46 bacterial strains were isolated from different locations of the campus and tested for their resistant to 5 common metals in use (lead, zinc, copper, cadmium and nickel) by agar dilution method. The results of the present work revealed that there was a spatial variation of bacterial metal resistance in the soils of MG University campus, this may be due to the difference in metal contamination in different sampling location. All of the isolates showed resistance to one or more heavy metals selected. Tolerance to lead was relatively high followed by zinc, nickel, copper and cadmium. About 33% of the isolates showed very high tolerance (>4000μg/ml) to lead. Tolerance to cadmium (65%) was rather low (<100 μg/ml). Resistance to zinc was in between 100μg/ml - 1000μg/ml and the majority of them shows resistance in between 200μg/ml - 500μg/ml. Nickel resistance was in between 100μg/ml - 1000μg/ml and a good number of them shows resistance in between 300μg/ml - 400μg/ml. Resistance to copper was in between <100μg/ml - 500μg/ml and most of them showed resistance in between 300μg/ml - 400μg/ml. From the results of this study, it was concluded that heavy metal-resistant bacteria are widely distributed in the soils of MG university campus and the tolerance of heavy metals varied among bacteria and between locations

Piezoelectric Ultrasonic Micromotors

This report describes development of micro-fabricated piezoelectric ultrasonic motors and bulk-ceramic piezoelectric ultrasonic motors. Ultrasonic motors offer the advantage of low speed, high torque operation without the need for gears. They can be made compact and lightweight and provide a holding torque in the absence of applied power, due to the traveling wave frictional coupling mechanism between the rotor and the stator. This report covers modeling, simulation, fabrication and testing of ultrasonic motors. Design of experiments methods were also utilized to find optimal motor parameters. A suite of 8 mm diameter x 3 mm tall motors were machined for these studies and maximum stall torques as large as 10^(- 3) Nm, maximum no-load speeds of 1710 rpm and peak power outputs of 27 mW were realized. Aditionally, this report describes the implementation of a microfabricated ultrasonic motor using thin-film lead zirconate titanate. In a joint project with the Pennsylvania State University Materials Research Laboratory and MIT Lincoln Laboratory, 2 mm and 5 mm diameter stator structures were fabricated on 1 micron thick silicon nitride membranes. Small glass lenses placed down on top spun at 100-300 rpm with 4 V excitation at 90 kHz. The large power densities and stall torques of these piezoelectric ultrasonic motors offer tremendous promis for integrated machines: complete intelligent, electro-mechanical autonomous systems mass-produced in a single fabrication process.

Chemical profile of rums as a function of their origin. The use of chemometric techniques for their identification

To identify chemical descriptors to distinguish Cuban from non-Cuban rums, analyses of 44 samples of rum from 15 different countries are described. To provide the chemical descriptors, analyses of the the mineral fraction, phenolic compounds, caramel, alcohols, acetic acid, ethyl acetate, ketones, and aldehydes were carried out. The analytical data were treated through the following chemometric methods: principal component analysis (PCA), partial least square-discriminate analysis (PLS-DA), and linear discriminate analysis (LDA). These analyses indicated 23 analytes as relevant chemical descriptors for the separation of rums into two distinct groups. The possibility of clustering the rum samples investigated through PCA analysis led to an accumulative percentage of 70.4% in the first three principal components, and isoamyl alcohol, n-propyl alcohol, copper, iron, 2-furfuraldehyde (furfuraldehyde), phenylmethanal (benzaldehyde), epicatechin, and vanillin were used as chemical descriptors. By applying the PLS-DA technique to the whole set of analytical data, the following analytes have been selected as descriptors: acetone, sec-butyl alcohol, isobutyl alcohol, ethyl acetate, methanol, isoamyl alcohol, magnesium, sodium, lead, iron, manganese, copper, zinc, 4-hydroxy3,5-dimethoxybenzaldehyde (syringaldehyde), methaldehyde (formaldehyde), 5-hydroxymethyl-2furfuraldehyde (5-HMF), acetalclehyde, 2-furfuraldehyde, 2-butenal (crotonaldehyde), n-pentanal (valeraldehyde), iso-pentanal (isovaleraldehyde), benzaldehyde, 2,3-butanodione monoxime, acetylacetone, epicatechin, and vanillin. By applying the LIDA technique, a model was developed, and the following analytes were selected as descriptors: ethyl acetate, sec-butyl alcohol, n-propyl alcohol, n-butyl alcohol, isoamyl alcohol, isobutyl alcohol, caramel, catechin, vanillin, epicatechin, manganese, acetalclehyde, 4-hydroxy-3-methoxybenzoic acid, 2-butenal, 4-hydroxy-3,5-dimethoxybenzoic acid, cyclopentanone, acetone, lead, zinc, calcium, barium, strontium, and sodium. This model allowed the discrimination of Cuban rums from the others with 88.2% accuracy.

Estudo da associação de elementos traços com a fração orgânica e inorgânica do carvão do leão

O presente trabalho refere-se à determinação dos elementos cobre, chumbo, zinco, cobalto, níquel, cromo, vanádio e manganês no carvão da Mina do Leão, com o objetivo de verificar a distribuição e ocorrência dos mesmos, com ênfase ao estudo da associação com as frações orgânica e inorgânica do carvão. O estudo da associação revelou que o cobre, cobalto, níquel, cromo e vanádio, estão associados à fração orgânica do carvão. O chumbo e o zinco, estão predominantemente associados a fração orgânica, contudo, para altos teores de cinzas, verifica-se também associação com a fração inorgânica. O manganês, está dominantemente associado à fração inorgânica.