Implementação computacional do modelo carga-fluxo de carga-fluxo de dipolo para cálculo e interpretação das intensidades do espectro infravermelho

The first computational implementation that automates the procedures involved in the calculation of infrared intensities using the charge-charge flux-dipole flux model is presented. The atomic charges and dipoles from the Quantum Theory of Atoms in Molecules (QTAIM) model was programmed for Morphy98, Gaussian98 and Gaussian03 programs outputs, but for the ChelpG parameters only the Gaussian programs are supported. Results of illustrative but new calculations for the water, ammonia and methane molecules at the MP2/6-311++G(3d,3p) theoretical level, using the ChelpG and QTAIM/Morphy charges and dipoles are presented. These results showed excellent agreement with analytical results obtained directly at the MP2/6-311++G(3d,3p) level of theory.

Óxidos do tipo perovskita para reação de redução de no com CO

In this work, the perovskite-type oxides LaNiO3, LaMnO3, La0,7Sr0,3NiO3 and La0,7Sr0,3MnO3 were prepared by co-precipitation and tested in the NO reduction with CO at 400 and 500 ºC for 10 h. The catalysts were characterized by X-ray diffraction, temperature programmed reduction with hydrogen, nitrogen adsorption and chemical analysis. The nonstoichiometric oxygen was quantified by temperature programmed reduction, and the catalytic tests showed that the La0,7Sr0,3MnO3 catalyst presented the higher performance for the reduction reaction of NO with CO. The partial substitution of lanthanum by strontium increased the NO conversion and the N2 yield.

Remoção de compostos orgânicos em água empregando carvão ativado impregnado com óxido de ferro: ação combinada de adsorção e oxidação em presença de H2O2

In this work, composites based on activated carbon/iron oxide (AC/Fe) were prepared in two different proportions (AC/Fe 5/1 and 1/1) and evaluated in the removal of the organic dye methylene blue (MB). Physical-chemical properties of the composites were determined by X-ray diffraction (XRD), adsorption/dessorption of N2 isotherm, temperature programmed reduction (TPR) and scanning electron microscopy (SEM). Results showed that goethite (α- FeOOH), with nanometer particle size, was formed over carbon surface for both composites. These materials showed high efficiency to remove MB from solution by combined adsorption and oxidation process. The AC/Fe 1/1 showed to be more active in (MB) oxidation then AC/Fe 5/1.

Síntese e caracterização de nanopartículas de óxido de ferro suportadas em matriz carbonácea: remoção do corante orgânico azul de metileno em água

In this work were prepared composites of iron oxide and carbonaceous materials in two different weight proportions (Carbon/Fe 1/1 and 1/2). The physico-chemical properties of the composites were determined by temperature programmed reduction (TPR), adsorption/dessorption of N2, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and pulse titration H2. The XRD and XPS analysis showed a cubic iron oxide phase, identified as maghemite, formed over the carbon surface. The particle size of maghemite showed to be within 10-30 nm. Carbon/Fe 1/2 was the most active in MB removal kinetics and ESI-MS studies showed that MB removal by both composites leads to oxidized intermediates.

Sistema RTP: uma técnica poderosa para o monitoramento da formação de nanotubos de carbono durante o processo por deposição de vapor químico

In this work, a TPR (Temperature Programmed Reduction) system is used as a powerful tool to monitor carbon nanotubes production during CVD (Chemical Vapour Deposition), The experiments were carried out using catalyst precursors based on Fe-Mo supported on Al2O3 and methane as carbon source. As methane reacts on the Fe metal surface, carbon is deposited and H2 is produced. TPR is very sensitive to the presence of H2 and affords information on the temperature where catalyst is active to form different forms of carbon, the reaction kinetics, the catalyst deactivation and carbon yields.

Construção de uma câmara para monitoramento in situ do processo de secagem de geis e sólidos porosos

The present work deals with the design and construction of an equipment for studying the drying process of gels and solids. The equipment was built using mainly a commercial oven and others peripherals for programmed control of temperature, humidity and data acquisition. The system allows the in situ monitoring of the gel drying, registering the weight loss, and the shrinkage of sample and the oven temperatures. This set of allowed parameters makes possible to establish the main steps involved in the drying of meso and nanostructured porous materials.

Efeito da adição de lantânio em catalisadores de Ni/ZrO2 aplicados na reação de reforma a vapor de etanol

The catalytic performance of Ni/ZrO2 catalysts loaded with different lanthanum content for steam reforming of ethanol was investigated. Catalysts were characterized by BET surface area, X-ray diffraction, UV-vis spectroscopy, temperature programmed reduction, and X-ray absorption fine structure techniques. Results showed that lanthanum addition led to an increase in the degree of reduction of both NiO and nickel surface species interacting with the support, due to the higher dispersion effect. The best catalytic performance at 450 ºC was found for the Ni/12LZ catalyst, which exhibited an effluent gaseous mixture with the highest H2 yield.

Palladium-supported catalysts in methane combustion: comparison of alumina and zirconia supports

Palladium catalysts supported on alumina and zirconia were prepared by the impregnation method and calcined at 600 and 1000 ºC. Catalysts were characterized by BET measurements, XRD, XPS, O2-TPD and tested in methane combustion through temperature programmed surface reaction. Alumina supported catalysts were slightly more active than zirconia supported catalysts, but after initial heat treatment at 1000 ºC, zirconia supported palladium catalyst showed better performance above 500 ºC A pattern between temperature interval stability of PdOx species and activity was observed, where better PdOx stability was associated with more active catalysts.

Estudo da oxidação parcial do etanol em catalisadores de Rh por DRIFTS

The partial oxidation of ethanol on γ-Al2O3, CeO2, ZrO2 and Ce xZr1-xO2 supported rhodium catalysts was investigated by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). The catalysts were characterized by temperature-programmed reduction (TPR) and cyclohexane dehydrogenation. DRIFTS studies on the partial oxidation of ethanol showed that ethanol is adsorbed dissociatively, through O-H bond breaking, with the formation of ethoxy species, followed by successive dehydrogenation to acetaldehyde and acetyl species. Further oxidation to acetate and carbonate species lead to the formation of CO, CH4 and H2 by decomposition. The presence of CeO2 in the catalysts favored the oxidation steps due to its oxygen storage capacity.

Estudo de catalisadores de níquel suportados em cinza de casca de arroz na reforma de metano com dióxido de carbono visando a produção de hidrogênio e gás de síntese

Rice husk ash (RHA) is used as a silica source for several purposes, among them to obtain metal catalysts, as was done in this work. The catalysts were characterized by chemisorption, physisorption, thermal analyses (TG, DSC), X-ray diffraction, X-ray fluorescence, temperature-programmed reduction and scanning electron microscopy. The catalysts synthesized with different Ni loadings supported on RHA were applied to the reaction of dry reforming of methane. The reaction was tested at three temperatures of catalytic reduction (500, 600 and 700 ºC). All synthesized catalysts were active for the studied reaction, with different H2/CO ratios achieved according to degree of metallic dispersion.

SMB-laitteiston suunnittelu hydrometallurgisiin sovelluksiin

Työn tarkoituksena oli suunnitella, ohjelmoida ja koekäyttää SMB-laitteisto (Simulated Moving Bed) hydrometallurgisiin erotuksiin. Simuloitu liikkuvapeti saadaan aikaan vaihtamalla sisään- ja ulostuloporttien paikkaa nestevirran suuntaan. Tällöin aikaansaadaan kiintoaineen vastavirtaus minkä johdosta erotustehokkuus kasvaa. Komponenttien retentiotaipumuseroista johtuen komponentit liikkuvat eri nopeuksilla kolonnijärjestelmässä. Enemmän pidättäytyvät komponentit liikkuvat nestevirtaa vastaan ja vähemmän pidättäytyvät komponentit nestevirran mukana. Hydrometallurgiassa vastavirtauksen käyttöä ei ole tieteellisissä julkaisuissa käsitelty laajalti ja saatavilla oleva informaatio onkin kaupallisten yritysten tuottamaa. Hydrometallurgiassa vastavirtausta käyttävissä ioninvaihtolaitteistoissa hyödynnetään irrallisia regenerointivyöhykkeitä. Venttiilijärjestelmän osalta päädyttiin ratkaisuun jossa käytetään yhtä kiertoventtiiliä kullekin virralle, minkä lisäksi kolonnien väleillä käytetään solenoidiventtiiliä. Tämä järjestelmä mahdollistaa yleisimpien SMB-menetelmien käytön mukaan lukien irralliset vyöhykkeet. Laitteiston ohjauksesta vastaa LabVIEW 2010:llä ohjelmoitu ohjelmisto, joka sisältää kaikkien tarvittavien laitteiden ohjausrutiinit. Se mahdollistaa venttiilien synkroniset ja epäsynkroniset vaihdot. Laitteiston puhdistusta varten on ohjelmistoon rakennettu oma rutiini venttiilejä varten. Pumppujen osalta ohjelmisto mahdollistaa vakiovirtauksen sekä lineaaristen ja porrasmuotoisten gradienttien käytön. Ongelmatilanteita varten ohjelmisto valvoo pumppujen ja venttiilien toimintaa ja pysäyttää laitteiston tarvittaessa. Koekäytön avulla pystyttiin todentamaan laitteiston toimivuus.

Kannettavan kaasuilmaisimen suunnittelu ja toteutus

Työn tarkoituksena on suunnitella ja toteuttaa kannettava kaasuilmaisin, joka soveltuu erityisesti tavallisen kuluttajan tarpeisiin. Kaasuilmaisin on herkkä haihtuville palaville kaasuille, sekä orgaanisille kaasuille. Työssä käytetään Atmelin ATMega164P- mikrokontrolleria, piirin ohjelmointiin käytetään AVR-ISP-II, ja kehitystyökaluina AVRStudio 4:ää. Piirilevy on suunniteltu Cadsoftin Eagle- piirieditorilla. Työssä käydään läpi kokonaisvaltainen sulautetun järjestelmän suunnitteluprosessi, tuotteen spesifikaatioiden määrityksistä aina valmiin fyysisen tuotteen valmistuttamiseen asti. Tuote suunnitellaan Environics Oy:lle.

Lethal weapons : novel approaches for receptor-targeted cancer cell elimination

The currently used forms of cancer therapy are associated with drug resistance and toxicity to healthy tissues. Thus, more efficient methods are needed for cancer-specific induction of growth arrest and programmed cell death, also known as apoptosis. Therapeutic forms of tumor necrosis factor-related apoptosis-inducing ligand (TRAIL) are investigated in clinical trials due to the capability of TRAIL to trigger apoptosis specifically in cancer cells by activation of cell surface death receptors. Many tumors, however, have acquired resistance to TRAIL-induced apoptosis and sensitizing drugs for combinatorial treatments are, therefore, in high demand. This study demonstrates that lignans, natural polyphenols enriched in seeds and cereal, have a remarkable sensitizing effect on TRAIL-induced cell death at non-toxic lignan concentrations. In TRAIL-resistant and androgen-dependent prostate cancer cells we observe that lignans repress receptor tyrosine kinase (RTK) activity and downregulate cell survival signaling via the Akt pathway, which leads to increased TRAIL sensitivity. A structure-activity relationship analysis reveals that the γ-butyrolactone ring of the dibenzylbutyrolactone lignans is essential for the rapidly reversible TRAIL-sensitizing activity of these compounds. Furthermore, the lignan nortrachelogenin (NTG) is identified as the most efficient of the 27 tested lignans and norlignans in sensitization of androgen-deprived prostate cancer cells to TRAIL-induced apoptosis. While this combinatorial anticancer approach may leave normal cells unharmed, several efficient cancer drugs are too toxic, insoluble or unstable to be used in systemic therapy. To enable use of such drugs and to protect normal cells from cytotoxic effects, cancer-targeted drug delivery vehicles of nanometer scale have recently been generated. The newly developed nanoparticle system that we tested in vitro for cancer cell targeting combines the efficient drug-loading capacity of mesoporous silica to the versatile particle surface functionalization of hyperbranched poly(ethylene imine), PEI. The mesoporous hybrid silica nanoparticles (MSNs) were functionalized with folic acid to promote targeted internalization by folate receptor overexpressing cancer cells. The presented results demonstrate that the developed carrier system can be employed in vitro for cancer selective delivery of adsorbed or covalently conjugated molecules and furthermore, for selective induction of apoptotic cell death in folate receptor expressing cancer cells. The tested carrier system displays potential for simultaneous delivery of several anticancer agents specifically to cancer cells also in vivo.

Sähköauto osana älykästä sähköverkkoa – Ohjaus ja toiminnallisuudet

Tulevaisuudessa sähköverkko kohtaa monia haasteita, kun sähköautot yleistyvät, vaatien suuren tehotarpeen. Uusiutuvan energiantuotannon epävarma huipputehon tuotanto ei välttämättä pysty kattamaan sähköautoista johtuvaa suurta tehopiikkiä, jos suuret määrät ajoneuvoista kytketään yhtä aikaa lataukseen. Jos sähköajoneuvot voidaan ladata ohjatusti, ei välttämättä tarvita lisäenergian tuotantoa kattamaan kasvanutta huipputehon tarvetta. Lisäksi sähköajoneuvojen akut toimivat koko sähköverkolle energiavarastoina, jollaista ei ole ennen ollut. Älykkäällä sähköverkolla voidaan ohjata sähköajoneuvon latausta, mikäli ajoneuvossa on ohjausjärjestelmä ja akkujen varaustilan mittaus. Tässä kandidaatin työssä ohjelmoidaan mittaus- ja ohjauskortti plug-in hybridiautoa varten, jossa on V2G-ominaisuus. Ohjainkortista toteutetaan toimintakuvaus, jonka mukaan se myös ohjelmoidaan. Ohjainkortti mittaa akkujen jännitettä ja virtaa, joista voidaan määrittää akkujen varaustilat. Ohjainkortti lähettää tiedot eteenpäin PC:lle, jolta ohjainkortti saa käskyn toimintatilasta. Mittaustietojen perusteella voidaan seurata mahdollisia vikatilanteita. Kandidaatintyön aikana ohjainkorttia ei ehditty asentamaan ajoneuvoon, mutta laboratoriotestien mukaan voidaan todeta, että ohjainkortti on ohjelmallisesti toimiva. Mittauksissa selvisi, että ohjainkortin mittaustulot eivät olleet tarpeeksi tarkkoja käyttökohteeseen. Todettiin, että ohjainkortti vaatii rakenteellisia muutoksia mittaustuloksien parantamista varten, ennen ohjainkortin käyttöönottoa, mutta kandidaatintyön tavoitteet saavutettiin.

CFD Modelling of Direct Contact Condensation in Suppression Pools by Applying Condensation Models of Separated Flow

The condensation rate has to be high in the safety pressure suppression pool systems of Boiling Water Reactors (BWR) in order to fulfill their safety function. The phenomena due to such a high direct contact condensation (DCC) rate turn out to be very challenging to be analysed either with experiments or numerical simulations. In this thesis, the suppression pool experiments carried out in the POOLEX facility of Lappeenranta University of Technology were simulated. Two different condensation modes were modelled by using the 2-phase CFD codes NEPTUNE CFD and TransAT. The DCC models applied were the typical ones to be used for separated flows in channels, and their applicability to the rapidly condensing flow in the condensation pool context had not been tested earlier. A low Reynolds number case was the first to be simulated. The POOLEX experiment STB-31 was operated near the conditions between the ’quasi-steady oscillatory interface condensation’ mode and the ’condensation within the blowdown pipe’ mode. The condensation models of Lakehal et al. and Coste & Lavi´eville predicted the condensation rate quite accurately, while the other tested ones overestimated it. It was possible to get the direct phase change solution to settle near to the measured values, but a very high resolution of calculation grid was needed. Secondly, a high Reynolds number case corresponding to the ’chugging’ mode was simulated. The POOLEX experiment STB-28 was chosen, because various standard and highspeed video samples of bubbles were recorded during it. In order to extract numerical information from the video material, a pattern recognition procedure was programmed. The bubble size distributions and the frequencies of chugging were calculated with this procedure. With the statistical data of the bubble sizes and temporal data of the bubble/jet appearance, it was possible to compare the condensation rates between the experiment and the CFD simulations. In the chugging simulations, a spherically curvilinear calculation grid at the blowdown pipe exit improved the convergence and decreased the required cell count. The compressible flow solver with complete steam-tables was beneficial for the numerical success of the simulations. The Hughes-Duffey model and, to some extent, the Coste & Lavi´eville model produced realistic chugging behavior. The initial level of the steam/water interface was an important factor to determine the initiation of the chugging. If the interface was initialized with a water level high enough inside the blowdown pipe, the vigorous penetration of a water plug into the pool created a turbulent wake which invoked the chugging that was self-sustaining. A 3D simulation with a suitable DCC model produced qualitatively very realistic shapes of the chugging bubbles and jets. The comparative FFT analysis of the bubble size data and the pool bottom pressure data gave useful information to distinguish the eigenmodes of chugging, bubbling, and pool structure oscillations.