Máscaras mecânicas de sombra por eletrocorrosão para dispositivos eletro-ópticos

Shadow masks are used in manufacturing processes for electro-optic devices to transfer patterns with different shapes and dimensions. For fabrication of organic based devices, shadow masks should be made of materials stable against organic solvents, high temperature, and robust, remaining unchanged after multiple cycles of use and fixation. Thus, stainless steel is suitable for shadow masks. A simple, cheap and quick method of obtaining shadow masks by electrochemical corrosion of stainless steel is reported. The shadow mask was used to evaporate cathode material to obtain an organic light emitting diode with active area of 9 mm². This device exhibited a turn-on voltage of 5 V and luminance of 14 cd/m².

Isolamento do verbacosídeo e validação de método analítico para padronização do extrato bruto das partes aéreas de Buddleja stachyoides Cham. & Schltdl. (Scrophulariaceae)

Phenylpropanoid glycoside verbascoside was isolated and identified from the ethyl acetate fraction of the aerial parts of Buddleja stachyoides Cham. & Schltdl. by 1H-NMR. A method using high-performance liquid chromatography has been developed and validated for determination of verbascoside in alcoholic crude extract of the aerial parts of B. stachyoides. Analysis was performed on a Phenomenex® Gemini-NX C18 analytical column (250 mm × 4.6 mm; 5 µm) using a mobile phase (pump A - aqueous solution containing H2SO4 (0.01 M), H3PO4 (0.4%), and (C2H5)2NH (0.4%); pump B - methanol:aqueous (95:5) solution containing H2SO4 (0.05 M), H3PO4 (2%), and (C2H5)2NH (0.2%); pump C - acetonitrile:aqueous (90:10) solution containing H2SO4 (0.05 M) and H3PO4 (2%)) and a diode array detector at 325 nm. The method was validated in accordance with ANVISA guidelines and may be applied to quality control of herbal medicine with aerial parts of B. stachyoides.

Phenolic composition and antioxidant properties of Brazilian honeys

The antioxidant activities and polyphenolic levels of "assa peixe," "cambara," and "morrão de candeia" Brazilian honeys were investigated. Phenolic extracts of 11 honeys were evaluated spectrophotometrically to determine their total phenolic and flavonoid contents, and their antioxidant activities were measured using DPPH, ABTS, and FRAP assays. High-performance liquid chromatography coupled with diode array detection was applied to determine the phenolic composition of the honey extracts. The presence of fourteen phenolic compounds was established (eleven phenolic acids and three flavonoids), as well as HMF and abscisic acid. Principal component analysis was applied to classify the honey samples according to their floral origins.

DETECTION AND QUANTIFICATION OF PHYTOCHEMICAL MARKERS OF Ilex paraguariensis BY LIQUID CHROMATOGRAPHY

Ilex paraguariensis (yerba-mate) is used as a beverage, and its extract requires adequate quality control methods in order to guarantee quality and safe use. Strategies to develop and optimize a chromatographic method to quantify theobromine, caffeine, and chlorogenic acid in I. paraguariensis extracts were evaluated by applying a quality by design (QbD) model and ultra high-performance liquid chromatography (UHPLC). The presence of these three phytochemical markers in the extracts was evaluated using UHPLC-MS and was confirmed by the chromatographic bands in the total ion current traces (m/z of 181.1 [M+H]+, 195.0 [M+H]+, and 353.0 [M−H]−, respectively). The developed method was then transferred to a high-performance liquid chromatography (HPLC) platform, and the three phytochemical markers were used as external standards in the validation of a method for analyses of these compounds in extracts using a diode array detector (DAD). The validated method was applied to quantify the chlorogenic acid, caffeine, and theobromine in the samples. HPLC-DAD chromatographic fingerprinting was also used in a multivariate approach to process the entire data and to separate the I. paraguariensis extracts into two groups. The developed method is very useful for qualifying and quantifying I. paraguariensis extracts.

COMPARAÇÃO DE MÉTODOS POR CROMATOGRAFIA LÍQUIDA NA DETERMINAÇÃO DE MULTIRRESÍDUOS DE AGROTÓXICOS EM MORANGOS

Liquid chromatography is often used for the determination of pesticide multiresidues in foods. In Brazil, the strawberry crop is an example of a food with high levels of irregularities because of the application of pesticides. This is a major concern from the perspective of food safety, environmental protection, and certification for food export. The purpose of this study is to evaluate and compare chromatographic separation and detection methods in relation to a newly developed and validated method using ultra high performance liquid chromatography (LC) coupled with tandem mass spectrometry (MS/MS) for the analytical determination of pesticides in strawberries. The comparisons were based on evaluations of the analysis time, consumption of the solvent in the mobile phase, injection volume, detectability, matrix effect, and recovery. The results showed that the LC–MS/MS and UHPLC–MS/MS techniques were both extremely efficient at analyzing pesticide residues with different physico-chemical parameters that were present at low concentrations in a complex matrix. The UHPLC separation method provided better chromatographic performance and productivity, which contributed favorably to routine analytical determinations. Detection by MS/MS had better detectability and selectivity compared with the diode array detector.

ESTUDO FITOQUÍMICO, ATIVIDADE ANTIMICROBIANA E CITOTÓXICA DE ESPÉCIMES DE Leonotis nepetifolia L. R. (Br)

Specimens of Leonotis nepetiflolia were obtained from cultivated and wild environments to verify their influences in chemical composition. Phytochemical analyses were conducted for the ethyl acetate phase obtained by partitioning the crude ethanol extract from the cultivated leaves of L. nepetifolia. In doing so, flavonoid 3',4',5-trimethoxy-6,7-dihidroxyflavone (cirsiliol), a chemotaxonomic marker of the family Lamiaceae, was isolated. The results reveal that all phases and extracts tested exhibited weak to moderate antimicrobial activity against the strains of bacteria tested. The evaluation of in vitrocytotoxic and antitumor activity showed that the ethyl acetate phases obtained from both wild and cultivated leaves exhibit high potential cytotoxic and antitumor (> 78.0% of inhibition) activity. The major component of these phases was identified by high-performance liquid chromatography-diode array detector and nuclear magnetic resonance analyses using both 1D and 2D methods. The results further indicate that the flavonoid cirsiliol is the agent responsible for the activity observed in these phases.

MCR-ALS APLICADO NO MONITORAMENTO QUANTITATIVO DO PROCESSO DE ELETRODEGRADAÇÃO DA ATRAZINA USANDO ESPECTROS UV: RESULTADOS COMPARATIVOS COM HPLC-DAD COMO UM MÉTODO DE REFERÊNCIA

Electrodegradation of atrazine in water was performed using homemade (PA and PB) and purchased (PC) boron-doped diamond anodes. The degradation was monitored off-line by analyzing total organic carbon and high performance liquid chromatography with diode array detector (HPLC-DAD) and at-line by UV spectroscopy. The spectra were recorded every 2 min. The rank deficiency problem was resolved by assembling an augmented column-wise matrix. HPLC was employed to separate the original and byproducts degradation components. Aiming the same goal, multivariate curve resolution - alternating least squares (MCR-ALS) was applied to resolve the UV spectroscopic data. Comparison between HPLC and MCR-ALS separations is presented. By using MCR-ALS the spectra of atrazine and two byproducts were successfully resolved and the resulted concentration profiles properly represented the system studied. The ALS explained variance (R2) for PA, PB and PC was equal to 99.99% for all of them and the lack of fit for PA, PB and PC were 0.39, 0.34 and 0.54 respectively. The correlation (R) between the recovered and pure spectra were calculate for each electrodegradation, validating the MCR-ALS results. The average R was equal to 0.997. The spectral and concentration profiles described with this new approach are in agreement with HPLC-DAD results. The proposed method is an alternative to classical analyses for monitoring of the degradation process, mainly due to the simplicity, fast results and economy.

LOW COST ANALYZER FOR THE DETERMINATION OF PHOSPHORUS BASED ON OPEN-SOURCE HARDWARE AND PULSED FLOWS

The need for automated analyzers for industrial and environmental samples has triggered the research for new and cost-effective strategies of automation and control of analytical systems. The widespread availability of open-source hardware together with novel analytical methods based on pulsed flows have opened the possibility of implementing standalone automated analytical systems at low cost. Among the areas that can benefit from this approach are the analysis of industrial products and effluents and environmental analysis. In this work, a multi-pumping flow system is proposed for the determination of phosphorus in effluents and polluted water samples. The system employs photometric detection based on the formation of molybdovanadophosphoric acid, and the fluidic circuit is built using three solenoid micropumps. The detection is implemented with a low cost LED-photodiode photometric detection system and the whole system is controlled by an open-source Arduino Uno microcontroller board. The optimization of the timing to ensure the color development and the pumping cycle is discussed for the proposed implementation. Experimental results to evaluate the system behavior are presented verifying a linear relationship between the relative absorbance and the phosphorus concentrations for levels as high as 50 mg L-1.

Tasajännitetason nosto polttokennosovelluksessa

Polttokennojen, erityisesti SOFC-kennojen, tutkimuksessa on viime vuosina saavutettu merkittäviä edistysaskelia ja mahdollisuudet kennojen laajamittaiseen hyödyntämiseen paranevat koko ajan. Polttokennojen yleistyessä tarvitaan tehoelektroniikkaa muokkaamaan kennojen tasajännite verkkoon sopivaksi vaihtojännitteeksi. Verkkovaihtosuuntaaja vaatii korkeamman jännitetason, kuin polttokennosta on saatavissa, joten tasajännitetasoa on ensin nostettava. Tässä diplomityössä esitellään kolme eri hakkuritopologiaa ja perehdytään kokosiltahakkurin optimointiin. Hakkurin pääasialliset häviölähteet olivat toision diodisilta ja transistorit. Diodien vaihtaminen piidiodeista piikarbididiodeihin ei parantanut hyötysuhdetta, koska toision jännite tarkastellussa sovelluksessa oli matala. Muuntajan käämiminen litz-johtimella paransi hyötysuhdetta merkittävästi.

Design and implementation of a multipurpose reactor for scale-up studies

In the theoretical part, the different polymerisation catalysts are introduced and the phenomena related to mixing in the stirred tank reactor are presented. Also the advantages and challenges related to scale-up are discussed. The aim of the applied part was to design and implement an intermediate-sized reactor useful for scale-up studies. The reactor setting was tested making one batch of Ziegler–Natta polypropylene catalyst. The catalyst preparation with a designed equipment setting succeeded and the catalyst was analysed. The analyses of the catalyst were done, because the properties of the catalyst were compared to the normal properties of Ziegler–Natta polypropylene catalyst. The total titanium content of the catalyst was slightly higher than in normal Ziegler–Natta polypropylene catalyst, but the magnesium and aluminium content of the catalyst were in the normal level. By adjusting the siphonation tube and adding one washing step the titanium content of the catalyst could be decreased. The particle size of the catalyst was small, but the activity was in a normal range. The size of the catalyst particles could be increased by decreasing the stirring speed. During the test run, it was noticed that some improvements for the designed equipment setting could be done. For example more valves for the chemical feed line need to be added to ensure inert conditions during the catalyst preparation. Also nitrogen for the reactor needs to separate from other nitrogen line. With this change the pressure in the reactor can be kept as desired during the catalyst preparation. The proposals for improvements are presented in the applied part. After these improvements are done, the equipment setting is ready for start-up. The computational fluid dynamics model for the designed reactor was provided by cooperation with Lappeenranta University of Technology. The experiments showed that for adequate mixing with one impeller, stirring speed of 600 rpm is needed. The computational fluid dynamics model with two impellers showed that there was no difference in the mixing efficiency if the upper impeller were pumping downwards or upwards.

Ledivalaisimet rautatiealueiden valaistuksessa

Leditekniikan kehitys viime vuosina on mahdollistanut niiden käytön yleisvalaistuksessa. Tässä työssä tehdään katsaus leditekniikan nykytilaan ja tulevaisuuteen, sekä osoitetaan, että ledivalaisimien energiankulutuksessa ja huoltokustannuksissa tehdyillä säästöillä voidaan kattaa suuremmat hankintakustannukset ja päästä yhtä suuriin tai pienempiin elinkaarikustannuksiin verrattuna perinteisiin kaasupurkausvalaisimiin. Valaisimien määrät on laskettu Dialux-valaistuslaskentaohjelmalla siten että rautatieasemien avolaitureiden ja katettujen laitureiden valaistusvaatimukset täyttyvät. Tuloksia voi soveltaa muihin vastaaviin tiloihin kuten asematunneleihin tai kevyen liikenteen väylille.

Mobile system for pump working point estimation

In the current economy situation companies try to reduce their expenses. One of the solutions is to improve the energy efficiency of the processes. It is known that the energy consumption of pumping applications range from 20 up to 50% of the energy usage in the certain industrial plants operations. Some studies have shown that 30% to 50% of energy consumed by pump systems could be saved by changing the pump or the flow control method. The aim of this thesis is to create a mobile measurement system that can calculate a working point position of a pump drive. This information can be used to determine the efficiency of the pump drive operation and to develop a solution to bring pump’s efficiency to a maximum possible value. This can allow a great reduction in the pump drive’s life cycle cost. In the first part of the thesis, a brief introduction in the details of pump drive operation is given. Methods that can be used in the project are presented. Later, the review of available platforms for the project implementation is given. In the second part of the thesis, components of the project are presented. Detailed description for each created component is given. Finally, results of laboratory tests are presented. Acquired results are compared and analyzed. In addition, the operation of created system is analyzed and suggestions for the future development are given.

Energiankulutuksen vähentäminen jäähdytyspiirin pumppausprosessissa

Pumppujen oikean mitoituksen lisäksi niiden tuoton säätämisellä on merkitystä pumppausprosessin energiankulutukseen. Työssä tarkastellaan pyörimisnopeussäädön ja virtauksen kuristamisen eroja pumppauksen tilavuusvirran säätämisessä erityisesti energiatehokkuuden kannalta. Työn kokeellisessa osiossa tarkastellaan erään jäähdytyspiirin pumppujen hyötysuhteita ja lasketaan mahdollinen energiansäästöpotentiaali, mikäli pumppujen säätäminen olisi toteutettu pyörimisnopeussäädöllä.

Teollisuuden ja yhdyskuntien energiatehokkuusselvitykset, auditoinnit 2008–2010

Nykypäivänä energiansäästötavoitteet ovat haasteena yhä useammalle energiankuluttajalle. Tavoitteisiin päästäkseen yritykset ja kunnalliset energiankuluttajat kaipaavat usein apua kannattavien energiansäätökeinojen löytämiseksi. Erilaiset energiakatselmukset vastaavat tähän tarpeeseen ja ovat esimerkki tuloksellisesta energiansäästöstä. Lappeenrannan teknillinen yliopisto on tutkinut energiatehokkuutta pitkään erilaisissa projekteissa teollisuuden kanssa yhteistyössä. Osa LUT:n energiatehokkuustutkimusta ovat energia-auditoinnit yrityksille ja kunnille, joita LUT Energian projektin puitteissa alettiin kehittää vuoden 2008 syksyllä. Energia-auditointien fokuksena on pyritty pitämään pumppausprosessien energiatehokkuuden optimointia, sillä aihetta on tutkittu yliopistolla laajasti. Pumppausprosesseissa on todettu olevan merkittävä energiansäästöpotentiaali: pumppauksen kuluttamasta energiasta voi olla mahdollista säästää jopa 50 % erilaisilla laite- ja säästötaparatkaisuilla. Pumppausprosessien energia-auditointeja on tehty teollisuuden pumppauskohteisiin kuin myös kunnallisiin vesi-huoltolaitoksiin. Lisäksi energia-auditointien puitteissa on tutkittu energiansäästömahdollisuuksia rakennuksissa. Energiansäästökohteita etsitään sekä lämpö- että sähköenergian osalta. Energia-auditoinneissa pumppausten osalta energiansäästöpotentiaalia on todettu olevan etenkin suuren kokoluokan pumpuissa, joilla on pitkä vuosittainen käyttöaika. Myös pumppujen säätötavalla on suuri merkitys energiankulutukseen. Rakennusten osalta on pyritty selvittämään, kuinka energiankulutus jakautuu eri kulutusryhmien kesken. Säästökohteita on löydetty muun muassa rakennusten tiiviydestä, ilmanvaihdosta kuin valaistuksestakin. Monia auditointien asiakkaita on kiinnostanut etenkin led-teknologian hyödyntäminen yleisvalaistuksessa sekä muut keinot säästää valaistuksen energiankulutuksessa. Pyrkimyksenä on kehittää energia-auditointeja projektin aikana saavutettujen kokemusten avulla sekä myös liiketaloudellisessa mielessä opinnäytetutkielmien avulla. Menestyksekäs palveluliiketoiminta edellyttää määriteltyjä toimintatapoja, riittävän tarkkaa palvelujen rajausta ja koko energia-auditointiprosessin kehittämistä aina asiakassuhteen luomisesta sen jatko-hoitoon saakka.

Pumppauksen energiansäästökartoitus teollisuuslaitoksessa

Tässä diplomityössä on suoritettu pumppauksen energiansäästökartoitus Nordkalkin Lappeenrannan teollisuuslaitoksessa. Tavoitteena on kuvata teollisuuslaitoksen nykyistä pumppauksen tarvetta sekä etsiä energiansäästökohteita. Työn valmistelussa on käytetty apuna energiankulutustiedoista koostettuja energiataseita sekä yrityksen valmistelemia pumppulistoja. Energiansäästökohteita haettaessa tässä tarkastelutyössä huomio on kohdistettu pumppujen säätötapoihin ja mahdollisuuksiin vähentää virtaamaa tai pumppujärjestelmän kokonaisnostokorkeutta. Pumppujärjestelmän toiminnan määrittämisessä on käytetty hyväksi tilavuusvirran ja sähkötehon mittauksia sekä teoreettista tarkastelua kokonaisnostokorkeuden ja pumpun toimintapisteen selvittämiseksi. Kaikkien tarkasteltavien pumppujen osalta on hyödynnetty laitevalmistajien tarjoamia tietoja. Pumppujen vuotuisen toiminnan arviointi on suoritettu tuotantotietojen sekä käyttöhenkilökunnan haastatteluilla kerätyn tiedon perusteella. Työn lopussa on esitetty tarkastelukohteiksi valittujen pumppujärjestelmien energiatehokkuuden parantamiseksi suositeltavia toimenpiteitä. Suositeltavien toimenpiteiden sisältäessä investointeja on niille laskettu nykyarvot sekä takaisinmaksuajat. Energiansäästökohteiksi valittujen pumppujärjestelmien yhteenlaskettu vuosittainen energiansäästö on 352 MWh/a (24640 €/a) investointikustannusten (hankintakustannukset) ollessa 12000 €.