Photocatalysis Studies under Visible Light Irradiation with TiO2 Obtained by Pulsed Electric Field Assisted Sol-Gel Method

The objective of this thesis was to study the effect of pulsed electric field on the preparation of TiO2 nanoparticles via sol-gel method under the visible light irradiation. The literature part introduces properties of different TiO2 crystal forms and principle of photocatalysis. It was expected that pulsed electric field would have an influence on degradation for oxalic acid and formic acid. TiO2 samples were prepared by using three frequencies (50Hz, 294Hz, and 963Hz) and two treatment times (12 minutes and 24 minutes) of pulsed electric field. The photocatalytic activities of TiO2 samples produced with sol-gel method were also compared with the TiO2 particles made by previous study and with the commercial TiO2 powder Aeroxide® (Evonic Degussa GmbH) at the same condition. Results show that pulsed electric field does have an effect on degradation for oxalic acid and formic acid. Generally, higher photocatalytic activities for oxalic acid and formic acid were obtained with lower frequency and longer treatment time of pulsed electric field.

Photodamage to Oxygen Evolving Complex - An Initial Event in Photoinhibition of Photosystem II.

Photosystem II (PSII) of oxygenic photosynthesis is susceptible to photoinhibition. Photoinhibition is defined as light induced damage resulting in turnover of the D1 protein subunit of the reaction center of PSII. Both visible and ultraviolet (UV) light cause photoinhibition. Photoinhibition induced by UV light damages the oxygen evolving complex (OEC) via absorption of UV photons by the Mn ion(s) of OEC. Under visible light, most of the earlier hypotheses assume that photoinhibition occurs when the rate of photon absorption by PSII antenna exceeds the use of the absorbed energy in photosynthesis. However, photoinhibition occurs at all light intensities with the same efficiency per photon. The aim of my thesis work was to build a model of photoinhibition that fits the experimental features of photoinhibition. I studied the role of electron transfer reactions of PSII in photoinhibition and found that changing the electron transfer rate had only minor influence on photoinhibition if light intensity was kept constant. Furthermore, quenching of antenna excitations protected less efficiently than it would protect if antenna chlorophylls were the only photoreceptors of photoinhibition. To identify photoreceptors of photoinhibition, I measured the action spectrum of photoinhibition. The action spectrum showed resemblance to the absorption spectra of Mn model compounds suggesting that the Mn cluster of OEC acts as a photoreceptor of photoinhibition under visible light, too. The role of Mn in photoinhibition was further supported by experiments showing that during photoinhibition OEC is damaged before electron transfer activity at the acceptor side of PSII is lost. Mn enzymes were found to be photosensitive under visible and UV light indicating that Mn-containing compounds, including OEC, are capable of functioning as photosensitizers both in visible and UV light. The experimental results above led to the Mn hypothesis of the mechanism of continuous-light-induced photoinhibition. According to the Mn hypothesis, excitation of Mn of OEC results in inhibition of electron donation from OEC to the oxidized primary donor P680+ both under UV and visible light. P680 is oxidized by photons absorbed by chlorophyll, and if not reduced by OEC, P680+ may cause harmful oxidation of other PSII components. Photoinhibition was also induced with intense laser pulses and it was found that the photoinhibitory efficiency increased in proportion to the square of pulse intensity suggesting that laser-pulse-induced photoinhibition is a two-photon reaction. I further developed the Mn hypothesis suggesting that the initial event in photoinhibition under both continuous and pulsed light is the same: Mn excitation that leads to the inhibition of electron donation from OEC to P680+. Under laser-pulse-illumination, another Mn-mediated inhibitory photoreaction occurs within the duration of the same pulse, whereas under continuous light, secondary damage is chlorophyll mediated. A mathematical model based on the Mn hypothesis was found to explain photoinhibition under continuous light, under flash illumination and under the combination of these two.

Metallien laserporaus

Lasertarkkuusporauksella on tämän hetken teollisuudessa useita sovelluksia, kuten esimerkiksi mustesuihkukirjoittimet, dieselmoottoreiden polttoainesuuttimet, lääketieteen instrumentit, turbiinien lapojen jäähdytysreiät ja stensiilit. Tässä työssä on tutkittu laserporauksen mahdollisuuksia 99,9 % kupariin sekä EN 1.4301 ruostumattomaan teräkseen (vastaava AISI 304). Ainepaksuuksia oli käytettävissä kolmea: 0,1 mm, 0,5 mm ja 1,0 mm. Vertailun vuoksi valittiin tutkimukseen mukaan ainepaksuudeltaan 1,0 mm EN 1.4432 haponkestävää terästä (vastaava AISI 316L). Tutkimuksessa käytettiin kolmea eritehoista 1,064 µm aallonpituuden Nd:YAG – laseria ja yhtä CO2 – laseria. Poratut reiät kuvattiin elektronimikroskoopilla ja jokaisesta reiästä mitattiin halkaisija, ympyrämäisyys ja kartiokkuus. Lisäksi reiän laatua arvioitaessa tarkasteltiin purseen määrää reikien ympärillä. Tutkimus osoitti, että eri materiaaleihin voidaan porata, laserin säteen laadusta ja aallonpituudesta riippuen, hyvin erikokoisia reikiä. Kartiokkuuteen havaittiin voitavan vaikuttaa polttopisteen paikkaa siirtämällä.

Markkinoinnin seuranta - Case Telia Finland

Tutkimuksen tavoitteena oli selvittää, miten järjestetään yritysmarkkinoinnin seurantamalli sekä seurannan tietojärjestelmätuki. Erityistä huomiota kiinnitettiin markkinoinnin seurannan ja liiketoimintastrategian kytkökseen. Tutkimusmenetelmänä käytettiin case-tutkimusta. Käsittely oli lineaaris-analyyttinen. Markkinoinnin seurannan tietojärjestelmätuen kehittämisen osalta tutkimus omaa myös jonkin verran systeemianalyyttisiä piirteitä. Case-tutkimuksen tiedonhankinnassa käytettiin yrityksen markkinointihenkilöille jaettua kyselytutkimusta. Markkinoinnin seuranta jaoteltiin strategisen tason ja operatiivisen tason seurantaan. Tutkimuksessa todettiin, että liiketoiminnan kilpailuympäristö, valittu kilpailustrategia ja yrityksen elinkaariasema vaikuttavat liiketoimintastrategiaan ja sitä kautta markkinoinnin seurannan järjestämiseen ja että markkinoinnin strategisen tason seurannan tavoitteena on varmistaa, että markkinointitoiminta toteuttaa valittua liiketoimintastrategiaa. Markkinoinnin operatiivisen tason seurannan tehtäväksi todettiin yrityksen markkinointitoiminnan myynnillisten sekä taloudellisten tulosten, sekä kannattavuuden ja tehokkuuden seuranta ja raportointi. Yritysmarkkinoinnin strategisen tason seurantaan soveltuu parhaiten eteenpäinkytkentäinen, tavoiteltavia tuloksia edeltävien muutosten seurantaan keskittyvä malli. Markkinoinnin operatiiivisen tason seurantaan soveltuu laajan markkinoinnin seurannan perusmittariston sisältävä malli, jolla voidaan palvella nykyisiä seurannan tarpeita ja laatia tarvittaessa uusia seurantakokonaisuuksia. Yritysmarkkinoinnin seurannan tietojärjestelmätuen järjestämiseen soveltuu parhaiten asiakastietokantapohjainen tietojärjestelmämalli. Näin voidaan hallita asiakkaaseen kohdistetut markkinointitoimenpiteet sekä niiden seuranta. Case-tutkimus vahvisti tarpeen kehittää kokonaisvaltainen suunnitelma markkinoinnin strategisen ja operatiivisen tason seurannasta sekä sitä tukevista tietojärjestelmistä. Ilman kokonaissunnitelmaa seuranta muodostuu organisaatioyksiköittäin ja seuranta-alueittain epätasaiseksi, eikä yrityksen asemasta markkinoilla ole muodostettavissa kokonaiskuvaa.

Energiansäästö kotitalouksien valaistuksessa Suomessa

Tässä työssä arvioidaan kotitalouksien energiansäästöpotentiaalia valaistuksen osalta Suomessa. Euroopan Unioni on ratifioinut päästövähennystavoitteen 20 % koskien kaikkia primäärienergiantuotantomuotoja. Päästövähennystavoite on tarkoitus toteuttaa vuoteen 2020 mennessä. Tässä kandidaatintyössä arvioidaan saavutettavissa olevaa energiansäästöpotentiaalia Suomessa kotitalouksissa laitesähkön osalta. Energiansäästöpotentiaalin arviointi perustuu hehkulampun korvaamismahdollisuuksien vertailuun. Valaistuksessa voidaan saavuttaa jopa 75 % sähkönsäästö, kun korvataan yksi 60 W hehkulamppu vastaavan valomäärän tuottavalla energiansäästölampulla. Kokonaisuudessa kotitalouksien valaistuksessa on tehostamispotentiaalia noin 60 %. Valaistuksen tehostamisella saavutetaan noin 1,5 TWh säästö Suomen kokonaissähkökulutuksessa. Saavutettavat säästöt voivat olla jopa suuremmatkin, jos käytetään lisäksi älykästä valonohjausta. Johtopäätöksenä voidaan todeta, että tehostamispotentiaalia on merkittävästi ja tehostaminen on yksittäiselle kotitaloudelle taloudellisesti kannattavaa. Energiansäästöpotentiaalin toteuttamisen vaikutuksia kansantalouteen ei ole arvioitu.

Photoinhibition of Photosystem II. Kinetics, Photoprotection and Mechanism

Photosystem II (PSII) is susceptible to light-induced damage defined as photoinhibition. In natural conditions, plants are capable of repairing the photoinhibited PSII by on-going degradation and re-synthesis of the D1 reaction centre protein of PSII. Photoinhibition is induced by both visible and ultraviolet light and photoinhibition occurs under all light intensities with the same efficiency per photon. In my thesis work, I studied the reaction kinetics and mechanism of photoinhibition of PSII, as well as photoprotection in leaves of higher plants. Action spectroscopy was used to identify photoreceptors of photoinhibition. I found that the action spectrum of photoinhibition in vivo shows resemblance to the absorption spectra of manganese model compounds of the oxygen evolving complex (OEC) suggesting a role for manganese as a photoreceptor of photoinhibition under UV and visible light. In order to study the protective effect of non-photochemical quenching, the action spectrum was measured from leaves of wild type Arabidopsis thaliana and two mutants impaired in nonphotochemical quenching of chlorophyll a excitations. The findings of action spectroscopy and simulations of chlorophyll-based photoinhibition mechanisms suggested that quenching of antenna excitations protects less efficiently than would be expected if antenna chlorophylls were the only photoreceptors of photoinhibition. The reaction kinetics of prolonged photoinhibition was studied in leaves of Cucurbita maxima and Capsicum annuum. The results indicated that photoinhibitory decrease in both the oxygen evolution activity and ratio of variable to maximum fluorescence follows firstorder kinetics in vivo. The persistence of first-order kinetics suggests that already photoinhibited reaction centres do not protect against photoinhibition and that the mechanism of photoinhibition does not have a reversible intermediate. When Cucurbita maxima leaves were photoinhibited with saturating single-turnover flashes and continuous light, the light response curve of photoinhibition was found to be essentially a straight line with both types of illumination, suggesting that similar photoinhibition mechanisms might function during illumination with continuous light and during illumination with short flashes.

Customized agile development process for embedded software development

Agile software development has grown in popularity starting from the agile manifesto declared in 2001. However there is a strong belief that the agile methods are not suitable for embedded, critical or real-time software development, even though multiple studies and cases show differently. This thesis will present a custom agile process that can be used in embedded software development. The reasons for presumed unfitness of agile methods in embedded software development have mainly based on the feeling of these methods providing no real control, no strict discipline and less rigor engineering practices. One starting point is to provide a light process with disciplined approach to the embedded software development. Agile software development has gained popularity due to the fact that there are still big issues in software development as a whole. Projects fail due to schedule slips, budget surpassing or failing to meet the business needs. This does not change when talking about embedded software development. These issues are still valid, with multiple new ones rising from the quite complex and hard domain the embedded software developers work in. These issues are another starting point for this thesis. The thesis is based heavily on Feature Driven Development, a software development methodology that can be seen as a runner up to the most popular agile methodologies. The FDD as such is quite process oriented and is lacking few practices considered commonly as extremely important in agile development methodologies. In order for FDD to gain acceptance in the software development community it needs to be modified and enhanced. This thesis presents an improved custom agile process that can be used in embedded software development projects with size varying from 10 to 500 persons. This process is based on Feature Driven Development and by suitable parts to Extreme Programming, Scrum and Agile Modeling. Finally this thesis will present how the new process responds to the common issues in the embedded software development. The process of creating the new process is evaluated at the retrospective and guidelines for such process creation work are introduced. These emphasize the agility also in the process development through early and frequent deliveries and the team work needed to create suitable process.

Enhancing performance of paper coatings by tailor-made plastic pigments

The paper industry is constantly looking for new ideas for improving paper products while competition and raw material prices are increasing. Many paper products are pigment coated. Coating layer is the top layer of paper, thus by modifying coating pigment also the paper itself can be altered and value added to the final product. In this thesis, synthesis of new plastic and hybrid pigments and their performance in paper and paperboard coating is reported. Two types of plastic pigments were studied: core-shell latexes and solid beads of maleimide copolymers. Core-shell latexes with partially crosslinked hydrophilic polymer core of poly(n-butyl acrylate-co-methacrylic acid) and a hard hydrophobic polystyrene shell were prepared to improve the optical properties of coated paper. In addition, the effect of different crosslinkers was analyzed and the best overall performance was achieved by the use of ethylene glycol dimethacrylate (EGDMA). Furthermore, the possibility to modify core-shell latex was investigated by introducing a new polymerizable optical brightening agent, 1-[(4-vinylphenoxy)methyl]-4-(2-henylethylenyl)benzene which gave promising results. The prepared core-shell latex pigments performed smoothly also in pilot coating and printing trials. The results demonstrated that by optimizing polymer composition, the optical and surface properties of coated paper can be significantly enhanced. The optimal reaction conditions were established for thermal imidization of poly(styrene-co-maleimide) (SMI) and poly(octadecene-co-maleimide) (OMI) from respective maleic anhydride copolymer precursors and ammonia in a solvent free process. The obtained aqueous dispersions of nanoparticle copolymers exhibited glass transition temperatures (Tg) between 140-170ºC and particle sizes from 50-230 nm. Furthermore, the maleimide copolymers were evaluated in paperboard coating as additional pigments. The maleimide copolymer nanoparticles were partly imbedded into the porous coating structure and therefore the full potential of optical property enhancement for paperboard was not achieved by this method. The possibility to modify maleimide copolymers was also studied. Modifications were carried out via N-substitution by replacing part of the ammonia in the imidization reaction with amines, such as triacetonediamine (TAD), aspartic acid (ASP) and fluorinated amines (2,2,2- trifluoroethylamine, TFEA and 2,2,3,3,4,4,4-heptafluorobuthylamine, HFBA). The obtained functional nanoparticles varied in size between 50-217 nm and their Tg from 150-180ºC. During the coating process the produced plastic pigments exhibited good runnability. No significant improvements were achieved in light stability with TAD modified copolymers whereas nanoparticles modified with aspartic acid and those containing fluorinated groups showed the desired changes in surface properties of the coated paperboard. Finally, reports on preliminary studies with organic-inorganic hybrids are presented. The hybrids prepared by an in situ polymerization reaction consisted of 30 wt% poly(styrene- co-maleimide) (SMI) and high levels of 70 wt% inorganic components of kaolin and/or alumina trihydrate. Scanning Electron Microscopy (SEM) images and characterization by Fourier Transform Infrared Spcetroscopy (FTIR) and X-Ray Diffraction (XRD) revealed that the hybrids had conventional composite structure and inorganic components were covered with precipitated SMI nanoparticles attached to the surface via hydrogen bonding. In paper coating, the hybrids had a beneficial effect on increasing gloss levels.

Painesuodattimen automatisoidun kankaanvaihtolaitteen kehittäminen ja tekninen tuotteistaminen

Tässä työssä tarkastellaan CE-merkintään vaadittavia teknisen tuotteistamisen vaiheita käyttäen esimerkkinä painesuodattimen automatisoidun kankaanvaihtolaitteen suunnitteluprosessia. Työssä selvitetään, mitä vaihtoehtoja on painesuodattimen lisälaitteiden luokitteluksi, että ne saadaan tuotteistettua Euroopan talousalueella (ETA). Esimerkkinä käytettävä kankaanvaihtolaite on suunniteltu käyttäen järjestelmällisen koneensuunnittelun menetelmää. CE-merkinnän vaatima riskianalyysi on tehty laitteelle standardin SFS-EN ISO 12100:2010 mukaisesti. Tuloksena saatu laitteen prototyyppi täyttää pääosin laitteelle asetettavat vaatimukset. Kustannusarvio ylittää kuitenkin toivotun omakustannehinnan valoverhojen suhteellisen kalliin hinnan takia. Kustannusarvion mukaan prototyyppi voidaan kuitenkin valmistaa edullisesti, sillä valoverhot eivät ole pakollisia laitteen toiminnallisissa testeissä. Ennen tuotteistamista valoverhojen korvaamisen mahdollisuutta muulla turvatekniikalla on kuitenkin tutkittava. Suunnitteluvaiheen jälkeen laitteen turvallisuuden voidaan todeta olevan vähintään riittävällä tasolla. Riskianalyysi on kuitenkin päivitettävä dokumentti, ja laitteen turvallisuus täytyy varmistaa prototyyppiä testaamalla. Työn perusteella voidaan todeta, että huomioimalla laitteen mahdollisesti aiheuttamat vaaratilanteet jo tuotesuunnittelun alussa, voidaan tuotekehitysprosessia nopeuttaa. Tunnistamalla vaaratilanteet suunnittelun varhaisessa vaiheessa voidaan vähentää riskien määrää, ja siten tarvetta riskien pienentämiselle. Näin vähennetään rakenteen suunnittelun ja riskianalyysin iterointikierrosten määrää, jolloin myös tuotteistamisprosessi nopeutuu.

Spectrally Tuned Lanthanide Photoluminescence for Point-of-Care Testing

Point-of-care (POC) –diagnostics is a field with rapidly growing market share. As these applications become more widely used, there is an increasing pressure to improve their performance to match the one of a central laboratory tests. Lanthanide luminescence has been widely utilized in diagnostics because of the numerous advantages gained by the utilization of time-resolved or anti-Stokes detection. So far the use of lanthanide labels in POC has been scarce due to limitations set by the instrumentation required for their detection and the shortcomings, e.g. low brightness, of these labels. Along with the advances in the research of lanthanide luminescence, and in the field of semiconductors, these materials are becoming a feasible alternative for the signal generation also in the future POC assays. The aim of this thesis was to explore ways of utilizing time-resolved detection or anti-Stokes detection in POC applications. The long-lived fluorescence for the time-resolved measurement can be produced with lanthanide chelates. The ultraviolet (UV) excitation required by these chelates is cumbersome to produce with POC compatible fluorescence readers. In this thesis the use of a novel light-harvesting ligand was studied. This molecule can be used to excite Eu(III)-ions at wavelengths extending up to visible part of the spectrum. An enhancement solution based on this ligand showed a good performance in a proof-of-concept -bioaffinity assay and produced a bright signal upon 365 nm excitation thanks to the high molar absorptivity of the chelate. These features are crucial when developing miniaturized readers for the time-resolved detection of fluorescence. Upconverting phosphors (UCPs) were studied as an internal light source in glucose-sensing dry chemistry test strips and ways of utilizing their various emission wavelengths and near-infrared excitation were explored. The use of nanosized NaYF :Yb3+,Tm3+-particles enabled the replacement of an external UV-light source with a NIR-laser and gave an additional degree of freedom in the optical setup of the detector instrument. The new method enabled a blood glucose measurement with results comparable to a current standard method of measuring reflectance. Microsized visible emitting UCPs were used in a similar manner, but with a broad absorbing indicator compound filtering the excitation and emission wavelengths of the UCP. This approach resulted in a novel way of benefitting from the non-linear relationship between the excitation power and emission intensity of the UCPs, and enabled the amplification of the signal response from the indicator dye.

Survival and early seedling growth of conifers with different shade tolerance in a Sitka spruce spacing trial and relationship to understorey light climate

Abstract