Freezing and low temperature photoinhibition tolerance in cultivated potato and potato hybrids

Selostus: Perunan ja perunahybridien jäätymisen ja fotoinhibition kestävyys

Reliability of SMD interconnections on flexible low-temperature substrates with inkjet-printed conductors

julkaisumaa: NLD

Polymer surface modification by atomic layer deposition

Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.

Characterisation of Laser Beam and Paper Material Interaction

It is known already from 1970´s that laser beam is suitable for processing paper materials. In this thesis, term paper materials mean all wood-fibre based materials, like dried pulp, copy paper, newspaper, cardboard, corrugated board, tissue paper etc. Accordingly, laser processing in this thesis means all laser treatments resulting material removal, like cutting, partial cutting, marking, creasing, perforation etc. that can be used to process paper materials. Laser technology provides many advantages for processing of paper materials: non-contact method, freedom of processing geometry, reliable technology for non-stop production etc. Especially packaging industry is very promising area for laser processing applications. However, there are only few industrial laser processing applications worldwide even in beginning of 2010´s. One reason for small-scale use of lasers in paper material manufacturing is that there is a shortage of published research and scientific articles. Another problem, restraining the use of laser for processing of paper materials, is colouration of paper material i.e. the yellowish and/or greyish colour of cut edge appearing during cutting or after cutting. These are the main reasons for selecting the topic of this thesis to concern characterization of interaction of laser beam and paper materials. This study was carried out in Laboratory of Laser Processing at Lappeenranta University of Technology (Finland). Laser equipment used in this study was TRUMPF TLF 2700 carbon dioxide laser that produces a beam with wavelength of 10.6 μm with power range of 190-2500 W (laser power on work piece). Study of laser beam and paper material interaction was carried out by treating dried kraft pulp (grammage of 67 g m-2) with different laser power levels, focal plane postion settings and interaction times. Interaction between laser beam and dried kraft pulp was detected with different monitoring devices, i.e. spectrometer, pyrometer and active illumination imaging system. This way it was possible to create an input and output parameter diagram and to study the effects of input and output parameters in this thesis. When interaction phenomena are understood also process development can be carried out and even new innovations developed. Fulfilling the lack of information on interaction phenomena can assist in the way of lasers for wider use of technology in paper making and converting industry. It was concluded in this thesis that interaction of laser beam and paper material has two mechanisms that are dependent on focal plane position range. Assumed interaction mechanism B appears in range of average focal plane position of 3.4 mm and 2.4 mm and assumed interaction mechanism A in range of average focal plane position of 0.4 mm and -0.6 mm both in used experimental set up. Focal plane position 1.4 mm represents midzone of these two mechanisms. Holes during laser beam and paper material interaction are formed gradually: first small hole is formed to interaction area in the centre of laser beam cross-section and after that, as function of interaction time, hole expands, until interaction between laser beam and dried kraft pulp is ended. By the image analysis it can be seen that in beginning of laser beam and dried kraft pulp material interaction small holes off very good quality are formed. It is obvious that black colour and heat affected zone appear as function of interaction time. This reveals that there still are different interaction phases within interaction mechanisms A and B. These interaction phases appear as function of time and also as function of peak intensity of laser beam. Limit peak intensity is the value that divides interaction mechanism A and B from one-phase interaction into dual-phase interaction. So all peak intensity values under limit peak intensity belong to MAOM (interaction mechanism A one-phase mode) or to MBOM (interaction mechanism B onephase mode) and values over that belong to MADM (interaction mechanism A dual-phase mode) or to MBDM (interaction mechanism B dual-phase mode). Decomposition process of cellulose is evolution of hydrocarbons when temperature is between 380- 500°C. This means that long cellulose molecule is split into smaller volatile hydrocarbons in this temperature range. As temperature increases, decomposition process of cellulose molecule changes. In range of 700-900°C, cellulose molecule is mainly decomposed into H2 gas; this is why this range is called evolution of hydrogen. Interaction in this range starts (as in range of MAOM and MBOM), when a small good quality hole is formed. This is due to “direct evaporation” of pulp via decomposition process of evolution of hydrogen. And this can be seen can be seen in spectrometer as high intensity peak of yellow light (in range of 588-589 nm) which refers to temperature of ~1750ºC. Pyrometer does not detect this high intensity peak since it is not able to detect physical phase change from solid kraft pulp to gaseous compounds. As interaction time between laser beam and dried kraft pulp continues, hypothesis is that three auto ignition processes occurs. Auto ignition of substance is the lowest temperature in which it will spontaneously ignite in a normal atmosphere without an external source of ignition, such as a flame or spark. Three auto ignition processes appears in range of MADM and MBDM, namely: 1. temperature of auto ignition of hydrogen atom (H2) is 500ºC, 2. temperature of auto ignition of carbon monoxide molecule (CO) is 609ºC and 3. temperature of auto ignition of carbon atom (C) is 700ºC. These three auto ignition processes leads to formation of plasma plume which has strong emission of radiation in range of visible light. Formation of this plasma plume can be seen as increase of intensity in wavelength range of ~475-652 nm. Pyrometer shows maximum temperature just after this ignition. This plasma plume is assumed to scatter laser beam so that it interacts with larger area of dried kraft pulp than what is actual area of beam cross-section. This assumed scattering reduces also peak intensity. So result shows that assumably scattered light with low peak intensity is interacting with large area of hole edges and due to low peak intensity this interaction happens in low temperature. So interaction between laser beam and dried kraft pulp turns from evolution of hydrogen to evolution of hydrocarbons. This leads to black colour of hole edges.

Physico-chemical properties of sol-gel synthesized titanosilicates for the uptake of radionuclides from aqueous solutions

Harnessing the power of nuclear reactions has brought huge benefits in terms of nuclear energy, medicine and defence as well as risks including the management of nuclear wastes. One of the main issues for radioactive waste management is liquid radioactive waste (LRW). Different methods have been applied to remediate LRW, thereunder ion exchange and adsorption. Comparative studies have demonstrated that Na2Ti2O3SiO4·2H2O titanosilicate sorption materials are the most promising in terms of Cs+ and Sr2+ retention from LRW. Therefore these TiSi materials became the object of this study. The recently developed in Ukraine sol-gel method of synthesizing these materials was chosen among the other reported approaches since it allows obtaining the TiSi materials in the form of particles with size ≥ 4mm. utilizing inexpensive and bulk stable inorganic precursors and yielded the materials with desirable properties by alteration of the comparatively mild synthesis conditions. The main aim of this study was to investigate the physico-chemical properties of sol-gel synthesized titanosilicates for radionuclide uptake from aqueous solutions. The effect of synthesis conditions on the structural and sorption parameters of TiSi xerogels was planned to determine in order to obtain a highly efficient sorption material. The ability of the obtained TiSis to retain Cs+, Sr2+ and other potentially toxic metal cations from the synthetic and real aqueous solutions was intended to assess. To our expectations, abovementioned studies will illustrate the efficiency and profitability of the chosen synthesis approach, synthesis conditions and the obtained materials. X-ray diffraction, low temperature adsorption/desorption surface area analysis, X-ray photoelectron spectroscopy, infrared spectroscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy was used for xerogels characterization. The sorption capability of the synthesized TiSi gels was studied as a function of pH, adsorbent mass, initial concentration of target ion, contact time, temperature, composition and concentration of the background solution. It was found that the applied sol-gel approach yielded materials with a poorly crystalline sodium titanosilicate structure under relatively mild synthesis conditions. The temperature of HTT has the strongest influence on the structure of the materials and consequently was concluded to be the control factor for the preparation of gels with the desired properties. The obtained materials proved to be effective and selective for both Sr2+ and Cs+ decontamination from synthetic and real aqueous solutions like drinking, ground, sea and mine waters, blood plasma and liquid radioactive wastes.

Ydinvoimalan paineakun mallinnus

Tässä työssä on käytetty VTT:n ja Fortumin kehittämääAPROS simulaatio-ohjelmistoa vesi-ilma -täytteisen paineakun käyttäytymisen tutkimiseen. Tavoitteena oli tarkastella APROSin paineakkumallin käyttäytymistä alhaisessa lämpötilassa käyttäen 6-yhtälömallia sekä rakentaa vaihtoehtoiseksi laskentamenetelmäksi kaksi analyyttistä laskentamallia korvaamaan APROSin sisäinen laskenta. Kyseiset analyyttiset mallit ovat isentrooppinen ja isoterminen ja ne on rakennettu kokonaan käyttäen APROSin omia moduuleja. Työ sisältää APROSin version 5.06 sekä työn aikana kehitetyn kehitysversion vertailut eri alkulämpötiloista alkaneissa paisunnoissa, vertailun Pactelin purkaus¬kokeesta saadulla massavirralla sekä osion, jossa analyyttiset mallit on yhdistetty kokonaiseen Pactelin APROS-malliin. Myös purkauksen kulkeutumista primääripiirissä on tarkasteltu. Simulaatiot vahvistavat, että versiolla 5.06 on vaikeuksia paineen laskennassa, kun paisunnan alkulämpötila on alle 30 ºC. Kehitysversiossa painekäyttäytyminen on selvästi parantunut, mutta versio kärsii ongelmista, jotka liittyvät kaasun lämpötilan painumiseen APROSin sisäisten rajoitusten alapuolelleja tätä kautta ongelmiin materiaali¬ominaisuuksien ennustamisessa. Tämän johdosta APROSin kehitysversio päätyy erilaisiin tuloksiin myös tilanteissa, joissa alkuperäinen 5.06 ei kärsi alhaisen lämpötilan ongelmista. Analyyttisistä malleista isentrooppinen malli päätyy antamaan säännönmukaisesti muita malleja ja versioita alempia paineita. Isoterminen malli sen sijaan näyttää päätyvän version 5.06 kanssa melko samankaltaisiin tuloksiin. On kuitenkin muistettava, että kummatkin analyyttiset mallit olettavat kaasun olevan kuivaa ja jättävät massasiirron faasien välillä kokonaan huomiotta.

Eräiden paperinvalmistuksessa käytettävien vahadispersioiden stabiilisuuden hallinta

Diplomityön tavoitteena oli selvittää millainen laaduntarkastus AKD-dispersioille tulisi suorittaa kuormien vastaanotossa ja tulisiko dispersioiden laatu tarkastaa uudelleen ennen annostelua. Tätä varten seurattiin toimituserien laadun tasaisuutta ja tarkasteltiin varastointiolosuhteiden vaikutusta dispersioiden säilyvyyteen. Lisäksi kartoitettiin dispersioiden käsittelyssä ja kartonginvalmistusprosessissa esiintyvien riskitekijöiden vaikutuksia kaupallisten dispersioiden stabiilisuuteen. Kirjallisuusosassa perehdyttiin kolloidisiin dispersioihin sekä niiden stabiilisuuteen vaikuttaviin tekijöihin. AKD-dispersiot valmistetaan emulgointitekniikoiden avulla, joten dispergointimenetelmien ohella käsiteltiin myös emulsioiden valmistamista. Lisäksi luotiin katsaus dispersioteknologian tärkeimpiin analyysimenetelmiin. Alkyyliketeenidimeerin osalta käsiteltiin emulgoinnin lisäksi vahan ja muiden lisäaineiden vaikutuksia dispersioiden stabiilisuuteen ja myös niiden merkitystä dispersioiden formuloinnissa. AKD-liimauksen osalta esiin tuotiin AKD:n tärkeimmät reaktiomekanismit, sillä ne liittyvät osittain myös dispersioiden stabiilisuuteen. Lopuksi luotiin lyhyt katsaus AKD-dispersioiden stabiilisuutta käsittelevään tutkimukseen, jota on toistaiseksi julkaistu varsin niukasti. Kokeellisessaosassa tarkastelun kohteeksi valittiin neljä kaupallista alkyyliketeenidimeerinvesidispersiota, joiden koostumus ja ominaisuudet selvitettiin perusteellisesti. Tarkoituksena oli auttaa ymmärtämään dispersioiden stabiilisuudessa mahdollisesti esiintyviä eroja. Laajamittainen dispersioiden karakterisointi näyttää olevan tarpeen ainakin otettaessa uutta AKD-laatua käyttöön, sillä dispersioiden koostumus ja ominaisuudet voivat vaihdella merkittävästi. AKD-dispersioiden laadussa esiintyi vaihtelua eri toimituserien välillä. Suurimmat vaihtelut havaittiin dispersioiden varaustiloissa ja partikkelikokojakaumissa. Laadun epätasaisuuden vuoksi vastaanottotarkastuksen merkitys korostuu. Vastaanottotarkastuksessa syytä olisi kiinnittää dispersion kuiva-ainepitoisuuden ohella sen viskositeettiin, varaustilaan, tehoainepitoisuuteen sekä rakenteeseen. Rakenteen tarkastelussa optinen mikroskooppi voi rutiininomaisessa seurannassa korvata partikkelikokojakauman määrittämisen. Varastointilämpötilan vaikutus dispersioidenlaatuun on merkittävä. Dispersiot säilyvät parhaiten viileässä, joten jos varastosäiliöissä ei ole jäähdytystä, on dispersioiden laadun tarkastus tarpeen myös ennen annostelua. Jotta dispersion kunnosta saadaan luotettava arvio, on viskositeetin määrittämiseen yhdistettävä vähintään rakenteen tarkastelu optisella mikroskoopilla. Mekaaninen rasitus voi dominoivasta stabilointimekanismistariippuen aiheuttaa dispersiossa hienoaineen muodostumista tai partikkelien flokkaantumista. Stabilointimekanismi vaikuttaa niin ikään partikkelien käyttäytymiseen korkeissa lämpötiloissa. Dispersioiden stabiilisuuden todettiin heikkenevän pH:n kohotessa emäksiselle alueelle. Elektrolyyttikonsentraatio vaikuttaa partikkelien mikroelektroforeettiseen ioniliikkuvuuteen merkittävästi. Kartonkikoneen märkäosan kemikaaleista anionisen retentioaineen (BMA) todettiin vuorovaikuttavan kationisten AKD-partikkelien kanssa selvimmin. Mikroelektroforeettisen ioniliikkuvuuden mittaaminen kiertovedessä todettiin tärkeäksi, sillä se kuvaa dispersion käyttäytymistä sen käyttöympäristössä.

Jätekeskuksen jasuljetun kaatopaikan jätevesien esikäsittelyn tehostamismahdollisudet

Tämän diplomityön tavoitteena oli tutkia toiminnassa olevan jätekeskuksen ja suljetun kaatopaikan jätevesien esikäsittelyn tehostamismahdollisuuksia. Tutkimuksessa pyrittiin löytämään niitä teknisiä keinoja, joilla jätevesien esikäsittelyä voidaan tehostaa erityisesti ammoniumtypen osalta. Tapausesimerkkinä työssä käytettiin Jätekukko Oy:n toiminnassa olevaa Kuopion jätekeskusta ja Kuopion kaupungin suljettua Silmäsuon kaatopaikkaa. Kohteiden jätevedet johdetaan kunnalliselle jätevedenpuhdistamolle, jossa jätevesien korkea ammoniumtyppipitoisuus ja matala lämpötila ovat häirinneet puhdistusprosessia. Tutkimuksen taustana selvitettiin jätekeskusten jakaatopaikkojen jätevesien käsittelyyn vaikuttavaa lainsäädäntöä, jätevesien ominaisuuksia ja niiden käsittelytekniikoita. Jätevesien käsittelyn nykytilaa Suomessa kartoitettiin jätehuoltoyhtiöille ja kunnille suunnatulla kyselyllä. Lisäksitutkimus perustui kenttäkokeisiin, joissa tutkittiin Kuopion jätekeskuksen nykyisen tasausaltaan toimivuutta vuoden ajan. Sekä Kuopion jätekeskuksen että Silmäsuon suljetun kaatopaikan jätevesistä otettiin vesien tarkkailuohjelmaan kuuluvien näytteiden lisäksi ylimääräisiä näytteitä, joilla pyrittiin saamaan uutta tietoa jäteveden laatumuuttujien vuodenaikaisvaihtelusta. Kuopion jätekeskuksen ja Silmäsuon suljetun kaatopaikan jätevesien käsittelyä tulevaisuudessa tarkasteltiin erilaisilla tilannemalleilla. Tutkimuksessa havaittiin, että Kuopion jätekeskuksen ja Silmäsuon suljetun kaatopaikan jätevedet olivat laadultaan ja määrältään erilaisia. Jätekeskuksen nykyinen jätevesien tasausallas poistaa ammoniumtyppeä vain kesäisin. Jätekeskuksen jätevesien nykyisen tasausaltaan toiminnan tehostaminen ei ole taloudellisesti perusteltua, vaan resurssit on kohdistettava uuden tasausaltaan rakentamiseen. Kuopion jätekeskuksen jätevesienesikäsittely ilman Silmäsuon suljetun kaatopaikan jätevesiä ei ole tarkoituksenmukaista, koska jätevedet johdetaan jätevedenpuhdistamolle samaa viemärilinjaa pitkin. Tällöin Silmäsuon suljetun kaatopaikan jätevedet tulevat mitätöimään jätekeskuksella tehdyn esikäsittelyn puhdistustuloksen Mahdollisen jätevesien yhteisen esikäsittelymenetelmän tulee olla fysikaalis-kemiallinen, jätevesien ominaisuuksista johtuen. Jos jätevesiä ei esikäsitellä yhdessä, jätekeskuksen jätevesien käsittelyksi riittävät uusi tasausallas ja siihen asennettava ilmastus. Tässä tapauksessa jätekeskuksen ympäristölupamääräysten ammoniumtyppipitoisuuden raja-arvoa on arvioitava uudelleen.

Levylämmönsiirtimen mitoitus ja optimointi erityisesti lämpöpumpuissa

Työn tavoitteena on laatia käsikirjamainen läpileikkaus levylämmönsiirtimen rakenteesta ja käytöstä lämpöpumppulaitteistoissa. Kylmäprosessin tarkastelun lisäksi on eri lähteistä haettu yhtälöitä lämmönsiirron ja painehäviönlaskentaan. Lähdeaineistona on käytetty lämmönsiirron oppikirjoja, joiden lisäksi on käyty läpi suuri joukko tieteellisen tutkimuksen julkaisemia tutkimusraportteja levylämmönsiirtimen mitoituksesta erilaisissa käyttökohteissa. Oppikirjoissa ei ole esitetty varsinaisesti levylämmönsiirtimen laskentamenetelmiä, vaan niissä esitetään lämmönsiirron perusyhtälöt. Varsinainen lämmönsiirtolevyprofiilin laskentaan perustuva lähdeaineisto on löytynyt lämmönsiirtoon erikoistuneista julkaisuista. Lämmönsiirto tapahtuu aina kuumemmasta kylmempään tilaan. Lämmönsiirto eri virtausaineiden välillä toteutetaan lämmönsiirtimien avulla. Lämmönsiirrintyyppejä on olemassa lukuisia, joista yksi yleisesti käytetty tyyppi on levylämmönsiirrin. Tässä konstruktiossa on mahdutettu paljon lämmönsiirtopintaa ulkomitoiltaan pieneen tilaan. Tämä siirrintyyppi on eduksi silloin, kun virtaavat aineet ovat puhtaita ja niillä ei ole likaavaa vaikutusta lämmönsiirtopinnoille. Lämpöpumpulla tarkoitetaan laitetta, jolla voidaan käyttää hyödyksi lämmönlähteen matalaa lämpötilatasoa nostamalla lämpötilatasoa kompressorin puristustyön avulla korkeampaan lämpötilatasoon. Lämpöpumppulaitteiston toiminta perustuu kylmäprosessin toimintaan. Kylmäprosessin läpikäynti auttaa lukijaa hahmottamaan, millainen prosessi on kysymyksessä ja mitä komponentteja liittyy kylmäprosessiin. Tässä diplomityössä esitetyt yhtälöt antavat suuntaa, millä tavalla levylämmönsiirtimien ominaisuuksia voidaan laskea ja mitkä tekijät vaikuttavat siirtimien mitoittamiseen. Tarkemmat vaihdinkohtaiset laskentakorrelaatiot muotoutuvat vasta sitten, kun valmis tuote on testattu laboratorio-olosuhteissa ja siitä on saatu lämpötila-, virtaus- ja painesuhteet selville. Tämän jälkeen voidaan mittaustuloksiin perustuen rakentaa matemaattinen malli, jolla laskennallisesti määritelläänvaihtimien ominaisuudet. Lisäksi on esitetty yleisiä tapoja, joilla voidaan määritellä lämmönsiirtimien lämpöpintoja.

Selective catalytic reduction of nitrogen oxides with ammonia in forced unsteady state reactors - Case based reasoning and mathematical model simulation reasoning

The application of forced unsteady-state reactors in case of selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3) is sustained by the fact that favorable temperature and composition distributions which cannot be achieved in any steady-state regime can be obtained by means of unsteady-state operations. In a normal way of operation the low exothermicity of the selective catalytic reduction (SCR) reaction (usually carried out in the range of 280-350°C) is not enough to maintain by itself the chemical reaction. A normal mode of operation usually requires supply of supplementary heat increasing in this way the overall process operation cost. Through forced unsteady-state operation, the main advantage that can be obtained when exothermic reactions take place is the possibility of trapping, beside the ammonia, the moving heat wave inside the catalytic bed. The unsteady state-operation enables the exploitation of the thermal storage capacity of the catalyticbed. The catalytic bed acts as a regenerative heat exchanger allowing auto-thermal behaviour when the adiabatic temperature rise is low. Finding the optimum reactor configuration, employing the most suitable operation model and identifying the reactor behavior are highly important steps in order to configure a proper device for industrial applications. The Reverse Flow Reactor (RFR) - a forced unsteady state reactor - corresponds to the above mentioned characteristics and may be employed as an efficient device for the treatment of dilute pollutant mixtures. As a main disadvantage, beside its advantages, the RFR presents the 'wash out' phenomena. This phenomenon represents emissions of unconverted reactants at every switch of the flow direction. As a consequence our attention was focused on finding an alternative reactor configuration for RFR which is not affected by the incontrollable emissions of unconverted reactants. In this respect the Reactor Network (RN) was investigated. Its configuration consists of several reactors connected in a closed sequence, simulating a moving bed by changing the reactants feeding position. In the RN the flow direction is maintained in the same way ensuring uniformcatalyst exploitation and in the same time the 'wash out' phenomena is annulated. The simulated moving bed (SMB) can operate in transient mode giving practically constant exit concentration and high conversion levels. The main advantage of the reactor network operation is emphasizedby the possibility to obtain auto-thermal behavior with nearly uniformcatalyst utilization. However, the reactor network presents only a small range of switching times which allow to reach and to maintain an ignited state. Even so a proper study of the complex behavior of the RN may give the necessary information to overcome all the difficulties that can appear in the RN operation. The unsteady-state reactors complexity arises from the fact that these reactor types are characterized by short contact times and complex interaction between heat and mass transportphenomena. Such complex interactions can give rise to a remarkable complex dynamic behavior characterized by a set of spatial-temporal patterns, chaotic changes in concentration and traveling waves of heat or chemical reactivity. The main efforts of the current research studies concern the improvement of contact modalities between reactants, the possibility of thermal wave storage inside the reactor and the improvement of the kinetic activity of the catalyst used. Paying attention to the above mentioned aspects is important when higher activity even at low feeding temperatures and low emissions of unconverted reactants are the main operation concerns. Also, the prediction of the reactor pseudo or steady-state performance (regarding the conversion, selectivity and thermal behavior) and the dynamicreactor response during exploitation are important aspects in finding the optimal control strategy for the forced unsteady state catalytic tubular reactors. The design of an adapted reactor requires knowledge about the influence of its operating conditions on the overall process performance and a precise evaluation of the operating parameters rage for which a sustained dynamic behavior is obtained. An apriori estimation of the system parameters result in diminution of the computational efforts. Usually the convergence of unsteady state reactor systems requires integration over hundreds of cycles depending on the initial guess of the parameter values. The investigation of various operation models and thermal transfer strategies give reliable means to obtain recuperative and regenerative devices which are capable to maintain an auto-thermal behavior in case of low exothermic reactions. In the present research work a gradual analysis of the SCR of NOx with ammonia process in forced unsteady-state reactors was realized. The investigation covers the presentationof the general problematic related to the effect of noxious emissions in the environment, the analysis of the suitable catalysts types for the process, the mathematical analysis approach for modeling and finding the system solutions and the experimental investigation of the device found to be more suitable for the present process. In order to gain information about the forced unsteady state reactor design, operation, important system parameters and their values, mathematical description, mathematicalmethod for solving systems of partial differential equations and other specific aspects, in a fast and easy way, and a case based reasoning (CBR) approach has been used. This approach, using the experience of past similarproblems and their adapted solutions, may provide a method for gaining informations and solutions for new problems related to the forced unsteady state reactors technology. As a consequence a CBR system was implemented and a corresponding tool was developed. Further on, grooving up the hypothesis of isothermal operation, the investigation by means of numerical simulation of the feasibility of the SCR of NOx with ammonia in the RFRand in the RN with variable feeding position was realized. The hypothesis of non-isothermal operation was taken into account because in our opinion ifa commercial catalyst is considered, is not possible to modify the chemical activity and its adsorptive capacity to improve the operation butis possible to change the operation regime. In order to identify the most suitable device for the unsteady state reduction of NOx with ammonia, considering the perspective of recuperative and regenerative devices, a comparative analysis of the above mentioned two devices performance was realized. The assumption of isothermal conditions in the beginningof the forced unsteadystate investigation allowed the simplification of the analysis enabling to focus on the impact of the conditions and mode of operation on the dynamic features caused by the trapping of one reactant in the reactor, without considering the impact of thermal effect on overall reactor performance. The non-isothermal system approach has been investigated in order to point out the important influence of the thermal effect on overall reactor performance, studying the possibility of RFR and RN utilization as recuperative and regenerative devices and the possibility of achieving a sustained auto-thermal behavior in case of lowexothermic reaction of SCR of NOx with ammonia and low temperature gasfeeding. Beside the influence of the thermal effect, the influence of the principal operating parameters, as switching time, inlet flow rate and initial catalyst temperature have been stressed. This analysis is important not only because it allows a comparison between the two devices and optimisation of the operation, but also the switching time is the main operating parameter. An appropriate choice of this parameter enables the fulfilment of the process constraints. The level of the conversions achieved, the more uniform temperature profiles, the uniformity ofcatalyst exploitation and the much simpler mode of operation imposed the RN as a much more suitable device for SCR of NOx with ammonia, in usual operation and also in the perspective of control strategy implementation. Theoretical simplified models have also been proposed in order to describe the forced unsteady state reactors performance and to estimate their internal temperature and concentration profiles. The general idea was to extend the study of catalytic reactor dynamics taking into account the perspectives that haven't been analyzed yet. The experimental investigation ofRN revealed a good agreement between the data obtained by model simulation and the ones obtained experimentally.

Magnetic and transport properties of II-V diluted magnetic semiconductors doped with manganese and nickel

This thesis is devoted to investigations of three typical representatives of the II-V diluted magnetic semiconductors, Zn1-xMnxAs2, (Zn1-xMnx)3As2 and p-CdSb:Ni. When this work started the family of the II-V semiconductors was presented by only the compounds belonging to the subgroup II3-V2, as (Zn1-xMnx)3As2, whereas the rest of the materials mentioned above were not investigated at all. Pronounced low-field magnetic irreversibility, accompanied with a ferromagnetic transition, are observed in Zn1-xMnxAs2 and (Zn1-xMnx)3As2 near 300 K. These features give evidence for presence of MnAs nanosize magnetic clusters, responsible for frustrated ground magnetic state. In addition, (Zn1-xMnx)3As2 demonstrates large paramagnetic response due to considerable amount of single Mn ions and small antiferromagnetic clusters. Similar paramagnetic system existing in Zn1-xMnxAs2 is much weaker. Distinct low-field magnetic irreversibility, accompanied with a rapid saturation of the magnetization with increasing magnetic field, is observed near the room temperature in p- CdSb:Ni, as well. Such behavior is connected to the frustrated magnetic state, determined by Ni-rich magnetic Ni1-xSbx nanoclusters. Their large non-sphericity and preferable orientations are responsible for strong anisotropy of the coercivity and saturation magnetization of p- CdSb:Ni. Parameters of the Ni1-xSbx nanoclusters are estimated. Low-temperature resistivity of p-CdSb:Ni is governed by a hopping mechanism of charge transfer. The variable-range hopping conductivity, observed in zero magnetic field, demonstrates a tendency of transformation into the nearest-neighbor hopping conductivity in non-zero magnetic filed. The Hall effect in p-CdSb:Ni exhibits presence of a positive normal and a negative anomalous contributions to the Hall resistivity. The normal Hall coefficient is governed mainly by holes activated into the valence band, whereas the anomalous Hall effect, attributable to the Ni1-xSbx nanoclusters with ferromagnetically ordered internal spins, exhibits a low-temperature power-law resistivity scaling.

Polttomoottorivoimalan energiatehokkuuden parantaminen hukkalämpövirtojen sähköksi muunnolla

Tämä diplomityö on osa FCEP hankeen Lappeenrannan teknillisessä yliopistossa tehtävää tutkimusta polttomoottoreiden energiatehokkuuden parantamisesta. Työn tavoitteena on saada tutkimustietoa polttomoottoreiden hukkalämpövirtojen hyödyntämisestä sähköntuotannossa. Tavoitteena on kartoittaa polttomoottorin hukkalämpövirtojen sähköksi muunnon potentiaalia valituilla menetelmillä ja tekniikoilla. Työssä tarkasteltavaksi moottoriksi valittiin DF- monipolttoainemoottori. DF-moottorin polttoaineena voidaan käyttää joko kaasua tai polttoöljyä. Laskennat suoritettiin moottorin valmistajan antamien hukkalämpövirtojen arvojen ja moottorin lämpötaseen avulla. Laskennan perusperiaatteena oli vesihöyryprosessin ja ORC-prosessien vertailu pakokaasulämmön hyödyntämisessä sekä matalalämpöisten hukkalämpövirtojen hyödyntäminen ORC-prosesseilla. Lisäksi työssä tutkittiin korkealla painesuhteella ja korkealla hyötysuhteella toimivan turboahtimen vaikutusta hukkalämpövirroista saatavaan tehoon. Diplomityössä tarkasteltiin moottorin lämpötaseen mukaisten arvojen lisäksi moottorin parametrien muuttamisen vaikutusta hukkalämpövirroista saatavaan tehoon. Moottorin parametrien muuttamisen vaikutusta moottorin akselitehoon tai moottorin lämpötaseeseen ei kuitenkaan tämän tutkimuksen puitteissa tarkasteltu. Työssä saatiin arvokasta tietoa polttomoottoreiden hukkalämpövirtojen muuntamisesta sähköksi eri menetelmillä sekä moottorin energiatehokkuuden parantamisesta.

Leaf-Targeted Ferredoxin-NADP+-Oxidoreductase (FNR): Electron Transfer Properties and Thylakoid Association in Arabidopsis thaliana

Photosynthetic reactions are divided in two parts: light-driven electron transfer reactions and carbon fixation reactions. Electron transfer reactions capture solar energy and split water molecules to form reducing energy (NADPH) and energy-carrying molecules (ATP). These end-products are used for fixation of inorganic carbon dioxide into organic sugar molecules. Ferredoxin-NADP⁺ oxidoreductase (FNR) is an enzyme that acts at the branch point between the electron transfer reactions and reductive metabolism by catalyzing reduction of NADP+ at the last step of the electron transfer chain. In this thesis, two isoforms of FNR from A rabidopsis thaliana, FNR1 and FNR2, were characterized using the reverse genetics approach. The fnr1 and fnr2 mutant plants resembled each other in many respects. Downregulation of photosynthesis protected the single fnr mutant plants from excess formation of reactive oxygen species (ROS), even without significant upregulation of antioxidative mechanisms. Adverse growth conditions, however, resulted in phenotypic differences between fnr1 and fnr2. While fnr2 plants showed downregulation of photosynthetic complexes and upregulation of antioxidative mechanisms under low-temperature growth conditions, fnr1 plants had the wild-type phenotype, indicating that FNR2 may have a specific role in redistribution of electrons under unfavorable conditions. The heterozygotic double mutant (fnr1xfnr2) was severely devoid of chloroplastic FNR, which clearly restricted photosynthesis. The fnr1xfnr2 plants used several photoprotective mechanisms to avoid oxidative stress. In wild-type chloroplasts, both FNR isoforms were found from the stroma, the thylakoid membrane, and the inner envelope membrane. In the absence of the FNR1 isoform, FNR2 was found only in the stroma, suggesting that FNR1 and FNR2 form a dimer, by which FNR1 anchors FNR2 to the thylakoid membrane. Structural modeling predicted formation of an FNR dimer in complex with ferredoxin. In this thesis work, Tic62 was found to be the main protein that binds FNR to the thylakoid membrane, where Tic62 and FNR formed high molecular weight complexes. The formation of such complexes was shown to be regulated by the redox state of the chloroplast. The accumulation of Tic62-FNR complexes in darkness and dissociation of complexes from the membranes in light provide evidence that the complexes may have roles unrelated to photosynthesis. This and the high viability of fnr1 mutant plants lacking thylakoid-bound FNR indicate that the stromal pool of FNR is photosynthetically active.

Simulation of hydrogen peroxide direct synthesis in a microreactor

A set of models in Aspen plus was built to simulate the direct synthesis process of hydrogen peroxide in a micro-reactor system. This process model can be used to carry out material balance calculation under various experimental conditions. Three thermodynamic property methods were compared by calculating gas solubility and Uniquac-RK method was finally selected for process model. Two different operation modes with corresponding operation conditions were proposed as the starting point of future experiments. Simulations for these two modes were carried out to get the information of material streams. Moreover, some hydrodynamic parameters such as gas/liquid superficial velocity, gas holdup were also calculated with improved process model. These parameters proved the proposed experimental conditions reasonable to some extent. The influence of operation conditions including temperature, pressure and circulation ratio was analyzed for the first operation mode, where pure oxygen was fed into dissolving tank and hydrogen-carbon dioxide mixture was fed into microreactor directly. The preferred operation conditions for the system are low temperature (2°C) and high pressure (30 bar) in dissolving tank. High circulation ratio might be good in the sense that more oxygen could be dissolved and fed into reactor for reactions, but meanwhile hydrodynamics of microreactor should be considered. Furthermore, more operation conditions of reactor gas/liquid feeds in both of two operation modes were proposed to provide guidance for future experiment design and corresponding hydrodynamic parameters were also calculated. Finally, safety issue was considered from thermodynamic point of view and there is no explosion danger at given experimental plan since the released reaction heat will not cause solvent vaporization inside the microchannels. The improvement of process model still needs further study based on the future experimental results.