Kartongin fysikaalisten ominaisuuksien vaikutus muovautuvuuteen

Työn tavoitteena oli kehittää menetelmä, jolla voitaisiin arvioida veto-ominaisuuksien avulla konvertointikoneen prässäysnopeuden ja muottien lämpötilan vaikutuksia kartongin muovautuvuuteen. Kirjallisuusosassa käsiteltiin kartongin muovautuvuuteen vaikuttavia ominaisuuksia sekä vetolujuuteen vaikuttavia tekijöitä. Lisäksi käsiteltiin kosteuden vaikutusta muovautuvuuteen sekä esiteltiin vuokakonvertointiprosessin periaate ja muovin sekä kartongin käyttäytymisen erot konvertointiprosessissa. Kokeellinen osa jakaantui kolmeen osaan. Esikokeissa tutkittiin laboratoriomittauksilla vetonopeuden ja kosteuden muutosten vaikutusta erilaisten kaupallisten kartonkimateriaalien vetolujuuteen ja murtovenymään. Tulosten perusteella valittiin prässäysnopeudet ja kosteustaso 2D- testauslaitteella suoritettuihin esi-pilot-mittakaavan kokeisiin sekä varsinaiseen pilot-koeajoon. Pilot-koeajossa pyrittiin arvioimaan prässäysnopeuden ja muottien lämpötilan vaikutuksia muovautuvuuteen vetolujuusarvojen avulla. Prässäysnopeudella ja vetolujuuslaitteen nopeudella ei havaittu yhteneväisyyksiä, jotta voitaisiin arvioida kartongin muovautuvuutta. Muovautuvuutta voidaan kuitenkin arvioida epäonnistuneisuusluvulla, jonka laskentapa kehitettiin työn aikana. Epäonnistuneisuusluku kuvaa hyvin kartongin muovautuvuutta ja on menetelmänä helppo, mutta sen heikkoutena on repeämien mittaamisen aiheuttama epätarkkuus. Esikokeissa havaittiin myös muovipäällysteiden veto-ominaisuuksien vastaavan kartongin ominaisuuksia 65 %:n suhteellisessa kosteudessa, jonka valittiin siten olevan optimaalinen olosuhde pilot-mittakaavan koeajoihin.

The effect of focal point parameters in fiber laser welding of structural steel

In this thesis the effect of focal point parameters in fiber laser welding of structural steel is studied. The goal is to establish relations between laser power, focal point diameter and focal point position with the resulting quality, weld-bead geometry and hardness of the welds. In the laboratory experiments, AB AH36 shipbuilding steel was welded in an I-butt joint configuration using IPG YLS-10000 continuous wave fiber laser. The quality of the welds produced were evaluated based on standard SFS-EN ISO 13919-1. The weld-bead geometry was defined from the weld cross-sections and Vickers hardness test was used to measure hardness's from the middle of the cross-sections. It was shown that all the studied focal point parameters have an effect on the quality, weld-bead geometry and hardness of the welds produced.

Neopentyyliglykolin ja propionihapon välisen esteröintireaktion kinetiikka

Glykolien esterit ovat haluttuja pintareaktiivisia aineita. Niitä voidaan valmistaa esteröintireaktiolla karboksyylihappojen kanssa katalyytin läsnä ollessa, jolloin toivottu reaktiotuote on yleensä muodostuva monoesteri. Monoesterin saannon lisäämiseksi reaktiossa muodostuvaa vettä voidaan poistaa jatkuvasti reaktiosta. Reaktion tasapainotilan tutkiminen on kuitenkin tärkeää, jotta reaktion kinetiikka tunnettaisiin mahdollisimman hyvin. Tällöin reaktiotuotteita ei poisteta reaktioseoksesta reaktion aikana. Glykolit esteröityvät happojen kanssa kahdessa vaiheessa. Ensimmäisessä vaiheessa muodostuu monoesteriä ja vettä ja toisessa vaiheessa diesteriä ja vettä. Kokeiden perusteella ensimmäinen vaihe on selvästi toista vaihetta nopeampi reaktio. Kirjallisuudessa on esitetty myös kaksi sivureaktiota, transesteröityminen ja disproportionaatio. Reaktion kinetiikka voidaan kuvata ilman näitä pieniä sivureaktiota, mutta täydellisen kuvaamisen vuoksi on ne myös otettava huomioon. Reaktion kinetiikan tutkimiseksi suoritettiin viisi laboratoriokoetta eri lämpötiloissa neopentyyliglykolilla ja propionihapolla homogeenisen para-tolueenisulfonihapon toimiessa katalyyttina. Lähtöaineiden ja tuotteiden konsentraatioita seurattiin ajan funktiona ja saatujen tulosten perusteella sovitettiin reaktiomekanismin differentiaaliyhtälöiden reaktionopeusvakiot. Nopeusvakioiden lämpötilariippuvuutta tutkittiin Arrheniuksen yhtälön avulla. Lisäksi määritettiin tasapainovakiot kullekin osareaktiolle.

Separation mechanisms in nanofiltration and retention changes of organic compounds

Orgaanisten yhdisteiden negatiivinen retentio nanosuodatuksessa on ilmiö, jota eiole kovin paljon tutkittu. Negatiivisen retentioon vaikuttavat syyt tai tekijäteivät ole kovin hyvin tiedossa. Erotusmenetelmänä negatiivinen retentio voi olla käyttökelpoinen tietyissä sovelluksissa. Työn kirjallisuusosa käsittelee nanosuodatuksen erotusmekanismeja ja retentioon vaikuttavia tekijöitä. Myös joitakin malleja on esitetty. Nanosuodatus on monimutkainen prosessi, josta ei voida löytää vain yhtä erotusmekanismia tai retentioon vaikuttavaa tekijää. Prosessit ovat kokonaisuuksia, joissa erottumiseen vaikuttavat syöttöliuoksen, erotettavan komponentin ja kalvon ominaisuudet, ja niiden väliset vuorovaikutukset. Työn kokeellisessa osassa koottiin mahdollisimman paljon esimerkkejä, joissa monosakkaridien negatiivinen retentio ilmenee. Muita orgaanisia ja epäorgaanisia yhdisteitä käytettiin 'häiriöyhdisteinä' syöttöliuoksessa monosakkaridien kanssa. Kokeet suoritettiin kahdella laboratoriomittakaavan suodatuslaitteella käyttäen kahta kaupallista nanosuodatuskalvoa. Negatiivinen retentio ilmeni useissa tapauksissa. Permeaattivuon ja 'häiriöyhdisteiden' pitoisuuksien havaittiin vaikuttavan voimakkaasti negatiivisen retention ilmenemiseen.

Painatuksen UV-stabiilisuuden optimointi fenolihartsatussa paperissa

Tässä diplomityössä tutkittiin painetun paperin ja siitä fenoliformaldehydihartsilla impregnoimalla valmistetun pinnoituskalvon UV-stabiilisuuden parantamis-mahdollisuuksia. Työn kirjallisuusosassa käsitellään painetun pinnoituskalvon valmistusprosessia ja painatuksen UV-valonkestoon vaikuttavia tekijöitä. Painovärin pigmentti, sen määrä ja käsittely, painovärin sideaine sekä fenoliformaldehydihartsi ja sen lisäaineet vaikuttavat pinnoitetun betonoimisvanerin säänkesto-ominaisuuksiin. Erilaisilla epäorgaanisilla valkoisilla pigmenteillä ja kidemuodoilla on erilainen UV-valonkesto ja taitekerroin. Päällystämällä titaanidioksidi esimerkiksi alumiini- tai zirkoniumoksideilla sen UV-valonkestoa voidaan parantaa merkittävästi. UV-hajoaminen voidaan havaita painetun pinnoitteen liituuntumisena. Liituuntumista voidaan pitää veden ja hapen välisenä reaktiona, jota titaanidioksidi ja UV-säteily katalysoivat. Sen takia myös muiden valkoisten epäorgaanisten pigmenttien ominaisuuksia ja käyttöä selvitettiin. Kokeissa käytettiin yhdeksää eri painoväriä, kahta eri paksuista paperia ja kahta eri tyyppistä hartsia. Painovärejä ohennettiin vedellä ja paperin painopuolta vaihdeltiin. Kaikissa painatuksissa käytettiin kolmea eri rasterointiasteen laattaa, jolloin painovärin määrää paperissa saatiin vähennettyä. Painetuista papereista mitattiin densiteetti, värimäärä, pisara-absorptio vedellä ja kontaktikulma hartsilla. Myös painovärin tunkeumaa selvitettiin paperin poikkileikeistä tehtyjen SEM-kuvien avulla. Painetut paperit impregnoitiin fenoliformaldehydihartsilla kalvoksi. Pinnoituskalvot puristettiin vanerin pinnalle laboratoriopuristimella. Koekappaleet altistettiin UV-valolle, sateelle ja pakkaselle sääkaapissa 400 h ajan, mikä vastaa noin 1,5 vuotta ulkona Suomen oloissa. Kappaleista mitattiin kiilto, värinmuutos ja liituuntuminen. Pinnoitteen liituuntumista tapahtui vähiten niissä koepisteissä, joissa painatus oli tehty 30 % rasteroidulla laatallaSäänkestävä TiO2 osoittautui hyväksi, mutta myös ZnO-pigmentillä saatiin hyviä tuloksia. ZnO-koepisteessä liituuntumisreaktio ei ole niin voimakkaasti katalysoitu kuin TiO2-koepisteissä. Paksun paperin painatuspuolella näytti olevan merkitystä säänkestoon. Huopapuolelle painettuna pinnoitteen liituuntuminen oli vähäisempää

Ammoniakin talteenottoprosessin kehitys

Diplomityössä kehitettiin ioninvaihtoon perustuva ammoniakin talteenottoprosessi NSSC (Neutral Sulphite Semi Chemical) -prosessin haihduttamon lauhteille. Tarkoituksena oli saada aallotuskartonkitehtaan kemi-kaalikiertoa suljettua ja sitä kautta ammoniakkipäästöjä vähennettyä. Ammoniakki tuli ottaa hyötymuodossa (ammoniakkihöyry tai ammoniumsulfiitti) talteen. Ammoniumsulfiittiliuosta käytetään NSSC-prosessissa keittonesteenä. Kirjallisuusosassa selvitetään strippaukseen perustuvia ammoniakin talteenottomahdollisuuksia. Tutkitaan ioninvaihdon teoriaa ja ammoniumin talteenottoon sopivien ioninvaihtomateriaalien ominaisuuksia ioninvaihtajina. Lisäksi esitetään ioninvaihtoprosesseihin liittyviä laitteistoratkaisuja ja prosessiolosuhteita. Työn kokeellisessa osassa on yleiskuvaus Powerflute Oy Savon Sellun prosesseista ja selvitetään ammoniakin merkitystä tehtaalle. Laboratoriokokein tutkittiin orgaanisten kationihartsien sekä epäorgaanisen luonnon zeoliitin soveltuvuutta ammoniumionien vaihtoon esihaihduttamon lauhteesta. Ammoniakin talteenottoprosessin toimivuutta teollisessa mittakaavassa selvitettiin rakennetulla pilotlaitteistolla suoritettujen kokeiden avulla. Lopuksi tehtiin ammoniakin talteenottoprosessin scale-up: laskettiin prosessin talteenottokapasiteetti, arvioitiin kustannuksia sekä annettiin lausunto prosessin toteutettavuudesta. Laboratoriokokeiden perusteella luonnon zeoliitti ja heikosti hapan ioninvaihtohartsi eivät sovellu ammoniumionien vaihtoon NSSC haihduttamon lauhteista. Vahvasti hapan kationihartsi toimi ammoniumin talteenotossa parhaiten, joten se valittiin pilotkokeiden ioninvaihtomateriaaliksi. Pilotkokeissa ioninvaihtomateriaaliin saatiin sidottua ammoniumia noin 30 g NH4+ / dm3 hartsia, kun materiaalin teoreettinen ioninvaihtokapasiteetti oli 32 g NH4+ / dm3 hartsia. Ammoniumin läpäisykäyrien muotoon vaikutti suuresti syöttölauhteen virtausnopeus ja ammoniumpitoisuus. Ioninvaihtomateriaalipedin syvyydellä ei ollut niinkään merkitystä. Pilotkokeiden regenerointitavoista tehokkaimmaksi osoittautui höyrystrippaus, jossa saavutettiin noin 90 %:n talteenottotehokkuus. Rikkihapokekäsittelyllä talteenottotehokkuus jäi 50 %:iin. Teollisen mittakaavan laitoksella voidaan vuosittain regenerointitavasta riippuen ottaa talteen esihaihdut-tamon lauhteesta noin 100-150 tonnia ammoniakkia. Prosessin käyttökustannukset ovat talteenotetusta ammoniakista saataviin säästöihin verrattuna suuret ja niihin vaikuttaa merkittävästi ioninvaihtohartsin käyttöikä sekä regenerointikemikaalien kulutus. Osittaisella kemikaalikierron sulkemisella saavutetaan NSSC-prosessissa sekundäärietuja, joiden vaikutuksen merkittävyys pitäisi tarkentaa lisätutkimuksilla.

Magnetic Resonance Experiments with Atomic Hydrogen

In this thesis three experiments with atomic hydrogen (H) at low temperatures T<1 K are presented. Experiments were carried out with two- (2D) and three-dimensional (3D) H gas, and with H atoms trapped in solid H2 matrix. The main focus of this work is on interatomic interactions, which have certain specific features in these three systems considered. A common feature is the very high density of atomic hydrogen, the systems are close to quantum degeneracy. Short range interactions in collisions between atoms are important in gaseous H. The system of H in H₂ differ dramatically because atoms remain fixed in the H₂ lattice and properties are governed by long-range interactions with the solid matrix and with H atoms. The main tools in our studies were the methods of magnetic resonance, with electron spin resonance (ESR) at 128 GHz being used as the principal detection method. For the first time in experiments with H in high magnetic fields and at low temperatures we combined ESR and NMR to perform electron-nuclear double resonance (ENDOR) as well as coherent two-photon spectroscopy. This allowed to distinguish between different types of interactions in the magnetic resonance spectra. Experiments with 2D H gas utilized the thermal compression method in homogeneous magnetic field, developed in our laboratory. In this work methods were developed for direct studies of 3D H at high density, and for creating high density samples of H in H₂. We measured magnetic resonance line shifts due to collisions in the 2D and 3D H gases. First we observed that the cold collision shift in 2D H gas composed of atoms in a single hyperfine state is much smaller than predicted by the mean-field theory. This motivated us to carry out similar experiments with 3D H. In 3D H the cold collision shift was found to be an order of magnitude smaller for atoms in a single hyperfine state than that for a mixture of atoms in two different hyperfine states. The collisional shifts were found to be in fair agreement with the theory, which takes into account symmetrization of the wave functions of the colliding atoms. The origin of the small shift in the 2D H composed of single hyperfine state atoms is not yet understood. The measurement of the shift in 3D H provides experimental determination for the difference of the scattering lengths of ground state atoms. The experiment with H atoms captured in H2 matrix at temperatures below 1 K originated from our work with H gas. We found out that samples of H in H2 were formed during recombination of gas phase H, enabling sample preparation at temperatures below 0.5 K. Alternatively, we created the samples by electron impact dissociation of H₂ molecules in situ in the solid. By the latter method we reached highest densities of H atoms reported so far, 3.5(5)x10¹⁹ cm^-3. The H atoms were found to be stable for weeks at temperatures below 0.5 K. The observation of dipolar interaction effects provides a verification for the density measurement. Our results point to two different sites for H atoms in H2 lattice. The steady-state nuclear polarizations of the atoms were found to be non-thermal. The possibility for further increase of the impurity H density is considered. At higher densities and lower temperatures it might be possible to observe phenomena related to quantum degeneracy in solid.

A study of combustion phenomena in circulating fluidized beds by developing and applying experimental and modelling methods for laboratory-scale reactors

The results shown in this thesis are based on selected publications of the 2000s decade. The work was carried out in several national and EC funded public research projects and in close cooperation with industrial partners. The main objective of the thesis was to study and quantify the most important phenomena of circulating fluidized bed combustors by developing and applying proper experimental and modelling methods using laboratory scale equipments. An understanding of the phenomena plays an essential role in the development of combustion and emission performance, and the availability and controls of CFB boilers. Experimental procedures to study fuel combustion behaviour under CFB conditions are presented in the thesis. Steady state and dynamic measurements under well controlled conditions were carried out to produce the data needed for the development of high efficiency, utility scale CFB technology. The importance of combustion control and furnace dynamics is emphasized when CFB boilers are scaled up with a once through steam cycle. Qualitative information on fuel combustion characteristics was obtained directly by comparing flue gas oxygen responses during the impulse change experiments with fuel feed. A one-dimensional, time dependent model was developed to analyse the measurement data Emission formation was studied combined with fuel combustion behaviour. Correlations were developed for NO, N2O, CO and char loading, as a function of temperature and oxygen concentration in the bed area. An online method to characterize char loading under CFB conditions was developed and validated with the pilot scale CFB tests. Finally, a new method to control air and fuel feeds in CFB combustion was introduced. The method is based on models and an analysis of the fluctuation of the flue gas oxygen concentration. The effect of high oxygen concentrations on fuel combustion behaviour was also studied to evaluate the potential of CFB boilers to apply oxygenfiring technology to CCS. In future studies, it will be necessary to go through the whole scale up chain from laboratory phenomena devices through pilot scale test rigs to large scale, commercial boilers in order to validate the applicability and scalability of the, results. This thesis shows the chain between the laboratory scale phenomena test rig (bench scale) and the CFB process test rig (pilot). CFB technology has been scaled up successfully from an industrial scale to a utility scale during the last decade. The work shown in the thesis, for its part, has supported the development by producing new detailed information on combustion under CFB conditions.

Thinking Outside the Box: Enhancing Science Teaching by Combining (Instead of Contrasting) Laboratory and Simulation Activities

The focus of the present work was on 10- to 12-year-old elementary school students’ conceptual learning outcomes in science in two specific inquiry-learning environments, laboratory and simulation. The main aim was to examine if it would be more beneficial to combine than contrast simulation and laboratory activities in science teaching. It was argued that the status quo where laboratories and simulations are seen as alternative or competing methods in science teaching is hardly an optimal solution to promote students’ learning and understanding in various science domains. It was hypothesized that it would make more sense and be more productive to combine laboratories and simulations. Several explanations and examples were provided to back up the hypothesis. In order to test whether learning with the combination of laboratory and simulation activities can result in better conceptual understanding in science than learning with laboratory or simulation activities alone, two experiments were conducted in the domain of electricity. In these experiments students constructed and studied electrical circuits in three different learning environments: laboratory (real circuits), simulation (virtual circuits), and simulation-laboratory combination (real and virtual circuits were used simultaneously). In order to measure and compare how these environments affected students’ conceptual understanding of circuits, a subject knowledge assessment questionnaire was administered before and after the experimentation. The results of the experiments were presented in four empirical studies. Three of the studies focused on learning outcomes between the conditions and one on learning processes. Study I analyzed learning outcomes from experiment I. The aim of the study was to investigate if it would be more beneficial to combine simulation and laboratory activities than to use them separately in teaching the concepts of simple electricity. Matched-trios were created based on the pre-test results of 66 elementary school students and divided randomly into a laboratory (real circuits), simulation (virtual circuits) and simulation-laboratory combination (real and virtual circuits simultaneously) conditions. In each condition students had 90 minutes to construct and study various circuits. The results showed that studying electrical circuits in the simulation–laboratory combination environment improved students’ conceptual understanding more than studying circuits in simulation and laboratory environments alone. Although there were no statistical differences between simulation and laboratory environments, the learning effect was more pronounced in the simulation condition where the students made clear progress during the intervention, whereas in the laboratory condition students’ conceptual understanding remained at an elementary level after the intervention. Study II analyzed learning outcomes from experiment II. The aim of the study was to investigate if and how learning outcomes in simulation and simulation-laboratory combination environments are mediated by implicit (only procedural guidance) and explicit (more structure and guidance for the discovery process) instruction in the context of simple DC circuits. Matched-quartets were created based on the pre-test results of 50 elementary school students and divided randomly into a simulation implicit (SI), simulation explicit (SE), combination implicit (CI) and combination explicit (CE) conditions. The results showed that when the students were working with the simulation alone, they were able to gain significantly greater amount of subject knowledge when they received metacognitive support (explicit instruction; SE) for the discovery process than when they received only procedural guidance (implicit instruction: SI). However, this additional scaffolding was not enough to reach the level of the students in the combination environment (CI and CE). A surprising finding in Study II was that instructional support had a different effect in the combination environment than in the simulation environment. In the combination environment explicit instruction (CE) did not seem to elicit much additional gain for students’ understanding of electric circuits compared to implicit instruction (CI). Instead, explicit instruction slowed down the inquiry process substantially in the combination environment. Study III analyzed from video data learning processes of those 50 students that participated in experiment II (cf. Study II above). The focus was on three specific learning processes: cognitive conflicts, self-explanations, and analogical encodings. The aim of the study was to find out possible explanations for the success of the combination condition in Experiments I and II. The video data provided clear evidence about the benefits of studying with the real and virtual circuits simultaneously (the combination conditions). Mostly the representations complemented each other, that is, one representation helped students to interpret and understand the outcomes they received from the other representation. However, there were also instances in which analogical encoding took place, that is, situations in which the slightly discrepant results between the representations ‘forced’ students to focus on those features that could be generalised across the two representations. No statistical differences were found in the amount of experienced cognitive conflicts and self-explanations between simulation and combination conditions, though in self-explanations there was a nascent trend in favour of the combination. There was also a clear tendency suggesting that explicit guidance increased the amount of self-explanations. Overall, the amount of cognitive conflicts and self-explanations was very low. The aim of the Study IV was twofold: the main aim was to provide an aggregated overview of the learning outcomes of experiments I and II; the secondary aim was to explore the relationship between the learning environments and students’ prior domain knowledge (low and high) in the experiments. Aggregated results of experiments I & II showed that on average, 91% of the students in the combination environment scored above the average of the laboratory environment, and 76% of them scored also above the average of the simulation environment. Seventy percent of the students in the simulation environment scored above the average of the laboratory environment. The results further showed that overall students seemed to benefit from combining simulations and laboratories regardless of their level of prior knowledge, that is, students with either low or high prior knowledge who studied circuits in the combination environment outperformed their counterparts who studied in the laboratory or simulation environment alone. The effect seemed to be slightly bigger among the students with low prior knowledge. However, more detailed inspection of the results showed that there were considerable differences between the experiments regarding how students with low and high prior knowledge benefitted from the combination: in Experiment I, especially students with low prior knowledge benefitted from the combination as compared to those students that used only the simulation, whereas in Experiment II, only students with high prior knowledge seemed to benefit from the combination relative to the simulation group. Regarding the differences between simulation and laboratory groups, the benefits of using a simulation seemed to be slightly higher among students with high prior knowledge. The results of the four empirical studies support the hypothesis concerning the benefits of using simulation along with laboratory activities to promote students’ conceptual understanding of electricity. It can be concluded that when teaching students about electricity, the students can gain better understanding when they have an opportunity to use the simulation and the real circuits in parallel than if they have only the real circuits or only a computer simulation available, even when the use of the simulation is supported with the explicit instruction. The outcomes of the empirical studies can be considered as the first unambiguous evidence on the (additional) benefits of combining laboratory and simulation activities in science education as compared to learning with laboratories and simulations alone.