Spray coating technique asa surface treatment for woodcontaining paper grades

The objective of this work was to introduce the emerging non-contacting spray coating process and compare it to the existing coating techniques. Particular emphasis was given to the details of the spraying process of paper coating colour and the base paper requirements set by the new coating method. Spraying technology itself is nothing new, but the atomisation process of paper coating colour is quite unknown to the paper industry. The differences between the rheology of painting and coating colours make it very difficult to utilise the existing information from spray painting research. Based on the trials, some basic conclusion can be made:The results of this study suggest that the Brookfield viscosity of spray coating colour should be as low as possible, presently a 50 mPas level is regarded as an optimum. For the paper quality and coater runnability, the solids level should be as high as possible. However, the graininess of coated paper surface and the nozzle wear limits the maximum solids level to 60 % at the moment. Most likelydue to the low solids and low viscosity of the coating colour the low shear Brookfield viscosity correlates very well with the paper and spray fan qualities. High shear viscosity is also important, but yet less significant than the low shear viscosity. Droplet size should be minimized and besides keeping the brrokfield viscosity low that can be helped by using a surfactant or dispersing agent in the coating colour formula. Increasing the spraying pressure in the nozzle can also reduce the droplet size. The small droplet size also improves the coating coverage, since there is hardly any levelling taking place after the impact with the base paper. Because of the lack of shear forces after the application, the pigment particles do not orientate along the paper surface. Therefore the study indicates that based on the present know-how, no quality improvements can be obtained by the use of platy type of pigments. The other disadvantage of them is the rapid deterioration of the nozzle lifetime. Further research in both coating colour rheology and nozzle design may change this in the future, but so far only round shape pigments, like typically calcium carbonate is, can be used with spray coating. The low water retention characteristics of spray coating, enhanced by the low solids and low viscosity, challenge the base paper absorption properties.Filler level has to be low not to increase the number of small pores, which have a great influence on the absorption properties of the base paper. Hydrophobic sizing reduces this absorption and prevents binder migration efficiently. High surface roughness and especially poor formation of the base paper deteriorate thespray coated paper properties. However, pre-calendering of the base paper does not contribute anything to the finished paper quality, at least at the coating colour solids level below 60 %. When targeting a standard offset LWC grade, spraycoating produces similar quality to film coating, but yet blade coating being on a slightly better level. However, because of the savings in both investment and production costs, spray coating may have an excellent future ahead. The porousnature of the spray coated surface offers an optimum substrate for the coldset printing industry to utilise the potential of high quality papers in their business.

Paperin spraypäällystys

Tässä työssä esitellään paperin spraypäällystykseen soveltuvaa tekniikkaa sekä yleistä sprayteknologiaa ja teoriaa sen taustalla. Lisäksi käydään läpi pohjapaperilta vaadittuja ominaisuuksia ja käsitellään spraypäällystykseen sopivan pastan koostumusta.

Development and characterization of thin printed films for gas sensing applications

The monitoring and control of hydrogen sulfide (H2S) level is of great interest for a wide range of application areas including food quality control, defense and antiterrorist applications and air quality monitoring e.g. in mines. H2S is a very poisonous and flammable gas. Exposure to low concentrations of H2S can result in eye irritation, a sore throat and cough, shortness of breath, and fluid retention in the lungs. These symptoms usually disappear in a few weeks. Long-term, low-level exposure may result in fatigue, loss of appetite, headache, irritability, poor memory, and dizziness. Higher concentrations of 700 - 800 ppm tend to be fatal. H2S has a characteristic smell of rotten egg. However, because of temporary paralysis of olfactory nerves, the smelling capability at concentrations higher than 100 ppm is severely compromised. In addition, volatile H2S is one of the main products during the spoilage of poultry meat in anaerobic conditions. Currently, no commercial H2S sensor is available which can operate under anaerobic conditions and can be easily integrated in the food packaging. This thesis presents a step-wise progress in the development of printed H2S gas sensors. Efforts were made in the formulation, characterization and optimization of functional printable inks and coating pastes based on composites of a polymer and a metal salt as well as a composite of a metal salt and an organic acid. Different processing techniques including inkjet printing, flexographic printing, screen printing and spray coating were utilized in the fabrication of H2S sensors. The dispersions were characterized by measuring turbidity, surface tension, viscosity and particle size. The sensing films were characterized using X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy and an electrical multimeter. Thin and thick printed or coated films were developed for gas sensing applications with the aim of monitoring the H2S concentrations in real life applications. Initially, a H2S gas sensor based on a composite of polyaniline and metal salt was developed. Both aqueous and solvent-based dispersions were developed and characterized. These dispersions were then utilized in the fabrication of roll-to-roll printed H2S gas sensors. However, the humidity background, long term instability and comparatively lower detection limit made these sensors less favourable for real practical applications. To overcome these problems, copper acetate based sensors were developed for H2S gas sensing. Stable inks with excellent printability were developed by tuning the surface tension, viscosity and particle size. This enabled the formation of inkjet-printed high quality copper acetate films with excellent sensitivity towards H2S. Furthermore, these sensors showed negligible humidity effects and improved selectivity, response time, lower limit of detection and coefficient of variation. The lower limit of detection of copper acetate based sensors was further improved to sub-ppm level by incorporation of catalytic gold nano-particles and subsequent plasma treatment of the sensing film. These sensors were further integrated in an inexpensive wirelessly readable RLC-circuit (where R is resistor, L is inductor and C is capacitor). The performance of these sensors towards biogenic H2S produced during the spoilage of poultry meat in the modified atmosphere package was also demonstrated in this thesis. This serves as a proof of concept that these sensors can be utilized in real life applications.

The effect of cationic-anionic polyelectrolyte multilayer surface treatment on inkjet ink spreading and print quality

The focus of the work reported in this thesis was to study and to clarify the effect of polyelectrolyte multilayer surface treatment on inkjet ink spreading, absorption and print quality. Surface sizing with a size press, film press with a pilot scale coater, and spray coating, have been used to surface treat uncoated wood-free, experimental wood-free and pigmentcoated substrates. The role of the deposited cationic (polydiallydimethylammonium chloride, PDADMAC) and anionic (sodium carboxymethyl cellulose, NaCMC) polyelectrolyte layers with and without nanosilica, on liquid absorption and spreading was studied in terms of their interaction with water-based pigmented and dye-based inkjet inks. Contact angle measurements were made in attempt to explain the ink spreading and wetting behavior on the substrate. First, it was noticed that multilayer surface treatment decreased the contact angle of water, giving a hydrophilic character to the surface. The results showed that the number of cationic-anionic polyelectrolyte layers or the order of deposition of the polyelectrolytes had a significant effect on the print quality. This was seen for example as a higher print density on layers with a cationic polyelectrolyte in the outermost layer. The number of layers had an influence on the print quality; the print density increased with increasing number of layers, although the increase was strongly dependent on ink formulation and chemistry. The use of nanosilica clearly affected the rate of absorption of polar liquids, which also was seen as a higher density of the black dye-based print. Slightly unexpected, the use of nanosilica increased the tendency for lateral spreading of both the pigmented and dye-based inks. It was shown that the wetting behavior and wicking of the inks on the polyelectrolyte coatings was strongly affected by the hydrophobicity of the substrate, as well as by the composition or structure of the polyelectrolyte layers. Coating only with a cationic polyelectrolyte was not sufficient to improve dye fixation, but it was demonstrated that a cationic-anionic-complex structure led to good water fastness. A threelayered structure gave the same water fastness values as a five-layered structure. Interestingly, the water fastness values were strongly dependent not only on the formed cation-anion polyelectrolyte complexes but also on the tendency of the coating to dissolve during immersion in water. Results showed that by optimizing the chemistry of the layers, the ink-substrate interaction can be optimized.

Ohutlevykotelon valmistettavuuden ja pinnoitettavuuden huomioiminen suunnittelussa

Korkean IP-luokituksen ohutlevykotelointi on haastava kokonaisuus. Koteloinnin tiivistys ruiskutettavalla polyureapinnoitteella edellyttää usean osa-alueen samanaikaista hallintaa. Kotelo on alusta alkaen suunniteltava pinnoitettavaksi, sillä pinnoitus asettaa lukuisia vaatimuksia ja rajoituksia esimerkiksi käytettäville muodoille, rakenteille ja liittämismenetelmille. Polyurea on elastomeeri, josta valmistettua pinnoitetta voidaan levittää erityisellä ruiskutuslaitteistolla. Polyureapinnoite sallii kotelon asentamisen vaikeisiin olosuhteisiin, sillä se kestää kemikaaleja, kulutusta ja iskuja sekä tarjoaa tiiveyden lisäksi korroosiosuojan koteloinnille. Pinnoitteen ominaisuuksia, kuten kovuutta, elastisuutta ja kemikaalien sekä UV-säteilyn kestoa voidaan räätälöidä käyttökohteen mukaan. Polyurepinnoitteeella pinnoitettavat pinnat on pyrittävä pitämään mahdollisimman yksinkertaisina, mikä tarkoittaa käytännössä kaikenlaisten kohoumien, ulkonevien osien, reikien ja muiden epäjatkuvuuskohtien välttämistä. Kaikki epäjatkuvuuskohdat vaativat erityishuomiota pinnoituksen aikana, sillä epäjatkuvuuskohtien onnistunut pinnoitus vaatii ruiskutusta useasta suunnasta, mikä lisää virhemahdollisuuksia ja siten vaarantaa koteloinnin tiiveyden. Liittämismenetelmät ovat yksinkertaisten muotojen ohella avainasemassa pinnoituksen onnistumisen kannalta. Menetelmistä tulee suosia sellaisia, joiden pinnoitettavaan pintaan aiheuttama epäjatkuvuuskohta on mahdollisimman vähäinen. Tällaisia menetelmiä ovat esimerkiksi vastuspistehitsaus ja puristeruuvi.

Modeling of Pressurizer Using APROS and TRACE Thermal Hydraulic Codes

Diplomityön tavoitteena on paineistimen yksityiskohtainen mallintaminen APROS- ja TRACE- termohydrauliikkaohjelmistoja käyttäen. Rakennetut paineistinmallit testattiin vertaamalla laskentatuloksia paineistimen täyttymistä, tyhjentymistä ja ruiskutusta käsittelevistä erilliskokeista saatuun mittausdataan. Tutkimuksen päätavoitteena on APROSin paineistinmallin validoiminen käyttäen vertailuaineistona PACTEL ATWS-koesarjan sopivia paineistinkokeita sekä MIT Pressurizer- ja Neptunus- erilliskokeita. Lisäksi rakennettiin malli Loviisan ydinvoimalaitoksen paineistimesta, jota käytettiin turbiinitrippitransientin simulointiin tarkoituksena selvittää mahdolliset voimalaitoksen ja koelaitteistojen mittakaavaerosta johtuvat vaikutukset APROSin paineistinlaskentaan. Kokeiden simuloinnissa testattiin erilaisia noodituksia ja mallinnusvaihtoehtoja, kuten entalpian ensimmäisen ja toisen kertaluvun diskretisointia, ja APROSin sekä TRACEn antamia tuloksia vertailtiin kattavasti toisiinsa. APROSin paineistinmallin lämmönsiirtokorrelaatioissa havaittiin merkittävä puute ja laskentatuloksiin saatiin huomattava parannus ottamalla käyttöön uusi seinämälauhtumismalli. Työssä tehdyt TRACE-simulaatiot ovat osa United States Nuclear Regulatory Commissionin kansainvälistä CAMP-koodinkehitys-ja validointiohjelmaa.

Thermal Stress in a Roll-to-Roll Printed Electronics Substrate

The Roll-to-Roll process makes it possible to print electronic products continuously onto a uniform substrate. Printing components on flexible surfaces can bring down the costs of simple electronic devices such as RFID tags, antennas and transistors. The possibility of quickly printing flexible electronic components opens up a wide array of novel products previously too expensive to produce on a large scale. Several different printing methods can be used in Roll-to-Roll printing, such as gravure, spray, offset, flexographic and others. Most of the methods can also be mixed in one production line. Most of them still require years of research to reach a significant commercial level. The research for this thesis was carried out at the Konkuk University Flexible Display Research Center (KU-FDRC) in Seoul, Korea. A system using Roll-to-Roll printing requires that the motion of the web can be controlled in every direction in order to align different layers of ink properly. Between printers the ink is dried with hot air. The effects of thermal expansion on the tension of the web are studied in this work, and a mathematical model was constructed on Matlab and Simulink. Simulations and experiments lead to the conclusion that the thermal expansion of the web has a great influence on the tension of the web. Also, experimental evidence was gained that the particular printing machine used for these experiments at KU-FDRC may have a problem in controlling the speeds of the cylinders which pull the web.

Changes in the thermal growing season in Nordic countries during the past century and prospects for the future

Selostus: Termisen kasvukauden muutokset Pohjoismaissa viimeisen vuosisadan aikana ja tulevaisuudessa

Thermal conductivity of low-decomposed Sphagnum peat used as growth medium

Kasvualustana käytetyn heikosti maatuneen rahkaturpeen lämmönjohtavuus

Experimental thermal hydraulic studies on the enhancement of safety of LWRs

The safe use of nuclear power plants (NPPs) requires a deep understanding of the functioning of physical processes and systems involved. Studies on thermal hydraulics have been carried out in various separate effects and integral test facilities at Lappeenranta University of Technology (LUT) either to ensure the functioning of safety systems of light water reactors (LWR) or to produce validation data for the computer codes used in safety analyses of NPPs. Several examples of safety studies on thermal hydraulics of the nuclear power plants are discussed. Studies are related to the physical phenomena existing in different processes in NPPs, such as rewetting of the fuel rods, emergency core cooling (ECC), natural circulation, small break loss-of-coolant accidents (SBLOCA), non-condensable gas release and transport, and passive safety systems. Studies on both VVER and advanced light water reactor (ALWR) systems are included. The set of cases include separate effects tests for understanding and modeling a single physical phenomenon, separate effects tests to study the behavior of a NPP component or a single system, and integral tests to study the behavior of the whole system. In the studies following steps can be found, not necessarily in the same study. Experimental studies as such have provided solutions to existing design problems. Experimental data have been created to validate a single model in a computer code. Validated models are used in various transient analyses of scaled facilities or NPPs. Integral test data are used to validate the computer codes as whole, to see how the implemented models work together in a code. In the final stage test results from the facilities are transferred to the NPP scale using computer codes. Some of the experiments have confirmed the expected behavior of the system or procedure to be studied; in some experiments there have been certain unexpected phenomena that have caused changes to the original design to avoid the recognized problems. This is the main motivation for experimental studies on thermal hydraulics of the NPP safety systems. Naturally the behavior of the new system designs have to be checked with experiments, but also the existing designs, if they are applied in the conditions that differ from what they were originally designed for. New procedures for existing reactors and new safety related systems have been developed for new nuclear power plant concepts. New experiments have been continuously needed.

Enzyme convertedstarch in pigment coating

Tämän diplomityön tavoitteena oli selvittää entsyymikonvertoinnin mahdollisuudet vaikuttaa sideainetärkkelyksen toiminnallisiin ominaisuuksiin. Tärkein tehtävä oli etsiä vastaukset kysymykseen, kuinka paljon entsyymikonvertointia optimoimalla voidaan maksimoida tärkkelyksen positiivisia vaikutuksia. Tavoitteena oli myös tutkia, voiko lisäaineita käyttämällä ja tärkkelystä plastisoimalla säilyttää tärkkelyksen vaikutus paperin jäykkyyteen ja saada tärkkelysfilmille joustavuutta. Kirjallisuusosassa tarkasteltiin tärkkelyksen entsyymikonvertointiin vaikuttavia tekijöitä, eri tärkkelysraaka-aineiden eroja, sekä konvertoinnissa käytettävien entsyymien ominaisuuksia. Kirjallisuusosassa tarkasteltiin myöstärkkelyksen käyttöä sideaineena pigmenttipäällystyksessä. Kokeellisessa osassakeskityttiin selvittämään entsyymikonvertoinnin olosuhteiden, käytettävän raakatärkkelyksen ja entsyymin vaikutusta konvertoidun tärkkelyksen ominaisuuksiin. Konvertoiduista tärkkelyksistä valmistettiin päällystyspastat, ja tutkittiin niinpastan kuin päällystetyn paperin ominaisuuksia. Myös erilaisten pehmentimien vaikutusta niin päällystyspastaan, kuin paperin pinnalle tutkittiin. Havaittiin, että konvertoimalla tärkkelysketjua entsymaattisesti, voidaan tärkkelysketjun pituutta säädellä. Tarkoituksena oli konvertoida tärkkelystä niin, että tärkkelyksen molekyyliketjujakaumat sisältävät lyhyitä, keskipitkiä sekäpitkiä molekyylejä. Päällystämisen havaittiin olevan vaikeaa Helicoaterilla varsinkin pitkäketjuista tärkkelystä suuren määrän sisältävillä pastoilla. Myös tärkkelys/lateksi-suhde vaihteli eri pastoilla. Päällystyspastojen reologisia ominaisuuksia testattaessa huomattiin, että tärkkelysketjun pituuden kasvaessa pastanviskositeetti lisääntyy ja vesiretentio vähenee. Havaittiin vain muutamia teknisiä paperiominaisuuksia, jotka korreloivat hyvin tärkkelysketjun pituuden kanssa. Näitä olivat kiilto, Gurley-Hill huokoisuus, taivutusvastus, taivutuspituus sekä IGT pintalujuus. Pehmentimien ei havaittu vaikuttavan moneenkaan paperin eri tekniseen ominaisuuteen. Suurimmat erot huomattiin paperin taivutuspituudessa ja taivutusvastuksessa.

Validation Studies of Thermal-hydraulic Code for Safety Analysis of Nuclear Power Plants

This thesis gives an overview of the validation process for thermal hydraulic system codes and it presents in more detail the assessment and validation of the French code CATHARE for VVER calculations. Three assessment cases are presented: loop seal clearing, core reflooding and flow in a horizontal steam generator. The experience gained during these assessment and validation calculations has been used to analyze the behavior of the horizontal steam generator and the natural circulation in the geometry of the Loviisa nuclear power plant. The cases presented are not exhaustive, but they give a good overview of the work performed by the personnel of Lappeenranta University of Technology (LUT). Large part of the work has been performed in co-operation with the CATHARE-team in Grenoble, France. The design of a Russian type pressurized water reactor, VVER, differs from that of a Western-type PWR. Most of thermal-hydraulic system codes are validated only for the Western-type PWRs. Thus, the codes should be assessed and validated also for VVER design in order to establish any weaknesses in the models. This information is needed before codes can be used for the safety analysis. Theresults of the assessment and validation calculations presented here show that the CATHARE code can be used also for the thermal-hydraulic safety studies for VVER type plants. However, some areas have been indicated which need to be reassessed after further experimental data become available. These areas are mostly connected to the horizontal stem generators, like condensation and phase separation in primary side tubes. The work presented in this thesis covers a large numberof the phenomena included in the CSNI code validation matrices for small and intermediate leaks and for transients. Also some of the phenomena included in the matrix for large break LOCAs are covered. The matrices for code validation for VVER applications should be used when future experimental programs are planned for code validation.