The effect of microfibrillated cellulose addition on drying shrinkage and dimensional stability of wood-free paper

Microfibrillated cellulose (MFC) is known to enhance strength properties of paper. Improved strength usually means increased bonding which is strongly connected to dimensional instability of paper. Dimensional instability is due to changes in moisture content of paper; when paper is moistened it expands and when dried, it shrinks. Hygroexpansion is linked to end-use problems and excessive drying shrinkage consumes strength potential. Effective use of materials requires controlling of these phenomena. There isn’t yet data concerning dimensional stability of papers containing MFC which restricts wider use of MFC. Main objective of the work was to evaluate dimensional stability of wood-free paper containing different amounts of MFC. Sheets were dried with different methods to see how drying strains effected on drying shrinkage and hygroexpansion. Also tensile strength was measured to find out the effect of MFC. Results were compared to sheets containing kraft fines and in some test points cationic starch was used alongside with MFC. MFC increased the dimensional instability of freely dried sheets. As the amounts of MFC increased the effects on dimensional stability became more severe. However the fineness of MFC didn’t play any important role. Both hygroexpansion and drying shrinkage were decreased with cationic starch addition. Prevention of drying shrinkage over powered the effects of additives on hygroexpansion. Tensile strength improved up till 7 % addition amount which could be set as the upper limit of MFC addition when paper preparation and tensile strength are concerned.

Pellettien laatu ja ominaisuudet eri raaka-aineilla ja niiden seoksilla

Diplomityö tehtiin osana Vapon toteuttamaa monivuotista pelletin kehitysohjelmaa. Kehitysohjelma koostuu useista pienemmistä osaprojekteista, jotka täydentävät toinen toisiaan. Pellettien raaka-ainepohjan laajentaminen on eräs näistä osaprojekteista. Tutkimustyön tavoitteena oli selvittää erilaisten potentiaalisten bioraaka-aineiden soveltuvuutta pelletointiin joko sellaisenaan tai erilaisina seoksina. Raaka-aineiden pelletoitavuutta tutkittiin kenttäolosuhteissa mobiilipelletointilaitoksella. Laitoksen pääkomponentit muodostivat Kahl C 38–780 tasomatriisipuristin, jäähdytin ja täryseula. Pelletointikokeissa tutkittuja raaka-aineita olivat mäntysahanpuru, männynkuori, harvennusranka, haapa, koivu, jyrsinturve ja ruokohelpi. Raaka-aineiden irtotiheys käyttökosteudessa vaihteli välillä 73–244 kg/m3 ja keskimääräinen kosteuspitoisuus 6,5–15 %. Useissa tapauksissa säkitettyjä raaka-aineita säkkikostutettiin haluttuun kosteuspitoisuuteen ennen pelletointia. Säkkikostutettujen raaka-aineiden kosteuspitoisuudet vaihtelivat tällöin välillä 12–14 m- %. Valtaosa tutkituista raaka-aineista ja niiden seoksista pystyttiin pelletoimaan puristimen matriisilla 8/40 mm, jossa puristuskanavan halkaisija oli 8 mm ja kanavan suoran osan pituus 40 mm. Vaikeuksia tuotti ainoastaan pelkän koivupurun ja ruokohelven pelletointi. Käytetty matriisi oli kanavapituudeltaan liian pitkä koivupurun pelletointiin nostaen puristusvastuksen suureksi. Ruokohelven pelletoinnin vaikeudet johtuivat pääasiassa pelletointiin liian karkeasta raaka-aineesta. Myös matriisia 8/55 mm kokeiltiin, mutta se osoittautui liian ”tiukaksi” valtaosalle puuraaka-aineista. Ainoastaan jyrsinturpeen pelletointi onnistui tällä matriisilla. Männynkuoren pelletointia ei matriisilla 8/55 mm yritetty. Kenttäkokeissa valmistetuista pelleteistä määritettiin erilaisia ominaisuuksia, kuten keskipituus, kosteuspitoisuus, irtotiheys, hienoaineksen määrä ja käsittelykestävyys. Lujuus mitattiin sekä Ligno-testillä että CEN-rummutuslujuuden määrityksellä. Lisäksi pelleteille määritettiin alkuaineanalyysi, tuhkapitoisuus ja lämpöarvo ENAS Oy:n laboratoriossa Jyväskylässä. Ligno-testauksessa parhaimman luokan pelletin tulee yltää arvoon 97,5 %. Pelletoitaessa raaka-aineita ja niiden seoksia tasomatriisikoneella sopivalla matriisilla yllettiin usein näihin tai parempiin tuloksiin. Puumateriaaleilla raaka-aineen optimaalinen lähtökosteus oli välillä 12–14 m- % ja turpeella sekä ruokohelvellä 14–16 m- %. Pelletointi onnistui tällöin vaivattomasti, kunhan sopivat puristimen ajoparametrit oli löydetty. Pellettiä alkoi muodostua matriisin puristuskanavien lämpötilan kohotessa noin 70 ºC. Pellettien lämpötila stabiilitilanteessa heti pelletoinnin jälkeen oli useissa tapauksissa 80–90 ºC. Pelletoinnin aikainen tehontarve vaihteli välillä 90–150 kWh/t, ollen suurimmillaan irtotiheydeltään keveillä materiaaleilla. Raaka-aineen suuri partikkelikoko kasvatti puristimen tehontarvetta. Tämä havaittiin selvästi lisättäessä karkeaa ruokohelpisilppua eri raaka-aineiden joukkoon. Kestävyydeltään erinomaisia pellettejä saatiin, kun raaka-aineena oli jyrsinturve, harvennusranka tai mäntypuru. Varsinkin jyrsinturpeen ja harvennusrangan seoksesta valmistetut pelletit osoittautuivat erittäin kestäviksi. Myös jyrsinturpeen ja ruokohelven sekä mäntypurun ja ruokohelven seoksien pelleteille määritettiin hyviä kestävyysarvoja. Männynkuoresta valmistetut pelletit jäivät Ligno-testauksessa kestävyydeltään alle 97,5 % rajan. Pääsyynä tähän oli kuoren pelletointiin käytetyn matriisin 8/40 mm liian lyhyet puristuskanavat.

Leniency - Kartellin ilmiantaminen ja seuraamusmaksusta vapautuminen tai sen alentaminen oikeustaloustieteellisestä näkökulmasta tarkasteltuna

The purpose of the study is to solve contents, functioning and potential improvements of European Union and Finlands leniency-system that is to say amnesty and reduction system from fines imposed from cartel activity. Law and economics was chosen as a research method, which has made possible to handle the subject in a comprehensive perspective. The study is based on literature, also legal cases, law and legislative history have been used as help. Leniency is a reasonably new system both in European Unions and in Finlands competition law. It makes possible to detect even secret cartels with the help of deterrent aimed at them. Companies experience the large amount of fines and the investigation concerning the cartel as big threats, therefore they all want to be the first one to report it in order to get full amnesty. However, this system needs improvements, for instance improving the transparency, unifying the European Unions leniency applications and finding answers to certain question concerning justice.

Non-wood massojen vedenpoiston arvioiminen märkäpuristuksessa

Yksivuotisten kasvien (non-wood) kuitua verrataan usein lehtipuukuituihin. Käytetyimpiä non-wood kasveja ovat vehnän olki, bambu, järviruoko ja bagassi. Non-wood massan erottaa puumassasta kuitenkin korkea silikaattipitoisuus sekä parenkyymisolupitoisuus, joka antaa massalle korkean hienoainepitoisuuden. Tämä yhdessä korkean hemiselluloosapitoisuuden ja lyhyen kuidun pituuden kanssa heikentävät voimakkaasti non-wood massan vedenpoisto-ominaisuuksia. Non-wood kuidulla voidaan korvata lehtipuumassaa hienopapereissa. Non-wood kuitu antaa paperille hyvän opasiteetin, korkean valonsirontakertoimen sekä sileän painopinnan. Massaan lisättävä pitkäkuituinen havupuumassa parantaa ajetta¬vuutta paperikoneella ja helpottaa massan vedenpoistoa. Non-wood massan vedenpoistoa voidaan tehostaa esimerkiksi poistamalla osa hienoaineesta, käyttämällä non-wood massalle sopivaa keittotapaa sekä käyttämällä märkä¬puristuksessa pitkänippityyppistä puristinratkaisua. Myös non-wood kuidun kuivaaminen parantaa vedenpoistoa. Tässä tutkimuksessa kirjallisuusosassa keskityttiin yleisimpiin paperin valmistuksessa käytettäviin non-wood kuidun lähteisiin, märkäpuristuksen teoriaan ja tapoihin tehostaa vedenpoistoa. Kokeellisessa osassa tutkittiin vehnänolkimassan käyttäytymistä märkäpuristuksessa erilaisten ominaisuuksien pohjalta. Tutkimuksen kohteena oli non-wood massan keittotapa (hapan/alkali), hienoainepitoisuus, silikaattipitoisuus sekä kuivattu/kuivaamaton kuitu. Vertailun vuoksi tutkimuksessa oli mukana myös yksi järviruokomassa. Tuloksista huomataan, että non-wood massan vedenpoistoon vaikuttaa hienoainepitoisuus, kuidun kuivaus sekä massan valmistustapa. Järviruokomassan veden¬poisto on tehokkaampaa kuin vehnänolkimassan paremman kuitu¬koostumuksensa takia. Jos hienopaperimassassa korvataan lehtipuumassaa non-wood kuidulla maksimissaan 40 %, massan vedenpoistoa voidaan hyvin arvioida erilaisten suotautuvuusmittojen, kuten freeneksen, vedenpidätyskyvyn ja suotautumisajan, avulla.

LWC-paperin opasiteetin parantaminen

LWC-syväpainopaperilta vaaditaan hyvän ajettavuuden, kiillon ja sileyden ohella hyvää opasiteettia. Tämä on asettanut haasteita LWC-paperin valmistajille paperin neliömassojen laskiessa. Tässä diplomityössä etsittiin keinoja parantaa kevyiden LWC-syväpainolajien opasiteettia heikentämättä oleellisesti muita tärkeitä paperin ominaisuuksia. Tavoitteena oli nostaa CR48-lajin opasiteetti tavoitearvoon 90 %. Työn kirjallisuusosassa perehdyttiin paperin optisten ominaisuuksien teoriaan sekä raaka-aineisiin ja prosessin osiin, joilla on vaikutusta paperin opasiteettiin. Työn kokeellisessa osassa tutkittiin olemassa olevan aineiston perusteella tekijöitä, joilla uskottiin olevan vaikutusta CR48-lajin opasiteettiin. Tutkimuksen ja kirjallisuuden perusteella ajettiin tehdaskoeajoa, joiden avulla pyrittiin parantamaan paperin opasiteettia. CR48-lajin opasiteettitavoite saavutettiin kolmella eri tavalla. Opasiteettitavoite saavutettiin, kun paperin vaaleus säädettiin tavoitearvoon pigmenttivärin avulla tumman hierteen sijasta. Tällöin väripigmentin määrää päällystyspastassa nostettiin 0,01 osaa ja valkaistun hierteen osuus kokonaishierteen määrästä oli 100 %. Vaaleuden säätö pastavärillä oli käytännössä hidasta ja hankalaa. Opasiteettitavoite saavutettiin myös, kun hierre jauhettiin täysin koeterillä. Koeterillä tapahtuva jauhatus oli rajumpaa ja katkovampaa kuin perinteisillä terillä, joten hienoaineen lisääntyminen ja kuidun lyheneminen paransivat paperin opasiteettia, mutta lujuudet huononivat. Lisäksi tavoiteopasiteetti saavutettiin, kun sellun osuutta vähennettiin 8 %-yksikköä. Lujuuden säilymisen kannalta sellun vähennys oli parempi keino opasiteetin parantamiseksi kuin hierteen jauhaminen koeterillä. Koeajojen perusteella pohjapaperin tuhkapitoisuuden nostolla ja hierteen CSF-luvun alentamisella ei ollut vaikutusta paperin opasiteettiin. Lisäksi 100 %:nen koeterillä jauhettu sahahakehierre antoi paperille huonomman opasiteetin kuin hierre, josta puolet oli jauhettu koeterillä ja raaka-aineesta 25 % oli sahahaketta.

Selective leaching of multimetal tailings

Depletion of high grade mineral resources, tightening of environmental regulations and the environmental impact of acid mine drainage caused by sulfidic minerals continuously increase the interest in processing tailings and other mine waste. Treating waste requires additional capital and operational input, but the decrease in size and need of tailings ponds and permits decrease the overall costs. Treatment and utilization of the tailings could also bring added revenue by the recovery of valuables. Leaching of metal sulfides is very demanding and time consuming and hence process conditions need to be carefully optimized. The leaching of sulfides is affected by for example the choice of leaching agent, its concentration and temperature, pH, the redox potential, pressure, pulp density and particle size distribution. With reference to the mine case study the leaching of nickel and copper sulfides, especially the primary minerals pentlandite and chalcopyrite were investigated. Leaching behavior and recoveries for nickel, copper and iron were found out by sulfuric and citric acid leaching experiments using tailings samples of high and low sulfur content. Moderate recoveries were obtained and citric acid seemed more attractive. Increase in temperature and decrease in pulp density had positive effect on the recovery and pH was also proven to have a significant effect on the recovery of valuables. The rate determining step was determined through kinetic modeling in case of all valuables separately. Leaching was controlled by diffusion. The investigated multimetal tailing showed moderate potential in recovering of metal valuables from low grade tailing deposits. The process conditions should however be further optimized.

The Effects of Some Furnish and Paper Structure Related Factors on Wet Web Tensile and Relaxation Characteristics

The objective of this thesis was to identify the effects of different factors on the tension and tension relaxation of wet paper web after high-speed straining. The study was motivated by the plausible connection between wet web mechanical properties and wet web runnability on paper machines shown by previous studies. The mechanical properties of wet paper were examined using a fast tensile test rig with a strain rate of 1000%/s. Most of the tests were carried out with laboratory handsheets, but samples from a pilot paper machine were also used. The tension relaxation of paper was evaluated as the tension remaining after 0.475 s of relaxation (residual tension). The tensile and relaxation properties of wet webs were found to be strongly dependent on the quality and amount of fines. With low fines content, the tensile strength and residual tension of wet paper was mainly determined by the mechanical interactions between fibres at their contact points. As the fines strengthen the mechanical interaction in the network, the fibre properties also become important. Fibre deformations caused by the mechanical treatment of pulp were shown to reduce the mechanical properties of both dry and wet paper. However, the effect was significantly higher for wet paper. An increase of filler content from 10% to 25% greatly reduced the tensile strength of dry paper, but did not significantly impair wet web tensile strength or residual tension. Increased filler content in wet web was shown to increase the dryness of the wet web after the press section, which partly compensates for the reduction of fibrous material in the web. It is also presumable that fillers increase entanglement friction between fibres, which is beneficial for wet web strength. Different contaminants present in white water during sheet formation resulted in lowered surface tension and increased dryness after wet pressing. The addition of different contaminants reduced the tensile strength of the dry paper. The reduction of dry paper tensile strength could not be explained by the reduced surface tension, but rather on the tendency of different contaminants to interfere with the inter-fibre bonding. Additionally, wet web strength was not affected by the changes in the surface tension of white water or possible changes in the hydrophilicity of fibres caused by the addition of different contaminants. The spraying of different polymers on wet paper before wet pressing had a significant effect on both dry and wet web tensile strength, whereas wet web elastic modulus and residual tension were basically not affected. We suggest that the increase of dry and wet paper strength could be affected by the molecular level interactions between these chemicals and fibres. The most significant increases in dry and wet paper strength were achieved with a dual application of anionic and cationic polymers. Furthermore, selectively adding papermaking chemicals to different fibre fractions (as opposed to adding chemicals to the whole pulp) improved the wet web mechanical properties and the drainage of the pulp suspension.

Effect of pulps fractionation on formation and strength properties of laboratory hand sheets

The objectives of the work were to study the effect of dewatering time varying on formation properties of papersheets, to determine the role of fines fraction in creation of paper with good formation and strength properties of papersheets, and also to study the effect of charge modification of fibers fractionations on formation properties of handsheets. The paper formation is one of the most important structural properties of paper. This property has effect on physical and optical characteristics of paper. In thi work the effect of formation on tensile strength was determined. The formation properties were analyzed by using the AMBERTEC Beta Formation Tester. The PAM addition as a f;locculant agent did some changes in the formation of paper. Paper sheets were also made from different furnishes of both birch and pine pulps. The fibers particles as a fines have great effect on drainability changes. Fines fraction played important role in papermaking. The two kinds of pulps (pine and birch pulps) were also used in this work for investigation of fines role. As it was expected the fines fraction gave positive effect on paper formation, but when fines fraction was added above initial fines content the formation of paper was deteriorated. The effect of paper formation on tensile strength was also determined. In many cases the poor formation of paper had negative effect on strength properties of paper..

Topochemistry of physical and chemical pretreatments of biomass as investigated by FE-SEM, XPS and ToF-SIMS

Surface chemistry is of great importance in plant biomass engineering and applications. The surface chemical composition of biomass which includes lignin, carbohydrates and extractives influences its interactions with chemical agents, such as pulp processing/papermaking chemicals, or enzymes for different purposes. In this thesis, the changes in the surface chemical composition of lignocellulosic biomass after physical modification for the improvement of resulting paper properties and chemical treatment for the enhancement of enzymatic hydrolysis were investigated. Low consistency (LC) refining was used as physical treatment of bleached softwood and hardwood pulp samples, and the surface chemistry of refined samples was investigated. The refined pulp was analysed as whole pulp while the fines-free fibre samples were characterized separately. The fines produced in LCrefining contributed to an enlarged surface specific area as well as the change of surface coverage by lignin and extractives, as investigated by X-ray photoelectron spectroscopy (XPS). The surface coverage by lignin of the whole pulp decreased after refining while the surface coverage by extractives increased both for pine and eucalyptus. In the case of pine, the removal of fines resulted in reduction of the surface coverage by extractives, while the surface coverage by lignin increased on fibre sample (without fines). In the case of eucalyptus, the surface coverage by lignin of fibre samples decreased after the removal of fines. In addition, the surface distribution of carbohydrates, lignin and extractives of pine and eucalyptus samples was determined by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). LC-refining increased the amounts of pentose, hexose and extractives on the surface of pine samples. ToF-SIMS also gave clear evidence about xylan deposition and reduction of surface lignin distribution on the fibre of eucalyptus. However, the changes in the surface chemical composition during the physical treatment has led to an increase in the adsorption of fluorescent whitening agents (FWAs) on fibres due to a combination of electro-static forces, specific surface area of fibres and hydrophobic interactions. Various physicochemical pretreatments were conducted on wood and non-wood biomass for enhancing enzymatic hydrolysis of polysaccharides, and the surface chemistry of the pretreated and enzymatically hydrolysed samples was investigated by field emission scanning electron microscopy (FE-SEM), XPS and ToF-SIMS. A hydrotrope was used as a relatively novel pretreatment technology both in the case of wood and non-wood biomass. For comparison, ionic liquid and hydrothermal pretreatments were applied on softwood and hardwood as well. Thus, XPS analysis showed that the surface lignin was more efficiently removed by hydrotropic pretreatment compared to ionic liquid or hydrothermal pretreatments. SEM analysis also found that already at room temperature the ionic liquid pretreatments were more effective in swelling the fibres compared with hydrotropic pretreatment at elevated temperatures. The enzymatic hydrolysis yield of hardwood was enhanced due to the decrease in surface coverage of lignin, which was induced by hydrotropic treatment. However, hydrotropic pretreatment was not appropriate for softwood because of the predominance of guaiacyl lignin structure in this material. In addition, the reduction of surface lignin and xylan during pretreatment and subsequent increase in cellulose hydrolysis by enzyme could be observed from ToF-SIMS results. The characterisation of the non-wood biomass (e.g. sugarcane bagasse and common reed) treated by hydrotropic method, alkaline and alkaline hydrogen peroxide pretreatments were carried out by XPS and ToF-SIMS. According to the results, the action for the removal of the surface lignin of non-wood biomass by hydrotropic pretreatment was more significant compared to alkaline and alkaline hydrogen peroxide pretreatments, although a higher total amount of lignin could be removed by alkaline and alkaline hydrogen peroxide pretreatment. Furthermore, xylan could be remarkably more efficiently removed by hydrotropic method. Therefore, the glucan yield achieved from hydrotropic treated sample was higher than that from samples treated with alkaline or alkaline hydrogen peroxide. Through the use of ToF-SIMS, the distribution and localization of lignin and carbohydrates on the surface of ignocelluloses during pretreatment and enzymatic hydrolysis could be detected, and xylan degradation during enzymatic hydrolysis could also be assessed. Thus, based on the results from XPS and ToF-SIMS, the mechanism of the hydrotropic pretreatment in improving the accessibility of enzymes to fibre and further ameliorating of the enzymatic saccharification could be better elucidated.