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.

Internet-markkinoinnin kehittäminen: Case Outotec HSC Chemistry

Kandidaatintyö käsittelee ohjelmistojen markkinointia internetissä ja markkinoinnin mittaamista. Työssä esitellään internetin eri markkinointikanavat käsitellen niiden toteutustapoja, vahvuuksia ja heikkouksia sekä kustannuksia. Internet-markkinoinnin mittaamisesta käsitellään erilaisia tunnuslukuja sekä mittaamisen käyttökohteita. Työ on pääasiassa kirjallisuuskatsaus, mutta samalla myös case: työssä käsitellään Outotecin toimeksiannosta sen kehittämän HSC Chemistry -ohjelmiston markkinointia internetissä. Työn tuloksissa suositellaan HSC Chemistrylle sopivia markkinointikanavia ja niiden kustannuksia. Lisäksi arvioidaan käsiteltyjen mittaamistapojen soveltuvuutta ohjelmiston tapauksessa.

Enhancement of ultrafiltration process by pretreatment in recovery of hemicelluloses from wood extracts

Hemicelluloses are potential raw material for several items produced in future wood-based biorefineries. One possible method for recovering hemicelluloses from wood extracts is ultrafiltration (UF). However, low filtration capacities and severe fouling restrict the use of tight UF membranes in the treatment of wood extracts. The lack of suitable commercial membranes creates a need for pretreatment which would decrease fouling and increase the filtration capacity. This thesis focuses on the evaluation of the possibility to improve the filtration capacity and decrease fouling with the pretreatment of wood extracts. Methods which remove harmful compounds and methods which degrade them are studied, as well as combinations of the methods. The tested pretreatments have an influence on both the concentration of different compounds and the molecular mass distribution of the compounds in the extract. This study revealed that in addition to which kind of compounds were removed, also the change in molecular size distribution affected the filtration capacity significantly. It was shown that the most harmful compounds for the filtration capacity of the hydrophobic 5 kDa membrane were the ones capable of permeating the membrane and fouling also the inner membrane structure. Naturally, the size of the most harmful compounds depends on the used UF membrane and is thus case-specific. However, in the choice of the pretreatment method, the focus should be on the removal of harmful compound sizes rather than merely on the total amount of removed foulants. The results proved that filtration capacity can be increased with both adsorptive and oxidative pretreatments even by hundreds of per cents. For instance, the use of XAD7 and XAD16 adsorbents increased the average flux in the UF of a birch extract from nearly zero to 107 kg/(m2h) and 175 kg/(m2h), respectively. In the treatment of a spruce extract, oxidation by pulsed corona discharge (PCD) increased the flux in UF from 46 kg/(m2h) to 158 kg/(m2h). Moreover, when a birch extract batch was treated with laccase enzyme, the flux in UF increased from 15 kg/(m2h) to 36 kg/(m2h). However, fouling was decreased only by adsorptive pretreatment while oxidative methods had a negligible or even negative impact on it. This demonstrates that filtration capacity and fouling are affected by different compounds and mechanisms. The results of this thesis show that filtration capacity can be improved and fouling decreased through appropriate pretreatment. However, the choice of the best possible pretreatment is case-specific and depends on the wood extract and the membrane used. Finding the best option requires information on the extract content and membrane characteristics as well as on the filtration performance of the membrane in the prevailing conditions and a multivariate approach. On the basis of this study, it can be roughly concluded that adsorptive pretreatment improves the filtration capacity and decreases fouling rather reliably, but it may lead to significant hemicellulose losses. Oxidation reduces the loss of valuable hemicelluloses and could improve the filtration capacity, but fouling challenges may remain. Combining oxidation with adsorptive pretreatment was not a solution for avoiding hemicellulose losses in the tested cases.

Chemical changes in biomass during torrefaction

Torrefaction is moderate thermal treatment (~200-300 °C) of biomass in an inert atmosphere. The torrefied fuel offers advantages to traditional biomass, such as higher heating value, reduced hydrophilic nature, increased its resistance to biological decay, and improved grindability. These factors could, for instance, lead to better handling and storage of biomass and increased use of biomass in pulverized combustors. In this work, we look at several aspects of changes in the biomass during torrefaction. We investigate the fate of carboxylic groups during torrefaction and its dependency to equilibrium moisture content. The changes in the wood components including carbohydrates, lignin, extractable materials and ashforming matters are also studied. And at last, the effect of K on torrefaction is investigated and then modeled. In biomass, carboxylic sites are partially responsible for its hydrophilic characteristic. These sites are degraded to varying extents during torrefaction. In this work, methylene blue sorption and potentiometric titration were applied to measure the concentration of carboxylic groups in torrefied spruce wood. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic group contents. Thus, both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction. This provides new information to the chemical changes occurring during torrefaction. The effect of torrefaction temperature on the chemistry of birch wood was investigated. The samples were from a pilot plant at Energy research Center of the Netherlands (ECN). And in that way they were representative of industrially produced samples. Sugar analysis was applied to analyze the hemicellulose and cellulose content during torrefaction. The results show a significant degradation of hemicellulose already at 240 °C, while cellulose degradation becomes significant above 270 °C torrefaction. Several methods including Klason lignin method, solid state NMR and Py-GC-MS analyses were applied to measure the changes in lignin during torrefaction. The changes in the ratio of phenyl, guaiacyl and syringyl units show that lignin degrades already at 240 °C to a small extent. To investigate the changes in the extractives from acetone extraction during torrefaction, gravimetric method, HP-SEC and GC-FID followed by GC-MS analysis were performed. The content of acetone-extractable material increases already at 240 °C torrefaction through the degradation of carbohydrate and lignin. The molecular weight of the acetone-extractable material decreases with increasing the torrefaction temperature. The formation of some valuable materials like syringaresinol or vanillin is also observed which is important from biorefinery perspective. To investigate the change in the chemical association of ash-forming elements in birch wood during torrefaction, chemical fractionation was performed on the original and torrefied birch samples. These results give a first understanding of the changes in the association of ashforming elements during torrefaction. The most significant changes can be seen in the distribution of calcium, magnesium and manganese, with some change in water solubility seen in potassium. These changes may in part be due to the destruction of carboxylic groups. In addition to some changes in water and acid solubility of phosphorous, a clear decrease in the concentration of both chlorine and sulfur was observed. This would be a significant additional benefit for the combustion of torrefied biomass. Another objective of this work is studying the impact of organically bound K, Na, Ca and Mn on mass loss of biomass during torrefaction. These elements were of interest because they have been shown to be catalytically active in solid fuels during pyrolysis and/or gasification. The biomasses were first acid washed to remove the ash-forming matters and then organic sites were doped with K, Na, Ca or Mn. The results show that K and Na bound to organic sites can significantly increase the mass loss during torrefaction. It is also seen that Mn bound to organic sites increases the mass loss and Ca addition does not influence the mass loss rate on torrefaction. This increase in mass loss during torrefaction with alkali addition is unlike what has been found in the case of pyrolysis where alkali addition resulted in a reduced mass loss. These results are important for the future operation of torrefaction plants, which will likely be designed to handle various biomasses with significantly different contents of K. The results imply that shorter retention times are possible for high K-containing biomasses. The mass loss of spruce wood with different content of K was modeled using a two-step reaction model based on four kinetic rate constants. The results show that it is possible to model the mass loss of spruce wood doped with different levels of K using the same activation energies but different pre-exponential factors for the rate constants. Three of the pre-exponential factors increased linearly with increasing K content, while one of the preexponential factors decreased with increasing K content. Therefore, a new torrefaction model was formulated using the hemicellulose and cellulose content and K content. The new torrefaction model was validated against the mass loss during the torrefaction of aspen, miscanthus, straw and bark. There is good agreement between the model and the experimental data for the other biomasses, except bark. For bark, the mass loss of acetone extractable material is also needed to be taken into account. The new model can describe the kinetics of mass loss during torrefaction of different types of biomass. This is important for considering fuel flexibility in torrefaction plants.

Tuotannon- ja materiaalinsuunnittelu ja sen ennustaminen Metsä Wood:n Suolahden koivuvaneritehtaalla

Tässä diplomityössä tutkitaan Metsä Woodin Suolahden koivuvaneritehtaan toimitustarkkuuteen negatiivisesti vaikuttavia tekijöitä. Tarkoituksena on löytää ne ongelmakohdat, mitkä heijastuvat toimitusten myöhästymisenä sekä muutostekijät, mitkä vaikuttavat toimitusviikon myöntämiseen. Lisäksi työssä kartoitetaan kuinka hyvin tietoa ja informaatiota on tarjolla sitä tarvitseville henkilöstötahoille. Teoriaosuudessa tarkastellaan tuotannonsuunnitteluun liittyviä teorioita sekä tiedon liikkumista organisaation sisällä. Työssä kuvataan Suolahden koivuvaneritehtaan nykyinen vanerin valmistusprosessi ja tuotannonsuunnittelu. Varsinainen tutkimustyö suoritetaan laadullisia tutkimusmenetelmiä hyväksikäyttäen. Tulosten tarkastelussa käsitellään työn aikana tapahtuneita muutoksia ja ongelmakohtia sekä analysoidaan kyselytutkimuksen tuloksia ja tulosten luotettavuutta. Yhteenvedossa esitetään pääongelmakohdat ja niiden ratkaisut ja esitetään uusia mielenkiintoisia jatkotutkimusaiheita.

Wood species identification by visual characterization of fibers

Kandidaatintyö tehtiin osana PulpVision-tutkimusprojektia, jonka tarkoituksena on kehittää kuvapohjaisia laskenta- ja luokittelumetodeja sellun laaduntarkkailuun paperin valmistuksessa. Tämän tutkimusprojektin osana on aiemmin kehitetty metodi, jolla etsittiin kaarevia rakenteita kuvista, ja tätä metodia hyödynnettiin kuitujen etsintään kuvista. Tätä metodia käytettiin lähtökohtana kandidaatintyölle. Työn tarkoituksena oli tutkia, voidaanko erilaisista kuitukuvista laskettujen piirteiden avulla tunnistaa kuvassa olevien kuitujen laji. Näissä kuitukuvissa oli kuituja neljästä eri puulajista ja yhdestä kasvista. Nämä lajit olivat akasia, koivu, mänty, eukalyptus ja vehnä. Jokaisesta lajista valittiin 100 kuitukuvaa ja nämä kuvat jaettiin kahteen ryhmään, joista ensimmäistä käytettiin opetusryhmänä ja toista testausryhmänä. Opetusryhmän avulla jokaiselle kuitulajille laskettiin näitä kuvaavia piirteitä, joiden avulla pyrittiin tunnistamaan testausryhmän kuvissa olevat kuitulajit. Nämä kuvat oli tuottanut CEMIS-Oulu (Center for Measurement and Information Systems), joka on mittaustekniikkaan keskittynyt yksikkö Oulun yliopistossa. Yksittäiselle opetusryhmän kuitukuvalle laskettiin keskiarvot ja keskihajonnat kolmesta eri piirteestä, jotka olivat pituus, leveys ja kaarevuus. Lisäksi laskettiin, kuinka monta kuitua kuvasta löydettiin. Näiden piirteiden eri yhdistelmien avulla testattiin tunnistamisen tarkkuutta käyttämällä k:n lähimmän naapurin menetelmää ja Naiivi Bayes -luokitinta testausryhmän kuville. Testeistä saatiin lupaavia tuloksia muun muassa pituuden ja leveyden keskiarvoja käytettäessä saavutettiin jopa noin 98 %:n tarkkuus molemmilla algoritmeilla. Tunnistuksessa kuitujen keskimäärinen pituus vaikutti olevan kuitukuvia parhaiten kuvaava piirre. Käytettyjen algoritmien välillä ei ollut suurta vaihtelua tarkkuudessa. Testeissä saatujen tulosten perusteella voidaan todeta, että kuitukuvien tunnistaminen on mahdollista. Testien perusteella kuitukuvista tarvitsee laskea vain kaksi piirrettä, joilla kuidut voidaan tunnistaa tarkasti. Käytetyt lajittelualgoritmit olivat hyvin yksinkertaisia, mutta ne toimivat testeissä hyvin.

Research progress in wood-plastic composites: A review

The interest towards wood-plastic composites (WPCs) is growing due to growing interest in materials with novel properties, which can replace more traditional materials, such as wood and plastic. The use of recycled materials in manufacture is also a bonus. However, the application ofWPCs has been limited because of their often poor mechanical and barrier properties, which can be improved by incorporation of the reinforcing fillers. Nanosized fillers, having a large surface area, can significantly increase interfacial interactions in the composite on molecular level, leading to materials with new properties. The review summarizes the development trends in the use on nanofillers for WPC design, which were reported in accessible literature during the last decade. The effect of the nanofillers on the mechanical properties, thermal stability, flammability and wettability ofWPC is discussed.

Reorganising purchasing organisation – Case Metsä Wood

The purpose of this study is to investigate how a global company should organise its purchasing operations. The theoretical framework of this study consists of organisation structures, management and coordination, purchasing organisational design, capabilities and outsourcing. The research is a qualitative case study and the used method was theme interview. Four global large scale companies were interviewed for this research in order to gain knowledge about how other companies have organised their purchasing functions and to gather their best practices. Interview results and theoretical framework were compared in order to test the theoretical framework and to create a detailed framework about how to organise purchasing operations in a global company. As a result a 14 point model about effective purchasing operation organisation for a global company was created. This model includes all the key determinants which should be considered when organising the purchasing operations. The results show that the organising decision should be always in line with company and purchasing strategies. Strategic purchasing operations should be centralized and operative tasks decentralized.