Surface characterization of chemically modified fiber, wood and paper

Inorganic-organic sol-gel hybrid coatings can be used for improving and modifying properties of wood-based materials. By selecting a proper precursor, wood can be made water repellent, decay-, moisture- or UV-resistant. However, to control the barrier properties of sol-gel coatings on wood substrates against moisture uptake and weathering, an understanding of the surface morphology and chemistry of the deposited sol-gel coatings on wood substrates is needed. Mechanical pulp is used in production of wood-containing printing papers. The physical and chemical fiber surface characteristics, as created in the chosen mechanical pulp manufacturing process, play a key role in controlling the properties of the end-use product. A detailed understanding of how process parameters influence fiber surfaces can help improving cost-effectiveness of pulp and paper production. The current work focuses on physico-chemical characterization of modified wood-based materials with surface sensitive analytical tools. The overall objectives were, through advanced microscopy and chemical analysis techniques, (i) to collect versatile information about the surface structures of Norway spruce thermomechanical pulp fiber walls and understand how they are influenced by the selected chemical treatments, and (ii) to clarify the effect of various sol-gel coatings on surface structural and chemical properties of wood-based substrates. A special emphasis was on understanding the effect of sol-gel coatings on the water repellency of modified wood and paper surfaces. In the first part of the work, effects of chemical treatment on micro- and nano-scale surface structure of 1st stage TMP latewood fibers from Norway spruce were investigated. The chemicals applied were buffered sodium oxalate and hydrochloric acid. The outer and the inner fiber wall layers of the untreated and chemically treated fibers were separately analyzed by light microscopy, atomic force microscopy and field-emission scanning electron microscopy. The selected characterization methods enabled the demonstration of the effect of different treatments on the fiber surface structure, both visually and quantitatively. The outer fiber wall areas appeared as intact bands surrounding the fiber and they were clearly rougher than areas of exposed inner fiber wall. The roughness of the outer fiber wall areas increased most in the sodium oxalate treatment. The results indicated formation of more surface pores on the exposed inner fiber wall areas than on the corresponding outer fiber wall areas as a result of the chemical treatments. The hydrochloric acid treatment seemed to increase the surface porosity of the inner wall areas. In the second part of the work, three silane-based sol-gel hybrid coatings were selected in order to improve moisture resistance of wood and paper substrates. The coatings differed from each other in terms of having different alkyl (CH3–, CH3-(CH2)7–) and fluorocarbon (CF3–) chains attached to the trialkoxysilane sol-gel precursor. The sol-gel coatings were deposited by a wet coating method, i.e. spraying or spreading by brush. The effect of solgel coatings on surface structural and chemical properties of wood-based substrates was studied by using advanced surface analyzing tools: atomic force microscopy, X-ray photoelectron spectroscopy and time-of-flight secondary ion spectroscopy. The results show that the applied sol-gel coatings, deposited as thin films or particulate coatings, have different effects on surface characteristics of wood and wood-based materials. The coating which has a long hydrocarbon chain (CH3-(CH2)7–) attached to the silane backbone (octyltriethoxysilane) produced the highest hydrophobicity for wood and wood-based materials.

Physico-chemical characterization of nanoparticle coated paper

Förståelse av olika ytors vätningsegenskaper är viktig i många pappers-relaterade industriella processer eftersom vätningen påverkar materialbeteendet, t.ex. vid bestrykning, tryckning och laminering. Förmågan att kontrollera vätningen är av intresse, därför att den ger nya möjligheter till modifikation av ytor. Vätningen styrs av ytans struktur och kemi. Kunskap om dessa egenskaper krävs både i fundamentala studier och för industriella applikationer. Nanopartiklar används ofta för att skapa funktionella ytor med mångsidiga egenskaper. Detta arbete strävar till att förstå de fysikalisk-kemiska egenskaperna hos papper och kartong som är bestrukna med nanopartiklar, för att sedan kunna förklara de observerade förändringarna i ytornas vätningsförmåga. Funktionella ytor med justerbar vätningsförmåga tillverkades genom att deponera nanopartiklar i en rulle-till-rulle vätskeflammasprutningprocess (LFS). TiO2 -nanopartikelbeläggningen skapar en superhydrofob yta som har över 160° kontaktvinkelmed vatten, medan SiO2-nanopartikelbeläggningar skapar mycket hydrofila ytor med kontaktvinklar så låga som 21° med vatten. Superhydrofobiciteten eller hydrofiliteten är ett resultat av den kombinerade effekten hos ytstrukturen och ytkemin, såsom nanopartiklarnas oxidationsnivå eller karbonatiseringsnivå. Kartongytor som är bestrukna med TiO2-nanopartiklar kan vara såväl superhydrofoba som hydrofila. Hydrofilitet kan induceras genom UVA-strålning, medan behandling i hög temperatur i ugn resulterar i en superhydrofob yta. Ett mål med arbetet var att förstå mekanismerna hos de kemiska för ändringar som sker under UVA-bestrålning och värmebehandling av ytor, bestrukna med TiO2-nanopartiklar. Ytornas abrasions- och kompressionsmotstånd samt relaterade förändringar i funktionella egenskaper undersöktes. Resultaten skapar en bättre förståelse för potentiell användning av LFS-nanopartikelbeläggningar i pappersrelaterade applikationer. En förståelse för stabiliteten hos nanopartikelbeläggningarna när de exponeras för externa krafter är viktig för att försäkra deras funktionalitet i industriella applikationer och för att garantera beläggningarnas miljö-, hälso- och säkerhetsaspekter. ------------------------------------------ Pinnan kastumisominaisuuksien hallinta on tärkeää monissa paperiteollisuuden prosesseissa, sillä pinnan kastuminen vaikuttaa esimerkiksi päällystämiseen, painamiseen ja laminointiin. Pinnan kastuvuuden säätäminen avaa mielenkiintoisia uusia mahdollisuuksia pintojen ominaisuuksien hallintaan. Pinnan kastuvuus määräytyy pinnan rakenteesta ja kemiasta, ja näiden ominaisuuksien ymmärtäminen on tärkeää sekä perustutkimuksessa että teollisissa sovelluksissa. Nanopartikkeleita käytetään usein toiminnallisten ja hallitusti kastuvien pintojen aikaansaamiseksi. Tässä työssä on tarkasteltu nanopartikkelipinnoitetun paperin ja kartongin fysikaalis-kemiallisia pintaominaisuuksia, jotka selittävät havaittuja muutoksia pinnan kastuvuudessa. Toiminnalliset pinnat säädettävillä kastuvuusominaisuuksilla valmistettiin nesteliekkiruiskutus (LFS) nanopartikkelipinnoituksella rullalta rullalle-menetelmällä. TiO2-nanopartikkelipäällystys saa aikaan superhydrofobisen pinnan, jonka veden kontaktikulma on suurempi kuin 160°. Toisaalta SiO2-nanopartikkelipäällystys muuttaa pinnan hyvin hydrofiiliseksi, veden kontaktikulman ollessa vain 21°. Pinnan superhydrofobisuus tai hydrofiilisyys riippuu nanopartikkelipinnan rakenteesta ja pintakemiasta kuten pinnan hapettumisasteesta ja hiilipitoisuudesta. TiO2-nanopartikkelipinnoitetun kartonkipinnan kastumista voidaan säätää superhydrofobisen ja hydrofiilisen välillä. Pinnan hydrofiilisyys saadaan aikaan UVA-valolla, kun taas superhydrofobinen pinta voidaan palauttaa korkeassa lämpötilassa uunissa. Tämän työn tavoitteena oli selvittää, millaisia muutoksia TiO2-nanopartikkelipäällystetyn pinnan kemiassa tapahtuu UVA-valon ja lämpökäsittelyn vaikutuksesta. Työssä tarkasteltiin myös pinnan mekaanisen hankauksen ja kokoonpuristuksen vaikutusta toiminnallisiin ominaisuuksiin. Työssä saavutetut tulokset auttavat ymmärtämään LFS-nanopartikkelipäällystettyjen pintojen soveltuvuutta paperiin liittyvissä sovelluksissa. Nanopartikkelipäällystettyjen pintojen stabiilius ulkoisten voimien alaisena on tärkeää toiminnallisten päällystysten ympäristö-, terveys- ja turvallisuusnäkökulmia tarkasteltaessa.

Oxalic acid and calcium oxalate in production of wood-containing paper : formation, analysis, and control

Papperstillverkningen störs ofta av oönskade föreningar som kan bilda avsättningar på processytor, vilket i sin tur kan ge upphov till störningar i pappersproduktionen samt försämring av papperskvaliteten. Förutom avsättningar av vedharts är stenliknande avlagringar av svårlösliga salter vanliga. I vårt dagliga liv är kalkavlagringar i kaffe- och vattenkokare exempel på liknande problem. I massa- och pappersindustrin är en av de mest problematiska föreningarna kalciumoxalat; detta salt är nästan olösligt i vatten och avlagringarna är mycket svåra att avlägsna. Kalciumoxalat är också känt som en av orsakerna till njurstenar hos människor. Veden och speciellt barken innehåller alltid en viss mängd oxalat men en större källa är oxalsyra som bildas när massan bleks med oxiderande kemikalier, t.ex. väteperoxid. Kalciumoxalat bildas när oxalsyran reagerar med kalcium som kommer in i processen med råvattnet, veden eller olika tillsatsmedel. I denna avhandling undersöktes faktorer som påverkar bildningen av oxalsyra och utfällningen av kalciumoxalat, med hjälp av bleknings- och utfällningsexperiment. Forskningens fokus låg speciellt på olika sätt att förebygga uppkomsten av avlagringar vid tillverkning av trähaltigt papper. Resultaten i denna avhandling visar att bildningen av oxalsyra samt utfällning av kalciumoxalat kan påverkas genom processtekniska och våtändskemiska metoder. Noggrann avbarkning av veden, kontrollerade förhållanden under den alkaliska peroxidblekningen, noggrann hantering och kontroll av andra lösta och kolloidala substanser, samt utnyttjande av skräddarsydd kemi för kontroll av avlagringar är nyckelfaktorer. Resultaten kan utnyttjas då man planerar blekningssekvenser för olika massor samt för att lösa problem orsakade av kalciumoxalat. Forskningsmetoderna som användes i utfällningsstudierna samt för utvärdering av tillsatsmedel kan också utnyttjas inom andra områden, t.ex. bryggeri- och sockerindustrin, där kalciumoxalatproblem är vanligt förekommande. -------------------------------------------- Paperinvalmistusta häiritsevät usein erilaiset epäpuhtaudet, jotka kiinnittyvät prosessipinnoille ja haittaavat tuotantoa sekä paperin laatua. Puun pihkan lisäksi eräs yleinen ongelma on niukkaliukoisten suolojen aiheuttamat kivettymät. Kalkkisaostuma kahvinkeittimessä on esimerkki vastaavasta ongelmasta arkielämässä. Massa- ja paperiteollisuudessa yksi hankalimmista kivettymien muodostajista on kalsiumoksalaatti, koska se on lähes liukenematonta ja sen aiheuttamat saostumat ovat erittäin vaikeasti poistettavia. Kalsiumoksalaatti on yleisesti tunnettu myös munuaiskivien aiheuttajana ihmisillä. Puu ja varsinkin sen kuori sisältää aina jonkin verran oksalaattia, mutta suurempi lähde on kuitenkin oksaalihappo jota muodostuu valkaistaessa massaa hapettavilla kemikaaleilla, kuten vetyperoksidilla. Kalsiumoksalaattia syntyy kun veden, puun ja lisäaineiden mukana prosessiin tuleva kalsium reagoi oksalaatin kanssa. Tässä väitöskirjatyössä tutkittiin oksaalihapon muodostumiseen ja kalsiumoksalaatin saostumiseen vaikuttavia tekijöitä valkaisu- ja saostumiskokeiden avulla. Tutkimuksen painopiste oli saostumien ehkäisemisessä puupitoisten painopaperien valmistuksessa. Työssä saadut tulokset osoittavat että oksaalihapon muodostumiseen ja kalsiumoksalaatin saostumiseen voidaan vaikuttaa sekä prosessiteknisten että märänpään kemian keinojen avulla. Tehokas puun kuorinta, optimoidut olosuhteet peroksidivalkaisussa, muiden liuenneiden ja kolloidisten aineiden hallinta sekä räätälöidyn kemian hyödyntäminen kalsiumoksalaattisaostumien torjunnassa ovat keskeisissä rooleissa ongelmien välttämiseksi. Väitöskirjatyön tuloksia voidaan hyödyntää massan valkaisulinjoja suunniteltaessa sekä kalsiumoksalaatin aiheuttamien ongelmien ratkaisemisessa. Tutkimusmenetelmiä, joita käytettiin saostumiskokeissa ja eri lisäaineiden vaikutusten arvioinnissa, voidaan hyödyntää massa- ja paperiteollisuuden lisäksi myös muilla alueilla, kuten sokeri- ja panimoteollisuudessa, joissa ongelma on myös yleinen.

Estrutura do cerradão e da transição entre cerradão e floresta paludícola num fragmento da International Paper do Brasil Ltda., em Brotas, SP

A biodiversidade existente no cerrado está seriamente ameaçada pela devastação, pois muitas das espécies que aí ocorrem possuem distribuição geográfica restrita. Pela posição central do cerrado no continente sul-americano, ocorrem associações entre a vegetação do cerrado e outras formações, dentre estas a floresta paludícola. Os objetivos deste trabalho foram conhecer a flora e descrever a comunidade arbustivo-arbórea de um cerradão e da transição entre esse cerradão e uma floresta paludícola em Brotas, e investigar as similaridades e diferenças florísticas entre levantamentos realizados em fisionomias similares no estado de São Paulo. No fragmento ocorreram 125 espécies de 91 gêneros e 49 famílias. Myrtaceae e Leguminosae foram as famílias mais ricas em espécies, um padrão consistente com o encontrado em outros levantamentos nos cerrados paulistas. Somente em Brotas, Lauraceae e Euphorbiaceae apresentaram alta riqueza específica. No levantamento fitossociológico, em 1,0 ha, foram amostrados 3.787 indivíduos com DAS > 3 cm (H' = 3,378 nats.indivíduo-1). As espécies de maior importância sociológica foram Xylopia aromatica, Vochysia tucanorum, Ocotea pulchella, Gochnatia polymorpha e Myrcia albo-tomentosa. Não foi encontrada correlação significativa entre a similaridade florística e a distância geográfica entre as 10 áreas de cerrado analisadas, devido à grande proporção de espécies comuns. Essa grande proporção de espécies comuns corrobora resultados de outros autores, de que o estado de São Paulo se localiza num centro de diversidade do cerrado, cuja composição florística é diferente de outros centros de diversidade no Brasil.

Printed platforms for paper-based analytical applications

Paper-based analytical technologies enable quantitative and rapid analysis of analytes from various application areas including healthcare, environmental monitoring and food safety. Because paper is a planar, flexible and light weight substrate, the devices can be transported and disposed easily. Diagnostic devices are especially valuable in resourcelimited environments where diagnosis as well as monitoring of therapy can be made even without electricity by using e.g. colorimetric assays. On the other hand, platforms including printed electrodes can be coupled with hand-held readers. They enable electrochemical detection with improved reliability, sensitivity and selectivity compared with colorimetric assays. In this thesis, different roll-to-roll compatible printing technologies were utilized for the fabrication of low-cost paper-based sensor platforms. The platforms intended for colorimetric assays and microfluidics were fabricated by patterning the paper substrates with hydrophobic vinyl substituted polydimethylsiloxane (PDMS) -based ink. Depending on the barrier properties of the substrate, the ink either penetrates into the paper structure creating e.g. microfluidic channel structures or remains on the surface creating a 2D analog of a microplate. The printed PDMS can be cured by a roll-ro-roll compatible infrared (IR) sintering method. The performance of these platforms was studied by printing glucose oxidase-based ink on the PDMS-free reaction areas. The subsequent application of the glucose analyte changed the colour of the white reaction area to purple with the colour density and intensity depending on the concentration of the glucose solution. Printed electrochemical cell platforms were fabricated on paper substrates with appropriate barrier properties by inkjet-printing metal nanoparticle based inks and by IR sintering them into conducting electrodes. Printed PDMS arrays were used for directing the liquid analyte onto the predetermined spots on the electrodes. Various electrochemical measurements were carried out both with the bare electrodes and electrodes functionalized with e.g. self assembled monolayers. Electrochemical glucose sensor was selected as a proof-of-concept device to demonstrate the potential of the printed electronic platforms.

The Effect of Plant Closures on Market Value: Empirical Evidence from Pulp and Paper Industry 2004-2012

The aim of this study was to research how plant closure announcements affect the market value of the largest pulp and paper industry companies in the world. Also the effect of announcements on competitors was researched and whether the location of plants, timing, reasons for the closures, and characteristics of the closing firms and competitors have an impact on the results. The overall sample included 57 events in the years 2004-2012 and event study was used as a research method. Main theories were signaling theory and spillover effect. According to empirical results, investors consider plant closure announcements as a positive signal for market value. The spillover effect on competitors was, on average, positive and characteristics of the firms and closures had an effect on the results. Furthermore, the market generally predicted the closures and overreacted to them on the announcement day and after it. It is possible for corporate management and investors to learn from the results and use them as support for their decision making.

The use of filter paper plasticized with polyvinyl alcohol-glutaraldehyde in ELISA

F1-antigen purified from Yersinia pestis was covalently linked to 5-mm diameter filter paper discs plasticized with polyvinyl alcohol-glutaraldehyde. These discs were used both for ELISA and dot-ELISA for the detection of anti-F1 IgG in rabbits. The best conditions were achieved using 1.25 µg of F1 antigen/disc, 3% w/v skim milk in PBS as blocking agent, anti-IgG peroxidase conjugate diluted 12,000 times, and serum from rabbits immunized or not against Y. pestis, diluted 6,400 times. The absorbance values obtained from the comparative study between this procedure and conventional ELISA were not significantly different but the low cost of the reagents employed in ELISA using the filter paper discs plasticized with polyvinyl alcohol-glutaraldehyde makes this method economically attractive.

The Cycle Times of Working Capital: Financial Value Chain Analysis Method

Interest towards working capital management increased among practitioners and researchers because the financial crisis of 2008 caused the deterioration of the general financial situation. The importance of managing working capital effectively increased dramatically during the financial crisis. On one hand, companies highlighted the importance of working capital management as part of short-term financial management to overcome funding difficulties. On the other hand, in academia, it has been highlighted the need to analyze working capital management from a wider perspective namely from the value chain perspective. Previously, academic articles mostly discussed working capital management from a company-centered perspective. The objective of this thesis was to put working capital management in a wider and more academic perspective and present case studies of the value chains of industries as instrumental in theoretical contributions and practical contributions as complementary to theoretical contributions and conclusions. The principal assumption of this thesis is that selffinancing of value chains can be established through effective working capital management. Thus, the thesis introduces the financial value chain analysis method which is employed in the empirical studies. The effectiveness of working capital management of the value chains is studied through the cycle time of working capital. The financial value chain analysis method employed in this study is designed for considering value chain level phenomena. This method provides a holistic picture of the value chain through financial figures. It extends the value chain analysis to the industry level. Working capital management is studied by the cash conversion cycle that measures the length (days) of time a company has funds tied up in working capital, starting from the payment of purchases to the supplier and ending when remittance of sales is received from the customers. The working capital management practices employed in the automotive, pulp and paper and information and communication technology industries have been studied in this research project. Additionally, the Finnish pharmaceutical industry is studied to obtain a deeper understanding of the working capital management of the value chain. The results indicate that the cycle time of working capital is constant in the value chain context over time. The cash conversion cycle of automotive, pulp and paper, and ICT industries are on average 70, 60 and 40 days, respectively. The difference is mainly a consequence of the different cycle time of inventories. The financial crisis of 2008 affected the working capital management of the industries similarly. Both the cycle time of accounts receivable and accounts payable increased between 2008 and 2009. The results suggest that the companies of the automotive, pulp and paper and ICT value chains were not able to self-finance. Results do not indicate the improvement of value chains position in regard to working capital management either. The findings suggest that companies operating in the Finnish pharmaceutical industry are interested in developing their own working capital management, but collaboration with the value chain partners is not considered interesting. Competition no longer occurs between individual companies, but between value chains. Therefore the financial value chain analysis method introduced in this thesis has the potential to support value chains in improving their competitiveness.

Financial controlling and management in recovered paper joint ventures

The objective of this Master’s thesis is to examine financial functions, controlling and management in joint ventures of Manufacturing Corporation Oyj Recovered Paper business area. This case study investigated the current situation of financial functions and find out causes that have led the situation. Current situation of financial functions in joint ventures is variable. The most of the companies is outsourced at least some tasks. However, narrow reporting and problems in reliability are the biggest lack of financial controlling and management. The result of study consists of two parts: short-term and long-term improvement. Short-term improvement includes selected solution to outsource all routine financial tasks to new outsourcing partner and improve financial functions. Long-term improvements aim to create better controlling and management system to joint ventures. It is formed corporate governance and performance measurement. In this study it developed new Balanced Scorecard (BSC) for recovered paper joint ventures. Dimensions of BSC are quality, delivery (time), price and financial controlling and management. Earlier researched are showed problems in success of joint venture relationships. Similar results are obtained in this study. In future research, suitable of developed Balanced Scorecard for other industries could be studied

Assessing negative priming by attended distractors in a paper-and-pencil task

The paper-and-pencil digit-comparison task for assessing negative priming (NP) was introduced, using a referent-size-selection procedure that was demonstrated to enhance the effect. NP is indicated by slower responses to recently ignored items, and proposed within the clinical-experimental framework as a major cognitive index of active suppression of distracting information, critical to executive functioning. The digit-comparison task requires circling digits of a list with digit-asterisk pairs (a baseline measure for digit-selection), and the larger of two digits in each pair of the unrelated (with different digits in successive digit-pairs) and related lists (in which the smaller digit subsequently became a target). A total of 56 students (18-38 years) participated in two experiments that explored practice effects across lists and demonstrated reliable NP, i.e., slowing to complete the related list relative to the unrelated list, (F(2, 44) = 52.42, P < 0.0001). A 3rd experiment examined age-related effects. In the paper-and-pencil digit-comparison task, NP was reliable for the younger (N = 8, 18-24 years) and middle-aged adults (N = 8, 31-54 years), but absent for the older group (N = 8, 68-77 years). NP was also reduced with aging in a computer-implemented digit-comparison task, and preserved in a task typically used to test location-specific NP, accounting for the dissociation between identity- and spatial-based suppression of distractors (Rao R(3, 12) = 16.02, P < 0.0002). Since the paper-and-pencil digit-comparison task can be administered easily, it can be useful for neuropsychologists seeking practical measures of NP that do not require cumbersome technical equipment.

Emerging market patterns in recycled paper trade

The international recovered paper trade serves two important functions: increasing raw material availability in the paper and board industry and providing economic incentives to recycle. The purpose of this paper is to shed further light on emerging patterns in this trade by empirically analysing the changes in the bilateral trade flows of recycled paper between 1992 and 2008. According to our estimations, two important changes have taken place in the 1990s and 2000s. First, the growing importance of developing economies in global recycled paper trade plays a significant role in import demand as a determinant of trade flows. Second, the changes in global trade patterns necessitate investigating the transportation cost measures used in applied research.