Value added logistics in supply and demand chain : COSTFIX : New operation model for maintenance material logistics in paper industry

This research report illustrates and examines new operation models for decreasing fixed costs and transforming them into variable costs in the field of paper industry. The report illustrates two cases – a new operation model for material logistics in maintenance and an examination of forklift truck fleet outsourcing solutions. Conventional material logistics in maintenance operation is illustrated and some problems related to conventional operation are identified. A new operation model that solves some of these problems is presented including descriptions of procurement and service contracts and sources of added value. Forklift truck fleet outsourcing solutions are examined by illustrating the responsibilities of a host company and a service provider both before and after outsourcing. The customer buys outsourcing services in order to improve its investment productivity. The mechanism of how these services affect the customer company’s investment productivity is illustrated.

Electro-Oxidation Treatment of Pulp and Paper Mill Circulating Waters and Wastewaters

Interest in water treatment by electrochemical methods has grown in recent years. Electrochemical oxidation has been applied particularly successfully to degrade different organic pollutants and disinfect drinking water. This study summarizes the effectiveness of the electrochemical oxidation technique in inactivating different primary biofilm forming paper mill bacteria as well as sulphide and organic material in pulp and paper mill wastewater in laboratory scale batch experiments. Three different electrodes, borondoped diamond (BDD), mixed metal oxide (MMO) and PbO2, were employed as anodes. The impact on inactivation efficiency of parameters such as current density and initial pH or chloride concentration of synthetic paper machine water was studied. The electrochemical behaviour of the electrodes was investigated by cyclic voltammetry with MMO, BDD and PbO2 electrodes in synthetic paper mill water as also with MMO and stainless steel electrodes with biocides. Some suggestions on the formation of different oxidants and oxidation mechanisms were also presented during the treatment. Aerobic paper mill bacteria species (Deinococcus geothermalis, Pseudoxanthomonas taiwanensis and Meiothermus silvanus) were inactivated effectively (>2 log) at MMO electrodes by current density of 50 mA/cm2 and the time taken three minutes. Increasing current density and initial chloride concentration of paper mill water increased the inactivation rate of Deinococcus geothermalis. The inactivation order of different bacteria species was Meiothermus silvanus > Pseudoxanthomonas taiwanensis > Deinococcus geothermalis. It was observed that inactivation was mainly due to the electrochemically generated chlorine/hypochlorite from chloride present in the water and also residual disinfection by chlorine/hypochlorite occurred. In real paper mill effluent treatment sulphide oxidation was effective with all the different initial concentrations (almost 100% reduction, current density 42.9 mA/cm2) and also anaerobic bacteria inactivation was observed (almost 90% reduction by chloride concentration of 164 mg/L and current density of 42.9 mA/cm2 in five minutes). Organic material removal was not as effective when comparing with other tested techniques, probably due to the relatively low treatment times. Cyclic voltammograms in synthetic paper mill water with stainless steel electrode showed that H2O2 could be degraded to radicals during the cathodic runs. This emphasises strong potential of combined electrochemical treatment with this biocide in bacteria inactivation in paper mill environments.

Paper for printed electronics and functionality

Mass-produced paper electronics (large area organic printed electronics on paper-based substrates, “throw-away electronics”) has the potential to introduce the use of flexible electronic applications in everyday life. While paper manufacturing and printing have a long history, they were not developed with electronic applications in mind. Modifications to paper substrates and printing processes are required in order to obtain working electronic devices. This should be done while maintaining the high throughput of conventional printing techniques and the low cost and recyclability of paper. An understanding of the interactions between the functional materials, the printing process and the substrate are required for successful manufacturing of advanced devices on paper. Based on the understanding, a recyclable, multilayer-coated paper-based substrate that combines adequate barrier and printability properties for printed electronics and sensor applications was developed in this work. In this multilayer structure, a thin top-coating consisting of mineral pigments is coated on top of a dispersion-coated barrier layer. The top-coating provides well-controlled sorption properties through controlled thickness and porosity, thus enabling optimizing the printability of functional materials. The penetration of ink solvents and functional materials stops at the barrier layer, which not only improves the performance of the functional material but also eliminates potential fiber swelling and de-bonding that can occur when the solvents are allowed to penetrate into the base paper. The multi-layer coated paper under consideration in the current work consists of a pre-coating and a smoothing layer on which the barrier layer is deposited. Coated fine paper may also be used directly as basepaper, ensuring a smooth base for the barrier layer. The top layer is thin and smooth consisting of mineral pigments such as kaolin, precipitated calcium carbonate, silica or blends of these. All the materials in the coating structure have been chosen in order to maintain the recyclability and sustainability of the substrate. The substrate can be coated in steps, sequentially layer by layer, which requires detailed understanding and tuning of the wetting properties and topography of the barrier layer versus the surface tension of the top-coating. A cost competitive method for industrial scale production is the curtain coating technique allowing extremely thin top-coatings to be applied simultaneously with a closed and sealed barrier layer. The understanding of the interactions between functional materials formulated and applied on paper as inks, makes it possible to create a paper-based substrate that can be used to manufacture printed electronics-based devices and sensors on paper. The multitude of functional materials and their complex interactions make it challenging to draw general conclusions in this topic area. Inevitably, the results become partially specific to the device chosen and the materials needed in its manufacturing. Based on the results, it is clear that for inks based on dissolved or small size functional materials, a barrier layer is beneficial and ensures the functionality of the printed material in a device. The required active barrier life time depends on the solvents or analytes used and their volatility. High aspect ratio mineral pigments, which create tortuous pathways and physical barriers within the barrier layer limit the penetration of solvents used in functional inks. The surface pore volume and pore size can be optimized for a given printing process and ink through a choice of pigment type and coating layer thickness. However, when manufacturing multilayer functional devices, such as transistors, which consist of several printed layers, compromises have to be made. E.g., while a thick and porous top-coating is preferable for printing of source and drain electrodes with a silver particle ink, a thinner and less absorbing surface is required to form a functional semiconducting layer. With the multilayer coating structure concept developed in this work, it was possible to make the paper substrate suitable for printed functionality. The possibility of printing functional devices, such as transistors, sensors and pixels in a roll-to-roll process on paper is demonstrated which may enable introducing paper for use in disposable “onetime use” or “throwaway” electronics and sensors, such as lab-on-strip devices for various analyses, consumer packages equipped with product quality sensors or remote tracking devices.

Improving the Supply Chain Performance Management System in a Finnish paper mill

This Master’s Thesis studies performance management system and its benefits, risks and costs. Objective of the thesis is to describe and evaluate currently used supply chain performance management system (SCPMS) in a Finnish paper mill and its interfaces with its business unit’s SCPMS. As a result, the host company has improvement road map for improving its SCPMS. Used SCPMS in the host company and its interfaces to business unit’s SCPMS are described based on interviews held in the host company and the business unit. Evaluation of the host company’s SCPMS is based on literature study. For improvement road map, three areas in need of improvements are chosen. The study shows the need of high level top management commitment in successful performance management system implementation and usage, especially when the system is deployed to lower levels in the organization.

Characterisation of waste for combustion : with special reference to the role of zinc

Waste combustion has gone from being a volume reducing discarding-method to an energy recovery process for unwanted material that cannot be reused or recycled. Different fractions of waste are used as fuel today, such as; municipal solid waste, refuse derived fuel, and solid recovered fuel. Furthermore, industrial waste, normally a mixture between commercial waste and building and demolition waste, is common, either as separate fuels or mixed with, for example, municipal solid waste. Compared to fossil or biomass fuels, waste mixtures are extremely heterogeneous, making it a complicated fuel. Differences in calorific values, ash content, moisture content, and changing levels of elements, such as Cl and alkali metals, are common in waste fuel. Moreover, waste contains much higher levels of troublesome trace elements, such as Zn, which is thought to accelerate a corrosion process. Varying fuel quality can be strenuous on the boiler system and may cause fouling and corrosion of heat exchanger surfaces. This thesis examines waste fuels and waste combustion from different angles, with the objective of giving a better understanding of waste as an important fuel in today’s fuel economy. Several chemical characterisation campaigns of waste fuels over longer time periods (10-12 months) was used to determine the fossil content of Swedish waste fuels, to investigate possible seasonal variations, and to study the presence of Zn in waste. Data from the characterisation campaigns were used for thermodynamic equilibrium calculations to follow trends and determine the effect of changing concentrations of various elements. The thesis also includes a study of the thermal behaviour of Zn and a full—scale study of how the bed temperature affects the volatilisation of alkali metals and Zn from the fuel. As mixed waste fuel contains considerable amounts of fresh biomass, such as wood, food waste, paper etc. it would be wrong to classify it as a fossil fuel. When Sweden introduced waste combustion as a part of the European Union emission trading system in the beginning of 2013 there was a need for combustion plants to find a usable and reliable method to determine the fossil content. Four different methods were studied in full-scale of seven combustion plants; 14Canalysis of solid waste, 14C-analysis of flue gas, sorting analysis followed by calculations, and a patented balance method that is using a software program to calculate the fossil content based on parameters from the plant. The study showed that approximately one third of the coal in Swedish waste mixtures has fossil origins and presented the plants with information about the four different methods and their advantages and disadvantages. Characterisation campaigns also showed that industrial waste contain higher levels of trace elements, such as Zn. The content of Zn in Swedish waste fuels was determined to be approximately 800 mg kg-1 on average, based on 42 samples of solid waste from seven different plants with varying mixtures between municipal solid waste and industrial waste. A review study of the occurrence of Zn in fuels confirmed that the highest amounts of Zn are present in waste fuels rather than in fossil or biomass fuels. In tires, Zn is used as a vulcanizing agent and can reach concentration values of 9600-16800 mg kg-1. Waste Electrical and Electronic Equipment is the second Zn-richest fuel and even though on average Zn content is around 4000 mg kg-1, the values of over 19000 mg kg-1 were also reported. The increased amounts of Zn, 3000-4000 mg kg-1, are also found in municipal solid waste, sludge with over 2000 mg kg-1 on average (some exceptions up to 49000 mg kg-1), and other waste derived fuels (over 1000 mg kg-1). Zn is also found in fossil fuels. In coal, the average level of Zn is 100 mg kg-1, the higher amount of Zn was only reported for oil shale with values between 20-2680 mg kg-1. The content of Zn in biomass is basically determined by its natural occurrence and it is typically 10-100 mg kg-1. The thermal behaviour of Zn is of importance to understand the possible reactions taking place in the boiler. By using thermal analysis three common Zn-compounds were studied (ZnCl2, ZnSO4, and ZnO) and compared to phase diagrams produced with thermodynamic equilibrium calculations. The results of the study suggest that ZnCl2(s/l) cannot exist readily in the boiler due to its volatility at high temperatures and its conversion to ZnO in oxidising conditions. Also, ZnSO4 decomposes around 680°C, while ZnO is relatively stable in the temperature range prevailing in the boiler. Furthermore, by exposing ZnO to HCl in a hot environment (240-330°C) it was shown that chlorination of ZnO with HCl gas is possible. Waste fuel containing high levels of elements known to be corrosive, for example, Na and K in combination with Cl, and also significant amounts of trace elements, such as Zn, are demanding on the whole boiler system. A full-scale study of how the volatilisation of Na, K, and Zn is affected by the bed temperature in a fluidised bed boiler was performed parallel with a lab-scale study with the same conditions. The study showed that the fouling rate on deposit probes were decreased by 20 % when the bed temperature was decreased from 870°C to below 720°C. In addition, the lab-scale experiments clearly indicated that the amount of alkali metals and Zn volatilised depends on the reactor temperature.

Brittleness of Paper

Brittleness is a well-known material characteristic but brittleness of paper is vaguely covered. The objective of this thesis was to characterize the phenomenon and causes around brittleness of paper and to clarify if it is a measurable property. Brittleness of paper was approached from the perspectives of paper physics and paper mills. Brittleness is a property of dry paper and it causes problems at the finishing stages of paper machine. According to paper physics, brittle materials fail in the elastic regime, while ductile materials can locally accumulate a plastic deformation prior to the fracture and they are often able to withstand higher stresses. Brittleness of paper is vastly affected by the surrounding conditions: paper as a hygroscopic material tries to get to the equilibrium. It is also affected by the quality of the pulp used. Measurement techniques can be divided into two categories: based on the viscoelastic behavior of paper and on the exposure to the mechanical stress of sort. The experimental part of the thesis was based on the trials with brittle and non-brittle mill-made LWC papers. It is divided into three parts: strength testing of the brittle and non-brittle papers, analysis of the conditions that may contribute the brittleness and the experimental methods to evaluate brittle behavior. The strength measurements confirmed the influence of the moisture content, but only tensile energy absorption and the fracture toughness measurements provided modest differences between the brittle and non-brittle papers. Versatile analysis of the possible contributing factors resulted into speculation, while the brittle papers contained higher amount of starch, triglycerides and steryl esters. The experimental research proved that the formation, the sensory impression and the variation of local strains may contain the crucial information of paper brittleness.

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.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

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.

Sellutehtaan TRS-hajapäästöjen hallinta

Diplomityön tavoitteena on selvittää TRS-hajapäästöjen muodostumista sekä päästöjen määrää UPM Kymmene Oyj:n Kaukaan sellu- ja paperitehtaalla. Työssä laaditaan TRS-hajapäästöjen mittausohjelma, minkä päivitetty massa- ja paperiteollisuuden BAT-vertailuasiakirja vaatii. Mittausohjelma täydentää tehdasintegraatin ilmapäästöjen valvontaohjelmaa. Hajapäästöjen lisäksi tavoitteena on selvittää häiriötilanteiden aiheuttamia TRS-päästömääriä. Kirjallisuusosassa selvitetään hajujen muodostumista sellun ja paperin valmistuksessa ja niiden käsittelyä ympäristövaikutusten minimoimiseksi. Lisäksi esitellään mittausmenetelmiä. Kokeellisessa osassa valituista kohteista mitataan TRS-pitoisuudet ja hajukaasujen virtaama, joiden perusteella lasketaan TRS-kuormitus. Kuormitus suhteutetaan sellutonnille. Osa kohteista on hajapäästökohteita ja osa kohteita, joista hajukaasut häiriötilanteissa johdetaan käsittelemättä ulos. Tulosten perusteella TRS-hajapäästöjä muodostuu sellun valmistuksessa noin 0,04 kgS/ADt ja jätevedenkäsittelyssä, pääasiassa lietteenkäsittelyssä 0,04 kgS/ADt. Hajapäästöjä syntyy eniten kohteissa, missä keräily on toteutettu kevyemmin tai sitä ei ole. Merkittävimmät kohteet Kaukaalla ovat lietteenkäsittely, koivukuitulinja ja mäntyöljylaitos. Havulinjan ja talteenotto-osaston hajapäästöt ovat muita osastoja vähäisemmät. Yhteensä sellutehtaan ja lietteenkäsittelyn TRS-hajapäästömäärä on 0,08 kgS/ADt, mikä on BAT vaihteluvälin (0,05-0,2 kgS/ADt) sisällä. TRS-häiriöpäästöjen osuus tehtaan TRS päästöistä voi häiriötilanteiden toistuessa nousta merkittäviksi. Tähän vaikuttaa merkittävästi häiriintyvä kohde.

Feasibility study of submerged membrane bioreactor (MBR) as an alternative to conventional activated sludge process (CASP) for municipal wastewater treatment: A pilot scale study

The conventional activated sludge processes (CAS) for the treatment of municipal wastewater are going to be outdated gradually due to more stringent environmental protection laws and regulations. The Membrane bioreactors (MBRs) are the most promising modern technology widely accepted in the world of wastewater treatment due to their highly pronounced features such as high quality effluent, less foot print and working under high MLSS concentration. This research project was carried out to investigate the feasibility and effectiveness of MBR technology compare to the CAS process based on the scientific facts and results. The pilot scale MBR pilot plant was run for more than 150 days and the analysis results were evaluated. The prime focus of the project was to evaluate the correlation of permeate flux under different operating MLSS concentrations. The permeate flux was found almost constant regardless of variations in MLSS concentrations. The removal of micropollutant such as heavy metals, PCPPs, PFCs, steroidal hormones was also studied. The micropollutant removal performance of MBR process was found relatively effective than CAS process. Furthermore, the compatibility of submerged membranes within the bioreactor had truly reduced the process footprint.