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Strategies for improving kraftliner pulp properties Stefan Antonsson Doctoral Thesis Royal Institute of Technology School of Chemical Science and Engineering Department of Fibre and Polymer Technology Division of Wood Chemistry and Pulp Technology Stockholm 2008 Strategies for improving kraftliner pulp properties Supervisor: Professor Mikael E. Lindström AKADEMISK AVHANDLING Som med tillstånd av Kungliga Tekniska Högskolan framläggs till offentlig granskning för avläggande av teknologie doktorsexamen, fredagen den 19 december 2008 kl. 14.00 i Sal E2, KTH, Lindstedtsvägen 3, Stockholm. Avhandlingen försvaras på svenska. TRITA-CHE-Report 2008:70 ISSN 1654-1081 ISBN 978-91-7415-175-6 ©Stefan Antonsson 2008 The following papers are reprinted with permission: Paper I © Elsevier 2008 Paper II © Springer 2008 Abstract A large part of the world paper manufacturing consists of production of corrugated board components, kraftliner and fluting, that are used in many different types of corrugated boxes. Because these boxes are stored and transported, they are often subjected to changes in relative humidity. These changes together with mechanical loads will increase the deformation of the boxes compared to the case where the same loads are applied in a static environment. This enlarged creep due to the changes in relative humidity is called mechano-sorptive or accelerated creep. Mechano-sorptive creep forces producers to use high safety factors when designing boxes, and therefore, this is one of the key properties of kraftliner boards. Different strategies to decrease mechano-sorptive creep, and to simultaneously gain more knowledge about the causes for this phenomenon in paper, are the aim of this work. Derivatised and underivatised black liquor lignins, a by-product produced in pulp mills in large quantities, have been used together with biomimetic methods, to modify the properties of kraftliner pulp. Furthermore, the properties of kraftliner pulp have been compared to other pulps in order to evaluate the influence of fibre morphological factors, such as fibre width and shape factor, on the mechano-sorptive creep. In addition the influence of the chemical composition of the kraftliner pulp has been evaluated both by means of treating a kraftliner pulp with chlorite and xylanase and by producing pulps with different chemical composition. By using lignin and biomimetic methods, to create radical coupling reactions, it has been shown that it is possible to increase the wet strength of kraftliner pulp sheets. This method of treating the pulp showed, however, no significant effects on the mechano-sorptive creep. The addition of an apolar suberin-like lignin derivative, which has been shown to be possible to produce from natural resources, did show a positive effect on mechano-sorptive creep properties, but at the expense of stiffness properties in constant climate. Different pulps were compared with a kraftliner pulp and it was observed that the ratio between tensile stiffness and hygroexpansion can be used to estimate the mechano-sorptive creep properties. The hardwood kraft pulps investigated had lower hygroexpansion, probably due to more slender and straighter fibres, and higher tensile stiffness, probably due to lower lignin content. As the lignin content was varied by different methods in kraft pulps, it was observed that increased lignin content gives an increased hygroexpansion and decreased tensile stiffness as well as an increased mechano-sorptive creep. There were also indications of increased mechano-sorptive creep due to higher xylan content. Keywords: lignin, xylan, kraftliner pulp, mechano-sorptive creep, hygroexpansion, stiffness, fibre shape, fibre width Sammanfattning En stor del av världens papperstillverkning utgörs av produktion av wellpappkomponenter, kraftliner och fluting, som används i en uppsjö av olika wellpapplådor. När dessa lådor lagras och transporteras utsätts de ofta för förändringar i relativa luftfuktigheten. Dessa förändringar tillsammans med mekanisk belastning ökar lådornas deformation jämfört med om samma belastning skulle ha applicerats vid ett statiskt klimat. Denna förhöjda krypning på grund av förändringarna i relativ luftfuktighet kallas mekanosorptiv- eller accelererad krypning. Mekanosorptiv krypning tvingar producenterna att ha höga säkerhetsmarginaler vid dimensioneringar av lådor och är därför en av nyckelegenskaperna för kraftliner. Olika strategier för att minska denna effekt, och på samma gång erövra mer kunskap om orsakerna till detta fenomen, har varit syftet med arbetet. Derivatiserade och oderivatiserade svartlutslignin, en biprodukt möjlig att få ut i stora kvantiteter från massabruk, har används tillsammans med biomimetriska metoder, för att modifiera kraftlinermassas egenskaper. Dessutom har kraftlinermassans egenskaper jämförts med andra massors egenskaper för att utvärdera inverkan av fibermorfologiska faktorer, såsom fiberbredd och fibreform på det mekanosorptiva krypet. Också inverkan av den kemiska sammansättningen av kraftliner massan har undersökts både genom behandling med klorit och xylanas och genom att producera massor med olika kemiska sammansättningar. Genom att använda lignin och biomimetriska metoder för att skapa radikal- kopplingsreaktioner har det visats på möjligheten att öka våtstyrkan i massa-ark. Det här sättet att behandla massa visade dessvärre inga signifikanta effekter på det mekanosorptiva krypet. Tillsatts av ett apolärt suberin-liknande ligninderivat, som visats möjligt att producera ur naturliga råmaterial, visade en positiv effekt på det mekanosorptiva krypegenskaperna även om det var på bekostnad av styvheten vid konstant klimat. Olika massor jämfördes med en kraftlinermassa och det observerades att relationen mellan dragstyvhet och hygroexpansion kan användas för att uppskatta de mekanosorptiva krypegenskaperna. Lövvedssulfatmassorna som undersöktes hade lägre hygroexpansion, antagligen beroende på smalare och rakare fibrer, och högre dragstyvhet, troligen beroende på en lägre ligninhalt. När ligninhalten varierades i sulfatmassor med olika metoder observerades att ökad ligninhalt ger en ökad hygroexpansion och minskad dragstyvhet liksom en ökad mekanosorptiv krypning. Dessutom fanns indikationer på en ökad mekanosorptiv krypning till följd av högre xylaninnehåll. Nyckelord: lignin, xylan, kraftlinermassa, mekanosorptivt kryp, hygroexpansion, styvhet, fiberform, fiberbredd List of Publications This thesis is based on the following papers that are appended at the end. They will be referred to with Roman numerals: I. Low MW-lignin fractions together with vegetable oils as available oligomers for novel paper-coating applications as hydrophobic barrier. Stefan Antonsson, Gunnar Henriksson, Mats Johansson and Mikael E. Lindström Industrial Crops and Products 27: 98 − 103, 2008 II. Laccase initiated cross-linking of lignocellulose fibres using a ultra-filtered lignin isolated from kraft black liquor Graziano Elegir, Daniele Bussini, Stefan Antonsson, Mikael E. Lindström and Luca Zoia. Applied Microbiology and Biotechnology 77(4): 809 − 817, 2007 III. Adding lignin derivatives to decrease the effect of mechano-sorptive creep in linerboard Stefan Antonsson, Gunnar Henriksson and Mikael E. Lindström. Appita Journal 61(6): 468 − 471, 2008 IV. Comparison of the physical properties between hardwood and softwood pulps Stefan Antonsson, Petri Mäkelä, Christer Fellers and Mikael E. Lindström Manuscript V. The relationship between hygroexpansion, tensile stiffness, and mechano– sorptive creep in bleached hardwood kraft pulps Stefan Antonsson, Iiro Pulkkinen, Juha Fiskari, and Mikael E. Lindström Manuscript VI. The influence of lignin and xylan on some kraftliner pulp properties Stefan Antonsson, Gunnar Henriksson and Mikael E. Lindström Manuscript VII. Applying a novel cooking technique to produce high kappa number pulps - the effect on physical properties Stefan Antonsson, Katarina Karlström and Mikael E. Lindström Manuscript Author’s contribution to appended papers: I. Principal author, performed the experimental work. II. Contributed as co-author to discussion part and to relevant pieces of experimental part, performed the preparation of the ultra-filtered lignin and kraftliner pulp. III. Principal author, performed the experimental work. IV. Principal author, performed all the experimental work except the isocyclic and isochronous creep measurements. V. Principal author, performed the hygroexpansion and isocyclic creep stiffness measurements VI. Principal author, performed the experimental work. VII. Contributed to roughly half the writing and experimental work. Results from some of the above publications have been presented on the following occasions: 13th ISWFPC: International Symposium on Wood, Fibre and Pulping Chemistry (incorporated with the 59th Appita Annual Conference and Exhibition), May 16-19 2005, Auckland, New Zealand, (2005) Antonsson, S., Henriksson, G., Johansson, M. and Lindström, M.E., Biomimetic synthesis of suberin for new biomaterials, Vol 2, p. 561 − 564 6th International Paper and Coating Chemistry Symposium, Stockholm, (2006) Antonsson, S. Henriksson, G. and Lindström, M.E. The Utilization of Lignin Derivatives and Radical Coupling reactions to Increase wet strength of Kraftliner, p. 55 1st Workshop on Chemical Pulping Processes, Karlstad, Sweden, (2006) Antonsson, S. and M. E. Lindström The influence on the mechanical properties of some different pulping raw materials - a comparison between some different hardwoods and softwoods. p.
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