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Dimensional Stability of Paper: Influence of Fibre-Fibre Joints and Fibre Wall Oxidation
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.ORCID iD: 0000-0002-7410-0333
2008 (English)Licentiate thesis, comprehensive summary (Other scientific)
Abstract [sv]

Papper är ett mycket mångsidigt material. Trots detta finns det ett flertal egenskaper som begränsar papperets användbarhet. Ett av de större problemen med cellulosa- och lignocellulosafibrer är att de sänker sin fria energi genom att sorbera vatten, och denna sorption förändrar papperets dimensioner. Detta fenomen kallas vanligtvis för bristfällig dimensionsstabilitet och uppträder i form av registerfel vid flerfärgstryck eller som krullning, buckling och vågiga papperskanter vid utskrift, kopiering och lagring, eller med en vidare definition som förkortad livslängd hos lådor på grund av mekanosorptivt kryp.

Avsikten med denna avhandling har varit att studera och kvantifiera vilka egenskaper som styr, och hur de påverkar, den vatteninducerade dimensionsförändringen som sker hos ett fibernätverk, samt hur dess dimensionsstabilitet kan förbättras. Detta har studerats både genom att ändra fiberns fuktsorptionsegenskaper och genom att förändra adhesionen och kontaktgraden mellan fibrerna i fiber-fiberfogarna. Fogegenskaperna har också varierats genom att tillverka laboratorieark torkade under inspänning samt ark torkade fritt för att minimera mängden inbyggda spänningar i arket.

Blekt kraftmassa har behandlats med polyelektrolytmultilager (PEM) för att förbättra adhesionen mellan fibrerna och för att öka kontaktgraden mellan fibrerna i fogen. Kontaktgraden har även minskats genom förhorning av fibrerna före arkformning. För de ark som fick torka fritt gav PEM-behandlingen en ökad hygroexpansionskoefficient, det vill säga dimensionsförändringen normaliserad mot förändringen i fuktinnehåll, vid samma förändring i relativ luftfuktighet medan förhorningen minskade hygroexpansionskoefficienten något. Om arken emellertid torkades under inspänning observerades ingen skillnad i hygroexpansionskoefficient mellan de olika fibermodifieringarna. Detta tolkades som ett resultat av en ökad kontaktzon och en större utbredning ut ur fogens plan, när arken torkades utan inspänning. En utbredning som medför att en större del av fiberns transversella expansion överförs som expansion i pappersplanet.

Fibrernas fuktsorptionsegenskaper förändrades genom natriumperjodatoxidering av 1,4-glukanernas C2-C3-bindning. Detta skapade sannolikt tvärbindningar i fiberväggen som förbättrade fiberväggens tålighet både genom att låsa fibrillerna närmare varandra och genom att ta bort potentiella adsorptionssäten som annars är tillgängliga för vattenadsorption. Perjodatoxidationen minskar också fibrernas kristallinitet och således frigjorde oxidationen hydroxylgrupper där vattenmolekyler kan adsorbera. Detta innebar att oxidationen både minskade och ökade interaktionen mellan vatten och fibervägg, men dock på olika strukturell nivå. Tvärbindningarna visade sig också märkbart reducera sorptionshastigheten när arken utsattes för en förändrad luftfuktighet så länge de inte tidigare utsatts för relativa luftfuktigheter nära mättnad. Som ett resultat av den lägre förändringen i fuktinnehåll vid en förändring i luftfuktighet från 20 till 85 % RF minskade dimensionsförändringens amplitud för de tvärbundna arken upp till 30 %. Emellertid uppvisade de tvärbundna arken en högre hygroexpansionskoefficeint, vilket innebär att de blev mer känsliga för absoluta förändringar i fuktinnehåll.

Abstract [en]

Paper is a very versatile material. Nevertheless, there are several factors limiting its usefulness, and one of the major issues is that cellulosic and ligno-cellulosic fibres lower their free energy by sorbing water and this water changes the dimensions of the paper. This phenomenon is usually referred to as a lack of dimensional stability and is often evident as misregister during multicolour printing or curl, cockle and wavy edges during printing, copying and storage or, with a wider definition, also as a shortened life-time of boxes during storage due to mechano-sorptive creep.

The work described in this thesis aims to study and quantify the importance of the different mechanisms causing water-induced dimensional changes in a fibre network and to investigate how to improve the dimensional stability of ligno-cellulosic materials. This has been done both by altering the fiber properties such as the moisture sorptivity and by changing the adhesion and degree of contact within the fibre-fibre joints. The properties of the fibre-fibre joints have been varied by drying laboratory sheets both under restraint and freely to minimise the generation of built-in stresses.

Bleached kraft fibres were treated using the polyelectrolyte multilayer (PEM) technique to improve the adhesion between the fibres and to increase the molecular contact within the joints. In contrast, the degree of contact was impaired by hornifying the fibres before sheet preparation. For sheets allowed to dry freely, the PEM-treatment increased the hygroexpansion coefficient, i.e. the dimensional movement normalised with respect to the change in moisture content, when subjected to changes in relative humidity whereas the hornification process resulted in a slightly lowered hygroexpansion coefficient. However, when the sheets were dried under restraint, the different joint and fibre modifications led to no difference in hygroexpansion coefficient. This was interpreted as being a result of an increase in the total contact zone between the fibres when the sheets were dried under restraint, with a greater extension in the outof- plain direction of the joint resulting in a transfer of a larger part of the transverse swelling to the in-plane expansion.

The sorptivity of the fibres was changed by oxidising the C2-C3 bond of the 1,4- glucans with periodate. This most likely created covalent cross-links in the fibre wall both improved the integrity of the fibre wall by locking adjacent fibril lamellae to each other and also removed possible sites for water sorption onto the cellulose surfaces. Periodate oxidation also led to a decrease in the crystallinity of the cellulose within the fibres, making more cellulose hydroxyl groups available for the adsorption of water molecules. This means that the oxidation both decreased and increased the interaction between the fibre wall and moisture but, on two different structural levels. The crosslinks significantly reduced the sorption rate when the papers was subjected to changes in relative humidity, as long as the fibres were not subjected to humidities close to saturation. The smaller change in moisture content when the relative humidity was changed between 20 and 85 % RH meant that the dimensional stability of the crosslinked sheets was increased. On the other hand, the hygroexpansion coefficient was increased in the case of papers made from fibres with the highest degree of oxidation, i.e. the sheets became more sensitive to absolute changes in moisture content.

Place, publisher, year, edition, pages
Stockholm: KTH , 2008. , ix, 39 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:8
National Category
Paper, Pulp and Fiber Technology
Identifiers
URN: urn:nbn:se:kth:diva-4635ISBN: 978-91-7178-862-7 (print)OAI: oai:DiVA.org:kth-4635DiVA: diva2:13175
Presentation
2008-02-22, STFI-salen, KTH, Drottning Kristinas väg 61, Stockholm, 14:00
Opponent
Supervisors
Note
QC 20101117Available from: 2008-02-12 Created: 2008-02-12 Last updated: 2013-10-29Bibliographically approved
List of papers
1. Influence of fibre-fibre joint properties on the dimensional stability of paper
Open this publication in new window or tab >>Influence of fibre-fibre joint properties on the dimensional stability of paper
2008 (English)In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 15, no 4, 515-525 p.Article in journal (Refereed) Published
Abstract [en]

Measurements have been performed to clarify the connection between fibre-fibre joint properties and dimensional stability using laboratory sheets prepared from never-dried fibres, from heavily hornified fibres having a low molecular contact area between the fibres, and from both hornified and never-dried fibres treated with a polyelectrolyte multilayer (PEM) technique to increase the molecular contact area in the fibre-fibre joint. The influence of the drying mode, i.e. whether the sheets are dried freely or under restraint, was also evaluated. The results showed that neither paper strength nor fibre-fibre joint contact area had any significant influence on the dimensional stability of sheets dried under restraint. On the other hand, when the sheets were dried freely, the PEM-treated sheets expanded to the same extent as, or to an even greater extent than the non-PEM-treated sheets, even though they adsorbed less water for a given change in relative humidity. There was also a correlation between drying shrinkage and dimensional stability, where greater shrinkage was associated with a greater hygroexpansion in the freely dried sheets.

Keyword
dimensional stability, drying, hornification, hygroexpansion, multilayer, polyelectrolytes, shrinkage, STRENGTH PROPERTIES, CELLULOSIC FIBERS, WOOD FIBERS, SURFACE, HYGROEXPANSIVITY, WATER, PULP
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-12168 (URN)10.1007/s10570-008-9203-y (DOI)000256909700002 ()2-s2.0-45949110424 (Scopus ID)
Note

QC 20150630

Available from: 2010-03-23 Created: 2010-03-23 Last updated: 2017-12-12Bibliographically approved
2. The influence of periodate oxidation on the moisture sorptivity and dimensional stability of paper
Open this publication in new window or tab >>The influence of periodate oxidation on the moisture sorptivity and dimensional stability of paper
2008 (English)In: Cellulose (London), ISSN 0969-0239, E-ISSN 1572-882X, Vol. 15, no 6, 837-847 p.Article in journal (Refereed) Published
Abstract [en]

The hygroexpansion of paper was significantly reduced, up to 28% lower amplitude of change when the paper was subjected to a change in relative humidity from 20 to 85% RH, by oxidation of the fibre wall. Never-dried bleached kraft fibres were oxidised with sodium periodate, which specifically oxidises the C2-C3 bond of 1,4-glucans so that the cellulose is partly converted into dialdehyde cellulose. Since both the dry and wet strength of laboratory sheets were significantly improved, the dry tensile strength increased from 24 kNm/kg up to 66 kNm/kg and the relative wet tensile strength increased from 1.5% up to 40%, it is suggested that the aldehydes form hemiacetal linkages within the fibre wall during the consolidation and drying of the sheets. The mechanical, hygroexpansive and moisture sorptive properties of the sheets made from the oxidised fibres were studied. The results showed that the main reason for the reduced hygroexpansion was a decrease in moisture sorptivity, i.e. when the sheets made of fibres with different degrees of cross-linking were subjected to the same change in relative humidity, the more cross-linked fibres showed a smaller change in moisture content. It was also shown that the hygroexpansion coefficient, i.e. the moisture-normalised dimensional change, was not significantly changed by the periodate oxidation, i.e. indicating that there are no improvement in dimensional stability if the paper is subjected to a specific amount of water.

Keyword
Cross-linking, Dimensional stability, Hygroexpansion, Moisture adsorption, Periodate oxidation, RELATIVE HUMIDITY CHANGES, POROUS STRUCTURE, FIBER JOINT, CELLULOSE, STRENGTH, WATER, WOOD, MECHANISM, CREEP
Identifiers
urn:nbn:se:kth:diva-12169 (URN)10.1007/s10570-008-9243-3 (DOI)000260307000009 ()2-s2.0-54949090722 (Scopus ID)
Note
QC20100616Available from: 2010-03-23 Created: 2010-03-23 Last updated: 2017-12-12Bibliographically approved

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