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Tailoring adhesion and wetting properties of cellulose fibers and model surfaces
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
2012 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

The layer-by-layer (LbL) technique was used to modify the surface of cellulose fibers by consecutive adsorption of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) followed by a final adsorbed layer of anionic paraffin wax colloids. Paper hand sheets made from the modified fibers were found to be highly hydrophobic with a contact angle of 150°. In addition to the significantly increased hydrophobicity, the sheets showed improved mechanical properties, such as a higher tensile strength. Heat treatment of the prepared sheets further enhanced both the mechanical properties and the hydrophobicity. These results demonstrate the flexibility and robustness of the LbL technique, which allows us to combine the known adhesive effect of PAH/PAA LbL films with the functionality of wax nanoparticles, creating a stronger and highly hydrophobic paper.

It was further observed that LbL modified sheets without wax also displayed increased hydrophobicity when heat treated. The mechanism was studied through model experiments where LbL films of PAH/PAA were assembled on flat non-porous model cellulose surfaces. Contact angle measurements showed the same trend due to heat treatment of the model films, although, the absolute value of the contact angles were smaller. Analysis using the highly interfacial sensitive vibrational sum frequency spectroscopy technique showed an enrichment of CH3 groups (from the polymer chain ends) at the solid/air interface. These results indicate that during the heat treatment, a reorientation of polymer chains occurs to minimize the surface energy of the LbL film.

In the second part of this work, the adhesive interactions between the main constituents of wood fibers were studied using high-resolution measuring techniques and well-defined model films of cellulose, hemicellulose and lignin. Successful surface modification of polydimethylsiloxane (PDMS) caps, needed in the Johnson-Kendall-Roberts (JKR) measuring methodology, by LbL deposition of nanofibrillated cellulose (NFC) and poly(ethylene imine) (PEI) allowed for the first known all-wood biopolymer JKR measurements of the adhesion between cellulose/cellulose, cellulose/lignin and the cellulose/glucomannan surfaces. The work of adhesion on loading and the adhesion hysteresis were similar for all three systems, suggesting that adhesion between the different wood biopolymers does not differ greatly.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. , 33 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2012:8
National Category
Materials Chemistry Paper, Pulp and Fiber Technology Nano Technology
Identifiers
URN: urn:nbn:se:kth:diva-91296ISBN: 978-91-7501-268-1 (print)OAI: oai:DiVA.org:kth-91296DiVA: diva2:509273
Presentation
2012-03-19, K1, KTH, Teknikringen 56, Stockholm, 14:00 (English)
Opponent
Supervisors
Note

QC 20120314

Available from: 2012-03-14 Created: 2012-03-12 Last updated: 2014-10-03Bibliographically approved
List of papers
1. Treatment of cellulose fibres with polyelectrolytes and wax colloids to create tailored highly hydrophobic fibrous networks
Open this publication in new window or tab >>Treatment of cellulose fibres with polyelectrolytes and wax colloids to create tailored highly hydrophobic fibrous networks
2012 (English)In: Colloids and Surfaces A: Physicochemical and Engineering Aspects, ISSN 0927-7757, E-ISSN 1873-4359, Vol. 414, 415-421 p.Article in journal (Refereed) Published
Abstract [en]

Paper is a versatile material with obvious advantages in being both inexpensive and environment friendly. However, a major drawback compared with many other materials, such as plastics, is that it is sensitive to both liquid water and moist air. Traditionally paper is protected from liquid water by sizing. The present work presents a new way to make paper water resistant by combining the layer-by-layer (LbL) technique with the adsorption of a colloidal wax onto the multilayer structure. After the adsorption of five layers of poly(allylamine hydrochloride) and poly(acrylic acid) followed by the adsorption of 8. mg paraffin wax per gram fibre, the contact angle measured 60. s after a drop of water was applied to the sheet was about 138°. If the sheets were cured for 30. min at 160. °C after sheet making, the contact angle was ca. 150°. The heat treatment of sheets prepared from LbL-modified fibres without the addition of wax gave a contact angle of about 113°. To decouple structural effects from changes in surface energy upon heat treatment of PAH/PAA LbL films, model experiments were carried out where LbL assemblies were prepared on silicon oxide and cellulose model surfaces. The contact angle increased when these films were heat treated but it did not exceed 90°. The reason for this is due to the lack of structure of the model surfaces on a micrometre scale. The adsorption of wax impaired the mechanical properties of paper sheets made from modified fibres compared to sheets from the LbL-modified fibres. However, at an adsorption of 8. mg paraffin wax per gram fibre there was still an increase by 37 ± 1% in tensile strength index compared to the untreated reference pulp (33.8 ± 0.7 and 24.7 ± 0.6. kNm/kg respectively).

Keyword
Cellulose fibres, Dry strength, Hydrophobicity, Polyelectrolyte multilayers, Wax nanoparticles
National Category
Materials Engineering Paper, Pulp and Fiber Technology Nano Technology
Identifiers
urn:nbn:se:kth:diva-91373 (URN)10.1016/j.colsurfa.2012.08.042 (DOI)000312472000055 ()2-s2.0-84868329804 (Scopus ID)
Note

QC 20121212. Updated from submitted to published.

Available from: 2012-03-13 Created: 2012-03-13 Last updated: 2017-12-07Bibliographically approved
2. Vibrational sum frequency spectroscopy on polyelectrolyte multilayers: modelling of hydrophobic fibres
Open this publication in new window or tab >>Vibrational sum frequency spectroscopy on polyelectrolyte multilayers: modelling of hydrophobic fibres
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Materials Chemistry Paper, Pulp and Fiber Technology Nano Technology
Identifiers
urn:nbn:se:kth:diva-91385 (URN)
Note

QC 20160620

Available from: 2012-03-14 Created: 2012-03-14 Last updated: 2016-06-20Bibliographically approved
3. Direct Adhesive Measurements between Wood Biopolyrner Model Surfaces
Open this publication in new window or tab >>Direct Adhesive Measurements between Wood Biopolyrner Model Surfaces
2012 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 13, no 10, 3046-3053 p.Article in journal (Refereed) Published
Abstract [en]

For the first time the dry adhesion was measured for an all-wood biopolymer system using Johnson-Kendall-Roberts (JKR) contact mechanics. The polydimethylsiloxane hemisphere was successfully surface-modified with a Cellulose I model surface using layer-by-layer assembly of nanofibrillated cellulose and polyethyleneimine. Flat surfaces of cellulose were equally prepared on silicon dioxide substrates, and model surfaces of glucomannan and lignin were prepared on silicon dioxide using spin-coating. The measured work of adhesion on loading and the adhesion hysteresis was found to be very similar between cellulose and all three wood polymers, suggesting that the interaction between these biopolymers do not differ greatly. Surface energy calculations from contact angle measurements indicated similar dispersive surface energy components for the model surfaces. The dispersive component was dominating the surface energy for all surfaces. The JKR work of adhesion was lower than that calculated from contact angle measurements, which partially can be ascribed to surface roughness of the model surfaces and overestimation of the surface energies from contact angle determinations.

Keyword
Adhesion, Angle measurement, Biomolecules, Biopolymers, Cellulose, Contact angle, Deformation, Interfacial energy, Loading; Silica, Silicones, Surface roughness
National Category
Chemical Sciences Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-104696 (URN)10.1021/bm300762e (DOI)000309488600005 ()2-s2.0-84867475444 (Scopus ID)
Note

QC 20121112. Updated from Manuscript to Article

Available from: 2012-11-12 Created: 2012-11-09 Last updated: 2017-12-07Bibliographically approved

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