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On the Adhesion Between Substrates Covered with Polyelectrolyte Multilayers
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis examines the formation of Polyelectrolyte Multilayers (PEM) on cellulose fibres as a new way of influencing the fibre surface and the adhesion between wood fibres. The aim of the study was to enhance the fundamental understanding of the adsorption mechanisms behind the formation of Polyelectrolyte Multilayers on cellulose fibres; to study how the properties of the layers can be influenced and to show how the properties of the layers influence the adhesion between the fibres and the strength of paper sheets made from the PEM treated fibres.

Different polyelectrolyte systems are known to form PEMs with different properties, and in this work two different polymer systems were extensively studied: poly(dimethyldiallylammonium chloride) (PDADMAC) / poly(styrene sulphonate) (PSS), which are both strong polylectrolytes (i.e. are highly charged over a wide range of pH) and poly allylaminehydrochloride (PAH) /poly acrylic acid (PAA), which are both weak polyelectorlytes (i.e. sensitive to pH changes). PEMs were also formed from PAH/ poly(3,4-ethylenedioxythiophene):PSS (PEDOT:PSS), in order to form electrically conducting PEMs on fibres and PEM-like structures were formed from polyethylene oxide (PEO) and polyacrylic acid (PAA).

In order to study the influence of the PEM on adhesion and paper strength, fibres were treated and used to form sheets which were physically tested according to determine the tensile index and strain at break. Both these systems were studied using different molecular mass fractions. High molecular mass PDADMAC/PSS (>500k/1000k) had a significantly greater influence as a function of the number of layers than low molecular mass PDADMAC/PSS (30k/80k). In contrast, sheets made from high molecular mass PAH/PAA (70k/240k) showed a significantly lower increase in strength than sheets made from low molecular PAH/PAA investigated earlier. Both these systems had a greater influence on paper strength when the cationic polyelectrolyte was adsorbed in the outermost layer. The amount of polyelectrolytes adsorbed on the fibres was determined using polylectrolyte titration (PET) and destructive analytical methods. Adsorption to model surfaces of silicon oxide was studied before the adsorption on fibres, in order to understand the influence on PEM properties of parameters such as salt concentration and adsorption time.

Adhesion studies of surfaces coated with PAH/PAA using AFM, showed an increase in adhesion as a function of the number of adsorbed layers. The adhesion was higher when PAH was adsorbed in the outermost layers. Individual fibres were also partly treated using a Dynamic Contact Angle analyser (DCA) and were studied with regard to their wettability. In general, the wettability was lower when the cationic polymer was outermost. The level of adhesion and paper strength are discussed in terms of rigidity and wettability and the PEMs demonstrating a large number of free chain ends, a large chain mobility and a low wettability was found to have the greatest influence to adhesion and paper strength.

Place, publisher, year, edition, pages
Stockholm: KTH , 2008. , viii, 60 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:27
Keyword [en]
fibre, polyelectorlyte, multilayer, wettability, contact angle, paper strength, atomic force microscopy, surface force apparatus
National Category
Paper, Pulp and Fiber Technology
Identifiers
URN: urn:nbn:se:kth:diva-4825ISBN: 978-91-7178-955-6 (print)OAI: oai:DiVA.org:kth-4825DiVA: diva2:14155
Public defence
2008-05-16, F3, Flodissalen, Lindstedtsvägen 26, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100823Available from: 2008-06-13 Created: 2008-06-13 Last updated: 2010-08-23Bibliographically approved
List of papers
1. Formation of polyelectrolyte multilayers on fibres: Influence on wettability and fibre/fibre interaction
Open this publication in new window or tab >>Formation of polyelectrolyte multilayers on fibres: Influence on wettability and fibre/fibre interaction
2006 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 296, no 2, 396-408 p.Article in journal (Refereed) Published
Abstract [en]

Polydimethyldiallylammonium chloride (PDADMAC) and polystyrene sulfonate (PSS) have been used to build-up polyelectrolyte multilayers (PEMs) on chemical soft wood fibres and on SiO2 at various electrolyte concentrations. Adsorption Onto SiO2 was studied using a stagnation point adsorption reflectometer (SPAR), and the adsorbed amount of PDADMAC and PSS on the fibres was determined using nitrogen analysis and Schoniger burning, respectively. The adsorption onto the two substrates was then compared. Paper testing showed that the tensile index (TI) increased by about 90% when 11 layers had been adsorbed, and that there was a correlation between the adsorbed amount and the increase in TI. It was also shown that the particular polymer present in the outermost layer significantly influenced the TI, and that PDADMAC produced a higher TI. A correlation between the adsorbed amount and the TI was also found. Individual fibres were partly treated with a PEM and analysed using a dynamic contact angle analyser (DCA) and environmental scanning electron microscopy (ESEM).

Keyword
polyelectrolyte; multilayer; adsorption; optical measurements; reflectance; contact angle; dynamics; environmental scanning electron microscopy; paper; mechanical properties
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-6022 (URN)10.1016/j.jcis.2005.09.017 (DOI)000236424600003 ()2-s2.0-33644987360 (Scopus ID)
Note

QC 20100823

Available from: 2006-06-25 Created: 2006-06-25 Last updated: 2015-05-26Bibliographically approved
2. Wettability changes in the formation of polymeric multilayers on cellulose fibres and their influence on wet adhesion
Open this publication in new window or tab >>Wettability changes in the formation of polymeric multilayers on cellulose fibres and their influence on wet adhesion
2007 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 314, no 1, 1-9 p.Article in journal (Refereed) Published
Abstract [en]

Individual wood fibres were partly treated with polyelectrolyte multilayers (PEMs) consisting of two different polymer combinations, poly allylamine (PAH)/poly acrylic acid (PAA) and polyethylene oxide (PEO)/PAA in order to study the influence of these polymers on fibre wettability. Single fibres were partly treated and analysed using a so-called dynamic contact analyser (DCA) where the fibres are wet under controlled conditions. When PAH/PAA was used, a stronger influence on fibre wettability was detected when PAH was adsorbed in the outermost layer of the multilayer than when PAA was adsorbed in the outermost layer. The wettability of fibres treated with PAH/PAA PEMs was also influenced by the pH of the adsorption. With the PEO/PAA system, however, the type of polymer adsorbed in the outermost layer caused no detectable difference. Tests of sheets prepared from fibres treated with PEO/PAA showed an increase of about 90% in the tensile index when 9 layers were adsorbed. These and other recently published results from similar experiments using PAH/PAA [S.M. Notley, M. Eriksson, L. Wagberg, J. Colloid Interface Sci. 292 (2005) 29] are compared to the results for the PEM-treated individual fibres. The results indicate that fibres with low wettability contribute to greater paper strength. AFM-force measurements, with the aid of a colloidal probe technique, have also been performed using PAH/PAA, showing that there is also a close correlation between lower wettability of the surfaces and a higher pull-off force between the PEM, treated surfaces, i.e. the flat surface and the colloidal probe. This is valid for the two pH strategies that are used for the formation for the PAH/PAA PEMs, which are studied using AFM-force measurements.

Keyword
polyelectrolyte; multilayer; adsorption; reflectance; contact angle; dynamics; paper; mechanical properties; individual; wood fibre
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-8744 (URN)10.1016/j.jcis.2007.04.046 (DOI)000248795100001 ()2-s2.0-34547514213 (Scopus ID)
Note
QC 20100823Available from: 2008-06-13 Created: 2008-06-13 Last updated: 2010-11-18Bibliographically approved
3. Polyelectrolyte multilayers on wood fibers: Influence of molecular weight on layer properties and mechanical properties of papers from treated fibers
Open this publication in new window or tab >>Polyelectrolyte multilayers on wood fibers: Influence of molecular weight on layer properties and mechanical properties of papers from treated fibers
2008 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 328, no 2, 233-242 p.Article in journal (Refereed) Published
Abstract [en]

This paper compares the influence of the molecular weight of polylelectrolytes forming polyelectrolyte multilayers (PEM) on wood fibers on adhesion and paper strength. Sheets were made from fibers treated with poly(allylamine hydrochloride) (PAH)/poly(acrylic acid) (PAA) of molecular mass 70,000 and 240,000, respectively, and of poly(dimethyldiallylammonium chloride) (PDADMAC)/poly(styrene sulfonate) (PSS) of molecular mass 30,000 and 80,000, respectively. The results were compared to what has recently been reported for PEM formation on fibers using a low-molecular-mass combination of PAH and PAA and a high-molecular-mass combination of PDADMAC/PSS. There was a less significant improvement in the case of the low-molecular-mass PDADMAC/PSS and the high-molecular-mass PAH/PAA. The adsorbed amounts of PAH and PDADMAC were also determined, showing a lower adsorbed amount of the low-molecular-mass PAH than of the high-molecular-mass PDADMAC. The amount of low-molecular-mass PDADMAC was similar to that found for high-molecular-mass PDADMAC/PSS. Individual fibers were partly treated and studied, showing a less significant decrease in wettability with low-molecular-mass PDADMAC/PSS than with the high-molecular-mass combination. The effect of the molecular weight on the adhesion was discussed in terms of the structure and wettability of the PEMs.

Keyword
Polyelectrolyte; Multilayer; Molecular mass; Adsorption; Reflectance; Contact angle; Dynamics; Paper; Mechanical properties; Individual; Cellulose fiber
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-8745 (URN)10.1016/j.jcis.2008.08.065 (DOI)000260845300003 ()2-s2.0-64849095165 (Scopus ID)
Note
QC 20100823. Uppdaterad från manuskript till artikel (20100823).Available from: 2008-06-13 Created: 2008-06-13 Last updated: 2010-08-23Bibliographically approved
4. Adhesive Interaction between Polyelectrolyte Multilayers of Polyallylamine Hydrochloride and Polyacrylic Acid Studied Using Atomic Force Microscopy and Surface Force Apparatus
Open this publication in new window or tab >>Adhesive Interaction between Polyelectrolyte Multilayers of Polyallylamine Hydrochloride and Polyacrylic Acid Studied Using Atomic Force Microscopy and Surface Force Apparatus
2009 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 25, no 5, 2887-2894 p.Article in journal (Refereed) Published
Abstract [en]

In the present work, the adhesion between substrates treated with identical polyelectrolyte multilayers (PEM) from polyallylamine hydrochloride (PAR) and poly(acrylic acid) (PAA) was studied using atomic force microscopy (AFM) and the Surface force apparatus (SFA). The AFM measurements, conducted under wet conditions for PEMs formed at pH 7.5, showed a higher adhesion (pull-off force) when PAH was adsorbed in the outermost layers. There was also a difference depending on the Molecular mass of the polymers, demonstrating a greater adhesion for the low molecular mass combination of polyelectrolytes. Furthermore, die time in contact showed to be of importance, with increasing pull-off forces with contact time at maximum load. The SFA measurements were conducted under dry conditions, at 100% RH, and under wet conditions for PEMs adsorbed at pH 7.5/3.5. The SFA adhesion measurements showed that under dry conditions, the adhesive forces between two high energetic mica substrates were lowered when they were covered by PEMs before the measurements. The thickness of the adsorbed layers was also measured using SFA. This showed that there was a significant swelling when the dry layers were exposed to 100% RH or to wet conditions. The swelling was higher, indicating a less rigid layer, when PAH was adsorbed in the outermost layer than when the PEM was capped with PAA.

Keyword
Adhesion measurements; Adhesive forces; Adhesive interactions; Adsorbed layers; AFM; Atomic forces; Atomic-force microscopies; Contact time; Dry conditions; Low molecular mass; Maximum loads; Mica substrates; Polyacrylic acids; Polyallylamine hydrochlorides; Polyelectrolyte multilayers; Pull-off forces; Surface force apparatus; Wet conditions
National Category
Paper, Pulp and Fiber Technology Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-9460 (URN)10.1021/la803628w (DOI)000263770800054 ()2-s2.0-65249127948 (Scopus ID)
Note

QC 20100823. Uppdaterad från manuskript till artikel (20100823). Tidigare titel: The Adhesive Interaction between Polyelectrolyte Multilayers of Polyallylamine Hydrochloride and Polyacrylic Acid studied using Atomic Force Microscopy (AFM) and Surface Force Apparatus (SFA)

Available from: 2008-11-05 Created: 2008-11-05 Last updated: 2016-05-16Bibliographically approved
5. A comparison of polyelectrolyte complexes and multilayers: Their adsorption behaviour and use for enhancing tensile strength of paper
Open this publication in new window or tab >>A comparison of polyelectrolyte complexes and multilayers: Their adsorption behaviour and use for enhancing tensile strength of paper
2009 (English)In: Nordic Pulp & Paper Research Journal, ISSN 0283-2631, Vol. 24, no 1, 77-86 p.Article in journal (Refereed) Published
Abstract [en]

This paper compares the adsorption behaviour and paper-strength-enhancing properties of polyelectrolyte complexes (PECs) and polyelectrolyte multilayers (PEMs) of polyallylamine hydrochloride and polyacrylic acid. Model adsorption experiments using SPAR (stagnation point adsorption reflectometry) and QCM-D (quartz crystal microbalance with dissipation) showed that the amount of complexes adsorbed was lower than the amount adsorbed when forming a multilayer using the same polymer system. From these experiments, in combination with AFM and ESEM imaging, it was concluded that the PEC adsorption stopped before full surface coverage was reached. Tensile testing of handsheets treated with PECs and PEM showed a significant increase in both tensile index and strain-at-break using both systems. The largest strength improvement was achieved with the fibres treated with the largest number of PEMs, but the largest effect per adsorbed amount of polymer was achieved by PEC treatment.

Keyword
Adsorption, Fibre modification, Jet mixing, Paper strength, Polyelectrolyte complex, Polyelectrolyte multilayer, QCM-D, SPAR
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-8769 (URN)10.3183/NPPRJ-2009-24-01-p077-086 (DOI)000265250200011 ()2-s2.0-65349186024 (Scopus ID)
Note
QC 20100819. Tidigare titel: A comparison between polyelectrolyte complexes and multilayers: their adsorption behaviour and use for enhancing tensile strength properties of paper. Correction in: Nordic Pulp & Paper Research Journal, vol. 24, issue. 2, p. 246Available from: 2008-06-17 Created: 2008-06-17 Last updated: 2012-05-08Bibliographically approved
6. Preparation of electrically conducting cellulose fibres utilizing polyelectrolyte multilayers of poly(3,4-ethylenedioxythiophene): poly(styrene sulphonate) and poly(allyl amine)
Open this publication in new window or tab >>Preparation of electrically conducting cellulose fibres utilizing polyelectrolyte multilayers of poly(3,4-ethylenedioxythiophene): poly(styrene sulphonate) and poly(allyl amine)
2007 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 43, no 10, 4075-4091 p.Article, review/survey (Refereed) Published
Abstract [en]

The primary goal with this work is to create electrically conductive cellulose fibres, this has been done to explore possible new applications for fibre based material. This research uses various methods to create polyelectrolyte multilayers (PEMs) on bleached softwood fibres and on SiO2 model surfaces, by sequentially treating these materials with poly(3,4ethylenedioxythiophene):poly(styrene sulphonate) (PEDOT:PSS) and poly(allyl amine) (PAH). Paper sheets were then produced from the PEM-modified pulp and evaluated in terms of tensile strength, adsorbed amount of polymer, and electrical conductivity. To evaluate the influence of fibre charge on the measured paper properties, pulps of two different initial fibre charge densities were prepared via carboxymethylation. Because of the bluish colour of PEDOT:PSS, the build-up of PEM could be easily followed, since the fibres grew increasingly darker blue throughout the modification sequence. The conductivity of the fibre network increased by 2-3 orders of magnitude when the pulp of a higher fibre charge density was used. This suggests that it is more important to create a fibrous network with a high fibre-fibre joint strength and a large total joined area in the sheet rather than to maximize the adsorbed amount of PEDOT:PSS. A difference in conductivity could also be noted depending on the polyelectrolyte adsorbed in the outer layer, PAH lowered the conductivity compared to PEDOT:PSS. Evaluating the mechanical properties revealed that the use of PEDOT:PSS reduces the tensile strength of the paper. When five double layers had been adsorbed onto the carboxymethylated sample in which PEDOT:PSS formed the outer layer, calculations indicated a 25% decrease in tensile strength compared to that of reference material without PEMs. ESEM studies indicate that PEM treatment produces a significantly changed and somewhat smoother fibre surface.

Keyword
electrical, conductive, polymer, polyelectrolyte, multilayer, mechanical properties, wood pulp fibers, paper strength, wettability, polymer, polyacetylene, derivatives, adsorption, joint, angle
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-17065 (URN)10.1016/j.eurpolymj.2007.03.053 (DOI)000250386600002 ()2-s2.0-34848827911 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2010-08-23Bibliographically approved

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