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A comparison of polyelectrolyte complexes and multilayers: Their adsorption behaviour and use for enhancing tensile strength of paper
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0001-8622-0386
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
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.

Place, publisher, year, edition, pages
2009. Vol. 24, no 1, 77-86 p.
Keyword [en]
Adsorption, Fibre modification, Jet mixing, Paper strength, Polyelectrolyte complex, Polyelectrolyte multilayer, QCM-D, SPAR
National Category
Paper, Pulp and Fiber Technology
Identifiers
URN: urn:nbn:se:kth:diva-8769DOI: 10.3183/NPPRJ-2009-24-01-p077-086ISI: 000265250200011Scopus ID: 2-s2.0-65349186024OAI: oai:DiVA.org:kth-8769DiVA: diva2:14183
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
In thesis
1. Polyelectrolyte complexes: their preparation, adsorption behaviour and effect on paper properties
Open this publication in new window or tab >>Polyelectrolyte complexes: their preparation, adsorption behaviour and effect on paper properties
2008 (English)Licentiate thesis, comprehensive summary (Other scientific)
Abstract [en]

In this work, the formation of polyelectrolyte complexes (PECs) has been studied using a jet mixing method not previously used for mixing polyelectrolytes. The PECs were formed from two weak polyelectrolytes, i.e., polyacrylic acid (PAA) and polyallylamine hydrochloride (PAH), with different mixing times, and the results were compared with those for PECs formed using the conventional polyelectrolyte titration method.

 

The adsorption behaviour of the formed PECs on silicon oxide substrates and pulp fibres was analysed, and the results were compared with those for polyelectrolyte multilayers (PEMs) prepared from the same two polyelectrolytes.

 

The results indicated that by using the jet mixer, the size of the formed PECs could be controlled, which was not the case with the polyelectrolyte titration method. The PECs produced by jet mixing were also found to be smaller than those produced by polyelectrolyte titration. From these results, a two-step mechanism for the formation of PECs was suggested: initial precomplex formation, which is a fast and diffusion-controlled process, followed by a reconformation process, during which the vigorous mixing in the jet mixer can partially limit secondary aggregation.

 

When the complexes were adsorbed to silicon oxide or pulp fibre surfaces, adsorption studies indicated that it was impossible to reach the same adsorption levels for PECs as for PEMs. This was explained in terms of free energy, entropical, reasons rather than to any geometric limitation of the surface. Despite the smaller amount of polyelectrolyte adsorbed from the PEC treatment than from the PEM treatment of pulp fibres, the PEC treatment had the greatest effect on paper strength per adsorbed amount of polymer. This was thought to be because the three-dimensional structure of the PECs, versus the smoother structure of PEMs, allows for the formation of multiple contact points between the macroscopically rough fibres and increased molecular contact area.

 

In the adsorption experiments, it was also found that net cationic complexes can adsorb to both anionic and cationic substrates. This phenomenon was explained by the occurrence of anionic patches on the surface of the net cationic PECs and the ability of the PECs, formed from weak polyelectrolytes, to partially change charge upon exposure to a surface of the same charge as the complex itself, due to a change of the degree of dissociation of the polyelectrolytes constituting the complex.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. 38 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:45
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-4833 (URN)978-91-7415-015-5 (ISBN)
Presentation
2008-06-13, 10:00
Opponent
Supervisors
Note
QC 20101102Available from: 2008-06-17 Created: 2008-06-17 Last updated: 2010-11-02Bibliographically approved
2. On the Adhesion Between Substrates Covered with Polyelectrolyte Multilayers
Open this publication in new window or tab >>On the Adhesion Between Substrates Covered with Polyelectrolyte Multilayers
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
fibre, polyelectorlyte, multilayer, wettability, contact angle, paper strength, atomic force microscopy, surface force apparatus
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-4825 (URN)978-91-7178-955-6 (ISBN)
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
3. Polyelectrolyte complexes: Preparation, characterization, and use for control of wet and dry adhesion between surfaces
Open this publication in new window or tab >>Polyelectrolyte complexes: Preparation, characterization, and use for control of wet and dry adhesion between surfaces
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis examines polyelectrolyte complex (PEC) preparation, adsorption behaviour, and potential use for control of wet and dry adhesion between surfaces.

PEC formation was studied using a jet-mixing method not previously used for mixing polyelectrolytes. The PECs were formed using various mixing times, and the results were compared with those for PECs formed using the conventional polyelectrolyte titration method. The results indicated that using the jet mixer allowed the size of the formed PECs to be controlled, which was not the case with the polyelectrolyte titration method, and a two-step mechanism for PEC formation was suggested.

Adsorption experiments comparing two types of PECs, both produced from PAA and PAH, but with different molecular weights, demonstrated that surface-induced aggregation occurred in the high-molecular-weight PECs, whereas the adsorption stopped at a low level in the low-molecular-weight PECs. It was suggested that the latter PECs consisted of two fractions of complexes and that the fraction with lower polymer density exerted a site-blocking effect, hindering further adsorption.

It was also demonstrated that particle-PECs (PPECs), in which one polyion was replaced with a silica nanoparticle, could be prepared. The purpose of preparing PPECs was to create a PEC structure that could create a joint with a special failure pattern referred to as disentanglement behaviour. Using the colloidal probe AFM technique, the expected disentanglement could be detected in PPECs, though the joint strength was low. Adhesion experiments demonstrated significantly higher pull-off values with polymer–polymer complexes than with PPECs. However, there was large spread in the data, possibly due to the surface inhomogeneity.

Experiments using low-molecular-weight PECs as a paper strength agent demonstrated that PECs can indeed increase paper strength. Comparing the PEC results with those for polyelectrolyte multilayers (PEMs) prepared from the same polyelectrolytes indicated that, since the PEM strategy enables higher adsorption levels than does the PEC strategy, greater absolute strength improvements could be achieved using PEMs. However, PEC treatment resulted in the greatest effect per adsorbed amount of polymer.

Abstract [sv]

Denna avhandling behandlar tillverkning av polyelektrolytkomplex (PEC), deras adsorption och potentiella användning för att öka adhesionen mellan ytor i vått och torrt.

PEC bildades med hjälp av jetmixningsmetoden, en metod som inte tidigare använts för PEC‑tillverkning. Resultaten av tillverkningen jämfördes med resultat för PEC bildade genom den tidigare ofta använda polyelektrolyt­titrerings­metoden. Jämförelsen visade att med jetmixningsmetoden kunde storleken på de bildade PECen styras med hjälp av blandningstiden, något som inte var möjligt med polyelektrolyttitreringsmetoden. Utifrån resultaten föreslås en två-stegsmekanism för PEC-bildandet.

Adsorptionsexperiment med två typer av PEC, båda tillverkade av PAA och PAH fast med olika molekylvikter, visade att för högmolekylära PEC skedde en ytinducerad aggregation, medan adsorptionen stannade på en låg nivå för de lågmolekylära PECen. De senare PECen antogs bestå av två olika fraktioner, av vilka en fraktion med lägre polymerdensitet föreslogs ha en ytblockerande effekt, och därigenom hindrades vidare adsorption.

Det visades också att partikel-PEC (PPEC), där ena polymerkomponenten bytts ut mot anjoniska nanopartiklar av kiseloxid, kunde tillverkas. Syftet var att skapa strukturer som kan åstadkomma ett brottmönster med uttrassling mellan ytor. Med hjälp av kolloidalprobs-AFM (atomkraftsmikroskopi) kunde det önskade uttrasslingsbeteendet påvisas, men fogstyrkan var låg. Adhesionsexperiment med polymer-polymer-PEC visade på högre styrkor än PPECen, men också stor spridning i data, troligen på grund av inhomogenitet i ytornas struktur.

Experiment där lågmolekylära PEC använts som styrkekemikalie för papper visade att tillsats av PEC kan öka pappersstyrkan. Jämförelse med resultat för poly­elektrolytmultilager (PEM) av samma komponenter visade att eftersom högre adsorptionsnivåer kan uppnås med PEM så kan större styrkeökningar erhållas med PEM. Däremot visades att den högsta styrkeökningen per adsorberad mängd polymer erhölls med PEC-behandlingen.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. 50 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:12
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-94138 (URN)978-91-7501-333-6 (ISBN)
Public defence
2012-05-31, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20120508Available from: 2012-05-08 Created: 2012-05-08 Last updated: 2012-05-08Bibliographically approved

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