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Surface-Induced Rearrangement of Polyelectrolyte Complexes: Influence of Complex Composition on Adsorbed Layer Properties
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.ORCID iD: 0000-0001-8622-0386
2010 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 26, no 18, 14606-14614 p.Article in journal (Refereed) Published
Abstract [en]

The adsorption characteristics of two different types of polyelectrolyte complexes (PECs). prepared by mixing poly(allylamine hydrochloride) and poly(acrylic acid) in a confined impinging jet (CIJ) mixer, have been investigated with the aid of stagnation point adsorption reflectometry (SPAR), a quartz crystal microbalance with dissipation (QCM-D), and atomic force microscopy (A FM) using SiO2 surfaces The two sets of PEC were prepared by combining high molecular mass PAH/FAA (PEC-A) and low molt:cubit mass PAH/PAA (PEC-B) The PEC-A showed a higher adsorption to the SiO2 surfaces than the PEC-B The adsorption of the PEC-A also showed a larger change in the dissipation (AD), according to the QCM-D measurements, suggesting that the adsorbed layer of these complexes had a relatively lower viscosity and a lower shear modulus Complementary investigations of the adsorbed layer using A FM imaging showed that the adsorbed layer of PEC-A was significantly different from that of PEC-B and that the changes in properties with adsorption time were very different for the two types of PECs The PEC-A complexes showed a coalescence into larger block of complexes on the SiO2 surface, but this was not detected with the PEC-B The size determinations of the complexes in solution showed that they were very stable over time, and it was therefore concluded that the coalescence of the complexes was induced I the interaction between the complexes and the surface The results also indicated that polyelectrolytes can migrate between the different complexes adsorbed to the surface The results also give indications that the preparation of PEC-B leads to the formation of two different types of polyelectrolyte complexes differing in the amount of polymer in the complexes: i.e., two populations of complexes were formed with similar sizes but with totally different adsorption structures at the solid-liquid interface.

Place, publisher, year, edition, pages
2010. Vol. 26, no 18, 14606-14614 p.
Keyword [en]
Adsorbed layers, Adsorption characteristic, Adsorption structures, Adsorption time, AFM imaging, Complex compositions, High molecular mass, Impinging jet, Low molecular mass, Poly(acrylic acid ), Poly(allylamine hydrochloride), Polyelectrolyte complexes, Quartz crystal microbalance with dissipation, Shear modulus, Solid-liquid interfaces, Stagnation point adsorption reflectometry, Adsorption, Atomic force microscopy, Carboxylic acids, Coalescence, Hydrogels, Medical problems, Molecular mass, Organic acids, Phase interfaces, Polyelectrolytes, Polyethylenes, Quartz, Quartz crystal microbalances, Silicon compounds
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-26678DOI: 10.1021/la.1022054ISI: 000281690600035ScopusID: 2-s2.0-77956576994OAI: diva2:373335
QC 20101130Available from: 2010-11-30 Created: 2010-11-26 Last updated: 2012-05-08Bibliographically approved
In thesis
1. 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.
Trita-CHE-Report, ISSN 1654-1081 ; 2012:12
National Category
Paper, Pulp and Fiber Technology
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)
QC 20120508Available from: 2012-05-08 Created: 2012-05-08 Last updated: 2012-05-08Bibliographically approved

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