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Polyelectrolyte complexes: Preparation, characterization, and use for control of wet and dry adhesion between surfaces
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
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: urn:nbn:se:kth:diva-94138ISBN: 978-91-7501-333-6 (print)OAI: oai:DiVA.org:kth-94138DiVA: diva2:525457
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
List of papers
1. 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, E-ISSN 2000-0669, 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: 2017-12-14Bibliographically approved
2. Using jet mixing to prepare polyelectrolyte complexes: Complex properties and their interaction with silicon oxide surfaces
Open this publication in new window or tab >>Using jet mixing to prepare polyelectrolyte complexes: Complex properties and their interaction with silicon oxide surfaces
2010 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 351, no 1, 88-95 p.Article in journal (Refereed) Published
Abstract [en]

The influence of mixing procedure on the properties of polyelectrolyte complexes (PECs) was investigated using two complexation techniques, polyelectrolyte titration and jet mixing, the latter being a new method for PEC preparation. For the low-molecular-weight polyelectrolytes polyacrylic acid (PAA) and polyallyl amine hydrochloride (PAH), shorter mixing times produced smaller PECs, whereas for higher molecular weights of the same polyelectrolytes, PEC size first decreased with decreasing mixing time to a certain level, after which it started increasing again. This pattern was likely due to the diffusion-controlled formation of "pre-complexes", which, in the case of low-molecular-weight polymers, occurs sufficiently quickly to form stable complexes; when polyelectrolytes are larger, however, non-equilibrium pre-complexes, more prone to aggregation, are formed. Comparing the techniques revealed that jet mixing produced smaller complexes, allowing PEC size to be controlled by mixing time, which was not the case with polyelectrolyte titration. Higher polyelectrolyte concentration during jet mixing led to the formation of larger PECs. It was also demonstrated that PEC size could be changed after preparation: increasing the pH of the PEC dispersion led to an irreversible increase in PEC size, whereas lowering the pH did not influence PEC size. The adsorption behavior of PECs formed from weak polyelectrolytes on model substrates was studied using QCM-D, SPAR, and AFM imaging; the results indicated that increasing the pH increased the amount of PECs adsorbed to model surfaces. However, the amount of PECs adsorbed to the model surfaces was low compared with other systems in all studied cases.

Keyword
Adsorption, Jet mixing, Mixing time, Polyelectrolytes, Polyelectrolyte complex
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-26660 (URN)10.1016/j.jcis.2010.07.027 (DOI)000282252700013 ()2-s2.0-77956228955 (Scopus ID)
Note
QC 20101202Available from: 2010-12-02 Created: 2010-11-26 Last updated: 2017-12-12Bibliographically approved
3. Surface-Induced Rearrangement of Polyelectrolyte Complexes: Influence of Complex Composition on Adsorbed Layer Properties
Open this publication in new window or tab >>Surface-Induced Rearrangement of Polyelectrolyte Complexes: Influence of Complex Composition on Adsorbed Layer Properties
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.

Keyword
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
Identifiers
urn:nbn:se:kth:diva-26678 (URN)10.1021/la1022054 (DOI)000281690600035 ()2-s2.0-77956576994 (Scopus ID)
Note

QC 20101130

Available from: 2010-11-30 Created: 2010-11-26 Last updated: 2017-06-08Bibliographically approved
4. Use of PECs and PEMs from polymers and nanoparticles to create sacrificial bonds between surfaces
Open this publication in new window or tab >>Use of PECs and PEMs from polymers and nanoparticles to create sacrificial bonds between surfaces
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-94154 (URN)
Note
QS 2012Available from: 2012-05-08 Created: 2012-05-08 Last updated: 2012-05-08Bibliographically approved
5. AFM adhesion imaging for comparison of polyelectrolyte complexes and polyelectrolyte multilayers
Open this publication in new window or tab >>AFM adhesion imaging for comparison of polyelectrolyte complexes and polyelectrolyte multilayers
2012 (English)Article in journal (Other academic) Submitted
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-94155 (URN)
Note

QC 2012

Available from: 2012-05-08 Created: 2012-05-08 Last updated: 2017-02-23Bibliographically approved

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