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Interactions between Bottle-Brush Polyelectrolyte Layers: Effects of Ionic Strength and Oppositely Charged Surfactant
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface Chemistry.
Department of Polymer Chemistry, Vilnius University.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface Chemistry.
2008 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 323, no 1, 191-202 p.Article in journal (Refereed) Published
Abstract [en]

Interactions between cationic bottle-brush polyelectrolyte layers adsorbed on mica across salt and oppositely charged surfactant solutions were investigated with the interferometric surface force apparatus, and the results were compared with what is known for similarly charged linear polyelectrolytes. Ellipsometric measurements demonstrated that the bottle-brush polyelectrolytes, which contain 45 units long poly(ethylene oxide) side chains, are more readily desorbed than linear equivalents when the ionic strength of the solution is increased. It is argued that this is due to the steric repulsion between the poly(ethylene oxide) side chains that reduces the surface affinity. The preadsorbed bottle-brush polyelectrolyte layers were also exposed to sodium dodecyl sulfate (SDS) solutions. It was found that the presence of SDS affected the force profiles less than observed for similarly charged linear polyelectrolytes. This observation was attributed to excluded volume constraints imposed by the poly(ethylene oxide) side chains that reduces the accessibility of the charged polyelectrolyte segments and counteracts formation of large aggregates within the layer.

Place, publisher, year, edition, pages
2008. Vol. 323, no 1, 191-202 p.
Keyword [en]
polyelectrolyte, brush polyelectrolyte, bottle-brush polyelectrolyte, comb polyelectrolyte, poly(ethylene oxide), surfactant, association, surface force apparatus (SFA), phase modulated ellipsometry, mica, sodium dodecyl sulfate
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-8155DOI: 10.1016/j.jcis.2008.02.071ISI: 000256646600027Scopus ID: 2-s2.0-44149114718OAI: oai:DiVA.org:kth-8155DiVA: diva2:13403
Note
QC 20100830Available from: 2008-03-27 Created: 2008-03-27 Last updated: 2010-08-30Bibliographically approved
In thesis
1. Polyelectrolytes: Bottle-Brush Architectures and Association with Surfactants
Open this publication in new window or tab >>Polyelectrolytes: Bottle-Brush Architectures and Association with Surfactants
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis has the dual purpose of raising awareness of the importance of the mixing protocol on the end products of polyelectrolyte-oppositely charged surfactant systems, and to contribute to a better understanding of the properties of bottle-brush polyelectrolytes when adsorbed onto interfaces.

In the first part of this thesis work, the effects of the mixing protocol and the mixing procedure on formed polyelectrolyte-oppositely charged surfactant aggregates were investigated. It was shown that the initial properties of the aggregates were highly dependent on the mixing parameters, and that the difference between the resulting aggregates persisted for long periods of time.

The second part of the studies was devoted to the surface properties of a series of bottle-brush polyelectrolytes made of charged segments and segments bearing poly(ethylene oxide) side chains; particular attention was paid to the effect of side chain to charge density ratio of the polyelectrolytes. It was shown that the adsorbed mass of the polyelectrolytes, and the corresponding number of poly(ethylene oxide) bearing segments at the interface, went through a maximum as the charge density of the polyelectrolyte was increased. Also, it was found that bottle-brush polyelectrolyte layers were desorbed quite easily when subjected to salt solutions. This observation was rationalized by the unfavourable excluded volume interactions between the side chains and the entropic penalty of confining them at an interface, which weaken the strength of the binding of the polyelectrolytes to the interface. However, it was shown that the same side chains effectively protect the adsorbed layer against desorption when the layer is exposed to solutions containing an oppositely charged surfactant. Investigation of the lubrication properties of the bottle-brush polyelectrolytes in an asymmetric (mica-silica) system also related the observed favourable frictional properties to the protective nature of the side chains. The decisive factor for achieving very low coefficients of friction was found to be the concentration of the side chains in the gap between the surfaces. Interestingly, it was shown that a brush-like conformation of the bottle-brush polyelectrolyte at the interface has little effect on achieving favourable lubrication properties. However, a brush-like conformation is vital for the resilience of the adsorbed layer against the competitive adsorption of species with a higher surface affinity.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. 39 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:18
Keyword
Polyelectrolyte, Surfactant, Bottle-Brush Polyelectrolyte, Comb Polyelectrolyte, Non-Equilibrium State, Polymer Architecture, Adsorption, Desorption, Association, Excluded Volume, Light Scattering, SFA, AFM, QCM-D, Turbidimeter, Mica, Silica, Surface Forces
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-4683 (URN)978-91-7178-903-7 (ISBN)
Public defence
2008-04-18, F3, Lindstedsvägen 28 100 44, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100830Available from: 2008-03-27 Created: 2008-03-27 Last updated: 2012-01-20Bibliographically approved

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