Polyelectrolytes on Surfaces and their Complexes with Surfactants, Thermodynamics versus kinetics

Research output: ThesisDoctoral Thesis (compilation)


The interfacial properties of polyelectrolytes, mainly cationic with various content of amphiphilic groups, and their complexes with an oppositely charged surfactant, sodium dodecyl sulfate (SDS), have been investigated using time-resolved ellipsometry. This thesis focuses on the kinetics and reversibility aspects of polymer adsorption and the control of the adsorption by regulating the electrostatic interactions.

The formed structure of adsorbed layer was found to be dependent not only on the bulk conditions, but also on the pre-applied conditions, that is the path used to obtain a particular solution condition (e.g. by changing pH and concentration of salt, surfactant or polymer).

The results indicate that polyelectrolyte adsorption appears only partially reversible, due to the high affinity to the surface, which slows down the rearrangement process. In general relaxation occurs more easily if the direction of the process is from low to the higher surface coverage.

By pre-applying certain bulk conditions, the desired conformation and enhanced (or reduced) concentration of the polymer in the interfacial layer can be achieved.

Association of the surfactant to the polymer seems to control the interfacial behavior, which depends on the surfactant concentration. In all cases, the maximum adsorption was obtained at a SDS concentration just before the expected phase separation region, while the complex in some cases could desorb from the surface at high SDS concentration (above the cmc).

Different results were obtained for coadsoption of amphiphilic polyelectrolytes when surfactant SDS was added to the preadsorbed layers and when complexes were preformed in the solution prior the adsorption.


  • Yulia Samoshina
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Physical Chemistry


  • Fysikalisk kemi, Polymer technology, Physical chemistry, SDS, amphiphilic polyelectrolytes, ellipsometry, reversibility, kinetics of adsorption, polyelectrolytes at solid-liquid interface, polyelectrolyte-oppositely charged surfactant complexes, biopolymers, Polymerteknik
Original languageEnglish
Awarding Institution
Supervisors/Assistant supervisor
  • [unknown], [unknown], Supervisor, External person
Award date2004 Nov 26
  • Department of Physical Chemistry, Lund University
Print ISBNs91-7422-066-7
Publication statusPublished - 2004
Publication categoryResearch

Bibliographic note

Defence details Date: 2004-11-26 Time: 10:15 Place: sal D, Chemical Center External reviewer(s) Name: Klitzing, Regine V Title: [unknown] Affiliation: Kiel University, Germany --- Article: 1. Equilibrium Aspects of Polycation Adsorption on Silica Surface – how the Adsorbed Layer Structure Responds to Changes in Bulk Solutionby Yulia Samoshina, Tommy Nylander, Victor Shubin, Rogert Bauer, Krister Esskilson, manuscript Article: 2. Adsorption of Cationic, Anionic and Hydrophobically Modified Polyacrylamides on Silica Surfacesby Yulia Samoshina, Antonio Diaz, Yvonne Becker, Tommy Nylander, BjÚrn Lindman, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2003, 231, 195-205 Article: 3. Adsorption and Aggregation of Cationic Amphiphilic Polyelectrolytes on Silicaby Yulia Samoshina, Tommy Nylander, Per Claesson, Karin ShillÎn, Ilias Iliopolous and BjÚrn Lindman, submitted to Langmuir Article: 4. Adsorption of Cationic Cellulose Derivatives/Anionic Surfactant Complexes onto Solid Surfaces. I. Silica Surfacesby Eiji Terada, Yulia Samoshina, Tommy Nylander, BjÚrn LindmanLangmuir 2004, 20(5), 1753-1762 Article: 5. Adsorption of Cationic Cellulose Derivatives/Anionic Surfactant Complexes onto Solid Surfaces. II. Hydrophobized Silica Surfacesby Eiji Terada, Yulia Samoshina, Tommy Nylander, BjÚrn LindmanLangmuir, 2004; 20(16); 6692-6701. Article: 6. Cationic Amphiphilic Polyelectrolytes and Oppositely Charged Surfactants at the Silica-Aqueous Interfaceby Yulia Samoshina, Tommy Nylander and BjÚrn Lindman, manuscript