The interaction between water-soluble polymers and surfactant aggregates Brackman, Josephine Charlotte

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1 University of Groningen The interaction between water-soluble polymers and surfactant aggregates Brackman, Josephine Charlotte IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2006 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Brackman, J. C. (2006). The interaction between water-soluble polymers and surfactant aggregates s.n. Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date:

2 THE INTERACTION BETWEEN WATER-SOLUBLE POLYMERS AND SURFACTANT AGGREGATES

3 RWKSUNIVERSITEIT GRONINGEN THE INTERACTION BETWEEN WATER-SOLUBLE POLYMERS AND SURFACTANT AGGREGATES PROEFSCHRIFT ter verkrijging van het doctoraat in de Wiskunde en Natuurwetenschappen aan de Rijksuniversiteit Groningen op gezag van de Rector Magnificus Dr. L.J. Engels in het openbaar te verdedigen op vrijdag 30 november 1990 des narniddags te 2.45 uur precies door Josephine Charlotte Brachan geboren op 18 mei 1962 te Haarlem

4 Promotor: Prof. Dr. J.B.P.N. Engberts

5 VOORWOORD Nu zijn alle feiten en conclusies van vier jaar onderzoek vastgelegd op vele bladzijden en blijft er nog CCn pagina over om de mensen te bedanken, die ervoor gezorgd hebben dat die vier jaar zo plezierig zijn verlopen. Het allerbelangnjkst daarvoor zijn de waterlabgenoten geweest. Frank, Wilfried, Tino, en Saskia, mijn hartelijke dank voor wwel de gezelligheid als de wetenschappelijke respons. Niet rninder gaat mijn dank en waardering uit naar Jan Engberts, die mij het vertrouwen en de vrijheid heeft gegeven om mijn eigen gang te gaan, en dat steeds met zoveel belangstelling heeft gevolgd. De leden van de leescomrnissie, Prof.Dr. E.J.R. Sudholter, Prof.Dr. J. Lyklema, en Prof.Dr. R.M. Kellogg, ben ik zeer erkentelijk voor de vlotte correctie van, en nuttige cornmentaren op het manuscript. Verder dank aan Willem Kuil, voor snelle levering van vele mooie plaatjes; Marjan Ossebaard, voor het typewerk; Dr Jerzi Sek (Jerzi, thanks for the fun with the rheology) en Prof.Dr. L.P.B.M. Janssen, voor de inwijding in de viscometrie; Gert Haandrikrnan en Nico van Os, voor de microcalorimetrische experimenten; de werkgroepgenoten, voor de goede sfeer; en bovenal dank aan Jan Jaap.

6 CONTENTS Chapter 1 A bird's-eye view of polymer-micelle interaction 1.1 Introduction 1.2 Aggregation of surfactants 1.3 Introduction to the polymers 1.4 The development of the polymer-micelle model 1.5 Aims of the study 1.6 Survey of the contents Chapter 2 Interaction between nonionic surfactants and nonionic polymers: fact or fancy? 2.1 Introduction 2.2 The influence of polymers on the critical micelle concentrations 2.3 Clouding behavior and Krafft temperatures 2.4 Microcalorimetry 2.5 Discussion 2.6 Experimental section Chapter 3 The influence of polymers on the micellization of cetyltrimethylammonium salts Introduction Cetyltrimethylammonium salts Interaction of polymers with cationic surfactants Rodlike micelles of CTAX salts Critical micelle concentrations and aggregation numbers of CTAB 41

7 3.3 The sphere-to-rod transitions of CTATs 3.4 The polymer-induced transition from a non-newtonian to a Newtonian fluid 3.5 Experimental section Chapter 4 The effect of headgroup charge on polymer-micelle interaction: n-dodecyldimethylamine oxide 4.1 Introduction A brief glance at semipolar surfactants The effect of protonation on the micellization of DDAO 4.2 Critical micelle concentrations 4.3 Aggregation numbers 4.4 Clouding of PVME and PPO 4.5 Experimental section Chapter 5 The effect of headgroup charge on polymer-micelle interaction: mono-n-alkylphosphates 5.1 Introduction 5.2 Critical micelle concentrations 5.3 Clouding behavior of PVME P-NMR investigations Introduction P-NMR study of n-decylphosphate1pvme 5.5 Preliminary experiments on the effect of PVME on sodium didodecylphosphate vesicles 5.6 Experimental section

8 Chapter 6 The effect of headgroup charge on polymer-micelle interaction: spherical and rodlike micelles formed from Zalkylmalonate salts 6.1 Introduction 6.2 The aggregation behavior of mono- and di-salts of 2-alkylmalonic acids in aqueous solution 6.3 Aggregation of mono- and di-salts of 2-akylmalonic acids in polymer solution 6.4 Clouding behavior of PVME 6.5 Experimental section Chapter 7 SDS-induced enhancement of the viscosity and viscoelasticity of aqueous solutions of PPO 7.1 Introduction 7.2 The influence of SDS on the viscosity of a PEO solution 7.3 The influence of SDS on the viscoelasticity of a PEO solution 7.4 Experimental section Chapter 8 An attempt to model polymer-micelle interactions quantitatively 8.1 Introduction 8.2 The models for polymer-micelle interaction developed by Nagarajan and Ruckenstein 8.3 The 'dressed rnicelle' model of Evans and Ninharn Theory The 'dressed rnicelle' model applied to various polymer-micelle systems 8.4 Comparison of the models

9 8.5 Experimental section Chapter 9 Concluding remarks 9.1 Introduction 9.2 Conclusions 9.3 A criterion and a measure for polymer-micelle interaction 9.4 The driving force for polymer-rnicelle interaction 9.5 The role of the charge and structure of the surfactant headgroup References Summary Samenvatting 161