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Licensed Unlicensed Requires Authentication Published by De Gruyter April 11, 2013

Control of Rheological Behaviour with Oppositely Charged Polyelectrolyte Surfactant Mixtures

Kontrolle des rheologischen Verhaltens mittels entgegengesetzt geladenen Polyelektrolyt-Tensid-Mischungen
I. Hoffmann , S. Prévost , M. Medebach , S. Rogers , N. J. Wagner and M. Gradzielski


Mixtures of the cationic, cellulose based polyelectrolyte JR 400 and the anionic surfactant sodium dodecylbenzene sulfonate (LAS) have been used to control the rheological behaviour of aqueous solutions. Around charge equilibrium precipitation takes place, but both for the surfactant-rich and the polymer-rich side homogeneous solutions are formed. In these monophasic regions the rheology depends strongly on the mixing ratio between the two components and highly viscous systems can be obtained on the polyelectrolyte rich side upon the addition of relatively small amounts of surfactant. Here the viscosity increases by more than four orders of magnitude before reaching the phase boundary of precipitation. Small-angle neutron scattering (SANS) showed the formation of an interconnected network of rodlike aggregates composed of a polyelectrolyte/surfactant complex, which explains the observed high viscosity due to the high degree of interconnection by the polyelectrolyte.


Mischungen aus dem kationischen, zellulosebasierten Polyelektrolyten JR 400 und dem anionischen Tensid Natriumdodecylbenzensulfonat (LAS) ermöglichen die Kontrolle der rheologischen Eigenschaften wässriger Lösungen. Im Bereich des Ladungsgleichgewichts beobachtet man Präzipitation, während auf der tensidreichen und der polymerreichen Seite homogene Lösungen vorliegen. In diesen einphasigen Gebieten hängt die Rheologie stark vom Mischungsverhältnis der beiden Komponenten ab und hochviskose Systeme erhält man auf der polyelektrolytreichen Seite durch den Zusatz relativ geringer Mengen an Tensid. Dabei steigt die Viskosität vor der Phasengrenze zur Präzipitatregion um mehr als vier Größenordnungen an. Kleinwinkelneutronenstreuung (SANS) zeigte die Bildung eines Netzwerks stäbchenförmiger Aggregate aus einem Polyelektrolyt/Tensid-Komplex, das durch die Polyelektrolytketten vielfach vernetzt ist und somit das beobachtete rheologische Verhalten aufgrund dieser Vernetzung erklärt.

Prof. Dr. Michael Gradzielski, Dr. Ingo Hoffmann, TU-Berlin, Stranski-Laboratorium, Institut für Chemie, Fakultät II, Sekr. TC 7, Straße des 17. Juni 124, 10623 Berlin, Tel.: +493031423931, Fax: +493031426602. E-Mail: ,

Michael Gradzielski studied chemistry at the Universität Bayreuth and at the University of Wisconsin – Madison (UW). He did his dissertation at the Universität Bayreuth on the topic of microemulsions and micromulsion gels in 1992 in the group of Prof. H. Hoffmann. After a post-doctoral stay at the Ecole Normale Superieure, Paris, in the group of Prof. D. Langevin, he finished his habilitation for Physical Chemistry at the Universität Bayreuth in 2000. Since 2004 he is full professor for Physical Chemistry at the Technische Universität Berlin and responsible for the field “Physikalische Chemie/Molekulare Materialwissenschaften”.

Ingo Hoffmann studied chemistry at the Technische Universität Berlin, where he also did his PhD thesis on the topic of aggregation and adsorption of polymer-surfactant mixtures in the group of Prof. M. Gradzielski in 2010. Since 2011 he is post-doc at the ILL, Grenoble.

Norman J. Wagner studied chemical engineering at Carnegie Mellon University and Princeton University, where he received his PhD under the supervision of Prof. William B. Russel in 1988. After post-doctoral stays at the Universität Konstanz and Los Alamos National Laboratory, he became assistant professor in the department of chemical engineering at the University of Delaware in 1991. In 1995 he became associate professor, professor in 1999. He has been a visiting Professor at the ETH-Zurich (1997), Uni Konstanz (1997) and La Sapienza, Rome (2004). Since 2007 he is the chairman of the department of chemical engineering and is the Alvin B. and Julia O. Stiles named Professor. He is also the Director of the Center for Neutron Science at the University of Delaware, a cooperative agreement with the National Center for Neutron Research of NIST.

Sarah Rogers has been the Instrument Responsible for Sans2d at ISIS-STFC, since May 2010. She has been a facilities scientist on small-angle beamlines since August 2006, firstly as a junior beamline scientist on I22 at Diamond Light Source (DLS) Ltd and later joining ISIS as a member of the SANS team in February 2008. Before arriving at Diamond she was at the University of Bristol in the School of Chemistry, where she was undertaking an EPSRC funded PDRA position in the lab of Professor Julian Eastoe, studying the formation of gold nanoparticles in supercritical carbon dioxide. Prior to this she completed her PhD, titled ‘Fluorocarbon-Hydrocarbon Incompatibility in Micellar Polymerizations’, in the same lab in 2005. During her PhD she also was involved in many other projects including water-in-supercritical CO2 microemulsions, ionic liquid-in-oil microemulsions, novel surfactant synthesis and characterization and pH-degradable surfactants. Sarah also obtained her MSci in Chemistry from the University of Bristol in 2002.

Martin Medebach studied physics at the Universität Bonn. In 2004 he received his PhD in the group of Prof. T. Palberg at the Universität Mainz for his work on electrokinetics of concentrated colloidal suspensions. From 2005 to 2007 he worked at the Uninversität Graz in the group of Prof. O. Glatter. Since 2007 he works in the group of Prof. M. Gradzielski at the Technische Universität Berlin

Sylvain Prévost studied physical chemistry at the Graduate School of Chemistry and Physics of Bordeaux (ENSCPB). From 2002–2006 he did his dissertation at the University of Versailles-Saint-Quentin-en-Yvelines (UVSQ) under the supervision of Prof. C. Larpent and Dr. F. Testard about thermo sensitive, nonionic surfactants with chelating abilities toward metal ions. Since 2006, he works as a post-doc at TU Berlin and HZB.


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Received: 2011-07-07
Published Online: 2013-04-11
Published in Print: 2011-11-01

© 2011, Carl Hanser Publisher, Munich

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