In: Recent Developments in Silicone-Based Materials ISBN 978-1-61668-624-6 Editor: Maria Cazacu, pp. 33-75 © 2010 Nova Science Publishers, Inc. Chapter 2 SOLUTION BEHAVIOR OF POLYSILOXANES Maria Bercea, Simona Morariu, Cristina-Eliza Brunchi and Maria Cazacu Petru PoniInstitute of Macromolecular Chemistry, 41-A Grigore Ghica Vodǎ Alley, 700487 Iaşi, Romania ABSTRACT The thermodynamics of flexible polymers in solution have attracted the interest of many investigators. Because of its unique properties (low viscosity even at high molecular weight, high solubility in non-polar solvents, high volatility at low molecular weight, low surface tension, high refractive index, etc.), poly(dimethylsiloxane) has been the subject of various studies with respect to its solution properties. Several theories have been put forward in an effort to explain the various phenomena occurring when very flexible polymer molecules are dissolved in solvents of different qualities. The aim of this chapter is to review briefly the background of thermodynamic and rheological properties for different polysiloxanes in solution and to provide the recent achievements in this area. The applicability of the theories explaining the various phenomena that occur when very flexible polymer molecules are dissolved in solvents of different qualities was critically discussed for the particular case of the polysiloxanes. The extension of the Flory-Huggins theory by using the new concept of dimensional relaxation developed recently by Wolf [1,2] enables the modeling of several hitherto unexplainable anomalous phenomena, as for example the uncommon molecular weight dependencies of second virial coefficient of poly(dimethylsiloxane) in dilute solutions [3]. Rheological and optical properties of solutions of polysiloxanes can be regarded in correlations with their interest for practical applications. LIST OF SYMBOLS AP-PDMS -bis(3-aminopropyl)-poly(dimethylsiloxane) H 3 C-PDMS -bis(trimethylsilyl)-poly(dimethylsiloxane) H-PDMS -bis(H)-poly(dimethylsiloxane)