Transient entanglements and clusters in dilute polymer solutions

A convenient method to monitor polymer dissolution is to measure the pressure drop created by passing a polymer solution through a capillary constriction rheometer. In this work, we studied the dissolution of polyethylene oxide (PEO) and cationic starch (C‐starch). We found that for freshly dissolved and entangled PEO, the main contribution to the overall pressure drop is due to the contraction and expansion of PEO entanglements at the entrance and exit of the capillary, and that the friction in the capillary plays a minor role. On the other hand, for well‐dissolved PEO, because of the absence of PEO entanglements, the loss of pressure is mainly due to friction. At high velocities the contraction and expansion coefficient for freshly dissolved PEO was more than 20 times higher than for well‐dissolved PEO, resulting in a three times higher overall pressure drop. C‐starch consists of amylopectin (～ 85%) and amylose and is known to contain clusters when freshly dissolved, likely formed from the globular amylopectin molecules. For C‐starch, the main contribution to the overall pressure drop is due to friction. Entrance and exit effects contribute only 10% to the overall pressure drop, which might be due to the linear amylose molecules in C‐starch. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 253–262, 2008