SHEAR FRACTURE OF POLYSTYRENE MELTS AND SOLUTIONS

We find that symptoms of polymer melt fracture, such as a time-dependent decrease in apparent sample modulus and apparent slip, can be induced by oscillatory torsional shearing flow of polystyrene melts and solutions, even when the polymer molecular weight is below the entanglement threshold, and thre strain amplidute is as low as 3%. Visualization of samples during and after fracture show crack and bubble formation, as well as delamination of the polymer from the rheometer tools. For polystyrene melts, the critical stress for fracture is tau* almost-equal-to 0.1 - 1.0 MPa, depending on polymer molecular weight and temperature, and for solutions it is as low as 5 x 10(3) Pa. Since ''constitutive instabilities'' require the viscoelastic properties to be highly nonlinear, our observations of melt fracture in unentangled polymers at shearing strains well within the linear viscoelastic range rule out this mechanism for some of our experiments, and show that melt fracture is not always caused by constitutive instabilities.