Mechanochemical degradation kinetics of high-density polyethylene melt and its mechanism in the presence of ultrasonic irradiation

In this paper, the effect of ultrasonic intensity on the degradation of high-density polyethylene (HDPE) melt, degradation mechanism, ultrasonic degradation kinetics of HDPE melt as well as the development of molecular weight distribution of HDPE melt during ultrasonic degradation were studied. In the initial stage, the ultrasonic degradation of HDPE melt shows a random scission process, and the molecular weight distribution broadens. After that, the ultrasonic degradation of HDPE melt shows a nonrandom scission process, and the molecular weight distribution of HDPE melt narrows with ultrasonic irradiation time. The average molecular weight of HDPE decreases with the increase of ultrasonic intensity and increases and trends forward that of undegraded HDPE with the increase of distance from ultrasonic probe tip, indicating that attenuation of ultrasonic intensity in HDPE melt is very quick. Ultrasonic degradation kinetics of HDPE melt obeys the equation: M-1 = M-infinity + Ae(-kt). The theoretic calculation by this equation accords well with the experimental results. The plausible ultrasonic degradation mechanism of polymer melt based on molecular relaxation was also proposed in this paper. (C) 2003 Elsevier B.V. All rights reserved.