Ostwald ripening in immiscible polyolefin blends

Abstract

AbstractThe coarsening in the quiescent melt of the phase‐segregated particles of a polymer blend, composed of a narrow molecular weight fraction of an unbranched high‐density polyethylene (HDPE) and a highly branched (100 ethyl branches/1000 C atoms) hydrogenated polybutadiene (HPB) was studied. The system was effectively binary, due to the narrow molecular weight and composition distributions of each component. The system was composed of 90 wt % of the HDPE and 10 wt % of the HPB and it formed a two‐phase system in the melt at 177°C. The blend was precipitated from xylene solution in order to obtain an initially intimately mixed system. This was the third study in a series of studies of the coarsening of phase‐segregated particles in polymer blends. This study was unique in that the system studied was binary in this case while the previous systems were multicomponent. Since the present system was binary, exact thermodynamic calculations of the phase state of this system could be applied with a high level of confidence. The droplet phase particles, which were mainly composed of the HPB, were observed to coarsen on storage in the melt for times of from 5 s to 1 h. At the shortest storage time of 5 s the particles had an average radius of about 0.05 μm and coarsened to about 0.2 μm after 1 h storage in the melt state. Particle dimensions were measured by scanning electron microscopy of n‐heptane‐etched and gold‐coated sections. It was found that the volume of the particles increased linearly with time and that the rate constant of coarsening was Kexp = 1.23 × 10−18 cm3/s and this agreed fairly well with the rate constant calculated from Ostwald ripening theory of Kce = 0.86 × 10−18 cm3/s. In contrast the rate constant for direct particle diffusion and coalescence was Kc = 3.6 × 10−20 cm3/s. Since this was two orders of magnitude smaller than the rate constant for Ostwald ripening, it was concluded that, although the linear increase of volume with time was also consistent with the particle diffusion and coalescence mechanism, this was not a significant contributor to the coarsening mechanism. The major cause for the insignificance of the particle diffusion and coalescence mechanism was the high melt viscosity of the matrix polymers. The application of the Ostwald ripening theory to this system could be made with a high level of confidence because it was binary. It was found that the phase concentration of the droplet phase apparently underwent a rapid increase during the first 1‐2 min of storage in the melt, indicating that the system did not reach phase equilibrium (i.e., did not completely phase‐segregate) for about 1‐2 min. This further indicated that the long‐time coarsening regime was not entered until after this length of time. The particle size distributions remained approximately self‐similar over the period of coarsening, as predicted by Ostwald ripening theory. © 1995 John Wiley & Sons, Inc.