A detailed analysis of crystallization phenomena in isotactic polypropylene has been carried out in order to establish the dependence of kinetic parameters on molecular weight distribution.The crystallization rate is lower for samples having a very narrow distribution compared with polydisperse samples fused at the same temperature for equal length of time, provided that the temperature is not so high to destroy the previous crystalline ordered zones.Nucleation has been found to be predetermined when crystallization temperature is inferior to 150°C., and then spherulites grow radially. At temperatures above 15OoC., crystallization is governed mainly by sporadic nucleation if predetermined nuclei have been completely destroyed during fusion. Sporadic nucleation is more easily achieved for samples with narrow molecular weight distribution.
ZUSAMMENFASSUNG:Die Kinetik der primiiren Kristallisation von isotaktischem Polypropylen liif3t sich durch die Molekulargewichtsverteilung beeidussen.Wenn die vorher in heterogenen Polymeren anwesenden kristallinen Ordnungen durch die Temperatur nicht gbzlich zerstort werden, kristallisieren Proben mit der engsten Molekulargewichtsverteilung langsamer als polydisperse Proben, die die gleiche Zeit bei gleicher Temperatur geschmolzen worden waren.Bei Kristallisationstemperaturen To 5 150 "C zeigt die kinetische Untersuchung, daB athermische Keimbildung iibenviegt und daB dann die Sphiirolite radial wachsen. Bei To > 150°C ist die Keimbildung vorherrschend thermisch, wenn zuvor die vorhandenen Keime wihrend des Schmelzens zerstort worden waren. Die homogenen Proben erreichten leichter die Bedingungen, in denen die thermische Keimbildung vorliegt.
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