With short term shearing at low degrees of supercooling a method has been developed by which nucleation during shearing can effectively be separated from the subsequent crystal growth, which, in these experiments, mainly occurs after the cessation of the flow. In this way the kinetics of nucleation by shear could be unravelled for isotactic polypropylene. The required measurement consists of the monitoring of the optical retardation which increases with the monitoring time and levels off by saturation. From these measurements conclusions could be drawn with respect to the modes of formation of the nuclei and of their type. Model predictions could be confirmed with the aid of electron micrographs.
Short term shearing at low degrees of supercooling with subsequent monitoring of the crystallization process of isotactic polypropylenes leads to highly oriented surface layers and fine grained layers that reach further into the core of the solidified samples. This process is highly dependent on the content of long polymer chains or nucleating agents. The present paper shows a first experimental evidence for these facts together with theoretical considerations. If long polymer chains are present, as it is the case in reactor grades of iPP, shear induced crystallization is more sensitive to shear treatment. As a consequence, the orientation of the surface layers is much higher in these materials. Additionally, the surface layers -both, highly oriented and fine grained -are more distinct and, therefore, allow an easier quantitative determination. If the materials contain nucleating agents, highly oriented layers occur in materials containing long polymer chains as well as in rheology controlled grades. A first theoretical description of the possible role of nucleating agents is given.
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