Thermal Field-Flow Fractionation of Initially Dilute Polymer Solutions as a Shear Degradation Model. Scaling Model of Macromolecule Degradation at Concentrations Exceeding the Critical Entanglement Value
作者:
E.V. CHUBAROVA,
期刊:
Journal of Macromolecular Science, Part B
(Taylor Available online 2000)
卷期:
Volume 39,
issue 5-6
页码: 583-604
ISSN:0022-2348
年代: 2000
DOI:10.1081/MB-100102473
出版商: Taylor & Francis Group
关键词: Critical gradient;Field-flow fractionation;Shear degradation
数据来源: Taylor
摘要:
Experimental data are presented on thermal field-flow fractionation (TFFF) of anionic polystyrene (PS) samples in the rangeM= (4–12)·106. They show extensive degradation of macromolecular chains at relatively low rate gradients (G< 30 s−1). The possibility of the influence of relaxation effects on the shape of fractograms and the elution volumes of the samples was taken into account. Mean concentrations in accumulative zones were evaluated. It was shown that, in all cases when degradation was observed, the accumulative zones are the layers of entangled macromolecules. The use of the scaling approach made it possible to simulate layer extension toward the channel center under the influence of the rate gradient. It was shown that, during stretching, the layer is destroyed into blobs, the size of which is determined by experimental conditions. An expression for the critical gradient leading to layer degradation was derived. Quantitative evaluations of fragment sizes and critical gradients obtained from the model are in good agreement with experimental data. The model developed for specific experimental conditions confirms the proposed general mechanism of the so-called shear degradation of macromolecules. The physical picture of degradation in the TFFF channel was considered.
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