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Free Volume Approach to Polystyrene Melt Viscosity

 

作者: Malcolm L. Williams,  

 

期刊: Journal of Applied Physics  (AIP Available online 1958)
卷期: Volume 29, issue 10  

页码: 1395-1398

 

ISSN:0021-8979

 

年代: 1958

 

DOI:10.1063/1.1722956

 

出版商: AIP

 

数据来源: AIP

 

摘要:

The Doolittle approach to Newtonian viscosity assumes &eegr;=AexpB/f, whereAandBare constants independent of temperature andf, the relative free volume, is (v−v0)/v0. Herevis the specific volume andv0is the occupied volume. Using machine computations, this equation was applied to published data on polystyrene, replacingvby its equivalentvg+(dv/dT)(T−Tg), wherevgis the specific volume at the glass temperatureTg. The agreement between calculated and observed viscosities is at least as good, and perhaps better, than that afforded by other existing empirical expressions. The constantBis independent of molecular weight and temperature whilev0depends slightly on molecular weight. A log‐log plot ofAagainst molecular weightMproduces two straight lines intersecting atM=35 000. At higher values ofM, the slope is 3.4; at lower values, it is slightly greater than one. This treatment separates the melt viscosity of polystyrene into two factors,A, dependent only on structural parameters, andf, which is determined by the specific volume and is a function of temperature.

 

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