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High‐shear capillary viscosity studies on concentrated copolymer solutions

机译:High‐shear capillary viscosity studies on concentrated copolymer solutions

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AbstractFlow behavior of ten copolymer solutions of polyacrylonitrile and polymethyl methacrylate in concentrations up to 16 was studied at 30°C. with the use of capillaries of constant diameter but different lengths. The shear rate and shear stress range covered were up to 200,000 sec.−1and 800,000 dynes/cm.2, respectively. A rheological model of the form logD=A0+A1(log τ)β+A11(log τ)2βwas employed in determining the inflection point of the flow curve by computer analysis. A marked dependence of the flow curve upon the lenght‐to‐diameter ratio was observed whenl/dratio decreased to below 300. At shear rates above 50,000 sec.−1the capillary “end effect” corrections and the kinetic energy corrections were found to be large for the concentrated and dilute solutions, respectively. The flow curves were characterized in terms of the inflection point in accordance with the treatment of Schurz. An upper Newtonian viscosity η*was observed at shear rates above 150,000 sec.−1. Up to a concentration of about 1, the value of the upper Newtonian viscosity was such that the calculated ηsp/Cwas essentially independent ofCand equal to η* obtained by extrapolation to infinite dilution. The values of the heat of activation for viscous flow were found to be dependent upon the

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