Tracer Diffusion in the Blends of Polystyrene and

Macromolecules 1996,28, 1979-1989

1979

Tracer Diffusion in the Blends of Polystyrene and Tetramethylbisphenol A Polycarbonate Eugene Kim? Department of Chemistry, Baker Laboratory, Cornell University, Zthaca, New York 14853

Edward J. Kramer* Department of Materials Science and Engineering and the Materials Science Center, Cornell University, Zthaca, New York 14853

John 0. Osby Dow Chemical USA, Building B-1471, Freeport, Texas 77541 Received April 18, 1994; Revised Manuscript Received November 8, 1994@

ABSTRACT: The tracer diffusion coefficients (D*)of deuterated tetramethylbisphenol A polycarbonate (d-TMPC)and deuterated polystyrene (d-PS)into protonated blends of TMPCPS were measured in an effort to gain insight into the factors which determine the monomer friction coefficient of the individual components of a miscible polymer blend. Forward recoil spectrometry (FRES) was used t o obtain the depth profile of deuterium after diffusion well above the glass transition temperature (T,J The temperature dependence of the D*’s was measured for matrices with PS weight fraction w of 0,0.5, and 1; in all cases the D* of TMPC was more strongly temperature dependent than that of PS, which is in contrast with the results in blends of PS/poly(xylenyl ether)(PXE)and in disagreement with the simple free volume model of the dynamics of polymer melts. At high molecular weights of the protonated matrix, diffusion of the deuterated tracer molecules was independent of the molecular weight of the matrix and scaled as M+, where M is the molecular weight of the tracer polymer, strongly suggesting that reptation is the diffusion mechanism in this regime. The reptation model was used to extract monomer friction coefficients for the PS (c,,pg) and TMPC (~,,TM~C) from their respective D*’s measured as a function of w at T = T g+ 45 “C. The monomer friction coefficient of TMPC was larger than that for PS by more than 100 times. The 5, of each species depended strongly on composition at either constant T - T gor constant fractional free volume. However, cO,p5/