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Measurement of polydispersity of ultra‐narrow polymer fractions by thermal field‐flow fractionation
Author(s) -
Schimpf Martin E.,
Myers Marcus N.,
Giddings J. Calvin
Publication year - 1987
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1987.070330111
Subject(s) - dispersity , polystyrene , polymer , dispersion (optics) , field flow fractionation , materials science , analytical chemistry (journal) , thermal , non equilibrium thermodynamics , relaxation (psychology) , fractionation , polymer chemistry , chemistry , thermodynamics , chromatography , optics , composite material , physics , psychology , social psychology
In this paper we demonstrate that the polydispersity µ = M̄ w / M̄ N of narrow polymer fractions can be readily obtained by measuring band broadening and its velocity dependence in a thermal field–flow fractionation (thermal FFF) system. The thermal FFF method is shown to be more accurate than size exclusion chromatography for the determination of polymer polydispersities due to the simpler band dispersion function and the higher selectivity inherent to the technique. The polydispersities of a series of four narrow polystyrene samples prepared by anionic polymerization were consequently determined by thermal FFF and found to be much smaller (1.003–1.006) than the ceiling values (1.06) suggested by the suppliers. As part of this investigation, an experimental study of band dispersion in thermal FFF is used to examine current theory. The data show nonequilibrium to be the dominant factor, whereas relaxation effects are insignificant at lower flow rates and can be subdued at higher flow rates. A high correlation between nonequilibrium theory and experiment allows for the estimation of diffusion coefficients from plate height–velocity data.