TY - JOUR
T1 - Relaxation time spectrum molecular weight distribution relationships
AU - Friedrich, Christian
AU - Loy, Richard J.
AU - Anderssen, Robert S.
PY - 2009
Y1 - 2009
N2 - Single exponential decay exp(-t/tau) relationships, which define the molecular weight distribution (MWD) of a polymer as a function of the polymer-s relaxation time spectrum (RTS), have been derived by Wu (Polym Eng Sci 28:538-543, 1988 and Thimm et al. (J Rheol 43:1663 - 1672, Ref Citation1999). Experimental validation studies with monodisperse polymers, with quite precisely known MWDs, have been used to test their reliability. It has been established that neither formula is always able to accurately recover the MWDs of monodisperse polymers from their experimentally determined RTS. In this paper, different and more general relationships, based on theoretical results of Anderssen and Loy (Bull Aust Math Soc 65:449-460, 2002) for decays of the form (-theta(t)/tau), where the derivative of t) is a completely monotone function, are derived, analyzed, and applied. It is shown how to transform these general relationships to equivalent single exponential decay relationships for which Laplace transform solutions are derived. In order to illustrate the interrelationship between an RTS and its corresponding MWD, an explicit analytic solution is given. The paper concludes with a discussion of the rheological implications for the BSW model.
AB - Single exponential decay exp(-t/tau) relationships, which define the molecular weight distribution (MWD) of a polymer as a function of the polymer-s relaxation time spectrum (RTS), have been derived by Wu (Polym Eng Sci 28:538-543, 1988 and Thimm et al. (J Rheol 43:1663 - 1672, Ref Citation1999). Experimental validation studies with monodisperse polymers, with quite precisely known MWDs, have been used to test their reliability. It has been established that neither formula is always able to accurately recover the MWDs of monodisperse polymers from their experimentally determined RTS. In this paper, different and more general relationships, based on theoretical results of Anderssen and Loy (Bull Aust Math Soc 65:449-460, 2002) for decays of the form (-theta(t)/tau), where the derivative of t) is a completely monotone function, are derived, analyzed, and applied. It is shown how to transform these general relationships to equivalent single exponential decay relationships for which Laplace transform solutions are derived. In order to illustrate the interrelationship between an RTS and its corresponding MWD, an explicit analytic solution is given. The paper concludes with a discussion of the rheological implications for the BSW model.
KW - BSW spectrum
KW - Complete monotonicity
KW - Double reptation
KW - Laplace transformation
KW - Molarmass distribution
KW - Molecular weight distribution
KW - Monodisperse
KW - Relaxation time spectrum
UR - http://www.scopus.com/inward/record.url?scp=61349133485&partnerID=8YFLogxK
U2 - 10.1007/s00397-008-0314-z
DO - 10.1007/s00397-008-0314-z
M3 - Article
SN - 0035-4511
VL - 48
SP - 151
EP - 162
JO - Rheologica Acta
JF - Rheologica Acta
IS - 2
ER -