Nc. Andrews et al., CONFORMATIONAL AND RHEOLOGICAL DYNAMICS OF SEMIFLEXIBLE MACROMOLECULES UNDERGOING SHEAR-FLOW - A NONEQUILIBRIUM BROWNIAN DYNAMICS STUDY, Journal of rheology, 42(2), 1998, pp. 281-305
Nonequilibrium Brownian dynamics simulations (NEED) are used to model
the dynamics of semiflexible macromolecules undergoing shear how. The
mathematical model utilizes a discretized version of the Kratky-Porod
wormlike (or persistent) chain as the building block, generalized to i
nclude how. The Fokker-Planck equation resulting from such an analysis
is converted to a stochastic differential equation from which the sim
ulation algorithm for the NEED is obtained. Various conformational and
rheological quantities are monitored, under both steady-state and tra
nsient conditions, with the primary independent variable being the fle
xibility parameter beta, the bending constant of the chain. The model
qualitatively describes many of the experimentally observed effects in
such systems, most notably birefringence overshoots, cessation effect
s, and various steady-state effects. In addition, many of the qualitat
ive rheological features of both rigid rod (or flexible) polymers are
captured as beta is made very large (or small). The advantage of the N
EED over an analytical treatment is its ability to incorporate (analyt
ically intractable) effects such as hydrodynamic interactions and its
(natural) ability to obtain transient information, a facet useful in c
omprehending the differing dynamics of rigid and less rigid macromolec
ules. (C) 1998 The Society of Rheology. [S0148-6055(98)00602-6].