Viscoelasticity and nonlinear simple shear flow behavior of an entangled asymmetric exact comb polymer solution
Kirkwood, K. M.
Leal, L. G.
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Polymer Synthesis Laboratory
Online Publication Date2016-03-31
Print Publication Date2016-05
Permanent link to this recordhttp://hdl.handle.net/10754/608238
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AbstractWe report upon the characterization of the steady-state shear stresses and first normal stress differences as a function of shear rate using mechanical rheometry (both with a standard cone and plate and with a cone partitioned plate) and optical rheometry (with a flow-birefringence setup) of an entangled solution of asymmetric exact combs. The combs are polybutadienes (1,4-addition) consisting of an H-skeleton with an additional off-center branch on the backbone. We chose to investigate a solution in order to obtain reliable nonlinear shear data in overlapping dynamic regions with the two different techniques. The transient measurements obtained by cone partitioned plate indicated the appearance of overshoots in both the shear stress and the first normal stress difference during start-up shear flow. Interestingly, the overshoots in the start-up normal stress difference started to occur only at rates above the inverse stretch time of the backbone, when the stretch time of the backbone was estimated in analogy with linear chains including the effects of dynamic dilution of the branches but neglecting the effects of branch point friction, in excellent agreement with the situation for linear polymers. Flow-birefringence measurements were performed in a Couette geometry, and the extracted steady-state shear and first normal stress differences were found to agree well with the mechanical data, but were limited to relatively low rates below the inverse stretch time of the backbone. Finally, the steady-state properties were found to be in good agreement with model predictions based on a nonlinear multimode tube model developed for linear polymers when the branches are treated as solvent.
CitationViscoelasticity and nonlinear simple shear flow behavior of an entangled asymmetric exact comb polymer solution 2016, 60 (3):451 Journal of Rheology
SponsorsF.S. and D.V. acknowledge financial support by the EU through MC-ITN DYNACOP (Grant No. 214627). The authors thank G. Ianniruberto and G. Marrucci for helpful discussions.
PublisherSociety of Rheology
JournalJournal of Rheology