We have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts η0,linear to their ring counterparts η0,ring at isofrictional conditions is discussed as function of the number of entanglements Z. In the unentangled regime η0,linear/η0,ring is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation η0,linear/η0,ring=2. In the entanglement regime, the Z-dependence of rings viscosity is much weaker than that of linear polymers, in qualitative agreement with predictions from scaling theory and simulations. The power-law extracted from the available experimental data in the rather limited range 1
We present systematic, unique linear and nonlinear shear rheology data of an experimentally pure ring polystyrene and its linear precursor. This polymer was synthesized anionically and characterized by interaction chromatography and fractionation at the critical condition. Its weight-average molar mass is 84 kg/mol; i.e., it is marginally entangled (entanglement number Z ≈ 5). Its linear viscoelastic response appears to be better described by the Rouse model (accounting for ring closure) rather than the lattice-animal-based model, suggesting a transition from unentangled to entangled ring dynamics. The failure of both models in the terminal region may reflect the remaining unlinked linear contaminants and/or ring–ring interpenetration. The viscosity evolution at different shear rates was measured using a homemade cone-partitioned plate fixture in order to avoid edge fracture instabilities. Our findings suggest that rings are much less shear thinning compared to their linear counterparts, whereas both obey the Cox–Merz rule. The shear stress (or viscosity) overshoot is much weaker for rings compared to linear chains, pointing to the fact that their effective deformation is smaller. Finally, step strain experiments indicate that the damping function data of ring polymers clearly depart from the Doi–Edwards prediction for entangled linear chains, exhibiting a weak thinning response. These findings indicate that these marginally entangled rings behave like effectively unentangled chains with finite extensibility and deform much less in shear flow compared to linear polymers. They can serve as guideline for further investigation of the nonlinear dynamics of ring polymers and the development of constitutive equations.
Taming decoherence is essential in realizing quantum computation and quantum communication. Here we experimentally demonstrate that decoherence due to amplitude damping can be suppressed by exploiting quantum measurement reversal in which a weak measurement and the reversing measurement are introduced before and after the decoherence channel, respectively. We have also investigated the trade-off relation between the degree of decoherence suppression and the channel transmittance.
The intrinsic viscosity of cyclic polystyrenes (C-PS) and linear polystyrenes (L-PS) with molecular weight (MW) ranging from 16K to 370K was measured in THF using size exclusion chromatography coupled with a triple detection system. The C-PS samples were prepared by a ring-closure reaction of telechelic linear precursor synthesized by anionic polymerization. As-synthesized C-PS samples after the ringclosure reaction contain various byproducts, and they were fractionated by liquid chromatography at the critical condition to obtain highly pure C-PS. While the intrinsic viscosity of L-PS agrees well with the literature data, C-PS shows significantly lower value than the literature values. The Mark−Houwink exponent of C-PS is 0.67, somewhat lower than 0.70 for L-PS in the good solvent over the MW range examined. Therefore, the ratio of the intrinsic viscosity of C-PS to L-PS (g′ =[ η] C /[η] L) in THF is not MW independent but decreases as MW increases (0.63 ≥ [η] C /[η] L ≥ 0.57). The trend of intrinsic viscosity agrees well with the computer simulation result. The discrepancy in [η] C from the literature values can largely be attributed to the contamination of linear byproducts in the earlier studies.
Steady-state shear viscosity η(γ̇) of unconcatenated ring polymer melts as a function of the shear rate γ̇ is studied by a combination of experiments, simulations, and theory. Experiments using polystyrenes with Z ≈ 5 and Z ≈ 11 entanglements indicate weaker shear thinning for rings compared to linear polymers exhibiting power law scaling of shear viscosity η ∼ γ̇–0.56 ± 0.02, independent of chain length, for Weissenberg numbers up to about 102. Nonequilibrium molecular dynamics simulations using the bead-spring model reveal a similar behavior with η ∼ γ̇–0.57 ± 0.08 for 4 ≤ Z ≤ 57. Viscosity decreases with chain length for high γ̇. In our experiments, we see the onset of this regime, and in simulations, which we extended to Wi ∼ 104, the nonuniversality is fully developed. In addition to a naive scaling theory yielding for the universal regime η ∼ γ̇–0.57, we developed a novel shear slit model explaining many details of observed conformations and dynamics as well as the chain length-dependent behavior of viscosity at large γ̇. The signature feature of the model is the presence of two distinct length scales: the size of tension blobs and much larger thickness of a shear slit in which rings are self-consistently confined in the velocity gradient direction and which is dictated by the size of a chain section with relaxation time 1/γ̇. These two length scales control the two normal stress differences. In this model, the chain length-dependent onset of nonuniversal behavior is set by tension blobs becoming as small as about one Kuhn segment. This model explains the approximate applicability of the Cox–Merz rule for ring polymers.
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