Shear and extensional rheology of entangled polymer melts: Similarities and differences

This work extends our previous understanding concerning the nonlinear responses of entangled polymer solutions and melts to large external deformation in both simple shear and uniaxial extension. Many similarities have recently been identified for both step strain and startup continuous deformation, including elastic yielding, i.e., chain disentanglement after cessation of shear or extension, and emergence of a yield point during startup deformation that involves a deformation rate in excess of the dominant molecular relaxation rate. At a sufficiently high constant Hencky rate, uniaxial extension of an entangled melt is known to produce window-glass-like rupture. The present study provides evidence against the speculation that chain entanglements tie up into "dead knots" in constant-rate extension because of the exponentially growing chain stretching with time. In particular, it is shown that even Instron-style tensile stretching, i.e., extending a specimen by applying a constant velocity on both ends, results in rupture. Yet, in the same rate range, the same entangled melt only yields in simple shear, and the resulting shear banding is clearly not a characteristic of rupture. Thus, we conclude that chain entanglements respond to simple shear in the manner of yielding whereas uniaxial extension is rather effective in causing some entanglements to lock up, making it impossible for the entanglement network to yield at high rates.     

Insight into shear‐induced modification for improving processability of polymers: Effect of shear rate on the evolution of entanglement state

Many experimental results have revealed that the re‐entanglement kinetics of disentangled polymers is much slower than that predicted by tube theory. This retarded recovery of fully entangled state is of practical significance that shear‐induced modification may offer a way to improve processability for a polymer by reducing viscosity. This work tried to figure out the shear‐rate dependence variation of viscosity in the view of evolution of entanglement state through disentanglement and re‐entanglement, aiming to provide fundamental insights into application prospect of shear‐induced modification in preparing “in‐pellet” disentangled polymers prior to final processing. High‐density polyethylene was sheared on a parallel‐plate rotational rheometer with a linearly increased shear rate. Results showed that higher shear rate could induce further disentanglement, resulting in a lower viscosity with a reduction rate up to 93.7%, larger molecular weight between entanglements M_e , and longer re‐entanglement time. Additionally, less entanglement would give a larger lamellar thickness of sheared samples after nonisothermal crystallization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 598–606     

Constitutive equations from Gaussian slip-link network theories in polymer melt rheology

Allowing for flow-dependent slip in the junctions of a temporary junction network, we derive the constitutive equations of temporary slip-link networks. The stress tensor is determined by three material functions, namely, the time-dependent linear-viscoelastic memory function, and two strain-dependent functions describing slip and disentanglement of network strands. Slip and disentanglement are related via a mass balance for network strands.By specifying slip and disentanglement, the constitutive equations of Lodge, Wagner, Doi-Edwards, and Marrucci are shown to be special temporary slip-link constitutive equations. To demonstrate the predictive power of temporary slip-link network theories, we compare predictions and extensional flow data with step change in flow direction.Dedicated to Professor Arthur S. Lodge on the occasion of his 70th birthday and his retirement from the University of Wisconsin.     

Approximate Disentanglement

We construct a quantum machine which, by using an asymmetric cloner, disentangles an entangled state and nearly retains it. The attainable maximum value of the scaling parameter for disentangling is identical to that obtained in previous works. The fidelity of the output residual entangled state with respect to the input entangled state is state-dependent. The result shows that it is possible to deal with disentanglement and broadcasting entanglement in a single unitary evolution.     

Disentanglement of Two Qubits Coupled to an XY Spin Chain at Finite Temperature

The disentanglement evolution of bipartite spin-1/2 system coupled to a common surrounding XY chain in transverse fields at nonzero temperature is studied in this letter. The dynamical process of the entanglement is numerically and analytically investigated. We find that thermal effects can enhance disentanglement if the entangled initial state of the central spins does not in the decoherence free space. The critical phenomenon of quantum phase transitions reflected in the disentanglement can be washed out by the thermal effect eventually.     

Quantum Recoil Effects of Spontaneous Emission on Disentanglement

By taking into account spatial degrees of freedom of atoms, we study theinternal-state disentanglement dynamics of two atoms interacting with avacuum multi-mode noise field. We show that the complete internal-statedisentanglement of the two atoms, caused due to the atomic spontaneousemission can be achieved in a finite time.     

Disentanglement Dynamics in Nonequilibrium Environments

We theoretically study the non-Markovian disentanglement dynamics of a two-qubit system coupled to nonequilibrium environments with nonstationary and non-Markovian random telegraph noise statistical properties. The reduced density matrix of the two-qubit system can be expressed as the Kraus representation in terms of the tensor products of the single qubit Kraus operators. We derive the relation between the entanglement and nonlocality of the two-qubit system which are both closely associated with the decoherence function. We identify the threshold values of the decoherence function to ensure the existences of the concurrence and nonlocal quantum correlations for an arbitrary evolution time when the two-qubit system is initially prepared in the composite Bell states and the Werner states, respectively. It is shown that the environmental nonequilibrium feature can suppress the disentanglement dynamics and reduce the entanglement revivals in non-Markovian dynamics regime. In addition, the environmental nonequilibrium feature can enhance the nonlocality of the two-qubit system. Moreover, the entanglement sudden death and rebirth phenomena and the transition between quantum and classical nonlocalities closely depend on the parameters of the initial states and the environmental parameters in nonequilibrium environments.     

Tuning the π‐π stacking distance and J‐aggregation of DPP‐based conjugated polymer via introducing insulating polymer

The close π–π stacking and the high J‐aggregation during the formation of fibrillar morphology in films of the poly[[2,5‐bis(2‐octyldodecyl)?2,3,5,6‐tetrahydro‐3,6‐dioxopyrrolo[3,4‐c]pyrrole‐1,4‐diyl]‐alt–[[2,2′‐(2,5‐thiophene)bis‐thieno[3,2‐b]thiophen]‐5,5′‐diyl]] (PDPPTT‐T) are demonstrated via blending with polystyrene (PS). The hydrodynamic radius (R_h) of PDPPTT‐T is decreased from 16.7 nm in the neat solution to 12.7 nm in the blend solution at the ratio of 1/20(PDPPTT‐T/PS). This phenomenon suggests that blending PS is beneficial for the disentanglement of PDPPTT‐T. The disentanglement of PDPPTT‐T facilitates the formation of fibrillar morphology. The growth of the fibrils occurs along the molecular backbones and the width of the fibrils is parallel to the π–π stacking direction. The disentanglement of PDPPTT‐T helps the molecules adjust conformation to improve J‐aggregation and decrease the π–π stacking distance. The maximum absorption is red‐shifted from 825 nm to 849 nm and the relative intensity of J‐aggregation (the 0‐0/0‐1 ratio) is increased from 1.19 to 1.60. The π–π stacking distance decreases from 3.57 to 3.52 Å. The charge‐carrier mobility will be improved in the fibrillar morphology with close π–π stacking and high J‐aggregation. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 838–847     

Disentanglement of Qubit in Dephasing Model

We investigate the entanglement evolution of two qubits that are initially in Werner state under the classical phase noise. We discuss the influence of mixture degree on disentanglement. It is showed that the more mixed the state, the shorter is the time of disentanglement.     

Novel in situ NMR Measurement System for Evaluating Molecular Mobility during Drawing from Highly Entangled Polyethylene Melts

A novel in situ measurement system for evaluating molecular mobility during uniaxial drawing of polymeric materials was established by introducing drawing and stress‐detecting devices into a ¹H pulse nuclear magnetic resonance spectrometer. In this study, we analyze the changes in molecular motion of amorphous chains during melt‐drawing of ultra‐high molecular weight polyethylenes (UHMW‐PEs) with different molecular weight distributions. In the initial stage of drawing, a three‐component resolution was possible for the relaxation decay curve, which includes “rigid”, “intermediate”, and “mobile” amorphous components. The quality and quantity changes in these components demonstrated that this intermediate amorphous component could be regarded as the index of the change in molecular entanglement characteristics during the orientation of PE chains.