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Open accessJournal ArticleDOI: 10.1021/ACS.MACROMOL.0C02530

Unentangled Vitrimer Melts: Interplay between Chain Relaxation and Cross-link Exchange Controls Linear Rheology

02 Mar 2021-Macromolecules (American Chemical Society (ACS))-Vol. 54, Iss: 7, pp 3304-3320
Abstract: Vitrimers are polymer networks that engage in dynamic associative exchange reactions. Their covalent cross-links preserve network connectivity but permit topology fluctuations, making them both ins...

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Open accessJournal Article
Abstract: Associating polymers constitute a fascinating class of materials because of the richness in their rheological behavior. Their rheology is known to be mainly dictated by the nature and intrinsic stabilities of transient associations. Here, we provide a direct observation of the importance of free associating sites in the macroscopic relaxation of supramolecular networks constructed from ultrahigh molecular weight polymers with sparsely distributed stickers of finite functionality. Their rheological signature affords evidence that the macroscopic relaxation of supramolecular networks can be apparently dissociated from the intrinsic lifetime of the associating units, provided that diffusion processes do not lead to successful chain relaxation at the microscopic level.

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15 Citations


Open accessJournal ArticleDOI: 10.1021/ACS.MACROMOL.0C02744
11 May 2021-Macromolecules
Abstract: The composition of low-Tg n-butylacrylate-block-(acetoxyaceto)ethyl acrylate block polymers is investigated as a strategy to tune the properties of dynamically cross-linked vinylogous urethane vitrimers. As the proportion of the cross-linkable block is increased, the thermorheological properties, structure, and stress relaxation evolve in ways that cannot be explained by increasing cross-link density alone. Evidence is presented that network connectivity defects such as loops and dangling ends are increased by microphase separation. The thermomechanical and viscoelastic properties of block copolymer-derived vitrimers arise from the subtle interplay of microphase separation and network defects.

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5 Citations




Open accessJournal ArticleDOI: 10.1063/5.0072377
17 Nov 2021-Physics of Fluids
Abstract: The time-strain separable Kaye–Bernstein–Kearsley–Zappas model (tssKBKZM) is a popular integral constitutive equation that is used to model the nonlinear response of time-strain separable materials using only their linear viscoelastic properties and damping function. In oscillatory shear, numerical evaluation of tssKBKZM is complicated by the infinite domain of integration, and the oscillatory nature of the integrand. To avoid these problems, a spectrally accurate method is proposed. It approximates the oscillatory portion of the integrand using a discrete Fourier series, which enables analytical evaluation of the resulting integrals for the Maxwell model. The spectral method is generalized for arbitrary discrete and continuous relaxation spectra. Upper bounds for quadrature error, which can often be driven to machine precision, are presented. The Doi–Edwards model with independent-alignment approximation (DE-IA) is a special case of tssKBKZM; for DE-IA, the spectral method is compared with trapezoidal rule to highlight its accuracy and efficiency. The superiority of the proposed method is particularly evident at large strain amplitude and frequency. For continuous relaxation spectra, the spectral method transforms the double integral corresponding to the tssKBKZM to a single integral. Solutions computed to a specified level of accuracy using standard numerical libraries show that the spectral method is typically two to three orders of magnitude faster. Extensions to fractional rheological models, materials with nonzero equilibrium modulus, stretched exponential models, etc., are also discussed.

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Topics: Spectral method (58%), Trapezoidal rule (56%), Multiple integral (56%) ... read more

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136 results found


Open accessBook
01 Jan 1961-
Abstract: The Nature of Viscoelastic Behavior. Illustrations of Viscoelastic Behavior of Polymeric Systems. Exact Interrelations among the Viscoelastic Functions. Approximate Interrelations among the Linear Viscoelastic Functions. Experimental Methods for Viscoelastic Liquids. Experimental Methods for Soft Viscoelastic Solids and Liquids of High Viscosity. Experimental Methods for Hard Viscoelastic Solids. Experimental Methods for Bulk Measurements. Dilute Solutions: Molecular Theory and Comparisons with Experiments. Molecular Theory for Undiluted Amorphous Polymers and Concentrated Solutions Networks and Entanglements. Dependence of Viscoelastic Behavior on Temperature and Pressure. The Transition Zone from Rubberlike to Glasslike Behavior. The Plateau and Terminal Zones in Uncross-Linked Polymers. Cross-Linked Polymers and Composite Systems. The Glassy State. Crystalline Polymers. Concentrated Solutions, Plasticized Polymers, and Gels. Viscoelastic Behavior in Bulk (Volume) Deformation. Applications to Practical Problems. Appendices. Author & Subject Indexes.

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12,648 Citations


Open accessBook
01 Jan 1986-
Abstract: Introduction Static properties of polymers Brownian motion Dynamics of flexible polymers in dilute solution Many chain systems Dynamics of a polymer in a fixed network Molecular theory for the viscoelasticity of polymeric liquids Dilute solutions of rigid rodlike polymers Semidilute solutions of rigid rodlike polymers Concentrated solutions of rigid rodlike polymers Index.

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Topics: Polymer physics (59%), Worm-like chain (55%), Polymer architecture (55%) ... read more

10,219 Citations



Open accessBook
01 Jan 1977-

5,091 Citations


Journal ArticleDOI: 10.1063/1.1699180
Abstract: The necessary coordination of the motions of different parts of a polymer molecule is made the basis of a theory of the linear viscoelastic properties of dilute solutions of coiling polymers. This is accomplished by use of the concept of the submolecule, a portion of polymer chain long enough for the separation of its ends to approximate a Gaussian probability distribution. The configuration of a submolecule is specified in terms of the vector which corresponds to its end‐to‐end separation. The configuration of a molecule which contains N submolecules is described by the corresponding set of N vectors. The action of a velocity gradient disturbs the distribution of configurations of the polymer molecules away from its equilibrium form, storing free energy in the system. The coordinated thermal motions of the segments cause the configurations to drift toward their equilibrium distribution. The coordination is taken into account by the mathematical requirement that motions of the atom which joins two submolecules change the configurations of both submolecules. By means of an orthogonal transformation of coordinates, the coordination of all the motions of the parts of a molecule is resolved into a series of modes. Each mode has a characteristic relaxation time. The theory produces equations by means of which the relaxation times, the components of the complex viscosity, and the components of the complex rigidity can be calculated from the steady flowviscosities of the solution and the solvent, the molecular weight and concentration of the polymer, and the absolute temperature. Limitations of the theory may arise from the exclusion from consideration of (1) very rapid relaxation processes involving segments shorter than the submolecule and (2) the obstruction of the motion of a segment by other segments with which it happens to be in contact. Another possible cause of disagreement between the theory and experimental data is the polydispersity of any actual polymer; this factor is important because the calculated relaxation times increase rapidly with increasing molecular weight.

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Topics: Reptation (53%), Relaxation (NMR) (51%)

3,289 Citations


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No. of citations received by the Paper in previous years
YearCitations
20215
20171