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At least 19 records

Insights into mixing of non-isothermal multi-polymer melts for complex plastics recycling

Catalytic recycling or upcycling of plastics is often limited not by catalyst performance, but by transport, arising from highly viscous, non-Newtonian polymer melts. In this work, we develop a reactor-scale framework that integrates rheological measurements, constitutive modeling, computational fluid dynamics (CFD), and experiments to quantify mixing, heat transfer, and dispersion in surrogate hydrocarbon melts representing mixed plastics systems. Temperature- and shear rate-dependent viscosity of low-density polyethylene (LDPE) and high-density polyethylene (HDPE) is measured to create two surrogate polymers (PLD and PHD) that capture the dominant shear-thinning flow behavior while neglecting strong elastic effects, enabling tractable simulation of non-isothermal, polymer-melt mixing using a Carreau-Arrhenius generalized Newtonian framework. Three-dimensional CFD simulations are employed to evaluate impeller performance in PLD using mixing time, cavern volume, thermal uniformity, and interfacial area for regimes in which viscoelastic effects are not dominant. We show that magnetic stir bars commonly used in lab-scale studies produce large thermal gradients (~60 °C) and poor mixing, even under idealized power delivery and polymer flow conditions. In contrast, close-clearance anchor impellers achieve near-isothermal operation, reduce mixing times by up to 5×, and provide >90% active circulation volume. We further demonstrate that, at low pseudo-Deborah number (De*), motor power requirements can be predicted directly from shear rate-dependent rheology using the Carreau-Arrhenius framework, enabling rational selection of operating conditions. Extension to surrogate immiscible multi-polymer systems based on PLD and PHD shows that interfacial area is highly sensitive to operating conditions and impeller design, with coaxial anchor-turbine configurations enhancing dispersion by up to 4 × .

Close-clearance impellers↗

Smoother Surfaces Enhance Diffusion of Nanorods in Entangled Polymer Melts

Coarse-grained molecular dynamics simulations are used to study the diffusion of thin nanorods in entangled polymer melts for varying nanorod length and roughness. While prior studies observed a nanorod parallel diffusion constant scaling inversely with rod length D ∥ ~ l –1 , here, we show that this scaling is not universal and depends sensitively on the nanorod surface roughness. We observe D ∥ ~ l –k , where k < 1 and decreases with decreasing surface roughness. The weaker scaling is driven by the non-Gaussian diffusion of nanorods due to the emergence of an intermittent hopping process that becomes more pronounced with decreasing roughness at the monomer scale. Analysis shows that the mean hop size grows for smoother rods but shows little to no variation with rod length. The mean hopping frequency shows no dependence on either rod length or roughness, suggesting it originates from the polymer melt environment. Further, our results show that the small-scale features of the nanorod surface strongly influence the large-scale and long-time transport of nanorods in polymer matrices, creating new material design opportunities for precisely engineered nanocomposites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The Work of Mechanical Degradation in Elongating Polymer Melts

Molecular dynamics simulations are used to study the mechanical degradation of well-entangled polymer melts during uniaxial extensional flow. Simulations measure the transient rise in extensional stresses and relate them to the molecular alignment and scission of chain backbones. Intermolecular entanglements couple chain scission in space and time, making degradation sensitive to deformation history and strain rate in ways not displayed by dilute polymer solutions. The rate of chain scission is nonmonotonic and peaks at strains corresponding to the maximum extensibility of entanglement segments but prior to the full extension of chain backbones. We measure a specific work per scission event w* and decompose it into separate contributions associated with chain alignment, chemical bond breaking, and scission-induced plasticity. We find chain scission in melts requires activating plastic dissipation that is multiple orders of magnitude larger than the chemical work required to break a covalent backbone bond. Our findings underscore the critical need to consider bulk polymer mechanics and rheology in designing efficient mechanical degradation and mechanochemical processes.

36 MATERIALS SCIENCE↗

Mechanically Accelerated Depolymerization of Entangled Linear Polymer Melts

Mechanical forces can enhance the chemical depolymerization of synthetic polymers when shear flow accelerates chain scission. To quantify the extent of mechanically-accelerated scission, the effect of simple shear flow (duration and strength) with low Weissenberg and Deborah numbers was investigated by considering the impact of applied work in both simple shear and shear dominated mixed flows. Hydrogenated polyisoprene was chosen as a model linear, entangled system. The conditions (strain amplitude, frequency, and shearing time) necessary to increase chain scission were assessed in the rubbery melt. Shear flow accelerated chain scission at higher temperatures, suggesting an activated process. Isothermal scission versus work curves were superposed by applying shift factors a T,S , whose Arrhenius-like temperature dependence gave an apparent activation energy for chain scission of ~ 110 kJ/mol, which is likely a combination of the activation energy of viscosity and bond energy. This work provides a base for quantifying the impact of shear on depolymerization of polymer melts and highlight the connection between viscous dissipation and scission chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intermediate time sub-diffusion and stress relaxation in ring polymer melts

The slow dynamics of non-concatenated ring melts remains a frontier problem in polymer science with implications for many soft material environments including cellular biophysics. Here, in this work, we report large-scale simulations of model ring melts that analyze the monomer and center-of-mass (CM) mean square displacements (MSD) and stress relaxation function on intermediate time and length scales. The degree of dynamical slowing down is characterized by the maximally sub-diffusive fractional time scaling exponents. The data span an exceptionally wide range of ring degrees of polymerization and stiffnesses and are not successfully organized based on the classic measure linear chain entanglement, N/N e . Rather, we find that the crossover degree of polymerization, N D , based on ring macromolecular caging that successfully allows master curves to be constructed for the long-time CM self-diffusion constant also collapses these temporal dynamic scaling exponents. Different properties display different exponents and exhibit one or two regimes of linear variation with the logarithm of N D / N . A distinct crossover of the CM-MSD and stress relaxation exponents emerges at sufficiently large N or stiffness that is not found for the monomer MSD, indicating a novel form of dynamic decoupling. This crossover aligns with the predicted critical degree of polymerization for transitioning from a weak to strong caging regime, indicative of activated transport. The latter may reflect the emergence of an intermolecular collective contribution to stress in analogy with dense soft colloidal matter. Suggestions are made for future theoretical work to address the rich patterns of behavior discovered.

Anomalous diffusion↗

Numerical modeling and optimization of polymer melt processing operations

The application of finite element computer analyses to polymer flows of the type encountered in melt processing operations is described. A code capable of predicting values of fluid veleocity, pressure, shear stress, and temperature at any point within the flow field was developed. As such, is is of value in diagnosing such processing problems as regions of fluid stagnation at which thermal degradation may occur, or regions of excessive shear deformation which lead to thermomechanical damage. It is further able to generate predictions of the forces which must be applied to the melt to achieve the desired flow, and this information is of value in designing processing equipment of optimal efficiency and minimum energy consumption.

Roylance, D.↗

Quantifying molecular deformation in polymer melts by a generalized Zimm plot approach

The Zimm plot has been widely used to characterize the molecular dimensions of polymers from small-angle scattering experiments, where the reciprocal intensity is analyzed as a function of the square of the magnitude of the scattering wavevector Q. Here, this work explores the benefits of analyzing the reciprocal scattering intensity from deformed polymers, extending the original Zimm plot to anisotropic materials. In the small-angle limit, a tensorial extension of the Guinier law is found for the gyration tensor and the reciprocal single-chain structure factor. In the high-Q limit, application of the spherical harmonic expansion technique to the reciprocal structure factor permits direct model-independent analysis of spatially dependent molecular deformation of polymers. Additionally, the contributions from high-order spherical harmonics become insignificant in the reciprocal-intensity representation. The proposed generalized Zimm plot approach is demonstrated computationally with the affine deformation model and the Rouse model, and experimentally with small-angle neutron scattering measurements of deformed polystyrene melts.

36 MATERIALS SCIENCE↗

Shear Response of Ionizable Polymer Melts at the Crossover from Ionomers to Polyelectrolytes

Nonlinear shear response of polymers is affected by inherent barriers for diffusive motion, including entanglements and topology. In ionizable polymers, ionic clusters further constrain the intrinsic dynamics of the polymers, significantly enhancing their viscosity. Here, using fully atomistic molecular dynamics simulations, the nonlinear shear response of ionizable polymers is presented, across the transition from the ionomer regime where distinctive clusters dominate the structure to the polyelectrolyte regime where clusters percolate, in polystyrene randomly sulfonated with fractions of SO 3 − groups of f = 0.20 and 0.35, in pristine and tetrahydrofuran (THF) swollen polyelectrolyte melts. For f = 0.20, the ionic clusters first fracture into smaller clusters followed by splitting into individual ionic groups and eventually reform. At higher f, the clusters morph in shape but do not break under high shear. At very high shear rates, all of the chains stretch and recoil rapidly. As the shear rate is reduced, some chains stretch and recoil, while others remain largely unaffected by the shear. Macroscopically, for all systems, the shear viscosity displays initially an elastic response, followed by nonlinear shear stress overshoot and, eventually, a steady state. The evolution of viscosity with time and shear reflects that of the ionizable domains.

cluster chemistry↗

The Considere Condition and Rapid Stretching of Linear and Branched Polymer Melts

We analyze the onset of "necking" and subsequent filament failure during the transient uniaxial elongation of viscoelastic fluid samples in extensional rheometers. In the limit of rapid elongation (such that no molecular relaxation occurs), the external work applied is all stored elastically and the Considere criterion originally developed in solid mechanics can be used to quantitatively predict the critical Hencky strain to failure. By comparing the predictions of the Doi-Edwards model for linear homopolymer melts with those of the "Pom-Pom" model for prototypical branched melts we show that the critical strain to failure in rapid elongation of a rubbery material is intimately linked to the molecular topology of the chain, especially the degree of chain branching. The onset of necking instability is monotonically shifted to larger Hencky strains as the number of branches is increased. Numerical computations at finite Deborah numbers also show that there is an optimal range of deformation rates over which homogeneous extensions can be maintained to large strain. We also consider other rapid homogeneous stretching deformations, such as biaxial and planar stretching, and show that the degree of stabilization afforded by inclusion of material with long-chain branching is a sensitive function of the imposed mode of deformation.

McKinley, Gareth H.↗

Nanoparticle Diffusion in Miscible Polymer Nanocomposite Melts

X-ray photon correlation spectroscopy measurements were used to quantify the dynamics of bare and bimodal grafted silica nanoparticles mixed with PEO melts of different molecular weights. In dilute polymer nanocomposite (PNC) samples, we find diffusive NP behavior as described by the Stokes–Einstein relationship so long as the adsorbed PEO polymer layer is taken into account in determining both the effective NP size and its role on composite viscosity. The size of this bound layer was found to be approximately 2R g , where R g is the chain radius of gyration. We also expanded our system to investigate how the dynamics of grafted NPs differ from bare NPs with an adsorbed layer. We showed that the dynamics again can be determined by an effective NP radius at a scale smaller than the effective interparticle spacing; however, at larger length scales, the morphology and grafting parameters play a major role in the system dynamics. These results allow us to quantify NP ordering driven by polymer crystallization. It has previously been speculated that behavior is controlled by the relative ratio of time scale of crystal growth and the diffusive time scale of the NPs, a Peclet number. When the former time scale is longer, then the NPs are expected to be segregated into the interlamellar amorphous zones, while the NPs are too slow to be reorganized in the opposite case. We show here that this conjecture is quantitatively correct and the demarcation in behavior occurs for Pe = 1. Thus, we provide a way to estimate a critical spherulite growth rate for any semicrystalline PNC, at which a given NP can be ordered. Together, the results of this study permit us to tunably design PNCs through directed dispersion of NPs in a polymer matrix.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

High-Performance Polymers Having Low Melt Viscosities

High-performance polymers that have improved processing characteristics, and a method of making them, have been invented. One of the improved characteristics is low (relative to corresponding prior polymers) melt viscosities at given temperatures. This characteristic makes it possible to utilize such processes as resin-transfer molding and resin-film infusion and to perform autoclave processing at lower temperatures and/or pressures. Another improved characteristic is larger processing windows that is, longer times at low viscosities. Other improved characteristics include increased solubility of uncured polymer precursors that contain reactive groups, greater densities of cross-links in cured polymers, improved mechanical properties of the cured polymers, and greater resistance of the cured polymers to chemical attack. The invention is particularly applicable to poly(arylene ether)s [PAEs] and polyimides [PIs] that are useful as adhesives, matrices of composite materials, moldings, films, and coatings. PAEs and PIs synthesized according to the invention comprise mixtures of branched, linear, and star-shaped molecules. The monomers of these polymers can be capped with either reactive end groups to obtain thermosets or nonreactive end groups to obtain thermoplastics. The synthesis of a polymeric mixture according to the invention involves the use of a small amount of a trifunctional monomer. In the case of a PAE, the trifunctional monomer is a trihydroxy- containing compound for example, 1,3,5-trihydroxybenzene (THB). In the case of a PI, the trifunctional monomer is a triamine for example, triamino pyrimidine or melamine. In addition to the aforementioned trifunctional monomer, one uses the difunctional monomers of the conventional formulation of the polymer in question (see figure). In cases of nonreactive end caps, the polymeric mixtures of the invention have melt viscosities and melting temperatures lower than those of the corresponding linear polymers of equal molecular weights. The lower melting temperatures and melt viscosities provide larger processing windows. In cases of reactive end caps, the polymeric mixtures of the invention have lower melt viscosities before curing and the higher cross-link densities after curing (where branching in the uncured systems would become cross-links in the cured systems), relative to the corresponding linear polymers of equal molecular weights. The greater cross-link densities afford increased resistance to chemical attack and improved mechanical properties.

Jensen, Brian J.↗