Rheologica Acta最新文献

Polyurethane (PU) is a versatile polymer with many applications in a wide range of products. A novel 3D printing technology called liquid additive manufacturing (LAM) extended its possibilities by generating PU elastomers with gradient properties in continuous processing. LAM, being a relatively new technique, has not been extensively researched, particularly in terms of the curing behavior of the liquid resin. In this work, we investigated the effect of composition on gelation time t_GP as measured by time-resolved mechanical spectroscopy (TRMS) and analyzed using the Winter–Chambon criterion with the assistance of the IRIS software. This method is more accurate than the previous approach, which involved time sweeps with a constant frequency. It was found that the gel time t_GP first decreased and then increased with increasing polyol ratio, ranging from 231 to 378 min. Furthermore, the crosslink densities of the different PU elastomers measured from the rheological and tensile tests were calculated and compared based on the theory of rubber elasticity. The crosslink density decreased with an increasing polyol ratio in both methods. However, the crosslink density values obtained from the rheological measurements were higher than those from the tensile tests. These findings demonstrate that adjusting the polyol ratio is an effective means of achieving gradient properties. The composition effects we measured offer valuable insights for the design of LAM–PU elastomers.

Melt strain hardening is an interesting characteristic property of the elongational flow of polymers. While strain hardening of many unmodified polymer melts has been widely discussed, a comprehensive presentation of the influence of particles on this property is missing. Using literature data and own measurements, the effects of solid particles of various geometries are compared. Micro-sized particles generally reduce melt strain hardening and may even lead to strain thinning. This behavior is postulated to be due to shear flow components around the particles and resulting shear thinning of the polymer matrices that reduces the resistance to flow. More complex is the influence of nano-sized fillers and layered silicate nanoparticles, in particular. Weakly exfoliated particles show effects similar to micro-fillers, but for strongly exfoliated silicates distinct strain hardening is observed that increases with decreasing elongational rate. This behavior is particularly pronounced for polymers modified with maleic anhydrides and thought to be related to electrostatic forces between exfoliated platelets of the silicates and polymer molecules hindering molecular motions.

A variable-entanglement density constitutive model is developed for the description of the rheological properties of entangled polymer melts and concentrated polymer solutions using non-equilibrium thermodynamics (NET). It proposes two evolution equations: one for the average number of entanglements per chain and one for the orientation of entanglement strands. Direct comparison with non-equilibrium molecular dynamics simulation data shows that the model can accurately describe the loss of entanglements due to the applied flow for three molecular weights by using the same value for the convective constraint release (CCR) parameter. The CCR relaxation time depends on the trace of the inverse of the orientation tensor instead of an explicit dependency on the velocity gradient. Finally, the stress tensor contains an additional contribution inspired by the Curtiss-Bird or tumbling snake model. Overall, the model proposed here carefully derives via NET and builds upon the work of Ianniruberto-Marrucci when stretching is not considered.

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Increase in viscosity under increasing shear stress, known as shear thickening (ST), is one of the most striking properties of dense particulate suspensions. Under appropriate conditions, they exhibit discontinuous shear thickening (DST), where the viscosity increases dramatically and can also transform into a solid-like state due to shear-induced jamming (SJ). The microscopic mechanism giving rise to such interesting phenomena is still a topic of intense research. A phenomenological model proposed by Wyart and Cates shows that the proliferation of stress-activated interparticle frictional contacts can give rise to such striking flow properties. Building on this model, recent work proposes and verifies a universal scaling relation for ST systems where two different power-law regimes with a well-defined crossover point are obtained. Nonetheless, the difference in the nature of the flow in these two scaling regimes remains unexplored. Here, using rheology in conjugation with high-speed optical imaging, we study the flow and local deformations in various ST systems. We observe that with increasing applied stress, the smooth flow changes into a spatio-temporally varying flow across the scaling crossover. We show that such fluctuating flow is associated with intermittent dilatancy, shear-band plasticity, and fracture induced by system-spanning frictional contacts.

Viscoelastic materials (VEMs) have gained increasing popularity for their ability to dampen vibrations in various structural applications in recent years. The mechanical characteristics of VEMs can be effectively described using constitutive models featuring both integer and fractional derivatives. This study examines the mechanical behavior of VEMs using fractional Zener models with four, five, and six parameters, as well as the generalized Maxwell model with 16 parameters, which relies on integer derivatives. To accomplish this, the study formulates an optimization problem with the aim of minimizing an error function defined by the quadratic relative distance between theoretical model responses and experimental data. Solving the optimization problem involves the use of a hybrid optimization technique, which combines genetic algorithms and non-linear programming. After obtaining optimal designs for each viscoelastic model, qualitative assessments demonstrate that all analytical models provide satisfactory fits to the experimental data. Subsequently, a statistical analysis employing Akaike’s Information Criterion is conducted to identify the models that best describe the mechanical behavior of the analyzed VEMs. In this quantitative evaluation encompassing all viscoelastic models, it is noted that the generalized Maxwell model with 16 terms produces a lower relative error and statistically outperforms the fractional Zener models only in a global analysis. However, in a temperature-by-temperature analysis, the GMM16 proves to be inferior to all fractional models. Furthermore, when focusing solely on the fractional models, the five-parameter Fractional Zener Model exhibits the best statistical fit to the experimental data.

There is high market demand for increasing the viability of current plastic recycling processes. In this work rheology is used to evaluate the mechanical properties of a solvent dissolution recycled polymer compared to its virgin untreated precursor. Solvent dissolution and precipitation are used to target multi-layer, multi-component, industry films, which cannot be mechanically recycled. Polyethylene was chosen as the primary polymer of interest. Polymer thermal stability was monitored via time-resolved rheology; consecutive frequency sweeps over the course of an hour while under isothermal conditions. Additional rheological experiments were performed within the identified thermally stable conditions. Small-angle oscillatory shear was complemented with steady shear viscosity experiments over a wide range of shear rates. Extensional rheology was used to determine changes in molecular weight and cross link density. Rheological characterization is supplemented with gas chromatography–mass spectrometry of the solvent wash to determine components stripped from the virgin polymers during solvent treatment.

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The present work explores the shear and extensional rheology of immiscible multi-micro/nanolayered systems comprising low-density polyethylene (LDPE) paired with polystyrene (PS) and polycarbonate (PC) obtained from forced-assembly multilayer coextrusion. Firstly, miscible multilayer references based on LDPE/LLDPE layers were prepared with their miscibility characterized by shear and elongational measurements. Their strain hardening behaviors were found to be intricately linked to the number of layers and confinement. Secondly, for immiscible LDPE/PS and LDPE/PC multilayers with symmetric (50/50) and asymmetric (10/90) compositions, negative deviation of complex viscosities from neat polymers was highlighted because of the heightened confinement of LDPE chains by PS or PC and reduced entanglements at polymer–polymer interfaces. Intriguingly, LDPE/PC systems exhibited no strain hardening irrespective of layer configuration, while the geometric confinement imposed by PS layers facilitated interactions between single chains with long-chain branching (LCB), leading to strain hardening under specific conditions. Furthermore, the extensional viscosities were predicted using the Macosko model (C.W. Macosko et al. Journal of Rheology. 63 2019), accurately describing the behavior of 1024 layered films for both asymmetric (10/90) LDPE/PS and LDPE/PC systems, but not for 32 layers due to a limited number of interfaces. This study provides insights into quantifying interfacial tension properties in micro/nano-layered systems with high mismatched viscoelastic polymers, shedding light on their strain hardening properties in the presence of increased interfacial area.

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Understanding and controlling the rheology of electrode slurries for lithium-ion batteries is critical both for improving their manufacturing efficiency and for achieving desirable battery performance. Here, we show drastic “slurry-preparation-dependent” rheology in an anode slurry for lithium-ion batteries, focusing on the behaviour of carboxymethyl cellulose (CMC), which is the most popular dispersant for graphite particles in anode slurries. Slurry preparation with dry-state mixing, where water is added to a dry mixture of graphite and CMC powder, results in much higher viscosity, yield stress, and elastic modulus than those achieved with conventional wet-state mixing, where graphite is added to a CMC solution. Cryogenic scanning electron microscopy reveals strange CMC “clumps” formed among the graphite particles in the slurry prepared with dry-state mixing. We attribute the increases in viscosity, yield stress, and elastic modulus for the slurries prepared with dry-state mixing to these clumps of CMC, which can enhance the adhesion between graphite particles and thereby constrain their motion. We also show that pre-shearing irreversibly decreases viscosity, yield stress, and elastic modulus, suggesting that the clumps of CMC are irreparably broken down by applied shear. The influence of the slurry preparation method on the rheological properties of anode slurries has not received attention in previous studies. Hence, we believe that our results might provide new strategies for controlling the rheology of the anode slurry in the manufacturing process for lithium-ion batteries.

Abstract

The ability to manipulate rheological and electrical properties of colloidal carbon black gels makes them attractive in composites for energy applications such as batteries and fuel cells, where they conduct electricity and prevent sedimentation of ‘granular’ active components. While it is commonly assumed that granular fillers have a simple additive effect on the composite properties, new phenomena can emerge unexpectedly, with some composites exhibiting a unique rheological bi-stability between high-yield-stress and low-yield-stress states. Here we report such bi-stability in suspensions of non-Brownian graphite and colloidal carbon black in oil, a model system to mimic composite suspensions for energy applications. Steady shear below a critical stress elicits a transition to a persistent mechanically weak and poorly conducting state, which must be ‘rejuvenated’ using high-stress shear to recover a stronger, high-conductivity state. Our findings highlight the highly tunable nature of binary granular/gel composite suspensions and present new possibilities for optimising mixing and processing conditions for Li-ion battery slurries.

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