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1. Dynamics and extensional rheology of polymer–surfactant association complexes

   https://doi.org/10.1039/D1SM00335F  

   Martínez Narváez, Carina D.; Mazur, Thomas; Sharma, Vivek (June 2021, Soft Matter)

   null (Ed.)

   Understanding and characterizing the influence of polymers and surfactants on rheology, application, and processing is critical for designing complex fluid formulations for enhanced oil recovery, pharmaceuticals, cosmetics, foods, inks, agricultural sprays, and coatings. It is well-established that the addition of anionic surfactant like sodium dodecyl sulfate (SDS) to an aqueous solution of an oppositely-charged or uncharged polymer like poly(ethylene oxide) (PEO) can result in the formation of the polymer–surfactant association complexes (P 0 S − ACs) and a non-monotonic concentration-dependent variation in zero shear viscosity. However, the extensional rheology response of polymer–surfactant mixtures remains relatively poorly understood, partially due to characterization challenges that arise for low viscosity, low elasticity fluids, even though the response to strong extensional flows impacts drop formation and many processing operations. In this article, we use the recently developed dripping-onto-substrate (DoS) rheometry protocols to characterize the pinching dynamics and extensional rheology response of aqueous P 0 S − solutions formulated with PEO (P 0 ) and SDS (S − ), respectively. We find the PEO–SDS mixtures display a significantly weaker concentration-dependent variation in the extensional relaxation time, filament lifespan, and extensional viscosity values than anticipated by the measured shear viscosity. 

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2. Microfluidic rheology of methylcellulose solutions in hyperbolic contractions and the effect of salt in shear and extensional flows

   https://doi.org/10.1039/d0sm00371a  

   Micklavzina, Benjamin L.; Metaxas, Athena E.; Dutcher, Cari S. (June 2020, Soft Matter)

   Methylcellulose solutions are known to form microfibrils at elevated temperatures or in the presence of salt. The fibrils have a significant impact on the solution's rheological properties. Here, the shear and extensional properties of methylcellulose solutions with added salt are measured using hyperbolic microfluidic channels, allowing for new characterization at lower molecular weights and higher shear and strain rates that are difficult to access by macroscale rheology studies. 1 and 2 wt% methylcellulose solutions with molecular weight of 150 kg mol −1 with NaCl content between 0 to 5 wt% have been characterized. All solutions were found to be shear thinning, with power law thinning behavior at shear rates above 100 s −1 . The addition of NaCl up to 5 wt% had only small effects on shear viscosity at the shear rates probed (100 s −1 and 10 000 s −1 ). Extensional viscosities as low as 0.02 Pa s were also measured. Unlike the results for shear viscosity, the addition of 5 wt% NaCl caused significant changes in extensional viscosity, increasing by up to 10 times, depending on extension rate. Additionally, all solutions tested showed apparent extensional thinning in the high strain rate regime (>100 s −1 ), which has not been reported in other studies of methylcellulose solutions. These findings may provide insight for those using methylcellulose solutions in process designs involving extensional flows over a wide range of strain rates. 

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3. Ferrofluid droplets in planar extensional flows: Droplet shape and magnetization reveal novel rheological signatures of ferrofluid emulsions

   https://doi.org/10.1103/PhysRevFluids.8.063601  

   Guilherme, A L; Siqueira, I R; Cunha, L_H P; Thompson, R L; Oliveira, T F (June 2023, Physical Review Fluids)

   We present a three-dimensional computational study of the impact of external magnetic fields on the dynamics of superparamagnetic ferrofluid droplets and rheology of dilute ferrofluid emulsions in planar extensional flows. Specifically, we show how the intensity and direction of uniform magnetic fields affect the planar extensional rheology of ferrofluid emulsions by changing the shape and magnetization of the constituent ferrofluid droplets in suspension. We find that the two traditional extensional viscosities associated with the normal stresses of the bulk emulsion in extension either remain constant or increase with the field intensity; the only exception occurs when the field direction is perpendicular to the extension plane, where increasing the field intensity keeps the planar extensional viscosity constant and modestly decreases the second extensional viscosity. We also find that the droplet tilts in the flow when the external field is not aligned with one of the flow main directions, which changes the recirculation pattern and flow topology inside the droplet. At the microscopic level, the droplet experiences a magnetic torque because of a small misalignment between its magnetization and the external field direction. At the macroscopic level, the bulk emulsion experiences a field-induced internal torque that leads to a nonsymmetric stress tensor with unexpected shear components in extension. To account for this unconventional stress-strain response, we introduce new extensional material functions such as shear and rotational viscosity coefficients that unveil novel rheological signatures of ferrofluid emulsions in planar extensional flows. This study offers new insights into applications based on the field-assisted manipulation of ferrofluid droplets and sheds light on the potential of ferrofluid emulsions as a model system for chiral fluids with internal rotational degrees of freedom that can be activated and controlled by coupling static magnetic fields with hydrodynamic flows. 

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4. Effects of Dye Addition on the Rheological Properties of Aqueous Polymer Solutions

   https://doi.org/10.1021/acs.langmuir.4c01533  

   Upoma, Marufa Akter; He, Ziwen; Tran, Huy; Sivells, Tiara; Cyran, Jenée D; Pack, Min Young (September 2024, Langmuir)

   In many commercial applications, polymer–dye interactions are frequently encountered from food to wastewater treatment, and while shear rheology has been well characterized, the extensional properties are not well known. The extensional viscosity ηE and relaxation time λE are the extensional rheological parameters that provide valuable insights into how aqueous polymers respond during deformation, and this study investigated the effect of dyes on the extensional rheology of three different aqueous polymer solutions (e.g., anionic, cationic, and neutral) paired with two different dye salts (e.g., anionic and cationic) using drop pinch-off experiments. We have found that the influence of dyes on the pinch-off dynamics is complex but generally leads to a decrease in, for example, the apparent extensional relaxation time. We have utilized the dripping-onto-substrate method to probe the uniaxial deformation of widely used polymers such as xanthan gum (XG), poly(diallyldimethylammonium chloride) (PDADMAC), and poly(ethylene oxide) (PEO) as the anionic, cationic, and neutral polymers, respectively, paired with either fluorescein (Fl) or methylene blue (MB) as the anionic and cationic dyes, respectively. Polymer–dye pairs with opposite charges (e.g., XG–MB and PDADMAC–Fl) displayed a pronounced decrease in pinch-off times, but even PEO, which is a neutral polymer, resulted in decreased pinch-off times, which was restored by the addition of NaCl. The pinch-off times for the Boger fluid (mixture of poly(ethylene glycol) and PEO), however, were surprisingly uninfluenced by dyes. These results showed that not only did the small addition of dyes strongly decrease the polymer relaxation times, but the relative importance of the dye salts on the polymer pinch-off dynamics was also different from that of pure salts such as NaCl. 

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5. Dimethylformamide-Mediated Polymer Microstructure Dictates the Extensional Rheology of Aqueous PNIPAM Solutions

   https://doi.org/10.1021/acs.macromol.4c01658  

   Zhang, Diana Y; Schwendinger, Alec J; Calabrese, Michelle A (October 2024, Macromolecules)

   Polymer solution processability in extensional-flow dominated operations is strongly influenced by polymer conformation and solution phase behavior. Cosolvent addition can be used to tailor polymer conformation and solution phase behavior to yield formulations that are amenable to processes such as spraying and atomization, coating, and fiber spinning. The addition of N,N-dimethylformamide (DMF) to aqueous poly(N-isopropylacrylamide) (PNIPAM) solutions induces unique phase behavior and microstructure formation, yet the effects on solution processability have remained unexplored. In this work, the effect of DMF cosolvent content on the rheology (both shear and extensional) and microstructure of PNIPAM solutions is investigated. While all examined PNIPAM solutions exhibit nearly Newtonian steady shear behavior regardless of DMF content, the same solutions exhibit varying degrees of extensibility. Surprisingly, the extensional relaxation time increases by more than twenty-fold with increasing DMF content in the water-rich regime. In the DMF-rich regime, however, solution extensibility dramatically decreases. Interestingly, this unique variation in extensional flow behavior does not scale as expected based on changes in the measured intrinsic viscosity and radius of gyration. Instead, a mechanism is proposed that relates the extensional flow behavior to the solution microstructure, which is found to vary with DMF content in light scattering measurements. In the water-rich regime, DMF molecules are proposed to bridge PNIPAM chains via hydrogen bonding and hydrophobic interactions, resulting in physically crosslinked aggregates. In extensional flows, these aggregates behave like a polymer with higher apparent molecular weight, increasing the extensional relaxation time. In the DMF-rich regime, non-bridging DMF molecules increasingly solvate individual PNIPAM chains; consequently, more individual chains are stretched in extensional flows, leading to a reduction in the extensional relaxation time. These findings demonstrate that interactions between components in these ternary systems have unexpected but significant implications in solution extensional flow behavior. Additionally, in the case of PNIPAM/DMF/water, the processability of polymer-containing formulations can be modulated for spraying or for fiber spinning applications just by varying cosolvent (DMF) content. 

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