Temperature-controlled dripping-onto-substrate (DoS) extensional rheometry of polymer micelle solutions

Zhang, Diana Y.; Calabrese, Michelle A.

doi:10.1039/d2sm00377e

Cited by 12 publications

(11 citation statements)

References 90 publications

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“…These comparisons suggest that, perhaps as expected, the higher molecular weight of P188 solutions (8.4 kDa vs. ~1 kDa for polysorbates) substantially contributes to the higher elasticity and lower concentration at which weak elasticity is observed in those solutions. Additionally, the comparable P188 solutions consisted primarily of unimers, 23 which may undergo more chain stretching than spherical micelles; prior DoS experiments on spherical poloxamer micelles showed no weakly elastic flow behavior, albeit at lower solution concentrations 71 …”

Section: Resultsmentioning

confidence: 98%

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Polysorbate identity and quantity dictate the extensional flow properties of protein‐excipient solutions

2022

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While protein medications are promising for treatment of cancer and autoimmune diseases, challenges persist in terms of development and injection stability of highconcentration formulations. Here, the extensional flow properties of proteinexcipient solutions are examined via dripping-onto-substrate extensional rheology, using a model ovalbumin (OVA) protein and biocompatible excipients polysorbate 20 (PS20) and 80 (PS80). Despite similar PS structures, differences in extensional flow are observed based on PS identity in two regimes: at moderate total concentrations where surface tension differences drive changes in extensional flow behavior, and at small PS:OVA ratios, which impact the onset of weakly elastic flow behavior.Undesirable elasticity is observed in ultra-concentrated formulations, independent of PS identity; higher PS contents are required to observe these effects than in analogous polymeric excipient solutions. These studies reveal novel extensional flow behaviors in protein-excipient solutions, and provide a straightforward methodology for assessing the extensional flow stability of new protein-excipient formulations.

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Section: Resultsmentioning

confidence: 98%

“…Additionally, the comparable P188 solutions consisted primarily of unimers, 23 which may undergo more chain stretching than spherical micelles; prior DoS experiments on spherical poloxamer micelles showed no weakly elastic flow behavior, albeit at lower solution concentrations. 71…”

Section: Shear Rheologymentioning

confidence: 99%

Polysorbate identity and quantity dictate the extensional flow properties of protein‐excipient solutions

2022

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“…An apparatus with similar features was used by Dinic et al. (2015), Dinic, Jimenez & Sharma (2017) and Zhang & Calabrese (2022). After the droplet made contact with the substrate, a liquid bridge was formed between the nozzle outlet and the substrate.…”

Section: Experimental Methodologymentioning

confidence: 99%

“…Low-viscosity fluids typically have and a necking process dominated by inertial and capillary forces. In this regime, inertiocapillary (IC) thinning is described by a 2/3 power law: where is the filament break-up time, and is a multiplicative pre-factor between 0.4 and 1 (Zhang & Calabrese 2022). If , viscous forces are significant, and the evolution of is described by viscocapillary thinning, (McKinley & Tripathi 2000).…”

Section: Experimental Methodologymentioning

confidence: 99%

Polymer and surfactant flows through a periodically constricted tube

Warwaruk

Ghaemi

2023

J. Fluid Mech.

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The flow of three non-Newtonian fluids, comprising polymer and surfactant additives, in a periodically constricted tube (PCT) are experimentally compared. The radius of the tube walls is sinusoidal with respect to the streamwise direction. The three fluids are aqueous solutions of flexible polymers, rigid biopolymers and surfactants, which are typically used for drag-reduction in turbulent flows. Steady shear viscosity measurements demonstrate that rigid and flexible polymer solutions are shear-thinning, while surfactant solutions have a Newtonian and water-like shear viscosity. Capillary driven extensional rheology demonstrates that only flexible polymer solutions produce elastocapillary thinning. Particle shadow velocimetry is used to measure the velocity of each flow within the PCT at five Reynolds numbers spanning roughly 0.5 to 300. Relative to the Newtonian flows, rigid polymer solutions exhibit a blunt velocity profile. Flexible polymer solutions demonstrate a distinct chevron-shaped velocity contour and zones of opposing vorticity when the Deborah number exceeds 0.1. Using the vorticity transport equation, it is revealed that the opposing vorticity zones are coupled with a non-Newtonian torque. The PCT reveals that the surfactant solutions have similar non-Newtonian features as flexible polymer solutions – those being a chevron velocity pattern, opposing vorticity and a finite non-Newtonian torque. This observation is of practical importance since conventional shear and extensional rheometric measurements are not capable of demonstrating non-Newtonian features of the surfactant solutions. The investigation demonstrates that the PCT serves as a viable geometry for showing the non-Newtonian traits of dilute surfactant solutions.

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“…High-speed videos of the thinning liquid bridges were recorded to determine the minimum radius R over time, using image analysis as described in our prior work. [62][63][64] Prior to contact with the substrate, the surface tension σ of each solution was measured via an ImageJ plugin [65], and subsequently used to determine apparent extensional viscosities η E , where η E = σ 2dR(t)/dt . Radial decay profiles were used to determine the Hencky strain, ε H , where ε H = −ln(R/R 0 ); here, R 0 is the initial radius, defined as 80% of the radius of the nozzle extruding the drop.…”

Section: Extensional Rheology Via Capillary-driven Thinningmentioning

confidence: 99%

Development of microbeads from unmodified biomass with tunable size and competitive mechanical properties

Robertson

Hoover²,

Rott

et al. 2022

Preprint

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Despite national and international regulations, plastic microbeads are still widely used in personal care and consumer products (PCCPs) as exfoliants and rheological modifiers, causing significant microplastic pollution following use. As a sustainable alternative, microbeads were produced by extrusion of biomass solutions and precipitation into anti-solvent. Despite using novel blends of biodegradable, non-derivatized biomass including cellulose and Kraft lignin, resulting microbeads are within the shape, size, and stiffness range of commercial plastic microbeads, even without crosslinking. Solution processability and resulting bead shape and Young’s modulus can be tuned via biomass source, concentration, and degree of polymerization; biomass concentration, extrusion geometry, and precipitation and extraction conditions control the bead size. Lignin incorporation reduces the solution viscosity, which improves processability but also produces flatter beads with higher moduli than cellulose-only microbeads. While some lignin leaches from the beads when stored in water, adding surfactants like sodium dodecyl sulfate suppresses this effect, resulting in good mechanical stability over two months with no noticeable structural degradation. The stability of these mixed-source biomass microbeads - despite the absence of chemical crosslinking or derivatization - makes this route a promising, robust approach for obtaining environmentally-benign microbeads of tunable size and stiffness for use in PCCPs.

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Temperature-controlled dripping-onto-substrate (DoS) extensional rheometry of polymer micelle solutions

Abstract: Capillary-driven thinning of a liquid bridge is commonly used to measure the extensional rheology of macromolecular solutions for assessment of material sprayability, printability, and jettability. Methods like dripping-onto-substrate (DoS) rheometry...

Cited by 12 publications

References 90 publications

Polysorbate identity and quantity dictate the extensional flow properties of protein‐excipient solutions

Polysorbate identity and quantity dictate the extensional flow properties of protein‐excipient solutions

Polymer and surfactant flows through a periodically constricted tube

Development of microbeads from unmodified biomass with tunable size and competitive mechanical properties

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