SearcharxivSearch

arXiv subjects

Christopher W. Macosko

Publications and source records attributed to Christopher W. Macosko.

2 recordsLinked to original sources

DoS Dos and Don'ts

Dripping-onto-Substrate (DoS) rheometry is a well-established method for measuring the extensional rheology of low-viscosity liquids. However, clear guidelines on the capabilities and limitations of the technique are lacking. In the present work, we define operational limits for measuring a transient extensional viscosity directly from observation of the rate of filament thinning, as well as model-based bounds on calculating a viscosity $η$ and extensional relaxation time $τ_E$ of a liquid using DoS. Dilute solutions of polyethylene oxide (PEO) and polyacrylamide (PAM) are used to probe the lower limit of measurable $τ_E$, demonstrating that values as low as 0.1 ms can be resolved, provided (a) the intrinsic Deborah number (based on the ratio of the relaxation time and the Rayleigh breakup time scale) is $De \geq \mathcal{O}(0.1)$ and (b) an instrumental constraint related to spatial and temporal resolution is satisfied. This instrumental constraint is quantified through a new metric we define as the \textit{filament capture rate}, a ``figure of merit'' (expressed in Hz) that can be used to quantify the number of data points within the elasto-capillary regime that are available for extraction of $τ_E$. We also investigate the sensitivity to other experimental parameters including variations in nozzle radius and Bond number ($Bo$). Across the tested range ($0.2 < Bo < 0.7$), extensional relaxation times for the same fluid vary by less than $\pm16$ \%; however, experiments with low viscosity fluids at $Bo > 0.5$ exhibit damped gravitational oscillations that affect early-time dynamics. Collectively, these results provide a quantitative roadmap for reliable DoS rheometry and affirm its use for measuring sub-millisecond relaxation times in weakly elastic fluids.

cond-mat.soft

Interfacial silica nanoparticles stabilize cocontinuous polymer blends

We investigated the formation of cocontinuous structures in polymer blends. These polymeric bijels (bicontinuous interfacially jammed emulsion gels) were composed of polystyrene oligomer, polybutene and fluorescent hydrophobic silica nanoparticles. A micron-sized cocontinuous morphology was stabilized by a monolayer of silica nanoparticles at the interface. Real-time observation of coalescence dynamics in co-continuous polymer blends stabilized by interfacial particles was for the first time achieved via laser scanning confocal microscopy. We demonstrated that suppression of coalescence arises from coverage of interfaces by nanoparticles. Furthermore, by combining confocal microscopy with rheology, we correlated the rheological response of a cocontinuous structure with its morphology change. We found that the rheological behavior can be attributed to competition between interface shrinkage and particle network formation. In addition, we showed that a particle scaffold is maintained even after the remixing of two polymer phases above the spinodal point. Finally, we also discussed differences between the shear response of the particle-stabilized cocontinuous structure and normal colloidal gels: the former one is more fragile than the latter under shear.

cond-mat.soft