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This study seeks to understand the role of photodegradation of aqueous polymers in drop splashing. Polymer drop impact commonly occurs in various industrial applications such as inkjet printing, spray coating, and agrochemical sprays. In agrochemicals, the various constituent components (e.g., adjuvants) imparts multiple changes to the fluid dynamics and the wetting behaviors of the drops, as well as interacting with the environmental conditions. The environmental conditions (e.g., thermal-degradation, photo-degradation, and oxidation) of the chemicals affect the shelf stability of the intended physicochemical properties of the chemicals, which are added to stabilize drift from the spray nozzles and minimize drop bouncing from leaves. The aging effects of the adjuvants in tandem with the already low pesticide delivery efficiency has an unknown effect on the agrochemical delivery efficiency and the related environmental burden from the increased run off. Herein, we systematically photo-degraded polyethylene oxide (PEO) to probe the drop splashing behavior as a result of the simulated aging conditions. Dye was added to accelerate the degradation of the polymers and caused drops to splash at Weber numbers where the pure PEO case did not, confirming the need to consider environmental factors which contributes to adjuvant aging in agrochemical applications. We have also conducted experiments with various concentrations of PEO to probe the changes in the splash dynamics as well as including surfactants, which played a marginal role in altering the splash dynamics under our parameter space. The significance of the study is that the degradation of the polymers influences the splashing and increases the amount of splashed droplets, indicating the importance of controlling the environmental conditions under which polymer solutions are stored. 

Understanding the peripheral capillary wave propagation during droplet impact is crucial for comprehending the physics of wetting onset and droplet fragmentation. Although Newtonian droplets have been extensively studied, we show how capillary waves deform non-Newtonian droplets in such a way that rheological features, such as the critical concentrations for the overlap (c*) and entangled polymer molecules (c**), may be directly obtained from the deformation history. Determining these critical concentrations is essential as they mark transitions in the rheological behavior of aqueous polymeric solutions, influencing viscosity, elasticity, and associated fluid dynamics. We have also compared capillary waves among Newtonian, shear-thinning, and Boger fluid droplets and found that although the fluid kinematics appear to be purely biaxial extensional flow, the infinite-shear properties of the droplets dominate the physics of capillary wave formation and propagation. 

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. 

Recent studies have revealed the air-cushioning effect of droplet impact upon various surfaces and although pure water droplets have extensively been studied, the air entrainment dynamics for aqueous polymeric droplets was the focus of this study. Herein, droplets of low to moderate Weber numbers, [Formula: see text], displayed air film thickness gradients which was strongly influenced by the viscoelastic properties of the aqueous polymeric droplets in the dilute to the semidilute unentangled regimes. Aqueous polyethylene oxide droplets impacting a smooth thin oil film surface formed a submicrometer air layer, moments prior to impact, which was tracked by a high-speed total internal reflection microscopy technique. The radial changes in the air film thickness were related to the polymer concentration, thus providing an alternative tool for comparing the rheometer-derived overlap concentrations with a contactless optical technique. 

Marangoni flow is the motion induced by a surface tension gradient along a fluid–fluid interface. In this study, we report a Marangoni flow generated when a bath of surfactant contacts a pre-wetted film of deionized water on a vertical substrate. The thickness profile of the pre-wetted film is set by gravitational drainage and so varies with the drainage time. The surface tension is lower in the bath due to the surfactant, and thus a liquid film climbs upwards along the vertical substrate due to the surface tension difference. Particle tracking velocimetry is performed to measure the dynamics in the film, where the mean fluid velocity reverses direction as the draining film encounters the front of the climbing film. The effect of the surfactant concentration and the pre-wetted film thickness on the film climbing is then studied. High-speed interferometry is used to measure the front position of the climbing film and the film thickness profile. As a result, higher surfactant concentration induces a faster and thicker climbing film. Also, for high surfactant concentrations, where Marangoni driving dominates, increasing the film thickness increases the rise speed of the climbing front, since viscous resistance is less important. In contrast, for low surfactant concentrations, where Marangoni driving balances gravitational drainage, increasing the film thickness decreases the rise speed of the climbing front while enhancing gravitational drainage. We rationalize these observations by utilizing a dimensionless parameter that compares the magnitudes of the Marangoni stress and gravitational drainage. A model is established to analyse the climbing front, either in the Marangoni-driving-dominated region or in the Marangoni-balanced drainage region. Our work highlights the effects of the gravitational drainage on the Marangoni flow, both by setting the thickness of a pre-wetted film and by resisting the film climbing. 

Contact line dynamics is crucial in determining the deposition patterns of evaporating colloidal droplets. Using high-speed interferometry, we directly observe the stick-slip motion of the contact line in situ and are able to resolve the instantaneous shape of the inkjet-printed, evaporating pico-liter drops containing nanoparticles of varying wettability. Integrated with post-mortem optical profilometry of the deposition patterns, the instantaneous particle volume fraction and hence the particle deposition rate can be determined. The results show that the stick-slip motion of the contact line is a strong function of the particle wettability. While the stick-slip motion is observed for nanoparticles that are less hydrophilic ( i.e. , particle contact angle θ ≈ 74° at the water–air interface), which results in a multiring deposition, a continuous receding of the contact line is observed for more hydrophilic nanoparticles ( i.e. , θ ≈ 34°), which leaves a single-ring pattern. A model is developed to predict the number of particles required to pin the contact line based on the force balance of the hydrodynamic drag, interparticle interactions, and surface tension acting on the particles near the contact line with varying particle wettability. A three-fold increase in the number of particles required for pinning is predicted when the particle wettability increases from the wetting angle of θ ≈ 74° to θ ≈ 34°. This finding explains why particles with greater wettability form a single-ring pattern and those with lower wettability form a multi-ring pattern. In addition, the particle deposition rate is found to depend on the particle wettability and vary with time.