RESUMEN
When water droplets move over a hydrophobic surface, they and the surface become oppositely charged by what is known as slide electrification. This effect can be used to generate electricity, but the physical and especially the chemical processes that cause droplet charging are still poorly understood. The most likely process is that at the base of the droplet, an electric double layer forms, and the interfacial charge remains on the surface behind the three-phase contact line. Here, we investigate the influence of the chemistry of surface (coating) and bulk (substrate) on the slide electrification. We measured the charge of a series of droplets sliding over hydrophobically coated (1-5 nm thickness) glass substrates. Within a series, the charge of the droplet decreases with the increasing droplet number and reaches a constant value after about 50 droplets (saturated state). We show that the charge of the first droplet depends on both coating and substrate chemistry. For a fully fluorinated or fully hydrogenated monolayer on glass, the influence of the substrate on the charge of the first droplet is negligible. In the saturated state, the chemistry of the substrate dominates. Charge separation can be considered as an acid base reaction between the ions of water and the surface. By exploiting the acidity (Pearson hardness) of elements such as aluminum, magnesium, or sodium, a positive saturated charge can be obtained by the counter charge remaining on the surface. With this knowledge, the droplet charge can be manipulated by the chemistry of the substrate.
RESUMEN
Slide electrification experiments were performed on low-density polyethylene films (PE) and PE sprayed with five amphiphilic compounds, including antistatic and slip additives. Drops of aqueous solutions were delivered on the films and after sliding spontaneously acquired a net electrical charge (Qdrop), which is dependent on the pH and ionic strength. The slide electrification was detected in pristine PE films and those with five additives. An acid-base equilibrium model, based on the adsorption of hydroxides and protons on surface sites, accounted for the dependence of Qdrop on pH, allowing recovery of the acid-base equilibrium constants and the density of adsorption sites. The model was modified to account for ionic strength effects through activity factors. The surface conductivity, wettability, and friction coefficients were strongly modified by the additives. However, the observed trends are different from those observed in slide electrification, which better correlated with zeta potential determinations. This suggests that the interaction mechanisms among surface water, the considered additives, and the polymer, which are involved in slide electrification and the generation of zeta potential, are different from those associated with other surface processes involving surface water. Although additives are required for changing surface resistivity, friction coefficients, and wettability, the generation of sliding electrical charges in polyethylene is a spontaneous and highly effective process. For one specific additive, a simultaneous decrease in friction coefficients, zeta potential, and Qdrop was observed, assigned to the blockade of hydroxide adsorption sites and water repulsion by the compound.
RESUMEN
Here, a mathematical model is presented, which accounts for the dependence of the surface electrical charge density (σ) on pH and the concentration of added salts (Cs), generated when a water drop rolls or slides on the surface of a hydrophobic polymer, a process known as liquid-polymer contact electrification (LPCE). The same model was successfully applied to fit the isotherms of ξ-potential as a function of pH, reported in the literature by other authors for water-poly(tetrafluoroethylene) (PTFE) interfaces. Hence, the dependence of σ and ξ on pH was described using the same concept: acid-base equilibria at the water-polymer interface. Equilibrium constants were estimated by fitting experimental isotherms. The experimental results and the model are consistent with a number of 10-100 acid-base sites/µm2. The model predicts the increase of |σ| and |ξ| with pH in the range of 2-10 and the existence of a zero-charge point at pHzcp â 3 for PTFE (independent of Cs). Excellent fits were obtained with Ka/Kb â¼ 9 × 107, where Ka and Kb are the respective acid and base equilibrium constants. On the other hand, the observed decrease in |σ| and |ξ| with Cs at fixed pH is quantitatively described by introducing an activity factor associated with the quenching of water activity by the salt ions at the polymer-water interface, with quenching constant Kq. Additionally, the quenching predicts a decrease in |σ| and |ξ| at extreme pH, where I > (1/Kq) (I: ionic strength), in agreement with literature reports.
RESUMEN
Liquid-polymer contact electrification between sliding water drops and the surface of polytetrafluoroethylene (PTFE) was studied as a function of the pH and ionic strength of the drop as well as ambient relative humidity (RH). The PTFE surface was characterized by using SEM, water-contact-angle measurements, FTIR spectroscopy, XPS, and Raman spectroscopy. The charge acquired by the drops was calculated by detecting the transient voltage induced on a specifically designed capacitive sensor. It is shown that water drops become positively charged at pH > pHzch (pHzch being the zero charge point of the polymer) while they become negatively charged for pH < pHzch. The addition of non-hydrolysable salts (NaCl or CaCl2) to water decreases the electrical charge induced in the drop. The charge also decreases with increasing RH. These results suggest proton or hydroxyl transfer from the liquid to the hydrophobic polymer surface. A proposed thermodynamic model for the ion transfer process allows explaining the observed effects of RH, pH and ionic strength.