Phase separation dynamics in wetting ridges of polymer surfaces swollen with oils of different viscosities.

When drops are placed on a sufficiently soft surface, the drop surface tension drives an out of plane deformation around the contact line (i.e., a wetting ridge). For soft elastomeric surfaces that are swollen with a liquid, capillarity from a drop can induce a phase separation in the wetting ridge. Using confocal microscopy, we study the dynamics of phase separation at the wetting ridge of glycerol drops on silicone elastomers, which are swollen with silicone oils of varying viscosity (i.e., molecular weight). We show that the viscosity of the swelling oil plays a large role in the oil separation size and separation rate. For networks swollen to near their maximum swelling (i.e., saturated), lower viscosity oil separates more and separates faster at early times compared to larger viscosity oil. During late-stage wetting, the growth rate of the separation is a function of viscosity and swelling ratio, which can be described by a simple diffusive model and a defined wetting ridge geometry. In this late-stage wetting, the higher viscosity oil evidently grows faster, likely because it is further from reaching equilibrium. Interestingly, the separated oil phase region grows with a nearly constant, geometrically similar shape. Understanding how phase separation occurs on swollen substrates should provide information on how to control drop spreading, sliding, adhesion, or friction on such surfaces.

Visualizing Penetration of Fluorescent Dye through Polymer Coatings.

Understanding how small molecules penetrate and contaminate polymer films is of vital importance for developing protective coatings for a wide range of applications. To this end, rhodamine B fluorescent dye is visualized diffusing through polystyrene-polydimethylsiloxane block copolymer (BCP) coatings using confocal microscopy. The intensity of dye inside the coatings grows and decays non-monotonically, which is likely due to a combination of dye molecule transport occurring concurrently in different directions. An empirical fitting equation allows for comparing the contamination rates between copolymers, demonstrating that dye penetration is related to the chemical makeup and configuration of the BCPs. This work shows that confocal microscopy can be a useful tool to visualize the transport of a fluorophore in space and time through a coating.

Engineering ligand reactivity enables high-temperature operation of stable perovskite solar cells.

Perovskite solar cells (PSCs) consisting of interfacial two- and three-dimensional heterostructures that incorporate ammonium ligand intercalation have enabled rapid progress toward the goal of uniting performance with stability. However, as the field continues to seek ever-higher durability, additional tools that avoid progressive ligand intercalation are needed to minimize degradation at high temperatures. We used ammonium ligands that are nonreactive with the bulk of perovskites and investigated a library that varies ligand molecular structure systematically. We found that fluorinated aniliniums offer interfacial passivation and simultaneously minimize reactivity with perovskites. Using this approach, we report a certified quasi-steady-state power-conversion efficiency of 24.09% for inverted-structure PSCs. In an encapsulated device operating at 85°C and 50% relative humidity, we document a 1560-hour T85 at maximum power point under 1-sun illumination.

Phase Separation in Wetting Ridges of Sliding Drops on Soft and Swollen Surfaces.

Drops in contact with swollen, elastomeric substrates can induce a capillary mediated phase separation in wetting ridges. Using confocal microscopy, we visualize phase separation of oligomeric silicone oil from a cross-linked silicone network during steady-state sliding of water drops. We find an inverse relationship between the oil tip height and the drop sliding speed, which is rationalized by competing transport timescales of the oil molecules: separation rate versus drop-advection speed. Separation rates in highly swollen networks are as fast as diffusion in pure melts.

Hydrophobic surface patterning with soft, wax-infused micro-stamps.

HYPOTHESIS: Waxy hydrocarbons diffuse freely in polydimethylsiloxane (PDMS), and this capability can be leveraged to generate inexpensive surface micropatterns that modify adhesion and wetting. EXPERIMENTS: Patterns are created by placing a waxy Parafilm sheet on the back of a PDMS stamp containing microscale surface features. When heated, the paraffin liquefies and diffuses through the stamp, creating a thin liquid layer on the micropatterned stamp surface; when placed in contact with a target surface, the layer solidifies and is retained on the target when the stamp is removed. Micropatterns were generated on different materials and surface topographies; pattern geometry was evaluated using optical profilometry and changes in wetting were evaluated using contact angle goniometry. Diffusion of paraffin through PDMS was evaluated using XPS. FINDINGS: Wax micropatterns have submicron lateral resolution and thickness ranging from 85 to 380 nm depending on contact time. By using XPS analysis to track paraffin diffusion within the PDMS stamp during this process, we estimate the diffusion coefficient to be 5.3 × 10-7 cm2/s at 65 °C. This means that the paraffin layer at the stamp surface replenishes in less than a second after stamping, so it can be used multiple times without re-inking to deposit complex, multi-layer paraffin patterns.