Connecting monotonic and oscillatory motions of the meniscus of a volatile polymer solution to the transport of polymer coils and deposit morphology

TL;DR

This study links the motion of the meniscus during polymer solution evaporation to the resulting deposition patterns, revealing how different transport regimes lead to distinct, predictable morphologies.

Contribution

It systematically connects meniscus dynamics, polymer coil transport, and deposit morphology, highlighting the role of evaporation and Marangoni stresses in pattern formation.

Findings

Diffusion-dominated transport leads to continuous, uniform deposits.

Convection-dominated transport causes oscillatory, stripe-patterned deposits.

Meniscus motion varies between monotonic and oscillatory depending on transport regime.

Abstract

We study the connection between the polymer deposition patterns to appear following the evaporation of a solution of poly-methyl-methacrylate (PMMA) in toluene, the transport of the polymer coils in the solution, and the motion of the meniscus of the solution. Different deposition patterns are observed when varying the molecular mass and initial concentration of the solute and temperature and are systematically presented in the form of morphological phase diagrams. The modi of deposition and meniscus motion are correlated. They vary with the ratio between the evaporation-driven convective flux and diffusive flux of the polymer coils in the solution. In the case of a diffusion-dominated solute transport, the solution monotonically dewets the solid substrate by evaporation, supporting continuous contact line motion and continuous polymer deposition. However, a convection-dominated transport results in an oscillatory ratcheting dewetting-wetting motion of the contact line with more pronounced dewetting phases. The deposition process is then periodic and produces a stripe pattern. The oscillatory motion of the meniscus differs from the well documented stick-slip motion of the meniscus, observed as well, and is attributed to the opposing influences of evaporation and Marangoni stresses, which alternately dominate the deposition process.