Hypothesis The contact line pinning that appears in a flow coating process over substrates patterned with chemical or physical heterogeneities has been recently applied to deposit micro- and nanoparticles with great precision. However, the mechanism underlying pinning of a receding contact line at the nanoscale is not yet well understood. In the case of a contact line pinned at a chemical heterogeneity, we hypothesise that it is possible to establish a relation between the pinning time, the contact line velocity and the liquid/plate/heterogeneity affinity that can help to optimize particle deposition.
Methods We use large-scale molecular dynamic (MD) simulations of a finite liquid bridge formed between two parallel, non–identical, smooth solid plates. The top plate slides relative to the bottom plate inducing a displacement of the four different contact lines of the liquid bridge. The introduction of a chemical heterogeneity on the bottom plate by modifying locally the liquid–solid affinity provokes the transient pinning of the contact line in contact with the bottom substrate. By means of this simple MD simulation, we can study the mechanism of contact line pinning and its relation with the liquid/heterogeneity affinity and the contact line velocity. Additionally, we compare this mechanism with the case of the receding contact line pinned on a physical heterogeneity (a simple step discontinuity). Findings We propose an analytical model that predicts the values of the dynamic contact angles in the general case of a capillary liquid bridge confined between two parallel plates with different wettabilities versus the relative velocity of the top plate. These predictions are successfully validated by the results of the large–scale MD simulations. The model allows thus to predict the value of the dynamic contact angles for the different contact lines of the system versus the relative speed of the moving plate. Once the chemical heterogeneity is introduced in the bottom plate, we show that when the receding contact line reaches the patch it remains temporarily pinned while the receding contact angle evolves with time. Once the receding angle reaches the value of the equilibrium contact angle of the patch, the receding contact line overcomes pinning. A geometrical model able to predict the pinning time is proposed and validated by our MD simulations. The pinning time depends not only on the relative plate velocity and plate wettability properties but also on the separation distance between the plates confining the capillary bridge. The model can consequently be used to select the substrate wettability or meniscus geometry suitable to impose the pinning time required for specific applications. ... Read more

To evaluate compatibility between a substrate and a thermoplastic polymer, the established methodology is to estimate their surface composition in terms of surface energy components, utilizing the results of contact angle measurements of probe liquids onto substrate and polymer surfaces at room temperature. Using this methodology, polymer surfaces are studied in solid state, however, during spreading of polymers on a substrate, polymers are in molten state and at high temperature, having different surface energies and more complex polymer/substrate interactions due to polymer chain mobility. This paper presents a model study with practical relevance to predict polymer/substrate compatibility including contact angle measurements at high temperature directly performed between molten thermoplastics; polypropylene (PP), polyvinylidene fluoride (PVDF) and maleic anhydride-grafted polypropylene (MAPP), on smooth glass fibres and plates. The values of total surface energy of thermoplastics at high temperature (260 °C) are down to 57% of that measured at room temperature, which has a strong influence on the wetting prediction. Surface energies of both the polymer and the substrate were found not to be the only factor controlling the wetting behaviour of molten polymers and the level of adhesion with the substrate, but also some intrinsic characteristics of the polymer melt play a role. We also observed that the wetting behaviour of molten MAPP is affected by the maleic anhydride (MA) content, demonstrating dramatically different results to room temperature measurements, which is suspected to be due to the formation of covalent bonds of MA groups with the glass surface enhancing the interface strength beyond the shear strength of MAPP. ... Read more