Vincent Le Houérou

Bridged polysilsesquioxane films via photoinduced sol–gel chemistry

The synthesis and characterization of bridged polysilsesquioxane films was performed via a photoacid-catalyzed sol–gel method using a series of three precursors with different organic moiety structures.

Experimental evidence of ultrathin polymer film stratification by AFM force spectroscopy

By performing Atomic Force Microscopy measurements of pull-off force as a function of the temperature, we were able to probe the dynamic of supported thin polystyrene (PS) films. Thermal transitions induce modifications in the surface energy, roughness and surface modulus that are clearly detected by AFM and related to PS chain relaxation mechanisms. We demonstrated the existence of three transition temperatures that can be associated to the relaxation of polymer chains located at different depth regions within the polymer film. Independently of the film thickness, we have confirmed the presence of a region of high mobility for the polymer chains at the free interface. The thickness of this region is estimated to be above 7nm. The detection of a transition only present for film thicker than the gyration radius Rg is linked to the dynamics of polymer chains in a bulk conformation (i.e. not in contact with the free interface). We claim here that our results demonstrate, in agreement with other techniques, the stratification of thin polymer film depth profile in terms of relaxation behavior.Graphical abstract

Model Experimental Study of Scale Invariant Wetting Behaviors in Cassie−Baxter and Wenzel Regimes

In this work, we discuss quantitatively two basic relations describing the wetting behavior of microtopographically patterned substrates. Each of them contains scale invariant topographical parameters that can be easily expressed onto substrates decorated with specifically designed micropillars. The first relation discussed in this paper describes the contact angle hysteresis of water droplets in the Cassie-Baxter regime. It is shown that the energy at the origin of the hysteresis, that has to be overcome for moving the triple line, can be invariantly expressed for hexagonal pillars by varying the pillars width and interpillar distance. Identical contact angle hystereses are thus measured on substrates expressing this scale invariance for pillar widths and interpillar distances ranging from 4 to 128 μm. The second relation we discuss concerns the faceting of droplets spreading on microtopographically patterned substrates. It is shown in this case that the condition for pinning of the triple line can be fulfilled by simultaneously varying the height of the pillars and the interpillar distance, leading to faceted droplets of similar morphologies. The invariance of these two wetting phenomena resulting from the simultaneous and homothetic variation of topographical parameters is demonstrated for a wide range of pattern dimensions. Our results show that either of those two wetting behaviors can be simply achieved by the proper choice of a dimensionless ratio of topographical length scales.

Robust Alginate-Catechol@Polydopamine Free-Standing Membranes Obtained from the Water/Air Interface

The formation of polydopamine composite membranes at the water/air interface using different chemical strategies is reported. The use of either small molecules (urea, pyrocatechol) or polymers paves the way to understand which kind of compounds can be used for the formation of PDA-composite free-standing membranes produced at the water/air interface. On the basis of these screening results, we have found that alginate grafted with catechol groups allows the formation of robust free-standing films with asymmetric composition, stimuli-responsiveness, and self-healing properties. The stickiness of these membranes depends on the relative humidity, and its adhesion behavior on PDMS was characterized using the JKR method. Thus, alginate-catechol polydopamine films appear as a new class of PDA composites, mechanically robust through covalent cross-linking and based on fully biocompatible constituting partners. These results open the door to potential applications in the biomedical field.

Tensiometric Characterization of Superhydrophobic Surfaces As Compared to the Sessile and Bouncing Drop Methods

We have considered in this work the Wilhelmy plate tensiometer to characterize the wetting properties of two model surface textures: (i) a series of three superhydrophobic micropillared surfaces and (ii) a series of two highly water-repellent surfaces microtextured with a femtosecond laser. The wetting forces obtained on these surfaces with the Wilhelmy plate technique were compared to the contact angles of water droplets measured with the sessile drop technique and to the bouncing behavior of water droplets recorded at a high frame rate. We showed that it is possible with this technique to directly measure triple-line anchoring forces that are not accessible with the commonly used sessile drop technique. In addition, we have demonstrated on the basis of the bouncing drop experiments wetting transitions induced by the specific test conditions associated with the Wilhelmy plate tensiometer for the two series of textured surfaces. Finally, the tensiometer technique is proposed as an alternative test for characterizing the wetting properties of highly liquid-repellent surface, especially under immersion conditions.

Straightforward and precise approach to replicate complex hierarchical structures from plant surfaces onto soft matter polymer

The surfaces of plant leaves are rarely smooth and often possess a species-specific micro- and/or nano-structuring. These structures usually influence the surface functionality of the leaves such as wettability, optical properties, friction and adhesion in insect–plant interactions. This work presents a simple, convenient, inexpensive and precise two-step micro-replication technique to transfer surface microstructures of plant leaves onto highly transparent soft polymer material. Leaves of three different plants with variable size (0.5–100 µm), shape and complexity (hierarchical levels) of their surface microstructures were selected as model bio-templates. A thermoset epoxy resin was used at ambient conditions to produce negative moulds directly from fresh plant leaves. An alkaline chemical treatment was established to remove the entirety of the leaf material from the cured negative epoxy mould when necessary, i.e. for highly complex hierarchical structures. Obtained moulds were filled up afterwards with low viscosity silicone elastomer (PDMS) to obtain positive surface replicas. Comparative scanning electron microscopy investigations (original plant leaves and replicated polymeric surfaces) reveal the high precision and versatility of this replication technique. This technique has promising future application for the development of bioinspired functional surfaces. Additionally, the fabricated polymer replicas provide a model to systematically investigate the structural key points of surface functionalities.