We have investigated the wetting and surface diffusion of mesoporous colloidal silica particles at the water surface and the adsorption of cationic cetyltrimethylammonium (CTA+) surfactant on these particles. Porous silica colloids diffuse at the surface of water and in the volume, interacting with cationic surfactants that can adsorb inside the pores of the particles. We observed that surfactant adsorption on mesoporous silica depends dramatically not only on the particle pore size but also on specific counterion effects. We measured striking differences both on a macroscopic property of the interface, i.e., surface tension, and also at a single particle level by evaluating the translational diffusion of partially wetted particles at the fluid interface. We varied the pore size from 2 to 7 nm and explored the effects of ions possessing different hydration number and kosmotropic/chaotropic character. At concentrations lower than the critical micellar concentration, we evidence that cationic surfactants adsorb on silica as surface micelles and surfactant adsorption inside the pores occurs only if the pore diameter is larger than the size of surface micelles. With a view to understand the surprising different adsorption behavior of CTA+OH– and CTA+Br– on porous silica particles, we investigated the effect of counterions on the surfactant adsorption on porous silica colloids by tuning the pH and the counterion properties.

Heliconal nematic twist bend (NTB) phases are usually not well oriented in planar commercial cells, even in thin (~1 µm) ones where a micron-sized periodic texture is usually observed [1,2,3] (see Fig.1-a). The origin of the stripe patterns is attributed to the rapid shrinking of the pseudo-layers below the N-NTB phase transition temperature, which yields an undulation instability. The observed periodicity is found to be twice the cell gap [1].We have explored the effect of the strength of the anchorings of the substrates on the resulting patterns. We used polymer aligning layers of tunable azimuthal and zenithal strengths to design liquid crystal cells with surface anchorings ranging from ultraweak to strong. We then have studied the patterns formed by the NTB phase of 1,7-bis-4-(4-cyanobiphenyl) heptane (CB7CB). We will show how the period of the stripes can be varied in a large range in cells of the same thickness but with different anchoring preparations. With adequate anchoring conditions (see Fig.1-b-c), an excellent and spontaneous planar alignment of the NTB phase of CB7CB can be obtained much below the phase transition temperature.
References:
[1] Panov V.P. et al, Phys. Rev. Lett., 2010, 105; 167801.
[2] Challa P. K. et al, Phys. Rev. E: Stat., Nonlinear, Soft Matter Phys., 2014, 89, 060501.
[3] Vaupotič N. et al., Chem. Phys. Chem., 2018, 19,2566.

L’existence d’une phase « Nematique twist Bend » (NTB) a été prédite par I.Dozov dès 2001 [1] mais n’a été observée expérimentalement qu’en 2010 [2]. Cette phase est assez originale car elle présente optiquement des défauts de type coniques focales sans réel ordre translationnel observable en diffusion des rayons X. Généralement cette phase est présente à des températures élevées (au-dessus de 100°C) dans les corps purs. L’ajout d’un nématogène [comme le 4-Cyano-4'-pentylbiphenyl (5CB)] à un composé NTB [tels que le 1,7-bis (4-cyanobiphényl-4-yl) heptane (CB7CB)] permet de diminuer fortement la plage d’existence de la phase NTB [3] tout en modifiant continûment les propriétés thermiques et diélectriques. Dans ce travail, nous avons exploré les modifications dues à l’ajout au CB7CB de smectogènes, et en particulier du 4′-octyl-4-biphénylcarbonitrile (8CB). Le diagramme de phase de ce dernier mélange binaire présente des caractéristiques surprenantes. Malgré leur ressemblance macroscopique, les phases SmA et NTB semblent ainsi incompatibles et restent séparées par une phase nématique s’étendant à très basse température (-20 ° C) pour une fraction CB7CB de ϕ_c≈20%. Nous avons par ailleurs caractérisé les propriétés optiques, thermiques, diélectriques et d’ancrage des phases N et NTB des mélanges. Les propriétés optiques sont très différentes de celles du CB7CB sur une large gamme de composition et de forts effets pré-transitionnels sont observables à l'approche de ϕ_c≈20%. Les propriétés d’ancrage (fig1) sont également significativement modifiées par l'ajout de 8CB au CB7CB ce qui facilite l'alignement homéotrope, très difficilement obtenu pour le CB7CB.

Despite the relevance to environmental, biological and industrial processes, the motion of a colloidal particle close to a fluid interface and the way it interacts with the water surface are still largely elusive and intriguing physical phenomena.We explored the system of individual colloidal particles close to an air-water interface by recording highly resolved 3D trajectories through a dual wave reflection interference setup (DW-RIM). Contrary to other established experimental techniques, DW-RIM allows accurate measurements of the absolute particle-interface distance and thus does not require any calibration or assumption to know the location of the interface. The particle-interface system shows two different potential energy landscapes resulting to two different equilibrium particle-interface distances. The larger one can be fairly explained by Van der Waals and electrostatic interactions combined with gravity. The shorter one highlights the existence of an unexpected additional attractive interaction. Surface heterogeneities as possible origin of such an interaction are considered and discussed.Concerning the friction the particle undergoes, the air-water interface peculiarly acts as a slip boundary for the particle motion parallel to the interface and as a no-slip boundary for the perpendicular motion. This experimental result is rationalized considering recent models based on surface incompressibility.

Heliconal nematic twist bend (NTB) phases are usually not well oriented in planar commercial cells, even in thin (~1 µm) ones where a micron-sized periodic texture is usually observed [1,2,3] (see Fig.1-a). The origin of the stripe patterns is attributed to the rapid shrinking of the pseudo-layers below the N-NTB phase transition temperature, which yields an undulation instability. The observed periodicity is found to be twice the cell gap [1].
We have explored the effect of the strength of the anchorings of the substrates on the resulting patterns. We used polymer aligning layers of tunable azimuthal and zenithal strengths to design liquid crystal cells with surface anchorings ranging from ultraweak to strong. We then have studied the patterns formed by the NTB phase of 1,7-bis-4-(4-cyanobiphenyl) heptane (CB7CB). We will show how the period of the stripes can be varied in a large range in cells of the same thickness but with different anchoring preparations. With adequate anchoring conditions (see Fig.1-b-c), an excellent and spontaneous planar alignment of the NTB phase of CB7CB can be obtained much below the phase transition temperature.
[1] Panov V.P. et al; Spontaneous Periodic Deformations in Nonchiral Planar-Aligned Bimesogenswith a Nematic-Nematic Transition and a Negative Elastic Constant; Phys. Rev. Lett. ; 105; 167801; 2010.
[2] Challa P. K. et al; Twist-bend nematic liquid crystals in high magnetic fields; Phys. Rev. E: Stat., Nonlinear, Soft Matter Phys.; 89; 060501; 2014.
[3] Vaupotič N. et al.; Polarization Gratings Spontaneously Formed from a Helical Twist‐Bend Nematic Phase; Chem. Phys. Chem.; 19; 2566; 2018.

Heliconal nematic twist bend (NTB) phases are frequently found at high temperatures. In the last years the search of stable room-temperatures NTB phases has led to the synthesis of new compounds [1] and to the design of multicomponent systems. Mixtures of NTB compounds with nematogens ,such as 4-Cyano-4'-pentylbiphenyl (5CB) dimeric liquid crystal 1,7-bis(4-cyanobiphenyl-4-yl) heptane (CB7CB) decrease strongly the temperature range of the NTB phase and tune the optical, thermal and dielectric properties of NTB [2]. In this work we have explored the physical properties of mixtures of CB7CB with several smectogens with a particular focus on 4′-octyl-4-biphenylcarbonitrile (8CB). The 8CB/CB7CB phase diagram reveals striking features compared to the 5CB/CB7CB one. Despite their macroscopic resemblance, SmA and NTB domains appear incompatible and remain separated by a nematic phase that extends to very low temperature (-20°C) at a CB7CB fraction of ϕ_c≈20%. We have characterized the optical, thermal, dielectric and anchoring properties of the N and NTB phases of the mixtures. Compared to the pure CB7CB system, the N phase shows unusual behavior over a large range of composition and reveals strong pre-transitional effects when approaching ϕ_c. We also found that, for specific aligning substrates, adding 8CB to CB7CB drastically changes the anchoring properties (fig1) facilitating homeotropic alignment.
[1] Yuan Wang, Quan Li; Room temperature heliconical twist-bend nematic liquid crystal; Cryst. Eng. Comm; 17; 2778-2782; 2015.
[2] Nina Trbojevic and Mamatha Nagaraj; Dielectric properties of liquid crystalline dimer mixtures exhibiting the nematic and twist-bend nematic phases; Phys. Rev. E ;96; 052703; 2017.

Hypothesis: Rotational Brownian diffusions of colloidal particles at a fluid interface play important roles in particle self-assembly and in surface microrheology. Recent experiments on translational Brownian motion of spherical particles at the air-water interface show a significant slowing down of the translational diffusion with respect to the hydrodynamic predictions (Boniello et al., 2015). For the rotational diffusions of partially wetted colloids, slowing down of the particle dynamics can be also expected.Experiments: Here, the rotational dynamics of Janus colloids at the air-water interface have been experimentally investigated using optical microscopy. Bright field and fluorescent microscopies have been used to measure the in-plane and out-of-plane particle rotational diffusions exploiting the Janus geometry of the colloids we fabricated.Findings: Our results show a severe slowing down of the rotational diffusion Dr,⊥ connected to the contact line motion and wetting-dewetting dynamics occurring on particle regions located at opposite liquid wedges. A slowing down of the particle rotational diffusion about an axis parallel to the interfacial normal Dr,|| was also observed. Contact line fluctuations due to partial wetting dynamics lead to a rotational line friction that we have modelled in order to describe our results.