Free Energy Cost of Interdigitation of Lamellar Bilayers of Fatty Alcohols with Cationic Surfactants from Molecular Dynamics Simulations.

Cationic surfactant mixed with fatty alcohol as cosurfactant in excess water can form stable emulsions, known as "lamellar gel networks," that contain extended and interconnected networks of swollen bilayers, including ones with in-plane liquidlike disorder (Lα phase) and solidlike order (Lß phase). To study their structure and thermodynamics, molecular dynamics (MD) simulations with lateral pressure and temperature scans along reversible pathways were used to drive reversible phase changes, including formation at negative lateral pressure of the LßI phase with interdigitated tails of opposing leaflets. Thermodynamic integration, with extrapolations to infinitely slow scans, yielded a free energy difference between the interdigitated LßI and non-interdigitated Lß phases of 2.4 ± 0.5 kJ/mol, which is consistent with the spontaneous formation of the Lß phase under atmospheric pressure in simulation. Thermodynamic cycles involving temperature and lateral pressure for which the free energy difference is identically zero were constructed as negative controls to verify the method. Using lateral pressure, including negative lateral pressure, helps avoid kinetic bottlenecks that occur when temperature alone is used as the control variable. The method, using negative lateral pressure, should be widely applicable to other bilayers to identify molecular properties that control interdigitation and other bilayer properties.

Hydrophobic Inorganic Oxide Pigments via Polymethylhydrosiloxane Grafting: Dispersion in Aqueous Solution at Extraordinarily High Solids Concentrations.

Building on the recent demonstration of aqueous-dispersible hydrophobic pigments that retain their surface hydrophobicity even after drying, we demonstrate the synthesis of surface-modified Ti-Pure R-706 (denoted R706) titanium dioxide-based pigments, consisting of a thin (one to three monolayers) grafted polymethylhydrosiloxane (PMHS) coating, which (i) are hydrophobic in the dry state according to capillary rise and dynamic vapor sorption measurements and (ii) form stable aqueous dispersions at solid contents exceeding 75 wt % (43 vol %), without added dispersant, displaying similar rheology to R706 native oxide pigments at 70 wt % (37 vol %) consisting of an optimal amount of conventional polyanionic dispersant (0.3 wt % on pigment basis). The surface-modified pigments have been characterized via 29Si and 13C cross-polarization/magic angle spinning solid-state NMR spectroscopy; infrared spectroscopy; thermogravimetric and elemental analyses; and ζ potential measurements. On the basis of these data, the stability of the surface-modified PMHS-R706 aqueous dispersions is attributed to steric effects, as a result of grafted PMHS strands on the R706 surface, and depends on the chaotropic nature of the base used during PMHS condensation to the pigment/polysiloxane interface. The lack of water wettability of the surface-modified oxide particles in their dry state translates to improved water-barrier properties in coatings produced with these surface-modified pigment particles. The synthetic approach appears general as demonstrated by its application to various inorganic-oxide pigment particles.