Experiments have shown that near the boundary of a “nonsimple” fluid (such as nitrobenzene) on a solid substrate, there may exist an extended, so-called epitropic, phase with evidence of ordered arrangement of molecules (akin to that in a nematic liquid crystal). New data on the temperature dependence of the thickness of this phase in nitrobenzene on a metallic substrate are reported. These data (as well as earlier data for a nitrobenzene/quartz system) are interpreted in terms of a modified theoretical model of the epitropic phase as a pile of oligomers adhering to the substrate by means of adsorption forces. Ordering is essentially governed by lateral interactions in an ensemble of adsorbed oligomers. The possibility of boundary phase existence as a superheated crystal (in particular, nitrobenzene) stabilized by adsorption forces from the side of the substrate is discussed.
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However, a number of examples are known today when direct crystal–melt contact is avoided (see, e.g., , where it was reported that a silver single crystal encapsulated in an impermeable gold sheath was superheated by 25 K above Tm; see also ). It should be noted that the very possibility of latching the metastable state of a superheated crystal can be explained by the slow kinetics of transition to a stable fluid phase (for example, when its viscosity is large ).
Depending on the SiO2 surface modification, the concentration of silanol (OH-containing) groups equals 8–16 μmol/m2 , which corresponds to na = (4.8–9.6) × 1018 m–2. As to Wa, it is roughly equal to 0.1 eV, which is characteristic of the energy of physical adsorption for molecules on a real substrate .
These measurements were conducted with the participation of A.F. Butenko and A.Yu. Popovskii.
As characteristic length l0, we took the size of a benzene ring in a nitrobenzene molecule
Using the method of computer simulation, it was found that the distance between neighboring silanol groups is 0.378–0.547 nm, which corresponds to na ≈ (3.3–7.0) × 1018 m–2.
Optical anisotropy measurements were taken with the participation of E.A. Shatagina, A.A. Shatagina, and I.A. Shatagin, and the dichroism was measured by A.Yu. Popovskii and A.F. Butenko.
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The authors thank S.N. Savin for assistance.
The authors claim that there is no conflict of interest.
Translated by V. Isaakyan
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Altoiz, B.A., Bondarev, V.N. Quasi-Macroscopic Boundary Structures in “Nonsimple” Fluids: Experiment and Model. Tech. Phys. 65, 696–702 (2020). https://doi.org/10.1134/S1063784220050023