Langmuir, Vol.17, No.18, 5476-5485, 2001
Shear of molecularly confined liquid crystals. 2. Stress anisotropy across a model nematogen compressed between sliding solid surfaces
We have used a new design of the mica surface force balance (SFB), with extreme sensitivity in measuring normal and particularly shear or frictional forces between two surfaces sliding past each other, to measure the forces between two mica surfaces across a confined 4-cyano-4'-hexabiphenyl nematogen (6CB). In an earlier study (Langmuir 1997, 13, 4466, paper 1 of the series) we investigated the normal force-distance profiles and the orientation of the confined liquid crystal (LC). Here we extend this to study the shear forces F-s between the sliding mica surfaces across the 6CB nematogen as a function of orientation of the confined LC, the applied normal load F-n, the separation D of the mica surfaces, the shear velocity nu (s), and the relative shear direction of the confining surfaces (which may be varied using the new SFB design). Our results, where the shear forces are measured down to levels that are some orders of magnitude more sensitive than in earlier studies, show that the highly confined nematogen (D in the range from 16 to ca. 100 Angstrom) behaves under shear in a quasi-solidlike fashion for all three orientations studied: planar, planar twisted, and homeotropic. There is a linear relation between F-s and F-n for each of the three orientations, with the effective friction coefficient (dF(s)/dF(n)) largest for the homeotropic orientation and lowest for the planar twisted one. Intriguingly, for the planar orientation a clear increase in the friction could be observed when the initial shear direction was changed by 90 degrees. We attribute this to the effect of the initial shear in orienting the confined nematogen layer in the initial direction, so that subsequent sliding motion at right angles to this encounters greater resistance. We also find that within a range of some 40-fold in nu (s), there was little change in the shear force, in line with what is generally observed for solid-solid friction, and consistent with the fact that little relaxation in F-s is observed over macroscopic times on applying a step strain to the confined LC.