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Schmidt, J. W.

Publications and source records attributed to Schmidt, J. W..

Universal amplitude ratios and the interfacial tension near consolute points of binary liquid mixtures

The interfacial tension of the binary liquid mixtures triethylamine/heavy water, triethylamine/water, and cyclohexane/methanol near their consolute temperatures is determined experimentally by measuring the densities of the phases and the capillary lengths. The results are presented in tables and graphs and compared with published data obtained by other methods and with theoretical predictions. The findings are shown to be in good agreement with previous experiments, confirming the discrepancy between temperature-independent universal amplitude ratios calculated from such data and those predicted by renormalization-group calculations or Monte Carlo simulations of Ising models.

Moldover, M. R.↗

A search for the prewetting line

This paper describes efforts to locate the prewetting line in a binary liquid system (isopropanol-perfluoromethylcyclohexane) at the vapor-liquid interface. Tight upper bounds were placed on the temperature separation (0.2 K) between the prewetting line and the line of bulk liquid phase separation. The prewetting line in systems at equilibrium was not detected. Experimental signatures indicative of the prewetting line occurred only in nonequilibrium situations. Several theories predict that the adsorption of one of the components (the fluorocarbon, in this case) at the liquid-vapor interface should increase abruptly, at a temperature sightly above the temperature at which the mixture separates into two liquid phases. A regular solution calculation indicates that this prewetting line should have been easily detectable with the instruments used in this experiment. Significant features of the experiment are: (1) low-gradient thermostatting, (2) in situ stirring, (3) precision ellipsometry from the vapor-liquid interface, (4) high resolution differential index of refraction measurements using a novel cell design, and (5) computer control.

Schmidt, J. W.↗

The liquid-vapor interface of a binary liquid mixture near the consolute point

The present investigation is concerned with measurements of the reflectance of polarized light by the liquid-vapor interface above liquid mixtures of a fluorocarbon and an alcohol in the vicinity of the consolute point of the liquid mixture. The denser fluorocarbon is preferentially adsorbed at the interface. The denser fluorocarbon is preferentially adsorbed at the interface. The data are consistent with a simple model of the dielectric constant vs height profile in the interface region. Liquid mixtures of isopropanol (i-C3H7OH) and perfluoromethylcyclohexane (C7F14) near their consolute point (Tc = 363 K) are utilized in the conducted experiments. The primary quantity measured is the ellipticity as a function of temperature and liquid composition. Attention is given to details regarding the experimental techniques, model dielectric constant profiles, and the calculation of the ellipticity.

Schmidt, J. W.↗

Experimental and Theoretical Studies of Wetting and Multilayer Adsorption

The recent work with partially miscible binary liquid mixtures has established that the structure of the liquid-vapor interface can undergo a first-order phase transition from incomplete to complete wetting of the vapor as the temperature is raised. A discontinuity in the change of interfacial tension as a function of temperature at the phase transition has been predicted to occur in many systems and to play an important role in the growth of uniform composites from alloy melts at monotectic points. These measurements are the first to establish the order of the transition. Studies of capillary rise in SF6 in a unique interferometer have led to the first measurements of the thickness of wetting layers (or equivalently, multilayer adsorbed films) on a solid surface near a liquid-vapor critical point. Instabilities in wetting layers were observed. A theory for the instabilities is being developed and will be checked by both static and dynamic optical experiments. The effect of gravity on the apparent thickness of interfaces (as measured by ellipsometry) is under study.

Moldover, M. R.↗

Wetting layers and dispersion forces for a fluid in contact with a vertical wall

Ellipsometric measurements of the thickness of the wetting layer of sulfur hexafluoride that forms on a fused-silica surface partially immersed in the liquid are presented. The components of the experiment included a He-Ne laser (0.6328 micron), polarizer, and quarter-wave plate with 45-deg azimuth. An optical-grade fused-silica prism was polished to wavelength/20, and strain-induced birefringence was accounted for. It was found that the layer thickness decreases from 40 to 20 nm with a height increase from 0.7 to 3 mm above the liquid-vapor interface. The thickness is independent of the temperature between 10 and 0.1 K below the critical temperature (319 K). The results are compared in detail to the theory of Dzyaloshinskii et al. (1961), and are noted to coincide closely.

Kayser, R. F.↗

Wetting, multilayer adsorption, and interface phase transitions

When two fluid phases coexist near their mutual critical point, one fluid phase forms a layer which intrudes between the other fluid phase and any third phase that happens to be present. As the two fluid phases are taken away from their critical point, a phase transition often occurs such that the intruding layer vanishes. Recent evidence is presented that the transition from the complete wetting (intruding layer) configuration to the incomplete wetting (three-phase contact) configuration is a first-order phase transition. The thickness of the intruding layers has been measured for diverse systems. These data are not fully understood. The intruding layers are extreme examples of multilayer adsorption. Certain theories predict that a 'prewetting' transition from high adsorption to low adsorption is associated with the transition from complete wetting to incomplete wetting. Present search for this transition is inconclusive.

Moldover, M. R.↗

First-order wetting transition at a liquid-vapor interface

Evidence from reflectance and contact angle measurements is presented that three-phase mixtures of i-C3H7OH-C7F14 exhibit a first-order wetting phase transition at the liquid-vapor interface at 38 C. Equilibration phenomena support this interpretation. Ellipsometry was used to measure the apparent thickness of the intruding layer in the three-phase mixture. At temperatures slightly above the wetting temperature T(w), the intruding layer's thickness is several hundred angstroms and its variation with temperature is extremely weak. Below T(w), three-phase contact can occur between the vapor and both the upper and lower liquid phases; one of the angles which characterizes this contact has a very simple temperature dependence. The thickness of the intruding layer, monitored as the solutions approached equilibrium, is found to depend quite weakly on the height spanned by the upper liquid phase in the vicinity of a first-order wetting transition.

Schmidt, J. W.↗