At the beginning of an isothermal desorption process with the adsorbate argon, the nanopores of the porous glass sample remain virtually completely filled over a certain pressure range. A reduction of the external pressure p below the bulk vapour pressure of argon, p0, results, however, in the formation of concave menisci at the pore ends. The related decrease of the radius of curvature causes an increase of the negative Laplace pressure. This occurance is known to provoke a contraction of porous samples. Here we show that the Laplace pressure also influences the elastic properties of the filled porous sample. A decrease of the radius of curvature at the pore ends becomes noticeable in a decrease of the effective longitudinal modulus. The analysis of our ultrasonic measurements reveals that this decrease of the effective longitudinal modulus originates in a reduction of the longitudinal modulus of the adsorbate.

We have studied the phase transition of argon in completely filled mesopores. Our effective medium analysis of ultrasonic measurements clearly indicates a continuous phase transition of argon in completely filled pores over a broad temperature range of about 45 K. With decreasing temperature, the amount of frozen argon increases and below about 30 K all adsorbed argon (including the first few layers near the pore wall) is frozen with a shear modulus about equal to the bulk shear modulus. It is remarkable, that in a system showing such a pronounced confinement effect--a continuous phase transition over 45 K--the bulk properties are preserved. A comparison with temperature cycles with one and two adsorbed layers shows, that due to the presence of solid argon in the center of the pores the first few layers are already frozen at a higher temperature (30 K) compared to single layers (20 K). The transfer of our technique from the simple model system that we present in this Letter to other more complex adsorbates and different porous samples should help to enlighten the phase behavior under confinement in further studies.

We have measured sorption isotherms and determined the intrinsic longitudinal elastic modulus β(Ar,ads) of nanoconfined material via ultrasonic measurements combined with a special effective medium analysis. In the liquid regime the adsorbate only contributes to the measured effective properties when the pores are completely filled and the modulus is bulklike. At partial fillings its contribution is cancelled out by the high compressibility of the vapour phase. In contrast, at lower temperatures frozen argon as well as underlying liquid surface layers cause a linear increase of the effective longitudinal modulus upon filling. During sorption the contribution of the liquid surface layers near the pore wall β(Ar,surf) increases with the thickness of the solid layers reaching the bulk value β(Ar,liquid) only in the limit of complete pore filling. We interpret this effect as due to the gradual stiffening of the solid argon membrane. The measurements and their analysis show that longitudinal ultrasonic waves are well suited to the study of the elastic properties and liquid-solid phase transitions in porous systems. This method should also help to detect the influence of nanoconfinement on elastic properties in further research.

In this paper, we study the influence of temperature on the longitudinal modulus β Ar,ads and the density of liquid argon adsorbed in nanoporous Vycor glass. For this purpose, we have carried out systematic ultrasonic measurements for temperatures between boiling and freezing of the adsorbate. The study shows a continuous almost linear decrease of the longitudinal modulus of the pore condensate with increasing temperature. At all temperatures, the absolute values of the adsorbate's modulus are enhanced in comparison to bulk argon as a result of the adsorption stress. Nevertheless, the modulus's dependence on the temperature is similar to that for bulk argon. Furthermore, the temperature dependence of the adsorbate's density is similar to that of bulk argon. Summarizing, we have shown that for a given pore size the enhancement of the longitudinal modulus of the adsorbed liquid argon in comparison to liquid bulk argon does not noticeably depend on temperature. Consequently, nanoconfinement of a material can be used to achieve an enhancement of the longitudinal modulus; however, at least for a simple adsorbate like argon, a variation of temperature cannot be exploited to modify the strength of the enhancement.

No abstract