Klaus Schappert

Influence of the Laplace pressure on the elasticity of argon in nanopores

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.

Unexpected sorption-induced deformation of nanoporous glass: evidence for spatial rearrangement of adsorbed argon.

Sorption of substances in pores generally results in a deformation of the porous matrix. The clarification of this effect is of particular importance for the recovery of methane and the geological storage of CO2. As a model system, we study the macroscopic deformation of nanoporous Vycor glass during the sorption of argon using capacitative measurements of the length change of the sample. Upon desorption we observe an unpredicted sharp contraction and re-expansion peak, which contains information on the draining mechanism of the porous sample. We have modified the theoretical model by Gor and Neimark1 to predict the sorption-induced deformation of (partly) filled porous samples. In this analysis, the contraction is attributed to a metastable or nonequilibrium configuration where a thin surface layer on the pore walls coexists with capillary bridges. Alternatively, pore blocking and cavitation during the draining of the polydisperse pore network can be at the origin of the deformation peak. The results are a substantial step toward a correlation between the spatial configuration of adsorbate, its interaction with the host material, and the resulting deformation.

Elastic properties of liquid and solid argon in nanopores

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.

Elasticity and phase behaviour of n-heptane and n-nonane in nanopores

Here we present an ultrasonic study on the elasticity of normal alkanes (n-heptane and n-nonane) in the nanopores of porous Vycor glass (average pore radius ). Above the melting temperature we have found a non-zero shear modulus for both n-heptane and n-nonane, which is also typical for the rotator phases of bulk alkanes at temperatures below the melting temperature. This points to the formation of a special molecular order of the adsorbed alkanes. Furthermore, the alkanes undergo a continuous stiffening over a broad temperature range (of for heptane or for nonane). The results clearly indicate that nanoconfinement induces an extremely broad continuous transition of heptane and nonane into a crystalline low-temperature phase.

Correlation between the Sorption-Induced Deformation of Nanoporous Glass and the Continuous Freezing of Adsorbed Argon

In this article we study the dependence of the sorption-induced deformation of nanoporous glass on the liquid-solid phase transition of adsorbed argon. During cooling we observe a continuous reduction of the expansion of the porous glass matrix caused by the adsorbate. The contraction is attended by a likewise continuous change of the adsorbed argons phase state from liquid to solid. This simultaneous behavior evidences that the liquid-solid phase transition leads to a reduction of the pressure the adsorbate exerts on the pore walls. Furthermore, the study shows that small temperature changes can temporarily cause strong deformations of the porous material that decay in long time intervals of up to 1 week. We expect that our observations for the model system of argon and porous glass can be generalized to other systems. Consequently, this study will have implications when considering porous materials for applications, e.g., as a medium for storage.

Experimental method for the determination of adsorption-induced changes of pressure and surface stress in nanopores

The change of surface stress is an important quantity characterising the behaviour of nanoporous systems, however, it is difficult to assess experimentally. In this letter we develop and demonstrate an experimental method for the determination of adsorption-induced changes of the surface stress in nanoporous materials. With the aid of ultrasonic measurements we determine the dependence of the adsorbates longitudinal modulus [Formula: see text] on the adsorption-induced normal pressure, [Formula: see text], which is exerted by the adsorbate on the porous matrix. From this dependence we deduce the normal pressure at saturation, [Formula: see text], and thereby changes of the surface stress [Formula: see text] at the interface between the solid matrix and the liquid adsorbate. For the model system of argon in nanoporous glass (pore radius [Formula: see text] nm) the ultrasonic method reveals a value for [Formula: see text] that is in very good agreement with the theoretical value known for the argon-silica interface. The disclosure of this experimental method and its application on other systems will enable a better understanding of the behaviour of adsorbates in nanoporous materials.