L. Bruschi

Capillary Condensation and Evaporation in Alumina Nanopores with Controlled Modulations

Capillary condensation in nanoporous anodic aluminum oxide presenting not interconnected pores with controlled modulations is studied using adsorption experiments and molecular simulations. Both the experimental and simulation data show that capillary condensation and evaporation are driven by the smallest size of the nanopore (constriction). The adsorption isotherms for the open and closed pores are almost identical if constrictions are added to the system. The latter result implies that the type of pore ending does not matter in modulated pores. Thus, the presence of hysteresis loops observed in adsorption isotherms measured in straight nanopores with closed bottom ends can be explained in terms of geometrical inhomogeneities along the pore axis. More generally, these results provide a general picture of capillary condensation and evaporation in constricted or modulated pores that can be used for the interpretation of adsorption in disordered porous materials.

Adsorption hysteresis in self-ordered nanoporous alumina.

We performed systematic adsorption studies using self-ordered nanoporous anodic aluminum oxide (AAO) in an extended range of mean pore diameters and with different pore topologies. These matrices were characterized by straight cylindrical pores having a narrow pore size distribution and no interconnections. Pronounced hysteresis loops between adsorption and desorption cycles were observed even in the case of pores closed at one end. These results are in contrast with macroscopic theoretical models and detailed numerical simulations of the adsorption in a single pore. Extensive measurements involving adsorption isotherms, reversal curves, and subloops carried out in closed-bottom pores suggest that the pores do not desorb independently from one another.

The behavior of the4He viscosity near the superfluid transition

Measurements of the shear viscosity at saturated vapor pressure through the lambda transition indicate a singular behavior of the form |1 − (η/ηλ)|=Aεx, (where ε=|1−(T/Tλ)|, with equal values for the critical exponent on both sides of the transition.

Wetting on a geometrically structured substrate

We have measured the growth of liquid films of Ar and Kr adsorbed on a geometrically structured substrate obtained by machining on a lathe a thin Al disk with a sharp cutting tool. Near liquid–vapor bulk coexistence, the film mass is found to diverge as a power law of the chemical potential difference from saturation with an exponent x=−1.93±0.10, in very good agreement with recent scaling analysis results.

Inexpensive but accurate driving circuits for quartz crystal microbalances

The quartz crystal microbalance (QCM) is a common technique which finds a wide variety of applications in many different areas like adsorption, catalysis, analytical chemistry, biochemistry, etc., and more generally as a sensor in the investigation of viscoelastic films. In this article we describe some driving circuits of the quartz which we have realized and tested in our laboratory. These can be assembled with standard components which can be easily found. Their performance, in some cases, is as good as that of the much more expensive frequency modulation technique employed in very precise QCM measurements and which requires high-quality commercial radiofrequency generators and amplifiers.

WETTING OF ARGON ON CO2

We have studied the wetting transition of Ar adsorbed on solid CO2 by means of high-precision adsorption isotherms measured with a quartz microbalance. We observe triple-point wetting. At variance with many theoretical studies based on a model adsorption potential, which predict for this system a genuine prewetting transition around 100K we find that a detailed density-functional calculation employing a more realistic adsorption potential leads to triple-point wetting of Ar on CO2, in good agreement with the experiment.

Measurements of 4He viscosity near the superfluid transition

The 4He viscosity has been measured with a vibrating wire viscometer on the superfluid side of the λ transition. The results indicate that η should be singular at Tλ, in agreement with the suggestion advanced recently by G. Ahlers.

Frictional transition from superlubric islands to pinned monolayers

The inertial sliding of physisorbed submonolayer islands on crystal surfaces contains unexpected information on the exceptionally smooth sliding state associated with incommensurate superlubricity and on the mechanisms of its disappearance. Here, in a joint quartz crystal microbalance and molecular dynamics simulation case study of Xe on Cu(111), we show how superlubricity emerges in the large size limit of naturally incommensurate Xe islands. As coverage approaches a full monolayer, theory also predicts an abrupt adhesion-driven two-dimensional density compression on the order of several per cent, implying a hysteretic jump from superlubric free islands to a pressurized commensurate immobile monolayer. This scenario is fully supported by the quartz crystal microbalance data, which show remarkably large slip times with increasing submonolayer coverage, signalling superlubricity, followed by a dramatic drop to zero for the dense commensurate monolayer. Careful analysis of this variety of island sliding phenomena will be essential in future applications of friction at crystal/adsorbate interfaces.

Complete wetting of curved microscopic channels

We have measured the adsorption of argon films on arrays of microscopic nonlinear cusps and of semicircular channels. In the former case, we observe a distinct crossover from a planarlike to a geometry dependent growth behavior near liquid-vapor bulk coexistence, characterized by a growth exponent chi equal to -0.96+/-0.04 in very good agreement with the predictions of a recent scaling theory [C. Rascon and A. O. Parry, J. Chem. Phys. 112, 5175 (2000)]. The crossover location is also consistent with theory. Instead, on the concave channels we find a much steeper growth near saturation that may signal the formation of two menisci at both sides of the channel bottom.

Continuous adsorption in highly ordered porous matrices made by nanolithography

The exposed surface area of porous materials is usually determined by measuring the mass of adsorbed gas as a function of vapour pressure. Here we report a comprehensive study of adsorption in systems with closed bottom, not interconnected pores exhibiting different degrees of disorder, produced with methods encompassing nanolithography and dry and wet etching. Detailed adsorption studies of these matrices show hysteresis loops, as found always in pores having sizes of tens to hundreds of nanometres. The observed variations in the loop shape are associated with changes in the pore morphology. In regular pores formed by vertical and smooth walls, continuous adsorption is found for the first time in agreement with thermodynamic considerations valid for ideal pores. This suggests that irregularities in the walls and pore openings are the key factors behind the hysteresis phenomenon. Interestingly, pores having rough walls but a pyramidal shape also do not show any hysteresis.