Adsorption on Nanopores of Different Cross Sections Made by Electron Beam Nanolithography.

Adsorption on nanoporous matrices is characterized by a pronounced hysteresis loop in the adsorption isotherm, when the substrate is loaded and unloaded with adsorbate, the origin of which is a matter of immense debate in the literature. In this work, we report a study of argon adsorption at 85 K on nonconnecting nanopores with one end closed to the surrounding where the effects of different pore cross sections fabricated by electron beam lithography (EBL) are investigated. A polymethylmethacrylate (PMMA) resist is deposited on the electrodes of a sensitive quartz crystal microbalance without degradation of the resonance quality factor or the long-term and short-term stabilities of the device even at cryogenic temperatures. Four different pores' cross sections: circular, square, rectangular, and triangular, are produced from EBL, and the isotherms for these pore shapes exhibit pronounced hysteresis loops whose adsorption and desorption branches are nearly vertical and have almost the same slopes. No difference is observed in the hysteresis loops of the isotherms for the pores with triangular and square cross sections, whereas the hysteresis loop for the pore with circular cross sections is much narrower, suggesting that they are more regular than the other pores. All of these observations suggest that the hysteresis behavior resulted mainly from microscopic geometric irregularities present in these porous matrices.

Adsorption on ordered and disordered duplex layers of porous anodic alumina.

We have carried out systematic experiments and numerical simulations of the adsorption on porous anodic aluminum oxide (AAO) duplex layers presenting either an ordered or a disordered interconnecting interface between the large (cavity) and small (constriction) sections of the structured pores. Selective blocking of the pore openings resulted in three different pore topologies: open structured pores, funnel pores, and ink-bottle pores. In the case of the structured pores having an ordered interface, the adsorption isotherms present a rich phenomenology characterized by the presence of two steps in the condensation branch and the opening of one (two) hysteresis loops during evaporation for the ink-bottle (open and funnel) pores. The isotherms can be obtained by summing the isotherms measured on uniform pores having the dimensions of the constrictions or of the cavities. The numerical analysis of the three different pore topologies indicates that the shape of the junction between the two pore sections is only important for the adsorption branch. In particular, a conic junction which resembles that of the AAO pores represents the experimental isotherms for the open and funnel pores better, but the shape of the junction in the ink bottle pores does not matter. The isotherms for the duplex layers with a disordered interface display the same general features found for the ordered duplex layers. In both cases, the adsorption branches coincide and have two steps which are shifted to lower relative pressures compared to those for the ordered duplex. Furthermore, the desorption branches comprise hysteresis loops much wider than those of the ordered duplex layers. Overall, this study highlights the important role played by morphologies where there are interconnections between large and small pores.

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 on alumina nanopores with conical shape.

Adsorption on porous solids depends on the morphology of the pores, the cylindrical one being the most studied in the literature. In this work, we present the first experimental investigation of adsorption and evaporation on conical nanopores produced by anodization of aluminium oxide. The pores are about 50 µm long, with the wide ends having a diameter of ∼79 nm and the narrow ones of ∼30 nm. Three different pores configurations are considered: open at both ends, open only at the narrow end and open only at the wide end. Despite the very small value of the conical angle α, estimated to be ∼0.06°, just barely above α = 0° corresponding to a cylindrical pore, the adsorption isotherms look strikingly different from those measured on cylindrical pores of similar size. First of all, the hysteresis loops of the conical pores with two open ends and with open wide ends practically coincide. Furthermore, they are narrower and the adsorption and evaporation branches are broader than those of the cylindrical pores with similar size. Finally, conical pores with open narrow ends exhibit a large hysteresis indicative of pore blocking. To unravel the mechanisms underlying adsorption and evaporation in such conical pores, we also report complementary results obtained using on-lattice grand canonical Monte Carlo simulations.

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.

Adsorption in alumina pores open at one and at both ends.

We have studied adsorption in regular, self-ordered alumina pores open at both ends or only at one end. The straight, non-connected pores have diameters ranging from 22 to 83 nm, with a relative dispersion below 1% in the pore size. Adsorption isotherms measured in open pores with a torsional microbalance show pronounced hysteresis loops characterized by nearly vertical and parallel adsorption and desorption branches. Blocking one end of the pores with glue has a strong influence on adsorption, as expected from classical macroscopic arguments. However, the experimental measurements show an unexpectedly rich phenomenology dependent on the pore size. For large pores (Dp ≥ 67 nm), the isotherms for closed end pores present much narrower hysteresis loops whose adsorption and desorption boundaries envelop the desorption branches of the isotherms for the corresponding open pores of the same size. The loop for small closed end pores (Dp = 22 nm) is slightly wider than that for open pores while the adsorption branches coincide. For large pores, in contrast, the desorption branches of pores with the same Dp overlap regardless of the pore opening. These observations are in agreement with our grand canonical Monte Carlo (GCMC) simulations for a cylindrical pore model with constrictions, suggesting that the alumina pores could be modeled using a constricted pore model whose adsorption isotherm depends on the ratio of the constriction size to the pore size (Dc/Dp).

Thermolubricity of gas monolayers on graphene.

Nanofriction of Xe, Kr and N2 monolayers deposited on graphene was explored with a quartz crystal microbalance (QCM) at temperatures between 25 and 50 K. Graphene was grown by chemical vapour deposition and transferred to the QCM electrodes with a polymer stamp. It was found to strongly adhere to the gold electrodes at temperatures as low as 5 K and at frequencies up to 5 MHz. At low temperatures, the Xe monolayers are fully pinned to the graphene surface. Above 30 K, the Xe film slides and the depinning onset coverage beyond which the film starts sliding decreases with temperature. Similar measurements repeated on bare gold show an enhanced slippage of the Xe films and a decrease of the depinning temperature below 25 K. Nanofriction measurements of Kr and N2 confirm this scenario. This thermolubric behaviour is explained in terms of a recent theory of the size dependence of static friction between adsorbed islands and crystalline substrates.

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.

The order of condensation in capillary grooves.

We consider capillary condensation in a deep groove of width L. The transition occurs at a pressure p(co)(L) described, for large widths, by the Kelvin equation p(sat) - p(co)(L) = 2σ cosθ/L, where θ is the contact angle at the side walls and σ is the surface tension. The order of the transition is determined by the contact angle of the capped end θcap; it is continuous if the liquid completely wets the cap, and first-order otherwise. When the transition is first-order, corner menisci at the bottom of the capillary lead to a pronounced metastability, determined by a complementary Kelvin equation Δp(L) = 2σ sinθcap/L. On approaching the wetting temperature of the capillary cap, the corner menisci merge and a single meniscus unbinds from the bottom of the groove. Finite-size scaling shifts, crossover behaviour and critical singularities are determined at mean-field level and beyond. Numerical and experimental results showing the continuous nature of condensation for θcap = 0 and the influence of corner menisci on adsorption isotherms are presented.

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.

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.