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We have measured sorption isotherms for helium and nitrogen in wide temperature ranges and for a series of porous silicon samples, both native samples and samples with reduced pore mouth so that the pores have an ink-bottle shape. Combining volumetric measurements and sensitive optical techniques, we show that, at high temperature, homogeneous cavitation is the relevant evaporation mechanism for all samples. At low temperature, the evaporation is controlled by meniscus recession, the detailed mechanism being dependent on the pore length and on the mouth reduction. Native samples and samples with ink-bottle pores shorter than one micrometer behave as an array of independent pores. In contrast, samples with long ink-bottle pores exhibit long-range correlations between pores. In this latter case, evaporation takes place by a collective percolation process and not by heterogeneous cavitation as previously proposed. The variety of evaporation mechanisms points to porous silicon being an anisotropic three dimensional pore network rather than an array of straight independent pores.

The present paper investigates strain-induced sorption in mesoporous silicon. Contrarily to a previous report based on indirect evidence, we find that external mechanical strain or stress has no measurable impact on sorption isotherms, down to a relative accuracy of 10 −3 . This conclusion is in agreement with the analysis of the sorption-induced strain of porous silicon and holds for other stiff mesoporous materials such as porous silicas.

Metrics & MoreArticle RecommendationsT he purpose of this Addition and Correction is to correct the inclusion of an author name. The name "C. Nouŝ" (Camille Nouŝ) is fictitious and represents a consortium, rather than a person. This does not satisfy Langmuir's and ACS Publications' requirements for authorship according to the Ethical Guidelines to Publication of Chemical Research.

We have studied homogeneous cavitation in liquid nitrogen and normal liquid helium. We monitor the fluid content in a large number of independent mesopores with an ink-bottle shape, either when the fluid in the pores is quenched to a constant pressure or submitted to a pressure decreasing at a controlled rate. For both fluids, we show that, close enough to their critical point, the cavitation pressure threshold is in good agreement with the Classical Nucleation Theory (CNT). In contrast, at lower temperatures, deviations are observed, consistent with a reduction of the surface tension for bubbles smaller than two nanometers in radius. For nitrogen, we could accurately measure the nucleation rate as a function of the liquid pressure down to the triple point, where the critical bubble radius is about one nanometer. We find that CNT still holds, provided that the curvature dependence of the surface tension is taken into account. Furthermore, we evaluate the first- and second-order corrections in curvature, which are in reasonable agreement with recent calculations for a Lennard-Jones fluid.