Adsorption in non interconnected pores open at one or at both ends: A reconsideration of the origin of the hysteresis phenomenon

We report on an experimental study of adsorption isotherme of nitrogen onto porous silicon with non interconnected pores open at one or at both ends in order to check for the first time the old (1938) but always current idea based on Cohan's description which suggests that the adsorption of gaz should occur reversibly in the first case and irreversibly in the second one. Hysteresis loops, the shape of which is usually associated to interconnections in porous media, are observed whether the pores are open at one or at both ends in contradiction with Cohan's model.Comment: 5 pages, 4 EPS figure

Oxygen Absorption in Free-Standing Porous Silicon: A Structural, Optical and Kinetic Analysis

Porous silicon (PSi) is a nanostructured material possessing a huge surface area per unit volume. In consequence, the adsorption and diffusion of oxygen in PSi are particularly important phenomena and frequently cause significant changes in its properties. In this paper, we study the thermal oxidation of p+-type free-standing PSi fabricated by anodic electrochemical etching. These free-standing samples were characterized by nitrogen adsorption, thermogravimetry, atomic force microscopy and powder X-ray diffraction. The results show a structural phase transition from crystalline silicon to a combination of cristobalite and quartz, passing through amorphous silicon and amorphous silicon-oxide structures, when the thermal oxidation temperature increases from 400 to 900 °C. Moreover, we observe some evidence of a sinterization at 400 °C and an optimal oxygen-absorption temperature about 700 °C. Finally, the UV/Visible spectrophotometry reveals a red and a blue shift of the optical transmittance spectra for samples with oxidation temperatures lower and higher than 700 °C, respectively

Adsorption-Induced Deformation in Nanopores: Unexpected Results Obtained by Molecular Simulations

International audienceThe adsorption of a fluid in a nanoporous material induces deformations of the solid. The saturating regime, where the solid is filled with liquid, generally exhibits a linear relationship between the liquid pressure and the solid strain. This provides an experimental way to measure the elastic moduli of the solid walls. For large pores, the strain is determined by the pressure of the liquid saturating the pores and the mechanical properties of the porous solid. What happens at the nanometric scale, where liquid/matrix interfacial effects dominate? We have performed molecular simulations of a simple Lennard-Jones fluid confined between deformable nanoplatelets. The simulations provide the deformation of the nanopore as a function of the liquid pressure, in a way similar to what is done experimentally. The results show unexpected interface effects, which could be relevant to experimental data analysis

How reproducible are surface areas calculated from the BET equation?

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This round-robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called "BET surface identification" (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible

Gas oversolubility in nanoconfined liquids: Review and perspectives for adsorbent design

SSCI-VIDE+ING+DFAInternational audienceSolubilit

A perspective on Darcy's law across the scales: from physical foundations to particulate mechanics

This paper puts forward a perspective or opinion that we can demonstrate Darcy’s law is valid at any scale where fluid can be modelled/analyzed as a continuum. Darcy’s law describes the flow of a fluid through a porous medium by a linear relationship between the flow rate and the pore pressure gradient through the permeability tensor. We show that such a linear relationship can be established at any scale, so long as the permeability tensor is expressed as a function of adequate parameters that describe the pore space geometry, fluid properties and physical phenomena. Analytical models at pore scale provide essential information on the key variables that permeability depends on under different flow regimes. Upscaling techniques based on the Lippman-Schwinger equation, pore network models orEshelby’s homogenization theory make it possible to predict fluid flow beyond the pore scale. One of the key challenges to validate these techniques is to characterize microstructure and measure transport properties at multiple scales. Recent developments in imaging, multi-scale modeling and advanced computing offer new possibilities to address some of these challenges

Molecular Modeling of Glassy Surfaces

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