Rarefied gas flow in functionalized microchannels.

The interaction of rarefied gases with functionalized surfaces is of great importance in technical applications such as gas separation membranes and catalysis. To investigate the influence of functionalization and rarefaction on gas flow rate in a defined geometry, pressure-driven gas flow experiments with helium and carbon dioxide through plain and alkyl-functionalized microchannels are performed. The experiments cover Knudsen numbers from 0.01 to 200 and therefore the slip flow regime up to free molecular flow. To minimize the experimental uncertainty which is prevalent in micro flow experiments, a methodology is developed to make optimal use of the measurement data. The results are compared to an analysis-based hydraulic closure model (ACM) predicting rarefied gas flow in straight channels and to numerical solutions of the linearized S-model and BGK kinetic equations. The experimental data shows that if there is a difference between plain and functionalized channels, it is likely obscured by experimental uncertainty. This stands in contrast to previous measurements in smaller geometries and demonstrates that the surface-to-volume ratio of 0.4 µ m - 1 seems to be too small for the functionalization to have a strong influence and highlights the importance of geometric scale for surface effects. These results also shed light on the molecular reflection characteristics described by the TMAC.

Surface Functionalization of Mesoporous Membranes: Impact on Pore Structure and Gas Flow Mechanisms.

Membranes showing monomodal pore size distributions with mean pore diameters of 23, 33, and 60 nm are chemically functionalized using silanes with varying chain length and functional groups like amino, alkyl, phenyl, sulfonate, and succinic anhydrides. Their influence on the morphology, pore structure, and gas flow is investigated. For this, single-gas permeation measurements at pressures around 0.1 MPa are performed at temperatures ranging from 273 to 353 K using He, Ne, Ar, N2, CO, CO2, CH4, C2H4, C2H6, and C3H8. Results show pore size and pore volume linearly depending on the length of functional molecules, as expected for monolayer deposition. However, the gas flow through functionalized membranes is disproportionally decreased up to a factor of around 10. Hence, the decreased pore size and pore volume cannot explain the large decrease in flow. Furthermore, there is no specific dependency between the decrease in flow and temperature or gas type other than the relation proposed by Knudsen (√RTM)-1. Considering the large variety of functional molecules used, it is very surprising that no correlations between the type of functional group and the flow have been found. The decrease in flow, however, is strongly dependent on the chain length of the silanes (factor of 10 at ∼2 nm length). This leads to the conclusion that the observed effect is not caused by sorption driven processes. It is proposed that steric interactions between functional groups and gas molecules lead to increased residence times on the surface and longer molecular trajectories, which, in turn, lead to a decrease in flow. In membrane design, any surface modification should, therefore, make use of functionalizing agents with chain length as short as possible.

Physisorption of α-chymotrypsin on SiO2 and TiO2: A comparative study via experiments and molecular dynamics simulations.

In order to understand fundamental interactions at the interface between immobilized enzymes and ceramic supports, the authors compare the adsorption features of chymotrypsin on SiO2 and TiO2 colloidal particles by means of a combination of adsorption experiments and molecular dynamics simulations. While the dependency of the adsorption amount on pH is consistent with the trend predicted the Derjaguin-Landau-Verwey-Overbeek theory, other effects can only be rationalized if the atomic-scale details of the water-mediated protein-surface interactions are considered. On both surfaces, a clear driving force for the formation of a double monolayer at the saturation coverage is found. Although nearly equal free energies of adsorption are estimated on the two materials via a Langmuir adsorption analysis, about 50% more proteins per unit of surface can be accommodated on TiO2 than on SiO2. This is probably due to the lower surface diffusion mobility of the adsorbed protein in the latter case. Surface anchoring is realized by a combination of direct ionic interactions between charged proteins and surface sites (more pronounced for SiO2) and distinct structuring of the surface hydration layers in which the contact residues are embedded (more pronounced for TiO2). Finally, normalization of the data with respect to particle surface areas accessible to the proteins, rather than determined by means of the Brunauer-Emmett-Teller nitrogen adsorption isotherm, is crucial for a correct interpretation of the results.