Coating of Open Cell Foams

The interior surfaces of three-dimensional open cell foams were coated by a combination of dip coating and spin coating. Glycerol/water solutions were used as model Newtonian liquids, and the coating processes were studied on open cell carbon foams with 10 or 30 pores per inch (PPI). The amount of liquid retained in the foam structures after dip coating increased with withdrawal speed and coating viscosity, as expected from the conventional understanding of dip coating onto nonporous substrates such as flat plates and rods. However, the liquid retention and hence average coating thickness increased with surface tension, a result counter to the observation with coating onto nonporous substrates. Pockets of liquid were observed after dip coating and results with coatings of alumina suspension showed that after drying, the trapped liquid can block pore windows. Spinning the foams after dip coating resulted in uniform liquid distribution and uniform coatings. Foams were placed in a special apparatus and rotated using a commercial spin coater. The liquid layer thickness decreased with spinning time and rotational speed, and increased with the liquid viscosity, results consistent with spin coating theory. The coating thickness after spinning was not affected by the initial dip coating procedure. The dip and spin process was also used to create γ-alumina and zeolite coatings, which are of interest for catalysis applications

Understanding and Analyzing Freezing-Point Transitions of Confined Fluids within Nanopores

Understanding phase transitions of fluids confined within nanopores is important for a wide variety of technological applications. It is well known that fluids confined in nanopores typically demonstrate freezing-point depressions, Δ<i><i>T</i></i>_f, described by the Gibbs–Thomson (GT) equation. Herein, we highlight and correct several thermodynamic inconsistencies in the conventional use of the GT equation, including the fact that the enthalpy of melting, Δ<i><i>H</i></i>_m, and the solid–liquid surface energy, γ_SL, are functions of pore diameter, complicating their prediction. We propose a theoretical analysis that employs the Turnbull coefficient, originally derived from metal nucleation theory, and show its consistency as a more reliable quantity for the prediction of Δ<i><i>T</i></i>_f. This analysis provides a straightforward method to estimate Δ<i><i>T</i></i>_f of nanoconfined organic fluids. As an example, we apply this technique to ibuprofen, an active pharmaceutical ingredient (API), and show that this theory fits well to the experimental Δ<i><i>T</i></i>_f of nanoconfined ibuprofen

Mechanism and Prediction of Gas Permeation through Sub-Nanometer Graphene Pores: Comparison of Theory and Simulation

Due to its atomic thickness, porous graphene with sub-nanometer pore sizes constitutes a promising candidate for gas separation membranes that exhibit ultrahigh permeances. While graphene pores can greatly facilitate gas mixture separation, there is currently no validated analytical framework with which one can predict gas permeation through a given graphene pore. In this work, we simulate the permeation of adsorptive gases, such as CO₂ and CH₄, through sub-nanometer graphene pores using molecular dynamics simulations. We show that gas permeation can typically be decoupled into two steps: (1) adsorption of gas molecules to the pore mouth and (2) translocation of gas molecules from the pore mouth on one side of the graphene membrane to the pore mouth on the other side. We find that the translocation rate coefficient can be expressed using an Arrhenius-type equation, where the energy barrier and the pre-exponential factor can be theoretically predicted using the transition state theory for classical barrier crossing events. We propose a relation between the pre-exponential factor and the entropy penalty of a gas molecule crossing the pore. Furthermore, on the basis of the theory, we propose an efficient algorithm to calculate CO₂ and CH₄ permeances per pore for sub-nanometer graphene pores of any shape. For the CO₂/CH₄ mixture, the graphene nanopores exhibit a trade-off between the CO₂ permeance and the CO₂/CH₄ separation factor. This upper bound on a Robeson plot of selectivity <i>versus</i> permeance for a given pore density is predicted and described by the theory. Pores with CO₂/CH₄ separation factors higher than 10² have CO₂ permeances per pore lower than 10^–22 mol s^–1 Pa^–1, and pores with separation factors of ∼10 have CO₂ permeances per pore between 10^–22 and 10^–21 mol s^–1 Pa^–1. Finally, we show that a pore density of 10¹⁴ m^–2 is required for a porous graphene membrane to exceed the permeance-selectivity upper bound of polymeric materials. Moreover, we show that a higher pore density can potentially further boost the permeation performance of a porous graphene membrane above all existing membranes. Our findings provide insights into the potential and the limitations of porous graphene membranes for gas separation and provide an efficient methodology for screening nanopore configurations and sizes for the efficient separation of desired gas mixtures