Machine-Learned Free Energy Surfaces for Capillary Condensation and Evaporation in Mesopores

Using molecular simulations, we study the processes of capillary condensation and capillary evaporation in model mesopores. To determine the phase transition pathway, as well as the corresponding free energy profile, we carry out enhanced sampling molecular simulations using entropy as a reaction coordinate to map the onset of order during the condensation process and of disorder during the evaporation process. The structural analysis shows the role played by intermediate states, characterized by the onset of capillary liquid bridges and bubbles. We also analyze the dependence of the free energy barrier on the pore width. Furthermore, we propose a method to build a machine learning model for the prediction of the free energy surfaces underlying capillary phase transition processes in mesopores.

On the Formation of Hydrogen Peroxide in Water Microdroplets

Recent reports on the formation of hydrogen peroxide (H2O2) in water microdroplets produced via pneumatic spraying or capillary condensation have garnered significant attention. How covalent bonds in water could break...

The Effect of Capillary Condensation on the Geomechanical and Acoustic Properties of Tight Formations: An Experimental Study

Capillary condensation is the condensation of the gas inside nano-pore space at a pressure lower than the bulk dew point pressure as the result of multilayer adsorption due to the high capillary pressure inside the small pore throat of unconventional rocks. The condensation of liquid in nano-pore space of rock changes its mechanical and acoustic properties. Acoustic properties variation due to capillary condensation provides us a tool to monitor phase change in reservoir as a result of nano-confinement as well as mapping the area where phase change occurs as well as characterize pore size distribution. This is particularly important for tight formations where confinement has a strong effect on phase behavior that is challenging to measure experimentally. Theoretical studies have examined the effects of capillary condensation; however, these findings have not been verified experimentally. The main objective of this study is to experimentally investigate the effect of capillary condensation on the mechanical and acoustic properties of shale samples. The mechanical and acoustic characterization of the samples was carried out experimentally using a state-of-the-art tri-axial facility at the Colorado School of Mines. The experimental set-up is capable of the simultaneous acquisition of coupled stress, strain, resistivity, acoustic and flow data. Carbon dioxide was used as the pore pressure fluid in these experiments. After a comprehensive characterization of shale samples, experiments were conducted by increasing the pore pressure until condensation occurs while monitoring the mechanical and acoustic properties of the sample to quantify the effect of capillary condensation on the mechanical and acoustic properties of the sample. Experimental data show a 5% increase in Young's Modulus as condensation occurs. This increase is attributed to the increase in pore stiffness as condensation occurs reinforcing the grain contact. An initial decrease in compressional velocity was observed as pore pressure increases before condensation occurs which is attributed to the expansion of the pore volume when pore pressure increases. After this initial decrease, compressional velocity slightly increases at a pressure around 750 - 800 psi which is close to the condensation pressure. We also observed a noticeable increase in shear velocity when capillary condensation occurs, this could be due to the immobility of the condensed liquid phase at the pore throats. The changes of geomechanical and acoustic signatures were observed at around 750 - 800 psi at 27°C, which is the dew point pressure of the fluid in the nano-pore space of the sample at this temperature. While the unconfined bulk dew point pressure of carbon dioxide at the same temperature is 977 psi. Hence, this study marks the first measurement of the dew point of fluid in nano-pore space and potentially leads to the construction of the phase envelope of fluid under confinement.

Water cluster in hydrophobic crystalline porous covalent organic frameworks

Progress over the past decades in water confinement has generated a variety of polymers and porous materials. However, most studies are based on a preconception that small hydrophobic pores eventually repulse water molecules, which precludes the exploration of hydrophobic microporous materials for water confinement. Here, we demonstrate water confinement across hydrophobic microporous channels in crystalline covalent organic frameworks. The frameworks are designed to constitute dense, aligned and one-dimensional polygonal channels that are open and accessible to water molecules. The hydrophobic microporous frameworks achieve full occupation of pores by water via synergistic nucleation and capillary condensation and deliver quick water exchange at low pressures. Water confinement experiments with large-pore frameworks pinpoint thresholds of pore size where confinement becomes dominated by high uptake pressure and large exchange hysteresis. Our results reveal a platform based on microporous hydrophobic covalent organic frameworks for water confinement.

Hygrothermal performance of a brick wall with interior insulation in cold climate: Vapour open versus vapour tight approach

Interior insulation of historic buildings is well-studied in Central Europe; however, their conclusions might not be directly applicable to colder climates. Heat, air and moisture (HAM) modelling can be a valuable tool for studying those solutions in different conditions. Recently, incorporating the capillary condensation redistribution (CCR) test into the material characterization process has shown to cause dramatic improvement in correlating hygrothermal modelling results to measurements in certain situations. It is also noteworthy, that the HAM modelling errors made using material data from conventional characterization process can be severely non-conservative. In this article a parametric study of a 51 cm thick mass masonry wall is undertaken to determine the effect of the improved material properties on the reliability of a vapour open ‘capillary active’ autoclaved aerated concrete (AAC) and calcium silicate (CaSi) interior insulation solutions and to compare them to a vapour tight insulation system. A 49-year real weather dataset from Estonia is used. The results show that compared to conventionally characterized material properties the CCR-optimized material data causes more critical conditions directly behind the interior insulation, while having a similar performance in the exterior part of the masonry. The differences occur close to the performance limits and highlight the importance of using the CCR test in material characterization process. The vapour tight and vapour open systems showed a very similar impact on the freeze-thaw cycles and on the maximum ice saturation of the exterior part of the masonry. The vapour open solutions perform better than the vapour tight PIR in terms of frost damage and possible mould growth behind the insulation – even though the advantage has been reduced when using the CCR-optimized material data. Regardless of the insulation solution, a case-specific approach is still required to avoid damaging the original wall and/or the added insulation system.

Comparative study between adsorbents based on magnetic nanoferrite. Application to the removal of methyl orange from wastewater

Magnetic ferrite (Mg-doped bismuth ferrite) and its clay-based composite (Mg-doped bismuth ferrite-bentonite) were prepared by self-combustion method utilizing glycine as fuel and served for the removal of methyl orange (MO) from aqueous solutions. The ferrite-based adsorbents were characterized by the measurement of specific surface area (BET), scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD). The different experimental parameters that affect the performance of this reaction such as: temperature, contact time, initial dye concentration and mass of adsorbent were investigated. The point of zero charge pH (pHPZC) was determined for the two adsorbents. Langmuir and Freundlich adsorption models were employed to provide a description of the equilibrium isotherms. Adsorption tests showed that the equilibrium time is a function of the initial concentration of dye. The adsorption kinetic study indicated that the equilibrium adsorption is established after 300 minutes for Mg-doped bismuth ferrite, while it is established after 180 minutes for Mg-doped bismuth ferrite-bentonite composite. Furthermore, this suggests that the adsorption of MO on both adsorbents can be perfectly described by pseudo-second order kinetics. The maximum adsorption capacity determined by the mathematical model of Langmuir is equal to 181.8 mg.g-1 for Mg-doped bismuth ferrite and to 188.7 mg.g-1 for its composite, at 298 K. Adsorption isotherms shows that the Freundlich model perfectly represents adsorption of methyl orange to the prepared Mg-doped bismuth ferrite. The ferrite/bentonite composite has 2-50 nm-sized pores and is indeed a mesoporous material. The small pores observed on the surface of the adsorbents are in line with type IV isotherm, with possible capillary condensation of the adsorbate. Moreover, Langmuir model seems to be the most suitable model for the absorption of methyl orange on the Mg-doped bismuth ferrite-bentonite composite. The thermodynamic parameters related to the sorbent/adsorbate system indicate that adsorption is spontaneous and exothermic. The determination of isosteric heat of adsorption suggested that it is indeed a physisorption characterized by weak intermolecular forces between MO and the surface.