Experimental Study on Phase Transitions of Carbon Dioxide Confined in Nanopores: Evaporation, Melting, Sublimation, and Triple Point.

Capillary phase transitions (evaporation, melting, and sublimation) and the pore triple point of CO2 confined in MCM-41 mesoporous media with a pore diameter of 3.5 nm have been studied by using an isochoric heating procedure in a high-pressure low-temperature differential scanning calorimeter over a pressure range of 0.5-40.5 bar. The procedure is validated by the agreement between the measured conditions of bulk evaporation/sublimation and literature data. The main finding in this work is that the solid-to-fluid phase transitions of CO2 in MCM-41 shift to temperatures higher than those of the corresponding bulk phase transitions. It is also found that the formation of a solid phase of CO2 in MCM-41 does not require the presence of a liquid or solid in the bulk. The capillary-melting and capillary-evaporation curves approach each other as temperature decreases until they meet at the pore triple point. The effect of pressure on capillary melting temperature is significant at pressures close to the pore triple point. Furthermore, the capillary-melting curve approaches the bulk saturated vapor-pressure curve as temperature increases, thus hinting an agreement with the prediction by molecular dynamics simulation in the literature that the curves eventually intersect each other at a high temperature and pressure. Based on the measured capillary phase transitions, the pore triple-point temperature and pressure of nanoconfined CO2 are bracketed and found to be much lower than those of the bulk triple point.

Upscaling of dispersion in gas-liquid absorption on an inclined surface.

We extend the Taylor-Aris dispersion theory to upscale the gas absorption into a viscous incompressible liquid flowing along an inclined surface. A reduced-order model of advection-dispersion-reaction is developed with the aid of Reynolds decomposition and cross-sectional averaging techniques. The upscaled model allowed evaluation of the dispersion, advection, and absorption kinetics as a function of the Peclet number (Pe) and the Damköhler number (Da). The transport and kinetics parameters for the limiting cases of nonabsorption and absorption dominant are also evaluated. The upscaled model is solved analytically, and the obtained solution is used to evaluate the upscaled mass transfer between the gas and liquid. The results for the overall Sherwood number identify three regions: (i) advection dominant, (ii) transition where both advection and absorption play a role, and (iii) absorption dominant. The scaling relation between the Sherwood number (Sh) and the Da for the last region was determined to follow Sh∼Da^{1/2}. It is also revealed that in the first two regions, the Sherwood number versus the Peclet number exhibits a bell-shaped (or Gaussian) behavior, suggesting an optimal Pe that maximizes mass transfer between gas and liquid in these regions. The model and insights presented have the potential to be applied in a wide range of industrial separation processes involving the interaction of a gas exposed to a liquid flowing downward on an inclined surface under gravity.

Combined electroosmotic and pressure-driven transport of neutral solutes across a rough, porous-walled microtube.

A number of microfluidic systems of interest essentially consist of micro-scaled channels/tubes, whose walls are inherently rough. The novelty of the current study lies in exploring the impact of the wall roughness on mass transfer in the case of flow through a microtube with porous wall. The current investigation is possibly the first attempt at exploring the effect of mass transfer for a porous-walled, rough microtube, as earlier studies were limited to the analysis of hydrodynamic and thermal effects only in an impervious microtube. In particular, the effects of the corrugation amplitude and the wavenumber on the mass transport have been assessed in detail in this work, via a combination of perturbation approximations and numerical analysis. Several interesting revelations are elicited regarding the effects of these pertinent parameters on the mass transfer coefficient, permeation flux, wall surface concentration, and delivery flux of the neutral solute. It has been unveiled that it is possible to enhance the solute mass flux by 10% via appropriate tuning of corrugation amplitude. The findings of the study can help in better understanding of mass transport for a porous-walled, rough microtube, which has critical relevance in several important applications such as micromixers, targeted drug delivery, and so on.

Dispersion tensor in stratified porous media.

Dispersion in porous media is of great importance in many areas of science and engineering. While dispersion in porous media has been generally well discussed in the literature, little work has been done regarding a generalization of Taylor dispersion in stratified media. In this work, we generalized the Taylor dispersion theory and Stokes flow in porous media to derive a reduced-order model for tracer dispersion in stratified porous media. Our findings revealed that for a simple case of two-layer porous media, the hydrodynamic coupling between the two layers leads to the tensorial nature of dispersion and advection. The results showed that the obtained dispersion tensor and advection are not symmetric unless both porous layers have similar thickness, porosity, and molecular diffusion. We found that the main elements of the coefficient of the dispersion tensor remain positive while the off-diagonal elements can take negative values. On the contrary, all elements of the advection matrix may take negative values. On the basis of these observations, we report the manifestation of the dispersion barrier, uphill dispersion and advection, and osmotic dispersion during tracer transport in stratified porous media. In particular, the identified uphill advection reveals that the injected tracer in one layer could be transported countercurrent to the adjacent layer. Furthermore, we have shown that in the limiting case of Darcy flow, the Taylor dispersion is absent, and the tracer mixing between the two layers is restricted to the cross-diffusive flux between them. The results revealed that the field scale mixing may not necessarily originate from the Taylor dispersion and could be due to the modified advection terms and the cross-diffusive flux between the two layers.

First-order and gradual phase transitions of ethane confined in MCM-41.

The first-order phase transition of ethane confined in MCM-41, i.e., capillary condensation, has been measured using an isochoric cooling procedure by differential scanning calorimetry (DSC) under conditions ranging from 206 K and 1.1 bar up to the pore critical point (PCP). The PCP has also been determined using the three-line method developed earlier based on the vanishing heat of phase transition. As in the bulk phase, no first-order phase transition can occur above the critical point, which also implies that vapor can transform into liquid gradually by following a path around the critical point through the supercritical region. For the first time, the gradual phase transition is demonstrated with ethane in MCM-41, which is achieved through a multistep process with paths proceeding around the PCP without crossing the capillary-condensation curve. The occurrence of the gradual phase transition in nanopores, thus the confined supercriticality, is confirmed while our consistent DSC measurements are also well demonstrated.

Phase Transition and Criticality of Methane Confined in Nanopores.

For the first time, the phase transition and criticality of methane confined in nanoporous media are measured. The measurement is performed by establishing an experimental setup utilizing a differential scanning calorimeter capable of operating under very low temperatures as well as high pressures to detect the capillary phase transition of methane inside nanopores. By performing experiments along isochoric cooling paths, both the capillary condensation and the bulk condensation of methane are detected. The pore critical point of nanoconfined methane is also determined and then used to derive the parameters of a previously developed self-consistent equation of state based on the generalized van der Waals partition function. Using these parameters, the equation of state can predict the capillary-condensation curves that agree well with the experimental data.

Enhanced oil recovery from fractured carbonate reservoirs using nanoparticles with low salinity water and surfactant: A review on experimental and simulation studies.

Nearly half of the world's oil reserves are found in carbonate reservoirs, which have heterogeneous formation characteristics and are naturally fractured. Because of the permeability contrast between the matrix and fracture network in these reservoirs, primary and secondary oil recovery processes are ineffective. Consequently, there has been a growing interest in enhanced oil recovery (EOR) from fractured carbonate reservoirs (FCRs) over the past years and many successful attempts have involved the use of different thermal or non-thermal EOR methods to improve oil recovery. Nonetheless, many researchers have recently directed their studies towards the use of low salinity water (LSW), nanoparticles (NPs), and surfactant (LNS) as EOR agents in carbonates because they are environmentally friendly and incur low costs. Several studies have reported the successful application of the solutions of LSW, NPs, and surfactants either as individual solutions or in combinations, to carbonate formations. The challenges associated with their implementations such as fines migration for LSW flooding, surfactant adsorption onto the pore walls, and instability of NPs under harsh conditions, have also been identified in literature and addressed. However, relatively few investigations have been conducted on FCRs to study the effectiveness of these LNS EOR applications in the presence of fractures. This review, therefore, presents the reports of EOR in FCRs using LNS and identifies the mechanisms that influence these results. It has been shown that fines migration could either promote EOR or reduce recovery based on the occurrence of formation damage. In addition, surfactants with the tendency to form micro-emulsions will be efficient for EOR applications in FCRs. Finally, LNS solutions show promising results with emerging techniques such as alternating injection, which could be applied in FCRs. The findings from this study set the stage for future investigations into EOR in FCRs.

Isochoric measurement of the evaporation point of pure fluids in bulk and nanoporous media using differential scanning calorimetry.

As a continuation of recent series of work, a new approach applying an isochoric heating process using differential scanning calorimetry (DSC) is introduced to measure the evaporation point of pure fluids in both bulk phase and nanoporous media, as opposed to the previous approach of isochoric cooling to measure the condensation point [X. Qiu et al., Phys. Chem. Chem. Phys., 2018, 20, 26241-26248; X. Qiu et al., Phys. Chem. Chem. Phys., 2019, 21, 224-231]. Though these two approaches must arrive at the same phase-transition point for a specified density of bulk pure fluids, it is not necessarily true for confined fluids due to hysteresis in a temperature range sufficiently far below the bulk critical point. The isochoric heating process allows one to accurately measure the phase transition of non-volatile fluids that exist in liquid phase at relatively high temperatures. As the new approach operates without an inert gas, which substantially dissolves in the test sample at high pressures if the standard isobaric measurement ASTM E1782 is used, application to the high-pressure range is enabled with higher accuracy. This method can also be extended to confined systems, where the evaporation points of both bulk and confined fluids are successively measured in a single run of experiment. The results reveal that capillary evaporation, i.e., evaporation of fluids confined in nanoporous media, occurs at a higher temperature (isobarically), or at a lower pressure (isothermally), than that in bulk only after the liquid in bulk space is completely evaporated. The method introduced in this work paves a new way to study the condensation/evaporation hysteresis of confined fluids as well as the evaporation point of confined fluid mixtures.

Experimental Study on the Criticality of a Methane/Ethane Mixture Confined in Nanoporous Media.

For the first time, the critical region of a methane/ethane mixture confined in nanoporous media (SBA-15) is experimentally investigated using differential scanning calorimetry with an isochoric cooling procedure. The results reveal that the supercritical region of the confined fluid mixture exists at a lower pressure than its counterpart in the bulk space. The shift of the critical region is dependent on the pore size, which is similar to that of pure fluids [Tan et al., J. Phys. Chem. C, 2019, 123, 9824-9830]. Specifically, compared to that in bulk, the shift is greater for smaller pore size. The heat of capillary condensation of this mixture is also discussed. The findings in this work would shed some light on the understanding of confined phase behavior, especially criticality, in investigations toward more complex confined mixtures encountered in practical engineering application, for example, oil and gas recovery from unconventional reservoirs.

Passive microinjection within high-throughput microfluidics for controlled actuation of droplets and cells.

Microinjection is an effective actuation technique used for precise delivery of molecules and cells into droplets or controlled delivery of genes, molecules, proteins, and viruses into single cells. Several microinjection techniques have been developed for actuating droplets and cells. However, they are still time-consuming, have shown limited success, and are not compatible with the needs of high-throughput (HT) serial microinjection. We present a new passive microinjection technique relying on pressure-driven fluid flow and pulsative flow patterns within an HT droplet microfluidic system to produce serial droplets and manage rapid and highly controlled microinjection into droplets. A microneedle is secured within the injection station to confine droplets during the microinjection. The confinement of droplets on the injection station prevents their movement or deformation during the injection process. Three-dimensional (3D) computational analysis is developed and validated to model the dynamics of multiphase flows during the emulsion generation. We investigate the influence of pulsative flows, microneedle parameters and synchronization on the efficacy of microinjection. Finally, the feasibility of implementing our microinjection model is examined experimentally. This technique can be used for tissue engineering, cells actuation and drug discovery as well as developing new strategies for drug delivery.

Kinetics, thermodynamics, and physical characterization of corn stover (Zea mays) for solar biomass pyrolysis potential analysis.

Solar pyrolysis of agricultural waste has huge potential for sustainable production of fuel and chemical feedstock. In this paper, the kinetics, thermodynamics, and physical characterization of corn stover (CS) collected from Wyoming, USA was conducted with respect to solar pyrolysis. The kinetics and thermodynamics of the CS pyrolysis was analyzed in detail using the methods described by KAS (Kissinger-Akahira-Sunose) and FWO (Flynn-Wall-Ozawa), from which the activation energy, Gibbs energy, Arrhenius pre-exponential factor, enthalpy, and entropy were derived.14 other kinetics models based on reaction order, diffusion, nucleation, geometric contraction, power models were also examined, and models based on diffusion was found to be best suited. The CS was used for solar pyrolysis of biomass and the products were analyzed by mass spectroscopy, ICP-MS, GPC, micro-GC, and Elemental analyzer. The results show that CS is suitable for solar pyrolysis to produce chemicals and other fuels.

Simple and accurate isochoric differential scanning calorimetry measurements: phase transitions for pure fluids and mixtures in nanopores.

Various types of nanopores are encountered in many different engineering and science applications. Due to incomplete understanding of the phase behavior of fluids in nanosize confined space, the improvement of such applications has been largely based on experience and empirical approaches. Therefore, experimental studies on the phase behavior of confined fluids that are simple but accurate are still urgently needed. We recently developed a new isochoric procedure using a Differential Scanning Calorimeter (DSC) to measure the onset of vapor-liquid phase transitions, which has been successfully used in experiments measuring the vapor pressures of pure substances and the dew points of a bulk mixture in the absence of nanopores [Qiu et al., Phys. Chem. Chem. Phys., 2018, 20, 26241-26248]. It is the purpose of this work to extend the new method to confined fluids. To demonstrate the superior ability of the new method, we measure the capillary condensation of CO2 and the dew points of a binary methane/ethane gas mixture confined in SBA-15 with different pore diameters.

Novel isochoric measurement of the onset of vapor-liquid phase transition using differential scanning calorimetry.

A novel method for measuring the onset of vapor-liquid phase transition applying an isochoric procedure in a high-pressure micro differential scanning calorimeter is introduced for the first time. Isochoric dew-point measurement is used to measure vapor pressures of CO2 at different boiling temperatures and dew points of a methane/ethane gas mixture at different pressures or temperatures. The isochoric two-phase bubble-point measurement, similar to the isobaric method, is also demonstrated to measure vapor pressures of methanol at different boiling temperatures. All results are in agreement with the literature data. The isochoric method is found to be superior to the widely used isobaric method. It can be used to measure the onset of vapor-liquid phase transition for a wide range of substances and mixtures, including the ones for which the isobaric method is inapplicable, and it eliminates difficulties usually encountered in the isobaric method. The proposed method along with the findings of this study can pave the way for experimental measurements of phase equilibria in more complex systems.

Mathematical Modeling of the Function of Warburg Effect in Tumor Microenvironment.

Tumor cells are known for their increased glucose uptake rates even in the presence of abundant oxygen. This altered metabolic shift towards aerobic glycolysis is known as the Warburg effect. Despite an enormous number of studies conducted on the causes and consequences of this phenomenon, little is known about how the Warburg effect affects tumor growth and progression. We developed a multi-scale computational model to explore the detailed effects of glucose metabolism of cancer cells on tumorigenesis behavior in a tumor microenvironment. Despite glycolytic tumors, the growth of non-glycolytic tumor is dependent on a congruous morphology without markedly interfering with glucose and acid concentrations of the tumor microenvironment. Upregulated glucose metabolism helped to retain oxygen levels above the hypoxic limit during early tumor growth, and thus obviated the need for neo-vasculature recruitment. Importantly, simulating growth of tumors within a range of glucose uptake rates showed that there exists a spectrum of glucose uptake rates within which the tumor is most aggressive, i.e. it can exert maximal acidic stress on its microenvironment and most efficiently compete for glucose supplies. Moreover, within the same spectrum, the tumor could grow to invasive morphologies while its size did not markedly shrink.

Magnetically assisted intraperitoneal drug delivery for cancer chemotherapy.

Intraperitoneal (IP) chemotherapy has revived hopes during the past few years for the management of peritoneal disseminations of digestive and gynecological cancers. Nevertheless, a poor drug penetration is one key drawback of IP chemotherapy since peritoneal neoplasms are notoriously resistant to drug penetration. Recent preclinical studies have focused on targeting the aberrant tumor microenvironment to improve intratumoral drug transport. However, tumor stroma targeting therapies have limited therapeutic windows and show variable outcomes across different cohort of patients. Therefore, the development of new strategies for improving the efficacy of IP chemotherapy is a certain need. In this work, we propose a new magnetically assisted strategy to elevate drug penetration into peritoneal tumor nodules and improve IP chemotherapy. A computational model was developed to assess the feasibility and predictability of the proposed active drug delivery method. The key tumor pathophysiology, including a spatially heterogeneous construct of leaky vasculature, nonfunctional lymphatics, and dense extracellular matrix (ECM), was reconstructed in silico. The transport of intraperitoneally injected magnetic nanoparticles (MNPs) inside tumors was simulated and compared with the transport of free cytotoxic agents. Our results on magnetically assisted delivery showed an order of magnitude increase in the final intratumoral concentration of drug-coated MNPs with respect to free cytotoxic agents. The intermediate MNPs with the radius range of 200-300 nm yield optimal magnetic drug targeting (MDT) performance in 5-10 mm tumors while the MDT performance remains essentially the same over a large particle radius range of 100-500 nm for a 1 mm radius small tumor. The success of MDT in larger tumors (5-10 mm in radius) was found to be markedly dependent on the choice of magnet strength and tumor-magnet distance while these two parameters were less of a concern in small tumors. We also validated in silico results against experimental results related to tumor interstitial hypertension, conventional IP chemoperfusion, and magnetically actuated movement of MNPs in excised tissue.

Delivery of magnetic micro/nanoparticles and magnetic-based drug/cargo into arterial flow for targeted therapy.

Magnetic drug targeting (MDT) and magnetic-based drug/cargo delivery are emerging treatment methods which attracting the attention of many researchers for curing different cancers and artery diseases such as atherosclerosis. Herein, computational studies are accomplished by utilizing magnetic approaches for cancer and artery atherosclerosis drug delivery, including nanomagnetic drug delivery and magnetic-based drug/cargo delivery. For the first time, the four-layer structural model of the artery tissue and its porosity parameters are modeled in this study which enables the interaction of particles with the tissue walls in blood flow. The effects of parameters, including magnetic field strength (MFS), magnet size, particle size, the initial position of particles, and the relative magnetic permeability of particles, on the efficacy of MDT through the artery walls are characterized. The magnetic particle penetration into artery layers and fibrous cap (the covering layer over the inflamed part of the artery) is further simulated. The MDT in healthy and diseased arteries demonstrates that some of the particles stuck in these tissues due to the collision of particles or blood flow deviation in the vicinity of the inflamed part of the artery. Therefore the geometry of artery and porosity of its layers should be considered to show the real interaction of particles with the artery walls. Also, the results show that increasing the particles/drug/cargo size and MFS leads to more particles/drug/cargo retention within the tissue. The present work provides insights into the decisive factors in arterial MDT with an obvious impact on locoregional cancer treatment, tissue engineering, and regenerative medicine.

Shear dispersion in a capillary tube with a porous wall.

An analytical expression is presented for the shear dispersion during solute transport in a coupled system comprised of a capillary tube and a porous medium. The dispersion coefficient is derived in a capillary tube with a porous wall by considering an accurate boundary condition, which is the continuity of concentration and mass flux, at the interface between the capillary tube and porous medium. A comparison of the obtained results with that in a non-coupled system identifies three regimes including: diffusion-dominated, transition, and advection-dominated. The results reveal that it is essential to include the exchange of solute between the capillary tube and porous medium in development of the shear dispersion coefficient for the last two regimes. The resulting equivalent transport equation revealed that due to mass transfer between the capillary tube and the porous medium, the dispersion coefficient is decreased while the effective velocity in the capillary tube increases. However, a larger effective advection term leads to faster breakthrough of a solute and enhances mass delivery to the porous medium as compared with the classical double-porosity model with a non-coupled dispersion coefficient. The obtained results also indicate that the finite porous medium gives faster breakthrough of a solute as compared with the infinite one. These results find applications in solute transport in porous capillaries and membranes.