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Infrared (IR) microimaging is employed for selectively recording two‐dimensional plots of the individual distributions of the components n‐hexane (nC6) and 3‐methylpentane (3MP) over a single crystal of zeolite ZSM‐5 during mixture adsorption. At a pressure change from 0 to 0.02 mbar, the scenario of “overshooting” is observed, with the concentration of nC6 temporarily exceeding its equilibrium value. After the next pressure step from 0.02 to 2 mbar, 3MP is progressively driven out of the pores, in parallel with an increase in nC6 concentration. The IR microimaging results are corroborated by grand canonical Monte Carlo simulations, which help explain the peculiarities of mass transfer by providing visual representations of the distribution and packing densities of the guest molecules in the pores. [ABSTRACT FROM AUTHOR]

We discuss the application of the three-laser optical digital interferometry method for the determination of transport properties such as the thermodiffusion, the molecular diffusion and the Soret coefficients by the thermogravitational column technique. The primary objective of this study is to illustrate the capabilities and limitations of the method for quantifying these properties in both binary and ternary liquid mixtures from an optical viewpoint. It is concluded that the system is highly robust for the analysis of binary mixtures, with the combination of the results obtained by the three wavelengths increasing the accuracy of the measurement. The study of ternary mixtures, on the contrary, is limited to certain types of conditions. While the accuracy of a three-laser interferometer can be improved, the method may be compromised if the optical contrast factor matrices are poorly conditioned. [ABSTRACT FROM AUTHOR]

Single-particle tracking is a powerful technique to investigate the motion of molecules or particles. Here, we review the methods for analyzing the reconstructed trajectories, a fundamental step for deciphering the underlying mechanisms driving the motion. First, we review the traditional analysis based on the mean squared displacement (MSD), highlighting the sometimes-neglected factors potentially affecting the accuracy of the results. We then report methods that exploit the distribution of parameters other than displacements, e.g., angles, velocities, and times and probabilities of reaching a target, discussing how they are more sensitive in characterizing heterogeneities and transient behaviors masked in the MSD analysis. Hidden Markov Models are also used for this purpose, and these allow for the identification of different states, their populations and the switching kinetics. Finally, we discuss a rapidly expanding field—trajectory analysis based on machine learning. Various approaches, from random forest to deep learning, are used to classify trajectory motions, which can be identified by motion models or by model-free sets of trajectory features, either previously defined or automatically identified by the algorithms. We also review free software available for some of the analysis methods. We emphasize that approaches based on a combination of the different methods, including classical statistics and machine learning, may be the way to obtain the most informative and accurate results. [ABSTRACT FROM AUTHOR]

Oil is a complex mixture of liquid organic substances in which various solid hydrocarbons, resinous substances and accompanying gases are dissolved. In the article various methods of separation of complex mixtures into simpler compositions were examined. The bulk of the oil components is also determined. An important indicator in the identification of oil products is the amount of aromatic hydrocarbons in their content. In the methods used in the study of petroleum products in environmental objects, gas chromatographic analysis is preferred due to its highest selectivity, sensitivity and accessibility, using different types of detection. On the other hand, during the determination of PAHs in oils and middle distillates, in the chromatograms, the analyte appears against the background of the "naphthenic hump" and paraffins, which form fragments of molecules under electronic conditions, which overlap with each other. Fragments of molecules of substances analyzed in terms of ion mass are placed on them and their mass spectra are analyzed. When performing such analyses, it is practically impossible to identify, quantify, and accurately estimate the signal intensity of peaks associated with polycyclic condensed arenes. [ABSTRACT FROM AUTHOR]

Microfluidic devices have been widely used to measure the diffusion coefficients and hydrodynamic radii of various molecules, especially proteins. The existing devices that use diffusion-based gradient generation apply obstacles such as membranes or hydrogels to avoid additional fluid flow affecting the evolution of concentration distribution and precise measurement. Here, a free-diffusion based microfluidic device was developed which is capable of measuring the diffusion coefficients of various, different-sized proteins and dyes without using any obstacles by minimizing pressure differences due to its symmetrical geometry. The fluorescent detection and the ease of application of the device enable accelerated measurements and interpretation of results. Time-lapse pictures of 30 s were taken of the diffusion profiles and a custom-made self-written Python program was used to fit the profiles to the theoretical functions and calculate the diffusion coefficients. Diffusion coefficients of bovine serum albumin, immunoglobulin G and rhodamine B were determined with this method and compared to their theoretical and experimental values. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The problem of molecular diffusion in the soup of chemical reactions attracts mounting interest across fields ranging from chemistry to biophysics to material science. Chemical reactions involve bond breakup and formation, whose time scale is typically on the orders of fs to ps, while molecular diffusion occurs at time scales of μs to ms. The two processes are often considered orthogonal, given the vastly different scales. The serial results show that the enzyme's diffusion is enhanced in a substrate‐dependent manner, which was further extended to small molecule reaction systems, challenging this classical paradigm. However, the results from different groups using different techniques do not quantitatively agree, and a general mechanism is yet to be understood. We summarize experimental studies on diffusion problems and seek to reconcile the interpretation with understanding the limits of measurement tools and the chemical nature of reaction systems. Understanding molecular diffusion in chemical reactions will provide fresh thoughts in designing chemical systems such as molecular machines that harvest work at the nanoscale in a controllable manner. [ABSTRACT FROM AUTHOR]

Abstract Temporal resolution is a key parameter in the observation of dynamic processes, as in the case of single molecules motions visualized in real time in two-dimensions by wide field (fluorescence) microscopy, but a systematic investigation of its effects in all the single particle tracking analysis steps is still lacking. Here we present tools to quantify its impact on the estimation of diffusivity and of its distribution using one of the most popular tracking software for biological applications on simulated data and movies. We found important shifts and different widths for diffusivity distributions, depending on the interplay of temporal sampling conditions with various parameters, such as simulated diffusivity, density of spots, signal-to-noise ratio, lengths of trajectories, and kind of boundaries in the simulation. We examined conditions starting from the ones of experiments on the fluorescently labelled receptor p75NTR, a relatively fast-diffusing membrane receptor (diffusivity around 0.5–1 µm2/s), visualized by TIRF microscopy on the basal membrane of living cells. From the analysis of the simulations, we identified the best conditions in cases similar to these ones; considering also the experiments, we could confirm a range of values of temporal resolution suitable for obtaining reliable diffusivity results. The procedure we present can be exploited in different single particle/molecule tracking applications to find an optimal temporal resolution.

The effectiveness of Carbon Capture and Storage (CCS) as an imperative decarbonization technology relies on the sealing capacity of a fine-grained caprock to permanently store CO2 deep underground. Uncertainties in assessing the caprock sealing capacity increase with the spatial and temporal scales and may delay CCS deployment at the gigatonne scale. We have developed a computationally efficient transport model to capture the dynamics of basin-wide upward CO2 migration in a multi-layered setting over geological time scales. We find that massive capillary breakthrough and viscous flow of CO2, even through pervasively fractured caprocks, are unlikely to occur and compromise the storage security. Potential leakage from the injection reservoir is hampered by repetitive layering of overlying caprocks. This finding agrees with geologic intuition and should be understandable by the public, contributing to the development of climate policies around this technology with increased confidence that CO2 will be indefinitely contained in the subsurface.

Typical bulk‐heterojunction organic photovoltaics (OPV) suffer from instability due to the slowly diffusing small‐molecule acceptors (SMAs) under operational conditions. The originally well‐phase‐separated morphology will undergo SMA self‐aggregation to form over‐purified domains that will deteriorate the OPV performance. This issue can be partially alleviated in sequentially processed OPV cells with a planar‐mixed heterojunction absorber, which is intrinsically more robust due to larger domain sizes and a lower degree of mixing. To further enhance the morphological stability, a strategy is developed to inhibit the disordered molecular diffusion that leads to the loss of crystallinity of SMA domains. Two SMAs, C9‐4F and Y6‐OBO, are incorporated as guest acceptors to form an alloy‐like acceptor with the host acceptor BTP‐eC9. These alloy‐like acceptors improved the crystallinity of the acceptor phase by promoting more ordered molecular packing, effectively restraining the diffusion‐caused loss of SMA crystallinity upon illumination. This approach helps maintain favorable gradients and ultimately ensures OPV morphological stability. Consequently, the derived devices exhibited considerably enhanced stability, with the T80 lifetime of C9‐4F‐based devices reaching ≈790 h and a remarkable ≈1010 h for Y6‐OBO‐based devices, significantly surpassing the ≈450 h observed from binary devices. [ABSTRACT FROM AUTHOR]

Natural fractures are characterized by high internal heterogeneity. This internal variability is the cause of flow channeling, which in turn leads to contaminant transport taking place primarily along the high‐velocity channels. Mass exchange between the high‐velocity channels and the low‐velocity zones has the potential to enhance contaminant retention, due to solute diffusion into the low‐velocity zones and subsequent exposure to additional surface area for diffusion into the bordering rock matrix. Here, we derive a random walk particle tracking method for heterogeneous fractures, which includes an additional term to account for the aperture gradient. The method takes into account advection, diffusion in the fracture and matrix diffusion. The developed numerical framework is applied to assess the effect of low‐velocity zones in rough self‐affine fractures. The results show that diffusion into low‐velocity zones has a visible but modest impact on contaminant retention. The magnitude of this impact does not change considerably, regardless of whether diffusion into the rock matrix is considered in the model, and increases for a decreasing average Péclet number of the fracture. Key Points: Natural fractures are highly heterogeneous, comprising flowing channels and lower‐velocity zonesWe study the effects that diffusion into low‐velocity zones has in contaminant transport through rough fracturesAccounting for diffusion in low‐velocity zones has a relatively modest impact on contaminant retention [ABSTRACT FROM AUTHOR]

Innovations in drug delivery systems are crucial for enhancing therapeutic efficiency. Our research presents a novel approach based on using electro-fluid dynamic atomization (EFDA) to fabricate core-shell monophasic particles (CSMp) from sodium alginate blends of varying molecular weights. This study explores the morphological characteristics of these particles in relation to material properties and process conditions, highlighting their potential in drug delivery applications. A key aspect of our work is the development of a mathematical model that simulates the release kinetics of small molecules, specifically sodium diclofenac. By assessing the diffusion properties of different molecules and gel formulations through transport and rheological models, we have created a predictive tool for evaluating the efficiency of these particles in drug delivery. Our findings underscore two critical, independent parameters for optimizing drug release: the external shell thickness and the diffusivity ratios within the dual layers. This allows for precise control over the timing and intensity of the release profile. This study advances our understanding of EFDA in the fabrication of CSMp and offers promising avenues for enhancing drug delivery systems by tailoring release profiles through particle characteristic manipulation. [ABSTRACT FROM AUTHOR]

This study investigated the influence of the number of nucleation sites on the evolution of the dissolved CO2 concentration of beer contained in an etched glass comprising 0 to 70 etchings. Four identically shaped glasses were studied, three etched and one non-etched. We followed the temporal evolution of the liquid (i.e., beer) and gaseous (i.e., CO2) phases of the beer for each of them. The gaseous phase is monitored by measuring the evolution of the dissolved CO2 concentration in the beer once poured into the glass. Particle image velocimetry (PIV) techniques are used to quantify the mixing dynamics of the beer during the tasting. The results show that the CO2 concentration decreases approximately 3.7 times faster in the glass with 70 etchings than in the unetched glass. This study suggests a close link between the number of nucleation sites and the release of dissolved CO2 by different mechanisms: bubble bursting, molecular diffusion, and mass convection-diffusion, the latter being increased by liquid mixing mechanisms. On the one hand, too many bubbles will bother the consumer by causing a chemical sting and will quickly deplete the beer in dissolved gas. On the other hand, too few bubbles will not allow conveying the aromas to the surface and the consumer will judge the beer as too bland and not visually flattering, hence the need to find a compromise. [ABSTRACT FROM AUTHOR]

Micromixers, as crucial components of microfluidic devices, find widespread applications in the field of biochemistry. Due to the laminar flow in microchannels, mixing is challenging, and it significantly impacts the efficiency of rapid reactions. In this study, numerical simulations of four baffle micromixer structures were carried out at different Reynolds numbers (Re = 0.1, Re = 1, Re = 10, and Re = 100) in order to investigate the flow characteristics and mixing mechanism under different structures and optimize the micromixer by varying the vertical displacement of the baffle, the rotation angle, the horizontal spacing, and the number of baffle, and by taking into account the mixing intensity and pressure drop. The results indicated that the optimal mixing efficiency was achieved when the baffle's vertical displacement was 90 μm, the baffle angle was 60°, the horizontal spacing was 130 μm, and there were 20 sets of baffles. At Re = 0.1, the mixing efficiency reached 99.4%, and, as Re increased, the mixing efficiency showed a trend of, first, decreasing and then increasing. At Re = 100, the mixing efficiency was 97.2%. Through simulation analysis of the mixing process, the structure of the baffle-type micromixer was effectively improved, contributing to enhanced fluid mixing efficiency and reaction speed. [ABSTRACT FROM AUTHOR]

The physical process in which a substance moves from a location with a higher concentration to a location with a lower concentration is known as molecular diffusion. It plays a crucial role during the mixing process between different gases in porous media. Due to the petrophysical properties of the porous medium, the diffusion process occurs slower than in bulk, and the overall process is also affected by thermodynamic conditions. The complexity of measuring gas–gas diffusion in porous media at increased pressure and temperature resulted in significant gaps in data availability for modelling this process. Therefore, correlations for ambient conditions and simplified diffusivity models have been used for modelling purposes. In this study, correlations in dependency of petrophysical and thermodynamic properties were developed based on more than 30 measurements of the molecular diffusion of the binary system hydrogen–methane in gas storage rock samples at typical subsurface conditions. It allows reproducing the laboratory observations by evaluating the bulk diffusion coefficient and the tortuosity factor with relative errors of less than 50 % with minor exceptions, leading to a strong improvement compared to existing correlations. The developed correlation was implemented in the open-source simulator DuMux and the implementation was validated by reproducing the measurement results. The validated implementation in DuMux allows to model scenarios such as Underground Hydrogen Storage (UHS) on a field-scale and, as a result, can be used to estimate the temporary loss of hydrogen into the cushion gas and the purity of withdrawn gas due to the gas–gas mixing process. Article Highlights: Development of a correlation for effective binary diffusion coefficients for the system H 2 - CH 4 in porous media Depending on petrophysical and thermodynamic properties, this correlation is valid for typical subsurface conditions Implementation of the correlation in the open-source simulator DuMux for reproduction and validation purposes [ABSTRACT FROM AUTHOR]

Contaminants stored in low-permeability soils can continue to threaten the adjacent groundwater system even after the aquifer is considered remediated. The redistribution of contaminants from low-to-high-permeability aquifer zones (Back-Diffusion) can generate a long-term plume tail, commonly considered one of the main obstacles to effective groundwater remediation. In this paper, a laboratory test was performed to reproduce the redistribution process from low-permeability silt lenses (k ≈ 1 × 10−7 m/s) to high-permeability sand aquifers (k ≈ 1 × 10−3 m/s). The target of the experimental and numerical approach was finalized to verify what influence the shape and position of the lenses could have, with respect to the bulk flow, on the time necessary to complete the depletion of the dissolved substances present in the lenses. For this purpose, an image analysis procedure was used to estimate the diffusive flux of contaminants released by these low-permeability zones in different boundary conditions. The results obtained in the laboratory test were used to calibrate a numerical model implemented to simulate the Back-Diffusion process. Once calibrated, the numerical model was used to simulate further scenarios to evaluate the influence of the location and shape of the low-permeability lenses on the time necessary to diminish its contaminant content when subjected to a steady-state flow. The numerical model was also used to investigate the effect of different groundwater velocities on the depletion time of the process. The results show that the shape and position of the lens have an important impact on the time necessary to empty the lens, and an increase in the velocity field in the bulk medium (flow rate rising from 1.6 l/h to 2.5 l/h) does not correspond to diminishing total depletion times, as the process is mainly governed by diffusive transport inside the lens. This appears to be significant when the remediation approach relies on pumping technology. Future research will verify the behavior of the released plume in a strongly heterogeneous porous medium. [ABSTRACT FROM AUTHOR]

Single-particle tracking is a powerful technique to investigate the motion of molecules or particles. Here, we review the methods for analyzing the reconstructed trajectories, a fundamental step for deciphering the underlying mechanisms driving the motion. First, we review the traditional analysis based on the mean squared displacement (MSD), highlighting the sometimes-neglected factors potentially affecting the accuracy of the results. We then report methods that exploit the distribution of parameters other than displacements, e.g., angles, velocities, and times and probabilities of reaching a target, discussing how they are more sensitive in characterizing heterogeneities and transient behaviors masked in the MSD analysis. Hidden Markov Models are also used for this purpose, and these allow for the identification of different states, their populations and the switching kinetics. Finally, we discuss a rapidly expanding field—trajectory analysis based on machine learning. Various approaches, from random forest to deep learning, are used to classify trajectory motions, which can be identified by motion models or by model-free sets of trajectory features, either previously defined or automatically identified by the algorithms. We also review free software available for some of the analysis methods. We emphasize that approaches based on a combination of the different methods, including classical statistics and machine learning, may be the way to obtain the most informative and accurate results.

Abstract Aggregation‐induced emission has eliminated the problem of fluorescence quenching in the solid state, making molecules with this property excellent candidates for vapor sensing due to their portability and ease of interpretation. Here, films of polystyrene / 2‐[4‐vinyl(1,10‐biphenyl)‐40‐yl]‐cyanovinyljulolidine copolymers are reported that exhibit aggregation‐induced emission behavior for the detection of toluene, m‐xylene, dichloromethane, and chloroform. After exposure to the analytes, the emission of the copolymers shows significant changes in intensity and spectral shape corresponding to the reduced microviscosity of the molecular environment. However, these changes are similar for different analytes, resulting in low chemical selectivity. Therefore, label‐free selectivity is achieved by controlling the molecular diffusion of the four vapor analytes within the films using the Flory–Huggins solution theory with capping layers of cellulose acetate (CA) and poly(vinyl alcohol) (PVA) polymers.

Wax deposition in crude oil pipelines is a significant challenge that escalates under turbulent flow conditions. This phenomenon is initiated by the cooling of crude oil during its conveyance, causing wax constituents to solidify and adhere to the pipeline walls via molecular diffusion. This study embarks on an investigation of the impact of fluid flow velocity on wax accumulation in pipelines transporting heavy, viscous, and wax-laden fluids, such as crude oil. A rigorous exploration of this behavior was conducted, intertwining fundamental principles from fluid dynamics, heat transfer, and mass transport. The resultant complex governing equations were tackled utilizing numerical approaches. Our findings reveal a notable trend: an acceleration in fluid flow speed prompts an increase in pipeline wax deposition. The outcomes of this study bear substantial implications for pipeline management and construction, underlining the necessity to account for flow velocity to optimize operations, minimize maintenance, and promote cost-effective transportation of heavy, viscous fluids. This research initiates a critical conversation on the role of flow velocity in wax deposition, opening avenues for future investigations and potential mitigation strategies. [ABSTRACT FROM AUTHOR]

Microfluidics evolved with the appearance of polydimethylsiloxane (PDMS), an elastomer with a short processing time and the possibility for replication on a micrometric scale. Despite the many advantages of PDMS, there are well-known drawbacks, such as the hydrophobic surface, the absorption of small molecules, the low stiffness, relatively high cost, and the difficulty of scaling up the fabrication process for industrial production, creating a need for alternative materials. One option is the use of stiffer thermoplastics, such as the cyclic olefin copolymer (COC), which can be mass produced, have lower cost and possess excellent properties. In this work, a method to fabricate COC microfluidic structures was developed. The work was divided into process optimization and evaluation of material properties for application in microfluidics. In the processing step, moulding, sealing, and liquid handling aspects were developed and optimized. The resulting COC devices were evaluated from the point of view of molecular diffusion, burst pressure, temperature resistance, and susceptibility to surface treatments and these results were compared to PDMS devices. Lastly, a target DNA hybridization assay was performed showing the potential of the COC-based microfluidic device to be used in biosensing and Lab-on-a-Chip applications. [ABSTRACT FROM AUTHOR]

The relevance of the paper is caused by the need for more knowledge of the paraffin deposit formation on the inner surface of oilfield equipment. Research experience has shown inconsistent results, which indicates the absence of a generally accepted theory illustrating the process of wax deposit formation and the influence of different factors on the intensity of its formation. In addition, the properties of paraffin deposits significantly depend on the conditions of their formation. In this way, more accurate understanding of the principles of deposit formation makes it possible to predict growth of deposits and select effective ways to deal with this complication. The main aim of the research is to consider the primary mechanisms of asphalt-resin-paraffin deposits formation and analyze the results of previous work devoted to studying the intensity factors of their formation. Objects: wax deposit formation on the inner surface of oilfield equipment and the factors of the intensity of its formation. Methods: literature review and study of publications in peer-reviewed journals; analysis and comparison of the results of previous studies. Results. The main mechanisms of asphalt-resin-paraffin deposits formation on the inner surface of oilfield equipment are described as the following: molecular diffusion, shear effect, gravity settling, Brownian motion, and thermal diffusion. A review of previous studies on assessing the contribution of these mechanisms and intensity factors (water cut, flow rate, gas/oil ratio, crude oil composition and equipment surface properties) to the formation of paraffin deposits was presented. The analysis made it possible to identify contradicting results and dependencies, confirming the need for further study of the principles of paraffin deposit formation.

The effect of the existence of nanoparticles on foam stability, foamability, and the oil recovery factor (RF) has been studied experimentally, and influential phenomena and mechanisms have been examined. A sequence of experiments, including, 'foam bulk‐static experiments', 'surface tension (ST) measurements,' and 'micromodel foam flood,' were designed and then implemented to study the foam behaviour in two foam systems: (1) anionic‐nanoparticles + cationic‐surfactant and (2) anionic‐nanoparticles + anionic‐surfactant. This study provides a comprehensive insight into the mechanisms affecting the stability of nanoparticle‐stabilized foam. Also, despite previous studies, the effect of Marangoni flow on nanoparticle‐stabilized foam has been discussed briefly. Results show that the interactions of effective mechanisms work differently in the two series. In the like‐charge system, surfactant molecules accumulate in the interface of lamellas due to repulsive forces; therefore, stability and foamability improve as surface tension and molecular diffusion reduce. Additionally, Marangoni flow restitutes the negative impact of gravity drainage. In the unlike‐charge system, observations illustrate that nanoparticles reach the interface. The presence of nanoparticles at the interface increases detachment energy significantly, and as a result, the stability is boosted. The accumulation of nanoparticles in the interface changes it to a solid‐like surface with limited diffusibility and viscosity. Although Marangoni flow is lost, reducing molecular diffusion improves foam stability. Flooding tests show that foam stability increment improves sweep efficiency at near‐wellbore areas even when foamability is weak. Finally, it can be claimed that in the unlike‐charge system, the sweep efficiency and foam stability increase to a greater extent. [ABSTRACT FROM AUTHOR]

This study investigated the diffusion impact on the chemical perturbation of NOx and O3 caused by the streamer and leader parts of a blue jet in the low stratosphere (18–30 km), using the coupling of a detailed stratospheric chemistry model and a typical diffusion model. The study found that diffusion significantly impacted the evolution of chemical perturbations at both short-term and long-term time scales after the blue jet discharge, with changes in NOx and O3 concentrations observed at different altitudes (18–28 km). At 18 km, the concentrations of NOx and N2O that account for diffusion start to decrease after 1 s, whereas those without diffusion remain at their peak concentrations. Meanwhile, O3 is slowly destroyed with less NOx, rather than dropping to an unrealistic low value immediately after the discharge without diffusion. The perturbation caused by the blue jet discharge disappears within a few tens of seconds at 18 km when molecular diffusion is considered. At 30 km, the chemical perturbation from four point sources was observed through changes in NO2 concentrations. However, the total concentration of NO2 perturbed by the streamer part discharge at the given surface was negligible when considering diffusion. Overall, this study provided a useful model tool for a more accurate assessment of the chemical effects of individual blue jets. [ABSTRACT FROM AUTHOR]

A large part of the world's hydrocarbon resources are located in fractured reservoirs, and mass transfer phenomena play a crucial role in enhanced hydrocarbon recovery from these reservoirs. Pore‐network models have been widely used to study kinetic and pore‐scale micro‐mechanisms. Molecular diffusion involves mass transfer and liquid–vapour phase change and can be simulated by a modified invasion percolation model. Despite the existence of separate pore‐scale studies on molecular diffusion and gravity drainage, no articles have been published that evaluate the combined effect of both mechanisms. This study investigates the competitive roles of the two phenomena and the effective factors controlling each mechanism with the aid of pore‐network models. According to the results obtained, gravity drainage and molecular diffusion would have a synergic effect when they are simultaneously active. Although for a single‐component liquid system, there would be a capillary holdup residual saturation in the pure gravity drainage process (between 11% and 14% for the evaluated cases) and a slow and lengthy evaporation in pure molecular diffusion (between 47% and 57% longer for the cases under study), our investigation revealed that when the two mechanisms coexist, a faster process with no residual liquid is expected. Our findings clarify that when the system is strongly gravity dominated, the liquid body remains integrated, gas–liquid contact recedes in a piston‐like manner, and three‐stage liquid desaturation is observed. Furthermore, highly clustered liquid saturation is observed in strongly capillary‐dominated systems, and the liquid desaturation curve in a capillary‐dominated model has two distinguishable stages. The competitive contribution of gravity drainage and molecular diffusion as the main driving forces of liquid extraction from a single‐block model is quantified for the entire period of desaturation. Depending on the dominance of the production mechanisms, the process is either gravity‐assisted molecular diffusion or diffusion‐assisted gravity drainage. [ABSTRACT FROM AUTHOR]

Lake Nyos, a deep crater lake, located in the north-west of Cameroon, was permanently stratified below 50 m depth due to subaquatic sources supplying warm, salty and CO2-enriched water into the deepest reaches. The high CO2 content in these source waters caused the 1986 limnic eruption. The deep inflowing water is denser than the hypolimnetic water and maintains the stability of the water column, which is double-diffusively stratified. During the dry season in Feb 2002, cooling triggered the formation of a double-diffusive (DD) staircase, a sequence of homogeneously mixed layers separated by distinct stable interfaces. The initiation of the staircase was slightly below the permanent chemocline at ~ 50 m depth, from where the staircase expanded vertically in a diffusion-type manner for ~ 750 days to a maximal vertical extension of ~ 37 m. The staircase pattern caused the upward heat fluxes to increase which depleted the driving temperature gradient. Subsequently, the density ratio increased and reduced the upward heat flux divergence until DD progressively weakened and finally the staircase structure eroded. Based on 39 CTD profiles, we describe the DD phenomenon, explain the three distinct phases of this unique DD event, which lasted for ~ 850 days, and discuss the vertical extension of the DD zone in relation to the rates of new layer formation and layer decay. To our knowledge, this is the only observation over the entire lifespan—"from birth to death"—of a DD event in a natural water body. Article highlights: Early 2000s, Lake Nyos was double-diffusively stratified and developed a staircase of up to 27 layer-interface pairs Double-diffusive layering went through three phases (build-up, steadiness, and decay) and was active for ~ 850 days Upward heat flux divergence drove formation of new layers, which was in balance with layers decay for more than one year. [ABSTRACT FROM AUTHOR]

Micromixers, as crucial components of microfluidic devices, find widespread applications in the field of biochemistry. Due to the laminar flow in microchannels, mixing is challenging, and it significantly impacts the efficiency of rapid reactions. In this study, numerical simulations of four baffle micromixer structures were carried out at different Reynolds numbers (Re = 0.1, Re = 1, Re = 10, and Re = 100) in order to investigate the flow characteristics and mixing mechanism under different structures and optimize the micromixer by varying the vertical displacement of the baffle, the rotation angle, the horizontal spacing, and the number of baffle, and by taking into account the mixing intensity and pressure drop. The results indicated that the optimal mixing efficiency was achieved when the baffle’s vertical displacement was 90 μm, the baffle angle was 60°, the horizontal spacing was 130 μm, and there were 20 sets of baffles. At Re = 0.1, the mixing efficiency reached 99.4%, and, as Re increased, the mixing efficiency showed a trend of, first, decreasing and then increasing. At Re = 100, the mixing efficiency was 97.2%. Through simulation analysis of the mixing process, the structure of the baffle-type micromixer was effectively improved, contributing to enhanced fluid mixing efficiency and reaction speed.

Innovations in drug delivery systems are crucial for enhancing therapeutic efficiency. Our research presents a novel approach based on using electro-fluid dynamic atomization (EFDA) to fabricate core-shell monophasic particles (CSMp) from sodium alginate blends of varying molecular weights. This study explores the morphological characteristics of these particles in relation to material properties and process conditions, highlighting their potential in drug delivery applications. A key aspect of our work is the development of a mathematical model that simulates the release kinetics of small molecules, specifically sodium diclofenac. By assessing the diffusion properties of different molecules and gel formulations through transport and rheological models, we have created a predictive tool for evaluating the efficiency of these particles in drug delivery. Our findings underscore two critical, independent parameters for optimizing drug release: the external shell thickness and the diffusivity ratios within the dual layers. This allows for precise control over the timing and intensity of the release profile. This study advances our understanding of EFDA in the fabrication of CSMp and offers promising avenues for enhancing drug delivery systems by tailoring release profiles through particle characteristic manipulation.

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The effectiveness of Carbon Capture and Storage (CCS) as an imperative decarbonization technology relies on the sealing capacity of a fine‐grained caprock to permanently store CO2 deep underground. Uncertainties in assessing the caprock sealing capacity increase with the spatial and temporal scales and may delay CCS deployment at the gigatonne scale. We have developed a computationally efficient transport model to capture the dynamics of basin‐wide upward CO2 migration in a multi‐layered setting over geological time scales. We find that massive capillary breakthrough and viscous flow of CO2, even through pervasively fractured caprocks, are unlikely to occur and compromise the storage security. Potential leakage from the injection reservoir is hampered by repetitive layering of overlying caprocks. This finding agrees with geologic intuition and should be understandable by the public, contributing to the development of climate policies around this technology with increased confidence that CO2 will be indefinitely contained in the subsurface. Plain Language Summary: Massive and timely deployment of Carbon Capture and Storage (CCS) at the gigatonne scale is a critical component of the majority of pathways toward reaching the Paris Agreement emissions abatement targets to mitigate climate change. Although CCS has been successfully deployed at multiple sites around the world, concerns about long‐term containment, especially for gigatonne‐scale storage, are causing uncertainty about the ability of geological layers to permanently store CO2 underground. This uncertainty is delaying the widespread deployment of CCS. This paper focuses on assessing the possibility of basin‐wide CO2 leakage through a typical multi‐layered geological setting with a sequence of aquifers and fine‐grained caprocks (e.g., shales). Numerical transport models, constrained by hydraulic properties of intact and pervasively fractured caprocks (as the best‐ and worst‐case scenarios, respectively), enable us to draw unambiguous limits on the CO2 leakage rates over previously unexplored temporal and spatial scales. We show that CO2 leakage to shallow sediments in both extreme scenarios is quite unlikely and the injected CO2 will be contained in the subsurface over millions of years. These findings should offer confidence to industrial developers, policy‐makers, investors, and most importantly, the public that CCS provides a secure and environmentally sound carbon removal option. Key Points: We develop a numerical transport model to understand the long‐term fate of CO2 in gigatonne‐scale geologic carbon storageCO2 leakage is dominated by molecular diffusion at inherently slow rates, hardly approaching a meter per several thousands of yearsThe long‐term potential for CO2 leakage from a multi‐layered system is low, making geologic storage a secure decarbonization technology [ABSTRACT FROM AUTHOR]

Due to the slow diffusion of photovoltaic molecules, in particular, small-molecule acceptors (SMAs), under light and heating, the morphology of the active layer in organic solar cells (OSCs) prefers to deviate from the favorably metastable status, leading to the challenge of stability during long-term operation. Employing materials with a high glass transition temperature ( T ) as the third component to suppress molecular diffusion is an efficient method to achieve the balance of efficiency and stability of OSCs. Herein, a dimerized small-molecule acceptor denoted as F6D is synthesized by introducing a polyfluoride moiety as the linker to enhance the g ) as the third component to suppress molecular diffusion is an efficient method to achieve the balance of efficiency and stability of OSCs. Herein, a dimerized small-molecule acceptor denoted as F6D is synthesized by introducing a polyfluoride moiety as the linker to enhance the T g . Benefitting from a rational molecular design, F6D not only exhibits a higher T g , complementary absorption, and cascade energy levels with the host materials of the polymer donor PM6 and the SMA Y6 but also has excellent miscibility and multiple intermolecular interactions with Y6. As a result, a champion power conversion efficiency of 17.52% is achieved in the optimal PM6:Y6:F6D-based device. More importantly, the ternary device exhibits superior stability under continuous heating and lighting compared with the binary device.

This paper investigates wax deposition as one of the major problems encountered in oil and gas pipelines with a potential environmental damage and with huge financial implications. A molecular diffusion and aging mechanism model by Fick’s law is applied here to better predict wax deposition thickness in crude oil pipelines. Through theoretical derivation and numerical simulation, the diffusion rate into the deposit gel has been modified by modifying the deposit layer temperature to accommodate effect of flow velocity. Findings show that the wax deposit is not uniformly distributed along the pipe length. Data were analyzed based on impact changing oil inlet temperature, volumetric flow rate, and high viscosity using MATLAB software/Simulator. On validation series model convergence was found to perform better with reasonable agreement when compared with experimental data. The result of prediction can be used to determine other parameters in the pipe line such as effective diameter, actual pressure drop and volumetric flow rate in through the pipe.

This study investigated the diffusion impact on the chemical perturbation of NOx and O3 caused by the streamer and leader parts of a blue jet in the low stratosphere (18–30 km), using the coupling of a detailed stratospheric chemistry model and a typical diffusion model. The study found that diffusion significantly impacted the evolution of chemical perturbations at both short-term and long-term time scales after the blue jet discharge, with changes in NOx and O3 concentrations observed at different altitudes (18–28 km). At 18 km, the concentrations of NOx and N2O that account for diffusion start to decrease after 1 s, whereas those without diffusion remain at their peak concentrations. Meanwhile, O3 is slowly destroyed with less NOx, rather than dropping to an unrealistic low value immediately after the discharge without diffusion. The perturbation caused by the blue jet discharge disappears within a few tens of seconds at 18 km when molecular diffusion is considered. At 30 km, the chemical perturbation from four point sources was observed through changes in NO2 concentrations. However, the total concentration of NO2 perturbed by the streamer part discharge at the given surface was negligible when considering diffusion. Overall, this study provided a useful model tool for a more accurate assessment of the chemical effects of individual blue jets.

Density fluctuations of a clot of aerosol particles in the atmosphere are studied. A one-dimensional case is considered characteristic of the motion of particles in a narrow vertical fire column or in an aircraft trail. The effect of localization of clots is shown to be observed under certain conditions, which consists in the formation of compact areas of high density of aerosol particles surrounded by areas of low density. Knowledge of such properties of impurity density can be useful in solving inverse problems of aerosol optics. [ABSTRACT FROM AUTHOR]

In this work, a new approach based on the effect of molecular diffusion on oil recovery during CO2 injection in naturally fractured reservoirs has been proposed to examine the best condition for oil recovery in the matrix block. A homogeneous matrix block from one of Iran’s naturally fractured reservoirs has been investigated. The matrix block is filled with oil and connate water surrounded by fractures filled with injection gas from the top, bottom and right side. In which matrix block oil saturation and behavior of matrix block from inside for specific time are examined simultaneously. Sensitivity analyses on the matrix block at different saturation pressures showed first the positive effect of increasing saturation pressure could be seen when diffusion was involved. Secondly, as the pressure increased, the side of recovery changed from the top to the bottom just absolutely more effective when we had diffusion in the system. Third, gravity drainage at lower saturation pressures was dominant for 2 cases with and without diffusion and at higher saturation pressures capillary force becomes more involved.

A metal spark generated by grinding carbon steel has been recognized proceeding multiple bursting events, akin to the luminous branching fireworks. The mechanism of successive fragmentation observed in carbon steel spark, however, has not been elucidated yet. In the present study, we develop a new comprehensive analytical framework for estimating the droplet size of carbon steel sparks, time of flight, and time-variant temperature, combined with high-speed images of the spreading sparks, for the quantitative discussion of the timescale of bursting metal sparks. We find that the flight time to burst for a mother droplet is independent of the content of carbon, corresponding to the Fourier number for the molecular diffusion of unity. The successive fragmentation of carbon steel sparks is rate-controlled by the molecular diffusion of ambient oxygen inside the droplet. Since the measured temperature indicates that the heat is produced by the oxidation of iron, the successive fragmentation stops when the iron in the spark is fully oxidized, immediately becoming a solid particle. [ABSTRACT FROM AUTHOR]

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Solution-processed organic electronic devices often consist of layers of polar and non-polar polymers. In addition, either of these layers could be doped with small molecular dopants. It is extremely important for device stability to understand the diffusion behavior of these molecular dopants under the thermal stress and whether the dopants have preference for the polar or the non-polar polymer layers. In this work, a widely used molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) was chosen to investigate dopant site preference upon thermal annealing between the polar thiophene poly(thiophene-3-[2-(2-methoxy-ethoxy)ethoxy]-2,5-diyl) (S-P3MEET) and non-polar thiophene poly(3-hexylthiophene) (P3HT). F4TCNQ is able to p-type dope both P3HT and S-P3MEET. Further doping studies of S-P3MEET using near edge X-ray absorption fine structure spectroscopy, conductivity measurements and atomic force microscopy show that the F4TCNQ additive competes for doping sites with the covalently attached dopants on the S-P3MEET. Calorimetry measurements reveal that the F4TCNQ interacts strongly with the side-chains of the S-P3MEET, increasing the melting temperature of the side-chains by 30 °C with 5 wt% dopant loading. Next, the thermal stability of doping in the polar/non-polar (S-P3MEET/P3HT) bilayer architectures was investigated. Steady-state absorbance and fluorescence results show that F4TCNQ binds much more strongly in S-P3MEET than P3HT and very little F4TCNQ is found in the P3HT layer after annealing. In combination with reflectometry measurements, we show that F4TCNQ remains in the SP3MEET layer with annealing to 210 °C even though the sublimation temperature for neat F4TCNQ is about 80 °C. In contrast, F4TCNQ slowly diffuses out of P3HT at room temperature. We attribute this difference in binding the F4TCNQ anion to the ability of the ethyl-oxy side-chains of the S-P3MEET to orient around the charged dopant molecule and thereby to stabilize its position. This study suggests that polar side-chains could be engineered to increase the thermal stability of molecular dopant position.

Solution-processed organic electronic devices often consist of layers of polar and non-polar polymers. In addition, either of these layers could be doped with small molecular dopants. It is extremely important for device stability to understand the diffusion behavior of these molecular dopants under the thermal stress and whether the dopants have preference for the polar or the non-polar polymer layers. In this work, a widely used molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) was chosen to investigate dopant site preference upon thermal annealing between the polar thiophene poly(thiophene-3-[2-(2-methoxy-ethoxy)ethoxy]-2,5-diyl) (S-P3MEET) and non-polar thiophene poly(3-hexylthiophene) (P3HT). F4TCNQ is able to p-type dope both P3HT and S-P3MEET. Further doping studies of S-P3MEET using near edge X-ray absorption fine structure spectroscopy, conductivity measurements and atomic force microscopy show that the F4TCNQ additive competes for doping sites with the covalently attached dopants on the S-P3MEET. Calorimetry measurements reveal that the F4TCNQ interacts strongly with the side-chains of the S-P3MEET, increasing the melting temperature of the side-chains by 30 °C with 5 wt% dopant loading. Next, the thermal stability of doping in the polar/non-polar (S-P3MEET/P3HT) bilayer architectures was investigated. Steady-state absorbance and fluorescence results show that F4TCNQ binds much more strongly in S-P3MEET than P3HT and very little F4TCNQ is found in the P3HT layer after annealing. In combination with reflectometry measurements, we show that F4TCNQ remains in the SP3MEET layer with annealing to 210 °C even though the sublimation temperature for neat F4TCNQ is about 80 °C. In contrast, F4TCNQ slowly diffuses out of P3HT at room temperature. We attribute this difference in binding the F4TCNQ anion to the ability of the ethyl-oxy side-chains of the S-P3MEET to orient around the charged dopant molecule and thereby to stabilize its position. This study suggests that polar side-chains could be engineered to increase the thermal stability of molecular dopant position.

Geologic carbon storage in deep saline aquifers has emerged as a promising technique to mitigate climate change. CO2 is buoyant at the storage conditions and tends to float over the resident brine jeopardizing long-term containment goals. Therefore, the caprock sealing capacity is of great importance and requires detailed assessment. We perform supercritical CO2 injection experiments on shaly caprock samples (intact caprock and fault zone) under representative subsurface conditions. We numerically simulate the experiments, satisfactorily reproducing the observed evolution trends. Simulation results highlight the dynamics of CO2 flow through the specimens with implications to CO2 leakage risk assessment in field practices. The large injection-induced overpressure drives CO2 in free phase into the caprock specimens. However, the relative permeability increase following the drainage path is insufficient to provoke an effective advancement of the free-phase CO2. As a result, the bulk CO2 front becomes almost immobile. This implies that the caprock sealing capacity is unlikely to be compromised by a rapid capillary breakthrough and the injected CO2 does not penetrate deep into the caprock. In the long term, the intrinsically slow molecular diffusion appears to dominate the migration of CO2 dissolved into brine. Nonetheless, the inherently tortuous nature of shaly caprock further holds back the diffusive flow, favoring safe underground storage of CO2 over geological time scales. [ABSTRACT FROM AUTHOR]

Wax deposition inside the tubing walls endures being a critical operational challenge faced by the petroleum industry. The build-up of wax deposits may lead to the increase of pumping power, as well as the decrease of flow rate or, even, to the total blockage, with production losses and high operational costs.The current paper is a critical review of the main deposition mechanisms involved in wax deposition. Most of wax deposition models regard molecular diffusion as the dominant wax deposition mechanism. However, there are other deposition mechanisms which can also play a role.As most oil fields produce water along with crude oil, the deposition process for oil-water emulsions has also been investigated. Furthermore, carbon dioxide injection effects upon wax appearance temperature along its current applications onto wells have been reviewed.Having a total awareness of the wax deposition mechanisms background is the key factor to prevent the wax precipitation and control the deposition of solid wax crystals.

In order to analyze the effect of final cooling temperature on the wax deposition laws of the crude oil modified with additives, keep the same temperature difference of oil wall and control different final cooling temperatures, static wax deposition contrast test and dynamic shear contrast test were carried out on Daqing oil with nano pour point depressant, Daqing oil with EVA pour point depressant and Daqing blank oil using the wax deposition device of agitation tank, rheometer, differential scanning calorimeter and other test instruments. Then, based on the mechanisms of molecular diffusion and gelling, the wax deposition laws of Daqing oil modified with additives under different experimental conditions were investigated. It is shown that when the final cooling temperature is lower, the blank oil is low in the total wax deposition but its wax crystal structure is stronger; while the oil with additives is significantly higher than the blank oil in the total wax deposition, but there is more condensate in the total amount of wax deposition and the wax crystal structure is weaker. With the increase of the final cooling temperature, the wax deposition in the oil with additives and that in the blank oil decrease gradually and tend to be consistent. When the final cooling temperature is lower and the shear peel strength is weaker, the addition of pour point depressant can increase the wax deposition of pipeline transportation. And once the shear is high or the final cooling temperature is increased, the wax deposition of the oil with additives will be reduced significantly and the safety of pipeline transportation will be improved.

Hierarchical zeolites are regarded as promising catalysts due to their well‐developed porosity, increased accessible surface area, and minimal diffusion constraints. Thus far, the focus has been on the creation of mesopores in zeolites, however, little is known about a microporosity upgrading and its effect on the diffusion and catalytic performance. Here the authors show that the "birth" of mesopore formation in faujasite (FAU) type zeolite starts by removing framework T atoms from the sodalite (SOD) cages followed by propagation throughout the crystals. This is evidenced by following the diffusion of xenon (Xe) in the mesoporous FAU zeolite prepared by unbiased leaching with NH4F in comparison to the pristine FAU zeolite. A new diffusion pathway for the Xe in the mesoporous zeolite is proposed. Xenon first penetrates through the opened SOD cages and then diffuses to supercages of the mesoporous zeolite. Density functional theory (DFT) calculations indicate that Xe diffusion between SOD cage and supercage occurs only in hierarchical FAU structure with defect‐contained six‐member‐ring separating these two types of cages. The catalytic performance of the mesoporous FAU zeolite further indicates that the upgraded microporosity facilitates the intracrystalline molecular traffic and increases the catalytic performance. [ABSTRACT FROM AUTHOR]

This paper investigates wax deposition as one of the major problems encountered in oil and gas pipelines with a potential environmental damage and with huge financial implications. A molecular diffusion and aging mechanism model by Fick's law is applied here to better predict wax deposition thickness in crude oil pipelines. Through theoretical derivation and numerical simulation, the diffusion rate into the deposit gel has been modified by modifying the deposit layer temperature to accommodate effect of flow velocity. Findings show that the wax deposit is not uniformly distributed along the pipe length. Data were analyzed based on impact changing oil inlet temperature, volumetric flow rate, and high viscosity using MATLAB software/Simulator. On validation series model convergence was found to perform better with reasonable agreement when compared with experimental data. The result of prediction can be used to determine other parameters in the pipe line such as effective diameter, actual pressure drop and volumetric flow rate in through the pipe. [ABSTRACT FROM AUTHOR]

An experimental investigation is performed to investigate the effect of post-processing heat treatment on the interfacial fracture toughness of bi-material additively manufactured semi-crystalline polymer composite. An asymmetric double cantilever beam (ADCB) and single-leg bending (SLB) specimens made of polylactic acid (PLA) and Nylon are considered for the mode-I and mixed-mode fracture characterization, respectively. Specimens are isothermally heated in a forced convection oven for a wide range of temperatures and durations. Fracture toughness decreases significantly for both mode-I and mixed-mode conditions when specimens are annealed below the melting temperature of PLA (150 °C). An increase of the crystallinity at the high-temperature annealing prevents the polymer chain mobility, hinders the neck growth, and provides poor intermolecular diffusion resulting in decrease of fracture toughness by 88% as compared to the unannealed specimen. Annealing at 160 °C improves the bi-material interfacial fracture toughness by a maximum of 1225% via sufficient interfacial wetting, higher molecular diffusion, and a longer polymer chain entanglement process. Material transfer, void collapse, and filament impression on the fracture surface of high temperature annealed specimen indicate a better molecular diffusion and strong interlaminar bond at the interface.