Diffusive Mass Transport Research Articles

Structuring in thin films during meniscus-guided deposition.

We theoretically study the evaporation-driven phase separation of a binary fluid mixture in a thin film deposited on a moving substrate, as occurs in meniscus-guided deposition for solution-processed materials. Our focus is on the limit of rapid substrate motion where phase separation takes place far away from the coating device. In this limit, demixing takes place under conditions mimicking those in a stationary film because substrate and film move at the same speed. We account for the hydrodynamic transport of the mixture within the lubrication approximation. In the early stages of demixing, diffusive and evaporative mass transport predominates, consistent with earlier studies on evaporation-driven spinodal decomposition. In the late-stage coarsening of the demixing process, the interplay of solvent evaporation, diffusive, and hydrodynamic mass transport results in several distinct coarsening mechanisms. The effective coarsening rate is dictated by the dominant mass transport mechanism and therefore depends on the material properties, evaporation rate, and time: slow solvent evaporation results in initially diffusive coarsening that for sufficiently strong hydrodynamic transport transitions to hydrodynamic coarsening, whereas rapid solvent evaporation can preempt and suppress hydrodynamic and diffusive coarsening. We identify a novel hydrodynamic coarsening regime for off-critical mixtures, arising from the interaction of the interfaces between solute-rich and solute-poor regions in the film with the solution-gas interface. This interaction induces a directional motion of solute-rich droplets along gradients in the film thickness, from regions where the film is relatively thick to where it is thinner. The solute-rich domains subsequently accumulate and coalesce in the thinner regions.

Influence of the Molecular Characteristics of the Solvent and the Solute Cation on Diffusive Mass Transport in Binary Electrolyte Mixtures by Dynamic Light Scattering and Molecular Dynamics Simulations

Influence of the Molecular Characteristics of the Solvent and the Solute Cation on Diffusive Mass Transport in Binary Electrolyte Mixtures by Dynamic Light Scattering and Molecular Dynamics Simulations

Theoretical analysis of water-droplet condensation and evaporation in prescribed environment with radiation

Abstract A quasi-explicit algebraic solution of the problem of quasi-steady water droplet heat- and mass-transfer with condensation or evaporation in a prescribed environment including radiation has been obtained. The solution is based on the mass-fraction form of Fick’s law of species diffusive mass transport, which allows accounting for variation in gas density through the diffusion layer surrounding the droplet. A new term, the average vapor supersaturation through the diffusion layer, has been included that allows the model to be extended to environmental conditions significantly outside those for which it is theoretically derived (dilute or near-saturation), even to conditions of relatively high temperature, low relative humidity, and low pressure. The latter two have atmospheric significance because evaporative cooling can induce significant decrease in droplet temperature and possibly induce freezing. Basic modeling assumptions are confirmed by comparison with time-dependent temperature and evaporation-rate measurements of a laboratory laser-heated droplet. Accuracy of the new model is assessed by comparison with exact equations. For temperatures between −30 and 0°C and negligible radiation, relative-error magnitudes in droplet temperature and evaporation rate are less than 5%, even for relative humidity down to 10% and pressure down to 60 kPa. This represents an improvement in accuracy over the conventional model, in which property variations of density and supersaturation through the diffusion layer are not taken into account. Differences in predicted evaporation rates between the mass-fraction and the more common partial-density Fick’s laws, which can be significant (>10% above 70% relative humidity) in coupled, implicit equations, are shown to be made negligibly small (<0.5%) by linearizing about the saturation state.

Understanding the Effects of Forced and Bubble-Induced Convection in Transport-Limited Organic Electrosynthesis

Organic electrosynthesis offers a sustainable path to decarbonize the chemical industry by integrating renewable energy in chemical manufacturing. However, achieving the selectivity and energy efficiency required for industrial applications is challenging due to the inherent mass transport limitations of most electro-organic reactions. Electrochemical reactions rely on transport of reactants to the electrode surface and become mass transport-limited when the reactant diffusion rate is lower than the reaction rate at the electrode. In organic electrosynthesis with several possible products, mass transport limitations can result in decreased selectivity towards the desired product as the various reaction pathways compete. Convection can mitigate mass transport limitations, but fundamental engineering guidelines for selecting and scaling up convection methods in electrochemical systems do not exist. As a result, the impact of convection on industrial-scale complex organic electrochemical processes remain poorly understood. Here we show that the Sherwood number (Sh)—the ratio of convective mass transport to diffusive mass transport—is a crucial metric to characterize mass transport, determine reactor performance, and enable effective scale-up. We investigate the interplay between mass transport and electrochemical reaction rates under convective flows in the context of the electrosynthesis of adiponitrile, one of the largest organic electrochemical processes in the industry. We use experiments and data-driven predictive models to demonstrate that forced liquid convection and bubble-induced convection produce nearly equivalent mass transport conditions when the corresponding Sherwood numbers are equal. This conclusion shows that the Sherwood number characterizes the mass transport condition independent of the underlying convection mechanism. Additionally, we show that the reactor performance scales with the Sherwood number for a given current density and reactant concentration. This scaling enables accurate prediction of performance irrespective of the convection method, and demonstrates that adiponitrile Faradaic efficiencies of >80% can be achieved for current densities of up to 200 mA/cm2 when Sh > 100. Our results provide guidelines for the design and selection of convection methods, from lab to industrial scale, and contribute to the development of more sustainable chemical manufacturing processes.

Removing 65 Years of Approximation in Rotating Ring Disk Electrode Theory with Physics-Informed Neural Networks.

The rotating Ring Disk Electrode (RRDE), since its introduction in 1959 by Frumkin and Nekrasov, has become indispensable with diverse applications in electrochemistry, catalysis, and material science. The collection efficiency () is an important parameter extracted from the ring and disk currents of the RRDE, providing valuable information about reaction mechanism, kinetics, and pathways. The theoretical prediction of is a challenging task: requiring solution of the complete convective diffusion mass transport equation with complex velocity profiles. Previous efforts, including by Albery and Bruckenstein who developed the most widely used analytical equations, heavily relied on approximations by removing radial diffusion and using approximate velocity profiles. 65 years after the introduction of RRDE, we employ a physics-informed neural network to solve the complete convective diffusion mass transport equation, to reveal the formerly neglected edge effects and velocity corrections on , and to provide a guideline where conventional approximation is applicable.

Molecular Electrocatalysis under Finite Diffusive Mass Transport Conditions. An Analytical Approach

AbstractMolecular electrocatalysis has emerged as a crucial branch of molecular electrochemistry, finding applications across various fields such as energy generation, electroanalysis, and electrosynthesis. In recent years, the study of these processes within confined spatial domains, has been increasingly frequent. However, a significant gap exists in the theoretical understanding of the interplay between different kinetics (redox and chemical) and mass transport under these conditions, and how their combined effects influence the electrochemical response. As a first step to address the aforementioned gap, this manuscript presents a theoretical expression for the current‐potential‐time response of a catalytic reaction occurring under finite diffusive conditions. The results indicate that, when the chemical kinetics is not fast, there are significant differences in electrochemical responses due to mass transport influences. Thus, in the case of bounded finite diffusion, a loss of efficiency in the process is observed, resulting in lower currents compared to those corresponding to semi‐infinite diffusive conditions. The validity of well‐known methods, such as the analysis of the current plateau or the foot of the wave under stationary conditions, is discussed. Experimental validation of these results is also provided through the study of the oxidation of Solketal mediated by the oxidation of TEMPO radical.

Morphological and Dimensional Evolution of Nanosized Amorphous Silicon Nitride in α-Fe: Diffusional and Elastic Effects

We present a detailed analysis based on both experimental and 3D modelling approaches of the unique silicon nitride precipitation sequence observed in ferritic Fe-Si alloys upon nitriding. At 570 °C, Si3N4 silicon nitride was shown to form as an amorphous phase into α-Fe ferrite matrix, which is morphologically unstable over time. Precipitates nucleated with a spheroidal shape, then developed a cuboidal shape for intermediate sizes and octapod-like morphology for a longer time. Using transmission electron microscopy, we show that the transition between spheroid and cuboid morphology depended on particle size and resulted from competition between interfacial energy and elastic strain energy. The resulting morphology was then shown to be a cuboid shape whose faces were always parallel to the {100} planes of the α-Fe; the <100> directions of the matrix corresponded to the elastically soft directions. There was a critical size of around 45 nm for which the transition between the cuboid shape and the octapod-like morphology took place. This was characterised by a transformation of quasi-flat facets into concave ones and the development of lobes in the <111> directions of the bcc crystal. To better assess the kinetic effects of diffusion fields and internal stresses on the morphological instability observed, an original 3D model that explicitly coupled phase transformations and mechanical fields was developed and applied. The latter, validated on the basis of model cases, was shown to be able to describe the time-evolution of both chemical and mechanical fields and their interactions in diffusive mass transport. Using a model system, it was shown that the concentration field around the precipitates and the internal stresses played opposing roles in the cuboid to octapod-like morphological instability. This work gives some clarification regarding the morphological evolution of amorphous Si3N4 precipitates, an important point for controlling the mechanical properties of nitrogen steels.

Microscale advection governs microbial growth and oxygen consumption in macroporous aggregates.

Most microbial life on Earth is found in localized microenvironments that collectively exert a crucial role in maintaining ecosystem health and influencing global biogeochemical cycles. In many habitats such as biofilms in aquatic systems, bacterial flocs in activated sludge, periphyton mats, or particles sinking in the ocean, these microenvironments experience sporadic or continuous flow. Depending on their microscale structure, pores and channels through the microenvironments permit localized flow that shifts the relative importance of diffusive and advective mass transport. How this flow alters nutrient supply, facilitates waste removal, drives the emergence of different microbial niches, and impacts the overall function of the microenvironments remains unclear. Here, we quantify how pores through microenvironments that permit flow can elevate nutrient supply to the resident bacterial community using a microfluidic experimental system and gain further insights from coupled population-based and computational fluid dynamics simulations. We find that the microscale structure determines the relative contribution of advection vs diffusion, and even a modest flow through a pore in the range of 10 µm s-1 can increase the carrying capacity of a microenvironment by 10%. Recognizing the fundamental role that microbial hotspots play in the Earth system, developing frameworks that predict how their heterogeneous morphology and potential interstitial flows change microbial function and collectively alter global scale fluxes is critical.IMPORTANCEMicrobial life is a key driver of global biogeochemical cycles. Similar to the distribution of humans on Earth, they are often not homogeneously distributed in nature but occur in dense clusters that resemble microbial cities. Within and around these clusters, diffusion is often assumed as the sole mass-transfer process that dictates nutrient supply and waste removal. In many natural and engineered systems such as biofilms in aquatic environments, aggregates in bioremediation, or flocs in wastewater treatment plants, these clusters are exposed to flow that elevates mass transfer, a process that is often overlooked. In this study, we show that advective fluxes can increase the local growth of bacteria in a single microenvironment by up to 50% and shape their metabolism by disrupting localized anoxia or supplying nutrients at different rates. Collectively, advection-enhanced mass transport may thus regulate important biogeochemical transformations in both natural and engineered environments.

Oxidation Mechanism and Surface Characterization of Pyrolytic Graphite in Simulated Air for Pyrochemical Reprocessing Application

Accidental air ingress into the containment chamber of pyrochemical reprocessing of spent nuclear fuels can cause severe oxidation of graphite components. Pyrolytic graphite (PyG) coating on conventional high-density graphite (HDG) is proposed for protection against oxidation, molten salt, and molten metal corrosion. The aim of the present study is to evaluate the thermal stability and kinetic parameters and propose a suitable oxidation mechanism of PyG under simulated air using thermogravimetry analysis (TGA). In dynamic oxidation, a linear increase in the oxidation onset, peak, and burnout temperature is observed for PyG synthesized at increasing pyrolysis temperature from 1200 to 2400°C except for 1400°C. The isothermal oxidation study showed a similar trend i.e., a decrease in the linear oxidation rate constant value for any given isotherm with increasing pyrolysis. The Arrhenius plot showed two-stage oxidation regimes operating between 600 to 1000°C. In regime-I, between 600 to ∼800°C controlled by surface chemical reaction kinetics, the activation energy is measured between 100-200 kJ.mol−1. The graphite-oxygen reaction initiates and propagates preferentially along the prismatic planes at the sample edges, where the dangling bonds of stacked graphite layer structures are exposed. In regime-II operating above ∼800°C, the surface reaction rate is infinitely faster, and the diffusional mass transport becomes a rate-limiting factor. In this regime, the graphite-oxygen initiates by pore formation on defective reactive sites on the bulk surface and propagates by pore-widening and pore-coalescence mechanism. The observed differences in the oxidation rates for different pyrolysis PyG attributed to its intrinsic material properties are investigated. This work provides new insights into the oxidation mechanism of the PyG during accidental air ingress in a pyrochemical reprocessing plant.

Alkylaromatic mass transport – acidity properties correlation for commercial and mesostructured Y zeolites with the catalytic behavior of cracking reactions

A strategy to mitigate diffusion restrictions associated with heavy crude oil conversions is using mesostructured Y zeolite. In recent years, multiple routes have been proposed for obtaining materials with improved catalytic performance versus catalysts with higher molecular transport restrictions. Typically, after the implementation of these treatments, improvement in catalytic activity is correlated either with changes in textural properties (area and porous volume) or the modification of physicochemical properties (Si/Al ratio and acid strength); however, the correlation with diffusional mass transport characteristics is not typical. In this study, alkylaromatic molecules of different kinetic diameters, such as benzene, toluene, p–xylene, and m–xylene, were used as molecule probes to determine the effective diffusion through a pulse experiment under conditions of no adsorption or reaction. The studied solids include five commercial zeolites from the Zeolyst CBV series and four top–down mesostructured Y zeolites. The obtained concentration curves were fitted to an exponential decay model, a solution of the second Fick's law under defined experimental conditions, and correlation values between 0.9996 > R2 > 0.9896 were found. Furthermore, the implementation of the descriptors “Transport ratio (TRMR)” and “Corrected transport ratio (TRMRc)” was proposed, which allowed the combined representation of the change in the mass transport of aromatic probes and the changes in the acidity of the zeolite, after the application of top–down treatments. These descriptors proved simple and effective tools to correlate the changes after mesopore insertion with the catalytic performance in the 1,3,5–Triisopropylbenzene (TIPB) cracking reaction. Our approach is an integral method of screening mesostructured zeolites with an adequate balance of acidity and transport properties.

Measurement of binary diffusion at elevated Knudsen numbers using laser absorption spectroscopy

Mass diffusion coefficients of gas mixtures have been measured for more than 100 years. However, the experimental data for the mass diffusion coefficient of gas mixtures in the rarefied gas regimes at Knudsen numbers (Kn) above 0.01 are few and remain uncertain due to the inherent precision limitations of the available state-of-the-art measurement techniques. The increased frequency of gas-wall collision, wall-friction, and surface-diffusion over the wall surface at Kn > 0.01 increases the uncertainty of the diffusive mass transport processes for internal gas flow in microcapillaries. Due to the growing interest in microfluidic applications at rarefied gas conditions, accurate diffusion coefficient measurements are needed to inform theoretical predictions and empirical relations in rarefied gas regimes. Thus, this article introduces a new experiment methodology consisting of a two-bulb (TB) diffusion configuration accompanied by a tunable diode laser absorption spectroscopy (TDLAS) detection technique that uses the measured time history of path-integrated absorbance to provide a non-intrusive, species-specific, in situ measurement of mass diffusion for a He–CO2 binary gas mixture at Kn > 0.01. To demonstrate the TB-TDLAS method's capability, the effective diffusion coefficient for a He–CO2 binary gas mixture was measured in the transition gas regime at Knudsen numbers relative to the tube radius in the range 0.1 < Kn < 5.4, and the results are compared against the Bosanquet empirical relation.

The Elder Problem with Reactive Infiltration Effects

The occurrence of buoyancy-driven flow and reactive solute transport in a fluid-saturated porous medium can be induced by either natural processes or human activities. Typical examples include the groundwater salinization in carbonate-rock aquifers and the acid treatment of oil wells in petroleum drilling industry. In this paper, the classical Elder problem of buoyancy-driven convection in two-dimensional porous media is extended to include the local chemical interactions between the solute in the pore liquid (e.g. salt such as NaCl or acids such as HCl and HCl/HF mixtures) and the solid space of the porous medium (e.g. minerals such as calcite and dolomite). Effects of the geochemical processes on the flow and mass transport are investigated. For the reactive, strongly solute-driven case in the regime dominated by the diffusive mass transport, a decrease in the net solute concentration is found as compared to the non-reactive case. This decrease is pronounced at higher values of the Damköhler number when the solute reaction rate becomes larger than the solute diffusion rate. Furthermore, the flow structure is affected by products generated by the chemical reaction when the Rayleigh number for the products is sufficiently high. In that case, numerical simulations show the formation of diluted fluid tongues exhibiting damped periodic oscillations about a nonzero mean. The results are obtained using the pseudospectral numerical method, verified against the analytical solution for the non-reactive, purely diffusive case.

Abnormal Grain Growth: A Spontaneous Activation of Competing Grain Rotation

Unconventional white‐beam Laue synchrotron X‐ray diffraction is used on fine‐grained, as‐rolled magnesium alloy during an in situ heating experiment. At high temperatures, reflections of single grains are superimposed on the halo stemming from matrix grains. Some unique grain reflections spontaneously move, indicating grain rotations in response to torque expedited at grain boundaries. When a grain boundary spontaneously activates, it can begin to rotate, allowing diffusive mass transport and activating the boundaries of its other neighbors. Now the given grain can freely rotate toward coalescence; however, the multitude of grain boundaries compete in torque orientation and magnitude, resulting in zigzag rotations. After coalescence, the larger grain is still active and continues this scenario of growth, while the majority of the matrix grains remain inactive. The first‐time experimental observation of such erratic grain behavior supplies the missing puzzlestone leading to anomalous grain growth, long postulated in literature. The method of white beam Laue diffraction on fine‐grained polycrystalline materials delivers a novel experimental method to study the erratic behavior of grain reorientation, as requested long ago by the scientific community. Such findings apply to wide ranges of materials undergoing grain growth, creep, and superplasticity, including those in metal engineering, ceramics, and geophysical disciplines.

(Invited) Electrifying Nitrogen Transformations: Decarbonizing Ammonia Using Plasma Catalysis and Electrochemical Reduction of Nitrate in Wastewaters

Nitrogen fixation in fertilizers forms the basis of modern agriculture and mediates global food insecurity. Energy-dense nitrogen-based compounds also represent promising carbon-free alternative fuels when synthesized using sustainable energy and materials. However, conventional thermally-activated nitrogen conversion processes consume substantial amounts of fossil fuels as materials and energy inputs, leading to an unsustainable energy and carbon footprint. Therefore, electron-driven approaches are needed to establish fossil-free nitrogen interconversions. Electrochemical and plasma-activated reactions operate under mild conditions, enabling facile coupling to intermittent renewable energy sources to reduce CO2 emissions and reactive nitrogen pollution, facilitating storage and transportation of renewable energy in nitrogen-based fuels.Non-thermal plasma has been used to synthesize ammonia under mild conditions, but the dearth of fundamental understanding of plasma catalytic reactions handicaps the development of efficient plasma catalytic N2 conversion. Therefore, an in situ FTIR reactor was employed in combination with steady-state flow reactor experiments and plasma kinetic modeling to elucidate the surface reaction mechanisms and plasma-catalyst interactions. Ammonia yield can be influenced by plasma-derived intermediates and their interactions with catalyst surfaces, which lead to different reaction pathways. Furthermore, techno-economic analysis was employed to reveal the threshold efficiency required for a plasma process to become environmentally and economically competitive.Beyond electrification of N2 fixation for ammonia synthesis, existing waste streams containing fixed nitrogen as nitrate may be mined for fertilizer or carbon-free renewable energy storage while avoiding the need for H2 as a reagent, via selective nitrate electroreduction to ammonium. Nitrate electrochemical reduction can eliminate the production of concentrated waste streams while avoiding the addition of reductant or hole scavenger chemicals. However, major challenges for nitrate removal from water via electrochemical conversion involve reducing the use of expensive precious metal electrocatalysts while also improving the reaction activity and selectivity, stability, and mass transport of nitrate to electrocatalyst active sites. Therefore, electrochemical membranes were employed as porous flow-through electrodes to address these challenges based on improved mass transport and altered kinetics under flow conditions within membrane pores.Conductive electrified membranes, fabricated using inexpensive materials and green synthesis methods, showed significantly higher nitrate removal efficiency during electrified filtration compared to flow-by mode. The small pore sizes in the membrane reduced the diffusional boundary layer by several orders of magnitude with respect to flow-by mode, overcoming diffusional mass transport limitations. During electro-filtration, the nitrate conversion activity was easily controlled by tuning the permeate flow rate, regardless of applied potential. These multifunctional electrified membranes for reduction of nitrate in wastewaters have the potential to partially displace carbon-intensive industrially synthesized ammonia while simultaneously accomplishing water decontamination.

High temperature electromigration behavior of cobalt lines observed by in situ transmission electron microscopy

As industrial practices shift away from Cu as the initial back-end-of-line interconnect material due to size limitations, new candidate metals are being tested and characterized. Electromigration resistance is particularly important in ultra-narrow lines and an in situ study provides unique insight into the formation and progression of electromigration damage. This, in turn, helps to inform device design so that electromigration resistant circuits can be produced efficiently. In this work, the authors demonstrate an in situ transmission electron microscopy technique for electromigration analysis of Cu replacement metals in microelectronic interconnects. Using this method, candidate metal lines can be tested at high current densities, ∼5×106 A/cm2, at controllable temperatures over the range of 300–1000 °C. In this work, cobalt lines are tested in the range of the effective valence inversion temperature. The analysis examines void nucleation, growth, and migration as a function of temperature and line geometry. We find that there is a relative insensitivity of failure time to operating temperature, with samples tested between approximately 600 and 900 °C having roughly equivalent failure times. We ascribe this result to a combination of linewidth effects and a decrease in the magnitude of the effective valence approaching the inversion temperature. Failure mechanism is also not affected by temperature in this range, with the primary determining factor being the linewidth and corresponding availability of grain boundaries for diffusive mass transport. We also observe increased lifetimes of devices with uniform temperatures compared to those in which large thermal gradients exist.

An Expanded IrO2/Ti Durable Electrode for Electrochemical Degradation of Basic Red 46 Textile Dye in Both Single and Binary Mixture Solutions

The use of dimensionally stable anode (DSA) for degrading organic pollutants is of concern recently. The electrocatalytic technique can efficiently treat biodegradable organic matter like dye-containing effluent discharge. This study focuses on applying modified DSA meshed IrO2/Ti electrode for the electrochemical degradation of wastewater effluents of Basic Red 46 (BR46) textile dye using different supporting electrolytes; sodium sulfate (Na2SO4) or/and sodium chloride (NaCl). The parameters affecting the proposed electrochemical degradation process were evaluated to select the optimal operating conditions. The results revealed that using a mixture of supporting electrolyte Na2SO4 and NaCl enhanced the removal of dye color %, chemical oxygen demand (COD) %, and total organic carbon (TOC) % by 94.9%, 65.7%, and 76.0%, respectively. The UV-Vis and FT-IR spectroscopic techniques followed the degradation efficiency. FT-IR data were in good agreement with the COD, TOC, and UV-Vis measurements, confirming the high refractory performance of the BR46 dye. The redox process was performed on the surface of the modified electrode and explained via cyclic voltammetry (CV), and it showed a diffusion mass transport mechanism followed by product adsorption. The identification of the degradation products was assessed by gas chromatography–mass spectrometry (GC-MS) analysis. The electrochemical degradation and mineralization of a binary mixture of Basic Yellow (BY28) and BR46 textile dyes were also studied. It gave similar degradation and mineralization behavior to the same extent as the single dye in solutions.

The role of mixing and surface hydrophobicity on the operation of a continuous tubular slug flow crystalliser for lysozyme

Continuous crystallisation is currently seen as a more economic and efficient alternative compared to standard techniques for the purification of biopharmaceutical proteins. Despite being promising as continuous crystalliser platforms, tubular slug flow crystallisers pose their challenges due to the tendency of proteins to accumulate at solid surfaces, to form amorphous precipitates at high protein concentrations and to undergo slow diffusive mass transport. This work investigates the effect of equipment surface chemistry and physical mixing on the design and operability of a tubular slug flow crystalliser for lysozyme under laminar flow conditions (Re ∼ 1). Firstly, glass tubes with different surface functional groups, –OH or –CH3, with water contact angles between 9° and 99°, were investigated. CH3 surfaces resulted in a up to 33% delayed onset of nucleation, demonstrating lower heterogeneous nucleation rates, and therefore are better suited to prevent fouling. However, a surface chemistry-independent deposition of lysozyme was found, altering the water contact angle by up to 56°, resulting in an unstable slug flow and a reduction of the onset of nucleation by up to 11.5-fold. To achieve a stable slug flow and controlled nucleation, the surface functional groups were recovered by implementing surface-specific cleaning protocols comprising NaOH or liquid detergent. To overcome poor mixing and amorphous precipitation, a two-step mixing approach, consisting of an intermediate mixing step was developed. This novel mixing approach reduced the mixing time from > 10 min to < 10 s, allowing the achievement of an instantaneous homogeneous solution under laminar flow conditions. Overall, the findings of this study are therefore of crucial relevance to the future design and operation of tubular slug flow crystallisers as purification platforms for biopharmaceutical proteins.

Separating Convective from Diffusive Mass Transport Mechanisms in Ionic Liquids by Redox Pro-fluorescence Microscopy.

The study of electrochemical reactivity requires analytical techniques capable of probing the diffusion of reactants and products to and from electrified interfaces. Information on diffusion coefficients is often obtained indirectly by modeling current transients and cyclic voltammetry data, but such measurements lack spatial resolution and are accurate only if mass transport by convection is negligible. Detecting and accounting for adventitious convection in viscous and wet solvents, such as ionic liquids, is technically challenging. We have developed a direct, spatiotemporally resolved optical tracking of diffusion fronts which can detect and resolve convective disturbances to linear diffusion. By tracking the movement of an electrode-generated fluorophore, we demonstrate that parasitic gas evolving reactions lead to 10-fold overestimates of macroscopic diffusion coefficients. A hypothesis is put forward linking large barriers to inner-sphere redox reactions, such as hydrogen gas evolution, to the formation of cation-rich overscreening and crowding double layer structures in imidazolium-based ionic liquids.

Water Harvesting by Molecular Sieves Using Self-sustained Continuous Flow

A way of harvesting water from the air that avoids the discontinuity of the adsorption/desorption cycles is theoretically analyzed. A rectangular prism-shaped adsorbent bed is immersed in low-humidity air, at an angle to the horizontal and subject to a temperature gradient between two opposite and open faces. The other four faces of the prism remain isolated. Water is adsorbed on the adsorbent colder face, causing a density gradient in the surrounding air, parallel to the surface, that results in a self-sustained continuous air flow. On the opposite face, a self-sustained continuous air flow parallel to the surface also arises, but this time due to a temperature gradient in the air surrounding the hot bed face. In addition, its higher temperature causes the desorption of water from the adsorbent. This overall water exchange produces the enrichment of water content in one of the air streams that is crucial to produce water harvesting. The performance of Al-Fumarate, MOF-303, SAPO-34 and Zeolite 13X is tested, unveiling the key factors that increase flow rate and water concentration at the enriched phase. It has been found that the diffusive mass transport at the air-solid interphase is the bottleneck of water harvesting in continuous flow conditions. Therefore, if high concentration of water is desired, it is necessary to use porous materials with very high diffusitivities. These findings provide the foundations for the design of continuous water harvesting devices.

Sintering and deformation properties of forsterite + diopside aggregates in an electrical field

A new technique called “flash sintering” has been proposed in the field of materials science. When a compact powder of oxide material is sintered in an electrical field, densification accelerates at a certain temperature, and the sintering is completed in a shorter time at a lower temperature as compared with conventional sintering experiments. In addition, tensile deformation experiments conducted on a dense oxide body in an electrical field have shown that plastic deformation can be enhanced at lower temperatures with lower stresses, as compared with conventional deformation experiments. Fluctuations in the magnetic and electrical fields derived from outside Earth, such as solar activity, induce an electrical field inside Earth. The strength of the electrical field in Earth's mantle is still debated, but it could be up to 10−6 V/cm. Although electrical fields inside Earth may affect the deformation behavior of rocks, no experimental studies have been conducted on geomaterials to assess this effect. Therefore, based on these recent findings in materials science, we conducted sintering and deformation experiments to examine the effects of an electrical field on high-temperature mass transport. We used forsterite + diopside crystal aggregates, which are good analogs for Earth's mantle. The sintering experiments demonstrated that the relative density increases with an increasing electrical field at a constant temperature. In the deformation experiment with a constant displacement rate, the samples in an electrical field of 1000 V/cm were deformed by 4.4× lower stress than for samples not in an electrical field. These features suggest that diffusional mass transport is enhanced in an electrical field. We propose that the presence of an electrical field within Earth may accelerate the deformation of mantle materials.