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Thermal fluctuations have been shown to influence the thinning dynamics of planar thin liquid films, bringing predicted rupture times closer to experiments. Most liquid films in nature and industry are, however, non-planar. Thinning of such films not just results from the interplay between stabilizing surface tension forces and destabilizing van der Waals forces, but also from drainage due to curvature differences. This work explores the influence of thermal fluctuations on the dynamics of thin non-planar films subjected to drainage, with their dynamics governed by two parameters: the strength of thermal fluctuations, $\unicode[STIX]{x1D703}$, and the strength of drainage, $\unicode[STIX]{x1D705}$. For strong drainage ($\unicode[STIX]{x1D705}\gg \unicode[STIX]{x1D705}_{tr}$), we find that the film ruptures due to the formation of a local depression called a dimple that appears at the connection between the curved and flat parts of the film. For this dimple-dominated regime, the rupture time, $t_{r}$, solely depends on $\unicode[STIX]{x1D705}$, according to the earlier reported scaling, $t_{r}\sim \unicode[STIX]{x1D705}^{-10/7}$. By contrast, for weak drainage ($\unicode[STIX]{x1D705}\ll \unicode[STIX]{x1D705}_{tr}$), the film ruptures at a random location due to the spontaneous growth of fluctuations originating from thermal fluctuations. In this fluctuations-dominated regime, the rupture time solely depends on $\unicode[STIX]{x1D703}$ as $t_{r}\sim -(1/\unicode[STIX]{x1D714}_{max})\ln (\sqrt{2\unicode[STIX]{x1D703}})^{\unicode[STIX]{x1D6FC}}$, with $\unicode[STIX]{x1D6FC}=1.15$. This scaling is rationalized using linear stability theory, which yields $\unicode[STIX]{x1D714}_{max}$ as the growth rate of the fastest-growing wave and $\unicode[STIX]{x1D6FC}=1$. These insights on if, when and how thermal fluctuations play a role are instrumental in predicting the dynamics and rupture time of non-flat draining thin films.

This review addresses the inconsistencies in interpreting measurements of intrinsic catalyst properties using lab-scale devices. Any experiment must be analyzed in the framework of a model for which the choice and assumptions regarding the necessary parameters must be based on critical reasoning. Physical intuition about the properties of the system is required for both rigorous 3D computational and simplified analytic descriptions. Any divergence between hypothesis and characteristics of the systems affects both the investigation of intrinsic catalytic properties and the later industrial design where parameters are extrapolated outside their obtained operating range. In this work, we make an overview of the underlying physics of photocatalytic reactions, while focusing on pertinent hypothesis, and discuss the consequences for the most basic reactor designs for which guidelines and criteria are provided to meet their premise.

The initial thickness and radius of the film that forms upon close contact of two foam bubbles are known to influence the thinning dynamics and lifetime of the film. Various scalings of lifetime tr, with initial radius Rfilm and thickness ho, have been proposed in literature. In this paper, we present a hydrodynamic thin-film model that includes both surface tension, van der Waals forces, and drainage and that clarifies the various proposed scalings of lifetime. Our model equations were solved numerically for a range of Rfilm and ho as direct input parameters. Films with a large radius are found to thin locally at a dimple, while films with a small radius thin across the entire film. The observed dynamics and lifetime were interpreted by developing a simplified model that describes the early stage dimpled drainage and the late stage van der Waals thinning, using known similarity solutions. For large radii films, our simulations confirm earlier theoretical work on semi-infinite films that predicts tr∼Rfilm0h05/7. For small radii films, our numerical simulations show the opposite trend with lifetime being solely dependent on Rfilm, in fair agreement with the simplified model that predicts tr∼Rfilm10/7h00.

A key bottleneck in bioprocess development is that state-of-the-art tools used for screening of cells and optimization of cultivation conditions do not represent the conditions enforced at industrial scale. At industrial scale, cell growth is strictly controlled (“fed-batch”) to optimize the metabolites produced by the cells. In contrast, cell growth is uncontrolled (“batch”) in microwells commonly used for bioprocess development due to the difficulty to continuously supply minute amounts of nutrients to the cells in these wells over the course of the cultivation experiment. This work addresses this bottleneck through the development of a droplet-based fed-batch nanobioreactor. A key challenge addressed in this work is the implementation of the required non-steady droplet operations on chip to establish a semi-continuous nutrient supply, while keeping the chip and its operation as simple as possible. The ability to study micro-organisms under nutrient-controlled fed-batch conditions is demonstrated using the yeast Cyberlindnera (Pichia) jadinii, with the cell growth rate controlled through the glucose concentration. Given the relative ease of operation and the potential to extend its features, the presented nanobioreactor provides a solid platform technology for further development and use in the field of bioprocess development and beyond.

Transient physical disruption of cell membranes by electric pulses (or electroporation) has significance in biomedical and biological applications requiring the delivery of exogenous (bio)molecules to living cells. We demonstrate that actin networks regulate the cell membrane permeability during electroporation. Disruption of actin networks increases the uptake of membrane-impermeable molecules such as propidium iodide during electroporation. Our experiments at different temperatures ranging from 11 °C to 37 °C show that molecular uptake during electroporation increases with temperature. Furthermore, by examining the temperature-dependent kinetics of propidium iodide uptake, we infer that the activation energy barrier of electroporation is lowered when the actin networks are disrupted. Our numerical calculations of transmembrane voltage show that the reduced activation energy barrier for the cells with disrupted actin is not a consequence of the changes in transmembrane voltage associated with changes in the cell shape due to the disruption of actin, indicating that this could be due to changes in membrane mechanical properties. Our results suggest that the current theoretical models of electroporation should be advanced further by including the contributions of the cytoskeletal networks on the cell membrane permeability during the delivery of exogenous materials.

Delivery of naked DNA molecules into living cells via physical disruption of the membrane under electric pulses has potential biomedical applications ranging from gene electro-transfer, electro-chemotherapy, to gene therapy, yet the mechanisms involved in DNA transport remain vague. To investigate the mechanism of DNA translocation across the cell membrane, giant unilamellar vesicles (GUVs) were electroporated in the presence of DNA molecules keeping the size of the DNA molecules as a variable parameter. We experimentally determined the translocation efficiency for each size of the DNA molecule, to compare the results with the existing and conflicting theories of the translocation mechanism i.e. stochastic threading and bulk electrophoresis. We observed that the translocation efficiency is independent of DNA size (ranging from 25–20 000 bp, bp = base pairs), implying that DNA molecules translocate freely across the electro-pores in the lipid membrane in their native polymer conformation, as opposed to unravelling and threading through the electro-pore. Bulk electrophoretic mobility determines the relationship between translocation efficiency and the size of the DNA molecule. This research provides experimental evidence of the mechanistic understanding of DNA translocation across lipid membranes which is essential for devising efficient and predictable protocols for electric field mediated naked DNA delivery.

In industrial catalysis, the sintering of supported nanoparticles (NPs) is often associated with the loss of catalyst activity and thus with periodic plant downtime and economic burdens. Yet, sintering mechanisms are at play also during the synthesis of the catalyst itself. They can, in fact, determine the size distribution of the NPs, and thus the activity and the stability of the catalyst. Here, we examine the role of nanoparticle sintering in a technique borrowed from the semiconductor industry that promises to reconcile atomic-scale precision with scalability: atomic layer deposition. By modeling the cyclic influx of single atoms in concomitance with NP sintering via either dynamic coalescence or Ostwald ripening, we establish the “signature” of different growth regimes: the size distribution. In contrast, we show that integral quantities such as the mean diameter, the number of NPs per unit area, and the material loading are poor indicators of the underlying growth mechanism. In particular, a constant number of NPs cannot be interpreted as a sign of no sintering. Finally, we argue that NP sintering, if properly understood, can open up new avenues for the control over the size distribution of NPs, and thus over their catalytic activity and stability.

Understanding the spontaneous organization of atoms on well-defined surfaces promises to enable control over the shape and size of supported nanostructures. Atomic layer deposition (ALD) boasts atomic-scale control in the synthesis of thin films and nanoparticles. Yet, the possibility to control the shape of ALD-grown nanostructures remains mostly unexplored. Here, we report on the bottom-up formation of both linear and V-shaped anatase TiO2 nanorods (NRs) on graphene nanoplatelets during TiCl4/H2O ALD carried out at 300 °C. NRs as large as 200 nm form after only five ALD cycles, indicating that diffusional processes rather than layer-by-layer growth are behind the NR formation. In particular, high-resolution transmission electron microscopy reveals that the TiO2 NRs and graphene nanoplatelets are in rotational alignment as a result of lattice matching. Crucially, we also show that individual nanocrystals can undergo in-plane oriented attachment.

Transient permeabilisation of the cell membrane is a critical step to introduce drugs or DNA into living cells, yet challenging for both biological research and therapeutic applications. To achieve this, electroporation (or electropermeabilisation) has become a widely used method due to its simplicity to deliver almost any biomolecule to any cell type. Although this method demonstrates promise in the field of drug/gene delivery, the underlying physical mechanisms of the response of the heterogeneous cell membrane to strong electric pulses is still unknown. In this study, we have investigated the role of gel-phase lipids in the electroporation of binary giant unilamellar vesicles (GUVs), composed from DPPC (gel-phase) and DPhPC (fluid-phase) lipids (molar ratio 8:2 and 2:8). We have observed that the exposure to electric pulses leads to expel of fluid-phase lipids and concomitant decrease in GUV size, whereas the gel-phase domains become buckled. Based on experiments on pure fluid-phase and gel-phase GUVs, we have found that fluid-phase lipids can be expelled by electrical forces and the highly viscous gel-phase lipids cannot. Moreover, our analyses suggest that pore formation occurs primarily in fluid-phase domains and that the pore size is similar in all GUVs containing fluid-phase lipids, irrespective of the gel-phase percentage.

Fluidization is a technique used to process large quantities of nanopowder with no solvent waste and a large gas–solid contact area. Nonetheless, nanoparticles in the gas phase form clusters, called agglomerates, due to the relatively large adhesion forces. The dynamics within the fluidized bed influence the mechanism of formation, and thus, the morphology of the agglomerates. There are many theoretical models to predict the average size of fluidized agglomerates; however, these estimates of the average lack information on the whole size range. Here, we predict the agglomerate size distribution within the fluidized bed by estimating the mode and width using a force balance model. The model was tested for titania (TiO2), alumina (Al2O3), and silica (SiO2) nanopowders, which were studied experimentally. An in-situ method was used to record the fluidized agglomerates for size analysis and model validation.

Photocatalysts for water purification typically lack efficiency for practical applications. Here we present a multi-component (Pt:SiO2:TiO2(P25)) material that was designed using knowledge of reaction mechanisms of mono-modified catalysts (SiO2:TiO2, and Pt:TiO2) combined with the potential of atomic layer deposition (ALD). The deposition of ultrathin SiO2 layers on TiO2 nanoparticles, applying ALD in a fluidized bed reactor, demonstrated in earlier studies their beneficial effects for the photocatalytic degradation of organic pollutants due to more acidic surface Si&ndash, OH groups which benefit the generation of hydroxyl radicals. Furthermore, our investigation on the role of Pt on TiO2(P25), as an improved photocatalyst, demonstrated that suppression of charge recombination by oxygen adsorbed on the Pt particles, reacting with the separated electrons to superoxide radicals, acts as an important factor for the catalytic improvement. Combining both materials into the resulting Pt:SiO2:TiO2(P25) nanopowder exceeded the dye degradation performance of both the individual SiO2:TiO2(P25) (1.5 fold) and Pt:TiO2(P25) (4-fold) catalysts by 6-fold as compared to TiO2(P25). This approach thus shows that by understanding the individual materials&rsquo, behavior and using ALD as an appropriate deposition technique enabling control on the nano-scale, new materials can be designed and developed, further improving the photocatalytic activity. Our research demonstrates that ALD is an attractive technology to synthesize multicomponent catalysts in a precise and scalable way.

We experimentally investigate the flow of hydrolyzed polyacrylamide (HPAM) solution with and without salt in model porous media at high Weissenberg numbers (Wi > 1.0). The effect of pore shapes on the flow pattern and pressure drop is explored by using periodic arrays of circular and square pillars in aligned and staggered layouts. In the apparent shear-thinning regime, we observe stationary dead zones upstream of the pillars. In addition, we confirm that the size of stationary dead zones correlates with the level of shear-thinning, by varying the amount of salt in HPAM solution. At higher shear rates (or Wi), these dead zones are periodically washed away. We present the mechanism of this elastic instability and characterize it based on the pressure drop fluctuation spectral density.

Molecular conformations of individual polymers during flow through porous media are directly observed by single-DNA imaging in microfluidics. As the Weissenberg number increases during flow (Wi > 1), we observe two types of elastic instabilities: (a) stationary dead-zone and (b) time-dependant dead-zone washing. When stretched polymer chains enter a dead-zone, they first re-coil and, once inside the dead-zone, they rotate and re-stretch again. The probability distribution of DNA chains under the stretched condition inside the dead-zone is found to be heterogeneous with a broad distribution.

Size of DNA molecules governs their interaction with the cell membrane during electroporation and their subsequent transport inside the cell. In order to investigate the effect of DNA size on DNA-membrane interaction during electroporation, cells are electro-pulsed with DNA molecules; 15 bp, 25 bp, 50 bp, 100 bp and 1000 bp (bp = base pairs). Within the experimental parameter space, DNA-membrane complexes or DNA aggregates are observed at the cell membrane for DNA molecules containing 25 or more base pairs. No aggregates are observed for DNA molecules containing 15 bp. For all DNA sizes, direct access to the cytoplasm is observed, however the amount translocated decays with the size. The observed dependency of DNA aggregate formation on the size of the DNA molecules is consistent with the Onsager's theory of condensation of anisotropic rod-like molecules.

We show experimentally, and explain theoretically, what velocity is needed to break an elongated droplet entering a microfluidic T-junction. Our experiments on short droplets confirm previous experimental and theoretical work that shows that the critical velocity for breakup scales with the inverse of the length of the droplet raised to the fifth power. For long elongated droplets that have a length about thrice the channel width, we reveal a drastically different scaling. Taking into account that a long droplet remains squeezed between the channel walls when it enters a T-junction, such that the gutters in the corners of the channel are the main route for the continuous phase to flow around the droplet, we developed a model that explains that the critical velocity for breakup is inversely proportional to the droplet length. This model for the transition between breaking and nonbreaking droplets is in excellent agreement with our experiments.

We study the role of a biomimetic actin network during the application of electric pulses that induce electroporation or electropermeabilization, using giant unilamellar vesicles (GUVs) as a model system. The actin cortex, a subjacently attached interconnected network of actin filaments, regulates the shape and mechanical properties of the plasma membrane of mammalian cells, and is a major factor influencing the mechanical response of the cell to external physical cues. We demonstrate that the presence of an actin shell inhibits the formation of macropores in the electroporated GUVs. Additionally, experiments on the uptake of dye molecules after electroporation show that the actin network slows down the resealing process of the permeabilized membrane. We further analyze the stability of the actin network inside the GUVs exposed to high electric pulses. We find disruption of the actin layer that is likely due to the electrophoretic forces acting on the actin filaments during the permeabilization of the GUVs. Our findings on the GUVs containing a biomimetic network provide a step towards understanding the discrepancies between the electroporation mechanism of a living cell and its simplified model of the empty GUV.

Controlled diffusion, reaction and assembly of hydrogelator precursors can be used to create soft hydrogel objects of defined shape and size. In this study we show that controlling local reaction kinetics by means of pH, diffusion length and the concentrations of reactants allows control over the dimensions of formed supramolecular structures. By correlating a reaction diffusion model to experimental results, we show that the influence of all these control parameters can be unified using the Damko hler number, thus providing an easy-to-use relation between experimental parameters and structure dimensions. Finally, our study suggests that control over concentration gradients and chemical reactivity in combination with supramolecular chemistry is a promising platform for the design of soft matter objects of defined sizes, a concept that has received little attention up until now.

We describe the co-current flow pattern of gas and liquid through micro-fabricated beds of solid and pillars under variable (i) capillary number, (ii) contact angle or wettability and (iii) pillar arrangement, i.e. modifying the distance between pillars or their size and comparing regular with more chaotic systems. Laser-induced fluorescent microscopy and image analysis are used to study the hydrodynamic interactions in terms of dynamics, liquid hold-up, and gas-liquid interfacial area per reactor volume. Those parameters provide insights into the multiphase flow patterns in these systems, how to control them, maximize mass transfer rate and unlock the potential of microreactors to reveal further intrinsic information.

We study the role of a biomimetic actin cortex during the application of electric pulses that induce electroporation or electropermeabilization, using giant unilamellar vesicles (GUVs) as a model system. The actin cortex, a subjacently attached interconnected network of actin filaments, regulates the shape and mechanical properties of the plasma membrane of mammalian cells, and is a major factor influencing the mechanical response of the cell to external physical cues. We demonstrate that the presence of an actin shell inhibits the formation of macropores in the electroporated GUVs. Additionally, experiments on the uptake of dye molecules after electroporation show that the actin network slows down the resealing process of the permeabilized membrane. We further analyze the stability of the actin network inside the GUVs exposed to high electric pulses. We find disruption of the actin layer that is likely due to the electrophoretic forces acting on the actin filaments during the permeabilization of the GUVs. Our findings on the GUVs containing a biomimetic cortex provide a step towards understanding the discrepancies between the electroporation mechanism of a living cell and its simplified model of the empty GUV.

Stability of quantum dot (QD) films is an issue of concern for applications in devices such as solar cells, LEDs, and transistors. This paper analyzes and optimizes the passivation of such QD films using gas-phase deposition, resulting in enhanced stability. Crucially, we deposited alumina at economically attractive conditions, room temperature and atmospheric pressure, on (1,2-ethanediamine) capped PbSe QD films using an approach based on atomic layer deposition (ALD), with trimethylaluminum (TMA) and water as precursors. We performed coating experiments from 1 to 25 cycles on the QD films, finding that alumina formed from the first exposure of TMA. X-ray photoelectron spectroscopy points to the presence of oxygen-rich compounds on the bare QD films, most likely from entrapped solvent molecules during the assembly of the QD films. These oxygenated compounds and the amine groups of the organic ligands react with TMA in the first cycle, resulting in a fast growth of alumina. Using 10 cycles resulted in a QD film that was optically stable for at least 27 days. Depositing alumina at ambient conditions is preferred, since the production of the QD films is also carried out at room temperature and atmospheric pressure, allowing combination of both processes in a single go.

Here, we investigate separately the dependence of the mixing time on the size and velocity of micro-droplets moving through serpentine channels. We find that the mixing time scales linearly with droplet size. All experimental data collapse on a master-line, when the convective time scale is multiplied by the dimensionless droplet size.

We present a multiscale dynamic model as a means of understanding and optimizing the precursor utilization during atomic layer deposition (ALD) on nanoparticles and micron-sized nano-porous particles in fluidized bed reactors. We used as case study the deposition of alumina using trimethylaluminum and water on both, titania nanoparticles and micron-sized nano-porous γ -alumina particles under low (∼1 mbar) and atmospheric pressure. In doing so, we assess the effect of the precursor transport, from the inlet of the reactor to the particles active surface, on the precursor utilization efficiency. Our results show that, at proper operating conditions, fast ALD reaction kinetics enables the saturation of the particles surface area with hardly any loss of precursors. Finally, simple scaling rules for the optimization of the precursor utilization are proposed.

We present a numerical simulation technique to calculate the deformation of interfaces between a conductive and non-conductive fluid as well as the motion of liquid–liquid–solid three-phase contact lines under the influence of externally applied electric fields in electrowetting configuration. The technique is based on the volume of fluid method as implemented in the OpenFOAM framework, using a phase fraction parameter to track the different phases. We solve the combined electrohydrodynamic problem by coupling the equations for electric effects—Gauss’s law and a charge transport equation—to the Navier–Stokes equations of fluid flow. Specifically, we use a multi-domain approach to solving for the electric field in the solid and liquid dielectric parts of the system. A Cox–Voinov boundary condition is introduced to describe the dynamic contact angle of moving contact lines. We present several benchmark problems with analytical solutions to validate the simulation model. Subsequently, the model is used to study the dynamics of an electrowetting-based display pixel. We demonstrate good qualitative agreement between simulation results of the opening and closing of a pixel with experimental tests of the identical reference geometry.

A fundamental understanding of the interplay between ligand-removal kinetics and metal aggregation during the formation of platinum nanoparticles (NPs) in atomic layer deposition of Pt on TiO

We experimentally and theoretically describe the dynamics of evolution and eventual rupture of Landau-Levich-Bretherton films of partially wetting liquids in microchannels in terms of nonplanar interface curvatures and disjoining pressure. While both the early-stage dynamics of film evolution and near-collapse dynamics of rupture are understood, we match these regimes and find theoretically that the dimensionless rupture time, T-r, scales with kappa(-10/7). Here, kappa is the dimensionless curvature given by the ratio of the Laplace-pressure discontinuity that initiates film thinning to the initial strength of the disjoining pressure that drives the rupture. We experimentally verify the rupture times and highlight the crucial consequences of early film rupture in digital microfluidic contexts: pressure drop in segmented flow and isolation of droplets from the walls.

We tailored the size distribution of Pt nanoparticles (NPs) on graphene nanoplatelets at a given metal loading by using low-temperature atomic layer deposition carried out in a fluidized bed reactor operated at atmospheric pressure. The Pt NPs deposited at low temperature (100 °C) after 10 cycles were more active and stable towards the propene oxidation reaction than their high-temperature counterparts. Crucially, the gap in the catalytic performance was retained even after prolonged periods of time (>24 hours) at reaction temperatures as high as 450 °C. After exposure to such harsh conditions the Pt NPs deposited at 100 °C still retained a size distribution that is narrower than the one of the as-synthesized NPs obtained at 250 °C. The difference in performance correlated with the difference in the number of facet sites as estimated after the catalytic test. Our approach provides not only a viable route for the scalable synthesis of stable supported Pt NPs with tailored size distributions but also a tool for studying the structure-function relationship.

In this work, we report a method to change the surface finish of a standard polyester-based powder coating paint, from gloss to matt, by depositing ultrathin films of Al2O3 on the powder coating particles. The coating experiments were performed in a fluidized bed reactor at 1 bar and 27 °C, using a gas-phase coating process of alternating exposure of the particles to the two precursors (trimethylaluminium and water), similar to atomic layer deposition (ALD). We varied the number of coating cycles (1, 2, 3, 5, 7 and 9 cycles) to obtain film thicknesses of the alumina shell ranging from 1 to 30 nm. The average growth per cycle of the process is 3.5 nm, significantly larger than the one for pure self-limiting ALD. When the average alumina shell was thicker than 6 nm, the shell prevented the flow of the core particles, even though the powder particles did soften above the glass transition temperature. With the particles morphology intact, this resulted in a rough and matte surface finish of the coating after curing. The surface roughness, with a value around 9 μm determined by surface profilometry, is associated to the alumina coated particles as observed with SEM and EDX analysis. In addition, the matte finish coating showed mechanical resistance similar to that of uncoated powder particles.

This paper provides a simple criterion to determine when the performance of an unmixed photocatalytic slurry reactor becomes limited by diffusion. We use a 1D description of the reactor and the two-flux intensity model to describe the concentration profile in unmixed photoreactors. We show that the effect of diffusion limitation in optically thick photoreactors is negligible when the Dahmkohler number based on reactor length is smaller than 0.1 τ γ , where τ is the optical thickness and γ is the exponent that describes how the reaction rate varies with light intensity. For optically thin reactors, in contrast, we find that the maximum Dahmkohler number scales with the inverse of τ γ .

This paper reports an analysis of the parallelized production of bubbles in a microreactor based on the repeated break-up of bubbles at T-junctions linked in series. We address the question how to design and operate such a multi-junction device for the even distribution of bubbles over the exit channels. We study the influence of the three primary sources leading to the uneven distribution of bubbles: (1) nonuniformity in the size of bubbles fed to the distributor, (2) lack of bubble break-up, and (3) asymmetric bubble breakup caused by asymmetries in flow due to fabrication tolerances. Based on our theoretical and experimental analysis, we formulate two guidelines to operate the multi-junction bubble distributor. The device should be operated such that: (i) the capillary number exceeds a critical value at all junctions, Ca > Ca crit , to ensure that all bubbles break, and (ii) the parameter ( l s / w ) · Ca 1/3 is sufficiently large, with l s / w the distance between the bubbles normalized by the channel width. More quantitatively, ( l s / w ) · Ca 1/3 > 2 for fabrication tolerances below 2%, which are typical for devices made by soft lithography. Furthermore, we address the question whether including a bypass channel around the T-junctions reduces flow asymmetries and corresponding nonuniformities in bubble size. While bubble nonuniformities in devices with and without bypass channels are comparable for fabrication tolerances of a few percent, we find that incorporating a bypass channels does have a beneficial effect for larger fabrication tolerances. The results presented in this paper facilitate the scale-out of bubble-based microreactors.

We present an extensive analysis of the performance of the Volume of Fluid (VOF) method, as implemented in OpenFOAM, in modeling the flow of confined bubbles and droplets (“segmented flows”) in microfluidics. A criterion for having a sufficient grid solution to capture the thin lubricating film surrounding non-wetting bubbles or droplets, and the precise moment of breakup or coalescence is provided. We analyze and propose optimal computational settings to obtain a sharp fluid interface and small parasitic currents. To show the usability of our computational rules, numerical simulations are presented for three benchmark cases, viz. the steady motion of bubbles in a straight two-dimensional channel, the formation of bubbles in two- and three-dimensional T-junctions, and the breakup of droplets in three-dimensional T-junctions. An error analysis on the accuracy of the computations is presented to probe the efficacy of the VOF method. The results are in good agreement with published experimental data and experimentally-validated analytical solutions.

This paper provides a simple guideline to quantify at what gas fraction and bubble diameter bubbles start having a considerable effect on the performance of a bubbly slurry photocatalytic reactor. The local rate of photon absorption, responsible for local photoreaction rate, is affected in the presence of bubbles, as bubbles scatter the photons in all directions. Here, we consider a simple 1D description of a photoreactor, and implement a bidirectional scattering model for photocatalytic particles and bubbles to set up photon balances in the photoreactor. Both low and high light intensities are considered, with a linear and square root dependence of reaction rate on the local volumetric rate of photon absorption, respectively. The photon balances, coupled with component balances, lead to a closed-form expression for the critical gas fraction that causes a 5% deviation in the photoreaction rate, when compared to an ungassed reactor with the same amount of catalyst per unit reactor volume. We further show that in typical bubbly slurry photoreactors, with gas fractions smaller than 20% and bubble sizes of about 3 mm, the effect of bubbles on the rate of photon absorption and photoreaction is negligible. Moreover, the overall efficiencies are calculated at different gas fractions and bubble diameters. Other operational aspects of three-phase photoreactors are calculated and briefly discussed. The general conclusion is that the distribution of light inside a photoreactor is hardly affected by the presence of bubbles.

In this paper we investigate the stabilizing effect of pre-deforming the flow of a PEO/PEG Boger fluid before entering a microfabricated 83:1:83 planar contraction–expansion. Applying pre-deformation has a dramatic effect on the size and stability of the recirculation zones upstream of the contraction. This pre-deformation is generated by a cylinder placed in front of the contraction. Transverse flow past an unbounded cylinder is a combination of both shear and elongational flow, at the cylinder walls and the downstream wake respectively. The deformation of the polymer by the shear and elongational flow temporarily changes the rheological properties of the solution before it relaxes back to the original state. Deformation rates up to γ ˙ of 12000 s−1 are attained in the microfluidic device, resulting in the following ranges of dimensionless numbers for experiments performed: 0.003 16). Pre-deforming the flow is found to reduce vortex length up to 20% and to reduce the divergence of streamlines and vortex growth with increasing Weissenberg number significantly.

Micromodels have been increasingly employed in various ways in porous media research, to study the pore-scale behavior of fluids. Micromodels have proven to be a valuable tool by allowing the observation of flow and transport at the micron scale in chemical, biological, and physical applications. They have helped to improve our insight of flow and transport phenomena at both microscale and macroscale. Up to now, most micromodels that have been used to study the role of interfaces in two-phase flow were small, square, or nearly square domains. In this work, an elongated PDMS micromodel, bearing a flow network with dimensions 5×30 mm2 was manufactured. The pore network was designed such that the REV size was around 5×7 mm2. So, our flow network was considered to be nearly four times the REV size. Using such micromodels, we established that the inclusion of interfacial area between the wetting and the nonwetting fluids models the hysteretic relationship between capillary pressure and saturation in porous media. In this paper, we first present the procedure for manufacturing PDMS micromodels with the use of soft lithography. Then, we describe an innovative and novel optical setup that allows the real-time visualization of elongated samples. Finally, we present the results obtained by quasi-static, two-phase flow experiments.

We present an atomistic understanding of the evolution of the size distribution with temperature and number of cycles in atomic layer deposition (ALD) of Pt nanoparticles (NPs). Atomistic modeling of our experiments teaches us that the NPs grow mostly via NP diffusion and coalescence rather than through single-atom processes such as precursor chemisorption, atom attachment, and Ostwald ripening. In particular, our analysis shows that the NP aggregation takes place during the oxygen half-reaction and that the NP mobility exhibits a size- and temperature-dependent scaling. Finally, we show that contrary to what has been widely reported, in general, one cannot simply control the NP size by the number of cycles alone. Instead, while the amount of Pt deposited can be precisely controlled over a wide range of temperatures, ALD-like precision over the NP size requires low deposition temperatures (e.g., T < 100 °C) when growth is dominated by atom attachment.

We report the continuous production of microcapsules composed of an aqueous core and permeable hydrogel shell, made stable by the controlled photo-cross-linking of the shell of an all-aqueous double emulsion. While most previous work on water-based emulsions focused on active droplet formation, here double emulsion droplets were spontaneously generated at a three-dimensional flow-focusing junction through the break-up of a double jet formed by immiscible aqueous solutions of polyethylene glycol and cross-linkable dextrans. The capsules obtained with this lipid-free, organic-solvent-free, and surfactant-free approach displayed excellent stability under a variety of harsh conditions (3

The impact of two strategies to enhance the mass transfer of hydrophobic compounds, Taylor flow (or segmented flow) and the addition of an organic transfer vector (silicone oil), were investigated under abiotic and biotic conditions in a capillary bioreactor. The capillary bioreactor consisted of a capillary column (where Taylor flow was produced in a gas/liquid flow) and a gas–liquid separator at the outlet of the capillary column which was operated as a stirred tank with superficial aeration. It was shown that the system was limited by mass transfer and not by the biological reaction. Taylor flow in the capillary resulted in an increase of up to two orders of magnitude for the volumetric oxygen transfer coefficient (kLa) when compared to the coefficient for the gas–liquid separator, or values previously obtained in other turbulent contactors. The bioconversion rates of methane in the capillary column where found to be significantly higher than for conventional systems. Silicone oil addition increased kLa up to 38% in the gas–liquid separator, but reduced it with 38% in the capillary. Contrary to observations during abiotic kLa determinations, silicone oil addition increased the CH4 removal and O2 consumption by the methanotrophic consortium in both, gas–liquid separator and capillary. Increased gas flow rate gave an 19% increase in methane removal in the capillary bioreactor, an additional increase of 8% was obtained adding 5% of silicone oil at the same flow, while an additional increase of 47% was obtained adding 10% of silicone oil at the same flow with inoculum pre-adapted to transfer vector. The contribution of the capillary channel to the overall methane removal in the system was high considering that the volume of this channel was just 0.64% of the total volume in the bioreactor, indicating a good potential of further optimization of the reactor system.

Efficient nanopowder processing requires knowledge of the powder’s mechanical properties. Due to the large surface area to volume ratio, nanoparticles experience relatively strong attractive interactions, leading to the formation of micron-size porous structures called agglomerates. Significant effort has been directed towards the development of models and experimental procedures to estimate the elasticity of porous objects such as nanoparticle agglomerates; however, none of the existing models has been validated for solid fractions below 0.1. Here, we measure the elasticity of titania (TiO\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_2$$\end{document}2, 22 nm), alumina (Al\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_2$$\end{document}2O\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_3$$\end{document}3, 8 nm), and silica (SiO\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$_2$$\end{document}2, 16 nm) nanopowder agglomerates by Atomic Force Microscopy, using a 3.75 \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\upmu$$\end{document}μm glass colloid for the stress–strain experiments. Three sample preparations with varying degree of powder manipulation are assessed. The measured Young’s moduli are in the same order of magnitude as those predicted by the model of Kendall et al., thus validating it for the estimation of the Young’s modulus of structures with porosity above 90 %. Electronic supplementary material The online version of this article (doi:10.1007/s11051-016-3500-4) contains supplementary material, which is available to authorized users.

" We give guidelines, based on two-flux model, to study kinetics and efficiency. " To determine the quantum efficiency, an optically thick photoreactor is needed. " This means an optical thickness >3.5 for low and >6.5 for high photon fluxes. " To reliably determine kinetics, an optically differential photoreactor is needed. " An optically differential operation is ensured with an optical thickness

The mechanistic interpretation of the catalytic effect of phase transfer catalysts in the selective oxidation of ethyl benzene is hampered by mass transfer effects. We demonstrate that proper experiments lead to a more correct interpretation of the role of the quaternary ammonium salt (QAS) and its counterion. Specifically, experiments unequivocally show that the main action of the counterion is to enhance physical mass transfer processes, while its catalytic effect is limited to a shift in selectivity, not activity. The QAS as a whole accelerates the induction process in the ethyl benzene (EB) oxidation by degenerate branching of its hydroperoxide (EBHP). Proper mechanistic understanding of these phenomena in QAS catalysts is especially crucial under industrially relevant conditions

This paper presents a method to form micron-sized droplets in an aqueous two-phase system (ATPS) and to subsequently polymerize the droplets to produce hydrogel beads. Owing to the low interfacial tension in ATPS, droplets do not easily form spontaneously. We enforce the formation of drops by perturbing an otherwise stable jet that forms at the junction where the two aqueous streams meet. This is done by actuating a piezo-electric bending disc integrated in our device. The influence of forcing amplitude and frequency on jet breakup is described and related to the size of monodisperse droplets with a diameter in the range between 30 and 60 μm. Rapid on-chip polymerization of derivatized dextran inside the droplets created monodisperse hydrogel particles. This work shows how droplet-based microfluidics can be used in all-aqueous, surfactant-free, organic-solvent-free biocompatible two-phase environment.

The influence of hydrogen pressure on the performance of a γ -alumina-supported palladium catalyst was studied for the multiphase selective hydrogenation of benzonitrile to benzylamine and byproducts. Semi-batch experiments of benzonitrile hydrogenation in 2-propanol were performed with hydrogen pressures between 2.5 and 30 bar, at a constant temperature of 80 °C. The intrinsic property of palladium to absorb hydrogen into its lattice structure has a strong influence on activity and selectivity. The transformation to stable palladium β -hydride above a threshold hydrogen pressure of 10 bar induces a persistent change in turnover frequency and byproduct selectivity. The turnover frequency increases from 0.32 s −1 to a maximum of 0.75 s −1 at this threshold pressure and decreases to 0.25 s −1 with increasing hydrogen pressure. The palladium β -hydride phase suppresses the hydrogenolysis to toluene changing the selectivity from 6.5% to 2.0% and increasing the selectivity of the condensation to dibenzylamine from 1.6% to 2.7%, attributed to modified electronic interactions between catalyst and substrates. The selectivity to the desired product benzylamine is always high and increases with hydrogen pressure from 92.7% to 95.3%. The palladium catalyst state is mainly determined by the activation or operational hydrogen pressure, whichever was the highest, if the activation pressure was above 10 bar.

A fundamental understanding of the interplay between ligand-removal kinetics and metal aggregation during the formation of platinum nanoparticles (NPs) in atomic layer deposition of Pt on TiO2 nanopowder using trimethyl(methylcyclo-pentadienyl)platinum(IV) as the precursor and O2 as the coreactant is presented. The growth follows a pathway from single atoms to NPs as a function of the oxygen exposure (PO2 × time). The growth kinetics is modeled by accounting for the autocatalytic combustion of the precursor ligands via a variant of the Finke–Watzky two-step model. Even at relatively high oxygen exposures (> 120 mbar s. The deposition of more Pt leads to the formation of NPs that can be as large as 6 nm. Crucially, high PO2 (≥5 mbar) hinders metal aggregation, thus leading to narrow particle size distributions. The results show that ALD of Pt NPs is reproducible across small and large surface areas if the precursor ligands are removed at high PO2.

The influence of the concentration and nature of weakly bound capping agents on the catalytic activity and selectivity of gold nanoparticles is explored in the selective liquid phase oxidation of benzyl alcohol with oxygen and complemented with a detailed XPS analysis. Two nitrogen-based capping agents, dodecylamine (DDA) and poly(vinyl-pyrrolidone) (PVP) and different gold catalysts (supported and unsupported gold nanoparticles, a reference gold catalyst with and without exposure to capping agents) have been used. The colloid nanoparticle-based catalyst exhibits a high activity at mild conditions (TOF = ∼10 4 h −1 at 353 K in air). The interaction of alumina support–nanoparticle induces the presence of cationic gold and more surface gold atoms and, hence, catalytic activity although capping agent is still present. The activity is the highest for the largest gold particles (∼6.4 nm), correlating with sites in larger surface planes. Weakly bound capping agents lower the accessibility to the active sites and may act as catalyst surface poison. Selecting the appropriate capping agent for the nanoparticles synthesis (weakly adsorbing on the particle and promoting polycrystallinity), nanoparticles with twinning defects and enhanced catalyst activity are produced, compensating the negative effect of diffusional hindrance. On the other hand, the selectivity to benzaldehyde at higher conversions is dominated by gold particle size, increasing with decreasing size, and independent of the presence of capping agents and twinning defects.

A novel, versatile method is introduced for the fast and continuous preparation of nanoparticles with controlled size, based on the electrostatic spraying of a precursor solution into a reductive-surfactant solution at room temperature. The technique is demonstrated by the production of anisotropic gold nanoparticles and based on the electrostatic aerosol generation of a HAuCl4 precursor solution followed by the chemical reduction of Au3+ to metallic gold (Au0) by dodecylaminomethanol (DDAM), which is a bifunctional molecule that acts both as a reducing agent and, subsequently, as a stabilizing (capping) agent. The particle size depends on the droplet size in the spray and can be tuned by properly selecting the flow rate, precursor concentration, and applied voltage. In this way, small and uniform quasi-spherical gold nanoparticles of 4.5 nm edge size can be prepared within

The step response, including various startup procedures, in a three-phase microreactor of 2 mm internal diameter packed with nonporous particles of 100 μm is reported. We demonstrate that the bed behaves reproducibly through many cycles of operating conditions. Interestingly, we find that the different startup procedures have little effect on the steady state that is achieved. In other words, minimal hysteresis was observed, in sharp contrast to larger-scale reactors with larger particles where prewetting has a remarkable impact on the hydrodynamic behavior. The powder-packed beds have very high liquid saturation values, and prewetting is not needed. At least four liquid-residence times were needed to achieve stable pressure drop and dispersion values over the bed. This indicates that the hydrodynamic response into a stable operation may well be the limiting factor that determines the rate at which kinetic experiments can be performed in high-throughput equipment.

The oxidation of benzyl alcohol by air, catalyzed by the organocatalyst TEMPO and the enzyme laccase has been investigated. To establish the kinetically significant pathways and corresponding kinetic parameters, a series of experiments is conducted with synthesized stable oxidized and reduced forms of the organocatalyst, the oxoammonium cation, and hydroxylamine. The time course of TEMPO and its oxidized and reduced derivatives is monitored off line by a combination of GC analysis, UV/Vis spectroscopy, EPR spectroscopy, and FTIR spectroscopy. TEMPO is found to be regenerated through noncatalyzed comproportionation of the oxoammonium cation with hydroxylamine. A kinetic model is presented based on the experimentally determined kinetically significant pathways. The time dependences of the concentrations of the three redox states of TEMPO and benzyl alcohol are adequately described by the model. The results provide new leads for the development of a practical process for a combined laccase–TEMPO-catalyzed selective oxidation of alcohols

We describe the formation of water in oil droplets, which are commonly used in lab-on-a-chip systems for sample generation and dosing, at microfluidic T-shaped nozzles from elastic feed lines. A narrow nozzle forms a barrier for a liquid-liquid interface, such that pressure can build up behind the nozzle up to a critical pressure. Above this critical pressure, the liquid bursts into the main channel. Build-up of pressure is possible when the fluid before the nozzle is compressible or when the channel that leads to the nozzle is elastic. We explore the value of the critical pressure and the time required to achieve it. We describe the fluid flow of the sudden burst, globally in terms of flow rate into the channel and spatially resolved in terms of flow fields measured using micro-PIV. A total of three different stages-the lag phase, a spill out phase, and a linear growth phase-can be clearly discriminated during droplet formation. The lag time linearly scales with the curvature of the interface inside the nozzle and is inversly proportional to the flow rate of the dispersed phase. A complete overview of the evolution of the growth of droplets and the internal flow structure is provided in the digital supplement.