Chelator-impregnated resins have been studied earlier for the chemical separation of elements in aqueous solutions, but issues with their chemical stability have limited their use in the separation of (medical) radionuclides from their respective irradiated targets. We developed a polydimethylsiloxane (PDMS)-based chelator-impregnated resin that showed a high chemical stability against leaching. Several different chelators were tested in this study. After impregnation of the PDMS beads with the di-2-ethylhexylphosphoric acid (D2EHPA) chelator, an in-flow separation study with various radionuclides (Y-90, La-140, and Ac-225) was conducted. These three radionuclides have potential use in nuclear medicine and a production route through irradiation of Sr-, Ba-, and Ra-targets respectively, necessitating their chemical separation. The D2EHPA-impregnated beads achieved high adsorption efficiencies of 99.89% ± 0.14%, 99.50% ± 0.10%, and 98.51% ± 0.25%, for Y-90, La-140, and Ac-225, respectively, while co-adsorption of minor amounts (< 3%) of the targets were reported. These results, together with the high chemical stability of the PDMS-based resin, highlight the potential of chelator-impregnated resins in the rapidly growing field of (medical) radionuclide production.@en

In this study, the impact of different vibrational modes on the fluidization characteristics of cohesive micro- and nano-silica powder was examined. Fractional pressure drop, bed expansion measurements, and X-ray imaging were utilized to characterize the fluidization quality. The densities of the emulsion phase at the top and bottom of the column were quantified and compared, providing insights into the solid distribution within the fluidized bed. In the absence of vibration, neither powder could be fluidized within the considered range of superficial gas velocities. Vertical vibration was found to initiate fluidization for both powders. In contrast, elliptical vibration failed to overcome the channelling behavior when fluidizing the micro-powder. For nano-powder, combined channelling and powder compaction occurred when the bed was subjected to elliptical vibration. For the micro-powder, it was observed that bed homogeneity was independent of vertical vibration intensity but improved with increasing superficial gas velocity. For nano-powder, intensifying vertical vibration led to segregation, likely due to agglomerate densification. Furthermore, fractional pressure drop measurements proved to be a strong tool in assessing fluidization quality, providing insights that could not be attained by conventional indicators.

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Polydimethylsiloxane (PDMS) is one of the materials of choice for the fabrication of microfluidic chips. However, its broad application is constrained by its incompatibility with common organic solvents and the absence of surface anchoring groups for surface functionalization. Current solutions involving bulk-, ex-situ surface-, and in-situ liquid phase modifications are limited and practically demanding. In this work, we present a simple, novel strategy to deposit a metal oxide nano-layer on the inside of bonded PDMS microfluidic channels using atmospheric pressure atomic layer deposition (AP-ALD). Using three important classes of microfluidic experiments, i.e., (i) the production of micron-sized particles, (ii) the cultivation of biological cells, and (iii) the photocatalytic degradation in continuous flow chemistry, we demonstrate that the metal oxide nano-layer offers a higher resistance against organic solvent swelling, higher hydrophilicity, and a higher degree of further functionalization of the wall. We demonstrate the versatility of the approach by not only depositing SiO_x nano-layers, but also TiO_x nano-layers, which in the case of the flow chemistry experiment were further functionalized with gold nanoparticles through the use of AP-ALD. This study demonstrates AP-ALD as a tool to broaden the applicability of PDMS devices.

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In this study, we investigated the wettability and agglomeration characteristics of polymer microspheres coated with low-temperature deposited SiO₂ in a fluidized bed atomic layer deposition (ALD) setup. Surface characterization revealed the presence of a significant amount of deposited Si-OH groups within the first cycles. A drastic decrease in agglomerate size, water contact angle (WCA), and droplet absorption time of the powder was observed when coating was applied. Furthermore, we observed an increase in the amount of Si-OH present on the particle surface with increasing coating cycles, while no significant improvement in water affinity was found after the first coating cycles. Our findings suggest that surface coverage is the primary factor in improving the colloid stability of particles, coated at low temperatures. The low temperature operation of our system introduced a chemical vapor deposition (CVD) component to our coating process, which allowed full surface coverage to be achieved within the first two coating cycles.

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Stirred gas–solid fluidized bed reactors are commercially employed in polyolefin manufacturing, but the complex gas–solid contacting dynamics pose challenges in design, scale-up, and operation. In this study, the influence of agitation on the fluidization performance of Geldart B particles was investigated experimentally by X-ray imaging and pressure drop measurements and numerically by Computational Fluid Dynamics (CFD) - Discrete Element Method (DEM) - Immersed Boundary Method (IBM). The experimentally obtained minimum fluidization curve and time-averaged pressure drop show good qualitative agreement with the simulation results. Visual observations underscore that an increase in the angular velocity of the agitator results in reduced bubble size and improved bed homogeneity, as further evidenced by reduced pressure fluctuations. Furthermore, the simulations reveal that while the impeller enhances solids agitation, a proper design study is imperative, considering that static immersed bodies, such as the stirrer shaft, can adversely impact solids motion.@en

A new X-ray computed tomography technique for the purpose of imaging fluidized beds is presented. It consists of an experimental set-up with three stationary X-ray source and flat panel detector pairs, a geometric calibration and data processing workflow, and an image reconstruction algorithm. The technique enables sparse-angular tomographic reconstruction in large 3D regions of fluidized beds at framerates up to 200 Hz, and therefore images bubbles along their whole trajectories through the volume. It allows for a unique analysis of bubble dynamics in fluidized beds, including bubble velocities, bubble transformations, i.e., time evolution of the bubble distributions in space, and bubble–bubble interactions. In this article, we first analyze the main limitation of the technique, the sparse angular resolution, through numerical simulations. We then test the experimental set-up through imaging a series of phantoms. Lastly, we demonstrate results from a Geldart B bubbling fluidized bed.

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The most common way to protect metallic structures from corrosion is through the use of passive and active corrosion protection with coatings containing dispersed corrosion inhibitor particles. Current approaches use inorganic microparticles containing mostly toxic and/or critical elements (e.g. CrVI, Li-salts). Organic inhibitors have been identified as a potential replacement technology due to their high inhibiting efficiency in solution, high versatility and lower toxicity. Nevertheless, when brought into organic coatings these inhibitors lose their efficiency due to unwanted side reactions with the surrounding organic matrix (coating). In this work we propose a novel strategy to isolate the organic corrosion inhibitor microparticles from the surrounding matrix. The new approach is based on the gas-deposition of an oxide nanolayer on the microparticles using gas deposition in a fluidized bed reactor. As a result, the organic particles are better dispersed in the coating and do not react with the surrounding matrix. Upon coating damage the particles are exposed to water and release sufficiently high amounts of the organic corrosion inhibitor at the damaged location. The work introduces a technique that can be used in other applications with similar challenges and a new technology that enables for the first time to store large amounts of active organic corrosion inhibitors in reactive organic coatings for efficient protection of metallic infrastructure. This opens the path to the practical use of highly efficient organic inhibitors in coatings for corrosion protection.

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We explore the low-temperature limit of atomic layer deposition of Pt using MeCpPtMe3 and O2. We reveal that by supplying a sufficiently high O2 exposure, highly dispersed and thermally stable Pt sub-nanometer clusters can be deposited onto the surface of P25 TiO2 nanoparticles even at room temperature by atmospheric-pressure ALD.@en

Nanoparticles are usually fluidized as agglomerates, which are in dynamic states of agglomeration and fragmentation. It is critical to consider the size distribution of agglomerates in modeling of the fluidization of nanoparticle agglomerates. In this article, the fluidization behavior of nanoparticle agglomerates is investigated using a two-fluid model─population balance model. The model includes the agglomeration and breakage kernel functions based on the continuum theory of cohesive particles developed by Kellogg et al. (J. Fluid Mech. 2017;832:345-382). The ratio of the critical breakage velocity to the critical agglomeration velocity is defined to represent the cohesion of nanoparticles. The predictions of bed pressure drop, bed expansion ratio, and bed collapse curves agree well with those of experiments. By changing the critical agglomeration velocity and the ratio between the critical velocities, the transition from almost defluidization to uniform fluidization is predicted. Finally, the model’s ability to simulate the fluidization of fine particles with a few micrometers is also shown. This study provides a practical tool for simulating the fluidization of nanoparticle agglomerates.

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Stirring has been recognized in the literature as a promising technique for facilitating fluidization of cohesive powders, via inputting additional energy to counteract interparticle forces. However, the influence of operating conditions and stirrer configurations on flow behavior remains largely unknown, which impedes the practical implementation of stirred fluidization. Utilizing X-ray imaging, this research demonstrates that stirring enhances fluidization in cohesive micron-silica powder (Sauter mean diameter [Formula presented]) by collapsing the powder packing structure, and transitioning channeling beds into bubbling states. Comb-like configurations featuring fewer stirrers and blades, placed in the bottom region, have shown to be highly effective. Excessive stirring can lead to air pockets and a compacted phase of particles on the column walls, undermining the interaction between particles and stirrers. Additionally, the experiments show that maximizing the sweeping coverage, employing complex asymmetrical configurations, and avoiding tortuous gas pathways are preferable.

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Horizontal stirred bed reactors (HSBRs) are widely used in the commercial production of polypropylene (PP). Despite their commercial significance, a comprehensive understanding of the flow behavior in HSBRs remains elusive, primarily due to the lack of detailed experimental data. This study investigates the influence of operating parameters on the particle flow behavior of two types of PP reactor powder in a laboratory-scale HSBR using X-ray imaging. Our results indicate that the overall flow behavior and phase holdup in the HSBR are dominated by agitation. Moreover, gas injection through the inlet points at the bottom of the HSBR results in spouting behavior, which can lead to reduced gas–solid contacting and, in extreme cases, complete bypass. Finally, the presence of liquid (in this study, isopropyl alcohol) adversely affects the flow behavior of the PP reactor powder due to liquid bridging at the contact points of particles. Powders that comprise particles with relatively small sizes and dense surface morphology are particularly prone to reduced flow behavior when exposed to liquid.@en

Evaluation of the hydrodynamics of opaque multi-phase flows remains a challenging task, with implications for various industrial processes such as chemical processing, pharmaceutical, and mineral processing. Understanding how design and operational variables affect the complex behavior of multi-phase flow systems is essential for optimizing processing conditions and improving efficiency. Radioactive particle tracking (RPT) has been a proven measurement technique to evaluate hydrodynamics in multi-phase flow systems. However, a limitation of the classical RPT technique exists in the assumptions made in the simulation of the count rate received by the detectors in correcting for varying flow-induced fluctuations in the volume fraction of the dispersed phase, often encountered in industrial multi-phase flow systems. In this paper, we introduce a fundamentally novel experimental RPT method that directly uses detected incident photon hit locations for the reconstruction of the three-dimensional radioactive tracer particle position. We argue that this approach is inherently more robust as varying attenuation does not affect the reconstruction. The RPT setup consists of three identical γ-radiation slit collimator detectors that are placed equidistantly at 120° intervals. A subsequent calibration-experimentation procedure is established that allows reconstruction of the tracer particle position with spatial accuracy and precision in the order of 1 mm. We demonstrate the applications of this technique in evaluating hydrodynamics in multi-phase systems by characterizing the flow field of industrial-grade polypropylene reactor powder in a laboratory-scale horizontal stirred bed reactor.

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Horizontal stirred bed reactors are widely used in the commercial manufacturing of polypropylene. However, a comprehensive understanding of the particle dynamics in horizontal stirred bed reactors remains elusive, primarily due to the lack of detailed experimental data. In this work, we studied the influence of operating parameters on the particle flow dynamics in a laboratory-scale horizontal stirred bed reactor using single-photon emission radioactive particle tracking. The results show that the general solids flow behavior is strongly affected by both the agitator rotation speed and reactor fill level. Operation at low rotation speed and low fill level results in solids flow with poor radial and circumferential distribution due to internal bed circulation. On the contrary, at increased rotation speeds and fill levels, solids motion throughout the bed is continuous resulting in excellent solids distribution. The solids circulation was found to increase for both an increase in rotation speed and reactor fill level. The axial dispersion coefficient, on the other hand, shows a linear relation with the rotation speed, but no conclusive relation between the axial dispersion coefficient and the reactor fill level was found.

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Extending the lifetime of electrocatalytic materials is a major challenge in electrocatalysis. Here, we employ atomic layer deposition (ALD) to coat the surface of carbon black supported platinum nanoparticles (Pt/CB) with an ultra-thin layer of silicon dioxide (SiO2) to prevent deactivation of the catalyst during H2 evolution. Our results show that after an accelerated durability test (ADT) the current density at −0.2 V vs. reversible hydrogen electrode (RHE) of the unprotected Pt/CB catalyst was reduced by 34%. By contrast, after coating the Pt/CB catalyst with 2 SiO2 ALD cycles, the current density at the same potential was reduced by 7% after the ADT procedure, whereas when the Pt/CB sample was coated with 5 SiO2 ALD cycles, the current density was reduced by only 2% after the ADT. Characterization of the Pt particles after electrochemical testing shows that the average particle size of the uncoated Pt/CB catalyst increases by roughly 16% after the ADT, whereas it only increases by 3% for the Pt/CB catalyst coated with 5 cycles of SiO2 ALD. In addition, the coating also strongly reduces the detachment of Pt nanoparticles, as shown by a strong decrease in the Pt concentration in the electrolyte after the ADT. However, 20 cycles of SiO2 ALD coating results in an over-thick coating that has an inhibitory effect on the catalytic activity. In summary, we demonstrate that only a few cycles of SiO2 ALD can strongly improve the stability of Pt catalyst for the hydrogen evolution reaction.@en

To make green hydrogen more economically attractive, the energy losses in alkaline electrolysis need to be minimized while operating at high current densities (1 A cm⁻²). At these current densities the ohmic resistance and gas bubbles effects contribute largely to the energy losses. To mitigate the gas bubbles losses, we demonstrate, for the first time, a pressure swing to remove gas bubbles in a zero-gap alkaline water electrolyzer. The pressure swing leverages the ideal gas law to increase the volume of gas in the system periodically, for a short duration (<2 s). This temporal volume increase effectively removes bubbles from the electrolyzer. We show that pressure swing can be used to measure the effect of bubbles on the ohmic resistance (R_Bubbles). Our results reveal that foam electrodes have a significantly larger R_Bubbles than perforated plate electrodes (1.8 Ω cm² vs 0.3 Ω cm²). The time-averaged cell voltage reduces by 170 mV when applying pressure swings to an electrolyzer operating at 200 mA cm⁻² in 1 M KOH with foam electrodes. The bubble resistance further depends on the electrolyte conductivity (inversely proportional) and is only moderately affected by operating pressure (25 % lower when increasing pressure amplitude from 1–2 to 1–5 bar). By implementing these findings in a model, we estimate that the pressure swing could reduce the cell voltage by ∼0.1 V for an electrolyzer operating at industrial conditions (6 M KOH, 80 °C, 1 A cm⁻²) for foam electrodes. For perforated plate electrodes, however, the reduced cell voltage is lower and does not outweigh the additional compression energy.

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Vibro-assisted fluidization of cohesive micro-silica has been studied by means of X-ray imaging, pressure drop measurements, and off-line determination of the agglomerate size. Pressure drop and bed height development could be explained by observable phenomena taking place in the bed; slugging, channeling, fluidization or densification. It was observed that channeling is the main cause of poor fluidization of the micro-silica, resulting in poor gas-solid contact and little internal mixing. Improvement in fluidization upon starting the mechanical vibration was achieved by disrupting the channels. Agglomerate sizes were found to not significantly change during experiments.

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Separating medical radionuclides from their targets is one of the most critical steps in radiopharmaceutical production. Among many separation methods, solvent extraction has a lot of potential due to its simplicity, high selectivity, and high efficiency. Especially with the rise of polydimethylsiloxane (PDMS) microfluidic chips, this extraction process can take place in a simple and reproducible chip platform continuously and automatically. Furthermore, the microfluidic chips can be coated with metal-oxide nano-layers, increasing their resistance against the employed organic solvents. We fabricated such chips and demonstrated a parallel flow at a considerably large range of flow rates using the aqueous and organic solutions commonly used in medical radionuclide extraction. In our following case study for the separation of Ac-225 from radium with the chelator di(2-ethylhexyl)phosphoric acid (D2EHPA), a remarkable extraction efficiency of 97.1 % ± 1.5 % was reached within 1.8 seconds of contact time, while maintaining a near perfect phase separation of the aqueous and organic solutions. This method has the potential to enable automation of solvent extraction and faster target recycling, and serves, therefore, as a proof-of-concept for the applicability of microfluidic chip solvent extraction of (medical) radionuclides.@en

Aqueous electrolytes used in CO2 electroreduction typically have a CO2 solubility of around 34 mM under ambient conditions, contributing to mass transfer limitations in the system. Non-aqueous electrolytes exhibit higher CO2 solubility (by 5–8-fold) and also provide possibilities to suppress the undesired hydrogen evolution reaction (HER). On the other hand, a proton donor is needed to produce many of the products commonly obtained with aqueous electrolytes. This work investigates the electrochemical CO2 reduction performance of copper in non-aqueous electrolytes based on dimethylformamide (DMF), n-methyl-2-pyrrolidone (NMP), and acetonitrile (ACN). The main objective is to analyze whether non-aqueous electrolytes are a viable alternative to aqueous electrolytes for hydrocarbon production. Additionally, the effects of aqueous/non-aqueous anolytes, membrane, and the selection of a potential window on the electrochemical CO2 reduction performance are addressed in this study. Experiments with pure DMF and NMP mainly produced oxalate with a faradaic efficiency (FE) reaching >80%; however, pure ACN mainly produced hydrogen and formate due to the presence of more residual water in the system. Addition of 5% (v/v) water to the non-aqueous electrolytes resulted in increased HER and formate production with negligible hydrocarbon production. Hence, we conclude that aqueous electrolytes remain a better choice for the production of hydrocarbons and alcohols on a copper electrode, while organic electrolytes based on DMF and NMP can be used to obtain a high selectivity toward oxalate and formate.@en

Pre-treated silica with a plasma-deposited (PD) layer of polymerized precursors was tested concerning its compatibility with Natural Rubber (NR) and its influence on the processing of silica-silane compounds. The modification was performed in a tailor-made plasma reactor. The degree of deposition of the plasma-coated samples was analyzed by ThermoGravimetric Analysis (TGA). In addition, Diffuse Reflectance Infrared Fourier Transform spectroscopy (DRIFTs), X-ray Photoelectron Spectroscopy (XPS), and Transmission Electron Microscopy (TEM) were performed to identify the morphology of the deposited plasma polymer layer on the silica surface. PD silica samples were incorporated into a NR/silica model compound. NR compounds containing untreated silica and in-situ silane-modified silica were taken as references. The silane coupling agent used for the reference compounds was bis-(3-triethoxysilyl-propyl)disulfide (TESPD), and reference compounds with untreated silica having the full amount and 50% of silane were prepared. In addition, 50% of the silane was added to the PD silica-filled compounds in order to verify the hypothesis that additional silane coupling agents can react with silanol groups stemming from the breakdown of the silica clusters during mixing. The acetylene PD silica with 50% reduced silane-filled compounds presented comparable properties to the in-situ silane-modified reference compound containing 100% TESPD. This facilitates processing as lower amounts of volatile organic compounds, such as ethanol, are generated compared to the conventional silica-silane filler systems.

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Polymer nanocomposites (NCs) offer outstanding potential for dielectric applications including insulation materials. The large interfacial area introduced by the nanoscale fillers plays a major role in improving the dielectric properties of NCs. Therefore, an effort to tailor the properties of these interfaces can lead to substantial improvement of the material’s macroscopic dielectric response. Grafting electrically active functional groups to the surface of nanoparticles (NPs) in a controlled manner can yield reproducible alterations in charge trapping and transport as well as space charge phenomena in nanodielectrics. In the present study, fumed silica NPs are surface modified with polyurea from phenyl diisocyanate (PDIC) and ethylenediamine (ED) via molecular layer deposition (MLD) in a fluidized bed. The modified NPs are then incorporated into a polymer blend based on polypropylene (PP)/ethylene-octene-copolymer (EOC), and their morphological and dielectric properties are investigated. We demonstrate the alterations in the electronic structure of silica upon depositing urea units using density functional theory (DFT) calculations. Subsequently, the effect of urea functionalization on the dielectric properties of NCs is studied using thermally stimulated depolarization current (TSDC) and broadband dielectric spectroscopy (BDS) methods. The DFT calculations reveal the contribution of both shallow and deep traps upon deposition of urea units onto the NPs. It could be concluded that the deposition of polyurea on NPs results in a bi-modal distribution of trap depths that are related to each monomer in the urea units and can lead to a reduction of space charge formation at filler-polymer interfaces. MLD offers a promising tool for tailoring the interfacial interactions in dielectric NCs.

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