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The dissolved oxygen concentration must be well controlled in liquid Pb for use as a primary coolant of fast spectrum nuclear reactors. We have measured fundamental data of oxygen in liquid Pb. The Sieverts constant and solubility of oxygen were measured by coulometric titration. Thermal cycling of liquid Pb allowed a quantification of the excess oxygen above solubility required to initiate solid PbO nucleation, which is the metastable limit in liquid Pb. The data obtained in this study are as follows

As a step toward licensing a lead–bismuth eutectic (LBE) based reactor design, the adsorption behavior of iodine evaporated from LBE on fused silica was examined. Using inert and reducing carrier gases, depositions with an adsorption enthalpy of − 95 to − 113 kJ mol−1 were observed. These depositions are compatible with a single species, tentatively identified as bismuth monoiodide, BiI. When introducing oxidizing conditions, multiple iodine species with higher volatility form, with adsorption enthalpies ranging from − 67 to − 86 kJ mol−1. Based on an empirical correlation one of these species was identified as monatomic iodine. This work provides fundamental understanding of the LBE/iodine gaseous chemistry and related adsorption deposition behavior.

Lead oxide (PbO) formation can occur in Lead-Bismuth Eutectic (LBE)-cooled nuclear systems in case of oxygen ingress or temperature decrease of the coolant beyond the normal operation ranges. In the present work the formation of lead oxide in an actively cooled LBE flow is studied. Computational fluid dynamics (CFD) is used to predict the nucleation, growth and dissolution of PbO particles. Solid oxide particles are modeled as a pseudo-continuous phase, using the Kinetic Theory of Granular Flow (KTGF) to account for particle-flow interaction. The particle size distribution (PSD) is accounted for using Population Balance Equations/Models (PBE/PBM). The results obtained from the model are qualitatively in good agreement with experimental results obtained in the MEXICO loop at SCK·CEN. The calculated PSD reveals that the majority of the oxide particles are expected to be in the sub-micron range. Experimental results indicate that in the studied conditions PbO nucleates in the LBE bulk leading to suspended particles in the LBE flow.

Accelerator driven fast nuclear reactors cooled by lead-bismuth eutectic (LBE) are developed for transmuting long-lived radionuclides in spent nuclear fuel. Due to the nature of the coolant, operating the reactor will result in a production of 210Po by neutron capture. Understanding the behavior of this highly radiotoxic nuclide in the event of a failure of the window separating the evacuated proton beam guide from the reactor core is required for safety assessments. The present work aims at acquiring this knowledge by studying the evaporation of polonium from neutron-irradiated LBE and its deposition in a scaled down model of the beam tube. Experimental results along with Monte Carlo simulations indicate that polonium adsorbs as a single species with an adsorption enthalpy of approximately −156 kJ/mol.

To support the design of an external filtering and conditioning system for the lead-bismuth cooled MYRRHA reactor, the formation and transport of iron oxide particles from corrosion products in the reactor primary system have been investigated for normal operating conditions. The regions of the reactor with the highest probability of oxide formation are identified by a local chemical equilibrium model for magnetite formation. This analysis reveals that magnetite precipitation generally occurs in regions with large temperature gradients. For the specific case of the MYRRHA reactor, these regions correspond to the transition region between the barrel and the upper plenum, mainly at the location of the holes in the top part of the barrel. The transport behaviour of solid oxides from these regions is then investigated with a multi-phase Euler-Lagrange particle tracking model of the MYRRHA primary system. The simulations show that the majority of large oxide particles (above 100 µm) will eventually move to the free surface without passing through the reactor core, thereby allowing their removal by an external filtering system with surface extraction. This indicates that such large particles present a minimal risk for sudden core blockage, which does not compromise reactor safety. On the other hand, particles below a threshold diameter identified at 40 µm cannot be efficiently filtered out by an external system since the majority follows the carrier liquid and re-enters the core during each LBE flow-through cycle. The continuous purification of the coolant is therefore necessary to avoid undesired build-up of suspended particles in the primary system. A preliminary design value of the required mass flow rate through the filters is identified with the support of numerical simulations.

Corrosion of steels in lead bismuth eutectic (LBE) cooled reactors can be mitigated by forming a protective oxide layer on the steel surfaces. The amount of oxygen necessary to ensure continuous oxide layer formation on fuel cladding depends on the characteristics of the steel and on the local temperature, local oxygen concentration and velocity of the LBE in contact with the steel. The most critical areas from a corrosion point of view are high temperature and low oxygen concentration regions. Wire-wrapped fuel assemblies (FAs) which are foreseen to be used in LBE cooled reactors, are characterized by hot spots and quasi-stagnant areas where oxygen could be depleted. Experimental measurements to verify whether the oxygen concentration in those critical areas is sufficiently elevated for oxide layer formation, are practically impossible. This information can be however obtained by numerical modeling. This paper focuses on the development of a numerical model of oxygen mass transfer in a 19-pin scaled fuel assembly (FA) representative of the MYRRHA reactor core. Oxidation of steels and oxygen transport from the bulk of the LBE to the surface of steels were simulated simultaneously. The simulations provide a local oxygen concentration mapping at steel/LBE interface enabling to identify the regions of the core which could be prone to corrosion due to oxygen depleted LBE. Operation recommendations for the MYRRHA reactor were given based on the simulation results.

This article summarizes the results obtained studying the interaction between polonium and stainless steel 316L in different atmospheres by the thermochromatography method. This issue is particularly important in terms of licensing of the MYRRHA prototype ADS reactor, where highly radiotoxic α-emitting polonium isotopes are produced in lead-bismuth eutectic used as both spallation target material and coolant, while stainless steel 316L is going to be the main structural material. The polonium adsorption enthalpy on stainless steel 316L in inert atmosphere was measured as −147±6 kJ mol−1. The findings obtained using reducing atmospheres show that the affinity of polonium for stainless steel 316L increases with the metallic character of the stainless steel surface. The presence of moisture in inert and reducing atmosphere does not significantly influence the polonium adsorption. Oxidizing atmospheres induce the formation of polonium dioxide which has a stronger interaction with the stainless steel 316L, with an adsorption enthalpy of −225±6 kJ mol−1. A prolonged exposure of the stainless steel to strong oxidants, such as pure oxygen, reduces the metallic character of the stainless steel surface and, consequently, its affinity to the polonium oxide. Furthermore, it was found that in all experiments at least 5 ppm of the total polonium present in the starting material were not retained on the stainless steel 316L surface at all.

Accurate control of dissolved oxygen concentration is crucial in order to use liquid lead alloys as a coolant of advanced nuclear systems. An oxygen control system based on PbO mass exchanger (PbO MX) technology was implemented in order to control the dissolved oxygen concentration in the liquid lead--bismuth eutectic (LBE) loop MEXICO. The oxygen control system consisted of a packed bed of PbO spheres, an oxygen sensor and a pneumatic control valve. The concentration of dissolved oxygen in the loop was controlled by regulating the LBE flow through the PbO MX using a proportional–integral–derivative (PID) controller with feedback from the oxygen sensor. Highly accurate control of the dissolved oxygen concentration in the loop was achieved by this system.

Lead-Bismuth Eutectic (LBE) is an interesting candidate as coolant for future Accelerator Driven Systems (ADS) and Generation IV (Gen. IV) nuclear power plants. A well-known issue of liquid metal coolants is the need for coolant chemistry control and continuous purification. This paper presents a purification strategy for control of the dissolved oxygen content in LBE by means of a LBE cold trap. Although cold traps have been explored in the past for Sodium Fast Reactors (SFR) and more recently for lead-lithium (PbLi), advances on cold trapping for LBE are lacking behind. Formation of lead oxide (PbO) is promoted in a non-isothermal purification device (cold trap) to lower the dissolved oxygen concentration present in the liquid metal. Attachment of PbO particles to the stainless steel filter material is observed and continuous growth of captured PbO consumes oxygen from the liquid metal melt. A long-term purification campaign of more than one month is presented to demonstrate the increase in cold trap effectiveness with loading.

Oxygen control is one of the key technologies to limit corrosion or coolant oxidation in lead bismuth eutectic cooled nuclear reactors. In this paper, we show that a stirred bubble column reactor can be an efficient tool for addition and extraction of dissolved oxygen from lead-bismuth eutectic. The design criteria and the resulting layout of the HELIOS3 reactor are detailed and typical results obtained are described. Dissolved oxygen extraction rates are only given at high oxygen activity, as dissolved corrosion products and oxides can strongly influence the rate of addition or extraction of dissolved oxygen at low oxygen activity.

Detection and characterisation of voids in heavy liquid metals (HLM) is required for next generation nuclear reactor systems. However, its determination presents a challenge owing to their opaque nature and the high temperatures involved. Therefore, tools are needed that can be used to capture local, quantitative information at relevant nuclear operating conditions. In this work, the feasibility of using optical fibre sensors for the measurement of void fractions in liquid metals is presented. Since the functioning of optical probes is usually explained by a crude on-off model, the complexity of both the optical response and the hydrodynamic tip–interface interactions often remain hidden to new users. To clarify this point, well-controlled lab-scale experiments dealing with the response of three concept probe tip geometries are presented. Analysis of the obtained signal transients is used to provide guidelines for effective data processing. To conclusively demonstrate the principle, an optimal prototype system successfully determined the local void fraction and frequency in a pilot-scale reactor using liquid lead bismuth eutectic (LBE) as working fluid. The information obtained by the optical sensor allows for validation of computational fluid dynamics (CFD) models to aid the design of LBE-based nuclear reactors, as well as for other liquid metal–gas systems in general.

Fission and fusion reactors can only play a role in the future energy landscape if they are inherently safe by design. For some reactor concepts, a major remaining issue is the undesired production of radiotoxic Po-210. To filter out the volatile Po species, information on their molecular composition is needed. An experimental characterization is very challenging due to the large required amount of radioactive Po. An alternative quantum chemistry approach was taken to predict the temperature-dependent stability of relevant diatomic Po-containing molecules. Experimental data on lighter analogue molecules was used to establish a well-founded methodology. The relative occurrence of the Po species was estimated in the cover gas of (i) the lead-bismuth eutectic coolant in the accelerator-driven MYRRHA fission reactor and (ii) the Pb-Li eutectic tritium breeder in the DEMO fusion reactor. In both systems, Po is found to occur mainly as PbPo molecules and atomic Po.

An increased interest in the use of liquid metals for novel energy conversion systems is present today. The Accelerator Driven System (ADS) called MYRRHA under design at the Belgian Nuclear Research Centre (SCK-CEN) is an example of such an innovative system. The use of Lead-Bismuth Eutectic (LBE) as a coolant for this reactor implies that an accurate knowledge on the chemical properties of the coolant needs to be available. An important factor is the risk of coolant oxidation due to oxygen ingress in the system. Although the formation of lead oxide (PbO) is well understood, the deposition mechanism and kinetics are not yet studied. In this work the deposition mechanism of PbO on 316L stainless steel is investigated. The evolution of the dissolved oxygen concentration during thermal cycling of LBE indicates that fouling of isothermal surfaces by PbO can only proceed by particle deposition. On the other hand, the fouling of non-isothermal surfaces by PbO is dominated by crystallization fouling. A real-time measurement of the PbO deposition rate shows an asymptotic behavior of PbO crystallization fouling. By predicting the onset of PbO nucleation and subsequent growth, a kinetic model for the crystallization fouling is put forward. Quantitative agreement between deposition rate predictions and validation measurements is obtained around 673 K.

The development of integrated numerical codes based on Computational Fluid Dynamics (CFD) and high-fidelity chemical reaction modules, offers the opportunity of an accurate simulation of turbulent reactive transport in nuclear reactors. This is invaluable in the optimization of coolant chemistry for the safe operation of nuclear reactors. The aim of this article is to develop a multi-physics simulation tool, where the chemical equilibrium solver and database of the commercial HSC-Chemistry software are integrated with the widely used CFD code ANSYS FLUENT. The assumption of local chemical equilibrium is used for a coupled simulation. The coupling procedure between codes is performed by a sequential operator-splitting approach. In this framework, the HSC equilibrium solver is called sequentially from each cell of the FLUENT computational domain whose composition has changed from equilibrium. Both iterative and non-iterative time marching algorithms are implemented and can be selected, depending on the problem under investigation. Communication between the codes is handled by a custom-designed object-oriented coupler class. A compiled-linked-in integration between FLUENT, the coupler class and HSC is designed, in order to minimize CPU time by exchanging data directly in the main memory. The coupled simulator is verified and preliminary validated with examples of chemical systems relevant for Gen. IV nuclear reactors cooled by lead-bismuth eutectic (LBE). The tool shows good performances in terms of numerical accuracy and computational speed. Its complete functionality is then illustrated with an application related to localized-corrosion modeling in flowing LBE. This application showed that the integrated code based on FLUENT and HSC is a promising tool for a wide range of applications involving reactive transport simulations.

Potentiometric oxygen sensors with metal–metal oxide reference electrodes including Cu/Cu 2 O, Ni/NiO and Fe/Fe 3 O 4 were tested in oxygen saturated lead–bismuth eutectic (LBE) over the temperature range from 200 to 450 °C to assess their minimum operating temperature limit. The performance of sensors with the three reference electrodes was compared to that of a sensor with air/lanthanum strontium manganese oxide (LSM) reference electrode using the same solid electrolyte material and measurement setup. The sensor with Cu/Cu 2 O reference electrode performed well down to 200 °C in oxygen saturated LBE, while those with Ni/NiO and Fe/Fe 3 O 4 showed significant deviations from expected values below 300 °C. Furthermore, the sensor with Cu/Cu 2 O electrode showed a response to temperature variations as fast as that of the air/LSM electrode over the entire temperature range of interest in liquid LBE.

Electrochemical oxygen pumping method was applied in order to control the dissolved oxygen concentration in liquid lead–bismuth eutectic (LBE). The oxygen pump was fabricated using yttria partially stabilized zirconia (YPSZ) as a solid electrolyte and LSM (strontium-doped lanthanum manganite)–GDC (gadolinium-doped ceria) composite as a cathode. An oxygen control system, comprising of the oxygen pump, an oxygen sensor and a DC current source as well as a proportional-integral-derivative (PID) controller for the current control, was applied to regulate the dissolved oxygen concentration in liquid LBE. Highly accurate control of the oxygen concentration was achieved by this system. In addition, the feasibility of using the pumping system for measuring corrosion kinetics of structural steels in liquid LBE was demonstrated.

Qualitative and quantitative understanding of Po volatilization under different conditions is of key importance for safety assessments of lead-bismuth eutectic (LBE) based nuclear reactors, spallation targets and accelerator driven systems. In this work we explore the possibilities of the transpiration method in combination with simple models to study the equilibrium and kinetics of Po evaporation from highly diluted solutions in lead-bismuth eutectic between 600 and 1000 ℃ in Ar/5% H2 and Ar. On the basis of evaporation experiments at various carrier gas flow rates, we identified the conditions of vapor saturation allowing the determination of equilibrium constants. From the limiting behavior at high flow rates, values for the maximal evaporation rate of Po from LBE were estimated. Measurements of evaporation as a function of time were consistent with the assumption that polonium dissolved in LBE obeys Henry's law. A theoretical analysis furthermore suggested that diffusion of polonium in LBE was not a rate limiting factor for evaporation under vapor saturation conditions. Newly determined values for the Henry constant of Po in LBE between 600 and 1000 ℃ were consistent with previously derived correlations.

The evaporation of Po from its dilute solution in liquid lead–bismuth eutectic (LBE) was determined between 700 and 1000 °C in Ar/5%H2 by the transpiration method. Concurrent measurements of the evaporation of LBE could be well reproduced by calculations using literature data, confirming conditions of equilibrium and convective vapor transport in our transpiration method experiments. This allowed to model the Po evaporation data and extract accurate temperature correlations for the Henry constant for Po dissolved in LBE at two different Po concentrations. Extrapolations of the new correlations were in excellent agreement with existing data at lower temperature.

The evaporation behavior of polonium as one of the most hazardous radionuclides produced in spallation based neutron sources with liquid lead–bismuth targets has been quantified in this study. The normalized apparent vapor pressure, i.e. the Henry constant of polonium over liquid lead–bismuth eutectic was determined in the temperature range relevant for operation of such targets, i.e. 164–500 °C. For comparison and better fundamental understanding, the Henry constant of polonium over pure liquid bismuth was determined in a temperature range of 300–500 °C. The Henry constants of polonium in this temperature range were found to be orders of magnitude higher than expected from earlier studies at higher temperatures. Possible mechanisms responsible for this unexpected behavior are discussed.

A new, single-step protocol for wrapping individual nanosized β-casein micelles with silica is presented. This biomolecule-friendly synthesis proceeds at low protein concentration at almost neutral pH, and makes use of sodium silicate instead of the common silicon alkoxides. This way, formation of potentially protein-denaturizing alcohols can be avoided. The pH of the citrate-buffered synthesis medium is close to the isoelectric point of β-casein, which favours micelle formation. A limited amount of sodium silicate is added to the protein micelle suspension, to form a thin silica coating around the β-casein micelles. The size distribution of the resulting proteinsilica structures was characterized using DLS and SAXS, as well as 1H NMR DOSY with a dedicated pulsed-field gradient cryo-probehead to cope with the low protein concentration. The degree of silica-condensation was investigated by 29Si MAS NMR, and the nanostructure was revealed by advanced electron microscopy techniques such as ESEM and HAADF-STEM. As indicated by the combined characterization results, a silica shell of 2 nm is formed around individual β-casein micelles giving rise to separate protein coresilica shell nanoparticles of 17 nm diameter. This alcohol-free method at mild temperature and pH is potentially suited for packing protein molecules into bio-compatible silica nanocapsules for a variety of applications in biosensing, therapeutic protein delivery and biocatalysis.

Liquid lead-bismuth eutectic (LBE) is an important candidate to become the primary coolant of future, generation IV, nuclear fast reactors and Accelerator Driven System (ADS) concepts. One of the main challenges with the use of LBE as a coolant is to avoid its oxidation which results in solid lead oxide (PbO) precipitation. The chemical equilibria governing PbO formation are well understood. However, insufficient kinetic information is currently available for the development of LBE-based nuclear technology. Here, we report the results of experiments in which the nucleation, growth and dissolution of PbO in LBE during temperature cycling are measured by monitoring dissolved oxygen using potentiometric oxygen sensors. The metastable region, above which PbO nucleation can occur, has been determined under conditions relevant for the operation of LBE cooled nuclear systems and was found to be independent of setup geometry and thus thought to be widely applicable. A kinetic model to describe formation and dissolution of PbO particles in LBE is proposed, based on Classical Nucleation Theory (CNT) combined with mass transfer limited growth and dissolution. This model can accurately predict the experimentally observed changes in oxygen concentration due to nucleation, growth and dissolution of PbO, using the effective interfacial energy of a PbO nucleus in LBE as a fitting parameter. The results are invaluable to evaluate the consequences of oxygen ingress in LBE cooled nuclear systems under normal operating and accidental conditions and form the basis for the development of cold trap technology to avoid PbO formation in the primary reactor circuit.

Iron released by steel corrosion was found to be a key impurity in reactions with dissolved oxygen in liquid lead–bismuth eutectic alloys. The iron–oxygen–magnetite equilibrium was characterized, allowing the quantification of phenomena that are important for long-term operation of lead-alloy based installations such as corrosion rate control and management of precipitates.

Potentiometric oxygen sensors fabricated with yttria partially stabilized zirconia (YPSZ) and a Bi/Bi2O3 reference electrode were tested in oxygen saturated lead–bismuth eutectic (LBE) and oxygen saturated tin (Sn), respectively, in order to estimate the accuracy of the oxygen sensors prior to applying them to R&D work for MYRRHA. The accuracy of these sensors was estimated in the temperature range of 673–733 K by measuring the electromotive force (emf) of eight sensors. The standard deviation on the measured emf data was about 0.79 mV in the case of oxygen saturated LBE and was about 1.25 mV in the case of oxygen saturated Sn. These values result in a standard deviation of 4% on the oxygen concentration in LBE which is calculated from the measured emf.

Hexagonally ordered mesoporous silica coined COK-12 was synthesized in a continuous process by combining streams of sodium silicate and citric acid/sodium citrate buffered solution of (ethylene oxide)(20)-(propylene oxide)(70)-(ethylene oxide)(20) triblock copolymer (Pluronic P123) from separate reservoirs. COK-12 precipitated spontaneously upon combining both streams at nearly neutral pH and ambient temperature. Stable intermediates of the COK-12 formation process could be prepared by limiting sodium silicate addition. Investigation of these intermediates using small-angle X-ray scattering revealed COK-12 formed via an assembly process departing from spherical uncharged core-shell P123-silica micelles. The sterical stabilization of these micelles decreased upon accumulation of silicate oligomers in their shell. Aggregation of the spherical micelles led to cylindrical micelles, which aligned and adopted the final hexagonal organization. This unprecedentedly fast formation of P6m ordered mesoporous silica was caused by two factors in the synthesis medium: the neutral pH favoring uncharged silicate oligomers and the high salt concentration promoting hydrophobic interactions with surfactant micelles leading to silica accumulation in the PEO shell. The easy continuous synthesis process is convenient for large-scale production. The platelet particle morphology with short and identical internal channels will be advantageous for many applications such as pore replication, nanotube or fiber growth, catalytic functionalization, drug delivery, film and sensor development, and in nano dyes as well as for investigation of pore diffusion phenomena.

Zeogrids and Zeotiles are hierarchical materials built from assembled MFI zeolite precursor units. Permanent secondary porosity in these materials is obtained through self assembly of nanoparticles encountered in MFI zeolite synthesis in the presence of supramolecular templates. Hereon, the aggregated species are termed nanoslabs. Zeogrids are layered materials with lateral spacings between nanoslabs creating galleries qualifying as supermicropores. Zeotiles present a diversity of tridimensional nanoslab assemblies with mesopores. Zeotile-1, -4 and -6 are hexagonal mesostructures. Zeotile-1 has triangular and hexagonal channels; Zeotile-4 has hexagonal channels interconnected via slits. Zeotile-2 has a cubic structure with gyroid type mesoporosity. The behavior of Zeogrids and Zeotiles in adsorption, membrane and chromatographic separation and catalysis has been characterized and compared with zeolites and mesoporous materials derived from unstructured silica sources. Shape selectivity was detected via adsorption of n- and iso-alkanes. The mesoporosity of Zeotiles can be exploited in chromatographic separation of biomolecules. Zeotiles present attractive separation properties relevant to CO2 sequestration. Because of its facile synthesis procedure without hydrothermal steps Zeogrid is convenient for membrane synthesis. The performance of Zeogrid membrane in gas separation, nanofiltration and pervaporation is reported. In the Beckmann rearrangement of cyclohexanone oxime Zeogrids and Zeotiles display a catalytic activity characteristic of silicalite-1 zeolites. Introduction of acidity and redox catalytic activity can be achieved via incorporation of Al and Ti atoms in the nanoslabs during synthesis. Zeogrids are active in hydrocracking, catalytic cracking, alkylation and epoxidation reactions. Zeogrids and Zeotiles often behave differently from ordered mesoporous materials as well as from zeolites and present a valuable extension of the family of hierarchical silicate based materials.

Researchers in need of an ordered nanoporous material tend to rely on the original synthesis protocols which often demand hydrothermal synthesis and involve harsh chemical conditions, expensive sacrificial templates and long synthesis times. Considerable efforts have been invested in developing new pathways to simplify synthesis procedures. While in the area of zeolites even with optimum templates intrinsic energy barriers of the crystallization process obstruct the development of easy room temperature synthesis, the synthesis of ordered mesoporous materials and metal organic frameworks (MOFs) are examples of materials for which synthesis can be rationalized and simplified. One key element for the development of room temperature synthesis is the selection of highly efficient templates.

The initial molecular steps of the acid-catalyzed silica sol-gel process departing from tetraethylorthosilicate (TEOS) were investigated by in situ Si-29 NMR and UV-Raman spectroscopy. The use of a substoichiometric H2O:TEOS molar ratio (r-value 0.2-1.2) slowed the silicate oligomerization reaction and allowed unraveling the initial steps of silica condensation. Molecular modeling confirmed Raman signal and Si-29 NMR shift assignment. A comprehensive listing of all Raman and Si-29 NMR assignments is provided, including unique Raman assignments of cyclosilicates and the linear tetramer. The combination of experiment and modeling allowed an analysis of the reaction kinetics. The derived kinetic model and the experimental observation both revealed that the H2O:TEOS molar ratio had a strong influence on the reaction kinetics but not on the reaction pathways. The multianalytical approach led to development of an oligomerization scheme. As dominant oligomerizations, chain growth, cyclodimerization, and branching were identified. Under the investigated conditions, chains did not grow longer than pentamer, and ring sizes were limited to 6-rings. Chains of 4 Si atoms and 4-rings were abundant species. Branched rings and chains were formed by attachment of dimers and trimers. Gelation proceeded from branched 4-rings and branched chains with limited hydroxyl functionalities.

In concentrated clear sol prepared from tetraethylorthosilicate, tetrapropylammonium hydroxide, and water suitable for crystallization of Silicalite-1 zeolite, the main part of the silica is present in nanoparticles. The nature of these nanoparticles and their evolution during the induction period and the stage of early crystal growth was investigated via dissolution experiments in the presence of excess TPAOH. The dissolution process was monitored in situ using static and dynamic light scattering (SLS/DLS) and synchrotron small-angle X-ray scattering (SAXS). The complete dissolution of an individual nanoparticle was observed to occur in one step. Dissolution transformed a nanoparticle into a cluster of silicate oligomers. Larger grown nanoparticles dissolved slower. Exponential dissolution rate constants scaled inversely proportional with the volume of the nanoparticle’s silica core. This experimentally observed dissolution behavior was modeled by assuming that a nanoparticle dissolved to oligomers via a...

Cracking experiments using 2,2,4-trimethylpentane as a model component have been performed on five FAU and three MFI zeolites. In addition to these eight commercially available catalysts, two newly developed zeotype materials with bimodal pore structure, BIPOMs, have been investigated. Both BIPOMs possess an MFI ultramicropore (

Hexagonal mesoporous solids were synthesized from solutions containing TS-1 seeds. The products were characterized by XRD, nitrogen and argon physisorption, TEM, TG/DTA of template decomposition (also after extraction of the mesopore template), UV–Vis and IR spectroscopy, and XANES at the TiK edge. Their catalytic activities were assessed for cyclohexene epoxidation in hydrophilic and hydrophobic environment (CH3OH/water, with H2O2 oxidant, and decane, with tert-butyl hydro-peroxide oxidant, respectively) and for n-hexene epoxidation in hydrophilic environment. The mesopore system was clearly documented by XRD, physisorption measurements, and TEM, whereas evidence for micropores by physisorption proved elusive. However, the micropore template was detected in the solids by TG/DTA even after extraction of the mesopore template, and among the Ti sites, which were confirmed to be tetrahedrally coordinated by UV–Vis and XANES, a clear majority was able to coordinate two water molecules. It was concluded that the pore walls had been built up from nanoparticulate TS-1 precursors resulting in walls of ca. 1.5 nm thickness, which resemble rather the exterior layers of a TS-1 crystallite than its (hydrophobic) interior. In cyclohexene epoxidation, the micro-mesophases were by 1–2 orders of magnitude more active than TS-1 and outperformed also Ti-MCM-41, at similar selectivity in hydrophobic medium. With 1-hexene in hydrophilic medium, however, the micro-mesophases failed completely whereas TS-1 exhibited high activity.

The very first stages of the incorporation of tetraethoxysilane (TEOS) into aqueous tetrapropylammonium hydroxide (TPAOH) by hydrolysis are investigated to clarify the formation of silicate species in solution: oligomers and nanoparticles. Silicate speciation of both oligomers and nanoparticles were characterized using quantitative 29Si NMR, electrospray ionization mass spectrometry (ESI-MS), dynamic light scattering (DLS), and 1H diffusion-ordered NMR spectroscopy (DOSY). The main parameter measured for following this formation with the advancement of hydrolysis of TEOS is the evolution of silicon connectivity, in oligomers as well as in nanoparticles. At the beginning of TEOS hydrolysis, small oligomers are formed, which grow in number and size as the reaction progresses, with an average connectivity going from 0 to 2.1. At Si/TPAOH ratio of 1.0 and above, nanoparticles form through aggregation of oligomers with some additional condensation. Their connectivity varies from 2.4 to 3.1. These nanoparticles...

Discrete electron tomography is a new approach for three-dimensional reconstruction of nanoscale objects. The technique exploits prior knowledge of the object to be reconstructed, which results in an improvement of the quality of the reconstructions. Through the combination of conventional transmission electron microscopy and discrete electron tomography with a model-based approach, quantitative structure determination becomes possible. In the present work, this approach is used to unravel the building scheme of Zeotile-4, a silica material with two levels of structural order. The layer sequence of slab-shaped building units could be identified. Successive layers were found to be related by a rotation of 120°, resulting in a hexagonal space group. The Zeotile-4 material is a demonstration of the concept of successive structuring of silica at two levels. At the first level, the colloid chemical properties of Silicalite-1 precursors are exploited to create building units with a slablike geometry. At the second level, the slablike units are tiled using a triblock copolymer to serve as a mesoscale structuring agent.

The adsorption of linear and branched C5-C9 alkanes in the temperature range 50-250 °C on mesoporous MCM-48 material and its microporous/mesoporous variant Zeotile-2 at low surface coverage is investigated using the pulse chromatographic technique. On MCM-48, the differences in adsorption between linear and branched alkanes are merely a result of differences in volatility, indicating that the MCM-48 material does not present shape-selective adsorption sites. On Zeotile-2, there is a preferential adsorption of linear over branched alkanes. The difference arises from a difference in adsorption entropy rather than enthalpy. Upon their adsorption on Zeotile-2 branched alkanes lose relatively more entropy than their linear isomers do. Zeolitic molecular pockets embedded in the walls of the mesoporous Zeotile-2 impose steric constraints on the bulky isoalkanes. Zeotile-2 combines adsorption properties from microporous and mesoporous materials. Compared to the nitrogen molecule, linear and branched C5-C9 alkanes are superior probes for investigating micropores and micropockets in hierarchical materials.

Concentrated clear solutions, as used for the preparation of Silicalite-1 zeolite, were synthesized from tetrapropylammonium hydroxide, tetraethylorthosilicate, and water. The solutions were analyzed using three techniques: quantitative 29Si NMR, synchrotron small-angle X-ray scattering (SAXS), and dynamic light scattering (DLS). 29Si NMR showed the coexistence of silicate oligomers and particles. For the first time, both fractions were analyzed simultaneously, providing a global, quantitative description of the clear solution microstructure. The SAXS patterns, typical of interacting particles, could be used together with the 29Si NMR deduced particle volume fraction to estimate a particle size. A careful analysis of DLS data of the dynamics of the suspensions revealed the occurrence of two diffusive processes. The faster process is a collective particle diffusion. The slower process corresponds to the particle self-diffusion and is present because of the presence of polydispersity in size, shape, and/or...

Accurate knowledge of polonium evaporation from lead–bismuth eutectic (LBE) is crucial for the design of accelerator driven nuclear systems in which LBE is used as target material or coolant. In this work we investigated the relation between the oxygen content and its distribution in liquid LBE samples and polonium evaporation from these samples at 400 °C. A fraction of the polonium was rapidly released, and we found a correlation between the amount of this fast-released polonium and the amount of oxygen concentrated in an oxide layer on top of the LBE sample. A qualitative model describing the polonium evaporation behavior in relation to oxygen content and distribution in polonium-doped LBE samples is outlined.

Ordered mesoporous materials with specific microporosity in the mesopore walls can be assembled by a secondary templating synthesis departing from a clear subcolloidal suspension dedicated to the tetrapropylammonium (TPA) mediated synthesis of colloidal Silicalite-1. A typical member of this material family is Zeotile-2. Zeotile-2 is mesostructurally similar to the cubic MCM-48 material with exceptional long-range order of the mesostructure. Zeotile-2 samples in which the TPA was either left or evacuated were prepared by leaching in boiling ethanolic acetic acid and calcination. The evacuation of the TPA gave rise to a substantial micropore volume revealed with nitrogen adsorption isotherms. The mesoporosity was independent of the presence of the TPA. Molecular separations of isooctane/octane mixtures illustrated the occurrence of molecular shape selectivity similar to MFI-type zeolites.

It is widely recognized that the control of the activity of dissolved oxygen is essential for the use of lead–bismuth eutectic (LBE) as primary coolant for nuclear systems. A lead oxide mass exchanger (PbO MX) comprised of a packed bed of lead oxide spheres is a promising solution to regulate the dissolved oxygen activity in the LBE. In order to design and operate a PbO MX properly, the dissolution kinetics of PbO in flowing LBE should be determined. A high-fidelity Computational Fluid Dynamic (CFD) model of solid-to-liquid mass transfer has been developed to determine the mass transfer coefficient of a PbO MX in flowing LBE. We validated the developed CFD model against experimental data obtained from the LBE test loop CRAFT, at SCK•CEN. The model is in good agreement with the experimental data. The effect of the channel to particle diameter ratio ( R ) on the mass transfer coefficient was evaluated by using the validated model. A mass transfer correlation for PbO MX was obtained, in terms of the Sherwood number, by fitting the simulation results for the general case of a random packed bed with a porosity of about 0.4.

Understanding polonium evaporation from lead-bismuth eutectic (LBE) is required for the design of nuclear installations that use liquid LBE as coolant or spallation target. In the present study we measured the time-dependent release of polonium from LBE samples in Ar/5 %H2 and Ar between room temperature and 500 C. Our experiments revealed that the majority of polonium in the samples evaporated according to established temperature correlations for the Henry constant of polonium in LBE. However a small fraction of polonium in the LBE behaved differently, causing a relatively large but transient polonium release at the start of evaporation experiments. We showed that this volatile fraction of polonium was located near the sample surface and was formed after prolonged exposure of the samples to air at room temperature. We speculate that the peculiar evaporation behavior of this surface polonium is caused by enrichment and association with an oxide layer. ispartof: Journal Of Radioanalytical And Nuclear Chemistry vol:302 issue:1 pages:195-200 status: published