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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.

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.

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.

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.

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.

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...

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.

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...

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.

Transparent and smooth silica thin films with a very high porosity were prepared by linking zeolitic nanoslabs into open mesoporous networks. Calcined films characterized by ellipsometric porosimetry presented pore sizes in the range of 6–18 nm and porosities of 70–90% depending on the temperature of assembly of the nanoslabs in the presence of Pluronic P123 triblock copolymer. The films were disordered according to grazing incidence small angle X-ray scattering and transmission electron microscopy. The most spacious film had a very low refractive index of 1.08 (at 632.8 nm) and exhibited reversible shrinkage of up to 30% of its original thickness upon capillary condensation of adsorbate vapor. The mechanical flexibility of the film was confirmed by the low Young modulus of 0.9 GPa determined by nano-indentation. The full accessibility of the porosity and the convenience for chemical functionalization were demonstrated using Atomic Layer Deposition (ALD) of TiO2 monitored with Rutherford Backscattering Spectroscopy. Using ALD the porosity and mechanical flexibility of the film could be fine tuned.

We propose in this paper a generic model of a non-standard aggregation mechanism for self-assembly processes of a class of materials involving the mediation of intermediates consisting of a polydisperse population of nano-sized particles. The model accounts for a long induction period in the process. The proposed mechanism also gives insight on future experiments aiming at a more comprehensive picture of the role of self-organization in self-assembly processes., To appear in J. Chem. Phys.

A new synthesis procedure is presented to prepare P6m ordered mesoporous silica at room temperature and quasi-neutral pH in a buffered medium using a cheap silicon source.