Dense and homogeneous MOX fuel pellets manufactured using the freeze granulation route

MOX fuels (UO₂-PuO₂) are used in light water nuclear reactors of several countries and are also potential candidates for the fast neutron reactors. Industrial MOX is currently manufactured by a dry route process, involving steps with fine powders. To reduce dusting, enhance MOX powder flow properties, and decrease manufacturing scrap rate, a new wet route process is investigated: the freeze granulation of concentrated water-based powder suspensions having optimized rheology and dispersion properties. Highly flowable, dustless, and easy-to-press MOX granules have been elaborated. Sintering green compacts made of such granules gives highly dense and defect-free pellets that have a very homogeneous U-Pu spatial distribution, thus improving the fuel characteristics. Indeed, MOX fuels devoid of large Pu-rich aggregates are thought to have a better behavior under irradiation in reactors by limiting/preventing the formation of the typical high burnup structure.     

Preparation and co-dispersion of TiO2-Y2O3 suspensions through the study of their rheological and electrokinetic properties

The development of Generation IV sodium-cooled fast reactors (SFR) is currently studied by several countries, France in particular. To manufacture the UO₂-PuO₂ fuels for these new types of reactors, new innovative wet colloidal processing routes are investigated. Among these wet colloidal processes, some involve at first the preparation of high solid content water-based suspensions. This key step needs to be investigated in order to obtain highly and easily processable suspensions, featuring optimal viscosity and dispersion state. The structures and properties for all intermediate and final products involved in such ceramic manufacturing processes are heavily affected by these suspension characteristics. Therefore, they are critical to ensure a compliant final product (i.e. fuel pellets) with the required density, homogeneity, mechanical strength and absence of defects. In this scope, preparation process of such suspensions was developed by the use of UO₂ and PuO₂ surrogating (i.e. mimicking) powders, TiO₂ and Y₂O₃ respectively.     

Atmospheric plasma spraying coatings from alumina–titania feedstock comprising bimodal particle size distributions

In this work, Al₂O₃–13 wt% TiO₂ submicron-nanostructured powders were deposited using atmospheric plasma spraying. The feedstocks were obtained by spray drying two starting suspensions of different solids content, prepared by adding nanosized TiO₂ and submicron-sized Al₂O₃ powders to water. The spray-dried granules were heat-treated to reduce their porosity and the powders were fully characterised in both untreated and thermally treated state. Comparison with two commercial feedstocks was carried out. Characterisation allowed a temperature for the thermal treatment to be chosen on the basis of the sprayability of the feedstock and the preservation as much as possible of the submicron-sized structure of the unfired agglomerates.Optimisation of the deposition conditions enabled the reconstituted powders to be successfully deposited, yielding coatings that were well bonded to the substrate. The coating microstructure, characterised by SEM, was mostly formed by a matrix of fully molten particles where the presence of semi-molten feedstock agglomerates was also observed.Moreover, microhardness, toughness, adhesion and tribological behaviours were determined, and the impact of the granule characteristics on these properties was studied. It was found that changing the feedstock characteristics allows controlling the coating quality and properties. In general, good mechanical properties were obtained using a feedstock comprising a binary mixture of submicrometric Al₂O₃ and nanometric TiO₂ particles in the spray-dried powder.     

Optimization of spray freeze drying parameters for spark plasma sintering of transparent MgAl2O4 spinel

Magnesium aluminate spinel (MgAl₂O₄) is considered as one of the most important spinels possessing desirable mechanical properties, with a wide range of applications at high temperatures. Powder granulation by spray freeze drying can lead to better powder flow and distribution in the mold, resulting in a specimen with high green density and strength. Accordingly, this study aimed at investigating the influential parameters on the granulation process of spinel powders via the spray freezing drying method. At first, spinel powders with various weight percents of 20, 25, 30, 35 and 50, and PVA binders with 0, 1, 2 and 8 wt% were investigated to prepare the optimal solution. Finally, the granules were sintered using the SPS method. The obtained bodies were tested by X-ray diffraction, SEM, FE-SEM, Viscosity and UV–Vis. The results showed that the optimal amount of the binder to obtain uniform granules in this process was 3%. Also, 35 wt% of solid loads represented the optimum amount for slurries, forming granules with the size range of 10–50 μm. By powder granulation, density experienced an increase of about 20%, leading to the growth of more than 15% in the in-line transmission for the IR range.     

Dense nanocrystalline UO2+x fuel pellets synthesized by high pressure spark plasma sintering

Nanocrystalline UO_2+x powders are prepared by high‐energy ball milling and subsequently consolidated into dense fuel pellets (>95% of theoretical density) under high pressure (750 MPa) by spark plasma sintering at low sintering temperatures (600°C‐700°C). The grain size achieved in the dense nano‐ceramic pellets varies within 60‐160 nm as controlled by sintering temperature and duration. The sintered fuel pellets are single phase UO_2+x with hyper‐stoichiometric compositions as derived by X‐ray diffraction, and micro‐Raman measurements indicate that random oxygen interstitials and Willis clusters dominate the single phase nano‐sized oxide pellets of UO_2.03 and UO_2.11, respectively. The thermal conductivities of the densified nano‐sized oxide fuel pellets are measured by laser flash, and the fuel stoichiometry displays a dominant effect in controlling thermal transport properties. A reduction in thermal conductivity is also observed for the dense nano‐sized pellets as compared with micron‐sized counterparts reported in the literature. The correlation among the SPS sintering parameters—microstructure control—properties is established, and the nano‐sized UO_2+x pellets with controlled microstructure can serve as the model systems for fundamental understandings of fuel behaviors and obtaining critical experimental data for multi‐physics MARMOT model validation.     

Kinetic behaviour of the adsorption and photocatalytic degradation of salicylic acid in aqueous TiO2 microsphere suspension

A new photocatalyst, named TiO₂ microspheres, prepared by a sol‐spraying‐calcination method, can freely suspend with air bubbling in its aqueous suspension and easily settle down from a water phase under gravity. The experimental results demonstrated that TiO₂ microspheres had better adsorption capacity than conventional TiO₂ powders, due to large surface area, large pore volume, and also a porous structure. The photocatalytic activity of TiO₂ microspheres in aqueous suspension was evaluated using salicylic acid (SA) as a model substrate. It was found that the Langmuir–Hinshelwood model in its integral form described the kinetics of SA photocatalytic degradation in the TiO₂ microsphere suspensions better than its simplified form as a first‐order reaction model, since the significant substrate adsorption on the catalysts was not negligible. The kinetics of SA photocatalytic degradation with different initial concentrations and pH was further investigated. The experiments demonstrated that the change of pH could significantly affect the adsorption of SA in the TiO₂ microsphere suspensions. The effects of substrate adsorption rate and photoreaction rate on the overall performance of photocatalytic degradation is also discussed on the basis of experimental data. Copyright © 2004 Society of Chemical Industry     

Processing of ThO2/CeO2 Ceramic Fuel

The paper describes an effective procedure for mixing and conditioning ThO₂ and CeO₂ powders so they are suited for pressing and sintering into high‐density (Th_0.9,Ce_0.1)O₂ ceramic pellets – this material being a “pilot” for (Th,Pu)O₂ fuels. Wet ball milling with an organic dispersant aided the powder dispersing process by reducing the agglomeration of very small oxide particles. Homogeneous elemental distributions were seen within the calcined powder mixture. Heat treatments were applied to the calcined, mixed ThO₂/CeO₂ mix to study phase and surface area transformations. Solid solution formation commences at around 1300°C and goes to completion at a temperature of 1500°C. We also report the effect of a granulation strategy that can be applied to the production of high quality, mixed ThO₂ nuclear fuel ceramics. Sized granules of blended ThO₂/CeO₂ powder were produced from precompacted disks of this material that were subsequently heat treated. This had a positive effect on die filling and compaction into green pellets, as well as on final sintered (Th,Ce)O₂ pellet density. The microstructure of the sintered (Th,Ce)O₂ ceramic was characterized using SEM‐based electron back‐scatter diffraction from which a uniform density and grain size were readily apparent. XRD results showed that a single phase Th_0.9Ce_0.1O₂, fuel ceramic had been produced. Its density was ~94% TD.     

A feasibility study of using CeO2 as a surrogate material during the investigation of UO2 thermal conductivity enhancement

A possible substitution of UO₂ for research purposes is the cerium dioxide (CeO₂) owing to its chemical and physical properties. Neutronic properties are different and fission is absent in the case of CeO₂; however, similarities were studied recently to have a possibility to compare the neutronic influence of secondary additives into the matrix. This paper deals with increasing the thermal conductivity of UO₂ nuclear fuel on surrogate material (CeO₂); the main focus of the research is given on the sintering behaviour of CeO₂. The incorporation of highly thermally conductive material (SiC) is the investigated concept of thermal conductivity enhancement. Conventional sintering and spark plasma sintering (SPS) were applied to compare the behaviour of CeO₂ and UO₂ reported in the literature. High temperature thermal conductivity measurements did not confirm the positive influence of SiC additive inside the CeO₂ matrix mainly due to grain boundary disruptions. Similar behaviour was also previously reported for UO₂ pellets with SiC.     

Impact of Al2O3-40 wt.% TiO2 feedstock powder characteristics on the sprayability,microstructure and mechanical properties of plasma sprayed coatings

Atmospheric plasma sprayed (APS) Al₂O₃-TiO₂ coatings have found a wide range of industrial application due to their favorable properties, combined with low costs and a high availability. However, the detailed effect of the phase composition and the element distribution of the feedstock powders on the coating properties and the spraying process have only crudely been investigated so far. Here the impact of aluminum titanate (Al₂TiO₅) on the microstructural features and mechanical properties of Al₂O₃-40 wt.% TiO₂ APS coatings is demonstrated by investigating the detailed phase composition and the distribution of aluminum and titanium in three fused and crushed feedstock powders and the respective coatings. Thereby, a direct influence of Al₂TiO₅ content on the deposition efficiency, the porosity, the elastic modulus, and the hardness of the coatings is revealed. The results emphasize the need for a more detailed specification of commercial Al₂O₃-TiO₂ feedstock powders to ensure a high reliability of the coating properties.     

Distinct dispersion stability of various TiO2 nanopowders using ammonium polyacrylate as dispersant

The dispersion stabilities of three titania (TiO₂) nanopowders with different particle sizes and surface chemistries in aqueous suspensions containing a common water-based dispersant, ammonium polyacrylate (PAA-NH₄), have been investigated and compared. According to adsorption isotherm and Fourier transform infrared spectroscopy analyses, the adsorption conformations of PAA-NH₄ are distinct for the different TiO₂ nanopowders. In addition, PAA-NH₄ exhibited the greatest adsorption affinity to the larger, hydrophilic TiO₂ nanopowder and the least affinity to smaller, hydrophobic nanopowder. From sedimentation and rheological results, the dispersion stability of the larger, hydrophilic TiO₂ nanopowder was demonstrated to be the greatest. Based on thermodynamic and kinetic calculations for the stabilization energies, the larger, hydrophilic TiO₂ nanopowder was also shown to be the best-stabilized powder, although it settles faster than the smaller, hydrophilic TiO₂ nanopowder; this is due to the greater affection of sedimentation flux on the larger nanopowder. In contrast, the hydrophobic TiO₂ nanopowder formed a gel-like structure in the aqueous suspension when the solid content was greater than 10 wt%, which is attributed to polymer bridging between PAA-NH₄-adsorbed TiO₂ nanoparticles.     

Investigating slip casting of ceramics based on stabilized ZnO2 obtained by the chemical coprecipitation method

Conclusions We studied the influence of a number of technological parameters (heat-process temperature, dispersion of solid phase, pH, and concentration of suspension) on the rheological properties of the water suspensions and certain technical properties of castings and materials made from yttria-stabilized ZrO₂, obtained by the method of coprecipitation from salt solutions.We demonstrated the essential influence of the structure of the original powders, the content of Y₂O₃, and the bonded chlorides on the properties of the castings and the sintered material.Translated from Ogneupory, No. 1, pp. 24–28, January, 1986.     

Direct ink writing of macroporous lead-free piezoelectric Ba0.85Ca0.15Zr0.1Ti0.9O3

Direct ink writing (DIW) has become a widespread additive manufacturing technique for material engineering, but its application in lead-free Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃ piezoelectric ceramics from aqueous systems has not been reported so far to our knowledge. The main obstacle is the high extent of hydrolysis reactions undergone by the starting powders when dispersed in water, hindering the attainment of stable water-based colloidal suspensions. This paper reports on the preparation of stable aqueous inks from a deagglomerated and surface-treated powder synthesized by solid-state reaction and on DIW of macroporous lead-free piezoelectrics. Based on zeta potential and rheological measurements, the optimal amounts of processing additives (dispersant, binder, and coagulating agent) were selected to transform the initial fluid suspension to a viscoelastic paste with sufficient stiffness and stability for the printing process. Dielectric and piezoelectric properties of samples sintered under different temperatures were also investigated.     

Surface Interaction of PuO2, UO2+x and UO3 with Water Ice

The interaction of PuO₂, UO_2+x and UO₃ with water ice was studied using ultraviolet photoelectron spectroscopy (UPS). Water was adsorbed at 80–120 K as thick ice multilayers. Surface modification after desorption of the ice around 200 K was investigated. Main information on the surface oxidation state was obtained by highly surface sensitive UPS-HeII spectra, probing primarily the first monolayer. The oxidation state was directly deduced from the intensity of the actinide 5f levels. The surface character of the phenomenon was further confirmed by comparing HeII spectra with the more bulk sensitive HeI spectra. Spectral interpretation was done using the cross-section variations in HeI and HeII spectra and by comparing the spectra with theoretical density of states curves, obtained by LSDA + U calculations. It was shown previously that reduction to Pu₂O₃ takes place, when the ice covered PuO₂ films are warmed up under UV light and ice is desorbed. In this paper, this effect was investigated in further detail. It was shown that only the top surface layer is reduced. Reduction is inhibited by surface diffusion of oxygen trapped in the films during sputter deposition and not incorporated in the lattice. UO_2+x and UO₃ also undergo reduction, but to a significant lesser extent than PuO₂. Reoxidation of surface U by bulk oxygen was much slower than that of surface Pu. It was shown that for all oxides, reduction needs the illumination of an ice overlayer by UV light. Surface reduction by atomic hydrogen was investigated to check for possible influence of ice photolysis products. UO₃ was shown to be reduced to UO₂ while PuO₂ is not further reduced. The observations are explained by photochemical decomposition of water by the UV light (used for UPS) at the oxide-ice interface. It is thought that the oxide acts as photocatalyst, absorbing light and splitting adsorbed water. The thick ice layer traps the reaction products on the surface, thereby enabling them to react and reduce the surface. Why only the reductants (probably H) and not the concomitant oxidants react with the surface is still unknown.     

TiB2 Powders Synthesis by Borothermal Reduction in TiO2 Under Vacuum

TiB₂ powders were synthesized by borothermal reduction in nanoscale TiO₂ with boron under vacuum. Reaction processes were investigated, and the effect of by‐product B₂O₃ was evaluated. Results showed that TiO₂ was firstly reduced by boron to form TiBO₃ and Ti₂O₃, and then to produce TiB₂ and B₂O₃ with increasing temperature. The reaction processes of TiB₂ powders synthesis included two‐step reduction in TiO₂ by boron and the removal of B₂O₃. The presence of B₂O₃, which was previously reported as the most important factor in promoting the coarsening of ZrB₂ and HfB₂ powders by borothermal reduction, did not lead to significant coarsening of TiB₂ powders. Due to the minor effect of B₂O₃, TiB₂ powders with small particle size and low oxygen content could be prepared by direct heat treatment of TiO₂ and boron at 1550°C under vacuum for 1 h. The particle size and oxygen content of synthesized TiB₂ powders were ~0.9 μm and ~1.7 wt%, respectively.     

Suspension high velocity oxy-fuel spraying of a rutile TiO2 feedstock: Microstructure,phase evolution and photocatalytic behaviour

Nano-structured TiO₂ coatings were produced by suspension high velocity oxy fuel (SHVOF) thermal spraying using water-based suspensions containing 30 wt% of submicron rutile powders (~180 nm). By changing the flame heat powers from 40 kW to 101 kW, TiO₂ coatings were obtained with distinctive microstructures, phases and photocatalytic behaviour. Spraying with low power (40 kW) resulted in a more porous microstructure with the presence of un-melted nano-particles and a lower content of the anatase phase; meanwhile, high powers (72/101 kW) resulted in denser coatings and rougher surfaces with distinctive humps but not necessarily with a higher content of anatase. Linear sweep voltammetry (LSV) was used to evaluate the photocatalytic performance. Surprisingly, coatings with the lowest anatase content (~20%) using 40 kW showed the best photocatalytic behaviour with the highest photo-conversion efficiency. It was suggested that this was partially owing to the increased specific surface area of the un-melted nano-particles. More importantly, the structural arrangement of the similarly sized TiO₂ nano-crystallites between rutile and antase phases also created catalytic “hot spots” at the rutile−anatase interface and greatly improved the photo-activity.     

Colored films produced by electron beam deposition from nanometric TiO2 and Al2O3 pigment powders obtained by modified polymeric precursor method

Synthesis and the characterization of TiO₂:5%Co (green), TiO₃:5%Fe (brown-reddish), TiO₂:2%Cr (brown), Al₂O₃:5%Co (blue), Al₂O₃:5%Fe (brown-reddish) and Al₂O₃:2%Cr (light green) nanometric pigment powders using polymeric precursor (modified Pechini's method) is reported. Colored thick films were deposited on amorphous quartz substrates by electron beam physical vapor deposition (EB-PVD) using pellets of the pigment powders as target. The evaporation process was carried out in vacuum of 4 × 10⁻⁶ Torr and the amorphous quartz substrates were kept at 350 °C during deposition. The TiO₂-based pigment powders presented crystalline anatase phase and the Al₂O₃-based pigment powders showed corundum phase, investigated by X-ray diffraction (XRD). The average particle size of the pigment powders was about 20 nm, measured by scanning electron microscopy with field emission gun (SEM-FEG). Diffuse reflectance spectra and colorimetric coordinates L¹, a¹, b¹ using the CIE-L¹a¹b¹ method are shown for the pigment powders, in the 350–750 nm range. The colored thick films were characterized by transmittance (UV–Vis) and atomic force microscopy (AFM). The average film roughness was ∼5.5 nm and the average grain size obtained in the films was around 75 nm. Films with thickness from 400 nm to 690 nm were obtained, measured by talystep profiler. Transmission spectra envelop method has been used to obtain refractive index and thickness of the Al₂O₃ colored thick films.     

Phase transitions in (1−x)BaZr0.2Ti0.8O3−xBa0.7Ca0.3TiO3 powders and ceramic pellets

The phase transitions in (1−x)BaZr_0.2Ti_0.8O₃−xBa_0.7Ca_0.3TiO₃ (BZT-xBCT) powders and ceramic pellets were studied. It is found that the phase compositions in the pellets are different from that in the powders, which may be caused by the stress in the pellets. The monoclinic phase exists near the morphotropic phase boundary (MPB) in the ceramics. The piezoelectric coefficient (d₃₃) measurement of the ceramics shows that the higher piezoelectric properties are corresponding to higher content of monoclinic phase.     

The photocatalytic oxidation of water to O2 over pure CeO2, WO3, and TiO2 using Fe3+ and Ce4+ as electron acceptors

We report here the results from a study on the photocatalytic decomposition of water to oxygen over pure WO₃, CeO₂, and TiO₂. It has been demonstrated that Fe_aq³⁺ and Ce_aq⁴⁺ species are efficient electron acceptors during the photoproduction of O₂ over a variety of oxides, even at very low concentrations. The O₂ yield was found to depend on the type and surface activity of the cation used as an electron acceptor, and the salt counter anion. While Ce_aq⁴⁺ gives slightly higher initial O₂ rates, Fe_aq³⁺ tends to give higher long-term O₂ yields. The O₂ yield was found to be mainly sensitive to the intrinsic properties of a given material, such as the type of the oxide used and its physicochemical characteristics, e.g. crystal structure and level of crystallinity. For the powders tested, O₂ production was independent of the BET surface area and the activity does not correlate directly with the onset of light absorption of the powders. With a light having λ≥330 nm, O₂ production activity decreased in the order TiO₂-rutile>TiO₂-anatase>WO₃>CeO₂⪢amorphous TiO₂, whereas with a light having λ≥420 nm, it decreased in the order WO₃>TiO₂>CeO₂. Small amounts of Sn on TiO₂-rutile markedly improved its activity. In addition, the O₂ yield strongly depended on the concentration of the electron acceptor and the pH of the suspension. During the reaction, small amounts of hydrogen were also produced. The reaction pathways for electron scavenging by Ce_aq⁴⁺ and Fe_aq³⁺, and the process leading to O₂ evolution will be discussed.     

Neutron adsorption performance of Dy2TiO5 materials obtained from powders synthesized by the molten salt method

Dy₂TiO₅ powders were synthesized by molten salt and solid-state methods. The influences of molten medium on phase compositions and microstructures were analyzed. The addition of molten salt lowered significantly the synthesis temperature and resulted in uniform powders. Green bodies compacted from the prepared powders were pressureless sintered at 1600 °C. Sinterability, mechanical properties and neutron absorption performance of the sintered pellets were studied. Results showed that molten salt synthesis resulted in materials with higher fracture toughness and bending strength, excellent hardness and neutron adsorption performance compared to the solid-state process. The neutron absorption rate reached 86.6% for 8 cm thick pellets.     

Hydrothermal synthesis of uranium dioxide and graphene composite and its application as an additive for uranium-dioxide-based accident tolerant fuel

A novel kind of composite constructed by uranium dioxide and reduced graphene oxide (RGO) was developed via a one-step hydrothermal reduction method, named as UO₂@G. The introduction of graphene oxide (GO) to the reaction system brought significant changes: in the control experiment without GO, the reductant of ethylenediamine itself could only reduce uranyl ions to mainly U₃O₈, and the final solid products appear in the form of flakes; by introducing GO to the system, the final products are pure UO₂ in homogenous nanospheres. By employing UO₂@G as an additive in the UO₂ fuel pellet (the final volume ratio of graphene materials was controlled to be around 10%), the thermal conductivity is increased by 35.4%, which is significantly higher than that of the pellet prepared by simply mixing UO₂ powders and commercial graphene nanosheets. The simulation results show that the core temperature of the pellet containing the UO₂@G composite additives is much lower than that of the one without UO₂@G composite additives, showing the potential as novel kind of accident tolerant fuel.