Fabrication of homogenous pellets by freeze granulation of optimized TiO2-Y2O3 suspensions

MOX fuels are used in nuclear reactors. To ensure the manufacture of MOX, wet processes are investigated. Freeze granulation of water-based powder suspension seems a promising way to yield homogenous and easy-to-press UO₂-PuO₂ granules. These granules are expected to form dense and homogenous pellets by uniaxial pressing. Granules and pellet properties are affected by suspension formulation and atomization conditions. Therefore, these conditions must be studied and optimized to produce granules with good processability and thus MOX pellets with compliant density, homogeneity and absence of defects. In this scope, key properties of water-based suspensions of UO₂ and PuO₂ surrogate powders, TiO₂ and Y₂O₃ respectively, were firstly studied to assess their suitability for the freeze granulation process. These properties were compared to those of UO₂ and PuO₂ suspensions to verify and confirm the correctness in the choice of surrogate powders. Then, the freeze granulation process itself was investigated focusing on TiO₂-Y₂O₃ suspensions.     

Characterization by electron probe microanalysis,Raman spectroscopy and transmission electron microscopy of a MOX fuel sintered from a freeze-granulated powder

The microstructure of a 98.7 % dense U_0.856Pu_0.144O_1.993 sintered sample (average grain size around 1.5 µm) has been characterized by electron probe microanalysis, Raman spectroscopy and transmission electron microscopy. Raman spectroscopy gives results comparable to electron probe microanalysis in terms of studying the spatial distribution of plutonium in a homogeneous sintered MOX fuel. The use of transmission electron microscopy allows additional characterizations of great interest for investigating the chemical homogeneity of sintered MOX fuels. At the scale of the elementary grains constituting the sintered polycrystal, a variation in the Pu/(U+Pu) content has been observed which can change typically from 0 to about 40 at% over a short distance (from 100 to 150 nm). Thereby, the thorough characterization of the microstructure of MOX fuels by transmission electron microscopy is a critical step to understand their genesis and to apprehend their dissolution properties with a view to their reprocessing.     

Fabrication and characterization of minor actinides bearing fuels obtained by conventional powder metallurgy process

The CEA is currently assessing minor actinides (MA) recycling in nuclear fuels in fast neutrons reactors (FNR). Two routes are investigated: homogeneous recycling, where MA are added up to several percents in UPu-type fuel to be used in the whole core, and heterogeneous recycling, which consists in higher amounts of MA in uranium oxide fuel used in the periphery of the core. The studies include various subject areas: neutronics, thermo-physical properties, coolant type (sodium, lead, bismuth, helium), etc…, and experimental work concerning the fabrication of minor actinides compounds.The first part of this work consisted in the structural study by XRD of AmO₂. We studied the lattice parameter change versus time due to α self-irradiation. In this context, AmO₂ powder was prepared in the ATALANTE facility in the CEA Marcoule. It is a first approach of swelling phenomenon at the structural scale which has been extended at the macroscopic scale in the second part of the work with the study of the geometrical stability in time of UO₂ sintered pellets containing 30% Am. Pellets were fabricated by conventional powder metallurgy process in hot cell at the laboratory scale. Swelling behaviour has been studied by accurate diameter measurements performed along the pellets and correlated to the cumulative α decay dose. Up to 2.1 × 10¹⁷ α decay in the sample, no evidence of pellet macroscopic swelling was observed.     

Low-cost fabrication of Li2TiO3 tritium breeding ceramic pebbles via low-temperature solid-state precursor method

Lithium metatitanate (Li₂TiO₃) ceramic pebbles were fabricated from the powder synthesised via low-temperature solid-state precursor method. Solid H₂TiO₃ and LiOH·H₂O react chemically during ball milling process to form a nano-sized precursor powder. Pure β-Li₂TiO₃ powder can be obtained by calcining the precursor powder at 500 °C, which is half the temperature of conventional solid-state method. The synthesis process is simple and low-cost, which would be more available to achieve batch production among all feasible techniques. The low-temperature calcination will effectively avoid hard particle aggregates and poor sinterability caused by high-temperature heat treatment, which is conducive to prepare ceramics with good properties. The results show that the powder exhibits high sinterability with small particle size of 19 nm. The Li₂TiO₃ ceramic pebbles sintered at 800 °C have small grain size (470 nm), high relative density (83%) and good crush load (45 N), which has great potential as tritium breeding materials for fusion reactors.     

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.     

In-situ synthesized nanocrystalline UO2/SiC composite with superior thermal conductivity

In this study, a novel UO₂/SiC nanocomposite pellet was constructed via in-situ hydrothermal synthesis and SPS. Such method could avoid the problem of traditional mechanical mixing that could obtained the molecular level mixing during a chemical process. Using such method, SiC was dispersed uniformly in the UO₂ matrix. Its thermal conductivity is significantly higher than those of UO₂ pellet fabricated using hydro-thermally prepared powder and traditional UO₂ pellets at both working temperature (400 °C) and near-accident temperature (1000 °C). The thermal conductivity of UO₂/SiC nanocomposite pellet increased 23.7 % over traditional UO₂ and 48.9 % over UO₂ pellet fabricated using hydro-thermally prepared powder at 400 °C. It also increased 33.6 % over traditional UO₂ and 74.8 % over UO₂ pellet fabricated using hydro-thermally prepared powder at 1000 °C. These advantages are expected to maintain high thermal conductivity of fuels, enhance heat transferring efficiency of reactors, and minimize risks of pellet failure in the entire fuel life cycle.     

Research on the preparation of Ni/Al2O3 powder by fluidized crystallization granulation–hydrogen reduction

This paper proposes a new process route for the preparation of Ni/Al₂O₃ composite powder through fluidized crystallization granulation–hydrogen reduction and investigates the effects of process feasibility, nickel concentration, nucleation method, and hydrogen reduction on Ni/Al₂O₃-coated powder. The decrease in nickel concentration, heterogeneous nucleation, and natural air-drying properties of precursor particles was beneficial to the formation of a complete and uniform cladding layer, and the increase in hydraulic retention time could improve the thickness of the cladding layer. The optimum process involves a nickel concentration of 50 mg/L; hydraulic residence time of 75 h to ensure heterogeneous nucleation; two-step hydrogen reduction of precursor particles to obtain a complete and uniform Ni/Al₂O₃ cladding layer; and a powder surface nickel content of 59.5%.     

Effects of starting powder on microstructure and thermal conductivity of pressureless-sintered fully ceramic microencapsulated fuels

The effects of the starting SiC powder (α or β) with the addition of 5.67 wt% AlN–Y₂O₃–CeO₂–MgO additives on the residual porosity and thermal conductivity of fully ceramic microencapsulated (FCM) fuels were investigated. FCM fuels containing ～41 vol% and ～37 vol% tristructural isotropic (TRISO) particles could be sintered at 1870 °C using α-SiC and β-SiC powders, respectively, via a pressureless sintering route. The residual porosities of the SiC matrices in the FCM fuels prepared using the α-SiC and β-SiC powders were 1.1% and 2.3%, respectively. The thermal conductivities of FCM pellets with ～41 vol% and ～37 vol% TRISO particles (prepared using the α-SiC and β-SiC powders, respectively) were 59 and 41 Wm^?1K^?1, respectively. The lower porosity and higher thermal conductivity of FCM fuels prepared using the α-SiC powder were attributed to the higher sinterability of the α-SiC powder than that of the β-SiC powder.     

Preparation of spherical AlN powders by combined microemulsion method and carbothermal method

In this study, a two-step strategy for the preparation of micron-sized spherical aluminium nitride (AlN) powder by the combined micro-emulsion method in conjunction with the carbothermal reduction nitridation (CRN) route was designed. The spherical AlN powder with perfect dispersibility was prepared after a heat treatment at 1550 °C for 2 h in flowing N₂. The effects of the aluminium fluoride (AlF₃) content, reaction temperature and the introduction of yttrium oxide (Y₂O₃) on the nitridation ratio and on the morphology of granules, in particular, were investigated by XRD analysis and SEM. Additionally, the promotion mechanism of AlF₃ and Y₂O₃ on the nitridation reaction was also discussed. Specifically, one of the underlying formation mechanisms of the spherical granules with the aid of AlF₃ and Y₂O₃, and suggestions on the selection of additives for the CRN synthesis of spherical AlN powder were logically proposed.     

Spray-dried ceramic powders: A quantitative correlation between slurry characteristics and shapes of the granules

The characteristics and consequently the properties of ceramic coatings performed using plasma spraying means depend not only on the operating conditions but also on the powder feedstock. Oxide powders are commonly prepared in one stage or in a combination of stages of fusing, crushing, agglomerating and sintering. The spray drying process (which corresponds to the agglomerating route) is a technique in which small constituent particles dispersed in water (which is called slurry) are sprayed in hot air and granulated thanks to a binder (latex or PVA). Spray drying is carried out for a variety of reasons, two major motivations being the production of composite and shape controlled powders for thermal spray applications. The aim of the present work was to establish a correlation between the slurry formulation and the characteristics of the spray dried granules for two oxide ceramics: Al₂O₃ and Y₂O₃-ZrO₂. Detailed studies on the dispersion and stability of the slurries were performed using sedimentation tests, electrophoretic mobility measurements as well as adsorption isotherms experiments. Then, a drying experimental test based on the drying of a suspended droplet was developed to assess the drying mechanisms, identify the correlation between the slurry characteristics and the morphology of the dried granules and finally to predict the shapes of the spray-dried powders. It was shown that there is a qualitative relation between the sedimentation behaviour (as measured by the sediment ratio) and the granule shape (solid or hollow) and a quantitative relation between the thickness of the shell (for hollow granule) and the state of dispersion and the nature of the binder used. Finally, several powder batches were prepared in the spray-dryer which confirm the reliability of the drying simulation test.     

Nearly dense Ti–6Al–4V/TiB composites manufactured via hydrogen assisted BEPM

Titanium matrix composites reinforced with in situ formed titanium boride whiskers have long aroused significant interest for advanced applications in fields such as aerospace, biomedicine, and armaments. However, processing approaches dedicated to fabricating these composites have usually been limited by the cost-performance dilemma, thereby limiting commercial success. Blended elemental powder metallurgy (BEPM) has historically been the most economical route to produce titanium-based composites. At the same time, the need to reduce undue sinter porosities has imposed complicated and expensive extra thermomechanical steps in BEPM manufacturing. In the present study, nearly dense Ti–6Al–4V-based composites reinforced with in situ synthesized titanium monoborides (TiB) are prepared by simple press-and-sinter hydrogen-assisted BEPM without hot deformation or hot pressing using TiH₂, TiB₂, and master alloy (Al–V) powder blends as starting material. Vacuum sintering of compacted powder blends results in the formation of a dehydrogenated Ti–6Al–4V matrix with excessive porosity and unevenly distributed partially reacted TiB₂ particles. Such an inappropriate pre-sintered microstructure can be completely transformed into low-porosity uniform Ti–6Al–4V/TiB composites with tailored grains by using hydrogenation and milling of pre-sintered material into hydrogenated pre-alloyed powders and, finally, by using these powders in a second press-and-sinter processing step. The useful influence of hydrogen as a temporary alloying element on microstructure formation is discussed. The densification of hydrogenated powder compacts upon vacuum heating, and the hydrogen emission from the material is studied via dilatometric tests. The evolution of microstructure and phase composition during processing steps was investigated by scanning electron microscopy and x-ray diffraction. Compressive tests were used to evaluate the mechanical properties of materials produced after the first and second sintering. The results show that hydrogen-assisted BEPM can be a cost-effective route for in situ fabrication of Ti–6Al–4V/TiB composites with reliable mechanical properties.     

Wear resistance of chromium oxide nanostructured coatings

Nanostructured plasma-sprayed chromium oxide ceramic coatings, with a higher wear resistance than coatings obtained using micrometric powder as starting material have been developed. The influence of the starting powder, i.e. Cr₂O₃ fused crushed powders and Cr₂O₃ nanopowders having grains size of 100 nm, has been investigated. The nanopowders are reconstituted into spherical micrometer sized granules by the spray-drying process before plasma spraying. It is shown that due to their specific microstructure the wear resistance of the nanostructured coatings is more than 20 times higher compared to the coatings obtained using micrometric powder.     

Densification ability of combustion-derived Al2O3 powders

Nanocrystalline Al₂O₃ powders containing different amounts of MgO (0.1–5.0 mol%) or added boehmite (AlOOH) have been synthesized by combustion synthesis from aluminium nitrate and magnesium nitrate, using urea or sucrose as fuels. The as synthesized alumina powders were deagglomerated, compacted by dry pressing and sintered at 1625 °C for 2 h. For comparison purposes, a commercial high purity α-Al₂O₃ powder (ACC) was also processed following the same route. The sintered materials were characterized for bulk density (BD), apparent porosity (AP), and water absorption (WA) capacity, microstructure using SEM, and XRD phase composition. In comparison to boehmite, the MgO had a considerable effect on the densification behaviour of combustion-synthesized powder.     

Study of processing routes for WC-MgO composites with varying MgO contents consolidated by FAST/SPS

Two different preparation routes were applied to process WC-MgO composites with varying MgO contents (4.1 wt.% and 5.9 wt.% MgO). WC-MgO powder mixtures were synthesized by a milling process at 600 rpm for 6 h of partially oxidized WC (WC + WO₃), Mg₃N₂ and C. Alternatively, WC and MgO as initial powders were used. For consolidation of the powder mixtures the field-assisted sintering technology (FAST) was used. X-ray diffraction shows that samples out of different powder mixtures and sintered between 1600 °C and 1750 °C exhibited WC, MgO and the W₂C phase independent of the preparation route of the powder mixtures. A higher density and better mechanical properties (hardness and indentation fracture toughness) of WC-MgO were achieved of pure WC and MgO as initial powders were consolidated by FAST. It was found that a lower MgO content results in higher hardness values and in a slightly decreased indentation fracture toughness.     

Development of Cu-based oxygen carriers for chemical-looping combustion

In a chemical-looping combustion (CLC) process, gas (natural gas, syngas, etc.) is burnt in two reactors. In the first one, a metallic oxide that is used as oxygen source is reduced by the feeding gas to a lower oxidation state, being CO₂ and steam the reaction products. In the second reactor, the reduced solid is regenerated with air to the fresh oxide, and the process can be repeated for many successive cycles. CO₂ can be easily recovered from the outlet gas coming from the first reactor by simple steam condensation. Consequently, CLC is a clean process for the combustion of carbon containing fuels preventing the CO₂ emissions to the atmosphere. The main drawback of the overall process is that the carriers are subjected to strong chemical and thermal stresses in every cycle and the performance and mechanical strength can decay down to unacceptable levels after enough number of cycles in use.In this paper the behaviour of CuO as an oxygen carrier for a CLC process has been analysed in a thermogravimetric analyser. The effects of carrier composition and preparation method used have been investigated to develop Cu-based carriers exhibiting high reduction and oxidation rates without substantial changes in the chemical, structural and mechanical properties for a high number of oxidation-reduction cycles. It has been observed that the carriers prepared by mechanical mixing or by coprecipitation showed an excellent chemical stability in multicycle tests in thermobalance, however, the mechanical properties of these carriers were highly degraded to unacceptable levels. On the other hand, the carriers prepared by impregnation exhibited excellent chemical stability without substantial decay of the mechanical strength in multicycle testing. These results suggest that copper based carriers prepared by impregnation are good candidates for CLC process.     

High-performance ceramic parts with complex shape prepared by selective laser sintering: a review

ABSTRACT

Selective laser sintering (SLS) is an additive manufacturing technology which has shown great advantages in direct formation of the polymer, metal and their composites. However, ceramic parts prepared by the SLS still exhibit some fatal defects, including low density and poor mechanical properties. In this respect, recent advances for preparing ceramics have improved the final density and performance by adopting post-processing methods. In this review, three commonly used powder preparation approaches (i.e. mechanical mixing, solvent evaporation and dissolution-precipitation process) and two powder sintering mechanisms for the SLS are introduced. Porous ceramic parts are prepared directly through the SLS by virtue of their high porosity. And dense, high-performance Al₂O₃, ZrO₂, kaolin and SiC ceramic parts with complex shape are prepared by introducing CIP technology into the SLS, indicating that the hybrid technology could be the promising route for preparing high-performance ceramic parts used in various fields.     

Design and cost optimization of a hot fuel gas desulfurization process

A high temperature gas desulfurization process is proposed that effectively uses the iron oxides in the waste ashes from coal gasifiers to react with and sorb the H₂S, COS, and CS₂, in coal-derived fuels. The process is carried out at 1033 K and 2.22 MPa in packed bed reactors. Sulfided ash sorbents may be repeatedly regenerated to produce a 30/70 molar mixture of S₂ and SO₂, suitable for complete reduction to elemental sulfur or sulfuric acid manufacture.An optimization theory predicts the use of very shallow bed reactors, packed to 0.61 meters, operating in a cyclic sequence where the onstream time is only 0.37 hours. This markedly reduces the capital and operating costs.A plant treating 1.22 MM SCMH of 0.63 mole percent H₂S ladened fuel gas is estimated to have a 1981 cost of $7.638 million and an annual operating cost of $5.229 million. A modular plant for recovery of byproduct SO₂, as H₂SO₄ is estimated to cost an additional $11.38 million but shows an annual before-tax profit of $10.46 million based upon a selling price of $80/Ton for the acid. This large profit reflects the value of the by-product SO₂.     

Oxygen carriers for chemical looping combustion of solid fuels

A thermal analyzer-differential scanning calorimeter-mass spectrometer (TG-DSC-MS) was used to study oxygen carriers (OC) for their potential use for the application of chemical looping combustion (CLC) to solid fuels. Reaction rates, changes in reaction rates with repeated oxidation-reductions, exothermic heats during oxidation, and the effect of changing reduction gas compositions were studied. Oxidation rates were greater than reduction rates and reaction rates were reproducible through multiple oxidation-reduction cycles except where agglomeration occurred with powders. Iron oxide (Fe₂O₃ powder) and iron-based catalysts were found suitable for CLC of solid fuels having rapid reduction rates which increased with higher reducing gas concentrations. Fe₂O₃ powder was used to oxidize a high carbon coal char in an inert gas removing 88% of the carbon from the char. Other properties such as cost and durability indicated iron oxide OCs potential use for CLC of solid fuels.     

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.     

Synthesis of mesoporous TiO2/γ-Al2O3 composite granules with different sol composition and calcination temperature

Mesoporous TiO₂/γ-Al₂O₃ composite granules were prepared by combining sol-gel method and oil-drop method. After calcination at 450 °C, the composite granules showed anatase and γ-Al₂O₃ phases with the specific surface area of 240-310 m²/g. The phase composition and pore structure of the granules can be controlled by calcination temperature and the mixing ratio of boehmite sol and titania sol. The product granules can be used as a photocatalyst or adsorbent in moving or fluidized bed reactors.