Addition of Fe2O3 as oxygen carrier for preparation of nanometer-sized oxide strengthened steels

Nano-structured ferritic alloys, which are prepared almost exclusively via the mechanical alloying of Y₂O₃, have recently attracted much attention. Our preliminary results show that the usage of Fe₂O₃ as oxygen source leads to better control of powder properties than Y₂O₃ and a high density of nanometer-sized oxide particles can be formed by atomic mixing of Y, Ti and O. This may provide a new route with reduced costs and improved reproducibility for industrial production of nanometer-sized oxide strengthened steels.     

Creep behavior of oxide dispersion strengthened 8Cr-2WVTa and 8Cr-1W steels

Microstructures and creep behavior of two martensitic oxide dispersion strengthened (ODS) steels 8%Cr-2%W-0.2%V-0.1%Ta (J1) and 8%Cr-1%W (J2) with finely dispersed Y₂Ti₂O₇ have been investigated. Creep tests have been carried out at 670, 700 and 730 °C. Creep strength of J1 is stronger than that of any other ODS martensitic steels and the hoop strength of the ferritic ODS steel cladding. At the beginning of creep test, shrinkage was frequently observed for J1. This is one of the reasons for high creep strength of J1. The δ-ferrite, which is untransformed to austenite at hot isostatic press and hot rolling temperatures, was elongated along the rolling direction, and volume fraction of δ-ferrite in J1 is larger than J2. Although the elongated δ-ferrite affects the anisotropy of creep behavior, the extent of anisotropy in J1 is not so large as that of the ferritic ODS steel.     

Nanoscale characterization and formation mechanism of nanoclusters in an ODS steel elaborated by reactive-inspired ball-milling and annealing

Reactive-inspired ball-milling is proposed as a new production route for oxide dispersion strengthened (ODS) steels. So a Fe-14Cr-2W-1Ti-0.8Y-0.2O (wt.%) ODS steel is elaborated by ball-milling of FeCrWTi and YFe₃ plus Fe₂O₃ powders instead of Y₂O₃ and then by annealing at 800 °C for 5 min. Characterizations by Electron Probe MicroAnalysis and Atom Probe Tomography (APT) are performed after milling and after annealing. For the very first time, nanoclusters are observed after ball-milling by APT. Those nanoclusters are enriched in titanium, yttrium and oxygen and their mean radius is 0.8 nm. With annealing, the mean radius rises up to 1.4 nm and the number density as well as the enrichment factor in O, Ti and Y increase. So a new formation mechanism of nanoclusters is observed in those conditions of synthesis: ball-milling initiates the nanoclusters nucleation and during annealing, nucleation continues, accompanied by a slight growth of nanoclusters. Thus reactive-inspired ball-milling appears as a promising route for synthesizing ODS steels with a fine and dense dispersion of oxides.     

Development of 9Cr-ODS Martensitic Steel Claddings for Fuel Pins by means of Ferrite to Austenite Phase Transformation

For use as fuel cladding of liquid metal fast reactors, Fe-0.12C-9Cr-2W ODS martensitic steel claddings were developed by cold-rolling under the softened ferrite phase induced by slow cooling from austenite phase, subsequently by ferrite to austenite phase transformation to break up substantially elongated grains produced by cold-rolling at the final heat-treatment. The produced claddings showed noticeable improvement in tensile and creep rupture strength that are considerably superior to PNC-FMS and even austenitic PNC316 at higher temperature and extended time to rupture. The strength improvement is mainly attributed to titanium addition in ODS martensitic steels through its reduction of Y₂O₃ particle size and shortening inter-particles spacing. The behavior of oxide particle size reduction is associated with stoichiometry between Y₂O₃ and TiO₂.     

Chlorination of UO2, PuO2 and rare earth oxides using ZrCl4 in LiCl-KCl eutectic melt

A new chlorination method using ZrCl₄ in a molten salt bath has been investigated for the pyrometallurgical reprocessing of nuclear fuels. ZrCl₄ has a high reactivity with oxygen but is not corrosive to refractory metals such as steel. Rare earth oxides (La₂O₃, CeO₂, Nd₂O₃ and Y₂O₃) and actinide oxides (UO₂ and PuO₂) were allowed to react with ZrCl₄ in a LiCl-KCl eutectic salt at 773 K to give a metal chloride solution and a precipitate of ZrO₂. An addition of zirconium metal as a reductant was effective in chlorinating the dioxides. When the oxides were in powder form, the reaction was observed to progress rapidly. Cyclic voltammetry provided a convenient way of establishing when the reaction was completed. It was demonstrated that the ZrCl₄ chlorination method, free from corrosive gas, was very simple and useful.     

Influence of HIP pressure on tensile properties of a 14Cr ODS ferritic steel

An oxide dispersion strengthened ferritic steel with a nominal composition of Fe–14Cr–2W–0.3Ti–0.3Y₂O₃ (in wt.%) was consolidated by hot isostatic pressing at 1150 °C under various pressures in the range of 185–300 MPa for 3 h. The microstructure, microhardness and high temperature tensile properties of the steel were investigated. With increasing compaction pressure the density of specimens also increased, however OM and SEM observations revealed residual porosity in all tested specimens and similar ferritic microstructure with bimodal-like grains and numerous of large oxide particles, located at the grain boundaries. Mechanical testing revealed that compaction pressure has negligible influence on the hardness and tensile strength of the ODS steel, however improves the material ductility.     

HRTEM study of oxide nanoparticles in K3-ODS ferritic steel developed for radiation tolerance

Crystal and interfacial structures of oxide nanoparticles and radiation damage in 16Cr-4.5Al-0.3Ti-2W-0.37 Y₂O₃ ODS ferritic steel have been examined using high-resolution transmission electron microscopy (HRTEM) techniques. Oxide nanoparticles with a complex-oxide core and an amorphous shell were frequently observed. The crystal structure of complex-oxide core is identified to be mainly monoclinic Y₄Al₂O₉ (YAM) oxide compound. Orientation relationships between the oxide and the matrix are found to be dependent on the particle size. Large particles (>20 nm) tend to be incoherent and have a spherical shape, whereas small particles (<10 nm) tend to be coherent or semi-coherent and have a faceted interface. The observations of partially amorphous nanoparticles and multiple crystalline domains formed within a nanoparticle lead us to propose a three-stage mechanism to rationalize the formation of oxide nanoparticles containing core/shell structures in as-fabricated ODS steels. Effects of nanoparticle size and density on cavity formation induced by (Fe⁸⁺ + He⁺) dual-beam irradiation are briefly addressed.     

The effect of Y2O3 on the dynamics of oxidative dissolution of UO2

In this work, we have studied the impact of Y₂O₃ on the kinetics of oxidative dissolution of UO₂ and the consumption of H₂O₂. The second order kinetics of catalytic consumption of H₂O₂ on Y₂O₃ was investigated in aqueous Y₂O₃ powder suspensions by varying the solid surface area to solution volume ratio. The resulting second order rate constant is 10⁻⁸ m s⁻¹, which is of the same magnitude as for the reaction between H₂O₂ and UO₂. Powder experiments with mixtures of UO₂ and Y₂O₃ show that Y₂O₃ has no effect on the oxidative dissolution of UO₂, whereas the consumption of H₂O₂ seems to be slightly slower in the presence of Y₂O₃ and H₂ respectively. UO₂ pellets with solid inclusions of Y₂O₃ show a decrease in oxidative dissolution by a factor of 3.3 and 5.3 under inert and hydrogen atmosphere, respectively. The rate of H₂O₂ consumption is similar for all cases and is well in line with kinetic data from powder experiments. The effects of H₂ and Y₂O₃ on the oxidative dissolution of UO₂ under gamma irradiation are similar to those found in experiments with H₂O₂. No significant difference in dissolution between inert and reducing atmosphere can be observed for pure UO₂.     

Development and characterization of advanced 9Cr ferritic/martensitic steels for fission and fusion reactors

This paper presents the results on the physical metallurgy studies in 9Cr Oxide Dispersion Strengthened (ODS) and Reduced Activation Ferritic/Martensitic (RAFM) steels. Yttria strengthened ODS alloy was synthesized through several stages, like mechanical milling of alloy powders and yttria, canning and consolidation by hot extrusion. During characterization of the ODS alloy, it was observed that yttria particles possessed an affinity for Ti, a small amount of which was also helpful in refining the dispersoid particles containing mixed Y and Ti oxides. The particle size and their distribution in the ferrite matrix, were studied using Analytical and High Resolution Electron Microscopy at various stages. The results showed a distribution of Y₂O₃ particles predominantly in the size range of 5-20 nm. A Reduced Activation Ferritic/Martensitic steel has also been developed with the replacement of Mo and Nb by W and Ta with strict control on the tramp and trace elements (Mo, Nb, B, Cu, Ni, Al, Co, Ti). The transformation temperatures (A_c1, A_c3 and M_s) for this steel have been determined and the transformation behavior of the high temperature austenite phase has been studied. The complete phase domain diagram has been generated which is required for optimization of the processing and fabrication schedules for the steel.     

Photoluminescence and XEL in Y2O3:Eu phosphor

Eu-activated Y₂O₃ phosphors were prepared by combustion synthesis and also by precipitation techniques. Photoluminescence and X-ray excited luminescence of prepared Y₂O₃:Eu phosphor, under two different techniques were compared and reported in this paper. Y₂O₃:Eu³⁺ phosphor were prepared by precipitation technique followed by annealing at 900 °C. It gives cubic nature of the particle that may be more favourable for high lumen output. X-ray excited luminescence of Y₂O₃:Eu³⁺ phosphors also reported in this paper.     

Dual beam irradiation of nanostructured FeCrAl oxide dispersion strengthened steel

Nanostructured ferritic oxide dispersion strengthened (ODS) alloy is an ideal candidate for fission/fusion power plant materials, particularly in the use of a first-wall and blanket structure of a next generation reactor. These steels usually contain a high density of Y-Ti-O and Y-Al-O nanoparticles, high dislocation densities and fine grains. The material contains nanoparticles with an average diameter of 21 nm and was treated by several cold rolling procedures, which modify the dislocation density. Structural analysis with HRTEM shows that the chemical composition of the initial Y₂O₃ oxide is modified to perovskite YAlO₃ (YAP) and Y₂Al₅O₁₂ garnet (YAG). Irradiation of these alloys was performed with a dual beam irradiation of 2.5 MeV Fe⁺/31 dpa and 350 keV He⁺/18 appm/dpa. Irradiation causes atomic displacements resulting in vacancy and self-interstitial lattice defects and dislocation loops. Extended SRIM calculations for ODS steel indicate a clear spatial separation between the excess vacancy distribution close to the surface and the excess interstitials in deeper layers of the material surface. The helium atoms are supposed to accumulate mainly in the vacancies. Additionally to structural changes, the effect of the irradiation generated defects on the mechanical properties of the ODS is investigated by nanoindentation. A clear hardness increase in the irradiated area is observed, which reaches a maximum at a close surface region. This feature is attributed to synergistic effects between the displacement damage and He implantation resulting in He filled vacancies. Fine He cavities with diameters of a few nanometers were identified in TEM images.     

Formation of Y2O3 nanoclusters in nano-structured ferritic alloys: Modeling of precipitation kinetics and yield strength

The solubility product of Y₂O₃ in ferrite and the diffusion coefficient of yttrium in ferrite have been obtained by fitting a model based on the classical nucleation-growth-coarsening theory of precipitation, as adapted to an anisothermal heat treatment, to experimental small angle neutron scattering results of Y₂O₃ precipitate size distributions in a mechanically alloyed and consolidated Fe-15 at.%Cr-0.13 at.%Y-0.18 at.%O ferritic alloy. This precipitation model is coupled to a dispersed barrier model of structural hardening to predict the yield strength of the alloys as a function of heat treatment. The resulting model and thermodynamic/kinetic properties are then applied to better understand how the precipitation kinetics impact the yield stress in various anisothermal heat treatments, as compared to an isothermal heat treatment. The modeling results clearly indicate that the anisothermal heat treatments can be tailored to establish a higher density and a smaller size distribution of Y₂O₃ precipitates, which also increase the yield stress.     

Microstructural investigation of the stability under irradiation of oxide dispersion strengthened ferritic steels

Some fuel pin cladding made from a ferritic steel reinforced by titanium and yttrium oxides were irradiated in the French experimental reactor Phénix. Microstructural examination of this alloy indicates that oxides undergo dissolution under irradiation. This irradiation shows the influence of dose and, in a smaller part, of temperature. In order to better understand the mechanisms of dissolution, three ferritic steels reinforced by Y₂O₃ or MgO were irradiated with different charged particles. Inelastic interactions induced by 1 MeV He ion irradiation do not lead to any modification, neither in their chemical composition, nor in their spatial and size distribution. In contrast, isolated Frenkel pairs created by electron irradiation lead to significant oxide dissolution with a radius decrease proportional to the dose. Moreover, the comparison between irradiation with ions (displacements cascades) and electrons (Frenkel pairs only) shows the importance of free point defects in the dissolution phenomena.     

Laser-joined Al2O3 and ZrO2 ceramics for high-temperature applications

A laser process is presented that has been specially developed for joining oxide ceramics such as zirconium oxide (ZrO₂) and aluminium oxide (Al₂O₃). It details, by way of example, the design of the laser process applied for to producing both Al₂O₃-Al₂O₃ and ZrO₂-ZrO₂ joints using siliceous glasses as fillers.The heat source used was a continuous wave diode laser with a wavelength range of 808-1010 nm. Glasses of the SiO₂-Al₂O₃-B₂O₃-MeO system were developed as high-temperature resistant brazing fillers whose expansion coefficients, in particular, were optimally adapted to those of the ceramics to be joined. Specially designed measuring devices help to determine both the temperature-dependent emission coefficients and the synchronously determined proportions of reflection and transmission.The glass-ceramic joints produced are free from gas inclusions and macroscopic defects and exhibit a homogenous structure. The average strength values achieved were 158 MPa for the Al₂O₃ system and 190 MPa for the ZrO₂ system, respectively.     

Effect of thermo-mechanical treatments on the microstructure and mechanical properties of an ODS ferritic steel

The Fe-14Cr-2W-0.3Ti-0.3Y₂O₃ oxide dispersion strengthened (ODS) reduced activation ferritic (RAF) steel was fabricated by mechanical alloying of a pre-alloyed, gas atomised powder with yttria nano-particles, followed by hot isostatic pressing and thermo-mechanical treatments (TMTs). Two kinds of TMT were applied: (i) hot pressing, or (ii) hot rolling, both followed by annealing in vacuum at 850 °C.The use of a thermo-mechanical treatment was found to yield strong improvement in the microstructure and mechanical properties of the ODS RAF steel. In particular, hot pressing leads to microstructure refinement, equiaxed grains without texture, and an improvement in Charpy impact properties, especially in terms of the upper shelf energy (about 4.5 J). Hot rolling leads to elongated grains in the rolling direction, with a grain size ratio of 6:1, higher tensile strength and reasonable ductility up to 750 °C, and better Charpy impact properties, especially in terms of the ductile-to-brittle transition temperature (about 55 °C).     

Microstructure and oxidation properties of 16Cr–5Al–ODS steel prepared by sol–gel and spark plasma sintering methods

The 16Cr–5Al oxide dispersion strengthened (ODS) ferritic steel was fabricated by sol–gel method in combination with hydrogen reduction, mechanical alloying (MA) and spark plasma sintering (SPS) techniques. The phase characterization, microstructure and oxidation resistance of the 16Cr–5Al–ODS steel were investigated in comparison with the Al free 16Cr–ODS steel. X-ray diffraction (XRD) patterns showed that the Al free and Al added 16Cr–ODS steels exhibited typical ferritic characteristic structure. The microstructure analysis investigated by transmission electron microscopy (TEM) and energy dispersive spectrometry (EDS) revealed that Y–Ti–O complexes with particle size of 10–30 nm were formed in the Al free matrix and Y–Al–O complexes with particle size of 20–100 nm were formed in the Al contained high-Cr ODS steel matrix. These complexes are homogeneously distributed in the matrices. The fabricated 16Cr–5Al–ODS steel exhibited superior oxidation resistance compared with the Al free 16Cr–ODS steel and the commercial 304 stainless steel owing to the formation of continuous and dense Al₂O₃ film on the surface.     

Diffuse reflectance and X-ray photoelectron spectroscopy of uranium in ZrO2 and Y2Ti2O7

Diffuse reflectance measurements were made over the wavenumber range of 4000-20,000 cm⁻¹ at room temperature on monoclinic and stabilised ZrO₂, together with Y₂Ti₂O₇ having the pyrochlore structure, all of which were doped with U and sintered in various atmospheres. X-ray photoelectron spectroscopy measurements were also carried out on selected samples. In monoclinic and stabilised zirconia, U exhibited valence states of +4 and/or +5, depending on the sintering atmosphere and the presence of appropriate charge compensators. Using both diffuse reflectance and X-ray photoelectron spectroscopy, U was also observed as mainly U⁴⁺ and/or U⁵⁺ in U-doped Y₂Ti₂O₇ sintered at 1400 °C in air or Ar, although a small amount of U⁶⁺ also appeared to be present in some U-doped Y₂Ti₂O₇ samples heated in air.     

Defect volumes of BO2 doped Y2O3 (B = Ti, Zr, Hf and Ce)

Atomistic simulations have been employed to study the effect of BO₂ (fluorite) incorporation into the bixbyite oxide Y₂O₃. The energetically preferred defect mechanism and the associated lattice parameter changes that occur from BO₂ doping have been predicted. The addition of Group IV elements into Y₂O₃ can follow three different mechanisms. The energetically favourable method is through a mediated reaction for ZrO₂ and HfO₂ while for TiO₂ and CeO₂, reducing B⁴⁺ to B³⁺ provides the lowest energy reaction. ZrO₂ and HfO₂ doping results in the lowest volume changes.     

Frenkel pair accumulation induced crystallization of amorphous MgAl2O4

The epitaxial and homogeneous irradiation induced re-crystallization of amorphous MgAl₂O₄ was studied by means of continuous Frenkel pair accumulation in the molecular dynamics framework. Present results point out that the re-crystallization induced by Frenkel pair accumulation appears in both cases to be thermally enhanced but non diffusive. It is governed by a local rearrangement of each point defect in the homogeneous case, while spontaneous Frenkel pair recombination process in the crystalline part or at the interface drives the re-crystallization in the epitaxial case.