David Simeone

Investigation on the zirconia phase transition under irradiation

Zirconia, ZrO2, produced by the oxidation of zirconium alloys in nuclear reactors, possesses a high stability under neutron irradiation. No amorphisation of yttrium-stabilised zirconia has been observed even at high dpa values (≈100 dpa). In pure monoclinic zirconia, a phase transition monoclinic → cubic (tetragonal) induced by irradiation has already been observed. The aim of this work is to study in detail the mechanism responsible for this transition. For that purpose, different kinds of irradiations with electrons (to study point defects) and low energetic ions (to study clusters due to collision cascades) have been performed on zirconia samples. A local probe (Raman spectroscopy) and a non-local probe (grazing X-ray diffraction) have been used to characterise the phase formed during irradiation, which is clearly the tetragonal phase. For the ionic implantation, the grazing X-ray diffraction permits to separate effects due to the ballistic collisions and the implantation peak. Using this method, it was possible to show that the profile of the tetragonal phase was only linked to the dpa profile. This result associated to the results obtained by the Raman spectroscopy (broadening of Raman peaks) shows that the phase transition may be induced by clusters formed near the collision cascades.

Study of boron carbide evolution under neutron irradiation by Raman spectroscopy

Boron carbide, B12C3, is an absorbing material used to control the reactivity of nuclear reactors by taking advantage of nuclear reactions (e.g. 10 B(n,a) 7 Li), where neutrons are absorbed. During such reactions, radiation damages originating both from these nuclear reactions and from elastic collisions between neutrons and atoms lead to a partial destruction of this material, which gives the main limitation of its lifetime in nuclear reactors. In order to understand the evolution of B12C3 in nuclear plants, the eAect of neutron irradiation in B12C3 has been investigated by Raman and nuclear magnetic resonance (NMR) spectroscopies. Comparisons of B12C3 samples irradiated by 1 MeV electrons, 180 keV helium ions and neutrons are used to study the microstructure evolution of this material by Raman scattering. The analysis of Raman spectra of diAerent B12C3 samples irradiated by neutrons clearly shows that during the cascade displacements, the 485 and 527 cm ˇ1 modes disappear. These characteristic features of Raman spectra of the neutron irradiated samples are interpreted by a microscopic model. This model assumes that the CBC linear chain is destroyed whereas icosahedra are self-healed. 10 B atoms destroyed during the neutron irradiation are replaced in icosahedra by other boron and carbon atoms coming from the linear CBC chain. The 11 B NMR analysis performed on unirradiated and irradiated B4C samples shows the vanishing of a strong quadrupolar interaction associated to the CBC chain during the high neutron irradiation. The 11 B NMR spectroscopy confirms the previous Raman spectroscopy and the proposed microscopic model of B12C3 evolution under neutron irradiation. ” 2000 Elsevier Science B.V. All rights reserved.

Analysis of the monoclinic-tetragonal phase transition of zirconia under irradiation

Abstract Zirconia produced by the oxidation of zirconium alloys in nuclear reactors exhibits a phase transition under ionic irradiation, simulating a neutron irradiation. To understand the mechanism responsible for this irradiation driven phase transition, different kinds of projectiles were used to irradiate pure monoclinic zirconia samples. The evolution of these irradiated samples as a function of dpa has been studied using grazing X-ray diffraction. The Rietveld method has been applied on collected X-ray diffraction diagrams to study the phase produced under irradiation and the kinetics of its formation. Even at high dpa values, only the monoclinic and tetragonal phases were used to simulate X-ray diffraction diagrams. No amorphisation of zirconia was observed. The evolution of unit cells and short range strains in both phases under irradiation leads us to think that the irradiation driven transition is martensitic. Supposing that the inelastic stopping power in sub-cascades is responsible for the irradiation driven phase transition, we propose a model based on the Landau–Ginzburg effective hamiltonian to explain both the m → t transition observed under irradiation and the t → m transition measured during isochronal annealing after irradiation.

Application of nuclear reaction geometry for 3He depth profiling in nuclear ceramics

Abstract Direct observation of nuclear reactions leading to the emission of charged particles (p or α) allows to determine specifically the spatial distribution of isotopes of light elements from 1H to 23Na and despite low cross section values some heavier isotopes from 24Mg to 68Zn. After a brief overview of the analytical capabilities offered by μNRA, this contribution is focussed on the measurement of the thermal diffusion coefficient of 3He in crystalline ceramics. The experimental method is based on the observation of the 3He(d, p)α reaction. Due to the severe energy loss along the outgoing path, the choice of the detection of the high energy proton or recoil α nucleus depends on the average depth of the 3He distribution. For near surface distributions (

Refinement of the α-U4O9 crystalline structure: new insight into the U4O9 → U3O8 transformation.

The oxidation reaction of UO(2) into U(3)O(8) is studied as a function of the crystalline distortion of interstitial oxygen clusters, named cuboctahedra, which appear in U(4)O(9) and U(3)O(7) intermediate phases. For that purpose, the refinement of α-U(4)O(9) was performed because this phase undergoes a trigonal distortion from cubic β-U(4)O(9) when the temperature is decreased. In α-U(4)O(9), the cuboctahedra can be described as crumpled sheets taken from a fragment of U(3)O(8). The manner by which the accumulation of crumpled sheets can lead to the formation of U(3)O(8) is discussed.

3He thermal diffusion coefficient measurement in crystalline ceramics by μnra depth profiling

Abstract This contribution is devoted to the measurement of the thermal diffusion coefficient of 3He in crystalline nuclear ceramics. The experimental method is based on the observation of the 3He(d,p)α reaction. The detection of the high energy proton (12–14 MeV) is convenient for large implantation depths (5 μm

Rietveld refinements performed on mesoporous ceria layers at grazing incidence

Seven diffraction patterns were collected on a 100 nm Gd-doped ceria layer deposited on a silicon wafer under asymmetric reflection conditions. As the grazing-incidence angle decreases, large shifts (a few tens of degrees) and broadenings (two degrees below the critical angle) of hkl reflections are apparent in the diffraction patterns. The impact of these aberrations on the positions and profiles of the Bragg peaks is studied in detail in this work. On the basis of this analysis, diffraction patterns collected at different angles of incidence could then be refined using a unique structural model. From these refinements, the evolution of the coherent diffracting domains, the strain and the microstrain can clearly be traced as a function of depth.

Improving atomic displacement and replacement calculations with physically realistic damage models

Atomic collision processes are fundamental to numerous advanced materials technologies such as electron microscopy, semiconductor processing and nuclear power generation. Extensive experimental and computer simulation studies over the past several decades provide the physical basis for understanding the atomic-scale processes occurring during primary displacement events. The current international standard for quantifying this energetic particle damage, the Norgett−Robinson−Torrens displacements per atom (NRT-dpa) model, has nowadays several well-known limitations. In particular, the number of radiation defects produced in energetic cascades in metals is only ~1/3 the NRT-dpa prediction, while the number of atoms involved in atomic mixing is about a factor of 30 larger than the dpa value. Here we propose two new complementary displacement production estimators (athermal recombination corrected dpa, arc-dpa) and atomic mixing (replacements per atom, rpa) functions that extend the NRT-dpa by providing more physically realistic descriptions of primary defect creation in materials and may become additional standard measures for radiation damage quantification.The Norgett−Robinson−Torrens displacements per atom model is the benchmark to assess radiation damage in metals but has well-known limitations. Here, the authors use molecular dynamics to introduce material-specific modifications to describe radiation damage more realistically.

Structural Changes in the Local Environment of Uranium Atoms in the Three Phases of U4O9

The crystal structure of U4O9 remains an enigma because of its differences with U(4+) and U(5+) coordination polyhedral mixtures, as shown in the XANES experimental results. To better understand this crystal structure, its diffraction pattern was measured at seven different temperatures using neutron diffraction before being independently refined by Rietvelds method and pair distribution function analysis. The O cuboctahedron-a structural element consisting of 13 oxygen atoms-is a specific feature of the U4O9 crystal structure. The volume of the cuboctahedron decreases when the temperature increases, whereas the overall volume of the crystal cell increases. This feature can be correlated with the two U4O9 phase transitions that induce sharp changes in the cuboctahedron geometry, suggesting that this structural element has internal dynamics. In particular, these structural modifications in the γ phase suggest that the high-temperature phase can be described as a mixture of U(4+) and U(5+) coordination polyhedra, the latter having U-O distances shorter than 2.2 Å, that are absent in the former. These changes in uranium polyhedra as a function of temperature are tentatively interpreted using steric arguments. They also raise the question of charge localization on the different U ion sites in the low-temperature phases of U4O9.

Intricate disorder in defect fluorite/pyrochlore: a concord of chemistry and crystallography

Intuitively scientists accept that order can emerge from disorder and a significant amount of effort has been devoted over many years to demonstrate this. In metallic alloys and oxides, disorder at the atomic scale is the result of occupation at equivalent atomic positions by different atoms which leads to the material exhibiting a fully random or modulated scattering pattern. This arrangement has a substantial influence on the material’s properties, for example ionic conductivity. However it is generally accepted that oxides, such as defect fluorite as used for nuclear waste immobilization matrices and fuel cells, are the result of disorder at the atomic scale. To investigate how order at the atomic scale induces disorder at a larger scale length, we have applied different techniques to study the atomic composition of a homogeneous La2Zr2O7 pyrochlore, a textbook example of such a structure. Here we demonstrate that a pyrochlore, which is considered to be defect fluorite, is the result of intricate disorder due to a random distribution of fully ordered nano-domains. Our investigation provides new insight into the order disorder transformations in complex materials with regards to domain formation, resulting in a concord of chemistry with crystallography illustrating that order can induce disorder.