Solid state synthesis and X-ray diffraction characterization of Pu 3+(1-2x)Pu4+xCa2+xPO4

In the framework of the 1991 French law concerning nuclear waste management, several studies have been carried out in order to elaborate crystalline matrices for specific immobilization of the radionuclides. In the case of high level and long-lived minor actinides (Np, Am and Cm), which are high level and long-lived radioactive elements, monazite, a light rare earth (Re) orthophosphate with general formula Re3+PO4 (with Re = La to Gd), has been proposed as a host matrix, thanks to its high resistance to self irradiation and its low solubility. Monazite crystallizes in the monoclinic space group P21/n. In this structure, trivalent cations (Re3+) could be substituted by an equivalent amount of bivalent (A2+) and tetravalent (B4+) cations, allowing the simultaneous incorporation of Am3+, Cm3+ and Np4+. According to Podor's work1, the limit of a tetravalent element incorporation in monazite is related to its size in the ninefold coordination (RIX)

Removal of aqueous lead ions by hydroxyapatites: Equilibria and kinetic processes

Issu de : WasteEng05 Conference 1st international conference on engineering for waste treatment, Albi, FRANCE, 17-19 May 2005International audienceThe capacity of hydroxyapatite (HAp) to remove lead from aqueous solution was investigated under different conditions, namely initial metal ion concentration and reaction time. The sorption of lead from solutions containing initial concentrations from 0 to 8000 mg/L was studied for three different HAp powders. Soluble Pb and Ca monitoring during the experiment allows characterizing the mechanism of lead uptake. Dissolution of calcium is followed by the formation of a solid solution, PbxCa10−x(PO4)6(OH)2, with a Ca/P ratio decreasing continuously. Langmuir–Freundlich classical adsorption isotherms modeled adsorption data. The adsorption capacities calculated from this equation vary from 330 to 450 mg Pb/g HAp for the different solids. Modeling of the sorption process allows to determine theoretical saturation times and residual lead concentrations at equilibrium

Dynamic aspects of cerium dioxide sintering: HT-ESEM study of grain growth and pore elimination

International audienceSintering of CeO2 is studied in situ by high temperature scanning environmental microscopy (HT-ESEM) at T = 1400 °C. The morphological modifications of a single grains population are recorded for 6 h. Kinetic parameters are extracted from image series. The local grain growth determined from the single population studied in situ is compared to the general grain growth obtained by classical ex situ technique. Using HT-ESEM for sintering study is validated. The grain boundary velocities range between 0 and 5 μm h−1, with a mean value of about 1 μm h−1. The migration of the intragranular surface pores is described. Their velocities range between 0.4 and 1.2 μm h−1 and depend on pore diameters: the smaller the pore, the faster the pore velocity. The time required to fill a pore that arises at the sample surface is determined as a function of pore diameter. The time for pore elimination dependence with the pore diameters is also established

Solid-State Synthesis of Monazite-type Compounds Containing Tetravalent Elements

International audienceOn the basis of optimized grinding/heating cycles developed for several phosphate-based ceramics, the preparation of brabantite and then monazite/brabantite solid solutions loaded with tetravalent thorium, uranium, and cerium (as a plutonium surrogate) was examined versus the heating temperature. The chemical reactions and transformations occurring when heating the initial mixtures of AnO2/CeO2, CaHPO4·2H2O (or CaO), and NH4H2PO4 were identified through X-ray diffraction (XRD) and thermogravimetric/differential thermal analysis experiments. The incorporation of thorium, which presents only one stabilized oxidation state, occurs at 1100 °C. At this temperature, all the thorium−brabantite samples appear to be pure and single phase as suggested by XRD, electron probe microanalyses, and μ-Raman spectroscopy. By the same method, tetravalent uranium can be also stabilized in uranium−brabantite, i.e., Ca0.5U0.5PO4, after heating at 1200 °C. Both brabantites, Ca0.5Th0.5PO4 and Ca0.5U0.5PO4, begin to decompose when increasing the temperature to 1400 and 1300 °C, respectively, leading to a mixture of CaO and AnO2 by the volatilization of P4O10. In contrast to the cases of thorium and uranium, cerium(IV) is not stabilized during the heating treatment at high temperature. Indeed, the formation of Ca0.5Ce0.5PO4 appears impossible, due to the partial reduction of cerium(IV) into cerium(III) above 840 °C. Consequently, the systems always appear polyphase, with compositions of CeIII1-2xCeIVxCaxPO4 and Ca2P2O7. The same conclusion can be also given when discussing the incorporation of cerium(IV) into La1-2xCeIIIx-yCeIVyCay(PO4)1-x+y. This incomplete incorporation of cerium(IV) confirms the results obtained when trying to stabilize tetravalent plutonium in Ca0.5PuIV0.5PO4 samples

Structural transformations of bioactive glass 45S5next term with thermal treatments

International audienceWe report on the structural transformations of Bioglass® during thermal treatments. Just after the glassy transition, at 550 °C, a glassy phase separation occurs at 580 °C, with the appearance of one silicate- and one phosphate-rich phase. It is followed by the crystallization of the major phase Na2CaSi2O6, from 610 to 700 °C and of the secondary phase, silico-rhenanite, at 800 °C. The latter evolves from the phosphate-rich glassy phase, which is still present after the first crystallization. In order to control the processing of glass-ceramic products from Bioglass®, crystallization kinetics were studied via differential scanning calorimetry measurements in the range of 620–700 °C and temperature–time–transformation curves were established

Accurate characterization of pure silicon-substituted hydroxyapatite powders synthesized by a new precipitation route

International audienceThis paper presents a new aqueous precipitation method to prepare silicon-substituted hydroxyapatites Ca10(PO4)6-y(SiO4)y(OH)2-y(VOH)2-y (SiHAs) and details the characterization of powders with varying Si content up to y = 1.25 mol molSiHA−1. X-ray diffraction, transmission electron microscopy, solid-state nuclear magnetic resonance and Fourier transform infrared spectroscopy were used to accurately characterize samples calcined at 400°C for 2 h and 1000°C for 15 h. This method allows the synthesis of monophasic SiHAs with controlled stoichiometry. The theoretical maximum limit of incorporation of Si into the hexagonal apatitic structure is y < 1.5. This limit depends on the OH content in the channel, which is a function of the Si content, temperature and atmosphere of calcination. These results, particularly those from infrared spectroscopy, raise serious reservations about the phase purity of previously prepared and biologically evaluated SiHA powders, pellets and scaffolds in the literature

Development of innovative pH sensor to evaluate phagocytosis of nanoparticles

International audienceInhaled nanoparticles (NP) exhibit variable toxicity levels which mainly depend on their physicochemical characteristics (size, morphology, crystallinity, chemical surface composition...). Biological effects monitoring thanks to usual tests (ROS, TNFα, LDH) are performed on alveolar macrophages collected from the respiratory system. In this frame, evaluation of NP uptake by macrophages appears as complementary data useful for NP toxicity assessment. The aim of this work deals with the development of pH sensible NP allowing the quantification of NP phagocytosed by macrophages, specially the step of fusion between phagosomes and lysosomes

Biological response to purification and acid functionalization of carbon nanotubes

The final publication is available at Springer via: http://link.springer.com/article/10.1007/s11051-014-2507-yInternational audienceAcid functionalization has been considered as an easy way to enhance the dispersion and biodegradation of carbon nanotubes (CNT). However, inconsistencies between toxicity studies of acid functionalized CNT remain unexplained. This could be due to a joint effect of the main physicochemical modifications resulting from an acid functionalization: addition of surface acid groups and purification from catalytic metallic impurities. In this study, the impact on CNT biotoxicity of these two physiochemical features was assessed separately. The in vitro biological response of RAW 264.7 macrophages was evaluated after exposure to 15-240 µg x mL−1 of two types of multi-walled CNT. For each type of CNT (small: 20 nm diameter, and big: 90 nm diameter), three different surface chemical properties were studied (total of six CNT samples): pristine, acid functionalized and desorbed. Desorbed CNT were purified by the acid functionalization but presented a very low amount of surface acid groups due to a thermal treatment under vacuum. A Janus effect of acid functionalization with two opposite impacts is highlighted. The CNT purification decreased the overall toxicity, while the surface acid groups intensified it when present at a specific threshold. These acid groups especially amplified the pro-inflammatory response. The threshold mechanism which seemed to regulate the impact of acid groups should be further studied to determine its value and potential link to the other physicochemical state of the CNT. The results suggest that, for a safer-design approach, the benefit-risk balance of an acid functionalization has to be considered, depending on the CNT primary state of purification. Further research should be conducted in this direction

Quantification of microsized fluorescent particles phagocytosis to a better knowledge of toxicity mechanisms

International audienceBackground: The use of micro- or nanometric particles is in full expansion for the development of new technologies. These particles may exhibit variable toxicity levels depending on their physicochemical characteristics. We focused our attention on macrophages (MA), the main target cells of the respiratory system responsible for the phagocytosis of the particles. The quantification of the amount of phagocytosed particles seems to be a major element for a better knowledge of toxicity mechanisms. The aim of this study was to develop a quantitative evaluation of uptake using both flow cytometry (FCM) and confocal microscopy to distinguish entirely engulfed fluorescent microsized particles from those just adherent to the cell membrane and to compare these data to in vitro toxicity assessments. Methods: Fluorescent particles of variable and well-characterised sizes and surface coatings were incubated with MA (RAW 264.7 cell line). Analyses were performed using confocal microscopy and FCM. The biological toxicity of the particles was evaluated [lactate dehydrogenase (LDH) release, tumor necrosis factor (TNF)-α, and reactive oxygen species (ROS) production]. Results and conclusion: Confocal imaging allowed visualization of entirely engulfed beads. The amount of phagocytic cells was greater for carboxylate 2-µm beads (49±11%) than for amine 1-µm beads (18±5%). Similarly, side scatter geometric means, reflecting cellular complexity, were 446±7 and 139±12, respectively. These results confirm that the phagocytosis level highly depends on the size and surface chemical groups of the particles. Only TNF-α and global ROS production varied significantly after 24-h incubation. There was no effect on LDH and H2O2 production