A multiscale in situ high temperature high resolution transmission electron microscopy study of ThO2 sintering.

Two-grain model systems formed by ThO2 nanospheres have been used to experimentally study for the first time the initial stage of sintering from room temperature to 1050 °C using high temperature high resolution transmission electron microscopy. In each grain, oriented attachment drove the reorganization and growth of the crystallites up to 300 °C to form a pseudo single crystal. Crystallite size kept growing up to 950 °C. At this temperature, a fast transformation probably corresponding to the elimination of stacking faults or dislocation walls led to the formation of single-crystals. The contact formed at room temperature between the two grains was stabilized during heat treatment by a slight reorientation of the crystallographic planes (T≈ 400 °C), leading the neck to be formed by numerous boundaries between the crystallites. At higher temperatures, the neck evolved and stabilized in the form of a plane of crystallographic orientation mismatch between the grains, which corresponds to the usual definition of the grain boundary. The growth of the neck by the addition of atomic columns was further observed in real time and quantified. At T = 950 °C, the evolution of the microscopic sintering parameter λ was obtained from HT-HRTEM images and indicated that the neck formation mostly proceeded through volume diffusion.

Characterization of the boron profile and coordination in altered glass layers by EEL spectroscopy.

Electron energy-loss spectroscopy was used to characterize the boron profile and its coordination (BIII and BIV), along the complex alteration layer of glass samples altered for 511 days at 50 °C in solution containing FeCl2, MgCl2 and/or CaCl2. To reach this goal, the impact of both TEM operating conditions and sample preparation on the determination of the boron coordination was first studied using mineralogical and pristine glasses reference samples. Then, the boron concentration profiles were characterized in the glass alteration layer. These profiles were found to be S-shaped with a thickness around forty nanometers. The proportion of BIII was found to decrease with the boron total concentration (from the pristine glass to the gel layer), which suggests a higher bonding strength for BIV bonds than that of BIII bonds under the alteration conditions. These findings are of tremendous interest to advance further in the understanding of glass alteration mechanisms.

Evaluation and application of a new scintillator-based heat-resistant back-scattered electron detector during heat treatment in the scanning electron microscope.

A new high-temperature detector dedicated to the collection of backscattered electrons is used in combination with heating stages up to 1050°C, in high-vacuum and low-vacuum modes in order to evaluate its possibilities through signal-to-noise ration measurements and different applications. Four examples of material transformations occurring at high temperature are herein reported: grain growth during annealing of a rolled platinum foil, recrystallisation of a multiphased alloy, oxidation of a Ni-based alloy and complex phase transformations occurring during the annealing of an Al-Si coated boron steel. The detector could be potentially adapted to any type of SEM and it offers good opportunities to perform high-temperature experiments in various atmospheres.

In situ study of single-walled carbon nanotube growth in an environmental scanning electron microscope.

Monitoring individual single-walled carbon nanotubes (SWCNTs) during their growth is a highly sought-after goal in view of understanding the processes involved in the nucleation, elongation and termination which ultimately control the diameter and chiral selectivity. Here, we report on the first truly in situ observations of SWCNT growth in an environmental scanning electron microscope (ESEM). The CNT growth from lithographically patterned catalysts was investigated as a function of the catalyst type (Fe, Co or Ni), temperature, type of precursor (ethanol or acetylene), gas phase composition and pressure, and pretreatment conditions, and we report on the most appropriate conditions for SWCNT growth in ESEM conditions. We show that this approach allows the observation at the submicron scale of the different steps of the nanotube synthesis including the catalyst reduction, the growth and percolation of the nanotube network, and the deposition of individual nanotubes grown in the gas phase on the substrate. Despite these obvious advantages, we identified a few limitations which will need to be tackled for fully taking advantage of the approach, for instance for monitoring the growth of individual SWCNTs by ESEM, including the short lifetime of the catalyst nanoparticles, the preference for kite growth (by opposition to surface growth) and the influence of the electron beam on the nanotube growth.

Surface decoration of catanionic vesicles with superparamagnetic iron oxide nanoparticles: a model system for triggered release under moderate temperature conditions.

We report the design of new catanionic vesicles decorated with iron oxide nanoparticles, which could be used as a model system to illustrate controlled delivery of small solutes under mild hyperthermia. Efficient release of fluorescent dye rhodamine 6G was observed when samples were exposed to an oscillating magnetic field. Our system provides direct evidence for reversible permeability upon magnetic stimulation.

Stability and structural evolution of Ce(IV)(1-x)Ln(III)(x)O(2-x/2) solid solutions: a coupled µ-Raman/XRD approach.

Several CeO(2)-based mixed oxides with general composition Ce(1-x)Ln(x)O(2-x/2) (for 0 ≤ x ≤ 1 and Ln = La, Nd, Sm, Eu, Gd, Dy, Er, or Yb) were prepared using an initial oxalic precipitation leading to a homogeneous distribution of cations in the oxides. After characterization of the Ce/Nd oxalate precursors and then thermal conversion to oxides at T = 1000 °C, investigation of the crystalline structure of these oxides was carried out by XRD and µ-Raman spectroscopy. Typical fluorite Fm ̅3m structure was obtained for relatively low Ln(III) contents, while a cubic Ia ̅3̅ superstructure was evidenced above x ≈ 0.4. Moreover, since Nd(2)O(3) does not crystallize with the Ia ̅3̅-type structure, two-phase systems composed with additional hexagonal Nd(2)O(3) were obtained for x(Nd) ≥ 0.73 in the Ce(1-x)Nd(x)O(2-x/2) series. The effect of heat treatment temperature on these limits was explored through µ-Raman spectroscopy, which allowed determining the presence of small amounts of the different crystal structures observed. In addition, the variation of the Ce(1-x)Ln(x)O(2-x/2) unit cell parameter was found to follow a quadratic relation as a result of the combination between increasing cationic radius, modifications of cation coordination, and decreasing O-O repulsion caused by oxygen vacancies.

Synthesis, characterization, sintering, and leaching of beta-TUPD/monazite radwaste matrices.

To study the simultaneous incorporation of both tri- and tetravalent actinides in phosphate ceramics, we prepared several beta-TUPD/monazite-based radwaste matrices through two different chemical routes (called dry and wet routes) involving the initial precipitation of crystallized precursors of each phase, i.e., TUPHPH solid solutions on the one hand, and rhabdophane (LnPO(4).xH(2)O) on the other. The final material was obtained after heating above 1000 degrees C, and no additional phase was detected from elementary analyses and XRD. Moreover, the complete segregation of tri- and tetravalent cations was evidenced when using dry chemical processes. This method also allows for the preparation of dense pellets (90% < d(exp)/d(calc) < 95%) after only 10-20 h of heat treatment at 1250 degrees C. Finally, the chemical durability of the pellets was examined through several leaching experiments in acidic media. The normalized dissolution rate determined from the uranium release in the leachate varies from (8.2 +/- 0.7) x 10(-6) to (2.7 +/- 0.4) x 10(-2) g m(-2) day(-1) between 25 and 120 degrees C in 10(-1) M HNO(3). Near equilibrium, thorium and lanthanide ions were found to quickly precipitate as phosphate-based neoformed phases in the back end of the initial dissolution process. These phases were identified as uranium-depleted T(U)PHPH and as rhabdophane or monazite.