J.-Y. Colle

Volatile Molecule PuO3 Observed from Subliming Plutonium Dioxide.

Abstract Mass spectrometric measurements of effusing vapours over PuO2 and (U, Pu)O2 indicate the presence of volatile PuO3 (g) molecules. The formation of plutonium trioxide vapour is due to a chemical process involving oxygen adsorbed during oxidation of the sample. Although in the examined samples, the fraction of trioxide effusing in vacuo was of the order of 0.02 ppm of the plutonium content, under steady-state oxidation conditions it has been shown that the process can have a relevant effect on the sublimation rate of the dioxide.

Joint Raman spectroscopic and quantum chemical analysis of the vibrational features of Cs2RuO4

The Raman spectroscopic characterization of the orthorhombic phase of Cs2RuO4 was carried out by means of group theory and quantum chemical analysis. Multiple models based on ruthenate (VI+) tetrahedra were tested, and characterization of all the active Raman modes was achieved. A comparison of Raman spectra of Cs2RuO4, Cs2MoO4, and Cs2WO4 was also performed. Raman laser heating induced a phase transition from an ordered to a disordered structure. The temperature-phase transition was calculated from the anti-Stokes/Stokes ratio and compared with the ones measured at macroscopic scale. The phase transition is connected with tilting and/or rotations of RuO4 tetrahedra, which lead to a disorder at the RuO4 sites.

Advances in the mass spectrometric study of the laser vaporization of graphite

Reliable experimental data on graphite vaporization and especially on carbon vapor composition exist only up to 2500–3000 K. Data measured at higher temperatures are questionable due to several experimental limitations, such as the difficult temperature determination and the not straightforward correlation of measured temperatures and intensities of signals in mass spectra. That is why a new method of high-temperature mass spectrometry with laser vaporization was developed, in order to extend the accessible temperature range while overcoming these limitations and to shed more light on the still poorly known behavior of carbon at high temperatures. Thus, carbon sublimation relative partial pressures of the species C1, C2, C3, C4, and C5 were measured up to 4100 K. Moreover, the values of the relative vaporization coefficients of C1, C2, C3, C4, and C5, estimated by comparison of the experimentally obtained partial pressures with the predicted equilibrium ones, are proposed.

A mass spectrometry method for quantitative and kinetic analysis of gas release from nuclear materials and its application to helium desorption from UO2 and fission gas release from irradiated fuel

A new system has been developed to determine absolute quantities of gas (mainly noble gases) released during thermal desorption in the range from 10−12 to 10−5 mol with a precision of few percent. The system is actually designed for simultaneous measurement of gaseous elements like He, Xe, Kr, thermally released from nuclear fuel samples and also allows the determination of the release kinetics as a function of time. This system, called Quantitative GAs MEasurement System (Q-GAMES), is based on the principle of collecting, purifying and spiking the sample gas in a “high-pressure” chamber, and continuous sampling of the gas for mass spectrometric analysis without sample depletion during the experiment. It is equipped with its own spike generator and with different gas purification systems. It is shown that this system fulfills the requirement to work with two existing very high-temperature gas desorption facilities for nuclear materials. This paper describes the Q-GAMES principle, the spiking system, its calibration, its operative mode, the different quantification techniques, as well as its technical data, in combination with some examples of typical application.

Urania vapor composition at very high temperatures

Due to the chemically unstable nature of uranium dioxide its vapor composition at very high temperatures is, presently, not sufficiently studied though more experimental knowledge is needed for risk assessment of nuclear reactors. We used laser vaporization coupled to mass spectrometry of the produced vapor to study urania vapor composition at temperatures in the vicinity of its melting point and higher. The very good agreement between measured melting and freezing temperatures and between partial pressures measured on the temperature increase and decrease indicated that the change in stoichiometry during laser heating was very limited. The evolutions with temperature (in the range 2800–3400 K) of the partial pressures of the main vapor species (UO2, UO3, and UO2+) were compared with theoretically predicted evolutions for equilibrium noncongruent gas-liquid and gas-solid phase coexistences and showed very good agreement. The measured main relative partial pressure ratios around 3300 K all agree with calcu...

Very high temperature laser heated furnace for Knudsen cell mass spectrometry

A very high temperature furnace (up to 3000 degrees C) for the Knudsen cell mass spectrometry (KCMS) based on a laser heating technique has been developed. It is demonstrated that this system overcomes some of the typical technological problems encountered by the standard methods and can be more easily handled in special environments such as gloveboxes or hot cells. This paper describes the laser heated KCMS general design. The technology of the laser furnace along with its advantages, disadvantages, and applications is presented. Mechanical designs, some technical details, and the importance of the temperature control are also discussed.

Determination of the thermodynamic activities of LiF and ThF4 in the LixTh1-xF4-3x liquid solution by Knudsen Effusion Mass Spectrometry

Knudsen effusion mass spectrometry (KEMS) has been used to investigate the vapour pressure over the molten LiF-ThF4 salt and determine the thermodynamic activity of LiF and ThF4 in the liquid solution. As part of the study, the vaporization of pure LiF and pure ThF4 was examined and the results were compared with the literature values finding a good agreement. Next, the vapour pressure of the LixTh1-xF4-3x liquid solution was investigated by measuring four samples having different compositions (XLiF∼ 0.2, 0.4, 0.6, 0.8 mol%). In order to determine the thermodynamic activities, the vapour pressure of LiF and ThF4 species over the liquid solution, as calculated from our results, were compared with the vapour pressure over the pure LiF(l) and pure ThF4(l) systems. A strong deviation from the Raoults law was observed, more evident in case of LiF species, in agreement with the predictions by our thermodynamic model.

Properties of the high burnup structure in nuclear light water reactor fuel

Abstract The formation of the high burnup structure (HBS) is possibly the most significant example of the restructuring processes affecting commercial nuclear fuel in-pile. The HBS forms at the relatively cold outer rim of the fuel pellet, where the local burnup is 2–3 times higher than the average pellet burnup, under the combined effects of irradiation and thermo-mechanical conditions determined by the power regime and the fuel rod configuration. The main features of the transformation are the subdivision of the original fuel grains into new sub-micron grains, the relocation of the fission gas into newly formed intergranular pores, and the absence of large concentrations of extended defects in the fuel matrix inside the subdivided grains. The characterization of the newly formed structure and its impact on thermo-physical or mechanical properties is a key requirement to ensure that high burnup fuel operates within the safety margins. This paper presents a synthesis of the main findings from extensive studies performed at JRC-Karlsruhe during the last 25 years to determine properties and behaviour of the HBS. In particular, microstructural features, thermal transport, fission gas behaviour, and thermo-mechanical properties of the HBS will be discussed. The main conclusion of the experimental studies is that the HBS does not compromise the safety of nuclear fuel during normal operations.

A novel technique for Raman analysis of highly radioactive samples using any standard micro-Raman spectrometer

A novel approach for the Raman measurement of nuclear materials is reported in this paper. It consists of the enclosure of the radioactive sample in a tight capsule that isolates the material from the atmosphere. The capsule can optionally be filled with a chosen gas pressurized up to 20 bars. The micro-Raman measurement is performed through an optical-grade quartz window. This technique permits accurate Raman measurements with no need for the spectrometer to be enclosed in an alpha-tight containment. It therefore allows the use of all options of the Raman spectrometer, like multi-wavelength laser excitation, different polarizations, and single or triple spectrometer modes. Some examples of measurements are shown and discussed. First, some spectral features of a highly radioactive americium oxide sample (AmO2) are presented. Then, we report the Raman spectra of neptunium oxide (NpO2) samples, the interpretation of which is greatly improved by employing three different excitation wavelengths, 17O doping, and a triple mode configuration to measure the anti-stokes Raman lines. This last feature also allows the estimation of the sample surface temperature. Finally, data that were measured on a sample from Chernobyl lava, where phases are identified by Raman mapping, are shown.

Heat capacity, thermal expansion, and thermal diffusivity of NaUO2BO3

In the present studies, the thermal behaviour of NaUO2BO3 has been investigated. This compound is a potential product of interaction between the coolant (Na), control rods (B4C), and the oxide fuel, which could form under accidental conditions in sodium-cooled fast reactors. The thermal expansion, the heat capacity, and thermal diffusivity of NaUO2BO3 have been measured. The thermal conductivity of the material is derived from these results and presented here for the first time.