Phase equilibria in the ThF₄-PuF₃ system were measured by differential scanning calorimetry. Samples were encapsulated to prevent leakage during the measurements and to prevent fluoride contamination of the instrument. Formation of intermediate compounds and solid solutions was investigated by X-ray diffraction. A thermodynamic model based on the CALPHAD approach was developed for the measured system. Good fit between measurements and phase equilibria calculated using the model was achieved.

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The Molten Salt Reactor (MSR) is one of the six types of Generation IV nuclear energy systems with the main goals of sustainability, safety, reliability, economic competitiveness and proliferation resistance. This technology has spawn interest worldwide. Numerous universities, institutes and companies are carrying out research projects related to molten salt reactors. In Europe, the research is focused on the development of a fast-spectrum design, the Molten Salt Fast Reactor (MSFR). The peculiarity and innovation of the MSR technology is the use of liquid fuel; a molten salt mixture in which both fissile and fertile isotopes are dissolved. A number of technological challenges must be addressed for the design of the reactor and the safety approach must be established. The highest priority issues are in the area of fuel salt development, structural materials, on-site fuel processing and the licensing procedure. Fundamental research needs to be conducted to determine thermodynamic and kinetic data of fuel salts. One of the aims of the project that led to this thesis is the characterization of the fuel salt under normal and accidental conditions, providing the basis for the safety evaluation of the reactor. Reliable data on the thermal properties of molten salt mixtures are scarce. This research focuses on the experimental evaluation of some thermodynamic properties of molten salts. The thesis presents new methods for measuring thermal diffusivity and viscosity, and established methods for measuring melting point and dissolution of the salt in water...@en

A method based on ultrasonic wave propagation is applied for the determination of the viscosity of low viscous liquids. A waveguide is used to remotely transmit the ultrasonic waves from a shear piezoelectric transducer into the liquid. At the solid-liquid interface, a guided wave mode, the shear mode, is used to extract the liquid viscosity. The energy of the reflected ultrasonic wave depends upon its operating frequency, the physical properties of the liquid (viscosity and density), and the waveguide (density and shear modulus). The results show that the attenuation of the waves, and thus the viscosity of the liquid, can be retrieved using this method. Measurements on water, ethanol, and mixtures of water/glycerol illustrate that the method can monitor changes in attenuation due to the viscosity of the liquid. The range of viscosities measured was between 0.8 and 60 mPa s. Compared to literature values, the relative error for these measurements was lower than 12% while the uncertainty in the measurements was lower than 5%. Besides its ability to measure low viscosities, this method offers advantages such as the capability to perform in-situ measurements of liquids in harsh environments, the omission of mechanical parts, and the possibility to handle small volumes of liquid. These features make this method suitable for low viscous liquids that are radioactive, corrosive and at high temperature.

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The mixture LiF-ThF₄-UF₄-PuF₃ (77.5–6.6-12.3–3.6 mol%), a fuel option for the Molten Salt Fast Reactor (MSFR), has been measured by differential scanning calorimetry (DSC) for determination of phase transitions, and by Knudsen effusion mass spectrometry (KEMS) for measurement of partial vapour pressures. The boiling point of the mixture was determined by extrapolation of total vapour pressure to 1 bar. Thermodynamic calculations were performed and compared with the experimental results. Novel experimental data on pure plutonium trifluoride are presented: melting point, vaporization enthalpy, vapour pressure and ionization energies by electron impact.

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Some example applications are presented, in which the peculiar Raman fingerprint of PuO₂ can be used for the detection of crystalline Pu⁴⁺ with cubic symmetry in an oxide environment in various host materials, like mixed oxide fuels, inert matrices and corium sub-systems. The PuO₂ Raman fingerprint was previously observed to consist of one main T_2g vibrational mode at 478 cm⁻¹ and two crystal electric field transition lines at 2130 cm⁻¹ and 2610 cm⁻¹. This particular use of Raman spectroscopy is promising for applications in nuclear waste management, safety and safeguard.

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Major and severe accidents have occurred three times in nuclear power plants (NPPs), at Three Mile Island (USA, 1979), Chernobyl (former USSR, 1986) and Fukushima (Japan, 2011). Research on the causes, dynamics, and consequences of these mishaps has been performed in a few laboratories worldwide in the last three decades. Common goals of such research activities are: the prevention of these kinds of accidents, both in existing and potential new nuclear power plants; the minimization of their eventual consequences; and ultimately, a full understanding of the real risks connected with NPPs. At the European Commission Joint Research Centre’s Institute for Transuranium Elements, a laserheating and fast radiance spectro-pyrometry facility is used for the laboratory simulation, on a small scale, of NPP core meltdown, the most common type of severe accident (SA) that can occur in a nuclear reactor as a consequence of a failure of the cooling system. This simulation tool permits fast and effective high-temperature measurements on real nuclear materials, such as plutonium and minor actinide-containing fission fuel samples. In this respect, and in its capability to produce large amount of data concerning materials under extreme conditions, the current experimental approach is certainly unique. For current and future concepts of NPP, example results are presented on the melting behavior of some different types of nuclear fuels: uranium-plutonium oxides, carbides, and nitrides. Results on the high-temperature interaction of oxide fuels with containment materials are also briefly shown.

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Solid/liquid equilibria in the system UO₂–ZrO₂ are revisited in this work by laser heating coupled with fast optical thermometry. Phase transition points newly measured under inert gas are in fair agreement with the early measurements performed by Wisnyi et al., in 1957, the only study available in the literature on the whole pseudo-binary system. In addition, a minimum melting point is identified here for compositions near (U_0.6Z_r0.4)O_2+y, around 2800 K. The solidus line is rather flat on a broad range of compositions around the minimum. It increases for compositions closer to the pure end members, up to the melting point of pure UO₂ (3130 K) on one side and pure ZrO₂ (2970 K) on the other. Solid state phase transitions (cubic-tetragonal-monoclinic) have also been observed in the ZrO₂-rich compositions X-ray diffraction. Investigations under 0.3 MPa air (0.063 MPa O₂) revealed a significant decrease in the melting points down to 2500 K–2600 K for increasing uranium content (x(UO₂)> 0.2). This was found to be related to further oxidation of uranium dioxide, confirmed by X-ray absorption spectroscopy. For example, a typical oxidised corium composition U_0.6Zr_0.4O_2.13 was observed to solidify at a temperature as low as 2493 K. The current results are important for assessing the thermal stability of the system fuel – cladding in an oxide based nuclear reactor, and for simulating the system behaviour during a hypothetical severe accident.

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