Oxidation behaviour of uranium and neptunium in stabilised zirconia

Yttria stabilised zirconia (YSZ) based (Zr,Y,U)O_2−x and (Zr,Y,Np)O_2−x solid solutions with 6 and 20 mol% actinide were prepared with Y/Zr ratios ranging from 0.2 to 2.0 to investigate uranium and neptunium oxidation behaviour depending on the oxygen vacancies in the defect fluorite lattice. Sintering at 1600 °C in Ar/H₂ yields a cubic, fluorite-type structure with U(IV) and Np(IV). Annealing (Zr,Y,U)O_2−x with Y/Zr=0.2 at 800 °C in air results in a tetragonal phase, whereas (Zr,Y,U)O_2−x with higher Y/Zr ratios and (Zr,Y,Np)O_2−x retain the cubic structure. XANES and O/M measurements indicate mixed U(V)-U(VI) and Np(IV)-Np(V) oxidation states after oxidation. Based on X-ray diffraction, O/M and EXAFS measurements, different oxidation mechanisms are identified for U- and Np-doped stabilised zirconia. In contrast to U, excess oxygen vacancies are needed to oxidise Np in (Zr,Y,Np)O_2−x as the oxidation process competes with Zr for oxygen vacancies. As a consequence, U(VI) and Np(V) can only be obtained in stabilised zirconia with Y/Zr=1 but not in YSZ with Y/Zr=0.2.     

Radioactive waste partitioning and transmutation within advanced fuel cycles: Achievements and challenges

If nuclear power becomes a sustainable source of energy, a safe, robust, and acceptable solution must be pursued for existing and projected inventories of high-activity, long-lived radioactive waste. Remarkable progress in the field of geological disposal has been made in the last two decades. Some countries have reached important milestones, and geological disposal (of spent fuel) is expected to start in 2020 in Finland and in 2022 in Sweden. In fact, the licensing of the geological repositories in both countries is now entering into its final phase. In France, disposal of intermediate-level waste (ILW) and vitrified high-level waste (HLW) is expected to start around 2025, according to the roadmap defined by an Act of Parliament in 2006. In this context, transmutation of part of the waste through use of advanced fuel cycles, probably feasible in the coming decades, can reduce the burden on the geological repository. This article presents the physical principle of transmutation and reviews several strategies of partitioning and transmutation (P&T). Many recent studies have demonstrated that the impact of P&T on geological disposal concepts is not overwhelmingly high. However, by reducing waste heat production, a more efficient utilization of repository space is likely. Moreover, even if radionuclide release from the waste to the environment and related calculated doses to the population are only partially reduced by P&T, it is important to point out that a clear reduction of the actinide inventory in the HLW definitely reduces risks arising from less probable evolutions of a repository (i.e., an increase of actinide mobility in certain geochemical situations and radiological impact by human intrusion).     

Industrielle und natürliche Kernreaktoren

As described in the preceding article, all elements with atomic masses above that of iron and also the radioactive elements thorium and uranium have been formed by a supernova star explosion. Their long‐lived isotopes of thorium and uranium are now distributed in the earth crust. The chemistry of uranium and thorium is of less importance, but these elements can be used to produce enormous amounts of energy in nuclear power stations. It will be described how it works. Surprisingly, small natural nuclear reactors were producing heat during hundreds of thousand years. Subsequently, we are dealing with this phenomenon, the principle of nuclear fission, the different types of nuclear reactors, security aspects and new developments.     

Controllability cost of conservative systems: resolvent condition and transmutation

This article concerns the exact controllability of unitary groups on Hilbert spaces with unbounded control operator. It provides a necessary and sufficient condition not involving time which blends a resolvent estimate and an observability inequality. By the transmutation of controls in some time L for the corresponding second-order conservative system, it is proved that the cost of controls in time T for the unitary group grows at most like exp(αL²/T) as T tends to 0. In the application to the cost of fast controls for the Schrödinger equation, L is the length of the longest ray of geometric optics which does not intersect the control region. This article also provides observability resolvent estimates implying fast smoothing effect controllability at low cost, and underscores that the controllability cost of a system is not changed by taking its tensor product with a conservative system.     

Persistence of microstructural evolution in irradiated metals and its consequences at high radiation exposure

Abstract

A review is presented of a very general aspect of the response of all metals subjected to displacive irradiation. This aspect is referred to as «persistence» and describes the tendency of both radiation-induced microstructural evolution and the associated changes in material properties or dimensional stability to evolve to saturation states that resist further change upon continued irradiation. It is shown that new persistent states can develop on a longer time frame associated with the late-term loss of existing microstructural components or the gain of new components, especially when transmutation and/or segregation occurs. The persistent states are often dependent on the irradiation conditions, and if these are changed, the material usually adjusts to form the persistent state characteristic of the new conditions, with the memory of the former state often lost, and sometimes leaving no visible record of the former state in the new microstructure. Depending on the microstructural components involved, the transition toward the new persistent state can occur quickly or very slowly.     

SSNTD and radiochemical studies on the transmutation of nuclei using relativistic ions

Extended targets were irradiated for transmutation studies with relativistic heavy ions. For this, a metal core was surrounded by a paraffin moderator. The metal is either copper or lead and it was irradiated with deuterium, alpha, or carbon beams of 1.5 or 3.7 GeV/u at the SYNCHROPHASOTRON, LHE, JINR, Dubna, Russia. During this irradiation copious amounts of secondary neutrons are produced and studied with SSNTD detectors and radiochemical sensors, for example ¹³⁹La (n, γ) ¹⁴⁰La→β⁻. The yield of reaction products allows an estimation of secondary neutron fluxes. The yields of all kinds of reactions produced with deuterium and alpha beams obey to some extent the law of “limiting fragmentation”, i.e. they show little influence on the energy and the kind of incoming particles. However, one observes with 44 GeV ¹²C ions always enhanced nuclear cross-sections induced by secondary particles. This behavior could not be confirmed with theoretical estimations based on the Dubna Cascade Model in its Cascade Evaporation Model version (DCM-CEM). Finally, some results for transmutation studies on ¹²⁷I and Cu will be presented.     

The Existence of a Designer Al=Al Double Bond in the LiAl2H4− Cluster Formed by Electronic Transmutation

The Al=Al double bond is elusive in chemistry. Herein we report the results obtained via combined photoelectron spectroscopy and ab initio studies of the LiAl₂H₄⁻ cluster that confirm the formation of a conventional Al=Al double bond. Comprehensive searches for the most stable structures of the LiAl₂H₄⁻ cluster have shown that the global minimum isomer I possesses a geometric structure which resembles that of Si₂H₄, demonstrating a successful example of the transmutation of Al atoms into Si atoms by electron donation. Theoretical simulations of the photoelectron spectrum discovered the coexistence of two isomers in the ion beam, including the one with the Al=Al double bond.     

Remarks on Quantum Transmutation

It is shown how formulas of the author for general operator transmutation can be adapted to a quantum group context.     

Transmutation studies using SSNTD and radiochemistry and the associated production of secondary neutrons

Experiments using 1.5 GeV, 3.7 GeV and 7.4 GeV protons from the Synchrophasotron, LHE, JINR, Dubna, Russia, on extended Pb- and U-targets were carried out using SSNTD and radiochemical sensors for the study of secondary neutron fluences. We also carried out first transmulation studies on the long-lived radwaste nuclei ¹²⁹I and ²³⁷Np.

In addition, we carried out computer code simulation studies on these systems using LAHET and DCM/CEM codes. We have difficulties to understand rather large transmutation rates observed experimentally when they are compared with computer simulations. There seems to be a rather fundamental problem understanding the large transmutation rates as observed experimentally in Dubna and CERN, as compared to those theoretical computer simulations mentioned above.     

Transmutations and irregular singular points

We consider transumtations for a class of problems in partial differential equations where the underlying equation, involving two assignable parameters, is an associated ordinary differential equation with an irregular singular point. An integral formula for the solution of this associated problem, valid for negative values of a timelike variable t, permits relating the solution of the problems in partial differential equations to be bounded or slow groth solutions of generalized heat problems. Applications of the formulas are made to Cauchy and boundary type problems.