Electrochemistry of thorium in LiCl-KCl eutectic melts

This work presents a study of the electrochemical properties of Th chloride ions dissolved in a molten LiCl-KCl eutectic, in a temperature range of 693-823 K. Transient electrochemical techniques such as cyclic voltammetry and chronopotentiommetry have been used in order to investigate the reduction mechanism on a tungsten electrode and the diffusion coefficient of dissolved Th ions. All techniques showed that only one valence state was stable in the melt. The reduction into Th metal was found to occur according to a one-step mechanism, through an irreversible reaction controlled by a nucleation process which requires an overpotential of several 100 mV. At 723 K, the diffusion coefficient is DTh(723K) = 3.7 ± 0.2·10-5 cm2.s-1. EMF measurements indicated that, at 723 K, the standard apparent potential is *0ThCl4 /Th) E (723 K) = - 2.582 V vs. Cl2/Cl-, and the activity coefficient γThCl4(723 K) = 8·10-3 on the mole fraction scale (based on a pure liquid reference state)

Investigation of electrorefining of metallic alloy fuel onto solid Al cathodes

This work concerned the electrorefining of UZr and UPuZr alloys on a solid aluminium cathode, in the LiCl-KCl eutectic melt containing U3+, Pu3+, Np3+, Zr2+ or Zr 4+, Am3+, Nd3+, Y3+, Ce3+ and Gd3+ chlorides. During constant current electrolyses, the use of a cathodic cut-off potential (-1.25 V vs. Ag/AgCl) allowed to selectively deposit actinides (mainly U), while lanthanides remainedin the salt. The aim was to determine the maximal load achievable on a single aluminium electrode. The total exchange charge was 4300 C, which represents the deposition of 3.72 g of actinides in 4.17 g Al, yielding a composition of 44.6 wt% An in Al. It was shown that the melting of the cathode contributed to increase the total amount of actinides deposited on the aluminium

Electrochemistry of uranium in molten LiF–CaF2

This article is focused on the electrochemical behaviour of U ions in molten LiF–CaF2 (79–21 wt.%) eutectic. On aWelectrode, U(III) is reduced in one step to U metal and U(III) can be also oxidised to U(IV). Both systems were studied by cyclic and square wave voltammetry. Reversibility of both systems for both techniques was verified and number of exchanged electrons was determined, as well as diffusion coefficients for U(III) and U(IV). The results are in a good agreement with previous studies. On a Ni electrode,the depolarisation effect due to intermetallic compounds formation was observed. Electrorefining of U metal in a melt containing U and Gd ions was carried out using a reactive Ni electrode with promising results

Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

Pyrochemical processes in molten LiCl–KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide–aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide– aluminium alloys by chlorine gas and sublimation of the formed AlCl3. A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl3 alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl2/UAl3 molar ratio, providing complete chlorination of the alloy without formation of volatile UCl5 and UCl6. The results showed high efficient chlorination at a temperature of 150 °C

Electrorefining of U-Pu-Zr-alloy fuel onto solid Aluminium cathodes in molten LiCl-KCl

An electrorefining process in molten chloride salts using solid aluminium cathodes is being developed at ITU to recover actinides (An) from the spent nuclear fuel. The maximum possible loading of aluminium electrodes with actinides was investigated during the electrorefining of UPuZr alloy in a LiCl-KCl eutectic at 450°C. Two different electrolytic techniques were applied during the experiment and almost 6000 C has been passed, corresponding to 3.7 g of deposited actinides. A very high capacity of aluminium to retain actinides has been proven as the average Al:An mass ratio was 1:1.58 for galvanostatic and 1:2.25 for potentiostatic mode. The obtained deposits were characterized by XRD and SEM-EDX analysis and alloys composed of (U,Pu)Al3 were detected. The influence of zirconium co-oxidation during the process was also investigated and the presence of dissolved Zr ions in the melt yielded a significant deterioration of the quality of the deposit

Development of an evidence-informed and codesigned model of support for children of parents with a mental illness— “it takes a village” approach

Providing support to parents and their children to help address the cycle of intergenerational impacts of mental illness and reduce the negative consequences for children is a key focus of selective prevention approaches in public mental health. However, a key issue for children of parents with a mental illness is the lack of access to early intervention and prevention support when needed. They are not easily identifiable (until presenting with significant mental health issues of their own) and not easily accessing the necessary support that address the complex interplay of parental mental illness within families. There are significant barriers to the early identification of these children, particularly for mental health care. Furthermore, there is a lack of collaborative care that might enhance identification as well as offer services and support for these families. The “It takes a Village” project seeks to improve mental health outcomes for children through the co-development, implementation and evaluation of an approach to collaborative practice concerned with the identification of families where a parent has a mental illness, and establishing a service model to promote child-focused support networks in Austria. Here we describe the development of service delivery approach for the “It takes a Village” project that aims to improve identification and support of these children within enhancements of the existing service systems and informal supports. The paper describes the use of codesign and other implementation strategies, applied to a research setting, with the aim of impacting the sustainability of workforce reform to achieve lasting social impact. Results highlight the steps involved in translating evidence-based components, local practice wisdom and lived experience into the “It takes a Village” practice model for Tyrol, Austria. We highlight through this paper how regional context-specific solutions are essential in the redesign of care models that meet the complex needs of children of parents with a mental illness. Service system and policy formation with local and experienced stakeholders are also vital to ensure the solutions are implementation-ready, particularly when introducing new practice models that rely on organizational change and new ways of practice with vulnerable families. This also creates a solid foundation for the evaluation of the “It take a Village” approach for children of parents with a mental illness in Austria

Recovery of actinides from actinide–aluminium alloys by chlorination: Part II

A chlorination route is being investigated for recovery of actinides from actinide–aluminium alloys, which originate from pyrochemical recovery of actinides from spent metallic nuclear fuel by electrochemical methods in molten LiCl–KCl. In the present work, the most important steps of this route were experimentally tested using U–Pu–Al alloy prepared by electrodeposition of U and Pu on solid aluminium plate electrodes. The investigated processes were vacuum distillation for removal of the salt adhered on the electrode, chlorination of the alloy by chlorine gas and sublimation of the AlCl3 formed. The processes parameters were set on the base of a previous thermochemical study and an experimental work using pure UAl3 alloy. The present experimental results indicated high efficiency of salt distillation and chlorination steps, while the sublimation step should be further optimised

On the formation of U-Al alloys in the molten LiCl-KCl eutectic

U-Al alloy formation has been studied in the temperature range of 400 – 550 °C by electrochemical techniques in the molten LiCl-KCl eutectic. Cyclic voltammetry showed that underpotential reduction of U(III) onto solid Al occurs at a potential about 0.35 V more anodic than pure U deposition. Open circuit potential measurements, recorded after small depositions of U metal onto the Al electrode, did not allow the distinction between potentials associated with UAlx alloys and the Al rest potential, as they were found to be practically identical. As a consequence, a spontaneous chemical reaction between dissolved UCl3 and Al is thermodynamically possible and was experimentally observed. Galvanostatic electrolyses were carried out both on Al rods and Al plates. Stable and dense U-Al deposits were obtained with high faradic yields, and the possibility to load the whole bulk of a thin Al plate was demonstrated. The analyses (by SEM-EDX and XRD) of the deposits indicated the formation of different intermetallic phases (UAl2, UAl3 and UAl4) depending on the experimental conditions

Mitochondrial physiology

As the knowledge base and importance of mitochondrial physiology to evolution, health and disease expands, the necessity for harmonizing the terminology concerning mitochondrial respiratory states and rates has become increasingly apparent. The chemiosmotic theory establishes the mechanism of energy transformation and coupling in oxidative phosphorylation. The unifying concept of the protonmotive force provides the framework for developing a consistent theoretical foundation of mitochondrial physiology and bioenergetics. We follow the latest SI guidelines and those of the International Union of Pure and Applied Chemistry (IUPAC) on terminology in physical chemistry, extended by considerations of open systems and thermodynamics of irreversible processes. The concept-driven constructive terminology incorporates the meaning of each quantity and aligns concepts and symbols with the nomenclature of classical bioenergetics. We endeavour to provide a balanced view of mitochondrial respiratory control and a critical discussion on reporting data of mitochondrial respiration in terms of metabolic flows and fluxes. Uniform standards for evaluation of respiratory states and rates will ultimately contribute to reproducibility between laboratories and thus support the development of data repositories of mitochondrial respiratory function in species, tissues, and cells. Clarity of concept and consistency of nomenclature facilitate effective transdisciplinary communication, education, and ultimately further discovery

Mitochondrial physiology

As the knowledge base and importance of mitochondrial physiology to evolution, health and disease expands, the necessity for harmonizing the terminology concerning mitochondrial respiratory states and rates has become increasingly apparent. The chemiosmotic theory establishes the mechanism of energy transformation and coupling in oxidative phosphorylation. The unifying concept of the protonmotive force provides the framework for developing a consistent theoretical foundation of mitochondrial physiology and bioenergetics. We follow the latest SI guidelines and those of the International Union of Pure and Applied Chemistry (IUPAC) on terminology in physical chemistry, extended by considerations of open systems and thermodynamics of irreversible processes. The concept-driven constructive terminology incorporates the meaning of each quantity and aligns concepts and symbols with the nomenclature of classical bioenergetics. We endeavour to provide a balanced view of mitochondrial respiratory control and a critical discussion on reporting data of mitochondrial respiration in terms of metabolic flows and fluxes. Uniform standards for evaluation of respiratory states and rates will ultimately contribute to reproducibility between laboratories and thus support the development of data repositories of mitochondrial respiratory function in species, tissues, and cells. Clarity of concept and consistency of nomenclature facilitate effective transdisciplinary communication, education, and ultimately further discovery