103Pd is an important therapeutic radionuclide and has recently found great interest due to its higher radiobiologic effect. 109Cd decays by electron capture and is generally used as calibration sources in industrial and medical fields. A new method for the production of 103Pd and 109Cd using the 66 MeV proton beam of iThemba LABS on a tandem natural silver target (Ag/Ag) has been developed. The tandem targets (each target with a mass of 9 g and a thickness of 3 mm) were placed in the high energy slot (62.515 MeV - 40.173 MeV) and low energy slot (38.652 MeV – 0 MeV) to produce the bulk 103Pd and 109Cd, respectively. The radiochemical separation of the Pd radionuclides (103Pd, 100Pd) and the co-produced Rh radioisotopes (mainly 101Rh and 100Rh which are produced from decay of their Pd parents) from the bulk natAg was achieved using a Chelex chelating resin column. In the preliminary studies, different size columns (3 cm x 1 cm, 11 cm x 1 cm, 13 cm x 1 cm and 16 cm x 1.5 cm) were investigated to determine the optimal column conditions for the separation. It was determined that the optimal conditions for the chemical separation was with a 13 cm x 1 cm resin column with the elution of Rh and Ag radionuclides carried out with 1 M HNO3 and the elution of Pd radionuclides with 10 M HCl. No Ag or Rh impurities were detected in the final product and the average recovery of Pd was > 96 %. This work was repeated using a ―hot‖ irradiated Ag target and the chemical processing was done in a hot cell using the same resin column conditions. The recovery of the high purity 103Pd from the irradiated natAg target was found to be > 95 %. The radiochemical separation of 109Cd from the bulk natAg target was done in two parts. In the first part, the precipitation method was used to reduce the silver into a metallic form using 30 g of Cu turnings. The resulting 109Cd filtrate was loaded onto a AG-X10 anion exchange resin column (6 cm x 1 cm). For the optimal chemical separation, the elution of Ag and Cu(II) was carried out with 2 M HCl containing H2O2 and the elution of 109Cd was accomplished with 1 M HNO3. The recovery yield of 109Cd was > 99 %. / Chemistry / M.Sc. (Chemistry)

103Pd is an important therapeutic radionuclide and has recently found great interest due to its higher radiobiologic effect. 109Cd decays by electron capture and is generally used as calibration sources in industrial and medical fields. A new method for the production of 103Pd and 109Cd using the 66 MeV proton beam of iThemba LABS on a tandem natural silver target (Ag/Ag) has been developed. The tandem targets (each target with a mass of 9 g and a thickness of 3 mm) were placed in the high energy slot (62.515 MeV - 40.173 MeV) and low energy slot (38.652 MeV – 0 MeV) to produce the bulk 103Pd and 109Cd, respectively. The radiochemical separation of the Pd radionuclides (103Pd, 100Pd) and the co-produced Rh radioisotopes (mainly 101Rh and 100Rh which are produced from decay of their Pd parents) from the bulk natAg was achieved using a Chelex chelating resin column. In the preliminary studies, different size columns (3 cm x 1 cm, 11 cm x 1 cm, 13 cm x 1 cm and 16 cm x 1.5 cm) were investigated to determine the optimal column conditions for the separation. It was determined that the optimal conditions for the chemical separation was with a 13 cm x 1 cm resin column with the elution of Rh and Ag radionuclides carried out with 1 M HNO3 and the elution of Pd radionuclides with 10 M HCl. No Ag or Rh impurities were detected in the final product and the average recovery of Pd was > 96 %. This work was repeated using a ―hot‖ irradiated Ag target and the chemical processing was done in a hot cell using the same resin column conditions. The recovery of the high purity 103Pd from the irradiated natAg target was found to be > 95 %. The radiochemical separation of 109Cd from the bulk natAg target was done in two parts. In the first part, the precipitation method was used to reduce the silver into a metallic form using 30 g of Cu turnings. The resulting 109Cd filtrate was loaded onto a AG-X10 anion exchange resin column (6 cm x 1 cm). For the optimal chemical separation, the elution of Ag and Cu(II) was carried out with 2 M HCl containing H2O2 and the elution of 109Cd was accomplished with 1 M HNO3. The recovery yield of 109Cd was > 99 %. / Chemistry / M.Sc. (Chemistry)

L'analyse chimique est indispensable à de nombreuses étapes de la mise au point et dusuivi des procédés de retraitement des combustibles nucléaires usés, de la gestion des déchetsnucléaires, ou encore de l’optimisation des combustibles du futur. Le cycle global d’analysecomprend généralement plusieurs étapes de séparations chimiques longues, manuelles etdifficiles à mettre en oeuvre en raison de leur confinement en boite à gants. Il apparaîtaujourd’hui nécessaire de proposer des solutions innovantes et viables dans le butd’automatiser ces étapes mais aussi de réduire le volume de déchets radioactifs en fin de cycleanalytique. Une solution est alors la conception de plateformes analytiques miniaturiséesautomatisées et jetables.L’objectif de cette thèse est de concevoir un système miniaturisé alternatif à lapremière étape actuelle d’analyse des combustibles usés séparant, par chromatographied’échange d’ions, l’Uranium et le Plutonium des autres éléments constituant l’échantillon. Cesystème doit permettre à la fois de conserver les performances analytiques du processusactuel, de réduire drastiquement l’exposition des expérimentateurs par l’automatisation, ainsique le volume de déchets produits en fin de cycle analytique. Ainsi, la séparation a étéimplantée sur un microsystème jetable en plastique (COC), au design spécialement adapté àl’automatisation : un lab-on-CD.Le prototype développé intègre une micro-colonne séparative d’échange d’anionsremplie d’un polymère monolithique dont la synthèse in-situ ainsi que la fonctionnalisation desurface ont été optimisées spécifiquement pour la séparation voulue. Le développement duprotocole de séparation adapté à ces micro-colonnes a été réalisé à l’aide d’un outil desimulation de l’élution des différents éléments d’intérêts. Cet outil permet de prévoir lagéométrie de la colonne (section et longueur) afin d’obtenir, en fonction de l’échantillon, desfractions de collecte de l’Uranium et du Plutonium pures.Finalement, le prototype actuel est capable de conduire simultanément 4 séparationsde façon automatisée et permet de réduire à la fois le nombre de manipulations, le tempsd’analyse mais aussi de diviser approximativement par 1000 le volume des déchets liquidesgénérés. / The chemical analysis of spent nuclear fuels is essential to design future nuclear fuelscycle and reprocessing methods but also for waste management. The analysis cycle consistsof several chemical separation steps which are time consuming and difficult to implement dueto confinement in glove boxes. It is required that the separation steps be automated and thatthe volume of radioactive waste generated be reduced. The design of automated, miniaturizedand disposable analytical platforms should fulfill these requirements.This project aims to provide an alternative to the first analytical step of the spent fuelsanalysis: the chromatographic separation of Uranium and Plutonium from the minor actinidesand fission products.The goal is to design a miniaturized platform showing analytical performancesequivalent to the current process, and to reduce both the exposure of workers throughautomation, and the volume of waste produced at the end of the analysis cycle. Thus, theseparation has been implemented on a disposable plastic microsystem (COC), specificallydesigned for automation: a lab on a Compact Disk or lab-on-CD.The developed prototype incorporates an anion-exchange monolithic micro-columnwhose in-situ synthesis as well as surface functionalization have been optimized specificallyfor the desired separation. The development of an adapted separation protocol was carried outusing a simulation tool modeling the elution of the various elements of interest. This tool isable to predict the column geometry (length and cross section) suited to obtain pure fractionsof Uranium and Plutonium as a function of the sample composition.Finally, the prototype is able to automatically carry out four separationssimultaneously reducing the number of manipulations, the analysis time and reducing thevolume of liquid waste by a factor of 1000.