Report on Gd target production

Deliverable D10.1 Report on Gd target production This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 101008571 (PRISMAP). This document reflects only the view of the author(s). The Agency is not responsible for any use that may be made of the information it contains. Deliverable D10.1 ii Project Acronym PRISMAP Project Title The European medical isotope programme: Production of high purity isotopes by mass separation Grant Agreement No. 101008571 Topic INFRAIA-02-2020: Integrating Activities for Starting Communities Project start date 01 May 2021 Nature Report Dissemination level Public Due date M36 Date of delivery M36 Lead partner ARRONAX Contributing partner INFN Authors Sounalet T., Wang Y., Haddad F., Cisternino S., Kotliarenko A. Reviewer Corradetti S. (INFN) Point of Contact Haddad F. Institution ARRONAX E-mail [email protected] Phone +33228212121 © PRISMAP 2021. This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. Deliverable D10.1 iii Revision History Version Date Author Comment 0.1 05.04.2024 T. Sounalet, S. Cisternino, A.Kotliarenko, Y. Wang, F. Haddad. First draft 0.2 15.04.2024 S. Corradetti First review 0.3 16.04.2024 M. Manzolaro Second review 0.9 22.04.2024 V. Gobry, P. Ulrich, K. Leufgen Review and formatting. Version for review by the PRISMAP General Assembly 1.0 30.04.2024 K. Leufgen Final version, approved by the General Assembly Deliverable D10.1 iv Contents Abbreviations, Participant short names v ... v Abbreviations v … v Participant short names v List of Figures vi ...... vi // Keep this line in place. It is need to fix a Word-bug in the TOC. vi ... vi - vi Summary 1 ... 1 // Keep this line in place. It is need to fix a Word-bug in the TOC. 1 1. Context 2 2. Thin target preparation 3 2.1 ACo-deposition of enriched gadolinium 3 2.2 Electrodeposition in organic media 4 Electrodeposition in molten salts 5 3. Thick target preparation 6 3.1 Pelletizing enriched Gd2O3 at ARRONAX 6 3.2 Thick Target preparation at INFN-LNL 7 3.2.1 Materials and methods 7 3.2.2 Results and discussion 8 4. Conclusions 10 … 10 References 10 Deliverable D10.1 v Abbreviations, Participant short names ... Abbreviations … CA Consortium Agreement DoA Description of Action GA Grant Agreement EOB End of Beam SPECT Single Photon Emission Tomography SEM Scanning electron microscope Participant short names CERN European organisation for nuclear research NPL National Physical Laboratory PSI Paul Scherrer Institut CEA Commissariat à l’énergie atomique et aux énergies alternatives IST-ID Associação do Instituto Superior Técnico para a IST-ID Investigação e Desenvolvimento DTU Danmarks Tekniske Universitet CHUV Centre hospitalier universitaire vaudois GANIL Grand Accélérateur National d’Ions Lourds SCK CEN Studiecentrum voor Kernenergie / Centre d'étude de l'énergie nucléaire ARRONAX Groupement d’intérêt public ARRONAX ESS European spallation source ERIC TUM Klinikum rechts der Isar der technischen Universität München KULeuven Katholieke Universiteit Leuven MedAustron Entwicklungsund Betriebsgesellschaft MedAustron GmbH SCIPROM SCIPROM Sàrl MUI Medizinische Universität Innsbruck ILL Institut Max von Laue - Paul Langevin JRC JRC -Joint Research CentreEuropean Commission NCBJ Narodowe Centrum Badań Jądrowych GSI GSI Helmholtzzentrum fr Schwerionenforschung GmbH LU Latvijas Universitāte INFN Istituto Nazionale di Fisica Nucleare UiO Universitetet i Oslo Deliverable D10.1 vi List of Figures ...... // Keep this line in place. It is need to fix a Word-bug in the TOC. ... - Figure 1. Microscopic images of surface morphology and Gd2O3 distribution of the deposits. Loaded Gd2O3 was 6.5 g, stirring speed was 300 rpm, applied potential was -1.20 V/SHE. (e) corresponds to a lower magnification than (f). 4 Figure 2. Gd deposit on Ti foil after molecular plating. 4 Figure 3. Packaging process of the enriched pellet: (a) the enriched pellet made by the press; (b) the hand wrapped pellet by two aluminium foils; (c) the wrapped pellet in the press die; (d) the tightly wrapped pellet after the compression. 6 Figure 4. (a) Schematic diagram of the assembly of Ti foil and pellets in the capsule. The size and thickness of the foils are not drawn according to the real size. (b) Photo of the stack (without the Ti foil) and a part of the capsule. 6 Figure 5. SEM images of Gd2O3 powders: NANO (left), MICRO (centre) and enriched (right) at different magnifications. 8 Figure 6. Pictures of Gd2O3 (natural Gd) pellets before and after the irradiations. 9 Summary ... // Keep this line in place. It is need to fix a Word-bug in the TOC. Short-lived radionuclides of the terbium (Tb) family show great interest for application in nuclear medicine. Different production routes exist to produce these radionuclides, but the most obvious ones use gadolinium as target material. Within the WP10 of PRISMAP, INFN and ARRONAX have worked on Gd target preparation for both cross section measurements (thin targets) and radionuclide production (thick targets). This work used the preparation of gadolinium targets for Tb-155 production as a case study as developed techniques can easily be adapted to other enriched Gd isotopes. Thin target preparation using different electrochemical techniques has been explored as well as different methods to prepare pellets from Gd2O3 powder including sintering. Targets of both types were prepared and irradiated both in France and Italy. Deliverable D10.1 2 1. Context Short-lived radionuclides of the terbium (Tb) family are of great interest because through four radionuclides of the same element it is possible to get access to all radiations that are of interest for application in nuclear medicine: Tb-149 (T1/2 = 4.12 h) can be used for targeted alpha therapy. It is the lightest alpha emitter with suitable properties for a use in nuclear medicine. Tb-152 (T1/2 = 17.8784(95) h [1]) is a β+ emitter that can be used for imaging using the positron emission tomography (PET) technique. Tb-155 (T1/2 = 5.2346(36) d [2]) decays by electron capture emitting low energy gamma rays suitable for imaging using the single photon emission tomography (SPECT) technique. Tb-161 (T1/2 = 6.9637(29) d [3]) is a βemitter suitable for target therapy. In addition to βemission it shows ample emission of low energy conversion and Auger electrons, thus emitting in total about 2.27 electrons (with energies above 3 keV) per decay. These emissions may be beneficial to increase the cytotoxicity of Tb161 and is has often been identified as a possible alternative to Lu-177. Tb-161 also emits low energy γand X-rays that make it suitable for SPECT imaging. Different production routes exist to produce these radionuclides but the most obvious ones use gadolinium as a target material. It is therefore necessary to work on preparation of Gd targets in order to prepare the availability of these radionuclides for the research community. Depending on the application, target characteristics may differ. For cross section measurements, thin targets are needed of the order of 1-20 µm in thickness whereas for production batches, thick targets (hundreds of µm or more in thickness) are mandatory. Gadolinium suffers from several drawbacks. Natural gadolinium is composed of seven stable isotopes (Gd-152, Gd-154, Gd-155, Gd-156, Gd-157, Gd-158, Gd-160), five having similar natural abundance close to 20%. It is then necessary to work with enriched gadolinium to improve production yields and reduce contaminants. Gadolinium has a high reduction potential that prevents the use of electroplating in water solution. It is then necessary to explore other methods for target preparation, especially for thin targets. In this report we will present the work conducted at INFN and ARRONAX on Gd target preparations. Our work focussed on the preparation of gadolinium targets for Tb-155 production from enriched gadolinium for which recent studies [4,5] exist that have produced it from highly-enriched Gd-155 and Gd-156 oxide targets. Deliverable D10.1 3 2. Thin target preparation Cross-section data of the nuclide of interest and possible contaminants for a given production route are necessary to define the best irradiation parameters to use. They also allow to compare different production routes both in terms of produced quantities and purities. Finally, they allow to obtain the inventory of all radioactive species that will be present in the target after irradiation. This information will be used to define the purification process and anticipate nuclear waste management. The cross section of a given reaction depends on the incident energy of the projectile. As this energy decreases as the projectile enters into the target material, it is important to use thin targets for which the entrance energy and the output energy differ only slightly. For proton and deuteron beams typical target thicknesses vary from 1 µm to 25 µm. Electrodeposition is a standard method to prepare thin targets as it allows for homogeneous and dense deposits whose thicknesses can be controlled by the duration of the process. Electrodeposition is based on electrochemistry, which consists of reducing a cation to obtain a solid layer of metal, metal oxide, or metal salts. It is used in the vast majority of cases in an aqueous solution. Electrodeposition makes it possible to obtain layers of dense material with strong adhesion to the support, making it the technique of choice for producing radionuclides by irradiation with intense particle beams. In all these cases, the involved metals have standard potentials that allow the reduction while remaining in the water stability domain, i.e., between -2 V/SHE (standard hydrogen electrode) and 2 V/SHE. When attempting to apply this technique to gadolinium, it becomes apparent that working in an aqueous medium is not feasible due to the limitations imposed by its standard potential value, -2.40 V/SHE. To overcome this problem, at ARRONAX (Saint-Herblain, France), we are exploring different thin target preparation methods based on electrochemistry. The first one was the co-deposition technique we already finalised to conduct cross section measurements. Two others are still under study, namely molecular plating (under completion) and molten salts (just starting). These three methods are briefly described in the next sections. 2.1 A co-deposition of enriched gadolinium The co-deposition method [6] has been extensively studied to develop composite materials. The basic principle of this method is to mechanically transport and physically embed target particles (mixed in a bath) to the growing deposited layer. This method requires simple experimental conditions and allows to trap Gd atoms in a metal deposit allowing to make a thin target usable for cross section measurement in less than an hour. After extensive studies [7], we decided to use Gd2O3 because the enriched Gd-155 isotope is easily available in this form and to use nickel as the electroplating matrix metal because the experimental conditions are well known and it is possible to perform it in basic conditions, in which Gd2O3 remains stable. In addition, due to its insolubility in alkaline solution, the Gd2O3 powder can be easily recycled, which greatly improves the material utilisation rate which is of particular importance when isotopically enriched materials are used. In our study, we have looked at the influence of main process parameters (i.e., applied potential, concentration of Gd2O3 and stirring speed) on the deposit quality and defined our optimal experimental procedure. To obtain the Ni–Gd2O3 composite deposits, the following electrolyte was prepared: 0.5 mol/L (NH4)2SO4 + 0.5 mol/L NH4Cl + 0.14 mol/L NiSO4⋅6H2O + 1 mol/L NH3. The final pH of the electrolyte was fixed at 9.8, adjusted by 5 mol/L of NaOH. Insoluble Gd2O3 under powder form (less than 230 mesh size) in basic solution was then added to the solution. Considering the surface quality and deposited Gd quantity, the optimal condition for the co-deposition to apply are -1.2 V/SHE potential, with a load of 6.5 g Gd2O3 and a stirring speed of the electrolyte equal to 300 rpm. Deliverable D10.1 10 (Nb/Au or others). This type of configuration was already tested with different materials (Y-Nb and Cr-AuNb) using an automatic dissolution system developed by the LARAMED team, as described in [16]. 4. Conclusions … During the PRISMAP project, works have been done both at INFN and ARRONAX to manufacture Gd targets. The focus has been made on the production of Tb-155 using enriched Gd-155, but the developed techniques can easily be adapted to other enriched Gd isotopes. These targets are produced for both, cross section measurements to help define the best irradiation parameters, and large production batches. For cross section measurements, thin targets are needed and electrochemical techniques have been explored. Co-deposition of Gd2O3 in Ni have been developed and experiments with enriched Gd-155 oxide performed to get cross section data for the deuteron induced reaction. In parallel, molecular plating and electrodeposition in molten salts are being explored to obtain Gd metallic targets. First targets have been obtained with molecular plating and experiments are being scheduled in 2024. Molten salts require more work and we continue to work on it at ARRONAX. For large production batches, thicker targets are needed. At ARRONAX simple pelletizing targets have been developed and an irradiation performed on that pellet shows the good agreement between measured activities of terbium isotopes and the theoretical value extracted from cross section measurements. However, there is a limitation of the technique as it is needed to make rather thick targets to limit the brittleness of the pellets. One possibility to overcome this issue is to use the sintering technique. Pellets have been manufactured at LNL using different quality of Gd2O3 powder with this technique. Pellets of 304 µm and 610 µm thicknesses have been obtained using nanosize powder and another one of 600 µm using microsize powder. Nanosize powder pellets have successfully been irradiated at a biomedical cyclotron facility in Italy at low intensity opening the way to large batch production by increasing the intensity used on target. Within the work of WP10 of PRISMAP, several techniques to prepare Gd targets have been investigated and Gd targets of different thickness can be manufactured depending on the need. Developments continue to improve these techniques and look to alternative methods that leads to Gd metal targets. 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