Synthesis of the Metallocenes for the Production of Exotic High Energy Ion Beams Ntombizonke Yvonne Kheswa A thesis is submitted in fulfilment of the requirements for the degree of Doctor of Philosophy in the Department of Physics & Astronomy, University of the Western Cape, South Africa. Supervised by: Prof. J. N. Orce, Department of Physics & Astronomy University of the Western Cape Prof. S. Titinchi, Department of Chemistry, University of the Western Cape Dr. R. Thomae Accelerator and Engineering Department iThemba LABS March 2019 https://etd.uwc.ac.za DECLARATION I declare that Synthesis of the Metallocenes for the Production of Exotic High Energy Ion Beams is my own work, that it has not been submitted for any degree or examination in any other university, and that all the sources I have used or quoted have been indicated and acknowledged by complete references. Signed: Ntombizonke Kheswa Date: 1 March 2019 i https://etd.uwc.ac.za Synthesis of the Metallocenes for the Production of Exotic High Energy Ion Beams Department of Physics and Astronomy, University of the Western Cape, Private Bag X17, 7535 Bellville, South Africa. ABSTRACT The Subatomic Physics Department of iThemba Laboratory for Accelerated Based Sciences (iThemba LABS) conducts experiments that require a variety of particle beams in order to study nuclear properties (reaction, structure, etc.) of various nuclides. These particle beams are accelerated using the K-200 Separated Sector Cyclotron (SSC) and delivered to different physics experimental vaults. Prior to acceleration, the particle beam is first ionised using an Electron Resonance Ion Source (ECRIS). The main goal of this study is the production of exotic metallic beams of 60Ni8+ and 62Ni8+ using ECRIS4, which are required for the Coulomb excitation experiments approved by the Programme Advisory Committee (PAC) at iThemba LABS. In order to provide the metallic beams of nickel, a development study of organometallic materials containing 60Ni and 62Ni isotopes in a form of metallocene complexes was undertaken. The nickelocene (NiCp2) complex, a member of the organometallic family, was synthesised at the Physics Target Laboratory of iThemba LABS for the first time. Method development involved the use of natural nickel during the multi-step synthesis before the use of enriched nickel-60 (60Ni) and nickel-62 (62Ni). Nine samples of NiCp2 were synthesised; two were isotopically enriched nickelocene 60 62 ( NiCp2 and NiCp2). The percentage yields of the synthesised nickelocene samples ranged between 16 to 50 %, and samples were characterised by investigating their crystal structure and bonding arrangements in the complexes by X-ray diffraction (XRD) , Fourier Transform Infrared (FT-IR) spectroscopy, and Proton Nuclear Magnetic Resonance (1H NMR). The synthesised nickelocene were further used with ECRIS4 for the production of Ni beams on the Q-line of the cyclotron. The Metal Ions from Volatile Compounds (MIVOC) technique was used for the conversion of 60Ni and 62Ni to ion species. The method used the organometallic compounds which are volatile at specific pressures at ambient temperatures. ii https://etd.uwc.ac.za Metallic ion beams of nickel were successfully produced after a carefully pre-sample conditioning in the MIVOC container before connecting the MIVOC set-up to the new injection system of the ECRIS4. Measured beam intensities during the experiment for both 60Ni+ and 62Ni+ were approximately 30 µA, optimum for physics measurements. The development of the MIVOC technique opens up new beam-target combinations with the use of new exotic stable beams for new science cases at iThemba LABS. Reactions in inverse kinematics, multi-step Coulomb-excitation and other types of reactions will immensely benefit from these developments. iii https://etd.uwc.ac.za KEYWORDS - Organometallic compounds - Metallocenes - Nickelocene, NiCp2 - Nickelocene complexes - Enriched 60Ni and 62Ni - Metallic Ion Beams - Electron Cyclotron Resonance Ion Source (ECRIS4) - Metal Ions from Volatile Compounds (MIVOC) - Synthesis - X-ray Diffraction (XRD) - Fourier Transform Infrared (FT-IR) - Proton Nuclear Magnetic Resonance (1H NMR) iv https://etd.uwc.ac.za AKNOWLEDGEMENTS I would like to give thanks to the following: • NRF/iThemba LABS for affording me time and funding to complete my research studies. • To my supervisors who have been working with me throughout this research: • Prof. Nico Orce, for acknowledging the potential and capability in me that I am equally ready to take up such an important research study as a PhD. You provided me with academic guidance to ensure that this research go as planned and achieve its goal. I do appreciate also the background lessons in nuclear physics research and what it entails to perform some of those interesting experiments. • Prof. Salam Titinchi, thank you for your guidance and with the planning of the project with more emphasis on the chemistry part of which you are the expert. The time and advises provided during the sample preparations and their characterisations, provided a valuable component to my research study. Your guidance in interpretations of results and writing is well appreciated by me. • Dr Rainer Thomae, my colleague and the specialist in ECR-ion sources at NRF/iThemba LABS, my sincere gratitude to you as you had to take me through the ion sources process, from the beginning to the end. Making certain that my interpretation of results is of quality that is appreciated by special community. Thank you for all your patience. • To my supervisors, all your teachings are highly appreciated and are now part of me. I can assure all that this experience is priceless, my elders always said, never be afraid to learn, knowledge is weightless. • To Dr Hanno Abbo (UWC) and Mr Raimo Seppälä (JYFL) – thank you both for all the practical guidance you afforded me for the technique in the synthesis of the complexes. • To my colleagues and considering them as my younger brothers; from the National Metrology Institute of South Africa (NMISA) in Pretoria and Department of Subatomic Physics at iThemba LABS: Dr Tshepo Dinoko for the assistance during sample preparation and proof reading my work. Dr Peane Maleka for assisting with proof reading my work and willingness to read while avoiding any of the laboratory v https://etd.uwc.ac.za Dr Obed Shirinda for also making sure that the editing and style of the document are in order and allowed standard. Ngithi kini nobathathu Ubuntu mabande ningapheli amandla nangomuso. • MRD colleagues, Dr Khumalo and Dr Bucher, thank you for performing XRD characterisation on my samples. • To my colleagues and younger sisters, Dr Zina Ndlovu and Dr. Thifhe Bucher, thank you both for the moral support you provided, this was much appreciated. • To my friend at SUN, Dr Setati; Thank you for all the advice you gave me during my study and assistance to make sure that all is in order with my thesis. Kuthiwa indlela ibuzwa kwabaphambili ngoba bayazi kangcono. • To the University of the Western Cape, Faculty of Natural Science, Department of Physics and Astronomy for allowing me the opportunity to be part of the team. Kumndeni wami wonke ngithi lencwadi eqoshiwe ingeyenu. • Abazali bami: abakwaMdluli langizalwa khona kanye nakwaKheswa la engendela khona ngithi ngibonga ukuba nami kuloluhambo. Imikhuleko yenu njalo iye yangimisa idolo. • Myeni wani, NoZulu bengingeke ngilunge ukulihamba ngedwa loluhambo, ngiyabonga ukusolokho ungikhuthaza njalo. • Kumagcino wami Nqobile, anginawo amazwi anele okukubonga Ngelosi yami. Ukubakhona kwakho kunginike amandla ngoba ubuhlale ukukhathalele futhi ukuthokozela ukufunda kwami, ngiyethemba ukuthi lokhu kuzokunika ugqozi lokuthi uzithande izincwadi zakho. • To my big two☺ - Muke noLungi. Benikhathezeka umangabe ningibona sengizibe ilaptop yami, nibuze nithi kathi akusafundwa yini ma, ngoba nikhathazeka ukuthi angizukuqeda. Lemibuzo yenu ibingigqugquzela kakhulu noma sengiphelelwa yithemba. • Kuzingane zakwethu, uVusi, Thulani no Lindile kanye nezingane zabo ngithi ngibonga amazwi enu enkuthazo. Lencwadi eqoshiwe ngiyinikela kwintombi KaDonda, umaMbokazi ukhulu wami ongasekhoyo owayeyithanda imfundo ngendleala ebabazekayo. Ngithi gogo, sengiwuye udokotela namhlanje njengesifiso sakho. vi https://etd.uwc.ac.za TABLE OF CONTENT DECLARATION .................................................................................................................. I ABSTRACT ................................................................................................................ II KEYWORDS ............................................................................................................... IV AKNOWLEDGEMENT .................................................................................................... V TABLE OF CONTENT .................................................................................................. VII LIST OF FIGURES AND TABLES .................................................................................. X ABBREVIATIONS ..........................................................................................................XV CHAPTER 1 INTRODUCTION.................................................................................. 1 1.1 MOTIVATION ............................................................................................................. 1 1.2 GENERAL BACKGROUND OF ORGANOMETALLIC COMPOUNDS ........................................ 5 1.3 NEW PHYSICS WITH NEW BEAMS...............................................................................