2018 History of technetium studies in Russia Anna Kuzina

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Lecture is about the History of technetium studies in Russia and Anna Kuzina 100 anniversary of birthday Technetium separation in milligram, gram and kilogram ammounts 1957 - 1993
  • 1. The 10th International Symposium on Technetium and Rhenium, IPCE RAS, MOSCOW-2018 Prof. Anna Fedorovna KUZINA 100th Anniversary of birthday K. E. G e r m a n Russian Academy of Sciences A.N. Frumkin Institute of Physical Chemistry and Electrochemistry
  • 2. 100th Anniversary 1918 - 2018
  • 3. In IPC AN USSR, 1956 - 1990  Some fundamental chemistry  Initial studies of technetium irradiation of Mo in reactors for Tc (Krasnoyarsk) synthesis of new compounds electrochemistry of technetium analytical chemistry of technetium  Separation of Tc at PA Mayak  Conversion to Tc metal  Cluster compounds of technetium
  • 4. First micro-grams  Mo (n, g) Tc in nuclear reactor  Missions to Krasnoyarsk  Work with Anatoly Tsarenko
  • 5. First motivation for exploring Tc chemistry for the Closed Fuel Cycle  Tc-99 is a key dose contributor at HLW repositories if TRU elements are greatly reduced by recycling • long half-life of Tc (t1/2 = 2.14 x 105 years), • high mobility, and solubility under oxidizing conditions  Methods for managing the long-term threat of Tc to the environment • Stable waste form/repository system providing with strict limits for Tc release over a long period of time (~1 million years?). • Transmutation of radioactive Tc to stable Ru im nuclear rectors.
  • 6. Main problems of Tc  Tc is important item in Nuclear Industry  Tc redistribution in PUREX produces flows with long-lived high radioactive wastes  Tc interferes at U/Pu separation stage in PUREX process  Tc accumulation in High burn-up fuel together with Mo, Ru, Rh  Tc in nuclear waste vitrification: Tc-Mo- Ru metal phases, Tc(VII) volatility
  • 7. Russian reprocessing plant RT-1 , PUREX part
  • 8. Technetium interfering role in the PUREX Pu/U separation stage Reductive separation of U, Pu, Np (Tc) Reducing agent + complexing agent Extract U,Pu, Np (Tc(STc 1st extcyc =80 -90%)) Back extract Pu, Np (Tc(IV)) Extract U (Tc(VII)) 1. Variable red-ox states 2. Variable species  Difficulties in stability of U/Pu separation at UK, Russian and French facilities  Catalytic Tc effects in many chem. reactions  Variable Tc redox states  Tc - Waste problems  Tc-DTPA complex precipitation
  • 9. Tc + N2H5 + = ?= Конечные хим. формы в реакции Тс(VII) c N2H5 + согласно разным авторам варьируют от Tc(2+) до Tc(VII) = необходимы структ. и спектроскоп. данные Authors Order in [N2H5]0 Order in [H+ ] Order in по [TcO4 - ] Krinitsyn, Tsarenko, 1982 0 0 1 Kuzina et all., 1981 1 0 2 Koltunov ey all. 0.85 1.4 1 Ramazanov et all. 1 2 1.2 Kemp et all. - - кинет. циклы Zilberman, Mashkin HN3, catalytic cycles
  • 10. Best research of 1982-1986 at PO MAYAK  Main approach  Ion-exchange  100 kg separated during  Purification (Tc/DPu)
  • 11. Development of ion-exchange technology for Tc separation in IPCE RAS (1971-1976) Prof. A.F. Kuzina (Tc Group leader till 1987 ) presents her Tc samples prepared in the Institute from the concentrate separated from radioactive wastes generated at Krasnoyarsk Reprocessing Plant to Glean SEABORG (1978)
  • 12. Separation of macro amounts of Tc-99g in USSR  1 kg of Tc was converted to metal in hot cell of IPCE RAS and distributed among different Russian institutes  In 1971-1976 IPC RAS in collaboration with Krasnoyarsk Mining Enterprise has separated from HAW some kilograms of K99TcO4  In 1983 -1986 collaboration of PO “Mayak”, IPCE RAS and Radium Institute resulted in elaboration of anion-exchange technology for Tc separation and 40 kg of K99TcO4. This work was awarded with the special Diploma of the Russian authorities Prof. Anna KUZINA and acad. Victor SPITSYN analyzing the sample of Tc metal
  • 13. Searching technetium applications  Anti-corrosion protection  Anti-fouling protection  Light-matter defectoscopy  Catalysts  Ophtamo  Reference electro-current sources  Batteries  …
  • 14. A few examples of new Tc compound structures made in IPCE RAS (A. Kuzina, K.German, M.Grigoriev) [Me4N]3[Tc6Cl14] [Bu4N]TcO4 [Pr4N]TcO4
  • 15. The last work, ESCA, 1990, Italy, Tc&Re symp.
  • 16. 100th Anniversary 1918 - 2018  Anna Kuzina greatly supported international collaboration of IPC AN  With Czechoslivakia,  France, Poland, USA etc.  A message from Roald Hoffman, 2018
  • 17. The chemistry of rhenium and technetium is remarkably diverse and wide-ranging, given that one of the elements is among the rarest in the crust of the earth, and the other is almost entirely synthetic, the result of nuclear fission (I hope you like as much as I do, the image of nuclear physicists as synthetic chemists!) When these elements were first described nearly a hundred years ago, at much the same time, one could not have imagined that they would be used as superalloys and catalysts, tracers in medicine, or – in the Tc halide clusters – as examples of most unusual chemical bonding. But they are so used, of value to our economy and well-being, a stimulus to our thinking. I wish the explorers of the Tc and Re worlds good science and great fun! Roald Hoffmann, chemist and writer, who has worked, even if not much, with both Tc and Re chemistry, 08.08.2018 . Message to International Symposium on Technetium and Rhenium - Science and Utilization, 2018
  • 18. Walter Noddack, 125th Anniversary, 1893-2018  Discovery  of RHENIUM  + W.Noddack  + Ida Tacke  + O. Berg
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