Developing an in situ EXAFS experiment of microwave-induced gelation


Internal gelation is an advanced route to produce small spheres of metal from a nitrate solution. In this work, microwave heating is used to trigger the gelation of the solution. X-ray absorption spectroscopy is a powerful tool to follow the gelation advancement and verify the completeness of a reaction, but in order to use it on falling nitrate droplets, the study is split into two experiments. First, a fluorescence measurement has been carried out on a trickle of small falling cerium nitrate droplets generated at high frequency to verify that capturing a discontinuous signal would not generate too much noise. Then, a measurement of silver nitrate undergoing gelation in a microwave cavity has been performed in transmission mode, which proved that a fast recording method is suitable for following the evolution of chemicals during such a reaction. The combination of both analyses confirms that it is possible to study microwave gelation of falling droplets using X-ray absorption spectroscopy at the SuperXAS beamline.

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  1. 1.

    Abdala PM, Safonova OV, Wiker G, van Beek W, Emerich H, van Bokhoven JA, Sá J, Szlachetko J, Nachtegaal M (2012) Scientific opportunities for heterogeneous catalysis research at the SuperXAS and SNBL beam lines. CHIMIA Int J Chem 66(9):699–705. doi:10.2533/chimia.2012.699

  2. 2.

    Ankudinov AL, Nesvizhskii AI, Rehr JJ (2003) Dynamic screening effects in X-ray absorption spectra. Phys Rev B 67:115–120

  3. 3.

    Chadwick AV, Savin SLP (2009) MEASUREMENT METHODS|Structural plus electronic and chemical properties: X-ray absorption spectroscopy. In: Garche J (ed) Encyclopedia of electrochemical power sources. Elsevier, Amsterdam, pp 790–801.

  4. 4.

    Conradson SD, Begg B, Clark D, Auwerc CD, Ding M, Dorhout PK, Espinosa-Faller FJ, Gordon PL, Haire RG, Hess NJ, Hess RF, Keogh DWW, Lander GH, Manara D, Morales LA, Neu MP, Paviet-Hartmann P, Rebizan J, Rondinella VV, Runde W, Trait CD, Veirs DK, Villella P, Wastin F (2005) Charge distribution and local structure and speciation in the \(\text{ UO }_{\rm 2+x}\) and \(\text{ PuO }_{\rm 2+x}\) binary oxides for \(x \leq 0.25\). J Solid State Chem 178:521–535

  5. 5.

    Cozzo C, Cabanes-Sempere M, Pouchon MA (2012) Methods of advanced waste conditioning by microwave internal gelation: set up development and modeling. In: 12th information exchange meeting on actinide and fission product partitioning and transmutation. OECD/NEA, Prague, Czech Republic.

  6. 6.

    Cozzo C, Orlov A, Borca C, Degueldre C (2014) X-ray absorption in plutonium uranium mixed oxide fuel: thorium characterization. Prog Nucl Energy 72:91–95

  7. 7.

    Cozzo C, Vaucher S, Ishizaki K, Megias-Alguacil D, Pouchon MA (2011) Chemistry of uranium surrogate during microwave assisted internal gelation for fuel fabrication. In: Proceedings of Global 2011, Makuhari, Japan, December 11–16, 2011, Paper no. 392501

  8. 8.

    Degueldre C, Borca C, Cozzo C (2013) Curium analysis in plutonium uranium mixed oxide by X-ray fluorescence and absorption fine structure spectroscopy. Talanta 115:986–991. doi:10.1016/j.talanta.2013.06.021

  9. 9.

    Denecke MA (2006) Actinide speciation using X-ray absorption fine structure spectroscopy. Coord Chem Rev 250:730–754

  10. 10.

    Ganguly C, Hegde PV (1997) Sol–gel microsphere pelletisation process for fabrication of (U,Pu)O2, (U,Pu)C and (U,Pu)N fuel pellets for the prototype fast breeder reactor in India. J Sol-Gel Sci Technol 9(3):285–294. doi:10.1023/A:1018363412570

  11. 11.

    Hada H, Yonezawa Y, Yoshida A, Kurakake A (1976) Photoreduction of silver ion in aqueous and alcoholic solutions. J Phys Chem-US 80:2728–2731. doi:10.1021/j100566a003

  12. 12.

    Harada M, Inada Y, Nomura M (2009) In situ time-resolved XAFS analysis of silver particle formation by photoreduction in polymer solutions. J Colloid Interface Sci 337(2):427–438. doi:10.1016/j.jcis.2009.05.035

  13. 13.

    Miao Y, Aidhy D, Chen WY, Mo K, Oaks A, Wolf D, Stubbins JF (2014) The evolution mechanism of the dislocation loops in irradiated lanthanum doped cerium oxide. J Nucl Mater 445(13):209–217. doi:10.1016/j.jnucmat.2013.11.015

  14. 14.

    Milinski N, Ribar B, Sataric M (1980) Pentaaquatri nitrato cerium(III) monohydrate. Cryst Struct Commun 9:473–477

  15. 15.

    Newville M (2005) IFEFFIT: interactive XAFS analysis and FEFF fitting. J Synchr Rad 12:537–541

  16. 16.

    Ozdemir I, Yayl A, Ozbek I (2016) Thoria based inert matrix fuel production via sol–gel process. Prog Nucl Energy 86:63–70. doi:10.1016/j.pnucene.2015.10.004

  17. 17.

    Pouchon M (2009) Collaborators: PINE–Platform for innovative nuclear fuels. Annual activity reports, pp 35–36, CCEM.

  18. 18.

    Pouchon M, Ledergerber G, Ingold F, Bakker K (2012) Sphere-Pac and VIPAC fuel. In: Konings R, Yamanaka S (eds) Comprehensive nuclear materials. Elsevier, Amsterdam

  19. 19.

    Ravel B (2001) ATOMS: crystallography for the X-ray absorption spectroscopist. J Synchr Rad 8:314–316

  20. 20.

    Ravel B, Newville M (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J Synchr Rad 12:537–541

  21. 21.

    Seward T, Henderson C, Charnock J, Dobson B (1996) An X-ray absorption (EXAFS) spectroscopic study of aquated Ag+ in hydrothermal solutions to 350 °C. Geochim Cosmochim Acta 60:2273–2282

  22. 22.

    Simposio Nucleare Internazionale di Torino (1967) In: I process sol–gel per la produzione di combustibili ceramici. Torino, Italy

  23. 23.

    Slomkowski S, Alemin JV, Gilbert RG, Hess M, Horie K, Jones RG, Kubisa P, Meisel I, Mormann W, Penczek S, Stepto RFT (2011) Terminology of polymers and polymerization processes in dispersed systems (IUPAC Recommendations 2011). Pure Appl Chem. doi:10.1351/PAC-REC-10-06-03

  24. 24.

    Sutton LE (1965) Tables of interatomic distances and configuration in molecules and Ions: supplement 1956–59. Chemical Society, London

  25. 25.

    Symposium on sol–gel processes and reactor fuel cycles. CONF-700502. Gatlinburg (1970)

  26. 26.

    Yamaguchi T, Johannsson G, Holmberg B, Maeda M, Ohtaki H (1984) The coordination and complex formation of silver(I) in aqueous perchlorate, nitrate and iodide solutions. Acta Chem Scand A 38:437–451

  27. 27.

    Zamoryanskaya M, Burakov B (2000) Feasibility limits in using cerium as a surrogate for plutonium incorporation in zircon, zirconia and pyrochlore. In: Symposium scientific basis for nuclear waste management XXIV, MRS online proceedings library, vol 663. doi:10.1557/PROC-663-301.

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S. Valance is acknowledged for his assistance during the analysis of the results. This work was part of the PINE project and its follow-up MeAWaT and was partially financed by the Swiss Competence Center for Energy and Mobility. The authors greatly appreciate the financial support of the European Commission through Contract No. 295664 regarding the FP7 PELGRIMM project, as well as Contract No. 295825 regarding the FP7-ASGARD project.

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Cozzo, C., Ishizaki, K., Pouchon, M.A. et al. Developing an in situ EXAFS experiment of microwave-induced gelation. J Sol-Gel Sci Technol 78, 507–513 (2016) doi:10.1007/s10971-016-3992-5

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  • Internal gelation
  • Microwave
  • Reaction advancement