The study focuses on the elaboration of thin nanostructured ceria films, grown on
the stainless steel, in view of high temperature fuel cell applications. Films were
prepared electrochemically, via cathodic electrolytic deposition method, at low
temperature (30 0C). Structural, morphological and composition analysis of the asgrown
and annealed films were performed by means of XRD, Raman, SEM and
EDX measurements

Lair, Virginie

Lupan, Oleg

Ringuedé, Armelle

Živković, Ljiljana

Repository of the Vinča Nuclear Institute (VinaR)

       PHYSICAL CHEMISTRY 2010  10th International Conference on Fundamental and Applied Aspects of Physical Chemistry  Proceedings      The Conference is dedicated to the 100th Anniversary of the academician Pavle Savić birthday and 20th Anniversary of the Society of Physical Chemists of Serbia         21-24 September 2010 B E L G R A D E                            ISBN 978-86-82475-17-0 Title: Physical Chemistry 2010. (Proceedings) Editors: S. Anić and Ž. Čupić Published by: Society of Physical Chemists of Serbia, Studentski trg 12-16 P.O.Box 47, 11158 Beograd, 218, Srbija Publisher: Society of Physical Chemists of Serbia For Publisher: S. Anić, President of Society of Physical Chemists of Serbia Printed by: “Jovan” Printing and Publishing Company; 200 Copies; Number of pages 16 + 388, Format: B5; Printing finished in September 2010.  Text and Layout: “Jovan”  200 - Copy printing    II   The Society of Physical Chemists of Serbia  in co-operation with   Institute of Catalysis, Bulgarian Academy of Sciences  Boreskov Institute of Catalysis, Siberian Branch of  the Russian Academy of Sciences  Faculty of Physical Chemistry, University of Belgrade, Serbia  Institute of Chemistry Technology and Metallurgy, University of Belgrade, Serbia  Vinča Institute, University of Belgrade, Serbia   Institute of General and Physical Chemistry, Serbia                         IV  International Organizing Committee  Chairman:             S. Anić (Serbia) Vice-chairman:     N. Stepanov (Russia)                                B. Adnađević (Serbia)  Members: M. Gabrovska (Bulgaria), N. Cvijetićanin (Serbia), T. Grozdić (Serbia),  D. Jovanović (Serbia), M. Lalić (BiH), D. Marković (Serbia), B. Milosavljević (USA), N. Miljević (Serbia), M. Mojović (Serbia), N. Ostrovski (Serbia), C. Pona (Italy), B. Simonović (Serbia), D. Stanisavljev (Serbia), A. G. Stepanov (Russia), V. Vasić (Serbia), N. Vukelić (Serbia), V. Vukojević (Sweden)   International Scientific Committee  Chairman:              Ž. Čupić (Serbia) Vice-chairmans:     V. N. Parmon (Russia)                                 M. Franko (Slovenia)  V. Vasić (Serbia)  Members: A. Antić-Jovanović (Serbia), G. Bačic (Serbia), R. Cervellati (Italy), R. Compton (United Kingdom), V. Gaspar (Hungary),  M. Jeremić (Serbia), A. L. Kawczyñski (Poland), Lj. Kolar-Anić (Serbia), S. Kuchanov (Russia), R. Leblanc (USA),  S. Mentus (Serbia), S. Milonjić (Serbia), Lj. Morozova-Roche (Sweden),  D. Moscone (Italy), J. Nedeljković (Serbia), Z. Noszticzius (Hungary), M. Perić (Serbia), V. Petruševski (Macedonia), M. Plavšić (Serbia), G. Smulevich (Italy),  G. Schmitz (Belgium), I. Schreiber (Czech), P. Ševčik (Slovakia), N. Stepanov (Russia), M. Trtica (Serbia), D. Veselinović (Serbia)  Local Executive Committee  Chairman:              B. Adnadjević Vice-chairmans:    S. Blagojević                                 A. Ivanović  Members: A. Abu Rabi-Stanković, P. Banković, N. Begović, S. N. Blagojević,  N. Cvjetičanin, M. Daković, A. Đerić, A. Ignjatović, Lj. Ignjatović, A. Jović,  J. Krstić, S. Kuprešak, D. Lončarević, J. Maksimović, V. Marković, M. Milenković, M. Milojević, Z. Mojović, B. Nedić, I. Pašti, N. Pejić, A. Popović-Bjelić, M. Petković, N. Potkonjak, D. Ranković, R. Ranković, M. Stević,  I. Stojković, B. Šljukić, M. Vujković    VPROPERTIES OF CERIA FILMS GROWN ON STAINLESS STEEL BY ELECTRODEPOSITION METHOD  Lj. S. Živković,1,2 V. Lair,1 O. Lupan1,3 and A. Ringuedé1  1LECIME, UMR 7575 CNRS– ENSCP,Paris, France 2Vinča Institute of Nuclear Sciences, Belgrade, Serbia 3Technical University of Moldova   Abstract The study focuses on the elaboration of thin nanostructured ceria films, grown on the stainless steel, in view of high temperature fuel cell applications. Films were prepared electrochemically, via cathodic electrolytic deposition method, at low temperature (30 0C). Structural, morphological and composition analysis of the as-grown and annealed films were performed by means of XRD, Raman, SEM and EDX measurements.  Introduction Ceria (CeO2)-based films find many applications in Solid Oxide Fuel Cells (SOFCs), such as promising oxygen conducting electrolyte when doped, interfacial catalytic layer between electrode and electrolyte or protective coating for the interconnect materials [1-3]. Electrodeposition is a cost-effective technique suitable for producing high-quality ceria thin films. It provides an easy way to monitor process parameters (pH, T, reactant concentrations, deposition time) and, therefore, to control or design the deposit characteristics. The method is based on the reduction of oxygen precursor to form hydroxide ions in the vicinity of the working electrode. These OH- ions react with Ce3+ cations present in the electrolytic solution, forming, either via Ce(OH)22+ hydrolysis or Ce(OH)3 oxidation, thin oxide layer on the surface of working electrode [4,5]. All reported studies were carried out via a galvanostatic method. In this work we suggest depositing ceria by a potentiostatic method and focus on the characterization of composition, structure and morphology of as-deposited and annealed coatings.  Experimental Experimental details are given previously [3, 6]. Briefly, a classical three cell electrode was used with a stainless steel disk (Goodfellow, 316L, 0.8 cm diameter) as working electrode under rotation (300 rpm), a saturated calomel (SCE) as reference and a Pt wire as counter electrode. Electrolytic bath, made of NaNO3 (Riedel de Haen, 0.1 M) and Ce(NO3)3.6H2O (Alpha Aesar, 5 mM), kept at 30 0C, was saturated by molecular oxygen, and a slight O2 bubbling maintained during the deposition. Films were elaborated applying -0.8 V/SCE (EGG 263A) for 20 min. XRD was performed by Siemens D5000 unit. Powder Cell 2.4 program was used to determine the crystallite size and lattice strain. SEM images were made by Ultra 55 414Zeiss FEG microscope. Micro-Raman spectra were measured by Horiba Jobin HR system.  Results X-ray pattern for as-grown ceria, Fig.1, displays distinct diffraction peaks which match well the cubic fluorite CeO2 crystal structure, referring to JCPDS#34-0394. The line width is large, typical for small crystallite size. With annealing at 600 0C for 1h, crystallinity improves and line width becomes narrower, valid for all crystallographic planes. Average crystallite size of 12.1 and 14.8 nm was determined for as-grown and annealed films. Lattice strain was 0.2 % for as-grown, and negligible for annealed ceria. These values suggest that the stress is released with annealing. Raman spectroscopy was applied to further study the phase and crystal quality of fabricated films. Figure 2 shows that as-grown ceria spectrum is characterized by an intense band at 456 cm-1, attributed to the F2g mode of Ce-O vibrations, in good  agreement with reported data for non-calcinated particles [7]. The effect of thermal annealing is presented for comparison. As can be seen, the main peak becomes more symmetric, while its crystallinity enhances. Annealing also produces a shift in the maximum intensity of the Raman band towards bigger wave number, 465 cm-1.    Fig.2.  XRD patterns of as-grown   Fig.3. Raman spectra of as-grown and annealed ceria films    and annealed ceria films Surface morphology of as-grown film is shown in Fig. 5. Film is well-covering, dense and adherent to the substrate, with random cracks. Estimated thickness is around 2 µm. The EDX analysis revealed the presence of oxygen peak at 0.5 k eV in the elemental profile, while the Ce signals were registered at 0.9, 4.9 and 6.0 k eV.  415    Fig.5. SEM micrographs of ceria film electrodeposited on stainless steel-top view under different magnifications: (a) 5000 x and (b) 100 000 x  Conclusion Nanostructured ceria thin films have been grown on the stainless steel substrate by the electrodeposition method, applying for 20 min a potential of -0.8V/(SCE) at room temperature. XRD analysis and Raman spectroscopy confirmed the cubic-fluoride structure of deposited ceria. The thermal treatment was found to enhance crystallinity and improve crystal quality. EDX confirmed that Ce and O were electrodeposited. High resolution SEM analysis illustrates that dense and adherent coating of cca 2 µm in thickness covers fully the steel substrate.  Acknowledgements Authors acknowledge funding from the French Research Agency, ANR-JCC06-0131. L. Živković thanks also Ministry of Science of the Republic of Serbia (Pr .No 45012).  References [1]  B. Daslet, P. Blennow, P. Vang Hendriksen, N. Bonanos, D. Lybye, M. Morensen, Journal of Solid State Electrochemistry, 2006, 10, 547. [2]  T. Tsai, S. A. Barnet, Solid State Ionics, 1997, 98, 191. [3]  H. Elbelghiti, V. Lair, A. Ringuedé, M. Cassir, ECS Transactions, 2007, 10, 2261. [4]  I. Zhitomirsky, A. Petric, Ceramics International, 2001, 27,149. [5]  J. Schwitzer, American Ceramic Bulletin, 1987, 1521. [6]  V. Lair, A. Ringuedé, P. Vermaut, S. Griveau, Phys. Stat. Solidi C, 2008, 205 3492. [7]  E. C. C. Souza, E. N. S. Muccilo, Journal of Alloys and Compounds, 2009, 473, 560.   416

Properties of ceria films grown on stainless steel by electrodeposition method

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Properties of ceria films grown on stainless steel by electrodeposition method

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