The burnable poison Gadolinium oxide was incorporated into UO 2 in two of the 36 elements of the fuel assembly in the reload fuel of BWR Units I & II of Tarapur Atomic Power Station. This enabled loading of higher quantities of fuel and achieving a more flattened neutron flux distribution over a longer period of time in the nuclear reactor core. The UO 2 -Gd 2 O 3 pellets are made by powder pressing and sintering. In the early days of this author’s experience of the 1970s, the processing of UO 2 -Gd 2 O 3 turned out to be more complex than that of UO 2 alone. The small proportion of Gd 2 O 3 in the powder mixture (1.5%) is to be uniformly distributed in the UO 2 before and after sintering and substitutional solid solution formation must be complete prior to densification. The inadequacy of homogeneity in the powder and pressed pellets leads to severe defects in the sintering process. In this paper, the processing of U 2 -Gd 2 O 3 has been revisited. The defects in the product such as “free gadolinia”, low sintered density and bloating, caused by improper processing, have been brought out. The structural defect chemistry aspects of UO 2 -Gd 2 O 3 and diffusion processes relevant to sintering have also been discussed.
Balakrishna, P., Narayanan, P.S.A, Somayajulu, G.V.S.R.K. and Sinha, K.K. (1977) Special Features in the Fabrication of Mixed Oxides. Transactions of the Powder Metallurgy Association of India, 4, 25-31.
Balakrishna, P., Narayanan, P.S.A., Somayajulu, G.V.S.R.K. and Sinha, K.K. (1979) Fabrication of Burnable Poison Fuel Pellets for TAPS—Plant Experience. Symposium on Sintering and Sintered Products, Bhabha Atomic Research Centre, Bombay, October 29-31 1979, 401-421.
Balakrishna, P., Somayajulu, G.V.S.R.K., Sinha, K.K. and Kondal Rao, N. (1979) Special Features in Sintering UO2-Gd2O3 Compacts. Transactions of the Powder Metallurgy Association of India, 6, 80-89
Balakrishna, P., Nandi, D., Narayanan, P.S.A. and Somayajulu, G.V.S.R.K. (1986) Investigation of Alternative Routes for Producing UO2-Gd2O3 Mixed Oxide for Nuclear Fuel Applications. In: Ramanujam, M., Ed., Advances in particulate Technology, Proceedings of the International symposium on “Recent Advances in Particulate Technology”, I.I.T. Madras, Chennai, 8-10 December 1982,.
Balakrishna, P., Narayanan, P.S.A., Somayajulu, G.V.S.R.K. and Varma, B.P. (1986) Fabrication of UO2 (U,Gd)O2 and ThO2 Pellets, a View Point. Transactions of the Powder Metallurgy Association of India, 13, 63-67.
Balakrishna, P., Kulkarni, A.P., Somayajulu, G.V.S.R.K., Swaminathan, N. and Balaramamoorthy, K. (1991) Sintering UO2-Gd2O3. In: Vincenzini, P., Ed., Ceramics Today—Tomorrow’s Ceramics, Elsevier Science Publishers B.V., Amsterdam.
Balakrishna, P., Kulkarni, A.P., Krishnan, T.S., Balaramamoorthy, K., Ramamohan T. and Ramakrishnan, P. (1992) Retarded Densification and Desintering in Ceramic Bodies, In: Ramakrishnan, P., Ed., Advanced Ceramics, Oxford & IBH Publishing Co., New Delhi, 67-76.
Balakrishna, P., Kartha, R.M. and Ramakrishnan, P. (1993) Sintering of Co-Precipitated Ceramic Mixtures. Transactions of the Powder Metallurgy Association of India, 20, 41-48.
ASTM C922-14 Standard Specification for Sintered Gadolinium Oxide-Uranium Dioxide Pellets.
ASTM C968-12 Standard Test Methods for Analysis of Sintered Gadolinium Oxide-Uranium Dioxide Pellets.
Matzke, H.J. (1966) On the Effect of TiO2 Additions on Defect Structure, Sintering and Gas Release of UO2. AECL, 2585,
Ainscough, J.B., Rigby, F. and Osborn, S.C. (1974) The Effect of Titania on Grain Growth and Densification of Sintered UO2. Journal of Nuclear Materials, 52, 191-203. http://dx.doi.org/10.1016/0022-3115(74)90167-6
Diffusion
Heal, T.J., Littlechild, J.E. and Watson, R.M. (1973) Development of Stable Density UO2 Fuel. In: John, C.T., Wyles, B. and Moore, B., Eds., Nuclear Fuel Performance, Proceedings of International Conference, British Nuclear Energy Society, London, 15-19 October 1973, Paper No. 52.
Pope, J.M. and Radford, K.C. (1976) Stable Reactor Fuel of Controlled Density Using Active UO2 Powders. Materials Research Bulletin, 11, 585-592.
Radford, K.C. and Pope, J.M. (1977) Controlled Porosity Reactor Fuel. Journal of Nuclear Materials, 64, 289-299. http://dx.doi.org/10.1016/0022-3115(77)90081-2
Davis, H.H. and Potter, R.A. (1978) UO2-Gd2O3 Sintering Behaviour. In: Palmer, H., Davis, R.F. and Hare, T.M., Eds., Processing of Crystalline Ceramics, Materials Science Research, Vol. 11, Plenum Press, New York, 515-524
Song, K.W., Kim, K.S., Yoo, H.S. and Jung, Y.H. (1998) Effect of UO2 Powder Property and Oxygen Potential on Sintering Characteristics of UO2-Gd2O3 Fuel. Journal of Korean Nuclear Society, 30, 128-139.
Song, K.W., Kim, K.S., Yang, J.H., Kang, K.W. and Jung, Y.H. (2001) A Mechanism for the Sintered Density Decrease of UO2-Gd2O3 Pellets under an Oxidizing Atmosphere. Journal of Nuclear Materials, 288, 92-99. http://dx.doi.org/10.1016/S0022-3115(00)00721-2
Nishida, T. and Yuda, R. (1998) Effect of Particle Size and Oxygen Potential on UO2-Gd2O3 Pellet Sintering, Advances in Fuel Pellet Technology for Improved Performance at High Burnup. Proceedings of Technical Committee Meeting, IAEA TECH DOC, 1036, 73-84.
Ho, S.M. and Radford, K.C. (1986) Structural Chemistry of solid Solutions in the UO2-Gd2O3 System. Nuclear Technology, 73, 350-360.
Durazzo, M. and Riella, H.G. (2010) The Sintering Blockage Mechanism in the UO2-Gd2O3 System. Proceedings of the Transactions of the European Nuclear Conference, Barcelona, 30 May-2 June 2010, 4-10.
Durazzo, M., Saliba-Silva, A.M., Urano de Carvalho, E.F. and Riella, H.G. (2013) Sintering Behavior of UO2-Gd2O3 Fuel: Pore Formation Mechanism. Journal of Nuclear Materials, 433, 334-340. http://dx.doi.org/10.1016/j.jnucmat.2012.09.033
Song, K.W., Lee, Y.W., Yang, M.S., Sohn, D.S. and Kang, Y.H. (1994) Pore Growth in Sintered UO2. Journal of Nuclear Materials, 209, 263-269. http://dx.doi.org/10.1016/0022-3115(94)90261-5
Chalder, G.H. (1962) The Properties of Active Ceramic Oxide Powders in Relation to Sintering Behaviour. In: Knepper, W.A., Ed., Agglomeration, Interscience Publishers, New York, 111-114.
Kingery, W.D., Bowen, H.K. and Uhlmann, D.R., Eds. (1976) Introduction to Ceramics. 2nd Edition, John Wiley, New York.
Kang, S.J.L. and Yoon, K.J. (1989) Densification of Ceramics Containing Entrapped Gases. Journal of the European Ceramic Society, 5, 135-139. http://dx.doi.org/10.1016/0955-2219(89)90020-4
Barringer, E., Jubb, N., Fegley, B., Pober, R.L. and Bowen, H.K. (1984) Processing Monosized Powders. In: Hench, L.L. and Ulrich, D.R., Eds., Ultrastructure Processing of Ceramics, Glasses and Composites, John Wiley and Sons, New York, 315-333.
Balakrishna, P., Singh, A. and Sinha, K.K. (1997) Agglomerate Free Fine UO2 Powders. Proceedings of the International Conference, TOPFUEL’97, Manchester, 9-11 June 1997, 98-103.
Gunduz, G. and Uslu, I. (1996) Powder Characteristics and Microstructure of Uranium Dioxide and Uranium Dioxide-Gadolinium Oxide Fuel. Journal of Nuclear Materials, 231, 113-120. http://dx.doi.org/10.1016/0022-3115(96)00349-2
Restivo, T.A.G., Cláudio, A.E.L., Silva, E.D. and Pagano Jr., L. (2003) Effect of Additives on the Sintering Kinetics of the UO2Gd2O3 System. Proceedings of a Technical Committee Meeting, Brussels, 20-24 October 2003, 147-153.
Wada, T., Noro, K. and Tsukui, K. (1973) Behaviour of UO2-Gd2O3 Fuel. In: John, C.T., Wyles, B. and Moore, B., Eds., Nuclear Fuel Performance, British Nuclear Energy Society, London, 63.1-63.3.
Riella, H.G., Durazzo, M., Hirata, M. and Nogueira, R.A. (1991) UO2-Gd2O3 Solid Solution Formation from Wet and Dry Processes. Journal of Nuclear Materials, 178, 204-211. http://dx.doi.org/10.1016/0022-3115(91)90387-M
Kröger, F.A. and Vink, H.J. (1956) Relations between Concentrations of Imperfections in Crystalline Solids. In: Seitz, F. and Turnbull, D., Eds., Solid State Physics, Volume 3, Academic Press, New York, 307-435.
Matzke, H.J. (1982) Application of Diffusion Results in Technology: Increased Uranium Self Diffusion in UO2+x and (U,Nb)O2+x. European Institute for Transuranium Elements, Report EUR-7700.
Ruello, P., Petot-Ervas, G., Petot, C. and Desgranges, L. (2005) Electrical Conductivity and Thermoelectric Power of Uranium Dioxide. Journal of the American Ceramic Society, 88, 604-611. http://dx.doi.org/10.1111/j.1551-2916.2005.00100.x
Desgranges, L., Gramond, M., Petot, C., Petot-Ervas, G., Ruello, P. and Saadi, B. (2005) Characterisation of Uranium Vacancies in Hyper Stoichiometric Uranium Dioxide. Journal of the European Ceramic Society, 25, 2683-2686. http://dx.doi.org/10.1016/j.jeurceramsoc.2005.03.123
Leinders, G., Cardinaels, T., Binnemans, K. and Verwerft, M. (2015) Accurate Lattice Parameter Measurements of Stoichiometric Uranium Dioxide. Journal of Nuclear Materials, 459, 135-142. http://dx.doi.org/10.1016/j.jnucmat.2015.01.029
Venkata Krishnan, R., Panneerselvam, G., Manikandan, P., Antony, M.P. and Nagarajan, K. (2009) Heat Capacity and Thermal Expansion of Uranium-Gadolinium Mixed Oxides. Journal of Nuclear and Radiochemical Sciences, 10, 19-26.
Hertog, J. (2011) Lattice Parameter Evolution of Single Doped and Co-Doped UO2 Systems. External Report of the Belgian Nuclear Research Centre, SCK-CEN-ER-175.
McMurray, J.W. (2014) Thermodynamic Modeling of Uranium and Oxygen Containing Ternary Systems with Gadolinium, Lanthanum, and Thorium. Doctoral Dissertation, University of Tennessee, Knoxville.
Andersson, D.A., Baldinozzi, G., Desgranges, L., Conradson, D.R. and Conradson, S.D. (2013) Density Functional Theory Calculations of UO2 Oxidation: Evolution of UO2+x, U4O9–y, U3O7, and U3O8. Inorganic Chemistry, 52, 2769-2778. http://dx.doi.org/10.1021/ic400118p
Massih, A.R., Persson, S. and Weiss, Z. (1992) Modelling of (U,Gd)O2 Fuel Behaviour in Boiling Water Reactor. Journal of Nuclear Materials, 188, 323-330. http://dx.doi.org/10.1016/0022-3115(92)90492-4
Characteristics and Use of Urania Gadolinia Fuels, 3. Fuel Manufacturing, IAEA TECDOC-844, 50-58.
International Atomic Energy Agency (1991) Guidebook on QC of MOX and Gd Bearing Fuels. IAEA-TECDOC-584.
Manzel, R. and Dorr, W.O. (1980) Manufacturing and Irradiation Experience with UO2-Gd2O3 Fuel. Ceramic Bulletin, 59, 601-603 & 616.
Vollath, D. (1986) Uranium Self Diffusion. In: Hassce, V., Keller-Rudek, H., Manes, L., Schulz, B., Schumacher, G., Vollath, D. and Zimmermann, H., Eds., Gmelin Handbook of Inorganic Chemistry (U-Uranium, Supplement), 8th Edition, Springer-Verlag, Berlin Heidelberg, 113-118.
Alcock, C.B., Hawkins, R.S., Hills, A.W.D. and Mc Namara, P. (1966) A Study of Cation Diffusion in Stoichiometric U02 Using α-Ray Spectrometry. Thermodynamics, 2, 57-72.
Yajima, S., Furuya, T. and Hirai, H. (1966) Lattice and Grain-Boundary Diffusion of Uranium in UO2. Journal of Nuclear Materials, 20, 162-170. http://dx.doi.org/10.1016/0022-3115(66)90004-3
Hawkins, R.J. and Alcock, C.B. (1968) A Study of Cation Diffusion in UO2+x and ThO2 Using α-Ray Spectrometry. Journal of Nuclear Materials, 26, 112-122. http://dx.doi.org/10.1016/0022-3115(68)90162-1
Ferraz, W.B. and Sabioni, A.C.S. (2006) Diffusion of Gadolinium in the UO2 Nuclear Fuel. Ceramica, 52, 143-148. http://dx.doi.org/10.1590/S0366-69132006000300006
Matzke, H.J. (1969) On U Self Diffusion in UO2 and UO2+x. Journal of Nuclear Materials, 30, 26-35. http://dx.doi.org/10.1016/0022-3115(69)90165-2
Une, K. (1988) Effect of Oxygen Potential on the Initial Sintering of UO2 and UO2-Gd2O3 Compacts. Journal of Nuclear Materials, 158, 210-216. http://dx.doi.org/10.1016/0039-9140(91)80114-F