S. Sunder et al., ANODIC-OXIDATION AND DISSOLUTION OF CANDU FUEL (UO2) IN SLIGHTLY ALKALINE SODIUM-PERCHLORATE SOLUTIONS, Electrochimica acta, 43(16-17), 1998, pp. 2359-2372
The anodic dissolution of UO2 in aqueous sodium perchlorate solutions
at pH similar to 9.5 shows two distinct regions of oxidation/dissoluti
on behavior. In the potential (E) range 0.10E < 0.35 V (vs SCE) curren
ts decay continuously with time owing to the formation of oxidized sur
face films which gradually block further oxidation of the electrode. A
n analysis of anodic and cathodic charges (Q(A), Q(C), respectively) o
btained by integration of the anodic current-time plots (Q(A)) and cat
hodic potential scans to reduce accumulated oxidized surface films (Q(
C)) in this range, shows that 90% of the anodic oxidation current goes
to produce these films. The films blocking anodic dissolution appear
to be either UO2.67 Or, more probably, UO3 . xH(2)O. These may be loca
ted primarily at grain boundaries, although this has not been confirme
d. For E>0.35 V, steady-state currents are obtained and measurements o
f Q(A) and Q(C) show that the majority of the current goes to produce
soluble species. It is proposed that, at the higher potentials, rapid
oxidation and dissolution followed by the hydrolysis of dissolved uran
yl species leads to the development of acidic conditions in the grain
boundaries. At these lower pH values UO3 . 2H(2)O is soluble and does
not accumulate. Analyses of Tafel slopes suggest that the observed beh
avior is consistent with dissolution under acidic conditions, although
other possibilities have not been excluded. Crown copyright (C) 1998
Published by Elsevier Science Ltd. All rights reserved.