Role and properties of the gel formed during nuclear glass alteration: importance of gel formation conditions

A French SON 68 nuclear glass sample was experimentally altered to assess the mechanisms limiting the glass alteration kinetics, especially during the transition phase between the initial rate ro and the final rate under silicon saturation conditions. A glass specimen was altered at the initial rate for one week to form a silicon-depleted nonprotective gel; the specimen was then leached under static conditions at a glass-surface-to-solution-volume (SIV) ratio of 500 m(-1) and the alteration kinetics were compared with those of a pristine glass specimen altered under the same conditions. Unexpectedly, after static leaching the previously leached glass was 2.7 times as altered as the pristine specimen, and the steady-state silicon concentration was twice as high for the previously leached specimen. STEM characterization of the alteration films showed that the initial non-protective gel constituted a silicon pump with respect to the glass, and that the glass alteration kinetics were limited only when a fraction of the gel became saturated with silicon, and exhibited protective properties. This work also shows that silicon recondensation was uniform at micrometer scale: the silicon hydrolyzed at the reaction interface then diffused before recondensing over a length comparable to the gel thickness. In addition to these findings, this investigation suggests a reinterpretation of the effect of the SIV ratio on the glass alteration kinetics and on the steady-state dissolved silicon concentration. (C) 2001 Elsevier Science B.V. All rights reserved.