Origin and consequences of silicate glass passivation by surface layers

被引:249
作者
Gin, Stephane [1 ]
Jollivet, Patrick [1 ]
Fournier, Maxime [1 ]
Angeli, Frederic [1 ]
Frugier, Pierre [1 ]
Charpentier, Thibault [2 ]
机构
[1] CEA, DEN, DTCD, SECM, F-30207 Bagnols Sur Ceze, France
[2] CEA, DSM, IRAMIS, NIMBE,UMR 3299, F-91191 Gif Sur Yvette, France
关键词
LONG-TERM BEHAVIOR; BOROSILICATE GLASSES; NUCLEAR GLASS; DISSOLUTION RATE; DEGREES-C; RATE LAW; CORROSION; SI-29; STATE; MECHANISMS;
D O I
10.1038/ncomms7360
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Silicate glasses are durable materials, but are they sufficiently durable to confine highly radioactive wastes for hundreds of thousands years? Addressing this question requires a thorough understanding of the mechanisms underpinning aqueous corrosion of these materials. Here we show that in silica-saturated solution, a model glass of nuclear interest corrodes but at a rate that dramatically drops as a passivating layer forms. Water ingress into the glass, leading to the congruent release of mobile elements (B, Na and Ca), is followed by in situ repolymerization of the silicate network. This material is at equilibrium with pore and bulk solutions, and acts as a molecular sieve with a cutoff below 1 nm. The low corrosion rate resulting from the formation of this stable passivating layer enables the objective of durability to be met, while progress in the fundamental understanding of corrosion unlocks the potential for optimizing the design of nuclear glass-geological disposal.
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页数:8
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