材料研究学报  2004, Vol. 18 Issue (3): 225-231

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LiOH水溶液提高Zr--4合金腐蚀速率的机理

周邦新;刘文庆;李强(上海大学);姚美意

上海大学

Mechanism of LiOH aqueous solution accelerating corrosion rate of zircaloy--4

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上海大学

周邦新; 刘文庆; 李强上海大学; 姚美意 . LiOH水溶液提高Zr--4合金腐蚀速率的机理[J]. 材料研究学报, 2004, 18(3): 225-231.
, , , . Mechanism of LiOH aqueous solution accelerating corrosion rate of zircaloy--4[J]. Chin J Mater Res, 2004, 18(3): 225-231.

摘要 参考文献 相关文章 Metrics 全文: PDF(1991 KB)   摘要: 在不同水化学条件下的高压釜中研究了Zr--4合金在LiOH水溶液中的耐腐蚀性能. 结果表明, 不同的腐蚀介质对氧化膜内的压应力和$t$--ZrO$_{2}$的含量的影响有很大不同; Zr--4合金在LiOH或KOH水溶液中腐蚀时, Li$^{+}$比K$^{+}$进入氧化膜深而且浓度高; 在LiOH水溶液中腐蚀时, 氧化膜中OH$^{-}$的浓度比在KOH水溶液中高. 锆合金在LiOH水溶液中腐蚀时, 氧化膜的生长主要是通过OH$^{-}$从合金的表面向内扩散, 与锆反应生成氧化锆和原子氢. Li$^{+}$半径较小, 容易进入氧化膜, 因此较多的OH$^{-}$进入氧化膜的深处, 并与$t$--ZrO$_{2}$中的氧空位反应, 使$t$--ZrO$_{2}$向$m$--ZrO$_{2}$转变. 这导致氧化膜出现裂纹, 使氧化膜中的压应力松弛, 降低氧化膜的保护能力, 提高了锆合金的腐蚀速率. 关键词 ： 材料失效与保护,  Zr--4合金,  耐腐蚀性能     Abstract：Autoclave experiments in different water chemistry were conducted to clarify the degradation behavior of zircaloy--4 corroded in LiOH aqueous solution. It was found that the compressive stress and the tetragonal zirconia ($t$--ZrO$_{2}$) contents in oxide films formed in different media were different; when specimens were exposed in LiOH and KOH solutions with same concentration, the penetration depth is shallower and the intensity of K$^{+}$ is weaker than those of Li$^{+}$, and the penetration depth of OH$^{-}$ corroded in KOH solution is also shallower than that corroded in LiOH solution. Based on the results, it is suggested that the growth of oxide films is a process of OH$^{-}$ diffusing from outside of oxide into metal/oxide interface and reacting with zirconium to form ZrO$_{2}$ and hydrogen. It is easy for Li$^{+}$ to diffuse into oxide film because of small radius when specimen was exposed in LiOH aqueous solution, so more OH$^{-}$ would diffuse into oxide film deeply. The reaction between adequate OH$^{-}$ and oxygen vacancies in the $t$--ZrO$_{2}$ would promote the transformation from $t$--ZrO$_{2}$ to monoclinic zirconia ($m$--ZrO$_{2}$). The transformation would bring some cracks in the oxide, which relaxed the compressive stress in the oxide, degraded the protective ability of oxide films and caused an enhancement of corrosion rate of zircaloy--4 alloy. 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