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高温硫酸分解ガス環境下におけるステンレス鋼及びNi基合金の耐食性評価及び表面皮膜構造分析

Corrosion resistance and oxide film structure of stainless steels and Ni-based alloys under sulfuric decomposition gas at high temperature

広田 憲亮; 竹田 貴代子*; 橘 幸男; 正木 康浩*

Hirota, Noriaki; Takeda, Kiyoko*; Tachibana, Yukio; Masaki, Yasuhiro*

熱化学水素製造法(ISプロセス)の硫酸分解反応容器を想定した高温硫酸分解ガス環境下において、ステンレス鋼及びNi基合金の耐食性能評価を実施した。その結果、100時間の腐食試験ではSiを2.4%含有したNi基合金は、腐食速度が小さく、優れた耐食性能を示したほか、Alを3%含有したフェライト系ステンレス鋼(3Al-Ferrite)は、腐食速度が指標とするSiCの腐食速度(0.1mm/year)を下回る優れた耐食性能を示した。一方で3Al-Ferriteの腐食生成皮膜と同じコンセプトで、Al$$_{2}$$O$$_{3}$$皮膜を材料にプレフィルミングしたNi基合金の腐食速度は、3Al-Ferriteに対して大幅に速くなった。これらの酸化皮膜/母材界面の断面でEPMA分析を行った結果、2.4Si含有Ni基合金では、Si酸化皮膜が形成されていたが、長時間の腐食試験中にSi酸化皮膜に欠陥ができ、腐食環境から酸化皮膜を介して母材粒界へのS侵入が確認された。一方で3Al-Ferriteでは、薄い均一なAl$$_{2}$$O$$_{3}$$皮膜が形成されており、粒界へのS侵入は確認されなかった。またAl$$_{2}$$O$$_{3}$$皮膜をプレフィルミングしたNi基合金では、Al$$_{2}$$O$$_{3}$$皮膜に欠陥ができ、母材粒界へSが侵入していた。3Al-Ferriteに生成した腐食生成皮膜とプレフィルミングしたAl$$_{2}$$O$$_{3}$$の違いをX線回折で解析した結果、3Al-Ferriteの皮膜は、$$alpha$$-Al$$_{2}$$O$$_{3}$$のみからなるのに対し、プレフィルミングしたAl$$_{2}$$O$$_{3}$$$$alpha$$-Al$$_{2}$$O$$_{3}$$$$gamma$$-Al$$_{2}$$O$$_{3}$$が混在していることが分かった。これらの結果により、3Al-Ferriteの良好な耐食性能は、緻密な$$alpha$$-Al$$_{2}$$O$$_{3}$$が早期に母材表面に均一形成されたことによるものと推察される。

Corrosion resistance of stainless steels and Ni-based alloys were evaluated in a sulfuric acid decomposition gas at high temperature. The evaluation were carried out in an environment simulated in the sulfuric acid decomposition reaction vessel for thermochemical hydrogen production process (IS process). Their corrosion films were also analyzed for better understanding of the corrosion behavior. As a result, after 100 hour corrosion test, Ni-based alloy containing 2.4% Si showed good corrosion resistance. Ferritic stainless steel containing 3% Al (3Al-Ferrite) showed better corrosion resistance. Its corrosion rate was lower than that of SiC (0.1mm/year), which is a candidate material for the sulfuric acid decomposition reaction vessel. On the other hand, Ni-based alloy pre-filmed with Al$$_{2}$$O$$_{3}$$ is prepared as the relative corrosion film of 3Al-Ferrite. Its corrosion rate was significantly higher than that of 3Al-Ferrite. As the result of EPMA analysis of these oxide films, Ni-based alloy containing 2.4% Si formed Si oxide film which had some cracks after the long term corrosion test. Therefore S penetrated into grain boundaries of the matrix through the oxide film. 3Al-Ferrite formed a thin and uniform Al$$_{2}$$O$$_{3}$$ film, and the penetration of S into the grain boundaries was not observed. Al$$_{2}$$O$$_{3}$$ pre-film of Ni-based alloy also showed S penetration in the matrix because the Al$$_{2}$$O$$_{3}$$ pre-film had many small defects originally. The corrosion oxide film of 3Al-Ferrite consisted of only $$alpha$$-Al$$_{2}$$O$$_{3}$$, while the Al$$_{2}$$O$$_{3}$$ pre-film consist of $$alpha$$-Al$$_{2}$$O$$_{3}$$ and $$gamma$$-Al$$_{2}$$O$$_{3}$$. Those results suggest that the better corrosion resistance of 3Al-Ferrite is due to the uniform formation of dense $$alpha$$-Al$$_{2}$$O$$_{3}$$ film at the early stage of the corrosion.

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