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化学的緻密化法でコーティングされた材料の沸騰硫酸環境下での耐食性評価および表面皮膜分析

Evaluation of corrosion resistance and surface film analysis after corrosion testing of materials coated by chemical densified coating method under boiling sulfuric acid environment

広田 憲亮   ; 舟本 幸大*; 橘 幸男 

Hirota, Noriaki; Funamoto, Kodai*; Tachibana, Yukio

沸騰硫酸環境下で優れた耐食性を有する金属材料を開発すべく、コーティングした材料の耐食性の評価と各種表面形態の違いを調査した。その結果、化学緻密化法により8回コーティング・焼結した(S-ZAC)SUS304は、12時間の腐食試験後の時点では問題なかったが、100時間の腐食試験後には腐食速度が急激に増加した。試料の断面微細構造解析では、Cr$$_{2}$$O$$_{3}$$が完全に消失した一方で、少量のSiO$$_{2}$$のみが表面に残存していた。S-ZACの剥離メカニズムは、加熱による熱膨張で厚膜が湾曲しCr$$_{2}$$O$$_{3}$$とSiO$$_{2}$$の界面にクラックが発生したためと推測される。一方、コーティングと焼成を11回繰り返すことでCr$$_{2}$$O$$_{3}$$を高密度にコーティングしたSUS304(MS-ZAC)は、100h腐食試験後でもSiCと同様に優れた耐食性を示した。断面組織分析の結果、MS-ZACはS-ZACに比べ、Cr$$_{2}$$O$$_{3}$$濃度が高く、SiO$$_{2}$$粒径が細かく、気孔が少ないことがわかった。特に、MS-ZACの皮膜維持のメカニズムは、皮膜全体の薄膜化に加え、Cr$$_{2}$$O$$_{3}$$粒子層での積層構造の形成と推測される。

For the purpose of developing metallic materials with excellent corrosion resistance under boiling sulfuric acid environment, the coated materials were evaluated for their corrosion resistance and the differences in surface morphology were investigated. As a result, the corrosion resistance of SUS304 coated and sintered eight times by chemical densified coating method (S-ZAC) was maintained at the point after 12h corrosion test, but the corrosion rate rapidly increased after 100h corrosion test. The cross-sectional microstructural analysis of the specimens showed that only a small amount of SiO$$_{2}$$ remained on the surface, while Cr$$_{2}$$O$$_{3}$$ completely disappeared. The mechanism of film delamination in S-ZAC is assumed to be due to the thermal expansion caused by heating, which resulted in curvature of the thick film and cracks at the Cr$$_{2}$$O$$_{3}$$ and SiO$$_{2}$$ interfaces. On the other hand, SUS304 coated with higher density of Cr$$_{2}$$O$$_{3}$$ by repeating the coating and sintering eleven times (MS-ZAC) showed excellent corrosion resistance as well as SiC even after 100h corrosion test. The results of cross-sectional microstructuCr$$_{2}$$O$$_{3}$$ particle layer, in addition to the thinning of the entire film.

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