Fe-Si合金在600 ℃不同气氛中的腐蚀

doi:10.11902/1005.4537.2013.169

中国腐蚀与防护学报

2014, Vol. 34

Issue (4): 307-314 DOI: 10.11902/1005.4537.2013.169

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Fe-Si合金在600 ℃不同气氛中的腐蚀

刘兰兰^{1, 2}, 牛焱¹

1. 中国科学院金属研究所金属腐蚀与防护国家重点实验室沈阳 110016; 2. 武汉科技大学材料与冶金学院武汉 430081

Corrosion of Fe-Si Alloys in Reducing Oxidizing and Sulfidizing-oxidizing Atmospheres at 600 ℃

LIU Lanlan^{1, 2}, NIU Yan¹

1. State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China; 2. School of Materials and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China

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摘要: 研究了Fe-5Si,Fe-9Si和Fe-13Si合金在600 ℃下H₂-CO₂和H₂-CO₂-H₂S两种气氛中的腐蚀行为。结果表明：在两种气氛中,3种合金的腐蚀均遵循近似抛物线规律；并且合金在含S和不含S气氛中的抛物线速率常数数量级分别为10^-⁸和10^-¹⁰ g²cm^-⁴s^-¹。在H₂-CO₂气氛中合金氧化膜由Fe的氧化物外层、Fe与Si的混合氧化物内层及Si的内氧化区组成；在H₂-CO₂-H₂S气氛中则由层状的FeS外层和FeS+SiO₂混合内层组成。两种气氛中合金均没有生成连续的SiO₂外氧化膜。气氛中S的加入使合金表面生成了大量的FeS,FeS中较高的离子缺陷浓度为Fe²⁺向外扩散提供了通道,从而明显增大了合金的腐蚀速率。Si氧化物的生成提高了Fe在两种气氛中的耐腐蚀性。

关键词 ： Fe-Si合金, 硫化, 氧化, S的作用

Abstract：The corrosion of three Fe-Si alloys with approximately 5%, 9% and 13% (atomic fraction) Si was studied at 600 ℃ in H₂-CO₂ and H₂-H₂S-CO₂ mixtures providing oxygen and sulfur pressures of 10^-¹⁹and 10^-³ Pa, respectively. Oxidation and oxidation-sulfidation experiments were carried out by continuous and discontinuous methods. The corrosion kinetics of the alloys in the two gas mixtures followed approximately the parabolic rate law with K_p values of the order of 10^-⁸ and 10^-¹⁰ g²cm^-⁴s^-¹ for gases with and without sulfur. The scales formed in the oxidizing atmosphere were composed of an outermost layer of iron oxide, an intermediate complex layer containing a mixture of oxides of both elements and an internal oxidation zone of silicon. Conversely, the scales grown in oxidizing-sulfidizing atmosphere consisted of an outer multiple FeS layer plus an inner mixture of FeS and SiO₂. There was no external oxidation of silicon in the two gases. The corrosion rates of the alloys were extremely faster in the oxidizing-sulfidizing atmosphere than in the oxidizing gas due to the large quantities of FeS produced, providing a path for the rapid outward diffusion of iron ions due to its much higher defect concentration than the oxide of iron. The corrosion resistance of the base metal was clearly improved by the addition of silicon.

Key words： Fe-Si alloy sulfidation oxidation S effect

收稿日期: 2013-08-20

ZTFLH:

TG17

基金资助:国家自然科学基金项目(51371183和50971129) 资助

通讯作者: 通讯作者：牛焱,E-mail：yniu@imr.ac.cn E-mail: yniu@imr.ac.cn

作者简介: 刘兰兰，女，1987年生，博士生，研究方向为腐蚀科学与防护

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引用本文:

刘兰兰, 牛焱. Fe-Si合金在600 ℃不同气氛中的腐蚀[J]. 中国腐蚀与防护学报, 2014, 34(4): 307-314.
LIU Lanlan, NIU Yan. Corrosion of Fe-Si Alloys in Reducing Oxidizing and Sulfidizing-oxidizing Atmospheres at 600 ℃. Journal of Chinese Society for Corrosion and protection, 2014, 34(4): 307-314.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2013.169 或 https://www.jcscp.org/CN/Y2014/V34/I4/307

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