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金属学报  2021, Vol. 57 Issue (8): 989-999    DOI: 10.11900/0412.1961.2020.00451
  研究论文 本期目录 | 过刊浏览 |
超细晶铁素体-马氏体钢的高温氧化成膜特性及其对Pb-Bi腐蚀行为的影响
陈胜虎(), 戎利建
中国科学院金属研究所 中国科学院核用材料与安全评价重点实验室 沈阳 110016
Oxide Scale Formation on Ultrafine-Grained Ferritic-Martensitic Steel During Pre-Oxidation and Its Effect on the Corrosion Performance in Stagnant Liquid Pb-Bi Eutectic
CHEN Shenghu(), RONG Lijian
CAS Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
引用本文:

陈胜虎, 戎利建. 超细晶铁素体-马氏体钢的高温氧化成膜特性及其对Pb-Bi腐蚀行为的影响[J]. 金属学报, 2021, 57(8): 989-999.
Shenghu CHEN, Lijian RONG. Oxide Scale Formation on Ultrafine-Grained Ferritic-Martensitic Steel During Pre-Oxidation and Its Effect on the Corrosion Performance in Stagnant Liquid Pb-Bi Eutectic[J]. Acta Metall Sin, 2021, 57(8): 989-999.

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摘要: 

利用SEM、XRD、EPMA和XPS等研究了冷旋锻变形对9Cr2WVTa铁素体-马氏体钢在650℃空气中氧化膜形成过程的影响,在此基础上考察了预氧化制备氧化膜对9Cr2WVTa铁素体-马氏体钢在饱和氧液态Pb-Bi共晶 (LBE)中腐蚀行为的影响。结果表明,冷旋锻变形量的增加可提高样品的抗氧化性能,63%变形处理使抗氧化性能略有提高,94%变形处理可显著提高抗氧化性能。相较于回火态样品,63%变形处理样品形成的氧化物仍主要为(Fe, Cr)2O3,只是氧化物颗粒尺寸略有下降;94%变形获得的超细晶样品中,不仅氧化物颗粒尺寸显著减小,而且促进了富Mn氧化物(MnCr2O4和Mn2O3)的形成。超细晶样品中大幅度提高的空位浓度和位错密度、以及增加的晶界数量,显著提高了元素的扩散速率,Mn的异常快速扩散促进了富Mn氧化物的形成,稳定性好的富Mn氧化物提高了氧化膜的致密性。650℃空气中预氧化处理20 h后,超细晶样品表面获得致密性良好的富Mn氧化膜,在550℃饱和氧LBE中腐蚀500 h后,预氧化制备氧化膜可有效阻止LBE对铁素体-马氏体钢的侵蚀,并抑制了Fe的外扩散。Mn在LBE中较高的溶解度会加快富Mn氧化膜的溶解,随着Mn的不断溶解和LBE的持续侵蚀,预制备氧化膜的致密性不断下降而最终破裂,腐蚀2000 h后,样品表面形成了连续的Pb-Bi腐蚀产物。

关键词 超细晶铁素体-马氏体钢冷旋锻变形预氧化Pb-Bi腐蚀扩散    
Abstract

Liquid lead and lead-bismuth eutectic (LBE) are considered primary candidate materials for coolant in advanced lead fast reactors, and also, for coolant and spallation target in accelerator-driven systems because of their favorable thermal-physical and chemical properties. However, liquid lead and LBE exhibit substantial structural material corrosion, which is considered one of the critical challenges in the liquid lead or LBE application. Among the effective methods to reduce the corrosive effect, careful control of the oxygen content dissolved in the liquid introduces a protective oxide layer on the surface of the structural material. Ferritic-martensitic steels with (9%-12%)Cr (mass fraction) have been considered promising structural materials in the advanced lead fast reactor and accelerator-driven system. Oxide scale with duplex structure is formed on the (9%-12%)Cr ferritic-martensitic steels in oxygen-containing LBE, but the oxide scale grows rapidly enough to cause the substrate recession. Recently, pre-oxidation treatment was proposed to further improve the corrosion performance in LBE. As reported, grain refinement promoted the formation of oxide scale without chemical modification. However, grain refinement effects on the oxide scale formation of (9%-12%)Cr ferritic-martensitic steels are not clear, and the effect of oxide scale through pre-oxidation treatment on the corrosion performance in LBE is rarely reported. In this study, the oxide scale formation behavior during pre-oxidation in air at 650oC on the 9Cr2WVTa ferritic-martensitic steel after different cold rotary-swaging deformation rates was analyzed using SEM, XRD, EPMA, and XPS, and the effect of pre-oxide scale on the corrosion performance in stagnant oxygen-saturated LBE was further investigated. The results demonstrated that the high-temperature oxidation resistance in air was enhanced by increasing the diameter reduction. A slight improvement in oxidation resistance was observed after 63% deformation, while significant enhancement in oxidation resistance was present in ultrafine-grained sample fabricated by 94% deformation. The oxide particle size was slightly reduced in the sample produced after 63% deformation during air oxidation compared with the tempered sample, but (Fe, Cr)2O3 oxide particles were formed on both samples. The size of oxide particles was significantly reduced and Mn-riched oxide (MnCr2O4 and Mn2O3) was promoted in the ultrafine-grained sample. The presence of Mn-riched oxide with good stability improved the oxide scale compactness. The compact oxide scale on the ultrafine-grained sample using pre-oxidation treatment at 650oC for 20 h effectively suppressed the corrosive attack of LBE and the outward diffusion of Fe through the pre-oxide scale after exposure for 500 h to stagnant oxygen-saturated LBE at 550oC. The higher solubility of Mn in LBE promoted the dissolution of the Mn-riched pre-oxide scale. The gradual dissolution of Mn in pre-oxide scale and corrosive attack by LBE led to the breakdown of the pre-oxide scale, which was supported by the formation of a continuous corrosion product layer after exposure for 2000 h to stagnant oxygen-saturated LBE.

Key wordsultrafine-grained ferritic-martensitic steel    cold rotary-swaging deformation    pre-oxidation    Pb-Bi corrosion    diffusion
收稿日期: 2020-11-09     
ZTFLH:  TG174  
基金资助:国家自然科学基金项目(51871218);中国科学院青年创新促进会项目(2018227);辽宁省自然科学基金项目(2020-);MS-010,以及国防科技工业核材料技术创新中心基金项目(ICNM-2020-ZH-18)
作者简介: 陈胜虎,男,1986年生,副研究员,博士
图1  9Cr2WVTa铁素体-马氏体钢经不同变形量冷旋锻变形后的微观组织
图2  不同变形量的冷旋锻9Cr2WVTa铁素体-马氏体钢在650℃空气中的氧化增重曲线
图3  不同变形量的冷旋锻9Cr2WVTa铁素体-马氏体钢经650℃空气氧化20、100和500 h后表面形成氧化膜的SEM像
图4  不同变形量的冷旋锻9Cr2WVTa铁素体-马氏体钢经650℃空气氧化500 h后的XRD谱
图5  不同变形量的冷旋锻9Cr2WVTa铁素体-马氏体钢经650℃空气氧化20 h后氧化膜中元素含量随深度方向的变化
图6  未预氧化处理与预氧化处理的94%变形量样品经550℃饱和氧LBE腐蚀500和2000 h后氧化膜截面形貌的BSE像
图7  预氧化处理的94%变形量样品经550℃饱和氧LBE腐蚀2000 h后氧化膜的EPMA元素分布
图8  不同变形量的冷旋锻9Cr2WVTa铁素体-马氏体钢(110)、(200)、(211)和(220)的XRD峰
图9  预氧化处理的94%变形量样品经550℃饱和氧LBE腐蚀500和2000 h后的表面SEM像
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