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金属学报  2019, Vol. 55 Issue (4): 427-435    DOI: 10.11900/0412.1961.2018.00250
  本期目录 | 过刊浏览 |
合金元素对顶头钢氧化行为的影响
郑成明,田青超()
上海大学省部共建高品质特殊钢冶金与制备国家重点实验室 上海 200444
Effect of Alloy Elements on Oxidation Behavior of Piercing Plug Steel
Chengming ZHENG,Qingchao TIAN()
State Key Laboratory of Advanced Special Steels, Shanghai University, Shanghai 200444, China
引用本文:

郑成明, 田青超. 合金元素对顶头钢氧化行为的影响[J]. 金属学报, 2019, 55(4): 427-435.
Chengming ZHENG, Qingchao TIAN. Effect of Alloy Elements on Oxidation Behavior of Piercing Plug Steel[J]. Acta Metall Sin, 2019, 55(4): 427-435.

全文: PDF(9845 KB)   HTML
摘要: 

研究了20Cr2Ni3、30Cr3NiMo2V和H13等3种不同合金元素含量顶头钢在酒精-水滴注气氛下的高温氧化行为。通过调整酒精/水的比例,设计了先氧化后还原的两段式表面处理工艺,获得了外层主要含FeO的两层氧化膜结构。利用SEM、EDS和XRD等研究了氧化膜的形貌、成分和相组成,使用金相显微镜、显微硬度仪等研究了脱碳层的组织和硬度分布。结果表明,外层氧化膜厚度随Cr当量增加而降低,而内层氧化膜厚度基本不变。高温氧化过程中氧化膜内空位聚集成孔洞,其内挥发性的物质及气体集聚导致内压增大,使得外层氧化膜内部呈现向外“凸出”的缝隙。各合金元素在氧化传质过程中的作用不同,在950 ℃的滴注气氛下,Ni、Mo不具备氧化的热力学条件,而以单质形式存在。C的氧化决定了脱碳层的组织与性能,使得20Cr2Ni3和30Cr3NiMo2V脱碳层的硬度曲线呈“双平台”特征,而H13的硬度先缓慢升高而后快速升高后趋于平缓。最后从工程应用层面给出了顶头材料的选材建议。

关键词 顶头钢氧化形貌脱碳层动态传质热力学    
Abstract

Piercing plug is a key deformation tool during manufacturing the seamless steel tubular product while oxidation is the most economical and practical method for the surface treatment of the piercing plug. The high-temperature oxidation behavior of piercing plug steel was investigated by employing the materials 20Cr2Ni3, 30Cr3NiMo2V and H13 under drop-feeding mixed H2O-C2H5OH atmosphere. A two-stage surface treatment process of first oxidation and then reduction reaction was designed by adjusting the volume ratio of alcohol to water, and thus a two-layer oxide scale structure where the external layer mainly containing FeO was obtained subsequently. Morphology, chemical composition and phase constituents of the oxide scale were studied by using SEM, EDS and XRD, while the microstructure and hardness distribution of decarburization layer were studied by using OM and microhardness tester. The results show that the thickness of external oxide scale decreases with the increase of chromium equivalent, while the thickness of the inner oxide scale keeps basically unchanged. In the process of high temperature oxidation, the vacancy in oxide scale accumulates into micro holes, where the volatile substances and gases were concentrated to elevate the internal pressure high enough that makes the oxide scale "protrude" outwards. The mass transfer in oxidation process varied for different alloy elements. Ni and Mo cannot be oxidized in the specific atmosphere at 950 ℃ according to the oxidation thermodynamics, but exist in elemental form. The oxidation of C determines the microstructure and mechanical properties of the decarburization layer, where the hardness curves of 20Cr2Ni3 and 30Cr3NiMo2V exhibit a characteristic of "double-platform", while the hardness of H13 increases first slowly, then rapidly, and then gradually flattens out. Finally, the material selection for piercing plug steel is suggested from the viewpoint of engineering application.

Key wordspiercing plug steel    oxidation morphology    decarburization layer    dynamic mass transfer    thermodynamics
收稿日期: 2018-06-11     
ZTFLH:  TG178  
作者简介: 郑成明,男,1992年生,硕士生
MaterialCSiMnCrNiMoVFe
20Cr2Ni30.200.701.502.002.60--Bal.
30Cr3Ni-Mo2V

0.30

0.20

0.40

3.00

0.90

2.00

0.50

Bal.

H130.400.801.005.500.101.551.30Bal.
表1  实验材料的化学成分
图1  3种材料脱碳层的金相组织
图2  3种材料脱碳层处显微硬度分布
图3  3种材料的截面氧化膜形貌
图4  氧化膜厚度随Creq变化情况
图5  3种材料氧化膜线扫描结果
图6  H13内、外层氧化膜形貌及线扫描结果
图7  3种材料氧化膜EDS分析
图8  3种材料外层氧化膜的XRD谱
图9  不同气氛平衡分压
ReactantC→COSi→SiO2Mn→MnOCr→Cr2O3Ni→NiOMo→MoO3V→V2O3Fe→FeO
H2O-43927-167544-111405-936195912083466-124066-15062
FeO-28865-152482-96342-785567418398529-109004-
表2  950 ℃下不同元素氧化物的标准Gibbs自由能(ΔG?)
图10  外层氧化膜缝隙形成机理示意图
图11  H13氧化膜形貌放大图
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