合金元素对顶头钢氧化行为的影响

doi:10.11900/0412.1961.2018.00250

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 words： piercing 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

	服务

	把本文推荐给朋友
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	郑成明
	田青超
44.8K

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2018.00250 或 https://www.ams.org.cn/CN/Y2019/V55/I4/427

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

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

1	Cao J L, Li Q. Review of piercing plug surface oxide film [J]. Jiangxi Met., 2007, 27(3): 32
1	曹家龙, 李琼. 穿孔顶头表面氧化膜概述 [J]. 江西冶金, 2007, 27(3): 32)
2	Wang B, Yi D Q, Wu B T, et al. Failure type analysis and studies on prolonging service life of piercer plug for seamless steel tube [J]. Mater. Rev., 2006, 20(6): 82
2	王斌, 易丹青, 吴伯涛等. 无缝钢管穿孔顶头失效形式分析及提高使用寿命的研究进展 [J]. 材料导报, 2006, 20(6): 82)
3	Song J P, Zhang W J, Jing H. Formation techniques for surface oxide film of piercer plug [J]. Steel Pipe, 1994, (2): 10
3	宋箭平, 张维静, 敬华. 穿孔顶头表面氧化膜制取方法 [J]. 钢管, 1994, (2): 10)
4	Shi M Y, Zhan F, Zhang C Y. Trial-manufacture of 15Cr2Ni3MoW steel piercing plugs for seamless pipe production [J]. J. Univ. Sci. Technol. Beijing, 2012, 34(suppl.1): 78
4	石满鹰, 詹飞, 张程远. 15Cr2Ni3MoW钢穿孔顶头试制 [J]. 北京科技大学学报, 2012, 34(增刊1): 78)
5	Wang P, Huang Z Y, Wang G M. Study on oxidation process for piercing plug made of high-alloy steel [J]. Hot Work. Technol., 2010, 39(12): 106
5	王萍, 黄贞益, 王光明. 高合金钢管穿孔顶头氧化工艺的研究 [J]. 热加工工艺, 2010, 39(12): 106)
6	Saunders S R J, Monteiro M, Rizzo F. The oxidation behaviour of metals and alloys at high temperatures in atmospheres containing water vapour: A review [J]. Prog. Mater. Sci., 2008, 53: 775
7	Zhang J J, Yi D Q, Wang B, et al. Study on preparation process of perforated head oxide film for 15Cr2Ni3MoW steel [J]. Hot Work. Technol., 2011, 40(18): 133
7	张金菊, 易丹青, 王斌等. 15Cr2Ni3MoW钢管穿孔顶头氧化膜制备工艺的研究 [J]. 热加工工艺, 2011, 40(18): 133)
8	Osgerby S, Fry A T. The role of alloy composition on the steam oxidation resistance of 9-12%Cr Steels [J]. Mater. Sci. Forum., 2006, 522-523: 129
9	Sun Z. Study on high temperature oxidation layer under H2O-C2H5OH mixed drop-feeding atmosphere for plug steel [D]. Xi'an: Xi'an University of Technology, 2007
9	孙铮. 顶头钢在水添加酒精滴注式气氛中高温氧化层的研究 [D]. 西安: 西安理工大学, 2007
10	Zhang J Y. Physcial Chemistry of Metallurgy [M]. Beijing: Metall Industry Press, 2004: 223
10	张家芸. 冶金物理化学 [M]. 北京: 冶金工业出版社, 2004: 223)
11	Ye D L, Hu J H. Practical Inorganic Thermodynamic Data Manual [M]. Beijing: Metall Industry Press, 2002: 1
11	叶大伦, 胡建华. 实用无机物热力学数据手册 [M]. 北京: 冶金工业出版社, 2002: 1)
12	Min Y A, Wu X C, Wang R, et al. Prediction and analysis on oxidation of H13 hot work steel [J]. J. Iron Steel Res. Int., 2006, 13: 44
13	Birks N, Meier G H, Pettit F S, translated by Xin L, Wang W. Introduction to the High-Temperature Oxidation of Metals [M]. 2nd Ed., Beijing: Higher Education Press, 2010: 15
13	(Birks N, Meier G H, Pettit F S著, 辛丽, 王文译. 金属高温氧化导论 [M]. 第2版. 北京: 高等教育出版社, 2010: 15)
14	Li M D, Ni J F, Wang C F, et al. Oxidation behavior of T92 steel in high-temperature water-vapor atmosphere [J]. Sur. Technol., 2014, 43(3): 10
14	李茂东, 倪进飞, 王彩福等. T92钢在高温水蒸气中的氧化行为 [J]. 表面技术, 2014, 43(3): 10)
15	Chen R Y, Yuen W Y D. A study of the scale structure of hot-rolled steel strip by simulated coiling and cooling [J]. Oxid. Met., 2000, 53: 539
16	Chen R Y, Yuen W Y D. Review of the high-temperature oxidation of iron and carbon steels in air or oxygen [J]. Oxid. Met., 2003, 59: 433
17	Wang C, Yu Y, Niu T, et al. Growth mechanism of oxidized film of X80 pipeline steel at high temperature [J]. J. Iron steel Res., 2016, 28(5): 57
17	王畅, 于洋, 牛涛等. X80管线钢高温氧化膜的生长机理 [J]. 钢铁研究学报, 2016, 28(5): 57)
18	Wouters Y, Bamba G, Galerie A, et al. Oxygen and water vapour oxidation of 15Cr ferritic stainless steels with different silicon contents [J]. Mater. Sci. Forum, 2004, 461-464: 839
19	Opila E J. Variation of the oxidation rate of silicon carbide with water-vapor pressure [J]. J. Am. Ceram. Soc., 2010, 82: 625
20	Yang Y, Liu Z Y, Cao G Y, et al. Research on alloy elements high temperature oxidation character of low alloy steel [J]. Steel Roll., 2016, 33(6): 38
20	杨奕, 刘振宇, 曹光明等. 低合金钢中合金元素高温氧化行为研究 [J]. 轧钢, 2016, 33(6): 38)
21	Han J K, Yan H, Huang Y, et al. Structural features of oxide scales on weathering steel and their influence on atmospheric corrosion [J]. Acta. Metall. Sin., 2017, 53: 163
21	韩军科, 严红, 黄耀等. 耐候钢表面氧化皮的结构特征及其对大气腐蚀行为的影响 [J]. 金属学报, 2017, 53: 163
22	Li T F. The role of metallic grain boundary in high temperature oxidation [J]. J. Chin. Soc. Corros. Prot., 2002, 22: 180
22	李铁藩. 金属晶界在高温氧化中的作用 [J]. 中国腐蚀与防护学报, 2002, 22: 180
23	Hondros E D, Seah M P. Segregation to interfaces [J]. Inter. Met. Res., 1977, 22: 262
24	Dumbill S, Boothby R M, Williams T M. Grain boundary segregation in nimonic PE16 [J]. Mater. Sci. Technol., 1991, 7: 385
25	Tian Q C, Dong X P, Cui H C, et al. Characterization of the welded-joint of high-strength high-toughness seamless steel pipe under high-cycle fatigue condition [A]. Materials for Modern Technologies III (Proceedings of MST-S 2017, Chengdu) [C]. Switzerland: Trans. Tech. Publications, 2017, 896: 202
26	Lui Z C. Pearlite Transformation and Annealing [M]. Beijing: Chemical Industry Press, 2007: 26
26	刘宗昌. 珠光体转变与退火 [M]. 北京: 化学工业出版社, 2007: 26)
27	Gao J W, Zhao G, Xu Y W, et al. Analysis of surface decarburization of 75 Cr1 steel heating in furnace [J]. J. Iron steel Res., 2017, 29: 150
27	高建文, 赵刚, 徐耀文等. 75Cr1钢加热炉内表面脱碳分析 [J]. 钢铁研究学报, 2017, 29: 150
28	Jiang C, Liu Y Z, Zhang C L, et al. Effects of Nb-V micro-alloying on surface decarburization of spring steel 60Si2MnA [J]. Hot Work. Technol., 2011, 40: 180
28	姜超, 刘雅政, 张朝磊等. Nb-V微合金化对弹簧钢60Si2MnA表面脱碳的影响 [J]. 热加工工艺, 2011, 40: 180
29	Quadakkers W J, Ennis P J, Zurek J, et al. Steam oxidation of ferritic steels-laboratory test kinetic data [J]. Mater. High Temp., 2005, 22: 47
30	Shen J N, Zhou L J, Li T F. High-temperature oxidation of Fe-Cr alloys in wet oxygen [J]. Oxid. Met., 1997, 48: 347
31	Opila E J. Volatility of common protective oxides in high-temperature water vapor: Current understanding and unanswered questions [J]. Mater. Sci. Forum, 2004, 461-464: 765
32	Zhong X Y, Wu X Q, Han E H. The characteristic of oxide Scales on T91 tube after long-term service in an ultra-supercritical coal power plant [J]. J. Supercrit. Fluids, 2012, 72: 68
33	Hansson K, Tang J E, Halvarsson M, et al. The bene?cial effect of water vapour on the oxidation at 600 and 700℃ of a MoSi2-based composite [J]. J. Eur. Ceram. Soc., 2005, 25: 1

[1]	穆亚航, 张雪, 陈梓名, 孙晓峰, 梁静静, 李金国, 周亦胄. 基于热力学计算与机器学习的增材制造镍基高温合金裂纹敏感性预测模型[J]. 金属学报, 2023, 59(8): 1075-1086.
[2]	王寒玉, 李彩, 赵璨, 曾涛, 王祖敏, 黄远. 基于纳米活性结构的不互溶W-Cu体系直接合金化及其热力学机制[J]. 金属学报, 2023, 59(5): 679-692.
[3]	张月鑫, 王举金, 杨文, 张立峰. 冷却速率对管线钢中非金属夹杂物成分演变的影响[J]. 金属学报, 2023, 59(12): 1603-1612.
[4]	高建宝, 李志诚, 刘佳, 张金良, 宋波, 张利军. 计算辅助高性能增材制造铝合金开发的研究现状与展望[J]. 金属学报, 2023, 59(1): 87-105.
[5]	皇甫顥, 王子龙, 刘永利, 孟凡顺, 宋久鹏, 祁阳. W₁_-_x Ir _x 固溶合金几何结构、电子结构、力学和热力学性能的第一性原理计算[J]. 金属学报, 2022, 58(2): 231-240.
[6]	陈维, 陈洪灿, 王晨充, 徐伟, 罗群, 李谦, 周国治. Fe-C-Ni体系膨胀应变能对马氏体转变的影响[J]. 金属学报, 2022, 58(2): 175-183.
[7]	胡标, 张华清, 张金, 杨明军, 杜勇, 赵冬冬. 界面热力学与晶界相图的研究进展[J]. 金属学报, 2021, 57(9): 1199-1214.
[8]	冯苗苗, 张红伟, 邵景霞, 李铁, 雷洪, 王强. 耦合热力学相变路径预测Fe-C包晶合金宏观偏析[J]. 金属学报, 2021, 57(8): 1057-1072.
[9]	刘峰, 王天乐. 基于热力学和动力学协同的析出相模拟[J]. 金属学报, 2021, 57(1): 55-70.
[10]	黄远, 杜金龙, 王祖敏. 二元互不固溶金属合金化的研究进展[J]. 金属学报, 2020, 56(6): 801-820.
[11]	于家英, 王华, 郑伟森, 何燕霖, 吴玉瑞, 李麟. 热浸镀锌高强汽车板界面组织对其拉伸断裂行为的影响[J]. 金属学报, 2020, 56(6): 863-873.
[12]	王祖敏,张安,陈媛媛,黄远,王江涌. 金属诱导晶化基础与应用研究进展[J]. 金属学报, 2020, 56(1): 66-82.
[13]	黄宇, 成国光, 谢有. 稀土Ce对钎具钢中夹杂物的改质机理研究[J]. 金属学报, 2018, 54(9): 1253-1261.
[14]	赵九洲, 江鸿翔. 偏晶合金凝固过程研究进展[J]. 金属学报, 2018, 54(5): 682-700.
[15]	崔荣华, 王歆钰, 董正超, 仲崇贵. Mg_1-_xZn_x合金的弹性和热力学性质的第一性原理研究[J]. 金属学报, 2017, 53(9): 1133-1139.

Viewed

Full text

Abstract

Cited

Shared

Discussed