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金属学报  2026, Vol. 62 Issue (4): 611-626    DOI: 10.11900/0412.1961.2024.00269
  研究论文 本期目录 | 过刊浏览 |
稀土合金化石油套管钢精炼-连铸-轧制过程夹杂物演变行为
梁雨雨1,2, 倪培远1,2(), 刘麒麟3, 厉英1,2
1.东北大学 冶金学院 多金属共生矿生态化冶金教育部重点实验室 沈阳 110819
2.东北大学 冶金学院 辽宁省冶金传感器材料及技术重点实验室 沈阳 110819
3.宝山钢铁股份有限公司 上海 201900
Evolution Behavior of Inclusions in Rare Earth Metal Alloying Oil Casing Steel During Refining and Casting and Hot-Rolling Process
LIANG Yuyu1,2, NI Peiyuan1,2(), LIU Qilin3, LI Ying1,2
1.Key Laboratory for Ecological Metallurgy of MultiMetallic Mineral (Ministry of Education), School of Metallurgy, Northeastern University, Shenyang 110819, China
2.Liaoning Key Laboratory of Metallurgical Sensor Materials and Technology, School of Metallurgy, Northeastern University, Shenyang 110819, China
3.Baoshan Iron & Steel Co. Ltd. , Shanghai 201900, China
引用本文:

梁雨雨, 倪培远, 刘麒麟, 厉英. 稀土合金化石油套管钢精炼-连铸-轧制过程夹杂物演变行为[J]. 金属学报, 2026, 62(4): 611-626.
Yuyu LIANG, Peiyuan NI, Qilin LIU, Ying LI. Evolution Behavior of Inclusions in Rare Earth Metal Alloying Oil Casing Steel During Refining and Casting and Hot-Rolling Process[J]. Acta Metall Sin, 2026, 62(4): 611-626.

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摘要: 

非金属夹杂物是影响石油套管钢性能的重要因素之一,稀土(RE)能有效变质钢中的非金属夹杂物。本工作开展了套管钢精炼、连铸和热轧过程中稀土合金化改性夹杂物的工业实验研究,利用SEM-EDS、FactSage 8.3热力学计算软件及全自动夹杂物分析,对钢中夹杂物形貌、数量、尺寸等的演变行为进行了研究。结果表明,钢中稀土含量为4 × 10-6时,石油套管钢液全氧含量可降低到7 × 10-6,同时,钢中的Ca-Al-O类夹杂物转变为Ca-RE-Al-O夹杂物。稀土改性后铸坯样中夹杂物数量密度由44 mm-2增加至46 mm-2,尺寸为0~2 μm的夹杂物数量密度由13 mm-2增加到18 mm-2,而尺寸为5~30 μm的夹杂物数量密度由7 mm-2降低至5 mm-2,这表明稀土合金化工艺使钢液夹杂物尺寸减小。热力学计算和实验结果表明,CaS夹杂物在凝固阶段形成,其包裹在Ca-Al-O/Ca-RE-Al-O类夹杂物外围,夹杂物可能起到了异质形核的作用。在热轧过程中,未添加稀土的钢中出现条串状分布的夹杂物,而稀土合金化改性后夹杂物变形能力提高,未出现夹杂物破碎引起的条串状夹杂物。钢液/精炼渣反应、稀土类夹杂物的上浮去除等,是造成稀土收得率低的主要原因。

关键词 石油套管钢稀土合金化非金属夹杂物热力学计算    
Abstract

Oil casing steel plays a critical role in the oil and natural gas industry, and its performance is significantly influenced by non-metallic inclusions. Rare earth (RE) elements can effectively modify these inclusions. In this study, industrial experiments were conducted to investigate the effects of rare earth metal alloying on inclusion characteristics during the refining, continuous casting, and hot-rolling processes. The evolution of inclusion morphology, quantity, and size was analyzed using SEM-EDS, FactSage 8.3 thermodynamic software, and an OTS One Bond inclusion analysis system. Results show that when the rare earth content was 4 × 10-6, the total oxygen content decreased to 7 × 10-6. In addition, rare earth microalloying transformed Ca-Al-O inclusions into Ca-RE-Al-O inclusions. Following alloying, the inclusion number density in continuous casting billet samples increased from 44 mm-2 to 46 mm-2, with the number density of 0-2 μm inclusions rising from 13 mm-2 to 18 mm-2, while the number density of 5-30 μm inclusions fell from 7 mm-2 to 5 mm-2. Overall, the average inclusion size decreased after rare earth metal addition. XRD and XRF analyses revealed the formation of rare earth phases in the refined slag after vacuum degassing rare earth alloying. Thermodynamic calculations indicate that at 1600 oC, the Gibbs formation energies of CaO and CeAlO3 in steel were -357088.82 and -86892.89 J/mol, respectively, supporting the formation of these inclusions upon rare earth addition. In RE-free furnaces, both thermodynamic calculations and experimental results showed that CaS inclusions formed during solidification, with CaS precipitating around the edges of Ca-Al-O/Ca-RE-Al-O inclusions. In RE-containing furnaces, the addition of rare earth reduced the precipitation of calcium aluminate inclusions, leading instead to the formation of CaO·REAlO3 inclusions, which likely serve as nucleation sites for CaS precipitation during solidification. During hot-rolling, long strip inclusions were observed in steel without rare earth; however, rare earth alloying improved the deformation ability of inclusions, preventing the formation of long strips due to inclusion crushing. Notably, the modifications induced by rare earth were independent of the inclusions’ Ca content. In hot rolled tube samples without rare earth, only inclusions with moderate Ca content exhibited good deformability. The low yield of rare earth metal was primarily attributed to reactions between the molten steel and refining slag, as well as the removal of rare earth inclusions from the molten steel to the slag.

Key wordsoil casing steel    rare earth metal alloying    non-metallic inclusion    thermodynamic calculation
收稿日期: 2024-08-03     
ZTFLH:  TF769.9  
基金资助:国家自然科学基金项目(52374333);中央高校基本科研业务费专项资金项目(N2325010);辽宁省振兴人才计划项目(XLYC2203169)
通讯作者: 倪培远,nipeiyuan@smm.neu.edu.cn,主要从事极端环境用高性能钢与绿色智能钢铁冶金等研究
Corresponding author: NI Peiyuan, professor, Tel: 15640417628, E-mail: nipeiyuan@smm.neu.edu.cn
作者简介: 梁雨雨,男,1997年生,博士
图1  未添加稀土和添加稀土的石油套管钢的生产工艺及取样示意图
图2  精炼阶段试样加工示意图
SampleCSiMnCrMoAlST.OCaREFe
RF50.2730.2110.3320.9800.8540.01200.00080.00130.00200Bal.
R50.2780.2270.3500.9620.8620.01500.00080.00070.00200.0004Bal.
表1  未添加稀土和添加稀土的石油套管钢的化学成分 (mass fraction / %)
图3  热轧管坯试样加工示意图
图4  精炼和连铸过程中元素含量变化(a) content of RE in RE steel(b-d) contents of Ca (b), Al (c), and T.O and S (d) in RE-free and RE steels
图5  不加稀土炉次铸坯样中典型夹杂物形貌的SEM像、EDS分析结果和形貌示意图
图6  加稀土炉次铸坯样中典型夹杂物形貌的SEM像、EDS分析结果和形貌示意图
图7  精炼及连铸过程夹杂物种类分布示意图
图8  不同尺寸加稀土炉次精炼及连铸样夹杂物与不加稀土炉次和加稀土炉次试样真空吹氩脱气(VD)工位和铸坯样夹杂物的数量密度
图9  沿轧制方向(RD)不加稀土炉次和加稀土炉次热轧管坯样典型夹杂物形貌的SEM像和EDS分析
图10  沿横向(TD)不加稀土炉次和加稀土炉次热轧管坯样典型夹杂物形貌的SEM像和EDS分析
图11  沿法向(ND)不加稀土炉次和加稀土炉次热轧管坯样典型夹杂物形貌的SEM像和EDS分析
Slag sampleCaOSiO2Al2O3MgOFe2O3CeO2
LF slag sample before RE addition46.116213.078622.96253.09709.0426-
LF slag sample after RE addition58.82704.100230.29714.39101.3732-
VD slag sample after RE addition56.25133.662633.15215.46070.55390.0173
表2  钢包炉(LF)加稀土前渣样、LF加稀土后渣样及VD离位前渣样的XRF结果 (mass fraction / %)
图12  LF稀土合金化前、LF稀土合金化后和VD稀土合金化后渣样的XRD谱
图13  不加稀土炉次和加稀土炉次钢在冷却过程中夹杂物析出的热力学计算结果
图14  1600 ℃下不同Ce含量夹杂物平衡组成的热力学计算结果
图15  不加稀土炉次和加稀土炉次热轧管坯样不同Ca含量夹杂物的SEM像和EDS分析
MaterialB / GPaE / GPaG / MPaH / GPaρ / (kg·m-3)
Fe matrix173.1020685.807007874
Al2O3223.40387150.05> 19003980
Al2O3·CaO-113-> 2200-
CeAlO3194.75220125.9517336680
Ce2O3137.5912965.146606860
表3  基体和氧化物夹杂物的物理性质和力学性能[24,25]
图16  稀土变质夹杂物及冷却和轧制过程中夹杂物形成示意图
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