微量Ce对高级别管线钢洁净度与组织性能的影响
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摘要
随着全球范围内能源总量及清洁能源需求的增加,石油、天然气已经成为影响世界各国经济发展不可缺少的重要资源；人们欲采用高效率(高压,大流量)、高级别(X100、X120)的管线钢降低油、气管线建设成本和提高输送效率。因此,开发、研制“高强度、高韧性的石油、天然气输送管线用钢、满足能源供应需求”成为本世纪管线钢的发展方向之一。
众所周知,因石油、天然气从产地到消费终端要经地震带、不连续冻土带、深海等严峻的环境,要高速输送高压含H2S等腐蚀性流体,则要求管线钢具有高强韧性、高变形能、抗HIC、 SSCC能力和高能量焊接性能。为此、本研究作为开发高级别(X120)管线钢的基础研究环节,在简述高级别管线钢的发展背景、生产工艺、存在问题的基础上,整理、归纳、总结了稀土元素的性质及其在钢中的作用机理。为提高管线钢强韧性能、变形能力和抗HIC、 SSCC能力,解决钢材基体洁净化、细化和改变钢中夹杂物形态这两个关键科学问题,本研究完成以下4项任务。1.运用冶金热力学理论估算Ce含量对钢液过冷度的影响,计算钢中Ce、 O、 S夹杂物的热力学生成条件；2.用真空感应炉在8×102Pa的Ar氛中把3kg工业纯铁和辅料熔制成0.05%C-0.3%Si-2.0Mn%钢液,并向其中添加Ce元素,在1873K下(模拟RH真空精炼过程)精炼,用无氧化重力铸造、锻造方法制备了4组管线钢试样；3.用成分分析、金相观察、扫描电镜观察和能谱分析,拉伸及冲击实验等测试方法,研究、表征Ce对高级别管线钢的成分、夹杂物形态、微观组织结构和力学性能的影响；4.分析、研究、探讨Ce改善钢材显微组织、提高钢材拉伸及冲击性能的作用机理。通过理论计算、试验表征和分析探讨后,得出以下结论：
实验结果表明：当钢中Ce含量为0.0374%mass时,氧含量从0.0036%mass下降到0.0008%mass,硫含量从0.0065%mass下降到0.0010%]mass。说明稀土Ce元素有深脱氧,脱硫能力,且具有较快的脱除速率,能够实现净化钢液的作用。
同时Ce元素能够提高钢液过冷度,增加基体凝固时的形核数量,使得针状铁素体、粒状铁素体和马奥岛数量增多且细小均匀,从而使基体组织得到细化。
研究发现：在钢液中加入Ce元素,经1873K的高温精炼后,钢中O主要以Ce203的形式存在；在S含量较高的条件下Ce与O、S生成Ce202S.随Ce含量增加,原大体积,不规则形貌的MnS.Si02夹杂物转变为1μm左右、甚至纳米级球形Ce氧硫夹杂物；带尖角的大型复合夹杂物变为Ce复合夹杂物,其尺度减小了10倍左右；钢中小于2μm的夹杂物占到80%,大于10μm的夹杂物几乎消失。
最终钢材的综合力学性能得到提高,Ce含量在0～0.0374%范围内,管线钢的综合力学性能出现了先提高后略有下降的趋势；当Ce为0.0167%时,屈服强度Rp0.2、抗拉强度Rm、断面伸长率A分别达到了710MPa.764MPa.24％;比Ce含量为0时分别提高了33.1%、24.8%、54.9%；冲击功AK达到276J,也比Ce含量为0时提高了57.7%。
With the increase of the worldwide total energy and clean energy needs, oil, natural gas has become to affect the world economic development can not be missing important resources; people want to adopt a high efficiency (high pressure, high flow), high-level (X100X120) pipeline steel to reduce oil and gas pipeline construction costs and improve transmission efficiency. Therefore, the development, manufacture of high strength, high toughness of oil, natural gas transmission pipeline steel, meet the needs of energy supply"has become one of the development of this century Pipeline.
We all know, oil, natural gas from the producer to the consumer end to the seismic zone, discontinuous permafrost, deep sea and other severe environments, high-speed conveying high-pressure corrosive fluids containing H2S, requires pipeline steel with high strength and toughness, high-deformation energy, anti-the HIC and anti-the SSCC capacity and high heat input welding performance. To this end, the basic research aspects of the development of high-level (X120) pipeline steel in the development of the brief high-level pipeline steel background, production process, there is the problem on the basis of consolidation, summarized, summarizes the nature of the rare earth elements and the mechanism of steel. In order to improve the robust performance of pipeline steel, deformation capacity and anti-the HIC anti-the SSCC ability to solve the steel substrate clean, refine and change the steel inclusion morphology in these two key scientific issues.In this study, complete the following four tasks.1.The use of metallurgical thermodynamics theory to estimate the Ce content on the undercooling of liquid steel, the calculation of the thermodynamic formation conditions of Ce, O, S inclusions in the steel;2.In vacuum induction furnace, at8X102Pa Ar atmosphere, put the3kg Industrial pure iron and accessories into0.05%C-0.3%Si-2.0Mn%steel melting liquid, and then added Ce element, while the refining temperature was1873K (analog RH vacuum refining process for refining). And then4groups of pipeline steel were prepared by the no oxidation of gravity casting and forging method;3.Composition analysis, metallographic examination, SEM and EDS analysis, tensile and impact testing, testing methods, research, and characterization of Ce on the composition of the high-level pipeline steel, inclusion morphology, the influence of microstructure and mechanical properties;4.Analysis study on Ce to improve the microstructure of steel, steel tensile and impact properties of the mechanism. By theoretical calculation, experimental characterization and analysis, the following conclusions:
The experimental results show that:When the steel content of Ce is0.0374%mass, the oxygen content decreased from0.0036%mass to0.0008%mass, sulfur content decreased from0.0065%mass to0.0010%mass.Description of the Ce element has deep deoxidation and desulphurization of molten steel, realizes the purification effect.
At the same time, Ce elements can improve the liquid steel degree of supercooling, increase matrix organization of the nucleation coagulation of quantity, makes the acicular ferrite, granular ferrite and the M/A increasing number and small even uniform, so that the matrix organization get refined.
Study found that:In liquid steel by adding element Ce,1873K high-temperature refining, the steel O mainly in the form of Ce2O3; in S content under the conditions of Ce and O, S generate Ce2O2S. With the increase of Ce content, the original volume, irregular morphology of MnS, SiO2inclusion into1μm, even nanoscale spherical Ce oxygen sulfur inclusions; with a corner of large complex inclusion into Ce inclusions, its scale is reduced by a factor of10or so; steel is smaller than2μm inclusion accounted for80%, more than10μm inclusions almost disappeared.Ce elements in the steel, the original large size, irregular morphology of MnS, SiO2inclusions into about1μm, and even nanoscale spherical Ce oxygen and sulfur inclusions. Large complex inclusions with sharp corners is reduced to the small size of Ce composite inclusions, its scale is reduced by about10times; with increasing Ce content, accounted for80%less than2μm inclusions, inclusions larger than10μm were almost disappeared;
Finally the steel comprehensive mechanical performance improved, Ce content in0-0.0374%range, the comprehensive mechanical properties of pipeline steel appeared to improve after a slight downward trend; when the Ce is0.0167%, yield strengthRp0.2, tensile strength Rm, elongation at break of A section respectively,710MPa,764MPa,24%; Compared with the steel in which the content of Ce was0, Rp0.2, Rm and A were increased33.1%,24.8%,54.9%; Meanwhile, the impact energy AK reached276J,which also increased57.7%than the steel without Ce concent.
众所周知,因石油、天然气从产地到消费终端要经地震带、不连续冻土带、深海等严峻的环境,要高速输送高压含H2S等腐蚀性流体,则要求管线钢具有高强韧性、高变形能、抗HIC、 SSCC能力和高能量焊接性能。为此、本研究作为开发高级别(X120)管线钢的基础研究环节,在简述高级别管线钢的发展背景、生产工艺、存在问题的基础上,整理、归纳、总结了稀土元素的性质及其在钢中的作用机理。为提高管线钢强韧性能、变形能力和抗HIC、 SSCC能力,解决钢材基体洁净化、细化和改变钢中夹杂物形态这两个关键科学问题,本研究完成以下4项任务。1.运用冶金热力学理论估算Ce含量对钢液过冷度的影响,计算钢中Ce、 O、 S夹杂物的热力学生成条件；2.用真空感应炉在8×102Pa的Ar氛中把3kg工业纯铁和辅料熔制成0.05%C-0.3%Si-2.0Mn%钢液,并向其中添加Ce元素,在1873K下(模拟RH真空精炼过程)精炼,用无氧化重力铸造、锻造方法制备了4组管线钢试样；3.用成分分析、金相观察、扫描电镜观察和能谱分析,拉伸及冲击实验等测试方法,研究、表征Ce对高级别管线钢的成分、夹杂物形态、微观组织结构和力学性能的影响；4.分析、研究、探讨Ce改善钢材显微组织、提高钢材拉伸及冲击性能的作用机理。通过理论计算、试验表征和分析探讨后,得出以下结论：
实验结果表明：当钢中Ce含量为0.0374%mass时,氧含量从0.0036%mass下降到0.0008%mass,硫含量从0.0065%mass下降到0.0010%]mass。说明稀土Ce元素有深脱氧,脱硫能力,且具有较快的脱除速率,能够实现净化钢液的作用。
同时Ce元素能够提高钢液过冷度,增加基体凝固时的形核数量,使得针状铁素体、粒状铁素体和马奥岛数量增多且细小均匀,从而使基体组织得到细化。
研究发现：在钢液中加入Ce元素,经1873K的高温精炼后,钢中O主要以Ce203的形式存在；在S含量较高的条件下Ce与O、S生成Ce202S.随Ce含量增加,原大体积,不规则形貌的MnS.Si02夹杂物转变为1μm左右、甚至纳米级球形Ce氧硫夹杂物；带尖角的大型复合夹杂物变为Ce复合夹杂物,其尺度减小了10倍左右；钢中小于2μm的夹杂物占到80%,大于10μm的夹杂物几乎消失。
最终钢材的综合力学性能得到提高,Ce含量在0～0.0374%范围内,管线钢的综合力学性能出现了先提高后略有下降的趋势；当Ce为0.0167%时,屈服强度Rp0.2、抗拉强度Rm、断面伸长率A分别达到了710MPa.764MPa.24％;比Ce含量为0时分别提高了33.1%、24.8%、54.9%；冲击功AK达到276J,也比Ce含量为0时提高了57.7%。
With the increase of the worldwide total energy and clean energy needs, oil, natural gas has become to affect the world economic development can not be missing important resources; people want to adopt a high efficiency (high pressure, high flow), high-level (X100X120) pipeline steel to reduce oil and gas pipeline construction costs and improve transmission efficiency. Therefore, the development, manufacture of high strength, high toughness of oil, natural gas transmission pipeline steel, meet the needs of energy supply"has become one of the development of this century Pipeline.
We all know, oil, natural gas from the producer to the consumer end to the seismic zone, discontinuous permafrost, deep sea and other severe environments, high-speed conveying high-pressure corrosive fluids containing H2S, requires pipeline steel with high strength and toughness, high-deformation energy, anti-the HIC and anti-the SSCC capacity and high heat input welding performance. To this end, the basic research aspects of the development of high-level (X120) pipeline steel in the development of the brief high-level pipeline steel background, production process, there is the problem on the basis of consolidation, summarized, summarizes the nature of the rare earth elements and the mechanism of steel. In order to improve the robust performance of pipeline steel, deformation capacity and anti-the HIC anti-the SSCC ability to solve the steel substrate clean, refine and change the steel inclusion morphology in these two key scientific issues.In this study, complete the following four tasks.1.The use of metallurgical thermodynamics theory to estimate the Ce content on the undercooling of liquid steel, the calculation of the thermodynamic formation conditions of Ce, O, S inclusions in the steel;2.In vacuum induction furnace, at8X102Pa Ar atmosphere, put the3kg Industrial pure iron and accessories into0.05%C-0.3%Si-2.0Mn%steel melting liquid, and then added Ce element, while the refining temperature was1873K (analog RH vacuum refining process for refining). And then4groups of pipeline steel were prepared by the no oxidation of gravity casting and forging method;3.Composition analysis, metallographic examination, SEM and EDS analysis, tensile and impact testing, testing methods, research, and characterization of Ce on the composition of the high-level pipeline steel, inclusion morphology, the influence of microstructure and mechanical properties;4.Analysis study on Ce to improve the microstructure of steel, steel tensile and impact properties of the mechanism. By theoretical calculation, experimental characterization and analysis, the following conclusions:
The experimental results show that:When the steel content of Ce is0.0374%mass, the oxygen content decreased from0.0036%mass to0.0008%mass, sulfur content decreased from0.0065%mass to0.0010%mass.Description of the Ce element has deep deoxidation and desulphurization of molten steel, realizes the purification effect.
At the same time, Ce elements can improve the liquid steel degree of supercooling, increase matrix organization of the nucleation coagulation of quantity, makes the acicular ferrite, granular ferrite and the M/A increasing number and small even uniform, so that the matrix organization get refined.
Study found that:In liquid steel by adding element Ce,1873K high-temperature refining, the steel O mainly in the form of Ce2O3; in S content under the conditions of Ce and O, S generate Ce2O2S. With the increase of Ce content, the original volume, irregular morphology of MnS, SiO2inclusion into1μm, even nanoscale spherical Ce oxygen sulfur inclusions; with a corner of large complex inclusion into Ce inclusions, its scale is reduced by a factor of10or so; steel is smaller than2μm inclusion accounted for80%, more than10μm inclusions almost disappeared.Ce elements in the steel, the original large size, irregular morphology of MnS, SiO2inclusions into about1μm, and even nanoscale spherical Ce oxygen and sulfur inclusions. Large complex inclusions with sharp corners is reduced to the small size of Ce composite inclusions, its scale is reduced by about10times; with increasing Ce content, accounted for80%less than2μm inclusions, inclusions larger than10μm were almost disappeared;
Finally the steel comprehensive mechanical performance improved, Ce content in0-0.0374%range, the comprehensive mechanical properties of pipeline steel appeared to improve after a slight downward trend; when the Ce is0.0167%, yield strengthRp0.2, tensile strength Rm, elongation at break of A section respectively,710MPa,764MPa,24%; Compared with the steel in which the content of Ce was0, Rp0.2, Rm and A were increased33.1%,24.8%,54.9%; Meanwhile, the impact energy AK reached276J,which also increased57.7%than the steel without Ce concent.
引文
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