抽油泵泵筒内壁激光/渗氮复合改性研究
摘要
随着国内大部分油田进入高含水开发期,由于高含砂、高含水、高矿化度、高温蒸汽稠油开采、注聚合物开采及强腐蚀介质等因素的影响,抽油泵的腐蚀磨损日趋严重,严重影响油田开发。目前渗氮泵由于耐磨损、耐腐蚀而在油田使用较多,但由于气体渗氮层的脆性较大易造成剥落而使其受到一定影响,本文采用激光淬火/渗氮复合处理技术成功制备出性能优异的复合渗氮层,并对渗氮层的相组成、微观组织结构、硬度、耐磨性、耐蚀性及脆性进行系统分析,研究了激光淬火对渗氮层组织及性能的影响和催渗机理。
激光淬火表面层晶粒细化,晶界增多,N原子的扩散通道数量和扩散速度增加,位错、孪晶等缺陷增加,这些缺陷处于较高的能量状态,为氮化物的形成提供额外的驱动力,使得生成ε相和γ’相的标准自由能减小,在未达到渗氮温度(530℃)的升温阶段形成氮化物,同时N原子沿晶界的扩散通道增多,扩散速度提高,表面N浓度较低,渗氮层中N分布较均匀,浓度降低趋势平缓,而气体渗氮层表面N浓度较高,N浓度降低趋势陡峭。激光淬火可显著提高渗氮速度,增加渗氮层厚度,渗氮层深度由气体渗氮的0.2mm增加至0.3mm。
激光淬火/渗氮处理后γ’相双向溶解速率大于ε相储氮速率,ε相和γ’相的阻碍扩散作用降低,白亮层厚度减小,白亮层均由；ζ-Fe2N相、ε-Fe3N相和Cr2N组成。气体渗氮层中的ζ-Fe2N相、ε-Fe3N相和Cr2N的体积分数分别为79.95%、14.74%和5.31%。激光淬火/渗氮层对应的体积分数分别为25.03%、69.45%和5.52%。其中Cr2N的含量基本不变激光淬火/渗氮层内脆性大的ζ-Fe2N相含量减少,脆性小的ε-Fe3N相含量增加,渗氮层脆断的临界压力由气体渗氮层的3N提高到激光淬火/渗氮层的6N。
激光淬火/渗氮扩散层的γ’相和α-Fe相晶粒细小,γ’-Fe4N中存在超点阵结构,Fe原子和N原子在γ’相中有序排列,γ’相和α-Fe相存在一定的位向关系,二者的共格性和相容性优良,二者的结合强度高,同时细小渗碳体分布在条状下贝氏体组织中。复合渗氮中优先生成的Cr2N颗粒细小,且数量增多,而气体渗氮中的ε相和Cr2N颗粒较粗大,由于激光淬火/渗氮层中的Cr2N颗粒的硬度较高,细小的Cr2N颗粒起钉扎作用,其渗氮层硬度较气体渗氮层提高约100HV0.2。
由于激光淬火/渗氮层中韧性较好的γ’相和ε相的数量增加,细小合金氮化物耐磨硬质点阻碍了磨痕的发展,其阻碍和钉扎行为在摩擦过程中发挥了强烈的阻磨作用,激光淬火/渗氮层的磨擦磨损量为普通气体渗层的1/8,摩擦系数由气体渗氮的0.35降为气体渗氮层的0.29。
激光淬火/渗氮复合处理的耐蚀性能提高,复合处理后的渗氮层致密度提高,组织品粒细化,表层的氧化物含量降低,自腐蚀电流由普通渗氮层的57.68μA/cm2减小到激光/渗氮层的3.166μA/cm,复合渗氮层的耐蚀性提高。
在腐蚀磨损试验中,激光淬火/渗氮层的腐蚀磨损失重约为气体渗氮层的1/2,腐蚀优先在晶界或相界处发生,削弱了Cr2N颗粒与基体的结合力。Cr2N颗粒在磨损作用下发生少量脱落,因此腐蚀加剧了磨损。腐蚀磨损形貌为切削犁沟和腐蚀坑,腐蚀磨损机制为腐蚀磨粒磨损。由于激光淬火/渗氮层白亮层组织致密、脆性低、Cr2N颗粒不易脱落,其腐蚀磨损性能优于普通气体渗氮层。
With the majority of domestic oil fields entering high water-cut development stage, due to the influence of high water-cut, high sand content, hyper salinity, high-temperature steam heavy oil extract, polymer injection oil extract and the strong corrosive medium, the corrosion and wear of oil well tube get more and more serious.In the paper, compound nitriding layers were produced successfully by laser quenching/nitrided compound processing technique.The phase composition, microstructure, hardness, wear resistance, corrosion resistance, brittleness of nitriding layers were systematically analysised, the promotion effect of laser quenching on nitrding and the influence of laser quenching on the microstructure and properties were researched.
Both the white layers of gaseous nitriding and laser quenching/nitrided are composed ofζ-Fe2N、ε-Fe3N and Cr2N. The volume fractions ofζ-Fe2N,ε-Fe3N and Cr2N are separately 79.95%,14.74%,5.31% in the gaseous nitriding layers and 25.03%,69.45%,5.52% in the laser quenching/nitrided layers, of which the content of Cr2N stays stable, the N content inζ-Fe2N is higher and the white layers are looser. The structure ofε-Fe3N is body-centered hexagonal andε-Fe3N is less brittle.The structure ofζ-Fe2N is orthorhombic lattice structure and is more brittle.The content ofε-Fe3N increased in the laser quenching/nitrded layers and the content ofζ-Fe2N decreased. Brittle fracture Critical stresses of nitriding layers increased from 3N of gas nitriding to 8N of laser quenching/nitrided layers.
The grain ofεphase and Cr2N in gas nitriding layers are more coarse, while in the compound nitriding layers, the grain are finer and the quantities of Cr2N grain are more.Tiny Cr2N grains play a pinning effect and the micro hardness of compound nitriding layers increased by 100HV0.2,compared with gas nitrding layers.The micro hardness of laser quenching/nitrded layers dramatically improved.
Compared with gas nitriding layers,γ'phase andα-Fe in the laser quenching/nitrded layers are finer.The ultra lattice structure existed inγ'-Fe4N in the diffusion layer, in which the Fe and N atoms arranged orderly. There have been certain orientation relationship between y'-Fe4N and a-Fe.The coherency and compatibility of y'-Fe4N and a-Fe is very excellent.Tiny Fe3C grains dispersively distribute on the structure of the strip lower bainite.
The grains of surface layer processed by Laser quenching/nitrded were refined, which lead to the increase of the quantities of the grain boundary and the dislocation. These defects were at a higher energy state.Part of the energy can provide additional driving force to form the nitride compounds, making the standard free energy of generatingεphase andγ'phase reduced, and form the nitride compounds at the warming stage before reaching the nitriding temperature (530℃).Simultaneously, the diffusion path of N atoms along the grain boundaries increased and diffusion speed also increased, which increased the depth of laser quenching and nitriding layers.
The quantities of y'phase andεphase,which have excellent ductibility, in the laser quenching/nitrided layers increased. Tiny wearable nitride alloy particles hinder the development of gridding crack. The hindering and pinning effect play a forceful friction block effect during friction process, which make friction process more stable, decrease wear losses and friction coefficient.
In corrosive wear experiment, corrosion is inclined to start on grain boundary and phase boundary, which weaken the binding strength between Cr2N and base and make some Cr2N particles dropping from base during wear process.Therefore, corrosion speeds up wear process.Wear morphology of corrosive wear are Cutting furrows and corrosion pits.The mechanism of corrosive wear is corrosion abrasion wear. The white layers'microstructures of laser quenching/nitrided layers are denser, less brittle and less dropping.So the corrosion wear resistance of laser quenching/nitrided layers is better than that of gas nitriding layers.
激光淬火表面层晶粒细化,晶界增多,N原子的扩散通道数量和扩散速度增加,位错、孪晶等缺陷增加,这些缺陷处于较高的能量状态,为氮化物的形成提供额外的驱动力,使得生成ε相和γ’相的标准自由能减小,在未达到渗氮温度(530℃)的升温阶段形成氮化物,同时N原子沿晶界的扩散通道增多,扩散速度提高,表面N浓度较低,渗氮层中N分布较均匀,浓度降低趋势平缓,而气体渗氮层表面N浓度较高,N浓度降低趋势陡峭。激光淬火可显著提高渗氮速度,增加渗氮层厚度,渗氮层深度由气体渗氮的0.2mm增加至0.3mm。
激光淬火/渗氮处理后γ’相双向溶解速率大于ε相储氮速率,ε相和γ’相的阻碍扩散作用降低,白亮层厚度减小,白亮层均由；ζ-Fe2N相、ε-Fe3N相和Cr2N组成。气体渗氮层中的ζ-Fe2N相、ε-Fe3N相和Cr2N的体积分数分别为79.95%、14.74%和5.31%。激光淬火/渗氮层对应的体积分数分别为25.03%、69.45%和5.52%。其中Cr2N的含量基本不变激光淬火/渗氮层内脆性大的ζ-Fe2N相含量减少,脆性小的ε-Fe3N相含量增加,渗氮层脆断的临界压力由气体渗氮层的3N提高到激光淬火/渗氮层的6N。
激光淬火/渗氮扩散层的γ’相和α-Fe相晶粒细小,γ’-Fe4N中存在超点阵结构,Fe原子和N原子在γ’相中有序排列,γ’相和α-Fe相存在一定的位向关系,二者的共格性和相容性优良,二者的结合强度高,同时细小渗碳体分布在条状下贝氏体组织中。复合渗氮中优先生成的Cr2N颗粒细小,且数量增多,而气体渗氮中的ε相和Cr2N颗粒较粗大,由于激光淬火/渗氮层中的Cr2N颗粒的硬度较高,细小的Cr2N颗粒起钉扎作用,其渗氮层硬度较气体渗氮层提高约100HV0.2。
由于激光淬火/渗氮层中韧性较好的γ’相和ε相的数量增加,细小合金氮化物耐磨硬质点阻碍了磨痕的发展,其阻碍和钉扎行为在摩擦过程中发挥了强烈的阻磨作用,激光淬火/渗氮层的磨擦磨损量为普通气体渗层的1/8,摩擦系数由气体渗氮的0.35降为气体渗氮层的0.29。
激光淬火/渗氮复合处理的耐蚀性能提高,复合处理后的渗氮层致密度提高,组织品粒细化,表层的氧化物含量降低,自腐蚀电流由普通渗氮层的57.68μA/cm2减小到激光/渗氮层的3.166μA/cm,复合渗氮层的耐蚀性提高。
在腐蚀磨损试验中,激光淬火/渗氮层的腐蚀磨损失重约为气体渗氮层的1/2,腐蚀优先在晶界或相界处发生,削弱了Cr2N颗粒与基体的结合力。Cr2N颗粒在磨损作用下发生少量脱落,因此腐蚀加剧了磨损。腐蚀磨损形貌为切削犁沟和腐蚀坑,腐蚀磨损机制为腐蚀磨粒磨损。由于激光淬火/渗氮层白亮层组织致密、脆性低、Cr2N颗粒不易脱落,其腐蚀磨损性能优于普通气体渗氮层。
With the majority of domestic oil fields entering high water-cut development stage, due to the influence of high water-cut, high sand content, hyper salinity, high-temperature steam heavy oil extract, polymer injection oil extract and the strong corrosive medium, the corrosion and wear of oil well tube get more and more serious.In the paper, compound nitriding layers were produced successfully by laser quenching/nitrided compound processing technique.The phase composition, microstructure, hardness, wear resistance, corrosion resistance, brittleness of nitriding layers were systematically analysised, the promotion effect of laser quenching on nitrding and the influence of laser quenching on the microstructure and properties were researched.
Both the white layers of gaseous nitriding and laser quenching/nitrided are composed ofζ-Fe2N、ε-Fe3N and Cr2N. The volume fractions ofζ-Fe2N,ε-Fe3N and Cr2N are separately 79.95%,14.74%,5.31% in the gaseous nitriding layers and 25.03%,69.45%,5.52% in the laser quenching/nitrided layers, of which the content of Cr2N stays stable, the N content inζ-Fe2N is higher and the white layers are looser. The structure ofε-Fe3N is body-centered hexagonal andε-Fe3N is less brittle.The structure ofζ-Fe2N is orthorhombic lattice structure and is more brittle.The content ofε-Fe3N increased in the laser quenching/nitrded layers and the content ofζ-Fe2N decreased. Brittle fracture Critical stresses of nitriding layers increased from 3N of gas nitriding to 8N of laser quenching/nitrided layers.
The grain ofεphase and Cr2N in gas nitriding layers are more coarse, while in the compound nitriding layers, the grain are finer and the quantities of Cr2N grain are more.Tiny Cr2N grains play a pinning effect and the micro hardness of compound nitriding layers increased by 100HV0.2,compared with gas nitrding layers.The micro hardness of laser quenching/nitrded layers dramatically improved.
Compared with gas nitriding layers,γ'phase andα-Fe in the laser quenching/nitrded layers are finer.The ultra lattice structure existed inγ'-Fe4N in the diffusion layer, in which the Fe and N atoms arranged orderly. There have been certain orientation relationship between y'-Fe4N and a-Fe.The coherency and compatibility of y'-Fe4N and a-Fe is very excellent.Tiny Fe3C grains dispersively distribute on the structure of the strip lower bainite.
The grains of surface layer processed by Laser quenching/nitrded were refined, which lead to the increase of the quantities of the grain boundary and the dislocation. These defects were at a higher energy state.Part of the energy can provide additional driving force to form the nitride compounds, making the standard free energy of generatingεphase andγ'phase reduced, and form the nitride compounds at the warming stage before reaching the nitriding temperature (530℃).Simultaneously, the diffusion path of N atoms along the grain boundaries increased and diffusion speed also increased, which increased the depth of laser quenching and nitriding layers.
The quantities of y'phase andεphase,which have excellent ductibility, in the laser quenching/nitrided layers increased. Tiny wearable nitride alloy particles hinder the development of gridding crack. The hindering and pinning effect play a forceful friction block effect during friction process, which make friction process more stable, decrease wear losses and friction coefficient.
In corrosive wear experiment, corrosion is inclined to start on grain boundary and phase boundary, which weaken the binding strength between Cr2N and base and make some Cr2N particles dropping from base during wear process.Therefore, corrosion speeds up wear process.Wear morphology of corrosive wear are Cutting furrows and corrosion pits.The mechanism of corrosive wear is corrosion abrasion wear. The white layers'microstructures of laser quenching/nitrided layers are denser, less brittle and less dropping.So the corrosion wear resistance of laser quenching/nitrided layers is better than that of gas nitriding layers.
引文
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