钨铌钒无限冷硬铸铁组织与性能及碳化物的力学特性
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摘要
高镍铬无限冷硬铸铁（Indefinite Chill Double-Poured，ICDP）轧辊具有良好的耐热性、抗裂性、抗粘性、抗剥落性和耐磨性，一直用于板带钢热轧机后段作为精轧辊的首选材料。随着热轧机粗轧和精轧前架工作辊材质的改进，轧辊的在线周期延长，精轧后架的轧辊表现出耐磨性不足。提高ICDP轧辊的耐磨性，开发具有高耐磨性的改进型ICDP轧辊，成为解决板带钢热轧生产瓶颈的迫切任务。本论文在普通高镍铬无限冷硬铸铁成分的基础上，加入不同含量的钨、铌和钒三种合金元素，研究了它们对凝固过程、铸铁组织和耐磨性能的影响，深入分析了碳化物的微观结构和力学性能，为开发具有高耐磨性的ICDP轧辊提供理论和实践依据。
在普通高镍铬无限冷硬铸铁中，添加1-5wt%的W、Nb、V合金元素，熔炼出12中不同含量的合金冷硬铸铁。采用金相显微镜、扫描电镜、X射线衍射、差热分析、摩擦磨损和Thermo-cal软件等分析方法，研究合金元素对凝固—回火组织和硬度的影响。结果表明：添加W元素为1-2wt%时，对凝固过程基本不产生影响；添加W含量大于3%时，在凝固过程中有鱼骨状碳化物（Fe_4W_2C）沿晶界析出呈网状。添加Nb后，由于NbC相的领先析出，碳化物呈断续状分布。而增加钒的含量则可使碳化物由网状沿晶间分布（1wt%V），逐渐细化（2-3wt%），最终呈球状和短棒状，在基体均匀分布。
合金含量1-5wt%的铸铁试样在回火过程中，不同成分试样的硬度均随回火温度的升高存在二次硬化现象，其最大硬度出现在480-500℃左右。添加W、Nb、V回火最高硬度分别为HRC60，HRC59和HRC60；随合金元素含量的增加，铸铁的耐磨性提高。对于添加不同合金元素的无限冷硬铸铁，在干滑动摩擦磨损试验中，含V铸铁的耐磨性最好，含Nb铸铁次之，含W铸铁最差。钒含量为5wt%的合金铸铁，其相对耐磨性较1wt%的提高了约13倍。
对于高V合金铸铁，随着钒含量的增加，凝固过程由亚共晶转变（4wt%V）逐渐过渡到近似共晶转变（6wt%V），再到过共晶转变（8-10wt%V）。碳化物的分布由晶间分布逐渐过渡到均匀分布。高钒合金的耐磨性受基体硬度和碳化物分布的双重影响。碳化物均匀分布的V8%试样耐磨性能最好，V6%和V10%次之，V4%最差。
通过对8wt%V和5wt%Nb合金凝固组织中的钒/铌碳化物的提取，利用场发射扫描电镜、X射线、高分辨和纳米压痕等进行分析，发现高钒冷硬铸铁（V含量8wt%）中碳化钒呈树枝晶生长，是NaCl结构的c-VC，硬度和杨氏模量分别为33.3和436GPa；高铌冷硬铸铁（Nb含量5wt%）中的碳化铌呈不规则块体形貌；是具有NaCl结构的c-NbC；硬度和杨氏模量分别为24.5和406GPa。
利用第一性原理计算技术，研究了具不同化学剂量比V-C、Nb-C化合物的力学特性。计算辨明，随着C含量的增加，V-C/Nb-C化合物的剪切模量、杨氏模量和硬度单调增加，而体弹模量呈不规则变化。通过计算电子结构、布局数和原子排布分析研究了V-C/NbC化合物的弹性性质变化的起因。Nb-C体系中，Pnma-Nb2C和P3_1-Nb_6C_5是Nb-C体系相图中的基态结构，预测相Fm-3m-Nb_(23)C_6，Pnma-Nb3C，C_2/c-Nb_5C_2和P6_3mc-Nb_7C_3在热力学、动力学和力学上都是稳定的。
Indefinite Chill Double-Poured (ICDP) rolls which are widely recognized as the firstchoice for the later stand of hot rolling mill (HSM) due to its superior thermostability,good resistance to adherence and thermocracking, and wear resistance. However, as theimprovement of the early stands’ materials for rough and finish rolling as well as theextended working period, the wear resistance of the later stand is becoming insufficient.Therefore, it is an urgent task to develop enhanced ICDP roller with enhanced wearresistance. In this paper, we have added W, Nb and V element into the conventionalindefinite chill cast iron (ICCI) with the aim to increase the wear resistance, and to shedlight on the effect of those alloying elements on the microstructure and solidificationprocess of ICCI. Furthermore, in view of the pivotal role played by the micro-structureand mechanical properties of carbides in defining the wear resistance behavior of cast iron,we also investigated the crystal structure and mechanical properties of the vanadium andniobium carbides. The aim of this work is to provide theoretical and experimental basicdata for the development of ICDP roller with high wear resistance.
ICCI with12various contents of W, Nb, and V element ranges from1-5percent wereyielded by alloying. By the aid of Optical Microscopy (OM), Scanning ElectronMicroscope (SEM), X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC),wear resistance test, and Thermo-cal et al, the effect of alloying element on the solidifiedmicrostructure and properties of ICCI were investigated. Results show: the effect showsreliance on the type of alloying element. When the added W content is1-2%, there isalmost no effect on the solidified process; when the added W content is larger than3%,fishbone shape carbides (Fe_4W_2C) appears at grain boundary, but has trace influence onthe morphology of carbides that shows network shape at grain boundary. After adding Nbelement, carbides distribute in a discrete manner due to the prior precipitation of NbC.With the increase of added V alloying element, there is a gradual transformation for thecarbides from network at grain boundary (1%V), to increased refinement (2-3%), andfinally homogenously distributed in spherical and short rod-like shape.
During the tempering of1-5%alloyed cast iron samples, the hardness showssecondary hardening with the increase of tempering temperature, and peaks at about400-500℃. The maximum hardness that corresponds to W, Nb, and V alloying is HRC60,HRC59and HRC60, respectively. The wear resistance of alloyed cast iron increases withthe content of alloying element. For the different allying element, there is a gradualdecreasing trend in the sequence of V, Nb, and W. The most significant results come to the5%V alloying by which the wear resistance is improved by13times.
For the high-V alloyed cast iron, the solidified process changes from hypo-eutectic(4%V) to quasi-eutectic (6%V), and further to hyper-eutectic transformation (8-10%V).The distribution of carbides changes from inter-granular to chrysanthemum-likedistribution, and further to homogenous pattern. The wear resistance of heavy V alloyedcast iron depends not only on the hardness of matrix, but the distribution of the carbides.the8%V alloyed sample shows the highest wear resistance, followed by6%and10%Valloyed, and the4%alloyed sample shows the worst wear resistance enhancement.
By extracting the V and Nb carbides from the solidified alloyed cast iron andmicrostructure analysis method including Field Emission Scanning Electron Microscopy(FE-SEM), XRD, High Resolution Transmission Electron Microscopy (HR-TEM), andNano-indentation, We found the dendritic carbides in heavy V alloyed chilled cast iron(8%V) are cubic NaCl-type vanadium carbides (VC) whose hardness and Young modulusis33.3and436GPa, respectively. The niobium carbides (NbC) in the heavy Nb alloyedcast iron (5%Nb) also share the same crystal structure with NaCl and shows irregular bulkshape, and its hardness and Young's modulus is24.5and406GPa, respectively.
By the aid of first-principle calculation, the mechanical properties of VC and NbCwith various stoichiometries were investigated. Results show, the shear modulus, Young'smodulus and Vickers hardness increase monotonously with carbon content, but the bulkmodulus shows irregular trend. The reasons were discussed from the standpoint ofelectronic structure, Mulliken Overlap Population (MOP), and atomic configuration. In Nb-C system, pnma-Nb2C and P3_1-Nb_6C_5are found to be the ground state structures, andthe proposed phase: Fm-3m-Nb_(23)C_6, Pnma-Nb_3C, C_2/c-Nb_5C_2, and P6_3mc-Nb_7C_3areenergetically, mechanically, and dynamically stable.
在普通高镍铬无限冷硬铸铁中，添加1-5wt%的W、Nb、V合金元素，熔炼出12中不同含量的合金冷硬铸铁。采用金相显微镜、扫描电镜、X射线衍射、差热分析、摩擦磨损和Thermo-cal软件等分析方法，研究合金元素对凝固—回火组织和硬度的影响。结果表明：添加W元素为1-2wt%时，对凝固过程基本不产生影响；添加W含量大于3%时，在凝固过程中有鱼骨状碳化物（Fe_4W_2C）沿晶界析出呈网状。添加Nb后，由于NbC相的领先析出，碳化物呈断续状分布。而增加钒的含量则可使碳化物由网状沿晶间分布（1wt%V），逐渐细化（2-3wt%），最终呈球状和短棒状，在基体均匀分布。
合金含量1-5wt%的铸铁试样在回火过程中，不同成分试样的硬度均随回火温度的升高存在二次硬化现象，其最大硬度出现在480-500℃左右。添加W、Nb、V回火最高硬度分别为HRC60，HRC59和HRC60；随合金元素含量的增加，铸铁的耐磨性提高。对于添加不同合金元素的无限冷硬铸铁，在干滑动摩擦磨损试验中，含V铸铁的耐磨性最好，含Nb铸铁次之，含W铸铁最差。钒含量为5wt%的合金铸铁，其相对耐磨性较1wt%的提高了约13倍。
对于高V合金铸铁，随着钒含量的增加，凝固过程由亚共晶转变（4wt%V）逐渐过渡到近似共晶转变（6wt%V），再到过共晶转变（8-10wt%V）。碳化物的分布由晶间分布逐渐过渡到均匀分布。高钒合金的耐磨性受基体硬度和碳化物分布的双重影响。碳化物均匀分布的V8%试样耐磨性能最好，V6%和V10%次之，V4%最差。
通过对8wt%V和5wt%Nb合金凝固组织中的钒/铌碳化物的提取，利用场发射扫描电镜、X射线、高分辨和纳米压痕等进行分析，发现高钒冷硬铸铁（V含量8wt%）中碳化钒呈树枝晶生长，是NaCl结构的c-VC，硬度和杨氏模量分别为33.3和436GPa；高铌冷硬铸铁（Nb含量5wt%）中的碳化铌呈不规则块体形貌；是具有NaCl结构的c-NbC；硬度和杨氏模量分别为24.5和406GPa。
利用第一性原理计算技术，研究了具不同化学剂量比V-C、Nb-C化合物的力学特性。计算辨明，随着C含量的增加，V-C/Nb-C化合物的剪切模量、杨氏模量和硬度单调增加，而体弹模量呈不规则变化。通过计算电子结构、布局数和原子排布分析研究了V-C/NbC化合物的弹性性质变化的起因。Nb-C体系中，Pnma-Nb2C和P3_1-Nb_6C_5是Nb-C体系相图中的基态结构，预测相Fm-3m-Nb_(23)C_6，Pnma-Nb3C，C_2/c-Nb_5C_2和P6_3mc-Nb_7C_3在热力学、动力学和力学上都是稳定的。
Indefinite Chill Double-Poured (ICDP) rolls which are widely recognized as the firstchoice for the later stand of hot rolling mill (HSM) due to its superior thermostability,good resistance to adherence and thermocracking, and wear resistance. However, as theimprovement of the early stands’ materials for rough and finish rolling as well as theextended working period, the wear resistance of the later stand is becoming insufficient.Therefore, it is an urgent task to develop enhanced ICDP roller with enhanced wearresistance. In this paper, we have added W, Nb and V element into the conventionalindefinite chill cast iron (ICCI) with the aim to increase the wear resistance, and to shedlight on the effect of those alloying elements on the microstructure and solidificationprocess of ICCI. Furthermore, in view of the pivotal role played by the micro-structureand mechanical properties of carbides in defining the wear resistance behavior of cast iron,we also investigated the crystal structure and mechanical properties of the vanadium andniobium carbides. The aim of this work is to provide theoretical and experimental basicdata for the development of ICDP roller with high wear resistance.
ICCI with12various contents of W, Nb, and V element ranges from1-5percent wereyielded by alloying. By the aid of Optical Microscopy (OM), Scanning ElectronMicroscope (SEM), X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC),wear resistance test, and Thermo-cal et al, the effect of alloying element on the solidifiedmicrostructure and properties of ICCI were investigated. Results show: the effect showsreliance on the type of alloying element. When the added W content is1-2%, there isalmost no effect on the solidified process; when the added W content is larger than3%,fishbone shape carbides (Fe_4W_2C) appears at grain boundary, but has trace influence onthe morphology of carbides that shows network shape at grain boundary. After adding Nbelement, carbides distribute in a discrete manner due to the prior precipitation of NbC.With the increase of added V alloying element, there is a gradual transformation for thecarbides from network at grain boundary (1%V), to increased refinement (2-3%), andfinally homogenously distributed in spherical and short rod-like shape.
During the tempering of1-5%alloyed cast iron samples, the hardness showssecondary hardening with the increase of tempering temperature, and peaks at about400-500℃. The maximum hardness that corresponds to W, Nb, and V alloying is HRC60,HRC59and HRC60, respectively. The wear resistance of alloyed cast iron increases withthe content of alloying element. For the different allying element, there is a gradualdecreasing trend in the sequence of V, Nb, and W. The most significant results come to the5%V alloying by which the wear resistance is improved by13times.
For the high-V alloyed cast iron, the solidified process changes from hypo-eutectic(4%V) to quasi-eutectic (6%V), and further to hyper-eutectic transformation (8-10%V).The distribution of carbides changes from inter-granular to chrysanthemum-likedistribution, and further to homogenous pattern. The wear resistance of heavy V alloyedcast iron depends not only on the hardness of matrix, but the distribution of the carbides.the8%V alloyed sample shows the highest wear resistance, followed by6%and10%Valloyed, and the4%alloyed sample shows the worst wear resistance enhancement.
By extracting the V and Nb carbides from the solidified alloyed cast iron andmicrostructure analysis method including Field Emission Scanning Electron Microscopy(FE-SEM), XRD, High Resolution Transmission Electron Microscopy (HR-TEM), andNano-indentation, We found the dendritic carbides in heavy V alloyed chilled cast iron(8%V) are cubic NaCl-type vanadium carbides (VC) whose hardness and Young modulusis33.3and436GPa, respectively. The niobium carbides (NbC) in the heavy Nb alloyedcast iron (5%Nb) also share the same crystal structure with NaCl and shows irregular bulkshape, and its hardness and Young's modulus is24.5and406GPa, respectively.
By the aid of first-principle calculation, the mechanical properties of VC and NbCwith various stoichiometries were investigated. Results show, the shear modulus, Young'smodulus and Vickers hardness increase monotonously with carbon content, but the bulkmodulus shows irregular trend. The reasons were discussed from the standpoint ofelectronic structure, Mulliken Overlap Population (MOP), and atomic configuration. In Nb-C system, pnma-Nb2C and P3_1-Nb_6C_5are found to be the ground state structures, andthe proposed phase: Fm-3m-Nb_(23)C_6, Pnma-Nb_3C, C_2/c-Nb_5C_2, and P6_3mc-Nb_7C_3areenergetically, mechanically, and dynamically stable.
引文
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