工艺条件对高铬铸铁凝固组织及腐蚀行为的影响
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摘要
本文针对不同成分的高铬白口铸铁，通过改变工艺条件末研究高铬铸铁基体组织的形成特征；深入分析了工艺条件的变化对奥氏体析出量、稳定性的影响规律及对其腐蚀行为的影响；进一步探讨了高铬铸铁中碳化物的组成特征。研究结果表明：
对于含铬量为15％、碳量为2.6％的亚共晶高铬白口铸铁而言，随着冷却条件的改变，凝固组织也发生着显著的变化：在本实验条件下，当浇注尺寸为φ70×100mm时，得到了典型的亚共晶组织：马氏体+共晶组织；在砂型中浇注成尺寸为φ30×100mm高铬铸铁试样，凝固后的组织中初生奥氏体完全消失，得到全部的伪共晶组织。上述两种情况下的高铬铸铁中的初生和共晶奥氏体中固溶的碳、铬量不足以使其稳定地保留到室温，从而发生奥氏体→马氏体的转变；随着冷却速率的增大(浇注金属型中φ20×50mm和水冷φ10×25mm高铬铸铁试样)，初生奥氏体的析出量增加，共晶组织的数量减少，并且初生奥氏体中固溶的过饱和的碳、铬量增加。初生奥氏体中固溶的碳、铬量越多，奥氏体越稳定，但同时析出二次碳化物的趋势也越强。当二次碳化物未析出时，C、Cr原子的增加使初生奥氏体稳定性增加，而一旦二次碳化物析出，C、Cr原子的增加导致初生奥氏体稳定性变差。
冷却条件的改变带来高铬铸铁凝固组织的改变，相应地必然使其性能发生很大的变化，这在其耐腐蚀性能方面就有较深刻的体现。无论是对于Cr15还是Cr30高铬铸铁，快冷均使得同化学成分下的高铬铸铁的耐腐蚀性能显著增强。快冷使得Cr15高铬铸铁中奥氏体的析出量及其稳定性增强，同慢冷条件下以马氏体为基体的Cr15高铬铸铁相比，其耐腐蚀性能显著提高；对于Cr30高铬铸铁，虽然慢冷和快冷条件下得到的基体组织均为奥氏体，但快冷不仅使奥氏体中固溶的碳、铬量增加、均匀性更好，而且改善了碳化物的尺寸形态，降低了奥氏体基体与碳化物之间的电极电位差，从而从整体上显著提高了其耐腐蚀性能。
当高铬铸铁中的含铬量为15％、碳量为3.2％时，凝固组织中初生碳化物和共晶碳化物的类型均为(Fe，Cr)_7C_3型，但其中Fe、Cr原子的组成比例是有所不同的。仞生碳化物形成温度较高，C、Cr原子扩散供应充分，相应的初生碳化物的心部和边部Fe、Cr原子的组成比例一样，均为Fe_2Cr_5C_3；而对于共晶碳化物，由于其形成温度有所下降，C、Cr原子尤其是Cr原子扩散供应有所减缓，从而使共晶碳化物心部的原子组成比例仍为Fe_2Cr_5C_3，而边部原子的组成比例变为Fe_(2.4)Cr_(4.6)C_3。
The formation characteristics of matrix were studied by varying technological conditions aimed at different chemical compositions of high chromium white cast iron; the effects of technological conditions variation on austenite precipitation, its stability and corrosion-resistance behavior were analyzed profoundly; and the constituent characteristics of carbides in high chromium cast iron were further discussed. The results showed that:
As for as a 15%Cr, 2.6%C hypoeutectic white cast iron, solidified microstructure changed remarkably with increasing cooling rate: under our experimental conditions, when the pouring size of specimen was (?)70×100mm in crucible, the microstructure consisted of martensite and eutectic structure, which was typical hypoeutectic microstructure; as the pouring size was (?)30×100mm in sand mold, primary austenite disappeared and almost 100% pseudoeutectic structure was obtained. Both the primary and eutectic austenite in above-mentioned specimens were unstable due to low carbon、chromium content, thereby transforming into martensite. However, with the increase in cooling rate (that was pouring the specimen of (?)20×50mm in metallic mold and that of (?)10×25mm with hydro-cooling), the amount of primary austenite increased whereas that of eutectic structure decreased, and the amount of carbon、chromium atoms soluted in primary austenite increased. The more carbon、chromium atoms soluted in primary austenite were, the more stable austenite was, however, the tendency of secondary carbides precipitation also enhanced. The increase of carbon、chromium atoms leaded to primary austenite more stable when no secondary carbides precipitating, however, once secondary carbides precipitate, it resulted in the instability of primary austenite.
The solidified structure of high chromium cast iron changed with the cooling conditions variation, and its corrosion-resistance varied correspondingly. No matter Cr15 or Cr30 cast iron, both of them had better corrosion-resistance at rapid cooling velocity. The austenitic amounts and its stability of Cr15 cast iron increased at rapid cooling velocity, and compared with Cr15 cast iron with martensite matrix at slow cooling velocity, the corrosion-resistance of Cr15 white iron under rapid cooling conditions improved greatly; for Cr30 cast iron, although both of the matrix structure obtained at slow and rapid cooling velocity were austenite, the amount of austenite obtained at rapid cooling velocity increased, it soluted more carbon、chromium atoms and had better uniformity, which decreased the electrode potential difference between austenite matrix and carbides, and thus, the corrosion-resistance of Cr30 cast iron under rapid cooling conditions was significantly improved.
For a 15%Cr, 3.2%C white cast iron, the type of both primary and eutectic carbides was (Fe,Cr)_9C_3, however, the proportion between Fe and Cr atoms was varying. For primary carbides, because of its higher forming temperature and full diffusion of carbon and chromium atoms, its chemical formula was Fe_2Cr_5C_3; but for eutectic carbides, the chemical formula of its center was also Fe_2Cr_5C_3 ,while that of its periphery was Fe_(2.4)Cr_(4.6)C_3 due to the decrease of temperature and slowing up the diffusion of carbon、chromium atoms, especially chromium atoms.
对于含铬量为15％、碳量为2.6％的亚共晶高铬白口铸铁而言，随着冷却条件的改变，凝固组织也发生着显著的变化：在本实验条件下，当浇注尺寸为φ70×100mm时，得到了典型的亚共晶组织：马氏体+共晶组织；在砂型中浇注成尺寸为φ30×100mm高铬铸铁试样，凝固后的组织中初生奥氏体完全消失，得到全部的伪共晶组织。上述两种情况下的高铬铸铁中的初生和共晶奥氏体中固溶的碳、铬量不足以使其稳定地保留到室温，从而发生奥氏体→马氏体的转变；随着冷却速率的增大(浇注金属型中φ20×50mm和水冷φ10×25mm高铬铸铁试样)，初生奥氏体的析出量增加，共晶组织的数量减少，并且初生奥氏体中固溶的过饱和的碳、铬量增加。初生奥氏体中固溶的碳、铬量越多，奥氏体越稳定，但同时析出二次碳化物的趋势也越强。当二次碳化物未析出时，C、Cr原子的增加使初生奥氏体稳定性增加，而一旦二次碳化物析出，C、Cr原子的增加导致初生奥氏体稳定性变差。
冷却条件的改变带来高铬铸铁凝固组织的改变，相应地必然使其性能发生很大的变化，这在其耐腐蚀性能方面就有较深刻的体现。无论是对于Cr15还是Cr30高铬铸铁，快冷均使得同化学成分下的高铬铸铁的耐腐蚀性能显著增强。快冷使得Cr15高铬铸铁中奥氏体的析出量及其稳定性增强，同慢冷条件下以马氏体为基体的Cr15高铬铸铁相比，其耐腐蚀性能显著提高；对于Cr30高铬铸铁，虽然慢冷和快冷条件下得到的基体组织均为奥氏体，但快冷不仅使奥氏体中固溶的碳、铬量增加、均匀性更好，而且改善了碳化物的尺寸形态，降低了奥氏体基体与碳化物之间的电极电位差，从而从整体上显著提高了其耐腐蚀性能。
当高铬铸铁中的含铬量为15％、碳量为3.2％时，凝固组织中初生碳化物和共晶碳化物的类型均为(Fe，Cr)_7C_3型，但其中Fe、Cr原子的组成比例是有所不同的。仞生碳化物形成温度较高，C、Cr原子扩散供应充分，相应的初生碳化物的心部和边部Fe、Cr原子的组成比例一样，均为Fe_2Cr_5C_3；而对于共晶碳化物，由于其形成温度有所下降，C、Cr原子尤其是Cr原子扩散供应有所减缓，从而使共晶碳化物心部的原子组成比例仍为Fe_2Cr_5C_3，而边部原子的组成比例变为Fe_(2.4)Cr_(4.6)C_3。
The formation characteristics of matrix were studied by varying technological conditions aimed at different chemical compositions of high chromium white cast iron; the effects of technological conditions variation on austenite precipitation, its stability and corrosion-resistance behavior were analyzed profoundly; and the constituent characteristics of carbides in high chromium cast iron were further discussed. The results showed that:
As for as a 15%Cr, 2.6%C hypoeutectic white cast iron, solidified microstructure changed remarkably with increasing cooling rate: under our experimental conditions, when the pouring size of specimen was (?)70×100mm in crucible, the microstructure consisted of martensite and eutectic structure, which was typical hypoeutectic microstructure; as the pouring size was (?)30×100mm in sand mold, primary austenite disappeared and almost 100% pseudoeutectic structure was obtained. Both the primary and eutectic austenite in above-mentioned specimens were unstable due to low carbon、chromium content, thereby transforming into martensite. However, with the increase in cooling rate (that was pouring the specimen of (?)20×50mm in metallic mold and that of (?)10×25mm with hydro-cooling), the amount of primary austenite increased whereas that of eutectic structure decreased, and the amount of carbon、chromium atoms soluted in primary austenite increased. The more carbon、chromium atoms soluted in primary austenite were, the more stable austenite was, however, the tendency of secondary carbides precipitation also enhanced. The increase of carbon、chromium atoms leaded to primary austenite more stable when no secondary carbides precipitating, however, once secondary carbides precipitate, it resulted in the instability of primary austenite.
The solidified structure of high chromium cast iron changed with the cooling conditions variation, and its corrosion-resistance varied correspondingly. No matter Cr15 or Cr30 cast iron, both of them had better corrosion-resistance at rapid cooling velocity. The austenitic amounts and its stability of Cr15 cast iron increased at rapid cooling velocity, and compared with Cr15 cast iron with martensite matrix at slow cooling velocity, the corrosion-resistance of Cr15 white iron under rapid cooling conditions improved greatly; for Cr30 cast iron, although both of the matrix structure obtained at slow and rapid cooling velocity were austenite, the amount of austenite obtained at rapid cooling velocity increased, it soluted more carbon、chromium atoms and had better uniformity, which decreased the electrode potential difference between austenite matrix and carbides, and thus, the corrosion-resistance of Cr30 cast iron under rapid cooling conditions was significantly improved.
For a 15%Cr, 3.2%C white cast iron, the type of both primary and eutectic carbides was (Fe,Cr)_9C_3, however, the proportion between Fe and Cr atoms was varying. For primary carbides, because of its higher forming temperature and full diffusion of carbon and chromium atoms, its chemical formula was Fe_2Cr_5C_3; but for eutectic carbides, the chemical formula of its center was also Fe_2Cr_5C_3 ,while that of its periphery was Fe_(2.4)Cr_(4.6)C_3 due to the decrease of temperature and slowing up the diffusion of carbon、chromium atoms, especially chromium atoms.
引文
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