钢包内衬用MgO基和Al_2O_3基耐火材料对钢质量的影响研究
摘要
随着炼钢技术的发展，特别是洁净钢、低碳和超低碳钢等品种钢生产量的大幅增长，人们对耐火材料产品的要求从单纯强调抗侵蚀和长寿命逐渐转向强调耐火材料在使用过程中尽量少“污染”钢水，对耐火材料的选择从以前主要取决于经济效果(吨钢消耗及价格等)，转向更关注冶金效果和重视耐火材料在高温使用条件下对钢质量的影响，主要包括对钢中C、S、P和H等元素以及T[O]、钢中夹杂物、央杂物形态和变性处理等方面。
本试验采用Consarc．Co．VIM中频炉，选用不同MgO基和Al_2O_3基材质耐火材料做为炉衬材料，包括Al_2O_3-MgO(MgO含量为13.81％)、MgO-Al_2O_3(MgO含量为82.93％)和MgO-CaO系列材料(MgO-CaO材料中CaO含量从10-40％)。对选定钢种(82B和ML15)进行二次冶炼(试验时采用铝脱氧，同时添加试验渣进行保护)，冶炼期间采取虹吸管和钢杯对不同冶炼时间钢水进行取样，通过化学分析和扫描电镜方法研究对钢中磷和硫的影响；采用图像分析、扫描电镜和大样电解等方法研究钢中夹杂物的变化情况；选用不同碳源材料和应用静态法，利用化学分析、光学显微镜和扫描电镜方法研究不同碳源材料及碳含量对钢水增碳的影响；采用热力学方法(利用实验数据)对钢中夹杂物成分等进行预测。
MgO基和Al_2O_3基耐火材料(包括Al_2O_3-MgO、MgO-Al_2O_3和MgO-CaO系列材料)对钢中磷和硫、央杂物以及钢水增碳的影响有很大差异。不同材质炉衬材料对钢中P、S和夹杂物的影响可以排列为Al_2O_3-MgO＜MgO-Al_2O_3＜MgO-CaO。
Al_2O_3-MgO和MgO-Al_2O_3材料对去除钢水磷和硫的作用很小，而MgO-CaO系列材料中的游离CaO对磷和硫有明显的去除效果。磷在钢中可以无限溶解，但要去除磷只能是其氧化产物(P_2O_5)进一步与游离CaO生成稳定的化合物(Ca_4P_2O_9)；而去除钢中硫主要是通过液相完成的，即MgO-CaO材料中的游离CaO与硫反应生成CaS。Ca_4P_2O_9和CaS等在冶炼过程中被吸附在MgO-CaO内衬表面或上浮至渣中达到去除钢中磷和硫的效果。
Al_2O_3-MgO材料对去除钢中夹杂物没有作用，反而由于自身被熔蚀增加夹杂物的数量；MgO-Al_2O_3材料对钢水的净化作用有限，但至少不污染钢水；MgO-CaO材料对去除央杂物有明显作用，而且CaO含量越高作用越明显，试验条件下CaO含量大于30％时的效果最明显。
根据钢水各组元的实际活度与范特霍夫等温式ΔG=ΔG~θ+RTlnJ，可以计算一定温度下钢液中各反应实际反应自由能ΔG，从而判断可能形成的非金属夹杂物种类以及各种央杂物的生成条件。理论计算与实际检测结果基本吻合，即在已知钢液、炉渣和耐火材料成分以及钢中T[O]含量的基础上，可以通过热力学计算预测央杂物的成分。
MgO-CaO-C砖对钢中增碳研究表明，MgO-CaO-C砖碳含量越高，则碳向钢中溶解的速率越快且总量越大，对钢水的增碳作用越明显。采用炭黑作为碳源材料时对钢水的增碳率小于用传统天然鳞片石墨时的值。
With the development and requirements of clean steel, low carbon and ultra-lowcarbon steel in recent years, the study of refractory focus on the impacts of refractoryon the steel quality at high temperature, including C, S, P, N, H, T[O] and inclusions,rather than corrosion resistance and long life, i.e., refractory cost and consumption inthe past.
The intermediate frequency furnace with type of Consarc.Co.VIM is adopted inthe study. The MgO based and Al_2O_3 based refractorys are used for the lining, includingAl_2O_3-MgO(13.81%MgO), MgO-Al_2O_3 (82.93%MgO)and MgO-CaO with CaOcontent variation from 10% to 40%. The following steel grades, 82B, ML15 and pureiron are remelted with aluminum deoxidization and slag protection. The samplers aretaken by silica glass tube and steel cup during the melting process. Afterwards, theimpacts of refractory on steel, P, S and inclusions are analyzed by image analyzer, SEM,SLIM etc. Moreover, the phenomenon and mechanism of carbon pick-up areinvestigated with static method and different types of carbon by chemical analyses,optical microscope and SEM. Finally, the thermodynamic calculation is used forinclusions composition prediction.
The MgO based and Al_2O_3 based refractorys, including Al_2O_3-MgO, MgO-Al_2O_3and MgO-CaO lining have greatly impacts on steel quality, P, S, inclusions and carbonpick-up. It can be ranked as follows, Al_2O_3-MgO＜MgO-Al_2O_3＜MgO-CaO.
The results demonstrate that Al_2O_3-MgO and MgO-Al_2O_3 lining contribute little toP and S removal in the melt, however, MgO-CaO lining shows strong ability ofremoving P and S due to the dissociated CaO. P can dissolve into the steel infinitely,nevertheless,P can only be removed by the reaction between P_2O_5 and dissociated CaOto form stable compound, Ca_4P_2O_9. The mechanism of S removal is through liquid, inother words, the dissociated CaO in MgO-CaO lining reacted with sulphur to form CaS.Afterwards, Ca_4P_2O_9 and CaS is absorbed on the surface of MgO-CaO lining or float to the slag, and then the S and P is eliminated from the molten steel.
Al_2O_3-MgO has no effect on inclusion removal; on the contrary, it can increaseinclusions in the molten steel due to its erosion. MgO-Al_2O_3 lining contributes tocleaning the steel a little, in other words, it doesn't contaminate molten steel at least.MgO-CaO lining has strong ability of reducing inclusions, and it become obvious withCaO content increasing. The best effect appeared at 30% CaO in present trial.
The free energy AG at certain temperature can be calculated by element activity inthe melt and Van't Hoff isothermal equationΔG=ΔG~θ+RTlnJ, thus inclusion type andcorresponding condition can be predicted. The theorchical calculation is in a goodagreement with trial results, i.e., the inclusions composition can be forecasted bythermodynamic calculation while the composition of molten steel, slag and refractoryand the content of oxygen are predictable.
The investigation the influence of MgO-CaO-C bricks on carbon pick-up in thesteel indicates that the amount of carbon pick-up goes up with carbon content inMgO-CaO-C bricks, which promote the rate and total amount of carbon dissolution intomolten steel. By substituting charcoal for flake graphite, the extent of carbon pick-up inthe melt is reduced.
本试验采用Consarc．Co．VIM中频炉，选用不同MgO基和Al_2O_3基材质耐火材料做为炉衬材料，包括Al_2O_3-MgO(MgO含量为13.81％)、MgO-Al_2O_3(MgO含量为82.93％)和MgO-CaO系列材料(MgO-CaO材料中CaO含量从10-40％)。对选定钢种(82B和ML15)进行二次冶炼(试验时采用铝脱氧，同时添加试验渣进行保护)，冶炼期间采取虹吸管和钢杯对不同冶炼时间钢水进行取样，通过化学分析和扫描电镜方法研究对钢中磷和硫的影响；采用图像分析、扫描电镜和大样电解等方法研究钢中夹杂物的变化情况；选用不同碳源材料和应用静态法，利用化学分析、光学显微镜和扫描电镜方法研究不同碳源材料及碳含量对钢水增碳的影响；采用热力学方法(利用实验数据)对钢中夹杂物成分等进行预测。
MgO基和Al_2O_3基耐火材料(包括Al_2O_3-MgO、MgO-Al_2O_3和MgO-CaO系列材料)对钢中磷和硫、央杂物以及钢水增碳的影响有很大差异。不同材质炉衬材料对钢中P、S和夹杂物的影响可以排列为Al_2O_3-MgO＜MgO-Al_2O_3＜MgO-CaO。
Al_2O_3-MgO和MgO-Al_2O_3材料对去除钢水磷和硫的作用很小，而MgO-CaO系列材料中的游离CaO对磷和硫有明显的去除效果。磷在钢中可以无限溶解，但要去除磷只能是其氧化产物(P_2O_5)进一步与游离CaO生成稳定的化合物(Ca_4P_2O_9)；而去除钢中硫主要是通过液相完成的，即MgO-CaO材料中的游离CaO与硫反应生成CaS。Ca_4P_2O_9和CaS等在冶炼过程中被吸附在MgO-CaO内衬表面或上浮至渣中达到去除钢中磷和硫的效果。
Al_2O_3-MgO材料对去除钢中夹杂物没有作用，反而由于自身被熔蚀增加夹杂物的数量；MgO-Al_2O_3材料对钢水的净化作用有限，但至少不污染钢水；MgO-CaO材料对去除央杂物有明显作用，而且CaO含量越高作用越明显，试验条件下CaO含量大于30％时的效果最明显。
根据钢水各组元的实际活度与范特霍夫等温式ΔG=ΔG~θ+RTlnJ，可以计算一定温度下钢液中各反应实际反应自由能ΔG，从而判断可能形成的非金属夹杂物种类以及各种央杂物的生成条件。理论计算与实际检测结果基本吻合，即在已知钢液、炉渣和耐火材料成分以及钢中T[O]含量的基础上，可以通过热力学计算预测央杂物的成分。
MgO-CaO-C砖对钢中增碳研究表明，MgO-CaO-C砖碳含量越高，则碳向钢中溶解的速率越快且总量越大，对钢水的增碳作用越明显。采用炭黑作为碳源材料时对钢水的增碳率小于用传统天然鳞片石墨时的值。
With the development and requirements of clean steel, low carbon and ultra-lowcarbon steel in recent years, the study of refractory focus on the impacts of refractoryon the steel quality at high temperature, including C, S, P, N, H, T[O] and inclusions,rather than corrosion resistance and long life, i.e., refractory cost and consumption inthe past.
The intermediate frequency furnace with type of Consarc.Co.VIM is adopted inthe study. The MgO based and Al_2O_3 based refractorys are used for the lining, includingAl_2O_3-MgO(13.81%MgO), MgO-Al_2O_3 (82.93%MgO)and MgO-CaO with CaOcontent variation from 10% to 40%. The following steel grades, 82B, ML15 and pureiron are remelted with aluminum deoxidization and slag protection. The samplers aretaken by silica glass tube and steel cup during the melting process. Afterwards, theimpacts of refractory on steel, P, S and inclusions are analyzed by image analyzer, SEM,SLIM etc. Moreover, the phenomenon and mechanism of carbon pick-up areinvestigated with static method and different types of carbon by chemical analyses,optical microscope and SEM. Finally, the thermodynamic calculation is used forinclusions composition prediction.
The MgO based and Al_2O_3 based refractorys, including Al_2O_3-MgO, MgO-Al_2O_3and MgO-CaO lining have greatly impacts on steel quality, P, S, inclusions and carbonpick-up. It can be ranked as follows, Al_2O_3-MgO＜MgO-Al_2O_3＜MgO-CaO.
The results demonstrate that Al_2O_3-MgO and MgO-Al_2O_3 lining contribute little toP and S removal in the melt, however, MgO-CaO lining shows strong ability ofremoving P and S due to the dissociated CaO. P can dissolve into the steel infinitely,nevertheless,P can only be removed by the reaction between P_2O_5 and dissociated CaOto form stable compound, Ca_4P_2O_9. The mechanism of S removal is through liquid, inother words, the dissociated CaO in MgO-CaO lining reacted with sulphur to form CaS.Afterwards, Ca_4P_2O_9 and CaS is absorbed on the surface of MgO-CaO lining or float to the slag, and then the S and P is eliminated from the molten steel.
Al_2O_3-MgO has no effect on inclusion removal; on the contrary, it can increaseinclusions in the molten steel due to its erosion. MgO-Al_2O_3 lining contributes tocleaning the steel a little, in other words, it doesn't contaminate molten steel at least.MgO-CaO lining has strong ability of reducing inclusions, and it become obvious withCaO content increasing. The best effect appeared at 30% CaO in present trial.
The free energy AG at certain temperature can be calculated by element activity inthe melt and Van't Hoff isothermal equationΔG=ΔG~θ+RTlnJ, thus inclusion type andcorresponding condition can be predicted. The theorchical calculation is in a goodagreement with trial results, i.e., the inclusions composition can be forecasted bythermodynamic calculation while the composition of molten steel, slag and refractoryand the content of oxygen are predictable.
The investigation the influence of MgO-CaO-C bricks on carbon pick-up in thesteel indicates that the amount of carbon pick-up goes up with carbon content inMgO-CaO-C bricks, which promote the rate and total amount of carbon dissolution intomolten steel. By substituting charcoal for flake graphite, the extent of carbon pick-up inthe melt is reduced.
引文
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