Al_2O_3-BaO-B_2O_3系新型高铝钢连铸保护渣的应用基础研究
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摘要
高铝钢连铸过程中保护渣的SiO2被钢中的[Al]大量还原,造成渣中Si02含量大幅减少和碱度的明显上升,生成的Al2O3进入渣中导致保护渣的熔化温度、黏度急剧增加和玻璃形态的恶化,从而对铸坯表面质量和连铸工艺顺行产生不利影响。
为此,本研究首先进行了高铝钢连铸保护渣吸收Al2O3的热力学和动力学分析,并针对宝钢20Mn23AlV高铝钢用保护渣进行计算。结果表明：20Mn23AlV高铝钢连铸过程中,为阻止钢中[Al]与保护渣中SiO2反应,当提高渣中A1203含量至30%时,要求渣中SiO2含量小于5%。渣中Al2O3含量于浇铸开始后15min内迅速增加,然后缓慢增加并趋于平衡,其增量约为23wt%。渣中A1203含量随浇铸时间的变化主要与渣中Al2O3的初始含量w0、A12O3的反应平衡含量w*、渣中Al2O3的质量传输系数kF,A12O3、钢液中Al2O3夹杂含量WM和吸收比例常数β等影响因素有关。
建立了Al2O3-BaO-B2O3三元系的活度模型,讨论了BaO/Al2O3、B2O3含量和温度对各组元活度的影响,并绘制了Al2O3-BaO-B2O3三元系的等活度曲线图。根据计算结果初步选定适合于高铝钢连铸保护渣的Al2O3-BaO-B2O3三元渣系成分范围：Al2O3:40-50%, BaO:30-40%, B2O3:10～20%。通过Al2O3-BaO-B2O3系新型高铝钢保护渣的二次通用旋转设计试验,找出了适用于高铝钢连铸的保护渣成分范围：(CaO+BaO)/Al2O3:0.7-1.1,(B2O3+SiO2):12.5-20%, CaF2:7.5-12.5%,(Na2O+Li2O):11-17%, MnO:2-6%。
根据20Mn23AlV钢种特点及连铸工艺条件对保护渣的性能要求,在Al2O3-BaO-B2O3系新型高铝钢连铸保护渣成分范围研究的基础上,开发出适用于20Mn23AlV高铝钢浇铸的保护渣,熔化温度为980℃、黏度为2.45dPa.s、结晶率为0%。浇铸后该保护渣的熔化温度为1042℃、黏度为3.11dPa.s、结晶率为15%。浇铸前后保护渣成分及性能变化不大,能够满足连铸生产的要求。
通过扫描电镜和X射线衍射分析方法对比研究了不同高铝钢连铸保护渣的结晶矿相。结果表明：CaO-Al2O3-SiO2高铝钢连铸保护渣初始SiO2含量较高,属硅酸盐网络结构,保护渣的玻璃形态较好。浇铸过程中随着保护渣Al2O3含量的增加和SiO2含量的减少,保护渣的结晶率增加,玻璃性能变差。渣中主要析出Na3MgAl Si2O8、Na4Al2Si2O9、CaAl2Si2O8、Ba2Al2Si2O8、NaAlO2、Ca7MgAl10O23” Na4Ca3(A102)10等晶体。而Al2O3-BaO-B2O3系新型高铝钢连铸保护渣B2O3含量较高,保护渣的玻璃形态较好。浇铸过程中Al2O3含量小幅增加,渣中主要析出少量的NaAlSi3O8、CaAl2Si2O8等晶体。
通过对新型高铝钢连铸保护渣及其预熔料在室温-1300℃温度范围内的热重和差热分析,发现该渣在100℃左右脱出吸附水；440℃左右发生低熔点氧化物B2O3的熔化；500-690℃温度范围内发生碳酸盐的分解；玻璃化转变温度约为840℃：950℃左右发生碳酸钠的熔化；保护渣的熔化温度约为1150℃,并伴随NaF气体的挥发。
通过对新型高铝钢连铸保护渣与普通连铸保护渣在室温-1200℃温度范围内的比热测定可得,新型高铝钢保护渣的比热由1.046J/(g·K)增至2.291J/(g·K),总吸热量约为1925.6J/g,平均热容约为1.638J/(g·K)。普通保护渣的比热由1.046J/(g·K)增至2.514J/(g·K),总吸热量约为1751.7J/g,平均热容约为1.491J/(g·K)。
本论文研究工作有以下创新之处：
(1)建立了高铝钢连铸保护渣吸收Al2O3的动力学计算模型,系统研究了浇铸过程中高铝钢连铸保护渣Al2O3含量的变化及影响因素；
(2)进行了Al2O3-BaO-B2O3三元系的活度计算,讨论了不同因素对各组元活度的影响,并绘制了等活度曲线图；
(3)针对20Mn23AlV高铝钢,研制出以Al2O3-BaO-B2O3为基础渣系的新型高铝钢连铸保护渣。
During the continuous casting of high aluminum steel, Al in the molten steel reacts with SiO2in the mold slag, which can cause SiO2in the mold slag decreased dramatically while Al2O3increased greatly. As a result, the melting temperature as well as the viscosity rised dramatically and the glass property are deteriorated. Thus, the surface quality of the slab and the continuous casting process are affected.
On the basis of thermodynamic and kinetic analysis for the change of Al2O3in the mold slag for20Mn23AlV high aluminum steel, it is found that:In order to prevent [Al] reacted with (SiC2), it is required to control the content of SiO2to be lower than5%and that of Al2O3to be more than30%. The change of Al2O3in the mold slag during continuous casting of high aluminum steel which is mainly affected by the initial Al2O3concentration w0of the mold slag, the reaction equilibrium concentration w*of Al2O3at the slag-steel interface, the mass transfer coefficient kF,Al2O3in the molten steel, and the absorption coefficient in the molten steel.
The activity model of Al2O3-BaO-B2O3ternary slag system is established, and the influence of BaO/Al2O3, B2O3content and temperature on the activity of the system is investigated. The equal activity curves of Al2O3, BaO, B2O3are obtained. According to the activity calculation of Al2O3-BaO-B2O3system, the composition for high aluminum steel mold slag is selected as Al2O3:40～50%, BaO:30-40%, B2O3:10-20%. By using the quadratic general rotary testing, the composition range for the high aluminum steel is selected as (CaO+BaO)/Al2O3:0.7-1.1,(B2O3+SiO2):12.5-20%, CaF2:7.5-12.5%,(Na2O+Li2O):11～17%, MnO:2-6%.
According to the characteristics of20Mn23AlV steel and the requirements of performance of the mold slag in the continuous casting process, a new kind of mold slag was developed for the casting of20Mn23AlV steel, which is based on the composition range of Al2O3-BaO-B2O3high aluminum mold slag. The melting temperature, the viscosity and the corresponding crystallization rate have become to be1042℃,3.11dPa.s and15%, compared to the previous980℃,2.45dPa.s, and0%before the continous casting.
By the comparative study on the crystalline morphology of the mold slag of the high aluminum steel with SEM and XRD, it is found that the silicate network structure is the main formation in the CaO-Al2O3-SiO2mold slag for high aluminum steel. During continuous casting, the crystallization rate is increased with the growing concentration of A12O3and the decrease of SiO2The main crystals as Na3MgAlSi2O8, Na4Al2Si209, CaAl2Si208, Ba2Al2Si208, NaA102, Ca7MgAl10O23, Na4Ca3(A102)10are precipitated with the increase of A12O3content. At the same time, Al203-BaO-B2O3mold slag for high aluminum steel has a high B2O3content and good noncrystalline form. The content of Al2O3only has a slight increase, and a small amount of crystals NaAlSi3O8、CaAl2Si2O8were precipitated in this mold slag during continuous casting.
Thermogravimetric analysis and differential thermal analysis of the new high aluminum steel mold slag were carried out from room temperature to1300℃. The adsorption water is removed from the mold slag at100℃; the B2O3which has a low melting temperature in the mold slag is melting at about440℃; and the carbonates in the mold slag are decomposing in the range of500-690℃. The glass transition temperature of the mold slag is about840℃. The heat absorption in the mold slag at about950℃is mainly caused by the melting of sodium carbonate. The melting temperature of the mold slag is about1150℃, and the NaF which is a volatile gas will also generate when the temperature is above the1150℃.
The specific heat capacity of the new high aluminum steel mold slag and the previous common mold slag from room temperature to1200℃is measured with the differential scanning calorimetry method. When the temperature ranges from room temperature to1200℃, the specific heat capacity of the new high aluminum steel mold slag rises from1.046J/(g-K) to2.291J/(g-K), the total heat absorption is about1925.6J/g, and the average specific heat capacity is about1.638J/(g-K). However, the specific heat capacity of the common mold slag rises from1.046J/(g-K) to2.514J/(g-K), and the total heat absorption about1751.7J/g, and the average specific heat capacity is about1.491J/(g-K).
The key innovations of this paper are as follows:
(1) A kinetic model of the absorption of the Al2O3in mold slag for high aluminum steel is set up, and the change in the concentration of Al2O3in the mold slag during continuous casting is discussed;
(2) The activity model for ternary slag system of Al2O3-BaO-B2O3is calculated, and the equal activity curves are also obtained;
(3) A new kind of mold slag which is based on the Al2O3-BaO-B2O3ternary system is developed for the high aluminum steel20Mn23AlV.
为此,本研究首先进行了高铝钢连铸保护渣吸收Al2O3的热力学和动力学分析,并针对宝钢20Mn23AlV高铝钢用保护渣进行计算。结果表明：20Mn23AlV高铝钢连铸过程中,为阻止钢中[Al]与保护渣中SiO2反应,当提高渣中A1203含量至30%时,要求渣中SiO2含量小于5%。渣中Al2O3含量于浇铸开始后15min内迅速增加,然后缓慢增加并趋于平衡,其增量约为23wt%。渣中A1203含量随浇铸时间的变化主要与渣中Al2O3的初始含量w0、A12O3的反应平衡含量w*、渣中Al2O3的质量传输系数kF,A12O3、钢液中Al2O3夹杂含量WM和吸收比例常数β等影响因素有关。
建立了Al2O3-BaO-B2O3三元系的活度模型,讨论了BaO/Al2O3、B2O3含量和温度对各组元活度的影响,并绘制了Al2O3-BaO-B2O3三元系的等活度曲线图。根据计算结果初步选定适合于高铝钢连铸保护渣的Al2O3-BaO-B2O3三元渣系成分范围：Al2O3:40-50%, BaO:30-40%, B2O3:10～20%。通过Al2O3-BaO-B2O3系新型高铝钢保护渣的二次通用旋转设计试验,找出了适用于高铝钢连铸的保护渣成分范围：(CaO+BaO)/Al2O3:0.7-1.1,(B2O3+SiO2):12.5-20%, CaF2:7.5-12.5%,(Na2O+Li2O):11-17%, MnO:2-6%。
根据20Mn23AlV钢种特点及连铸工艺条件对保护渣的性能要求,在Al2O3-BaO-B2O3系新型高铝钢连铸保护渣成分范围研究的基础上,开发出适用于20Mn23AlV高铝钢浇铸的保护渣,熔化温度为980℃、黏度为2.45dPa.s、结晶率为0%。浇铸后该保护渣的熔化温度为1042℃、黏度为3.11dPa.s、结晶率为15%。浇铸前后保护渣成分及性能变化不大,能够满足连铸生产的要求。
通过扫描电镜和X射线衍射分析方法对比研究了不同高铝钢连铸保护渣的结晶矿相。结果表明：CaO-Al2O3-SiO2高铝钢连铸保护渣初始SiO2含量较高,属硅酸盐网络结构,保护渣的玻璃形态较好。浇铸过程中随着保护渣Al2O3含量的增加和SiO2含量的减少,保护渣的结晶率增加,玻璃性能变差。渣中主要析出Na3MgAl Si2O8、Na4Al2Si2O9、CaAl2Si2O8、Ba2Al2Si2O8、NaAlO2、Ca7MgAl10O23” Na4Ca3(A102)10等晶体。而Al2O3-BaO-B2O3系新型高铝钢连铸保护渣B2O3含量较高,保护渣的玻璃形态较好。浇铸过程中Al2O3含量小幅增加,渣中主要析出少量的NaAlSi3O8、CaAl2Si2O8等晶体。
通过对新型高铝钢连铸保护渣及其预熔料在室温-1300℃温度范围内的热重和差热分析,发现该渣在100℃左右脱出吸附水；440℃左右发生低熔点氧化物B2O3的熔化；500-690℃温度范围内发生碳酸盐的分解；玻璃化转变温度约为840℃：950℃左右发生碳酸钠的熔化；保护渣的熔化温度约为1150℃,并伴随NaF气体的挥发。
通过对新型高铝钢连铸保护渣与普通连铸保护渣在室温-1200℃温度范围内的比热测定可得,新型高铝钢保护渣的比热由1.046J/(g·K)增至2.291J/(g·K),总吸热量约为1925.6J/g,平均热容约为1.638J/(g·K)。普通保护渣的比热由1.046J/(g·K)增至2.514J/(g·K),总吸热量约为1751.7J/g,平均热容约为1.491J/(g·K)。
本论文研究工作有以下创新之处：
(1)建立了高铝钢连铸保护渣吸收Al2O3的动力学计算模型,系统研究了浇铸过程中高铝钢连铸保护渣Al2O3含量的变化及影响因素；
(2)进行了Al2O3-BaO-B2O3三元系的活度计算,讨论了不同因素对各组元活度的影响,并绘制了等活度曲线图；
(3)针对20Mn23AlV高铝钢,研制出以Al2O3-BaO-B2O3为基础渣系的新型高铝钢连铸保护渣。
During the continuous casting of high aluminum steel, Al in the molten steel reacts with SiO2in the mold slag, which can cause SiO2in the mold slag decreased dramatically while Al2O3increased greatly. As a result, the melting temperature as well as the viscosity rised dramatically and the glass property are deteriorated. Thus, the surface quality of the slab and the continuous casting process are affected.
On the basis of thermodynamic and kinetic analysis for the change of Al2O3in the mold slag for20Mn23AlV high aluminum steel, it is found that:In order to prevent [Al] reacted with (SiC2), it is required to control the content of SiO2to be lower than5%and that of Al2O3to be more than30%. The change of Al2O3in the mold slag during continuous casting of high aluminum steel which is mainly affected by the initial Al2O3concentration w0of the mold slag, the reaction equilibrium concentration w*of Al2O3at the slag-steel interface, the mass transfer coefficient kF,Al2O3in the molten steel, and the absorption coefficient in the molten steel.
The activity model of Al2O3-BaO-B2O3ternary slag system is established, and the influence of BaO/Al2O3, B2O3content and temperature on the activity of the system is investigated. The equal activity curves of Al2O3, BaO, B2O3are obtained. According to the activity calculation of Al2O3-BaO-B2O3system, the composition for high aluminum steel mold slag is selected as Al2O3:40～50%, BaO:30-40%, B2O3:10-20%. By using the quadratic general rotary testing, the composition range for the high aluminum steel is selected as (CaO+BaO)/Al2O3:0.7-1.1,(B2O3+SiO2):12.5-20%, CaF2:7.5-12.5%,(Na2O+Li2O):11～17%, MnO:2-6%.
According to the characteristics of20Mn23AlV steel and the requirements of performance of the mold slag in the continuous casting process, a new kind of mold slag was developed for the casting of20Mn23AlV steel, which is based on the composition range of Al2O3-BaO-B2O3high aluminum mold slag. The melting temperature, the viscosity and the corresponding crystallization rate have become to be1042℃,3.11dPa.s and15%, compared to the previous980℃,2.45dPa.s, and0%before the continous casting.
By the comparative study on the crystalline morphology of the mold slag of the high aluminum steel with SEM and XRD, it is found that the silicate network structure is the main formation in the CaO-Al2O3-SiO2mold slag for high aluminum steel. During continuous casting, the crystallization rate is increased with the growing concentration of A12O3and the decrease of SiO2The main crystals as Na3MgAlSi2O8, Na4Al2Si209, CaAl2Si208, Ba2Al2Si208, NaA102, Ca7MgAl10O23, Na4Ca3(A102)10are precipitated with the increase of A12O3content. At the same time, Al203-BaO-B2O3mold slag for high aluminum steel has a high B2O3content and good noncrystalline form. The content of Al2O3only has a slight increase, and a small amount of crystals NaAlSi3O8、CaAl2Si2O8were precipitated in this mold slag during continuous casting.
Thermogravimetric analysis and differential thermal analysis of the new high aluminum steel mold slag were carried out from room temperature to1300℃. The adsorption water is removed from the mold slag at100℃; the B2O3which has a low melting temperature in the mold slag is melting at about440℃; and the carbonates in the mold slag are decomposing in the range of500-690℃. The glass transition temperature of the mold slag is about840℃. The heat absorption in the mold slag at about950℃is mainly caused by the melting of sodium carbonate. The melting temperature of the mold slag is about1150℃, and the NaF which is a volatile gas will also generate when the temperature is above the1150℃.
The specific heat capacity of the new high aluminum steel mold slag and the previous common mold slag from room temperature to1200℃is measured with the differential scanning calorimetry method. When the temperature ranges from room temperature to1200℃, the specific heat capacity of the new high aluminum steel mold slag rises from1.046J/(g-K) to2.291J/(g-K), the total heat absorption is about1925.6J/g, and the average specific heat capacity is about1.638J/(g-K). However, the specific heat capacity of the common mold slag rises from1.046J/(g-K) to2.514J/(g-K), and the total heat absorption about1751.7J/g, and the average specific heat capacity is about1.491J/(g-K).
The key innovations of this paper are as follows:
(1) A kinetic model of the absorption of the Al2O3in mold slag for high aluminum steel is set up, and the change in the concentration of Al2O3in the mold slag during continuous casting is discussed;
(2) The activity model for ternary slag system of Al2O3-BaO-B2O3is calculated, and the equal activity curves are also obtained;
(3) A new kind of mold slag which is based on the Al2O3-BaO-B2O3ternary system is developed for the high aluminum steel20Mn23AlV.
引文
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