高品质低碳钢板坯连铸保护渣降Li2O的探索

Li₂O能有效改善连铸保护渣的熔化和流动性能,常用于高品质低碳钢板坯连铸保护渣的重要助熔剂。然而,近两年受下游需求强劲的影响,碳酸锂价格持续走高,增加了连铸坯生产成本。首先开展实验室研究,重点讨论了不同碱度下Li₂O对保护渣黏度和熔化温度的影响;然后分阶段开展了4轮工业试验,试验评价效果包括,结晶器铜板热电偶温度和摩擦力曲线,吨钢渣耗量和铸坯表面质量。实验室研究结果表明,当碱度为0.65～1.25时,随着Li₂O含量的增加,保护渣的熔点和黏度均呈现出降低的趋势,且黏度降低的幅度较明显。为了保证连铸顺行以及低碳钢铸坯表面质量,降低Li₂O的同时需要调整渣中Al₂O₃、Na₂O和F^-的含量,以达到协调熔渣的熔化和流动性能以及吸收Al₂O₃夹杂后性能的稳定性。优化渣的碱度为0.98、黏度为0.26 Pa·s、熔点为1 130℃,均在低碳钢保护渣性能要求范围内。原保护渣与优化渣...     

连铸保护渣渣膜矿相结构对不同钢种板坯冶金质量的影响

使用偏光显微镜,系统对比分析了邯郸钢厂超低碳钢SPHC(0.020%~0.055%C,70 mm板坯保护渣/%:33.14SiO₂,3.86Al₂O₃,3.88MgO,31.52CaO,8.27K₂O+Na₂O,7.55F^-1,3.93C)、包晶钢SS400(0.18%~0.22%C,70 mm板坯保护渣/%:29.62SiO₂,4.63Al₂O₃,2.05MgO,35.86CaO,10.43 K₂O+Na₂O,7.55F^-1,3.93C)和Ti微合金钢Q345B(0.15%~0.19C,0.04%~0.05%Ti,260 mm板坯保护渣/%:31.10SiO₂,5.21Al₂O₃,5.07MgO,35.46CaO,6.22K₂O+Na₂O,6.96F^-1,6.96C)对应的渣膜的矿相组成、结晶率和显微结构。结果表明,3种渣膜从铸坯至结晶器侧均呈现"结晶层-玻璃层"交替结构。SPHC钢渣膜有90%~95%的玻璃相,结晶相仅出现少量枪晶石,低结晶率有利于其润滑铸坯;SS400钢渣膜结晶率为55%~60%,析出较多的枪晶石和部分黄长石,有利于控制铸坯传热;Ti微合金钢Q345B渣膜结晶率略高于SS400钢,析出的黄长石、枪晶石和硅灰石能同时满足连铸对其润滑和控制传热的需求,可得到良好的铸坯质量。     

BaO对连铸保护渣熔化行为和结晶矿相的影响

实验研究和分析了BaO(2%～8%)对连铸结晶器保护渣(%:3～5MgO、1～2Al₂O₃、8Na₂O、3～4B₂O₃、2Li₂O、3～4C)熔化和结晶温度的影响以及无氟渣的结晶矿相。结果表明,随BaO含量由2%增加至8%,保护渣的熔化温度由1053℃降至1011℃,结晶温度降低较少,从954℃降至948℃;无氟渣的结晶矿相为黄长石,是铝黄长石(Ca₂Al₂SiO₇)、镁黄长石(Ca₂MgSi₂O₇)和钠黄长石(NaCaAlSi₂O₇)的固溶体,可通过调整渣膜中黄长石的析晶率,控制结晶器与坯壳间的传热。     

结晶器保护渣对300mm×360mm低碳钢连铸坯表面质量的影响和成分优化

钢厂使用原保护渣[/%:25.64CaO,22.72SiO₂,5.69MgO,8.29Al₂O₃,11.87(Na₂O+K₂O),5.49CaF₂,5.10BaO]生产的300mm×360 mm低碳钢连铸坯表面易产生网状裂纹。通过分析保护渣润滑性能与铸坯冶金质量之相关性和研究碱度、MgO和Al₂O₃对保护渣熔点的影响,CaF₂和碱土金属化合物含量对保护渣粘度影响,优化了保护渣的成分[/%:22.06CaO,23.63SiO₂,4.76MgO,8.29Al₂O₃,11.90(Na₂O+K₂O),2.32CaF₂,4.18BaO],应用结果表明,使保护渣液层的厚度由原保护渣的6~7.5 mm提高到7~10 mm,完全消除了连铸坯的网状裂纹。     

亚包晶钢板坯连铸保护渣凝固结晶行为的研究

对≤1.3 m/min常规拉速(TCaO/SiO₂=1.19)和≥1.5 m/min高拉速(TCaO/SiO₂=1.40)0.07～0.10C亚包晶钢板坯用两种保护渣(%:2.54～3.0Al₂O₃、7.34～8.35Na₂O、8.83～8.87F、0.79～3.00Li₂O)降温凝固过程中结晶特性以及结晶对熔渣粘度的影响进行了研究,得出高拉速保护渣在凝固之前有明显的结晶行为,结晶矿相主要为枪晶石(3CaO·2SiO2·CaF₂);常规拉速保护渣在凝固温度以上时,没有明显的结晶现象。与常规拉速保护渣相比,高拉速保护渣完全凝固后晶粒粗大,组织中有大量空隙,有利于增加渣膜热阻,减缓结晶器传热。TCaO/SiO₂=1.40保护渣在结晶温度以上时,具有较低的粘度,有利于结晶器润滑;结晶温度以下时,粘度迅速增加,有利于增加固渣膜厚度,减缓结晶器传热。     

CaF2和B2O3对中碳钢连铸结晶器保护渣物理性能的影响

用B₂O₃作为含氟渣中CaF2的替代熔剂,在保证两结晶器保护渣具有相近粘度和熔化温度的基础上,研究了成分为(%):31.1～35.5CaO、33.9～38.5SiO₂、12Al₂O₃、3MgO、5Na₂O、6～15CaF₂的含氟结晶器保护渣和(%):33.5～35.5CaO、36.5～39.5SiO₂、4Al₂O₃、5MgO、8～15Na₂O、2Li₂O、2～6B₂O₃的无氟结晶器保护渣的结晶温度、结晶能力以及对结晶器控制传热的影响。结果表明,8Na₂O-6B₂O₃无氟渣与5Na₂O-15CaF₂的含氟渣有相近的粘度和熔化温度,并对结晶器控制传热有相似的作用。      

Al2O3对超高碱度连铸保护渣理化性能的影响

Al₂O₃是一种两性氧化物,在高碱度条件下呈现酸性氧化物特征,而在低碱度条件下表现出碱性氧化物的行为,是冶金熔渣中常见的一种组元.以超高碱度保护渣(综合碱度R=1.75)为研究对象,分析了Al₂O₃对保护渣流动特性、熔化特性和凝固特性的影响规律.研究结果显示:渣中Al₂O₃质量分数每增加1%,熔化温度上升5℃左右,转折温度下降12℃左右,开始结晶温度平均下降11℃左右.平均结晶速率随渣中Al₂O₃质量分数的增加而减小.且随着Al₂O₃质量分数的增加,保护渣结晶矿相中晶体比例逐渐降低,但晶体保持枪晶石的种类不变.     

低碳钢薄板坯高速连铸保护渣研究与优化

 针对低碳钢薄板坯高速连铸过程中保护渣液渣层过薄、黏结报警频发、铸坯表面纵裂纹过多等问题,在充分考虑高拉速下低碳钢凝固收缩特性的基础上,确定了保护渣润滑与传热性能的优化方向并开展了工业试验。将保护渣碱度从1.10提高到1.30,Li₂O质量分数从0.57%提高到1.06%,Na₂O质量分数从5.48%提高到8.16%,碳质量分数由7.71%降低到6.72%。对2种保护渣的流变性能和渣膜3层结构进行了深入研究,发现优化后保护渣渣膜中的液渣层比例增加,渣膜润滑系数α增大;同时,渣膜中的结晶层比例也有一定程度的提高,渣膜热阻系数β增大,从而使保护渣的润滑性能和控制传热能力均得到改善。从矿相分析结果看出,保护渣碱度的提高在一定程度上会促进硅灰石的析出,导致渣膜结晶率提高、热阻增大,进而起到控制传热的目的。生产实践表明,在拉速提高后,使用新型保护渣基本避免了黏结和裂纹的产生,生产效率和铸坯质量均得到显著提高。     

无磁钢20Mn23AlV保护渣液渣和渣圈性能变化对连铸的影响

对高铝无磁钢20Mn23AIV(/%:0.14～0.20C、21.50～25.00Mn、1.50～2.50Al、0.04～0.10V)200 mm板坯连铸过程结晶器保护渣液渣和渣圈的化学组成、理化性能和结晶矿相进行了对比分析。保护渣原渣组成为(/%):31.91CaO、30.30SiO₂、6.58Al₂O₃、1.12MgO、3.02MnO、7.73Na₂0、7.10F。结果表明,连铸开浇后15 min,液渣和渣圈中的SiO₂含量分别降低至22%和18%, Al₂O₃含量分别提高至20.5%和25.5%,其碱度由原渣的1.05分别提高至1.7和2.0。此时液渣及渣圈的熔化温度和粘度大幅度增加,转折温度大幅度降低;渣圈的化学成分及理化性能的变化幅度均大于液渣。连铸开浇15 min后液渣及渣圈的成分与性能均趋于稳定。高熔点相钙铝黄长石的析出是促使渣圈形成的重要原因。     

低碱度高结晶率连铸保护渣的研究与应用

针对攀钢连铸 Q2 35 G等包晶钢生产中出现的铸坯表面裂纹问题 ,在调查分析裂纹特征及其产生原因的基础上 ,发现保护渣传热过强和保护渣流入不均是诱发角横裂产生的主要原因。通过对保护渣结晶特性的研究 ,开发出了低碱度 (Ca O/ Si O2 <1.0 )、高结晶率的新型包晶钢用连铸保护渣。工业试验表明 ,研制的保护渣具有良好的使用效果 ,所浇铸坯表面质量优良 ,铸坯裂纹较少 ,表面角横裂发生率降低到 4 .19% ,纵裂发生率为 3.4 2 % ,且保护渣润滑作用良好 ,未发生漏钢事故。     

Properties of High Basicity Mold Fluxes for Peritectic Steel Slab Casting

 In high speed continuous casting of peritectic steel slabs, mold fluxes with high basicity are required for less surface defect product. However, the basicity of remaining liquid slag film tends to decrease in casting process because of the crystallization of 3CaO·2SiO2·CaF2. Thus, a way is put forward to improve mold fluxes′ properties by raising the original basicity. In order to confirm the possibility of this method, the effect of rising original basicity on the properties of mold fluxes is discussed. Properties of high fluorine based mold fluxes with different basicities and contents of CaF2, Na2O, and MgO were measured, respectively. Then, properties of higher basicity mold fluxes were discussed and compared with traditional ones. The results show that increasing the basicity index can improve the melting and flow property of mold fluxes. With the increasing basicity, crystallization rate of mold fluxes increases obviously and crystallization temperature tends to decrease when the basicity exceeds 1.35. The method presented before is proved as a potential way to resolve the contradiction between horizontal heat transfer controlling and solidified shell lubricating for peritectic steel slab casting. But further study on improving the flow property of liquid slag is needed. This work can be used to guide mold fluxes design for high speed continuous casting of peritectic steel slabs.     

Solidification Properties of CaO-SiO2-TiO2 Based Mold Fluxes

 In continuous casting of peritectic steel grades sensitive to longitudinal cracking, the solidification properties of mold fluxes play an important role in keeping smooth running of continuous casting process and achieving high surface quality of casting strands. To reduce fluorine pollution in molten slag, types of CaO-SiO2-TiO2 (CTS) based mold fluxes were investigated. The solidification and crystallization properties, including viscosity η at 1573 K, break temperature Tbr, crystallization ratio Rc and solidification mineragraphy were measured, which were compared with those of CaO-SiO2-CaF2 based mold fluxes. The experiments show that there are unstable viscosity-high temperature properties and high Tbr in part of CTS slag system, which are bad for lubrication between liquid flux film and strand. And when temperature is below Tbr, the viscosities change slowly during cooling in some part of this slag system, which imply that liquid mold fluxes solidify slowly and it is easy to cause surface longitudinal cracks on strand. Major mineragraphy of the CaO-SiO2-TiO2 based mold fluxes are CaO·TiO2 or CaO·TiO2 and CaO·SiO2·TiO2. TiN and Ti(C,N) can be formed in mold fluxes bearing high TiO2 during the continuous casting.     

特厚板连铸保护渣系列规划

 针对特厚板连铸工艺的特点,分析了传统的中厚板连铸保护渣与特厚板连铸保护渣的作用特征差异。根据不同钢种在结晶器内的凝固特性,对新钢特厚板连铸保护渣进行了系列规划,分为高碳钢连铸保护渣、包晶钢连铸保护渣、中碳低合金钢连铸保护渣3大类。在此基础上,提出了保护渣熔化温度、黏度、转折温度、结晶比例的控制范围。生产实践表明,设计的保护渣浇铸过程结晶器内状况良好,渣面无结团、结块现象,液渣层厚度合适,保护渣消耗量正常,铸坯表面质量优良,连铸生产工艺顺行。     

无氟连铸结晶器保护渣的结晶性能

 结晶器与连铸坯间的保护渣膜直接影响着连铸坯的润滑及传热,而保护渣的结晶性能是影响润滑和传热的重要因素。通过测定保护渣的结晶温度、结晶率和结晶体几何尺寸,研究了碱度和TiO2含量对含钛无氟保护渣结晶性能的影响规律。结果表明：加大碱度和增加TiO2含量都能明显提高保护渣的结晶倾向性。     

Analysis of Crystallization Behavior of Mold Fluxes Containing TiO2 Using Single Hot Thermocouple Technique

The crystallization behavior of mold fluxes containing 0-8 mass% TiO 2 was investigated using the single hot thermocouple technique (SHTT)and X-ray diffraction (XRD)to study the possible effects on the coordination of heat transfer control and strand lubrication for casting crack-sensitive peritectic steels.Time-temperature-transforma-tion (TTT)and continuous-cooling-transformation (CCT)curves were plotted using the data obtained from SHTT to characterize the crystallization of the mold fluxes.The results showed that crystallization of the mold fluxes during isothermal and non-isothermal processes was suppressed with TiO 2 addition.From the TTT curves,it could be seen that the incubation and growth time of crystallization increased significantly with TiO 2 addition.The CCT curves showed that the crystallization temperature initially decreased,and then suddenly increased with increasing the TiO 2 content.XRD analysis suggested the presence of cuspidine in the mold fluxes with lower TiO 2 content (< 4 mass%),while both perovskite and cuspidine were detected in the mold fluxes when the TiO 2 content was increased to 8 mass%.In addition,the growth mechanisms of the crystals changed during the isothermal crystallization process from interface-controlled growth to diffusion-controlled growth with increasing the TiO 2 content.     

含氟连铸保护渣黏度检测与预测模型

采用旋转柱体法对不同类型的含氟连铸保护渣黏度进行检测,并基于Arrhenius方程通过非线性回归分析建立了新的黏度预测模型,分析了组分变化对黏度的影响。结合模型计算和实验检测,建立了CaF₂?Na₂O?Al₂O₃?CaO?SiO₂?MgO渣系的等黏度图。结果表明,与传统的含氟连铸保护渣黏度预测模型相比,该模型计算的偏差在10%以内,当渣中w（CaF₂）超过20%时,偏差逐渐增大,主要由于氟化物挥发造成炉渣成分变化,最终黏度实测值与炉渣初始成分不符,造成模型无法对黏度有效预测。此外,研究发现,CaF₂的增加能显著降低炉渣黏度,而Al₂O₃和Na₂O对黏度的影响受CaF₂含量的限制。当w(CaF₂)>17%,炉渣黏度随Al₂O₃含量增加而减小,当w(CaF₂)<17%,Al₂O₃的增加使炉渣黏度显著增大;当w(CaF₂)>11.5%,炉渣黏度随Na₂O含量增加显著下降,当w(CaF₂)<11.5%,Na₂O含量变化对黏度的影响并不明显。此外,该等黏度图表明低黏度区w(CaF₂)接近14%。通过调整等黏度图中各组分比例,可以改善保护渣的黏度和流动性,供钢铁工业应用。