Viscosity and Viscosity Estimate Model of Fluoride-free and Titanium-Bearing Mold Fluxes

The relationship between the binary basicity (CaO/SiO2),TiO2,Na2O,Li2O,MgO,MnO,B2O3 and viscosity for fluoride-free and titanium-bearing mold fluxes were systematically researched. The rotating cylinder method was employed in the experiment to measure the viscosity of the slag. The results indicate that Li2O, B2O3 and Na2O play major roles in decreasing viscosity, especially Li2O, which is the most effective flux, while MgO and MnO exert little influence on viscosity. Meanwhile, it can be concluded that with increasing TiO2 content, the viscosity of fluoride-free and titanium-bearing mold fluxes increases at first but then falls when the amount of TiO2 is greater than 6.0%. Based on large amounts of experimental statistics of the viscosity of fluoride-free and titanium-bearing mold fluxes, an available model in literature for predicting the mold-slag viscosity was modified. This modified model can be used to predict the viscosity of fluoride-free and titanium-bearing mold fluxes. In fact, the predicted values approximate the observed values with a ±10.6% average deviation. Compared with the classical models,the average deviation is higher and it was found that the modified model can be used to estimate the viscosity of fluoride-free and titanium-bearing mold fluxes.     

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。     

Effect of Strong Basic Oxide (Li_2O, Na_2O, K_2O and BaO) on Property of CaO-Based Flux

Intraditionalconvertersteelmakingprocess ,therephosphorizationofliquidsteelcausedbyladleslagstakesplacebecausetheoxidabilityandbasicityofslagsaredecreasedwhenthedeoxidizingandal loyingoperationsofsteelarecarriedoutinladle .Atpresent ,mainmeasuresofcontrollingrephosphori zationincludeincreasingoriginalbasicityandoxid abilityofslags ,whichcanincreasethemeltingpoint ,viscidityofslagsandtheamountofworkfordeoxidizationandalloyforalloying .Atthesametime ,theslagswithhighoxidabilityincreasetheox ygen…     

LF精炼渣低氟化研究进展

萤石对环境的污染日益受到重视,为了减少在精炼过程中CaF2的使用量,达到精炼渣低氟、无氟化的目的,开展了相关研究。综述了铝酸钙基精炼渣的性能以及B2O3,Li2O,BaO等替代物对精炼渣熔化温度、黏度以及脱硫能力、耐火材料侵蚀的影响。已有研究表明,使用铝酸钙基精炼渣能够有效降低CaF2的使用量,并具有良好的熔化性、发泡性以及脱硫性能;B2O3,Li2O,BaO等替代物都能够降低精炼渣的熔化温度和黏度,Li2O和BaO的加入增加了渣中O2-的活度,有利于提高精炼渣的脱硫能力。此外,精炼渣黏度的降低也促进了渣金界面反应的发生以及钢液中夹杂物的吸收。     

Crystallization Temperature and Crystallization Ratio of Mold Flux

Moldfluxformsaliquidphaseinfiltratinginto thegapbetweenthemoldandstrand.Thelayerof fluxfilmonthemoldplateisasolidglassylayer,whilethelayerclosesttothestrandremainsliquid andacrystallizationlayerliesbetweenthistwolay ers[1-3].Thecrystallizationtemperatureo…     

稀土氧化物对连铸保护渣结晶温度的影响

为了解决稀土钢浇注时因稀土氧化物进入保护渣导致保护渣性能改变的问题,用热重一差热分析仪系统地观测了稀土氧化物对不同碱度及BaO、B2O3和Li2O含量的保护渣结晶温度的影响。结果表明,稀土氧化物对保护渣结晶温度影响显著,特别是稀土氧化物从零增至5％时最为明显。随着稀土氧化物含量的继续增加,保护渣结晶温度缓慢升高。低碱度可以抑制保护渣中稀土矿物初生晶核的析出;BaO有利于稀土氧化物在保护渣中的溶解和扩散;B2O3基本上可消除稀土氧化物引起的保护渣结晶温度升高的不良影响;Li2O可阻止高熔点结晶相的析出,降低含稀土氧化物保护渣的结晶温度。     

BaO 和 Li2O 对 CaO 基脱硫精炼渣熔点和粘度的影响

以CaO(bal)-SiO₂(22.4%)-Al₂O₂(11.6%)-CaF₂(10%)精炼渣作为基础渣系,用BaO、Li₂O替代其中等量的CaO含量,固定(CaO+RxO)/SiO₂=2.5(RxO代表BaO或者Li₂O),对该脱硫精炼渣系的熔点和粘度进行了研究。结果显示在传统的CaO基熔渣中加入BaO、Li₂O可以降低渣系的熔点和粘度,有效地改善了渣钢反应的动力学条件。当(BaO,Li₂O)=15%时,熔渣的熔点分别为1267℃和1185℃,远低于不加添加剂时的熔点1326℃,当温度为1475℃时,熔渣粘度分别为0.98Pa·s和0.51Pa·s,远小于不加添加剂时的粘度1.79Pa·s,使渣系具有良好的流动性和熔化性能。     

B2O3在CaO-BaO-SiO2-Al2O3-CaF2精炼渣中的作用

选择w（CaO）=46％，w（BaO）=10％，w（SiO2）=11．2％，w（Al2O3）=11．6％的渣作基础渣系，将B2q作助熔剂替代CaF2，发现B2q和CaF2的助熔效果相当，B2q可用作环保型助熔剂。将CaO-SiO2-BaO-Al2O3-CaF2作基础渣系，B2O3作酸性氧化物，在碱度（m（CaO＋BaO）／m（SiO2＋B2O3））为2．5和2．8时，研究B2O3替代SiO2后精炼渣的熔化性能。结果表明，B2O3替代25％的SiO2后就可大幅度降低粘度，并且发现富硼精炼渣的高温熔化性能稳定，粘度值稳定在0．3～0．5Pa·s。在碱度为2．8wt进行脱硫工艺实验，当w（SiO2）=20．6％时渣剂脱硫率为80％，当w（SiO2）=10．3％，w（B2O3）=10．3％时渣剂脱硫率为91．3％，主要原因是熔化性能良好的熔渣有助于提高传质速率。     

Viscosity and Viscosity Estimate Titanium-Bearing Model of Fluoride-Free and Mold Fluxes

The relationship between the binary basicity (CaO/SiO₂), TiO₂, Na₂O, Li₂O, MgO, MnO, B₂O₃ and viscosity for fluoride-free and titanium-bearing mold fluxes were systematically researched. The rotating cylinder method was employed in the experiment to measure the viscosity of the slag. The results indicate that Li₂O, B₂O₃ and Na₂O play major roles in decreasing viscosity, especially Li₂O, which is the most effective flux, while MgO and MnO exert little influence on viscosity. Meanwhile, it can be concluded that with increasing TiO₂ content, the viscosity of fluoride-free and titanium-bearing mold fluxes increases at first but then falls when the amount of TiO₂ is greater than 6.0%. Based on large amounts of experimental statistics of the viscosity of fluoride-free and titanium-bearing mold fluxes, an available model in literature for predicting the mold-slag viscosity was modified. This modified model can be used to predict the viscosity of fluoride-free and titanium-bearing mold fluxes. In fact, the predicted values approximate the observed values with a ±10.6% average deviation. Compared with the classical models, the average deviation is higher and it was found that the modified model can be used to estimate the viscosity of fluoride-free and titanium-bearing mold fluxes.     

连铸低合金钢用保护渣的研制与应用

针对攀钢连铸低合金钢生产中出现的问题,在分析稀土氧化物对保护渣性能影响及稀土元素与熔渣反应的基础上,通过原材料的选择、熔剂对保护渣性能作用规律的研究,设计了具有较强吸收溶解稀土氧化物能力,并且组元不与稀土元素反应的保护渣,经工业试验表明,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,铸坯表面无清理率大于９０％,保护渣润滑作用良好,漏钢发生率低。     

高速连铸用保护渣

本文论述了与高速连铸密切相关的保护渣技术。指出高速连铸与常速连铸用保护渣在其物理性能上有较大差异。高速连铸保护渣应具有较低的粘度,较低的结晶、软化及熔融温度,合适的碱度以及较快的熔化速度。配制高速连铸保护渣时应限制CaF_2,Na_2O的加入量,适量添加BaO,B_2O_3,Li_2O,K_2O和MgO等助熔剂是有益的。     

高铝钢用低反应型保护渣成分对其黏度的影响

摘要：汽车轻量化有助于保护环境、节约能源,高铝钢有利于减轻汽车质量同时维持强塑性。但由于连铸过程中传统结晶器保护渣界面反应的制约,高合金钢铸坯质量和操作流畅性受到很大影响,引起裂纹、漏钢等问题。不仅会造成安全事故,还会增加成本。低反应型CaO Al2O3系保护渣相对于传统保护渣,SiO2质量分数在6%~10%之间,［Al］和(SiO2)渣钢界面反应程度显著减弱,具有提高铸坯质量和确保操作顺行的潜力。设计此类保护渣时应该考虑渣钢界面反应、渣中元素向钢液中富集对铸坯质量的影响以及可能的结晶相种类。探讨了低反应型保护渣中成分对黏度变化机制的影响,即熔渣结构的变化、渣系过热度的变化和结晶相的变化。分别讨论了CaO/Al2O3、B2O3、Na2O、Li2O和CaF2在CaO Al2O3渣系中的作用,旨在为满足高铝钢连铸生产的新一代低反应型保护渣系的设计与优化提供思路与便利。     

Viscous properties of new mould flux based on aluminate system with CeO_2 for continuous casting of RE alloyed heat resistant steel

The conventional mould fluxes can not be applied to the continuous casting of RE alloyed heat resistant steel, because severe slag-metal interface reactions occur generally in the mold. To restrain the interface reaction and improve conditions for continuous casting, a new mould flux based on aluminate system was devised. The viscous properties were investigated. Scanning electron microscopy and X-ray diffraction were applied to detect and characterize the crystalline phases in the continuous cooling process. The results showed that appropriate addition of CeO_2 could avoid the precipitation of CaO and decrease the viscosity of the mould flux. Increasing the mass ratio of CaO /Al_2O_3, especially to a value exceeding 1, could worsen the stability of the mould flux. With a content of less than 14 wt.%, Li_2O could reduce the viscosity and breaking temperature, but its effect could be weakened for the promoted precipitation of LiAlO_2. To obtain a mould flux with stable viscous properties, such as viscosity and breaking temperature, appropriate contents of CeO_2 and Li_2O should be controlled to around 10 wt.% and 14 wt.%, while the mass ratio of CaO /Al_2O_3 should not be more than 1.     

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。      

Study on Properties of Alumina‐Based Mould Fluxes for High‐Al Steel Slab Casting

During the continuous casting of high‐Al steel, the dynamic reduction of silica‐based mould fluxes by the aluminium in the steel leads to changes in their composition and physical properties. The alumina‐based mould flux has been suggested as an alternative to alleviate this reduction problem. However, until now, the smooth running of high‐Al steel continuous casting has been impeded by the lack of systematic investigation of properties of this slag. In this paper, the effects of typical components on the properties of alumina‐based mould fluxes are discussed. The experimental results show that: (a) an increase in F^? can reduce the viscosity while increasing the melting and break temperatures; (b) with increasing Li₂O, the viscosity, melting temperature, and break temperature first decrease and then increase; (c) with the addition of BaO, the viscosity, melting temperature, and break temperature remain at a low level, while a further increase in BaO causes a decrease in viscosity, an increase in melting temperature, and the stabilization of the break temperature; (d) BaO is favorable to stabilize the properties of mould fluxes for the dissolution of additional Al₂O₃; (e) the crystalline phases of the mould fluxes mainly contain 12CaO · 7Al₂O₃ and 11CaO · 7Al₂O₃ · CaF₂, and 12CaO · 7Al₂O₃ has great potential as a substitute for cuspidine.     

特殊组分对低氟保护渣凝固温度和结晶性能的影响

 氟含量过高的连铸保护渣不仅加剧伸入式水口的侵蚀，而且对连铸操作环境带来危害，为了降低保护渣中过高的氟含量，需要开发低氟或无氟保护渣。为避免保护渣中氟含量降低后性能指标的恶化，需要寻求氟化物的替代组分以协调保护渣各项冶金功能的正常发挥。为此，以高氟保护渣为参照点，设计了4组低氟连铸结晶器保护渣渣样。通过检测这些渣样的熔点、粘度、转折温度、结晶温度和结晶率，分析和比较实验数据发现，在不同碱度下，B2O3、Li2O、Cr2O3、TiO2均能部分替代渣中的CaF2，获得CaF2质量分数为45%的低氟保护渣。CeO2不能作为保护渣中CaF2的替代组分。     

CCT and TTT Diagrams to Characterize Crystallization Behavior of Mold Fluxes

The isothermal and non-isothermal experiments were performed to construct the continuous cooling transformation （CCT） and temperature time transformation （TTT） diagrams of four industrial mold fluxes through visual observations in an experimental apparatus based on the single hot thermocouple technique （SHTT）. The results of the CCT diagrams indicate that ① the crystallization temperature of mold fluxes lowers as the cooling rate increases, ② the mold fluxes have larger critical cooling rate, higher crystallization temperature, and less onset time of crystallization when the basicity increases or the viscosity decreases, ③ the influences of the melting points of the mold fluxes on their crystallization tendency are not significant. Isothermal tests show that the onset time of crystallization decreases at first, and then increases, and finally represents a ＂C＂ shape with increasing isothermal temperature. The TTT diagrams of four industrial mold fluxes were divided into two separate ＂C＂ shape regions. The crystal phase of C20A selected was analyzed by X-ray diffraction, which is cuspidine （Ca4 Si2 O7F2 ） over I 100 ℃ and calcium silicon oxide fluoride （Ca2SiO2F2） below 1 100℃. When compared with the TTT diagram, the CCT diagram can provide a more realistic estimate of the critical cooling rate of the mold fluxes. Thus, both the CCT and TTT diagrams can unambiguously describe the crystallization phenomena of the mold fluxes.     

Li2O对CaO-Al2O3基保护渣结晶性能的影响

摘要：高铝钢用新型CaO-Al2O3基连铸结晶器保护渣结晶性能较强，在连续浇铸过程中易出现润滑与传热功能协调不均的问题。基于此，针对新型CaO-Al2O3基保护渣，考察了典型助熔剂Li2O对保护渣析晶温度、析晶物相等性能的影响，并进行了相关结晶动力学分析。结果表明，提高Li2O含量可使保护渣的临界冷却速率和初始结晶温度呈现先降低后升高的趋势，当Li2O质量分数为4%时，保护渣结晶倾向最弱。随Li2O质量分数从0增至6%，保护渣的结晶孕育时间先延长后缩短。析晶物相由CaAl4O7+CaF2转变为CaAl4O7+CaF2+LiAlO2，Li2O的加入及其含量的提高促进了LiAlO2的析出。此外，随Li2O质量分数从0增至6%，保护渣结晶活化能先增大后减小，析晶过程受到的阻力先增强后减弱，与结晶性能的变化规律相吻合。     

连铸保护渣组分对粘度的影响

根据合金钢连铸保护渣多组分组成特点,设计了CaO-SiO2-Na2O-CaF2-Al2O3-MgO-MnO-BaO渣系,研究了该渣系组成与粘度的关系。研究结果表明,该渣系保护渣的粘度在CaO/SiO2=0.6~1.1、CaF2=5%~15%、Na2O=2%~10%、MgO=0~5%、MnO=0~5%、BaO=0~7%范围内随着含量增加而降低;在MgO=5%~8%、MnO=5%~8%、BaO=7%~12%范围内,连铸保护渣的粘度基本不变。通过研究还得出了粘度与组分之间的回归方程,对连铸保护渣的设计具有积极的指导意义。     

Crystallization Behavior in Fluoride-Free Mold Fluxes Containing TiO2/ZrO2

  The time temperature transformation (TTT) diagrams of fluoride free mold fluxes containing TiO2/ZrO2 were constructed through the confocal scanning laser microscope (CSLM) technique. It was found that the crystallization temperature of F free mold fluxes containing TiO2 or ZrO2 increases, while incubation time decreases with increasing basicity. The crystallization tendency increases with the zirconia addition in slag melt, as it may be thought that the addition solubility is limited in molten slag and the solid particles act as heterogeneous nucleation sites. Three types of crystal morphologies were observed, corresponding to different crystallization mechanisms. CaSiO3 and Ca3Si2O7 precipitate in the slag with low basicity, and Ca2SiO4 was formed with increasing basicity. The addition of TiO2 promotes the precipitation of CaTiO3. The logarithm of crystal growth rate increased with increasing isothermal temperature, suggesting that the crystal/melt interface reaction is the controlling step in the present experiment.