A Kinetic Study of the Effect of Basicity on the Mold Fluxes Crystallization

The effect of basicity on the mold fluxes crystallization was investigated in this article. The time-temperature-transformation (TTT) diagrams and continuous-cooling-transformation (CCT) diagrams of mold fluxes with different basicity were constructed by using single, hot thermocouple technology (SHTT). The results showed that with the increase of basicity, the incubation time of isothermal crystallization became shorter, the crystallization temperature was getting higher, and the critical cooling rate of continuous cooling crystallization became faster. The X-ray diffraction analysis suggested that calcium silicate (CaO·SiO₂) was precipitated at the upper part of the TTT diagram and cuspidine (Ca₄Si₂O₇F₂) was formed at the lower part, when the basicity of mold fluxes was within 1.0 to 1.2. However, when basicity was 0.8, only the cuspidine phase was formed. A kinetic study of isothermal crystallization process indicated that the increase of the basicity tended to enhance the mold flux crystallization, and the crystallization activation energy became smaller. The crystallization mechanism of cupsidine was changing from one-dimensional growth to three-dimensional growth with a constant number of nuclei, when the basicity of mold fluxes varied from 0.8 to 1.2.     

Effects of Basicity and B2O3 on the Crystallization and Heat Transfer Behaviors of Low Fluorine Mold Flux for Casting Medium Carbon Steels

An investigation was carried out to study the effects of basicity (CaO/Si₂O) and B₂O₃ on the crystallization and heat transfer behaviors of low fluorine mold flux for casting medium carbon steels. The double hot thermocouple technique (DHTT) was employed to study the crystallization behavior of mold flux with a different basicity and B₂O₃ content, under the simulated thermal gradient as in a real caster. The infrared emitter technique (IET) was also applied for the study of heat transfer behavior of the above mold fluxes. By combining the results of IET and DHTT, this article indicated that the increase of basicity would decrease the general heat transfer rate of mold flux, as it tends to promote crystallization of mold flux apparently, while B₂O₃ has the opposite function. The combined effects of basicity and B₂O₃ could be used to adjust the general crystallization and heat transfer properties of low fluorine mold flux for casting medium carbon steels, which would provide an instructive way for the design of Fluorine free mold flux for casting medium carbon steels.     

Crystallization Characteristics of CaO-Al2O3-Based Mold Flux and Their Effects on In-Mold Performance during High-Aluminum TRIP Steels Continuous Casting

Crystallization behaviors of the newly developed lime-alumina-based mold fluxes for high-aluminum transformation induced plasticity (TRIP) steels casting were experimentally studied, and compared with those of lime-silica-based mold fluxes. The effects of mold flux crystallization characteristics on heat transfer and lubrication performance in casting high-Al TRIP steels were also evaluated. The results show that the crystallization temperatures of lime-alumina-based mold fluxes are much lower than those of lime-silica-based mold fluxes. Increasing B₂O₃ addition suppresses the crystallization of lime-alumina-based mold fluxes, while Na₂O exhibits an opposite effect. In continuous cooling of lime-alumina-based mold fluxes with high B₂O₃ contents and a CaO/Al₂O₃ ratio of 3.3, faceted cuspidine precipitates first, followed by needle-like CaO·B₂O₃ or 9CaO·3B₂O₃·CaF₂. In lime-alumina-based mold flux with low B₂O₃ content (5.4 mass pct) and a CaO/Al₂O₃ ratio of 1.2, the formation of fine CaF₂ takes place first, followed by blocky interconnected CaO·2Al₂O₃ as the dominant crystalline phase, and rod-like 2CaO·B₂O₃ precipitates at lower temperature during continuous cooling of the mold flux. In B₂O₃-free mold flux, blocky interconnected 3CaO·Al₂O₃ precipitates after CaF₂ and 3CaO·2SiO₂ formation, and takes up almost the whole crystalline fraction. The casting trials show that the mold heat transfer rate significantly decreases near the meniscus during the continuous casting using lime-alumina-mold fluxes with higher crystallinity, which brings a great reduction of surface depressions on cast slabs. However, excessive crystallinity of mold flux causes poor lubrication between mold and solidifying steel shell, which induces various defects such as drag marks on cast slab. Among the studied mold fluxes, lime-alumina-based mold fluxes with higher B₂O₃ contents and a CaO/Al₂O₃ ratio of 3.3 show comparatively improved performance.     

Physicochemical Properties of CaO–SiO2–CaF2–NaF Slag system as a Mold Flux of Continuous Casting

The phase diagrams of CaO–SiO₂–CaF₂ and CaO–SiO₂–CaF₂–NaF systems were determined as a base system of mold fluxes. The commercial fluxes have the composition in which cuspidine first crystallizes. The thermodynamic stability of cuspidine was examined from the standard Gibbs energy of formation of cuspidine, which was measured, by two methods of the Galvanic cell method and the transpiration method. The effect of fluorine to silicate network was investigated. It is indicated that CaF₂ behaves as a neutral solvent for silicate slag. The crystallization in mold fluxes was measured by a high temperature XRD. Cuspidine predominantly appears because the construction of silicate glass with CaF₂ has CaF⁺ ion pair near non‐bridging oxygen. The over addition of Na₂O to mold flux prevents cuspidine from crystallizing.     

Effect of Li<Subscript>2</Subscript>O on the Behavior of Melting,Crystallization, and Structure for CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Based Mold Fluxes

The effect of Li₂O content on the behavior of melting, crystallization, and molten structure for CaO-Al₂O₃-based mold fluxes was investigated in this article, through use of single hot thermocouple technology (SHTT), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray diffraction (XRD). The SHTT results showed that the melting temperature range of the designed mold fluxes decreases and the crystallization of mold fluxes is inhibited first and then becomes enhanced when the Li₂O content increases from 1 to 6 mass pct. The FTIR and Raman spectroscopy results suggested that Li₂O could release O^2? ions to break the complex Al-O-Al structural unit into Al-O^? structure. Meanwhile, Li₂O could also stabilize the structural unit of Si-O-Al by link aluminate and Q ₀ ^Si structure through providing Li⁺ ions to merge into the network and compensate for the charges between Al³⁺ and Si⁴⁺. Besides, the XRD results indicated that the precipitation of LiAlO₂ in molten slag would enhance the crystallization behavior of mold flux when Li₂O content is over 4.5 mass pct.     

In-situ Crystallization of Highly Volatile Commercial Mold Flux Using an Isolated Observation System in the Confocal Laser Scanning Microscope

The in situ crystallization behavior of highly volatile commercial mold fluxes for medium carbon steels was investigated using the confocal laser scanning microscope (CLSM) equipped with an optimized isolated observation system. The highly volatile compounds of the mold flux were suppressed during heating allowing direct observation in the CLSM. Cooling rates of 25, 50, 100, 400, and 800 K/min were incorporated and continuous cooling transformation (CCT) diagrams of 4 different commercial mold fluxes for medium carbon steels were developed. Identification of the crystalline phase was conducted with XRD and SEM–EDS analysis. A cuspidine crystalline was observed in all samples at various cooling rates. With higher basicity, CaF₂, and NaF, the crystallization of the fluxes was enhanced according to the CCT diagram. As the slag structure becomes depolymerized, the diffusion rate of the cathodic ions seems to increase.     

Effects of Li2O and Na2O on the Crystallization Behavior of Lime-Alumina-Based Mold Flux for Casting High-Al Steels

With the development of advanced high strength steel (AHSS), a large amount of aluminum was added into steels. The reaction between aluminum in the molten steel and silica based mold flux in the continuous-casting process would tend to cause a series of problems and influence the quality of slabs. To solve the above problems caused by the slag–steel reaction, nonreactive lime-alumina-based mold flux system has been proposed. In this article, the effect of Li₂O and Na₂O on the crystallization behavior of the lime-alumina-silica-based mold flux has been studied by using the single hot thermocouple technology (SHTT) and double hot thermocouple technology (DHTT). The results indicated that Li₂O and Na₂O in the above mold flux system play different roles as they behaved in traditional lime-silica based mold flux, which would tend to inhibit general mold flux crystallization by lowering the initial crystallization temperature and increasing incubation time, especially in the high-temperature region. However, when their content exceeds a critical value, the crystallization process of mold fluxes in low temperature zone would be greatly accelerated by the new phase formation of LiAlO₂ and Na _x Al _y Si _z O₄ crystals, respectively. The crystalline phases precipitated in all samples during the experiments are discussed in the article.     

Heat-Transfer Behavior of Mold Fluxes for Continuous Casting of Invar Alloy

The heat-transfer behavior across mold fluxes for Invar alloy Fe-36Ni would introduce significant influence on the slab surface quality. A study on the heat-transfer property of mold flux film for Invar alloy Fe-36Ni was carried out by an interaction between laboratory simulation and field trial. The study results indicate that great effect on heat transfer across flux film is caused by chemical compositions of mold fluxes. An increase of basicity and CaF₂ content suppresses heat transfer across flux film; heat transfer across flux film increases when the Al₂O₃ content increases from 4 pct to 8 pct but decreases when Al₂O₃ content is above 8 pct. The crystalline phases of both the conventional mold fluxes and the improved mold fluxes are all cuspidine phases. However, crystallization capability of the improved mold fluxes decreases as the result of the increase of basicity and CaF₂ content as well as the decrease of Al₂O₃ content. The average thickness of flux film taken from mold is about 1.6 mm, and the crystalline fraction is only 21.4 pct. All these promote heat transfer across the flux film. The field trial of the improved mold fluxes shows that the properties of liquid slag are steady during continuous casting; comprehensive heat transfer across flux film meets the needs of continuous casting of Fe-36Ni. Border solidification structures of solidified shell are refined remarkably, and hot cracking gets avoidance eventually.     

TiO_2对连铸保护渣导热性能的影响

运用热线法测试了不同碱度（1.1、1.3）,不同TiO2含量（0～8%,质量分数,下同）的连铸保护渣在不同温度下（400～1 300℃）的热传导系数,并结合DSC和XRD分析结果,探讨了碱度和TiO2含量对保护渣导热性能的影响规律及原因。结果表明：本试验条件下液态渣（1 200～1 300℃）的导热系数为0.27～0....     

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.     

Observations of Crystallization in Mold Slags with Varying Al2O3/SiO2 Ratio

The present paper is an investigation into how the Al₂O₃/SiO₂ ratio in the compositions of mold slags influences the crystallization behavior of molten slags. The experimental work is based upon observing the crystallization events through a Confocal Scanning Laser Microscope equipped with a hot‐stage. The study is motivated by the variation in crystallization that might occur in mold slags due to the pickup of alumina during continuous casting of high Al containing TRIP steels. The crystallization temperature was found to increase with increasing Al₂O₃/SiO₂ ratio, and the crystal morphology was dependent upon the chemical composition and isothermal temperature. The crystallization path was complex, with CaF₂ found to precipitate first, and followed by a second precipitation event. In this second event, the precipitated phase depended on the chemical composition of mold slag and changed from cuspidine to gehlenite as the mass ratio of Al₂O₃/SiO₂ was increased beyond 0.65, and finally Al₂O₃ was observed when the alumina content was 30wt.% (corresponding to a mass ratio of = 1.42).     

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.     

Effect of Na2O and B2O3 on the Crystallization Behavior of Low Fluorine Mold Fluxes for Casting Medium Carbon Steels

An investigation has been conducted to study the effect of Na₂O and B₂O₃ on the crystallization behavior of low fluorine (F) mold powders for casting medium carbon (MC) steels in this article. The results of this study indicated that B₂O₃ tends to lower the crystallization temperature and increase crystallization incubation time of the low F powders; however, Na₂O plays an opposite role compared with that of B₂O₃. The crystalline phase of Ca₁₁Si₄B₂O₂₂ was formed in Sample D2 [F = 3 pct, Na₂O = 10 pct, B₂O₃ = 8 pct (in wt pct)], which exhibited the most similar crystallization behavior to that of cuspidine, such that Sample D2 showed closest crystallization kinetics to that of a conventional high-F mold slag for casting MC steels. The precipitated crystalline phases for all the samples have been analyzed and discussed in the article.     

Viscosity of Fluoride‐Free Mold Fluxes Containing B2O3 and TiO2

Viscosities of B₂O₃ and TiO₂‐bearing fluoride‐free mold fluxes have been measured by the rotating cylinder method in this work. Effects of different B₂O₃, TiO₂ content, and basicities on the viscosity characteristics have been examined. Viscosity of fluoride‐free mold fluxes containing B₂O₃ and TiO₂ was found to decrease with the increase of B₂O₃, TiO₂ content, and basicity. The values of apparent activation energy for viscous flow of slags decrease with additions of B₂O₃ and TiO₂ and the increase of basicity. Two parameters A and B in Riboud model were re‐evaluated based on the present experimental data, and the modified Riboud model was used to estimate the viscosity of fluoride‐free slag system investigated in present work. The viscosity values obtained by the experimental measurement were in good agreement with those calculated by the modified Riboud model.     

Na2O对超高碱度连铸保护渣性能的影响

 在包晶钢连铸过程中,裂纹类缺陷频繁出现。生产实践表明,采用结晶性能较强的保护渣可以有效减少纵裂纹的发生,但会恶化保护渣的润滑功能。近年来,超高碱度保护渣由于兼具开始结晶温度低、结晶速率快的特点,可以成功协调包晶钢连铸过程中润滑与传热的矛盾。但在超高碱度条件下,有关组分对保护渣结晶性能的影响研究不多,且相应的熔渣结构特征也鲜有报道。Na₂O作为保护渣中一种常见的组元,对调节保护渣性能具有重要作用。论文采用半球点熔化温度测试仪、旋转黏度计以及高温原位结晶性能测试仪分析了超高碱度下(综合碱度R=1.75)Na₂O对连铸保护渣熔化流动特性以及凝固结晶性能的影响规律和作用机制。研究结果发现,随着Na₂O含量增加,保护渣的黏度(1 300 ℃)、熔化温度、转折温度和结晶温度都呈下降趋势,结晶速率呈现先减小后增大的趋势,当Na₂O质量分数为6%时结晶速率最低。此外,研究还发现超高碱度保护渣中主要析出相为枪晶石(Ca₄Si₂F₂O₇),随着Na₂O含量进一步增加,渣中出现新的结晶相CaF₂和Na₂CaSiO₄F。     

Optimization of Mold Flux for the Continuous Casting of Cr-Contained Steels

To compensate the negative effect caused by the absorption of chromium oxide inclusions during the casting process of Cr-contained steels, a new mold flux system has been designed and investigated. The melting temperature range of the newly designed mold flux system is from [1124 K to 1395 K (851 °C to 1122 °C)]. The viscosity at 1573 K (1300 °C) and the break temperature increase with the addition of MnO and Cr₂O₃ but decrease with the addition of B₂O₃. The crystalline fraction of mold flux decreases from 81 to 42.1 pct with the addition of MnO and Cr₂O₃, and then further decreases to 25.3 pct with the addition of B₂O₃; however, it improves from 54.4 to 81.5 pct when the basicity increases. Besides, the heat-transfer ability of mold flux is inverse to the crystallization ratio of the slag. The comprehensive study of the properties for the four designed mold fluxes suggests that the mold flux with 1.15 basicity-3.01 pct B₂O₃-1.10 pct MnO-2.10 pct Cr₂O₃ shows the best properties for the continuous casting of Cr-contained steels.     

Effect of MgO on Crystallization and Heat Transfer of Fluoride-Free Mold Fluxes

The effect of MgO on crystallization and heat transfer of fluoride-free mold fluxes was studied using single/double-hot thermocouple technique (SHTT/DHTT) and infrared emitter technique (IET), respectively. SHTT experiments demonstrated that the increase of MgO concentration promoted the crystallization tendency of mold fluxes. XRD analysis showed that the dominant phases changed from CaSiO₃ to CaSiO₃/Ca₂MgSi₂O₇/Ca₁₁Si₄B₂O₂₂, and to Ca₂MgSi₂O₇ as the MgO content was increased. The heat flux across mold flux disks was reduced from 671 to 615 kW/m² in IET experiments when MgO concentration was increased from 0.9 to 4.9 mass pct.     

Removal of phosphorus from CaO-SiO2-MgO-Al2O3-P2O5 melts to the gas phase

The behavior of phosphorus in CaO-SiO₂-MgO-Al₂O₃-P₂O₅ melts is studied experimentally, so as to determine the potential for the removal of phosphorus from oxide melts to the gas phase. To identify the factors that affect the removal of phosphorus from oxide melts to the gas phase, experiments are conducted with different basicity CaO/SiO₂ and with the injection of N₂, Ar, and CO + CO₂ mixture (with different CO/CO₂ ratios). It is established that the basicity is the main factor affecting the transfer of phosphorus from the oxide melt to the gas. When the basicity is 1.0 or less, phosphorus is removed from oxide melts. At higher basicity, no transfer of phosphorus from the oxide melt to the gas is observed. These findings are confirmed by calculations based on the theory of regular ionic solutions for acidic slag, at different basicity values. Calculations show that, when the basicity is 1.05 or less, the activity of SiO₂ exceeds that of CaO, and correspondingly SiO₂ displaces P₂O₅ from its strong compound with CaO. That creates favorable conditions for the transfer of phosphorus from the oxide melt to the gas.     

Effects of MnO on Crystallization,Melting, and Heat Transfer of CaO-Al2O3-Based Mold Flux Used for High Al-TRIP Steel Casting

An investigation was carried out to study the effect of MnO on crystallization, melting, and heat transfer of lime-alumina-based mold flux used for high Al-TRIP steel casting, through applying the infrared emitter technique (IET) and the double hot thermocouple technique (DHTT). The results of IET tests showed that MnO could improve the general heat transfer rate through promoting the melting and inhibiting the crystallization of mold flux; meanwhile the radiative heat flux was being attenuated. DHTT experiments indicated that the crystallization fraction, melting temperature of mold flux decreased with the addition of MnO. The results of this study can further elucidate the properties of the CaO-Al₂O₃ slag system and reinforce the basis for the application of lime-alumina system mold fluxes for casting high Al steels.     

CaO-SiO2-Al2O3-Na2O-CaF2固态渣系的再结晶性能

 含铝钢连铸时,钢水中的铝与保护渣中SiO2反应导致保护渣中Al2O3含量增加而SiO2含量减少,导致保护渣的热物理性能发生变化,从而影响了铸坯的质量。在以前的研究基础上使用X射线衍射仪(XRD)和差热分析仪(DTA)以及扫描电镜(SEM)研究了高铝保护渣固态渣膜的结晶行为与晶体显微结构的变化规律。结果表明,高铝保护渣中CaF2的析出主要是因为SiO2含量的减少和Al2O3含量的增加导致大量的Ca2+的功能由电荷补偿变为网络修饰体,温度降低时CaF2首先析出;随着保护渣中Al2O3含量的增加,在同一加热速率下析晶温度升高;当保护渣中Al2O3含量较少时,析出晶体为枪晶石(Ca4Si2O7F2)和少量的CaF2,当Al2O3含量大于5%(质量分数,下同)时,霞石(NaAlSiO4)进一步析出,且随着Al2O3含量的增加,析出晶体的尺寸减小。