Non-isothermal Crystallization Kinetics of Mold Fluxes for Casting High-Aluminum Steels

This paper investigates the crystallization behavior of CaO-SiO₂- and CaO-Al₂O₃-based mold fluxes for casting high-aluminum steels using single hot thermocouple technology, developed kinetic models, and scanning electron microscope. The results showed that the crystallization ability of the typical CaO-SiO₂-based Flux A (CaO/SiO₂ 0.62, Al₂O₃ 2 mass pct) is weaker than that of CaO-Al₂O₃-based Flux B (CaO/SiO₂ 4.11, Al₂O₃ 31.9 mass pct) because of its higher initial crystallization temperature. The crystallization kinetics of Flux A was “surface nucleation and growth, interface reaction control” in the overall non-isothermal crystallization process, whereas that of Flux B was “constant nucleation rate, 1-dimensional growth, diffusion control, in the primary crystallization stage, and then transformed into constant nucleation rate, 3-dimensional growth, interface reaction control in the secondary crystallization stage.” The energy dispersive spectroscopy results for Flux B suggested that the variations in the crystallization kinetics for Flux B are due to different crystals precipitating in the primary (BaCa₂Al₈O₁₅) and secondary (CaAl₂O₄) crystallization periods during the non-isothermal crystallization process.     

连铸保护渣的结晶过程

 连铸保护渣在结晶器内的结晶行为无法直接观测。为了模拟保护渣在结晶器内的结晶行为,采用热丝法研究保护渣在高温下等温和连续冷却下结晶性能,直接观察保护渣析晶的全过程,发现温度影响析出晶体的形貌和结晶率。绘制保护渣TTT曲线和CCT曲线,表征保护渣析晶行为与时间、温度的关系。在冷却速率5~25 ℃/min范围内,DSC法测定保护渣结晶温度下降110 ℃;在冷却速率6~30 ℃/min范围内,热丝法测定保护渣结晶温度下降86 ℃。     

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。     

连铸结晶器保护渣结晶温度

实验采用WCT-2型微机差热天平,用来研究了保护渣的化学组成和冷却速率对其结晶温度的影响.结果表明:(1)在实验条件下,碱度升高,保护渣的结晶温度先升高后降低;(2)F-含量增加,保护渣的结晶温度提高;(3)随着Na₂O,Al₂O₃,MgO含量的增加,保护渣的结晶温度下降;(4)保护渣的结晶温度随冷却速率的增加略有下降.     

Development of Non-reactive F-Free Mold Fluxes for High Aluminum Steels: Non-isothermal Crystallization Kinetics for Devitrification

Metallurgical and Materials Transactions B - It is necessary to study crystallization from glass (devitrification) for non-reactive F-free CaO-Al2O3 based mold fluxes; this is especially important...     

冷却速率对连铸保护渣结晶性能的影响

采用 WCT-2型差热分析天平和LEITZ光学显微镜(配有 1350℃高温热台),研究了冷却速率对连铸保护渣结晶性能的影响.研究结果表明:随冷却速率提高,保护渣的结晶温度显著降低,结晶率降低,晶体尺寸减小,晶形也有很大改变.     

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.     

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.     

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.     

Crystallization Kinetics and Structure of Mold Fluxes with SiO2 Being Substituted by TiO2 for Casting of Titanium-Stabilized Stainless Steel

Crystallization kinetics and the structure of mold fluxes with SiO₂ being substituted by 0, 5, and 10 pct TiO₂ were studied by differential thermal analysis technique and Raman spectroscopy, respectively, to explore the effect of TiO₂ on the crystallization behavior of the slag. Crystallization kinetics analysis shows that the activation energy for crystal growth increases with the increase of TiO₂ substitution, implying that TiO₂ substitution for SiO₂ in mold fluxes produces negative effects on crystal growth and retards the crystallization process. Raman spectral study indicates that TiO₂ enters the system mainly in the form of [TiO₄] in monomer structure unit, and simultaneously, there appear relatively small amounts of [TiO₆] structure unit. The introduction of TiO₂ leads to a decrease of the dimer and chain Si-O-Si structure unit (Q¹ and Q²).     

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.     

结晶器保护渣吸收TiO2夹杂物的动力学研究

碱度0.85、CaO-SiO₂-Al₂O₃-MgO-Na₂O-CaF₂为基本渣系,采用旋转动力学方法研究了TiO₂棒的旋转角速度(50～120)r/min,碱度(0.7～1.15),熔渣温度(1300～1480℃),TiO₂(0～12%),CaF₂(5%～15%)对保护渣吸收TiO₂速率的影响。结果表明,分别随温度升高,碱度增加,TiO₂含量降低和CaF₂含量增加,使TiO₂在渣中的溶解速率升高,其中温度和碱度的影响最显著。TiO₂溶解的限制性环节是扩散过程,溶解过程的活化能为130.9kJ/mol。     

热丝法结晶器保护渣结晶性能的控制

为控制结晶器保护渣结晶性能,采用热丝法构建保护渣的CCT与TTT曲线以探讨Na2O含量对其结晶性能的影响规律。结果表明,随Na2O含量的增加,保护渣的临界冷却速度减小,其结晶性能受到抑制;同时,保护渣的析晶开始温度升高、孕育时间减少。     

连铸结晶器保护渣的凝固温度

研究了CaO-SiO2-Na2O-CaF2-Al2O3-MgO渣系凝固温度的影响因素。该连铸保护渣的凝固温度随渣中CaO/SiO2、Na2CO3和CaF2含量的增加而逐渐降低,加入5.5%-7.5%的MgO,可提高凝固温度的稳定性。     

Crystallization Temperature and Crystallization Ratio of Mold Flux

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

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.     

Prediction and Measurement of the Kinetics of Isothermal Crystallization and Devitrification of Mold Powder Slags

Metallurgical and Materials Transactions B - The rate and extent of formation of crystalline phases in the slag film that develops between the mold and the strand in steel continuous casting...