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.     

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 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.     

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.     

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.     

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.     

In Situ Observation and Investigation of Mold Flux Crystallization by Using Double Hot Thermocouple Technology

The crystallization processes of mold fluxes for casting low-carbon (LC) and medium-carbon (MC) steels were investigated by using double hot thermocouple technology (DHTT) in this article. The results showed that the glass phase was first formed at the cold side thermocouple (CH-2), when the LC mold flux (mold flux for casting low-carbon steel) was exposed to the temperature gradient of 1773 K (1500 °C) to 1073 K (800 °C); then, the fine crystals were precipitated at the liquid/glass interface and grew toward glass and later on to liquid phase. However, the crystals were directly formed at CH-2 when MC flux (mold flux for casting medium-carbon steel) was under the same thermal gradient. The growth rate of MC flux crystals was much faster than that of LC ones. Scanning electron microscope (SEM) and X-ray energy dispersive spectroscopy (EDS) analyses suggested that the crystals formed in LC mold flux were mainly dendritic cuspidine Ca₄Si₂O₇F₂, and the crystals formed from the liquid phase were larger than those from the glass. For MC mold flux, the earlier precipitated crystals were large dendritic Ca₄Si₂O₇F₂, whereas the later ones were composed of equiaxed Ca₂Al₂SiO₇ crystals. The results of DHTT measurements were consistent with the time-temperature-transformation (TTT) diagrams and X-ray diffraction (XRD) analysis.     

Crystallization Behaviors of CaO-SiO2-Al2O3-Na2O-CaF2-(Li2O-B2O3) Mold Fluxes

The effects of basicity (CaO/SiO₂), B₂O₃, and Li₂O addition on the crystallization behaviors of lime-silica-based mold fluxes have been investigated by non-isothermal differential scanning calorimetry (DSC), field emission scanning electron microscopy, X-ray diffraction (XRD), and single hot thermocouple technique. It was found that the crystallization temperature of cuspidine increased with increasing the basicity of mold fluxes. The crystallization of wollastonite was suppressed with increasing the mold flux basicity due to the enhancement of cuspidine crystallization. The addition of B₂O₃ suppresses the crystallization of mold flux. The crystallization temperature of mold flux decreases with Li₂O addition. The size of cuspidine increases, while the number of cuspidine decreases with increasing mold flux basicity. The morphology of cuspidine in mold fluxes with lower basicity is largely dendritic. The dendritic cuspidine in mold fluxes is composed of many fine cuspidine crystals. On the contrary, in mold fluxes with higher basicity, the cuspidine crystals are larger in size with mainly faceted morphology. The crystalline phase evolution was also calculated using a thermodynamic database, and compared with the experimental results determined by DSC and XRD. The results of thermodynamic calculation of crystalline phase formation are in accordance with the results determined by DSC and XRD.     

The Effect of Basicity on the Radiative Heat Transfer and Interfacial Thermal Resistance in Continuous Casting

The basicity of mold flux has been recognized to have a significant influence on the mold flux crystallization in continuous casting, which would in turn affect the heat-transfer rate between the solidified shell and mold. The research regarding the mold flux crystallization as well as its effect on the heat transfer has been conducted intensively. However, few studies have been developed to specify the effect of basicity introduced mold flux crystallization on the radiative heat transfer and interfacial thermal resistance in continuous casting. By using an infrared radiation emitter, a radiative heat flux was applied to a copper mold covered with a solid mold flux disk to simulate the heat-transfer phenomena in continuous casting. The crystallization behaviors of mold fluxes with different basicities and their impact on the radiative heat transfer were investigated dynamically. The interfacial thermal resistance between the solid mold flux and copper mold was also studied in this article. The results suggested that the basicity tends to enhance the mold flux crystallization, leading to the reduction of radiative heat-transfer rate and enlargement of interfacial thermal resistance.     

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.     

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.     

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.     

Nonisothermal Crystallization Kinetics of Glassy Mold Fluxes

Crystallization of the solid glassy mold flux film occurring in the gap between the initial shell and mold wall is important, as it determines the in-mold heat transfer and mold lubrication during the process of continuous casting. In order to study the nonisothermal crystallization behavior of the glassy mold flux film in the continuous casting mold, the continuous heating transformation diagram, crystallization mechanism, and precipitate phases were investigated using the single hot thermocouple technique, kinetic models, a scanning electron microscope, and an energy-dispersive spectrometer (EDS). The results show that the initial crystallization temperature for CaO-SiO₂ based flux A ranges from [1086 K to 1147 K (813 °C to 874 °C)], which is lower than the case of CaO-Al₂O₃ based flux B ranging from [1205 K to 1245 K (932 °C to 972 °C)]. The crystallization kinetics for flux A are constant nucleation rate, two-dimensional growth, and control by diffusion. For flux B, they are constant nucleation rate, three-dimensional growth, and control by interface reaction. Besides, the EDS results indicate that the precipitate crystals in fluxes A and B are CaSiO₃ and Ca₂AlSiO₄, respectively.     

An Investigation of the Mold-Flux Performance for the Casting of Cr12MoV Steel Using a Mold Simulator Technique

Mold flux plays important roles in the process of continuous casting. In this article, the performance of mold flux for the casting of Cr12MoV steel was investigated by using a mold simulator. The results showed that the slag film formed in the gap between the initial shell and mold hot surface is thin and discontinuous during the casting process with the Flux BM, due to the absorption of chromic oxide inclusions into the liquid slag, while the slag film formed in the case of the optimized Flux NEW casting process is uniform. The main precipitated crystals in Flux BM slag film are cuspidine (Ca₄Si₂O₇F₂) and Cr₃O₄, but only Ca₄Si₂O₇F₂ precipitated in the Flux NEW case. Besides, both the responding temperature and heat flux in the case of Flux BM are relatively higher and fluctuate in a larger amplitude. The surface of the shell obtained in the case of the Flux BM experiment is quite uneven, and many severe depressions, cracks, and entrapped slags are observed in the surface due to the lack of lubrication. However, the obtained shell surface in the case of the Flux NEW shows good surface quality due to the addition of B₂O₃ and the adjustment of basicity, which can compensate for the negative effects of the mold-flux properties caused by the absorption of chromic oxide during the casting process.     

The Effect of the Transition Metal Oxide Content of a Mold Flux on the Radiation Heat Transfer Rates

Heat transfer in the mold of a steel continuous casting machine strongly influences cast surface quality. Transition metal oxides have been widely used in mold slags in continuous casting to aid in liquid pool formation and enhance melting rates. Although a few research studies have been carried out to investigate the thermal properties of mold slags containing transition metal oxides, very few studies have directly correlated their effect on radiation heat transfer rate in continuous casting. This study investigates the radiation heat transfer rates across a mold flux film and determines the influence of the transition metal oxides, MnO and Fe₂O₃, on these rates. It is found that additions of 10% MnO or 5% Fe₂O₃ reduce the radiation heat transfer rate by approximately 25% and increase the adsorption coefficient from 400 to 1800 m^?1.     

保护渣晶粒尺寸对传热性能的影响

保护渣在连铸过程中具有重要的作用,其中有效控制钢液向结晶器的传热直接影响了铸坯质量;当保护渣热阻较小、不均匀传热时铸坯容易出现裂纹等缺陷.而保护渣的控热能力主要取决于保护渣的结晶性能,因此,有必要研究保护渣的结晶行为对传热性能的影响.利用双丝热电偶技术通过不同的温度制度,获得不同尺寸的单一结晶相,研究保护渣晶粒尺寸对传...     

Design of mould fluxes for continuous casting of special steels

The melting behaviour of mould powder during continuous casting is an important consideration with respect to caster performance, production rate and steel quality. Two important factors, powder composition and carbon addition, are critical to control the properties and melting behaviour of the mould flux. In this study, the effect of different carbonaceous materials on the melting characteristics of mould powders was evaluated. Correlations were established between the structural factors and chemical reactivity of carbon and melting behaviour of mould flux. In addition, two examples are given of the effect of flux composition on casting performance for specific steels. A flux with reasonable basicity and additives was designed for the casting of heat-resistant steel (Incoloy 800) to reduce surface cracks. Another flux was designed for the casting of non-magnetic steel containing high aluminium by partially replacing SiO₂ with Al₂O₃ to limit aluminium oxidation by SiO₂.     

Constitutional Segregation of Al2O3 in Mold Slag and Its Impact on Steel Cleanliness During Continuous Casting

The alumina pickup in a range of mold fluxes used for continuous casting of aluminum (Al)-killed ultralow carbon, low carbon, and peritectic steel have been measured. The Al₂O₃ pickup in slag varies approximately from 7 to 12 pct and depends on the slag basicity. Significantly higher Al₂O₃ pickup reported in basic slags and polynomial relationship exists between them. The effect of chemical composition on microstructure evolution and Al₂O₃ partitioning during crystallization was identified in all three types of mold slags. The microsegregation of Al₂O₃ inclusions in the constituent phase of CaO-SiO₂-Al₂O₃ based slag film is presented. Constitutional segregation of Al₂O₃ inclusion in slag was found to affect the Al₂O₃ pickup phenomena during continuous casting. Segregation of alkalis like Na and K was also observed in an Si-rich interdendritic matrix, whereas F was retained in the dendrites of all the slags studied. The Al₂O₃ inclusion partitioning and interdendritic segregation in the mold slag is studied with metallographic evidence.     

连铸结晶器保护渣渣膜传热特性研究进展

传统保护渣主要以CaO和SiO₂为基料,辅以适量助熔剂如CaF2等构成;而无氟保护渣则是选用B₂O₃、TiO₂等合适的助熔剂来替代CaF₂达到绿色环保的目的。从保护渣的碱度、化学成分和结晶性能三方面,分别综述了传统含氟渣系CaO-SiO₂-CaF₂和新型无氟渣系CaO-SiO₂-B₂O₃、CaO-SiO_2-TiO₂渣膜传热的影响规律,总结了近十年来冶金工作者对含氟和无氟保护渣渣膜传热的研究成果,得出无氟保护渣结晶矿相中硅硼酸钙和钙钛矿与传统保护渣中枪晶石具有相似的结晶行为,B₂O₃和TiO₂的含量在4%~8%和3%~11%可有效控制传热,从而减少铸坯纵裂纹的发生。并提出了开发新型高效无氟保护渣的进一步研究方向,即无氟渣中氟化物替代物的迁移赋存规律对渣膜传热性能的影响机理。     

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.