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 ℃。     

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.     

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。     

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.     

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.     

Crystallization behavior of F-free mold fluxes

The time-temperature-transformation (TTT) diagrams of F-flee mold fluxes was constructed using single hot thermocouple technique (SHTT) and confocal scanning laser microscopy (CSLM) to study the crystallization behavior of F-free mold fluxes. The tendency of crystallization is found to increase whereas the incubation time decreases with increasing basicity. Zirconia addition enhances the crystallization tendency due to its limited solubility in the slag melt and the solid particles acting as nucleation sites. Pseudo-wollastonite is found to precipitate in the slag with low basicity (CS-1 and CS-2), kilchoanite and larnite are formed with further increasing basicity (CS-3), and larnite is finally formed as the basicity beyond unit (CS-4). The crystal morphology changes with varying compositions and isothermal temperatures. The measured growth rate is found to be linear with time under isothermal conditions and decreases with increasing isothermal temperature.     

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.     

萤石含量对连铸保护渣结晶性能的影响

通过热丝法得出保护渣连续冷却转变（CCT）和时间-温度转变（TTT）曲线,并用偏光显微分析和X-射线衍射分析方法研究了萤石含量（8%~16%）对碱度1.0的薄板坯连铸结晶器保护渣结晶性能的影响。结果表明,萤石含量每增加2%,保护渣的临界冷却速度平均增加2.5℃;同一冷却速度下,随保护渣中萤石含量的增加,结晶温度升高,结晶率增大,有利于提高界面热阻,控制渣膜传热,减少铸坯表面裂纹产生;因萤石含量超过14%时,渣膜中大量生成结晶矿物枪晶石,对连铸润滑要求较高的钢种,应控制萤石含量≤14%。     

Crystallization Control in Metallurgical Slags Using the Single Hot Thermocouple Technique

With the single hot thermocouple technique (SHTT) the solidification behavior of metallurgical slags has been studied by in situ observation, constructing time–temperature–transformation (TTT) or continuous‐cooling‐transformation (CCT) diagrams. The SHTT is a unique apparatus that enables measurement of the slag sample temperature using a thermocouple while the sample is heated or cooled simultaneously. Due to the low heat capacity of the system sample/thermocouple high heating or cooling rates can be easily obtained (>3000°C/min). The following findings are reported in the present paper: (i) For the CaO–Al₂O₃ slag – 44% CaO, 56% Al₂O₃ (wt%) – the CCT diagram shows large differences between liquidus and the temperature for first crystals precipitation, even at low cooling rates, for example, 168°C below the liquidus when cooling at a rate of 6°C min^?1. (ii) For the CaO–SiO₂ slag – % CaO/% SiO₂ (wt%) = 0.7 – no crystal is observed for continuous cooling, even at low cooling rates, such as 10°C min^?1. During isothermal experiments crystallization was observed only at 1000°C with an incubation time of 76 s (average of six experiments, standard deviation 27 s). However, crystallization becomes much more intense for the CaO–SiO₂ slag when increasing the temperature after reaching lower temperatures (<1000°C), where probably the conditions for nucleation are better.     

基于JMatPro软件的X12CrMoWVNbN10-1-1钢析出相热力学模拟和分析

以火力发电用耐热钢X12CrMoWVNbN10-1-1钢(以下简称X12钢)为研究对象,利用JMatPro软件对其进行了平衡状态下的凝固、过冷奥氏体等温转变和连续冷却转变的模拟计算,并绘制了凝固相图、TTT曲线和CCT曲线.结合扫描电镜和透射电镜对热处理后基体中析出相进行观察和分析.研究结果表明:奥氏体化加热温度低于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.     

不同硼含量微合金钢的连续冷却相变行为

 利用热模拟试验技术对实验室制备的含硼微合金钢连续冷却转变形为进行了试验研究,利用光学显微镜研究冷却速度、变形对试验钢显微组织的影响,探讨了硼对转变行为的影响规律。结果表明：适量硼延缓多边形铁素体生成,有利于获得贝氏体组织;无硼及wB=00020%时,分别在1~25及05~25℃/s的冷速都能得到贝氏体组织;wB=00030%时,冷速在2℃/s 以上能得到贝氏体组织;与未变形相比,变形导致试验钢贝氏体冷速区间变窄。在同一冷速下,随硼含量增加贝氏体开始转变温度先降低再升高,显微硬度随硼含量增加先增加而后降低。     

不同温度条件下连铸保护渣矿相结构的研究

采用矿相显微镜及XRD研究了不同温度条件下连铸保护渣矿相结构的变化。结果表明,在本实验条件下的降温和升温过程中,连铸保护渣的结晶化率均随实验温度的升高而下降,结晶矿相主要为枪晶石、硅灰石、黄长石。枪晶石在1000 ℃和1200 ℃时结晶能力最强,1300 ℃时无枪晶石析出。硅灰石只在1000 ℃时析出,晶体发育程度很高。黄长石晶体在1300 ℃时发育良好且光学性质明显,1000 ℃和1200 ℃时生长缓慢,为细小的颗粒状雏晶。在相同的实验温度条件下,连铸保护渣在升温过程中结晶化率高、晶体细小、结构致密,降温过程中其晶体发育程度良好、晶体粗大     

Computer Model of Phase Transformation From Hot-Deformed Austenite in Niobium Microalloyed Steels

Based on thermodynamics and kinetics, a new mathematical model was developed to calculate the CCT diagrams and the transformation kinetics in low carbon niobium steels, in which the effect of deformation on the degree of supercooling was taken into account. The undercooling caused by deformation is the major reason for the increase of the starting transition temperature during continuous cooling. The critical cooling rate of bainite formation is within 2--5 ℃s for the studied niobium steels and deformation is suitable for the occurrence of pearlite. The ferrite volume fraction increases with the increase of the austenite boundary area, and decreases with the increase of the cooling rate. The calculated CCT diagrams and the volume fraction of each phase are in good agreement with the measurements.     

A Semiempirical Model for Sigma-Phase Precipitation in Duplex and Superduplex Stainless Steels

Sigma phase is known to reduce the mechanical properties and corrosion resistance of duplex and superduplex stainless steels. Therefore, heat treatments and welding must be carefully performed so as to avoid the appearance of such a detrimental phase, and clearly, models suitable to faithfully predict σ-phase precipitation are very useful tools. Most fully analytical models are based on thermodynamic calculations whose agreement with experimental results is not always good, so that such models should be used for qualitative purposes only. Alternatively, it is possible to exploit semiempirical models, where time-temperature-transformation (TTT) diagrams are empirically determined for a given alloy and the continuous-cooling-transformation (CCT) diagram is calculated from the TTT diagram. In this work, a semiempirical model for σ-phase precipitation in duplex and superduplex stainless steels, under both isothermal and unisothermal conditions, is proposed. Model parameters are calculated from empirical data and CCT diagrams are obtained by means of the additivity rule, whereas experimental measurements for model validation are taken from the literature. This model gives a satisfactory estimation of σ-phase precipitates during both isothermal aging and the continuous cooling process.     

The continuous δ-γ transformation during cooling of ferritic-austenitic iron-chromium-nickel alloys

Following previously published isothermal TTT diagrams, continuous TTT diagrams for the δ-γ transformation of a series of different iron-chromium-nickel-alloys containing 23.0–35.0 Cr and 6.45–15.6 Ni are presented. The microstructures and transformation behaviors indicate the same nucleation and growth process as in the isothermal reactions. The critical upper cooling rate for complete undercooling of the δ-γ transformation decreases with increasing chromium- and decreasing nickel contents.     

M-Si-B合金非晶形成能力的CALPHAD模式评估

Evaluation of the amorphous-forming ability of M-Si-B ternary alloys using CALPHAD approach@長谷部光弘$日本九州工业大学 @OHTANI Hiroshi$Department of Materials Science and Engineering, Kyushu Institute of Technology @HASEBE Mitsuhiro$Department of Materials Science and Engineering, Kyushu Institute of Technology…     

Effect of carbon content on the mechanical properties and weather resistance of high performance bridge steels

 The influence of carbon content on the mechanical properties of high yield strength bridge steel has been investigated. The results show that, the excellent mechanical properties and corrosion resistance were obtained for the steel with carbon content between 0.03 wt.%-0.05 wt.%. According to these results, a weathering bridge plate steel with 0.045 wt.% carbon content has been developed. The appropriate control cooling process has to be taken due to the results of CCT and TTT to ensure both microstructure and mechanical properties. Continuous cooling transformation (CCT) curve of the new developing steel presents that when accelerated cooled is faster than 5℃/s, the intermediate transformation products can be formed. The isothermal transformation test (TTT) displays that the intermediate transformation temperature range in 600℃~530℃. Yield strength of the new developing steels reached 500MPa, the elongation and toughness of which are both excellent.     

Crystallization Behavior of the CaO-Al2O3-MgO System Studied with a Confocal Laser Scanning Microscope

The crystallization behavior of a calcium-aluminate system with various MgO content from 2.5 to 7.5?wt pct and CaO/Al₂O₃ ratios between 0.8 and 1.2 has been examined using a confocal laser scanning microscope (CLSM). CCT (continuous cooling transformation) and time temperature transformation (TTT) diagrams were constructed to identify the primary crystal phase of slag at different compositions and at cooling rates between 25 and 800?K/minutes. In the slag at a CaO/Al₂O₃ ratio of 1.0, crystallization temperature increased during isothermal and continuous cooling with higher MgO content, and the shortest incubation time was observed at 5?wt pct MgO. When MgO content was fixed to be 5?wt pct, crystallization temperature increased with lower CaO/Al₂O₃ ratio. According to the slag composition, cooling rates and temperature, the primary phase could be CA, or C₅A₃, or C₃A, or C₃MA₂, or MgO, and the crystal morphology changes from dendrites to faceted crystals to columnar crystals in this composition range.     

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.