Development and prospects of molten steel deoxidation in steelmaking process

In the long traditional process of steelmaking,excess oxygen is blown into the converter,and alloying elements are used for deoxidation.This inevitably results in excessive deoxidation of products remaining within the steel liquid,affecting the cleanliness of the steel.With the increasing requirements for steel performance,reducing the oxygen content in the steel liquid and ensuring its high cleanliness is necessary.After more than a hundred years of development,the total oxygen content in steel has been reduced from approximately 100×10^(-6)to approximately 10×10^(-6),and it can be controlled below 5×10^(-6)in some steel grades.A relatively stable and mature deoxidation technology has been formed,but further reducing the oxygen content in steel is no longer significant for improving steel quality.Our research team developed a deoxidation technology for bearing steel by optimizing the entire conventional process.The technology combines silicon–manganese predeoxidation,ladle furnace diffusion deoxidation,and vacuum final deoxidation.We successfully conducted industrial experiments and produced interstitial-free steel with natural decarbonization predeoxidation.Non-aluminum deoxidation was found to control the oxygen content in bearing steel to between 4×10^(-6) and 8×10^(-6),altering the type of inclusions,eliminating large particle Ds-type inclusions,improving the flowability of the steel liquid,and deriving a higher fatigue life.The natural decarbonization predeoxidation of interstitial-free steel reduced aluminum consumption and production costs and significantly improved the quality of cast billets.

Ultrahigh cycle fatigue fracture mechanism of high-quality bearing steel obtained through different deoxidation methods

The mechanism of oxide inclusions in fatigue crack initiation in the very-high cycle fatigue(VHCF)regime was clarified by subjecting bearing steels deoxidized by Al(Al-deoxidized steel)and Si(Si-deoxidized steel)to ultrasonic tension-compression fatigue tests(stress ratio,R=−1)and analyzing the characteristics of the detected inclusions.Results show that the main types of inclusions in Si-and Al-deoxidized steels are silicate and calcium aluminate,respectively.The content of calcium aluminate inclusions larger than 15μm in Si-deoxidized steel is lower than that in Al-deoxidized steel,and the difference observed may be attributed to different inclusion generation processes during melting.Despite differences in their cleanliness and total oxygen contents,the Si-and Al-deoxidized steels show similar VHCF lives.The factors causing fatigue failure in these steels reveal distinct differences.Calcium aluminate inclusions are responsible for the cracks in Al-deoxidized steel.By comparison,most fatigue cracks in Si-deoxidized steel are triggered by the inhomogeneity of a steel matrix,which indicates that the damage mechanisms of the steel matrix can be a critical issue for this type of steel.A minor portion of the cracks in Si-deoxidized steel could be attributed to different types of inclusions.The mechanisms of fatigue fracture caused by calcium aluminate and silicate inclusions were further analyzed.Calcium aluminate inclusions first separate from the steel matrix and then trigger crack generation.Silicate inclusions and the steel matrix are closely combined in a fatigue process;thus,these inclusions have mild effects on the fatigue life of bearing steels.Si/Mn deoxidation is an effective method to produce high-quality bearing steel with a long fatigue life and good liquid steel fluidity.

Electro-deoxidation of V_2O_3 in molten CaCl_2-NaCl-CaO

The electro-deoxidation of V2O3 precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl2 and NaC1 with additions of CaO, a cathode of compact V2O3, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. 3 g of V2O3 could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V2O3 formed the intermediate product CaV2O4.

Explainable machine learning model for predicting molten steel temperature in the LF refining process

Accurate prediction of molten steel temperature in the ladle furnace(LF)refining process has an important influence on the quality of molten steel and the control of steelmaking cost.Extensive research on establishing models to predict molten steel temperature has been conducted.However,most researchers focus solely on improving the accuracy of the model,neglecting its explainability.The present study aims to develop a high-precision and explainable model with improved reliability and transparency.The eXtreme gradient boosting(XGBoost)and light gradient boosting machine(LGBM)were utilized,along with bayesian optimization and grey wolf optimiz-ation(GWO),to establish the prediction model.Different performance evaluation metrics and graphical representations were applied to compare the optimal XGBoost and LGBM models obtained through varying hyperparameter optimization methods with the other models.The findings indicated that the GWO-LGBM model outperformed other methods in predicting molten steel temperature,with a high pre-diction accuracy of 89.35%within the error range of±5°C.The model’s learning/decision process was revealed,and the influence degree of different variables on the molten steel temperature was clarified using the tree structure visualization and SHapley Additive exPlana-tions(SHAP)analysis.Consequently,the explainability of the optimal GWO-LGBM model was enhanced,providing reliable support for prediction results.

Deoxidation of H13 tool steel with CaF_(2)-MgO-CaO-Al_(2)O_(3)-SiO_(2) slags at 1873 K

Laboratory-scale experiments were performed to investigate the deoxidation of H13 tool steel with CaF_(2)-MgO-Al_(2)O_(3)-CaO-SiO_(2) slags at 1873 K.The calculation of thermodynamics and kinetics was also verified through the experimental results.The results show that[Si]-[O]reaction is the control reaction,and with the increase of basicity of slag,the limitation of deoxidation was decreased.The limitation of deoxidation is the lowest for the slag with basicity of 2.0.Under the conditions of the basicity of 2.0 and the content of CaF_(2) more than 50%,the limitation of deoxidation is less than 10×10^(−6),and it does not depend on the contents of Al_(2)O_(3) and CaF_(2) in slags.The mass transport of oxygen in the metal phase is the rate-controlling step,and the slag composition has no effect on the equilibrium time of deoxidation.Based on this finding,the optimized slag composition is designed and it contains the following components:51.5%CaF_(2),20.3%MgO,16.2%Al_(2)O_(3),8.2%CaO and 3.8%SiO_(2).In the case of the optimized deoxidizing slag,the total oxygen content in H13 steel can be reduced from 25×10^(−6) to 6×10^(−6).

Study on Flow and Mixing Characteristics of Molten Steel in RH and RH-KTB Refining Processes

The flow and mixing characteristics of molten steel during the vacuum circulation refining, including RH(Ruhrstahl Heraeus) and RH KTB(Ruhrstahl Heraeus Kawasaki top blowing) processes, were investigated on a 1/5 linear scale water model of a 90 t multifunction RH degasser. The circulation rate was directly and more accurately determined, using a new method by which the more reliable results can be obtained. The fluid flow pattern and flow field in the ladle were demonstrated, observed and analyzed. The mixing time of liquid in the ladle was measured using electrical conductivity method. The residence time distribution in the RH model was obtained by tracer response technique. The influence of the main technological and geometric factors, including the gas top blowing (KTB) operation, was examined. The results indicated that the circulation rate of molten steel in the RH degasser can be fairly precisely calculated by the formula: Q lp =0.0333 Q 0.26 g D 0.69 u D 0.80 d(t/min), where Q g-the lifting gas flow rate (NL/min); D u and D d-the inner diameters of the up and down snorkels (cm), respectively. The maximum value of circulation rate of molten steel in the case of the 30 cm diameters either of the up and down snorkels for the RH degasser (the “saturated” rate) is approximately 31 t/min. The corresponding gas flow rate is 900 NL/min. Blowing gas into the vacuum chamber through the top lance like KTB operation does not markedly influence the circulatory flow and mixing characteristics of the RH process under the conditions of the present work. There exist a major loop and a large number of small vortices and eddies in the ladle during the RH refining process. A liquid liquid two phase flow is formed between the descending stream from the down snorkel and the liquid around the stream. All of these flow situation and pattern will strongly influence and determine the mixing and mass transfer in the ladle during the refining. The correlation between the mixing time and the stirring energy density is τ m∝ε -0.50 for the RH degasser. The mixing time rapidly shortens with an increase in the lifting gas flowrate. At a same gas flow rate, the mixing times with the up and down snorkel diameters either of 6 and 7 cm are essentially same. The 30 cm diameters either of the up and down snorkels for the RH degasser would be reasonable. The concentration time curve showed that three circulation cycles are at least needed for complete mixing of the liquid steel in the RH degasser.

Effects of deoxidizing degree on the pitting corrosion behavior of carbon and manganese steels

Nine steels with different deoxidizing degrees and two comparative steels were selected. Their pitting initiation susceptibility was compared by means of potentiodynamic polarization tests in 3wt% NaCl solution. The pit propagation rate was evaluated in artificial sea water and 3wt% sea salt solution by simulating occluded corrosion cell （SOCC） test and hanging plate test, respectively. The composition of inclusions and corrosive feature were studied by scanning electron microscopy （SEM）, electron probe micro-analysis （EPMA）, and optical microscopy （OM）. The results indicate that sulfide inclusions in steel are the sites for pit nucleation. The sulphide inclusions vary in shape from short spindle-like to long strip-like with increasing deoxidizing degree. Under the same conditions, the lower the deoxidizing degree gets, the lower the pitting initiation susceptibility becomes, and the stronger the resistance to pit propagation exhibits. For steels with different deoxidizing degrees, their pitting initiation susceptibility is mainly influenced by thermodynamic stability, while the pit propagation rate is primarily subject to the characteristics of inclusions in steel.

Thermodynamic calculations and experiments on inclusions to be nucleation sites for intragranular ferrite in Si-Mn-Ti deoxidized steel

Microstructures and inclusions in the Si-Mn-Ti deoxidized steels after cooling in the furnace were investigated. The composition and morphology of the inclusions were analyzed using a field emission scanning electron microscope （FE-SEM） with energy dispersive X-ray spectrometry （EDS）. The kind and composition of the inclusions calculated from the thermodynamic database were in good agreement with the experimental results. There were two main kinds of inclusions formed in the Si-Mn-Ti deoxidized steels. One kind of inclusion was the manganese titanium oxide （Mn-Ti oxide）. Another kind of inclusion was the MnS inclusion with segregation points containing Ti and N. According to the thermodynamic calculation, those segregation points were TiN precipitates. The formation of intragranular ferrite （IGF） microstructures refined the grain size during the austenite-ferrite transformation. The mechanisms of IGF formation were discussed. Mn-Ti oxide inclusions with Mn-depleted zone （MDZ） were effective to be nucleation sites for IGF formation, because the MDZ increased the austenite-ferrite transformation temperature. TiN had the low misfit ratio with IGF, so the TiN precipitated on the MnS surface also promoted the formation of IGF because of decreasing interfacial energies.

SURFACE TENSION OF MOLTEN IF STEEL CONTAINING Ti AND ITS INTERFACIAL PROPERTIES WITH SOLID ALUMINA

Surface tension of molten IF steel containing Ti and contact angle between the liquid steel and solid alumina were measured with sessile droplet method under Ar gas atmosphere at 1500, 1575 and 1600°C. The results show that titanium decreases the surface tension of the molten IF steel and the contact angle. The interfacial tension between the molten IF steel containing Ti and solid alumina decreases with increase in titanium content. The work of adhesion between molten IF steel containing Ti and solid alumina decreases slightly at 1550°C, but increases at 1600°C with increasing titanium content. It can be deduced that fine bubbles and fine alumina inclusions are easily entrapped in solidifying interface for IF steel containing Ti.

Physical Modeling of the Vacuum Circulation Refining Process of Molten Steel

The available studies in the literature on physical modeling of the vacuum circulation (RH, i.e. Ruhrstahl Heraeus) refining process of molten steel have briefly been reviewed. The latest advances made by the author with his research group have been summarized. Water modeling was employed to investigate the flow and mixing characteristics of molten steel under the RH and RH KTB (Kawasaki top blowing) conditions and the mass transfer features between molten steel and powder particles in the RH PTB (powder top blowing) refining. The geometric similarity ratio between the model and its prototype (a multifunction RH degasser of 90 t capacity) was 1:5. The effects of the related technological and structural factors were considered. These latest studies have revealed the flow and mixing characteristics of molten steel and the mass transfer features between molten steel and powder particles in these processes, and have provided a better understanding of the refining processes of molten steel.

Mechanism and simulation of droplet coalescence in molten steel

Droplet coalescence in liquid steel was carefully investigated through observations of the distribution pattern of inclusions in solidified steel samples. The process of droplet coalescence was slow, and the critical Weber number(We) was used to evaluate the coalescence or separation of droplets. The relationship between the collision parameter and the critical We indicated whether slow coalescence or bouncing of droplets occurred. The critical We was 5.5, which means that the droplets gradually coalesce when We ≤ 5.5, whereas they bounce when We > 5.5. For the carbonate wire feeding into liquid steel, a mathematical model implementing a combined computational fluid dynamics(CFD)–discrete element method(DEM) approach was developed to simulate the movement and coalescence of variably sized droplets in a bottom-argon-blowing ladle. In the CFD model, the flow field was solved on the premise that the fluid was a continuous medium. Meanwhile, the droplets were dispersed in the DEM model, and the coalescence criterion of the particles was added to simulate the collision-coalescence process of the particles. The numerical simulation results and observations of inclusion coalescence in steel samples are consistent.

Vacuum Treatment for Simultaneous Desulphurization and Dephosphorization of Hot Metal and Molten Steel

The vacuum treatment for simultaneous desulphurization and dephosphorization of hot metal and molten steel with pre-melted CaO-based slag was carried out.For pre-treatment of hot metal,both desulphurization and dephosphorization are improved with the increase of CaO in slag,but deteriorated with the increase of CaF2 in slag.The average desulphurization and dephosphorization rate is 68.83 % and 78.46 %,respectively.For molten steel,the substitution of BaO for CaO in slag has minor effect on simultaneous desulphurization and dephosphorization.The desulphurization and dephosphorization rate is higher than 90% and 50% respectively with the lowest final sulfur and phosphorus mass percent being 0.001 2% and 0.010%,respectively.The overall effect of simultaneous desulphurization and dephosphorization of molten steel is better than that of hot metal.

Microstructure and Corrosion Resistance of CrN and CrN/TiN Coated Heat-Resistant Steels in Molten Aluminum Alloy

The components of the equipment for processing the Al melts into the molded parts can be markedly corroded by the molten Al. In this study, a 4 μm CrN coating or CrN/TiN multilayer coating for providing the physical and chemical barriers between the molten reactive Al and the steel substrate were deposited by Cathodic Arc Evaporation onto 10 mm-thick heat-resistant steel plates. The dipping tests were conducted in a 700℃ A356 melt for 1 to 21 h at intervals of 3 h. The damage of the coated steel was eva...

Application of Al-free deoxidizer in rail steel manufacture

Because there are a lot of influences of alumina inclusions on the performance of rail steel,it is reasonable to adopt the deoxidization method with Al-free deoxidizer. According to the characteristics of Al-free deoxidization process,the control of aluminum content,the deoxidization with ladle furnace（LF） slag,the deoxidization process under vacuum by carbon,and the inclusions modification technology by calcium treatment were studied. All of them were applied to practical production. The results indicate that the adoption of Al-free deoxidization process leads to the total oxygen content in the steel below 20 ppm,which meets the requirement of clean rail steel.

Copper Removal from Molten Steel by Gasification

A novel method is proposed to enhance the gasification and removal of copper from molten steel by adding ammonium salts or urea into molten steel under normal pressure.The decopperization experiments were conducted in a molybdenum-wire resistance furnace at 1 873 K.The copper content of about 400 g of a mild steel was reduced from 0.49%(mass fraction,the same below) and 0.51% to 0.31% and 0.38% using 0.7 g of NHC1 and 0.5 g of(NH)COrespectively,while the copper content of the molten steel was reduced from 0.61%to 0.56% using 2.00 g of NHCONH.

Change and control of nitrogen in molten steel production process

The change and control of nitrogen content in molten steel was investigated through the production process of "LDBAr-LF-RH-CC". Results show that nitrogen content reduces gradually in converter-steelmaking stage, rises rapidly from the end of converter process to the end of argon station process, continues to increase in ladle furnace process, and decreases slightly in RH refining stage. Since nitrogen is removed mainly by BOF steelmaking and vacuum refining operations, nitrogen in molten steel should be removed as much as possible in these two operations. However, nitrogen uptake should be minimized in other operations of molten steel production process.

Effects of oxygen potential and flux composition on dephosphorization and rephosphorization of molten steel

The dephosphorization experiments of low phosphorus containing steel by CaO-based and BaO-based fluxes were carried out. The effects of the oxygen potential in molten steel and the BaO content in the slag on dephosphorization and rephosphorization of molten steel were analyzed. The results showed that the dephosphorization ratio of more than 50% and the ultra-low phosphorus content of less than 0.005% in steel were obtained by the three kinds of dephosphorization fluxes as the oxygen potential of molten steel higher than 400×10^-6. Rephosphorization of molten steel was serious as the oxygen content of molten steel lower than 10×10^-6. BaO-based fluxes can improve the dephosphorization effect and reduce the phosphorus pick-up effectively under the condition of weak deoxidization of molten steel （the oxygen potential is about 100×10^-6）, but can not prevent rephosphorization under the condition of deep deoxidization of molten steel （the oxygen potential less than 10×10^-6）.

Study on the corrosion behavior of 316H stainless steel in molten NaCl–KCl–MgCl_(2) salts with and without purification

The corrosion behavior of 316H stainless steel(SS)in the impure and purified Na Cl–KCl–Mg Cl_(2) salt was investigated at700°C.Results indicate that the main deleterious impurity induced corrosion in the impure salt was the absorbed moisture,present in the form of Mg Cl_(2)·6H_(2)O.316H SS occurred severe intergranular corrosion with a corrosion depth of 130μm for1000 h in the impure Na Cl–KCl–Mg Cl_(2) salt.In contrast,the purification treatment of molten chloride salt by the dissolved Mg metal can remove the absorbed moisture,and the corresponding reactions were also discussed.As a result,the corrosiveness of Na Cl–KCl–Mg Cl_(2) salt is reduced significantly.316H SS occurred slight uniform corrosion with a depth of less than 5μm for 3000 h in the purified Na Cl–KCl–Mg Cl_(2) salt.

Preparation of zirconium by electro-deoxidization in molten salt

Metal zirconium was prepared by electro-deoxidization method. Using CaCl2 molten salt as electrolyte,sintered ZrO2 pallets as cathode,graphite rod as anode,the pallets were electrolyzed at 900 ℃ and 3.1 V for 8,10 and 12 h,respectively. The mechanism of electro-deoxidization of ZrO2 was studied preliminarily. The results show that the morphologies of cathode pallets affect the forming process of products. The process of electro-deoxidization of ZrO2 in the molten salt is conducted step by step,from exterior of cathode to its interior and from high valence oxide to low valence oxide until to metal.

Wettability of Molten Steel/Na2O-Li2O-SiO2-B2O3 Slag System

The vacuum treatment for simultaneous desulphurization and dephosphorization of hot metal and molten steel with pre melted CaO based slag was carried out. For pre treatment of hot metal, both desulphurization and dephosphorization are improved with the increase of CaO in slag, but deteriorated with the increase of CaF 2 in slag. The average desulphurization and dephosphorization rate is 68 83 % and 78 46 %, respectively. For molten steel, the substitution of BaO for CaO in slag has minor effect on simultaneous desulphurization and dephosphorization. The desulphurization and dephosphorization rate is higher than 90 % and 50 % respectively with the lowest final sulfur and phosphorus mass percent being 0 001 2 % and 0 010 %, respectively. The overall effect of simultaneous desulphurization and dephosphorization of molten steel is better than that of hot metal.