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.

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.

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.

Phase analysis of Al metal in complex deoxidizer

Complex deoxidizer is an important supplementary material for steelmaking,which can not only absorb liquid steel inclusions and improve the quality of molten steel,but also enhance deoxidation,desulfurization, dephosphorization,to prevent the molten steel suction and reduce the molten steel temperature loss.Currently,the complex deoxidizer all contain a certain amount of metal aluminium.The metal aluminium can not be determined for the steel.The entire aluminium contents were regarded as the content of approximate metal aluminium,that often bring great economic losses.Because A1,0,price is cheaper than metal aluminite powder,suppliers added a certain amount of Al_2O_3 in complex deoxidizer,pretend to be the metal aluminium to reap huge profits.This paper put forward a kind of method for determining aluminum,which would reduce loss of the enterprise.Research and put forward an iron triehloride,which extracted from Al metal from complex deoxidizer.Meantime,using orthogonal design of the experiment has been optimized for working conditions.The RSD of the samples are I. 07%-1.94%,the recoveries of the experiment results are 97.0%-110.0%,which expressed the precision and accuracy of the experiment are good.The establishment of the iron triehloride as a extractor,which is rapid and accurate for determination of Al metal in complex deoxidizer.

New steelmaking process based on clean deoxidation technology

After the converter steelmaking process,a considerable number of ferroalloys are needed to remove dissolved oxygen from the molten steel,but it also forms a lot of oxide inclusions that cannot be completely removed.At the same time,it increases the carbon emis-sions in the steel production process.After years of research,our team have developed a series of clean deoxidation technologies,includ-ing carbon deoxidation,hydrogen deoxidation,and waste plastic deoxidation of molten steel to address the aforementioned issues.In this study,thermodynamic calculations and laboratory experiments were employed to verify that carbon and hydrogen can reduce the total oxygen content in the molten steel melt to below 5×10^(-6) and 10×10^(-6),respectively.An analysis of the deoxidation mechanisms and ef-fects of polyethylene and polypropylene was also conducted.In addition,the applications of carbon deoxidation technology in different steels with the hot-state experiment and industrial production were discussed carefully.The carbon deoxidation experimental results of different steels were as follows:(1)the oxygen content of bearing steel was effectively controlled at 6.3×10^(-6) and the inclusion number density was lowered by 74.73%compared to aluminum deoxidized bearing steel;(2)the oxygen content in gear steel was reduced to 7.7×10^(-6) and a 54.49%reduction of inclusion number density was achieved with almost no inclusions larger than 5μm from the average level of industry gear steels;(3)a total oxygen content of M2 high-speed steel was as low as 3.7×10^(-6).In industrial production practice,car-bon deoxidation technique was applied in the final deoxidation stage for non-aluminum deoxidized bearing steel,and it yielded excellent results that the oxygen content was reduced to below 8×10^(-6) and the oxide inclusions in the steel mainly consist of silicates,along with small amounts of spinel and calcium aluminate.

Thermodynamic model for deoxidation of liquid steel considering strong metal-oxygen interaction in the quasichemical model framework

Herein,a thermodynamic model aimed at describing deoxidation equilibria in liquid steel was developed.The model provides explicit forms of the activity coefficient of solutes in liquid steel,eliminating the need for the minimization of internal Gibbs energy preliminarily when solving deoxidation equilibria.The elimination of internal Gibbs energy minimization is particularly advantageous during the coupling of deoxidation equilibrium calculations with computationally intensive approaches,such as computational fluid dynamics.The model enables efficient calculations through direct embedment of the explicit forms of activity coefficient in the computing code.The proposed thermodynamic model was developed using a quasichemical approach with two key approximations:random mixing of metallic elements(Fe and oxidizing metal) and strong nonrandom pairing of metal and oxygen as nearest neighbors.Through these approximations,the quasichemical approach yielded the activity coefficients of solutes as explicit functions of composition and temperature without requiring the minimization of internal Gibbs energy or the coupling of separate programs.The model was successfully applied in the calculation of deoxidation equilibria of various elements(Al,B,C,Ca,Ce,Cr,La,Mg,Mn,Nb,Si,Ti,V,and Zr).The limitations of the model arising from these assumptions were also discussed.

Calculation of phase diagram of Ti-Ni-O system and application to deoxidation of TiNi alloy

The Ti-Ni-O ternary system was assessed by means of Calphad method using ternary experimental data in previous study.Isothermal sections at 1 173 and 1 273 K were calculated.The result shows that the present calculated results are in good agreement with most of the experimental results.The consistent model parameter set determined in this work may provide theoretical guidance for the deoxidation of TiNi alloy.

Deoxidation Behavior of Alloys Bearing Barium in Molten Steel

The deoxidation behaviors of alloys bearing barium in pipe steel were researched with MgO crucible under argon atmosphere in MoSi2 furnace at 1 873 K.The total oxygen contents of molten steel,the distribution,size and morphology of deoxidation products in the steel were surveyed.The metamorphic mechanism for deoxidation products of alloy bearing barium was also discussed.The results show that applying alloy bearing barium to the pipe steel,very low total oxygen contents can be obtained,and deoxidation products,which easily float up from molten steel,can be changed into globular shape and uniformly distributed in steel.The equilibrium time of total oxygen is about 25 min,and the terminal total oxygen contents range from 0.002 0%to 0.002 2% after treating with SiCa wire.The best deoxidizers are SiAlBaCa and SiAlBaCaSr.

Deoxidization of CuCr25 alloys prepared by vacuum induction melting

The influence of crucible and vacuum on oxygen content of CuCr25 prepared by vacuum induction melting (VIM) has been investigated. The experimental results show that the selection of crucible is very important. Alkaline oxide MgO crucible can result in increment of oxygen content and segregation of Cr in the CuCr25 alloys prepared. Neutral oxide Al 2O 3 crucible has no contribution to oxygen in CuCr25. The results also indicate that some kinds of deoxidant, such as Al, are further beneficial to deoxidization of the alloys. [

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.

Al Preparation from Solid Al_2O_3 by Direct Electrochemical Deoxidation in Molten CaCl_2-NaCl at 550℃

Al was prepared by a new method in molten salt at low temperature. Sintered alumina pellets were used as cathode; graphite rod was employed as anode; and the molten CaCl2-NaCl was the electrolyte. A constant 3.2 V voltage was applied in this experiment, and oxygen in solid alumina cathode was reduced by direct electrochemical deoxidation at 550℃. In this process, the current gradually decreased with increasing time and the alumina pellets became grey and porous. The metallic particles were obtained and characterized by XRD （X-ray diffraction） and SEM （scanning electron microscopy）.

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.

Preparation of low-oxygen Ti powder from TiO_(2) through combining self-propagating high temperature synthesis and electrodeoxidation

An effective method was reported to prepare low-oxygen Ti powder,which included two experimental steps:the fast conversion of TiO_(2) to TiO_(x<1) powder by self-propagating high-temperature synthesis(SHS)process and the generation of low-oxygen Ti powder by electrodeoxidizing TiO_(x<1) powder at the cathode in molten CaCl_(2).The key intermediate steps were analyzed by XRD,SEM and electrochemical testing techniques.The results demonstrated that TiO_(x<1) powder(TiO_(0.325) and TiO_(0.97))was generated after acid leaching MgO in SHS products with TiO_(2)/Mg molar ratio of 1:2,and the TiO_(x<1) powder with 16.3 wt.%oxygen could be transformed into pure titanium powder with 0.121 wt.%oxygen by electrodeoxidation at a constant potential of−3.3 V for 10 h.The electrodeoxidation of TiO_(x<1) powder in CaCl_(2) molten salt follows the step-by-step deoxidation mode,and the lattice of TiO_(x<1) powder after electrodeoxidation shrinks.

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).

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.

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.

Mathematical model of deoxidization with post stirring in a combined blowing converter

Dissolved oxygen in the steel at the terminal of the converter smelting process is the main cause for the formation of oxide inclusions, and the high terminal oxygen content worsens the steel cleanness. However, post stirring in a combined blowing converter can promote the carbon-oxygen reaction in the liquid steel and reduce the dissolved oxygen content at the terminal of the converter smelting process. Thus, the mathematical model of deoxidization in the post stirring process was obtained, and the rationality of which was further verified by industrial tests. Finally, it is concluded that the product of dissolved carbon and oxygen, i.e. w[C]·w[O], decreases obviously after adopting the new technique of post stirring in the combined blowing converter.

Optimum Slag Basicity for Deoxidation DuringSecondary Refining Process

According to the coexistence theory of slag structures, the calculating model of the oxidizing capabilityfor CaO-MgO-FeO-Al2O3-SiO2 refining slag system has been deduced. Based on this model, the concept and thecalculating method of the optimum slag basicity are put forward. The results have proved that at this basicity,steel with lower oxygen content can be obtained and non-metallic indigenous globular inclusions can be avoidedmore effectively than at other basicity.

Effect of Zr-Ti combined deoxidation on impact toughness of coarse-grained heat-affected zone with high heat input welding

In this study, the effects of Zr-Ti combined deoxidation and AI deoxidation on the impact toughness of coarse- grained heat-affected zone in high-strength low-alloy steels were investigated. More fine oxides were formed in the Zr-Ti-killed steel than in Al-killed steel. It was also found that more acicular ferrite grains were formed in the coarse-grained heat-affected zone in the Zr-Ti-killed steel than in Al-killed steel. The impact toughness of coarse-grained heat-affected zone of Zr-Ti-kiUed steel was higher than that of Al-killed steel. The good impact toughness was attributable to the pinning effect of fine oxides and the formation of acicular ferrite grains on fine oxides.

Effect of TiO_2 cathode performance on preparation of Ti by electro-deoxidation

To resolve the problem of low current efficiency and low reaction rate when preparing metal by electro-deoxidization method,various contents of CaO and CaCO3 were added into the TiO2 powder,which were compacted into pellets and sintered,and then conducted as the cathode. The morphology and contents of the cathode and products were studied by scanning electron microscopy and X-ray diffractometry,the effect of the additives were studied. The results show that formation of calcium titanate and change of microstructure within the cathode enhance the velocity of the direct electrochemical reduction of solid TiO2 to Ti.