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...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.展开更多
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...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.展开更多
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 t...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.展开更多
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 ul...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.展开更多
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...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.展开更多
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 vol...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).展开更多
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 thecalcul...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.展开更多
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 form...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.展开更多
As the market competition of steel mills is severe,deoxidization alloying is an important link in the metallurgical process.To solve this problem,principal component regression analysis is adopted to reduce the dimens...As the market competition of steel mills is severe,deoxidization alloying is an important link in the metallurgical process.To solve this problem,principal component regression analysis is adopted to reduce the dimension of influencing factors,and a reasonable and reliable prediction model of element yield is established.Based on the constraint conditions such as target cost function constraint,yield constraint and non-negative constraint,linear programming is adopted to design the lowest cost batting scheme that meets the national standards and production requirements.The research results provide a reliable optimization model for the deoxidization and alloying process of steel mills,which is of positive significance for improving the market competitiveness of steel mills,reducing waste discharge and protecting the environment.展开更多
A thermodynamic model for predicting the equilibrium oxygens of 304 stainless steel was developed based on the theory of slag-steel equilibrium,the law of mass conservation,and the ion and molecule coexistence theory....A thermodynamic model for predicting the equilibrium oxygens of 304 stainless steel was developed based on the theory of slag-steel equilibrium,the law of mass conservation,and the ion and molecule coexistence theory.In the developed model,the Fe-Cr-Mn-Si-Al-S-O-melts reaction system and CaO-MgO-CaF_(2)-FeO-MnO-Al_(2)O_(3)-SiO_(2)-Cr2O_(3)slags were considered.The oxygen contents calculated by the model are in good agreement with experimental results and reference data.The equilibrium oxygen contents in 304 stainless steel mainly decrease with increasing binary basicity(w(CaO)/w(SiO_(2)),where w(i)is the mass percentage of component i)and decreasing temperature.Controlling binary basicity at 2.0 while maintaining temperatures lower than 1823 K will keep the oxygen contents in the 304 stainless steel lower than 15×10^(-6).The equilibrium oxygen contents may also be decreased with increasing content of MgO in slags,which is more significant at lower binary basicity.Besides,a small amount of FeO,MnO,and Al_(2)O_(3)(about 0-2.5 wt.%)in slags has little effect on equilibrium oxygen contents.Furthermore,it is found that the[C]-[O]reaction may occur during refining process but will not significantly affect the equilibrium oxygen contents.展开更多
Non-metallic inclusion in steel is a very key factor affecting the fatigue life and quality stability of high-quality bearing steel.Inclusions mainly affect the fatigue life and toughness of the material by affecting ...Non-metallic inclusion in steel is a very key factor affecting the fatigue life and quality stability of high-quality bearing steel.Inclusions mainly affect the fatigue life and toughness of the material by affecting the continuity of the steel matrix,thereby endangering the safety and stability of the equipment.The research progress of inclusion formation,removal and modification was discussed.Based on the current research status of Al deoxidation or Si deoxidation process,the feasibility of non-alloy deoxidation process for high-quality bearing steel was proposed and discussed.C or H_(2) is used as non-alloy deoxidizer,and the deoxidation products are CO and H_(2)O gases,which are easy to be removed from the molten steel.There are few studies on the non-alloy deoxidation process,especially the research and application of C or H_(2) deoxidation for high-quality bearing steel.However,the non-alloy deoxidation process is of great significance for reducing oxygen content and improving cleanliness of high-quality bearing steel.Therefore,it is necessary to study the mechanism and kinetics of C and H_(2) deoxidation and analyze the factors affecting deoxidation effect systematically,so as to provide a solid theoretical basis for the practice of non-alloy deoxidation process for high-quality bearing steel.展开更多
Mass action concentration (activity) calculation model was used to analyze the variation rule of mass action concentrations of slag compositions with basicity changing, and the effect of basicity on deoxidation capa...Mass action concentration (activity) calculation model was used to analyze the variation rule of mass action concentrations of slag compositions with basicity changing, and the effect of basicity on deoxidation capability and control of spinel and globular inclusions was investigated theoretically. From the calculation and experimental results, it was found that with the increase of basicity, the mass action concentration of Al2O3 and SiO2 decreases, while the mass action concentration of FeO and MgO increases at first and then decreases.Slag basicity below 3 to 4 would help to control spinel inclusions formation, and higher basicity improves formation of globular inclusions. Slag with basicity under 2 can effectively control the formation of globular inclusions. Deoxidation capability of slag increases with the increase of basicity, and slag with basicity about 4 could almost reach the maximum deoxidation capability. In order to smelt low oxygen steel with globular inclusions controlled, refining slag basicity should be controlled at about 4.展开更多
The thermodynamic characteristics of desulfurization reaction (CaO)+[S]=(CaS)+[O] is analyzed based on the detailed composition of liquid steel and slag of Steel Plate Hot Commercial (SPHC) in Jiuquan Iron & Steel...The thermodynamic characteristics of desulfurization reaction (CaO)+[S]=(CaS)+[O] is analyzed based on the detailed composition of liquid steel and slag of Steel Plate Hot Commercial (SPHC) in Jiuquan Iron & Steel Corporation(JISC), where the activities of CaO, CaS and Al2O3 in molten slag are calculated by thermodynamic software FactSage for a more accurate result. The critical values of [O%]/[S%] for desulfurization at different temperature is are obtained, typically 0.09 at 1873K, which shows directly that it should deoxidize adequately for obtaining a favorable desulfurization condition. In addition, the thermodynamic analysis indicates that the actual dissolved O is much higher than that of equilibrium calculation which shows Al-O reaction in LF is far away from equilibrium, but it is perfect agreement with the computing results when taking the activity of Al2O3 as 1 that due to the inclusion component in LF is mainly Al2O3. Besides, with the temperature rise, the sulfur partition ratio increases softly meanwhile the reaction between Al and O is limited to a great degree resulting in the increase a dissolved oxygen in liquid steel that decreases the sulfur partition ratio seriously. As a result, the sulfur partition ratio appears to decrease with temperature increase in Al killed steel.展开更多
Steel and slag samples were taken at the start and the end of LF refining for steel plate cold common (SPCC), in the compact strip production (CSP) process, and at the same time, the temperature and oxygen activit...Steel and slag samples were taken at the start and the end of LF refining for steel plate cold common (SPCC), in the compact strip production (CSP) process, and at the same time, the temperature and oxygen activity a[o] were measured by using an oxygen sensor. Furthermore, inclusions in steel samples were monitored by scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (EDS). It was confirmed that a [o] in liq- uid steel was in equilibrium with inclusion rather than with top slag during LF refining. Desulfurization was related to deoxidation since a[o] at slag-steel interface was clarified to be very close to that in liquid steel under the specific con- dition in LF with intense stirring by argon blowing and refined by highly basic low oxidizing slag for Al-killed steel. Sulfur partition ratio (Ls) was very sensitive to a[o]. Since a[o] increased rapidly with temperature rise, it not only offset promotion to desulfurization reaction with temperature rise but decreased Ls. For Al-killed steel, the.modifica- tion of Al2O3 for lowering the activity of Al2O3 in inclusion was believed to be favorable for both deoxidation and desulfurization during LF refining.展开更多
The deoxidation equilibrium of liquid steel was investigated from a new perspective. Dissolved associate MmOn was used to describe the interaction between dissolved M and dissolved oxygen instead of the interaction pa...The deoxidation equilibrium of liquid steel was investigated from a new perspective. Dissolved associate MmOn was used to describe the interaction between dissolved M and dissolved oxygen instead of the interaction parameter of Wagner. The concentration of unassociated oxygen could be considered as the activity of oxygen. Or, the percentage of unassociated oxygen in the total dissolved oxygen was the activity coefficient of oxygen. When the content of deoxidizer was low, the dissolved oxygen was mainly composed of the unassociated oxygen, while more and more MxO formed with gradually increasing M content. The present model gave a good description to the aluminum deoxidation equilibrium after considering AlO and Al2O. Furthermore, the higher the con- tent of A1 was, the higher the content of Al2O relative to the content of AlO would be.展开更多
The present work deals with thermodynamic modeling of oxide systems, in the context of slags and inclusions in steelmaking. The work has emphasis on oxides encountered during the production of tire – cord steel. Cont...The present work deals with thermodynamic modeling of oxide systems, in the context of slags and inclusions in steelmaking. The work has emphasis on oxides encountered during the production of tire – cord steel. Control of inclusion chemistry and variation in eutectic temperature and eutectic composition of MnO-Al2O3-SiO2 slag system have been studied, using Thermo-CalcR software. Relatively low liquidus temperatures are obtained for ratio of MnO / SiO2 = 0.5 - 1.5 and Al2O3 content from 10 - 20 mass%. It has been observed that the addition of Alumina leads to further increase in the liquidus temperature. The stability of inclusions is analyzed in terms of free energy values of related slag systems; and an appropriate minimum of Gibbs free energy value of slag phase observed at around 50 ppm of Oxygen. The observations could not be verified using thermodynamic experiments, but have been compared with findings in the open literature.展开更多
Based on the two-step nucleation mechanism, a multi-step thermodynamic model for alumina inclusion for- mation during aluminum deoxidation process was proposed in Fe-O-Al melt. Thermodynamic properties of metastable i...Based on the two-step nucleation mechanism, a multi-step thermodynamic model for alumina inclusion for- mation during aluminum deoxidation process was proposed in Fe-O-Al melt. Thermodynamic properties of metastable intermediates including (Al2O3)n clusters for prenucleation and α-Al2O3 nanoparticle for growth process were calculated using density functional theory. Furthermore, Gibbs free energy change of forming the intermediate by reaction between the dissolved aluminum (Al) and oxygen (O) in the melt was calculated. The results indicated that the thermodynamics of (Al2O3)n at steelmaking temperature are dependent on their structures, while that of α-Al2O3 nanoparticle are dependent on their size. The nuclei of α-Al2O3 which was originated from (Al2O3)n aggregated under a high supersaturation ratio of Al and O(Rs) in the melt. There existing excess oxygen because of the low Rs, but the secondary inclusions will be formed during the cooling process due to the excess oxygen. The nuclei lager than 20 nm can grow up spontaneously and instantaneously into primary inclusions because of thermodynamic drive. It is difficult to control the size of α-Al2O3 to be less than 20 nm, in the aluminum deoxidation process of the current conditions of steelmaking.展开更多
In this study,impurity-free porous graphene(PG) with intrinsic pore structure was synthesized through a facile acid-alkali etching-assisted sonication approach.The pore structure appears on the surface of graphene she...In this study,impurity-free porous graphene(PG) with intrinsic pore structure was synthesized through a facile acid-alkali etching-assisted sonication approach.The pore structure appears on the surface of graphene sheets due to intrinsic defects of graphene.The PG possessed an extremely high specific surface area of 2184 m^2/g,the size of^5 μm and layer numbers of 3-8.Additionally,PG contained micropores and mesopores simultaneously,with an average pore diameter of approximately 3 nm.The effects of acid,alkali,and ultrasound treatment on PG preparation were elucidated by transmission electron microscopy and fourier transform infrared spectroscopy.First,in an acidic solution,oxygen-containing functional groups(hydroxyls,carboxyl,and epoxides) were formed due to the hydrolysis of sulfate and continuous transformations of these functional groups on graphene oxide.Second,under the synergistic effects of alkali and ultrasound treatment,PG was obtained due to the loss of carboxyl and epoxide groups.A new route for preparing PG was provided by the proposed method.展开更多
The thermodynamic equilibrium of deoxidation reactions between molten slag and steel was calculated using a slag-steel coupling thermodynamic model and the mass conservation model based on the ion-molecular coexistenc...The thermodynamic equilibrium of deoxidation reactions between molten slag and steel was calculated using a slag-steel coupling thermodynamic model and the mass conservation model based on the ion-molecular coexistence theory.The study focused on the effects of slag composition and deoxidizer type on the oxygen content of low alloy steel during the electroslag remelting(ESR)process.The measured and predicted values of the oxygen content in remelted ingots,and the contents of FeO and MnO in slags were compared and analyzed.Results show that the measured content of total oxygen has a certain correlation with the trend of dissolved oxygen predicted by the model when using Ca-Si alloys as deoxidizer,but it is not correlated with the trend of dissolved oxygen predicted by the model when using Al as deoxidizer.The deoxidation mechanisms of Ca-Si and Al are different.Ca-Si alloy directly reacts with FeO and MnO in slag to reduce the oxygen potential of slag,hence it can inhibit the transfer of oxygen from the slag to molten steel.While,when Al deoxidizer is used,the oxygen content in steel is mainly reduced through floating up the alumina inclusions.Compared to Al,utilizing Ca-Si alloy as a deoxidizer is more effective in reducing the oxygen content and the amount of inclusions in ESR ingot.展开更多
The formation of oxide inclusions in one of the carbon steel productions of Mobarakeh Steel Complex of Isfahan has been evaluated. Several samples from different steps of steel production were taken, from arc furnace,...The formation of oxide inclusions in one of the carbon steel productions of Mobarakeh Steel Complex of Isfahan has been evaluated. Several samples from different steps of steel production were taken, from arc furnace, ladle furnace, tundish, and continuous casting mold. Moreover, samples of slab and hot rolling products were prepared. The samples were investigated by optical and scanning electron microscopes equipped with the EDS system. According to the results, the number, composition, and kind of inclusions were directly influenced by the production variables. It was found that when the amount of dissolved oxygen was high (say more than 0. 002 5%), the dissolved aluminum was able to reduce silicon oxide and react with the dissolved oxygen simultaneously, whilst, the dissolved aluminum could reduce the magnesium oxide only when the oxygen content was below 0. 000 5%. Based on this research, a mechanism for forming the complex inclusions was suggested. It was also found that if the aluminum is added to the melt as late as possible, a cleaner melt with fewer inclusions is prepared; this method will be more effective, especially in the case of complex inclusions.展开更多
基金supported by the National Natural Science Foundation of China(No.52174297).
文摘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.
基金financially supported by the National Natural Science Foundation of China (No.52174297)。
文摘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.
文摘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.
基金This work was financially supported by the National Natural Science Foundation of China(No.51774031)the Fundamental Research Funds for the Central Universities(No.FRF-TP-20-026A1)the State Key Laboratory of Advanced Metallurgy Foundation(No.41620001).
文摘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.
基金Item Sponsored by National Natural Science Foundation of China(50174012)Baoshan Iron and Steel Group Co
文摘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.
基金supported by the National Natural Science Foundation of China under grant No.50674026the Postgraduate Foundation of Northeastern University in China under grant No.18702016the Innovational Experiment Plan of Undergraduate Student of China under grant No.071014506
文摘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).
文摘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.
基金This work was supported by the China Postdoctoral Science Foundation C Grant No. 2014M550414 ) and the National Natural Science Foundation of China ( Grant No. 51401152).
文摘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.
文摘As the market competition of steel mills is severe,deoxidization alloying is an important link in the metallurgical process.To solve this problem,principal component regression analysis is adopted to reduce the dimension of influencing factors,and a reasonable and reliable prediction model of element yield is established.Based on the constraint conditions such as target cost function constraint,yield constraint and non-negative constraint,linear programming is adopted to design the lowest cost batting scheme that meets the national standards and production requirements.The research results provide a reliable optimization model for the deoxidization and alloying process of steel mills,which is of positive significance for improving the market competitiveness of steel mills,reducing waste discharge and protecting the environment.
基金This work was financially supported by Key R&D Plan of Shandong Province in 2021(Grant No.2021CXGC010209).
文摘A thermodynamic model for predicting the equilibrium oxygens of 304 stainless steel was developed based on the theory of slag-steel equilibrium,the law of mass conservation,and the ion and molecule coexistence theory.In the developed model,the Fe-Cr-Mn-Si-Al-S-O-melts reaction system and CaO-MgO-CaF_(2)-FeO-MnO-Al_(2)O_(3)-SiO_(2)-Cr2O_(3)slags were considered.The oxygen contents calculated by the model are in good agreement with experimental results and reference data.The equilibrium oxygen contents in 304 stainless steel mainly decrease with increasing binary basicity(w(CaO)/w(SiO_(2)),where w(i)is the mass percentage of component i)and decreasing temperature.Controlling binary basicity at 2.0 while maintaining temperatures lower than 1823 K will keep the oxygen contents in the 304 stainless steel lower than 15×10^(-6).The equilibrium oxygen contents may also be decreased with increasing content of MgO in slags,which is more significant at lower binary basicity.Besides,a small amount of FeO,MnO,and Al_(2)O_(3)(about 0-2.5 wt.%)in slags has little effect on equilibrium oxygen contents.Furthermore,it is found that the[C]-[O]reaction may occur during refining process but will not significantly affect the equilibrium oxygen contents.
基金Key Research and Development Projects in Hebei Province of China (21311002D)Hebei Natural Resources Fund Project of China (E2021417001)for supporting this work.
文摘Non-metallic inclusion in steel is a very key factor affecting the fatigue life and quality stability of high-quality bearing steel.Inclusions mainly affect the fatigue life and toughness of the material by affecting the continuity of the steel matrix,thereby endangering the safety and stability of the equipment.The research progress of inclusion formation,removal and modification was discussed.Based on the current research status of Al deoxidation or Si deoxidation process,the feasibility of non-alloy deoxidation process for high-quality bearing steel was proposed and discussed.C or H_(2) is used as non-alloy deoxidizer,and the deoxidation products are CO and H_(2)O gases,which are easy to be removed from the molten steel.There are few studies on the non-alloy deoxidation process,especially the research and application of C or H_(2) deoxidation for high-quality bearing steel.However,the non-alloy deoxidation process is of great significance for reducing oxygen content and improving cleanliness of high-quality bearing steel.Therefore,it is necessary to study the mechanism and kinetics of C and H_(2) deoxidation and analyze the factors affecting deoxidation effect systematically,so as to provide a solid theoretical basis for the practice of non-alloy deoxidation process for high-quality bearing steel.
基金Item Sponsored by National Natural Science Foundation of China(51134009)Fundamental Research Funds for Central Universities of China(N100102001)
文摘Mass action concentration (activity) calculation model was used to analyze the variation rule of mass action concentrations of slag compositions with basicity changing, and the effect of basicity on deoxidation capability and control of spinel and globular inclusions was investigated theoretically. From the calculation and experimental results, it was found that with the increase of basicity, the mass action concentration of Al2O3 and SiO2 decreases, while the mass action concentration of FeO and MgO increases at first and then decreases.Slag basicity below 3 to 4 would help to control spinel inclusions formation, and higher basicity improves formation of globular inclusions. Slag with basicity under 2 can effectively control the formation of globular inclusions. Deoxidation capability of slag increases with the increase of basicity, and slag with basicity about 4 could almost reach the maximum deoxidation capability. In order to smelt low oxygen steel with globular inclusions controlled, refining slag basicity should be controlled at about 4.
文摘The thermodynamic characteristics of desulfurization reaction (CaO)+[S]=(CaS)+[O] is analyzed based on the detailed composition of liquid steel and slag of Steel Plate Hot Commercial (SPHC) in Jiuquan Iron & Steel Corporation(JISC), where the activities of CaO, CaS and Al2O3 in molten slag are calculated by thermodynamic software FactSage for a more accurate result. The critical values of [O%]/[S%] for desulfurization at different temperature is are obtained, typically 0.09 at 1873K, which shows directly that it should deoxidize adequately for obtaining a favorable desulfurization condition. In addition, the thermodynamic analysis indicates that the actual dissolved O is much higher than that of equilibrium calculation which shows Al-O reaction in LF is far away from equilibrium, but it is perfect agreement with the computing results when taking the activity of Al2O3 as 1 that due to the inclusion component in LF is mainly Al2O3. Besides, with the temperature rise, the sulfur partition ratio increases softly meanwhile the reaction between Al and O is limited to a great degree resulting in the increase a dissolved oxygen in liquid steel that decreases the sulfur partition ratio seriously. As a result, the sulfur partition ratio appears to decrease with temperature increase in Al killed steel.
基金Item Sponsored by National Natural Science Foundation of China(61271303)
文摘Steel and slag samples were taken at the start and the end of LF refining for steel plate cold common (SPCC), in the compact strip production (CSP) process, and at the same time, the temperature and oxygen activity a[o] were measured by using an oxygen sensor. Furthermore, inclusions in steel samples were monitored by scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (EDS). It was confirmed that a [o] in liq- uid steel was in equilibrium with inclusion rather than with top slag during LF refining. Desulfurization was related to deoxidation since a[o] at slag-steel interface was clarified to be very close to that in liquid steel under the specific con- dition in LF with intense stirring by argon blowing and refined by highly basic low oxidizing slag for Al-killed steel. Sulfur partition ratio (Ls) was very sensitive to a[o]. Since a[o] increased rapidly with temperature rise, it not only offset promotion to desulfurization reaction with temperature rise but decreased Ls. For Al-killed steel, the.modifica- tion of Al2O3 for lowering the activity of Al2O3 in inclusion was believed to be favorable for both deoxidation and desulfurization during LF refining.
基金Item Sponsored by National Natural Science Foundation of China(51304018)
文摘The deoxidation equilibrium of liquid steel was investigated from a new perspective. Dissolved associate MmOn was used to describe the interaction between dissolved M and dissolved oxygen instead of the interaction parameter of Wagner. The concentration of unassociated oxygen could be considered as the activity of oxygen. Or, the percentage of unassociated oxygen in the total dissolved oxygen was the activity coefficient of oxygen. When the content of deoxidizer was low, the dissolved oxygen was mainly composed of the unassociated oxygen, while more and more MxO formed with gradually increasing M content. The present model gave a good description to the aluminum deoxidation equilibrium after considering AlO and Al2O. Furthermore, the higher the con- tent of A1 was, the higher the content of Al2O relative to the content of AlO would be.
文摘The present work deals with thermodynamic modeling of oxide systems, in the context of slags and inclusions in steelmaking. The work has emphasis on oxides encountered during the production of tire – cord steel. Control of inclusion chemistry and variation in eutectic temperature and eutectic composition of MnO-Al2O3-SiO2 slag system have been studied, using Thermo-CalcR software. Relatively low liquidus temperatures are obtained for ratio of MnO / SiO2 = 0.5 - 1.5 and Al2O3 content from 10 - 20 mass%. It has been observed that the addition of Alumina leads to further increase in the liquidus temperature. The stability of inclusions is analyzed in terms of free energy values of related slag systems; and an appropriate minimum of Gibbs free energy value of slag phase observed at around 50 ppm of Oxygen. The observations could not be verified using thermodynamic experiments, but have been compared with findings in the open literature.
基金financially supported by the National Natural Science Foundation of China (No. 51004054)Foundation from the Liaoning Province Education Department (No. L2013127)
文摘Based on the two-step nucleation mechanism, a multi-step thermodynamic model for alumina inclusion for- mation during aluminum deoxidation process was proposed in Fe-O-Al melt. Thermodynamic properties of metastable intermediates including (Al2O3)n clusters for prenucleation and α-Al2O3 nanoparticle for growth process were calculated using density functional theory. Furthermore, Gibbs free energy change of forming the intermediate by reaction between the dissolved aluminum (Al) and oxygen (O) in the melt was calculated. The results indicated that the thermodynamics of (Al2O3)n at steelmaking temperature are dependent on their structures, while that of α-Al2O3 nanoparticle are dependent on their size. The nuclei of α-Al2O3 which was originated from (Al2O3)n aggregated under a high supersaturation ratio of Al and O(Rs) in the melt. There existing excess oxygen because of the low Rs, but the secondary inclusions will be formed during the cooling process due to the excess oxygen. The nuclei lager than 20 nm can grow up spontaneously and instantaneously into primary inclusions because of thermodynamic drive. It is difficult to control the size of α-Al2O3 to be less than 20 nm, in the aluminum deoxidation process of the current conditions of steelmaking.
基金financially supported by the National Natural Science Foundation of China (Nos.11765010,51704136)the Applied Basic Research Programs of Yunnan Provincial Science and Technology Department (No.2016FB087)the Freely Exploring Fund for Academicians in Yunnan Province (No.2018HA006)
文摘In this study,impurity-free porous graphene(PG) with intrinsic pore structure was synthesized through a facile acid-alkali etching-assisted sonication approach.The pore structure appears on the surface of graphene sheets due to intrinsic defects of graphene.The PG possessed an extremely high specific surface area of 2184 m^2/g,the size of^5 μm and layer numbers of 3-8.Additionally,PG contained micropores and mesopores simultaneously,with an average pore diameter of approximately 3 nm.The effects of acid,alkali,and ultrasound treatment on PG preparation were elucidated by transmission electron microscopy and fourier transform infrared spectroscopy.First,in an acidic solution,oxygen-containing functional groups(hydroxyls,carboxyl,and epoxides) were formed due to the hydrolysis of sulfate and continuous transformations of these functional groups on graphene oxide.Second,under the synergistic effects of alkali and ultrasound treatment,PG was obtained due to the loss of carboxyl and epoxide groups.A new route for preparing PG was provided by the proposed method.
文摘The thermodynamic equilibrium of deoxidation reactions between molten slag and steel was calculated using a slag-steel coupling thermodynamic model and the mass conservation model based on the ion-molecular coexistence theory.The study focused on the effects of slag composition and deoxidizer type on the oxygen content of low alloy steel during the electroslag remelting(ESR)process.The measured and predicted values of the oxygen content in remelted ingots,and the contents of FeO and MnO in slags were compared and analyzed.Results show that the measured content of total oxygen has a certain correlation with the trend of dissolved oxygen predicted by the model when using Ca-Si alloys as deoxidizer,but it is not correlated with the trend of dissolved oxygen predicted by the model when using Al as deoxidizer.The deoxidation mechanisms of Ca-Si and Al are different.Ca-Si alloy directly reacts with FeO and MnO in slag to reduce the oxygen potential of slag,hence it can inhibit the transfer of oxygen from the slag to molten steel.While,when Al deoxidizer is used,the oxygen content in steel is mainly reduced through floating up the alumina inclusions.Compared to Al,utilizing Ca-Si alloy as a deoxidizer is more effective in reducing the oxygen content and the amount of inclusions in ESR ingot.
文摘The formation of oxide inclusions in one of the carbon steel productions of Mobarakeh Steel Complex of Isfahan has been evaluated. Several samples from different steps of steel production were taken, from arc furnace, ladle furnace, tundish, and continuous casting mold. Moreover, samples of slab and hot rolling products were prepared. The samples were investigated by optical and scanning electron microscopes equipped with the EDS system. According to the results, the number, composition, and kind of inclusions were directly influenced by the production variables. It was found that when the amount of dissolved oxygen was high (say more than 0. 002 5%), the dissolved aluminum was able to reduce silicon oxide and react with the dissolved oxygen simultaneously, whilst, the dissolved aluminum could reduce the magnesium oxide only when the oxygen content was below 0. 000 5%. Based on this research, a mechanism for forming the complex inclusions was suggested. It was also found that if the aluminum is added to the melt as late as possible, a cleaner melt with fewer inclusions is prepared; this method will be more effective, especially in the case of complex inclusions.