Laboratory experiments and thermodynamic calculations were performed to investigate the interfacial reactions between the MgO-C refractory and the steel with and without the lanthanum(La)addition.Following a reaction ...Laboratory experiments and thermodynamic calculations were performed to investigate the interfacial reactions between the MgO-C refractory and the steel with and without the lanthanum(La)addition.Following a reaction time of 50 min,a reaction layer comprised MgO and CaS with a thickness of 30μm was observed at the interface between the La-free steel and refractory.The MgO layer was observed in La-bearing steel after just 10 min of reaction.The addition of La to the steel accelerated the formation of the MgO layer.As the reaction time increased,a La-containing layer was formed at the La-bearing steel/refractory interface.This La-containing layer progressed through stages from La_(2)O_(2)S+La2O3→La-Ca-O-S→La-Ca-O→La-Ca-Al-O.Furthermore,the evolution of oxide inclusions in the La-free steel followed the sequence of MgO⋅Al_(2)O_(3),Ti-Ca-Al-O and Ti-Mg-Al-O→MgO·Al_(2)O_(3)and MgO with increasing the reaction time.In contrast,the sequence for the La-bearing steel was:La_(2)O_(2)S and La2O3→La_(2)O_(2)S and La-Ti-Al-Mg-O→La-Ti-Al-Mg-O,MgO and MgO·Al_(2)O_(3).The average penetration depth of the La-bearing steel into the refractory was notably lower than that of the La-free steel,revealing that the incorporation of rare earth element La in steel exhibits a significant inhibitory effect on the penetration of molten steel into the MgO-C refractory.展开更多
The effect of Al content in molten steel on the interaction between SPHC steel(0.005-0.068 wt.%Al,and 19×10^(-4)-58×10^(-4)wt.%O)and MgO-C refractory(11.63 wt.%C)was investigated.Non-metallic inclusions in t...The effect of Al content in molten steel on the interaction between SPHC steel(0.005-0.068 wt.%Al,and 19×10^(-4)-58×10^(-4)wt.%O)and MgO-C refractory(11.63 wt.%C)was investigated.Non-metallic inclusions in the steel were examined at various periods(0,5,15,30,45,and 60 min)as well as the MgO-C interface after 60 min of corrosion at 1600℃.The results show that when MgO-C refractory comes into contact with SPHC steel,the refractory interface consists of three layers arranged from the innermost to the outermost,including the original refractory layer,the dense MgO layer,and the iron infiltration layer.The carbon in the MgO-C refractories and the Al content in the molten steel undergo a reaction with the MgO in the refractories,resulting in an increase in Mg concentration in the steel.Increasing Al content in the molten steel from 0.005 to 0.068 wt.%causes a spinel layer to appear at the interface,and the disappearance time of Al_(2)O_(3) inclusions in the steel decreases from 60 to 30 min,while the average MgO content in inclusions increases.Therefore,controlling the Al content in the molten steel and the smelting duration can help regulate the formation of spinel inclusionsinthe steel.展开更多
In-situ magnesia-rich spinel fiber was formed resulting from the addition of ferrocene into MgO-C refractory matrixes. The formation of in-situ spinel fiber was detected to start at 1300 ℃. The amount, diameter and l...In-situ magnesia-rich spinel fiber was formed resulting from the addition of ferrocene into MgO-C refractory matrixes. The formation of in-situ spinel fiber was detected to start at 1300 ℃. The amount, diameter and length of the fibers increased with rising temperature. Ferrocene may have catalytic effects on the growth of the fibers in two aspects. First, the reaction between MgO and C and the decomposition of Al4C3 may be catalyzed at high temperature. Suitable concentration gaseous phase is then created for vapor-vapor reaction which could result in the in-situ formation of fibers. Second, Fe nanoparticle produced from ferrocene can act as catalytic droplets and catalyze the growth of the fibers. The fibers are formed via the vapor-liquid-solid and vapor-solid mechanisms. In terms of chemical thermodynamics, the partial pressure of CO and Mg（g） are found to play an important role in the in-situ fibers formation. Different concentration of vapors affects the size, amount and composition of the fibers at different temperatures. The mechanical properties of MgO-C brick was found to be improved by ferrocene addition.展开更多
Kinetics of oxidation of MgO-C refractories was investigated by shrinking core modeling of the gas-solid reactions taking place during heating the porous materials to the high temperatures. Samples containing 4.5-17 w...Kinetics of oxidation of MgO-C refractories was investigated by shrinking core modeling of the gas-solid reactions taking place during heating the porous materials to the high temperatures. Samples containing 4.5-17 wt pct graphite were isothermally oxidized at 1000-1350℃. Weight loss data was compared with predictions of the model. A mixed 2-stage mechanism comprised of pore diffusion plus boundary layer gas transfer was shown to generally control the oxidation rate. Pore diffusion was however more effective, especially at graphite contents lower than 10 wt pct under forced convection blowing of the air. Model calculations showed that effective gas diffusion coefficients were in the range of 0.08 to 0.55 cm^2/s. These values can be utilized to determine the corresponding tortuosity factors of 6.85 to 2.22. Activation energies related to the pore diffusion mechanism appeared to be around （46.44±2） kJ/mol. The estimated intermolecular diffusion coefficients were shown to be independent of the graphite content, when the percentage of the graphite exceeded a marginal value of 10.展开更多
Graphite, used as a carbon source in a conventional magnesia-carbon(MgO-C) refractory, was modified with an acid reagent, resulting in a negative charge on the surface of graphite, to enhance the coating efficiency of...Graphite, used as a carbon source in a conventional magnesia-carbon(MgO-C) refractory, was modified with an acid reagent, resulting in a negative charge on the surface of graphite, to enhance the coating efficiency of aluminum(Al) phase, which was compared to the pristine graphite through its dispersibity and oxidation behavior. The graphite particles with and without surface modification were added, respecticely, in an Al(NO3)3 suspension used as a coating reagent, and then filtered at room temperature. The modified graphite shows better disperbility than the pristine graphite, indicating that the coating efficiency of Al precursor is enhanced in the modified graphite. With respect to oxidation behavior, the modified graphite without the coating layer is totally reacted with oxygen at heat treatment of 900 °C in air. However, the Al-coated graphite starts to react with oxygen at heat treatment of 900 °C and fully reacted with oxygen at heat treatment of 1000 °C, showing the gray and white colors, respectively. It is verified that the Al layer is individually and uniformly formed on the surface of graphite and the oxidation resistance of graphite is enhanced owing to the increased coating efficiency of Al precursor.展开更多
Nitrogen gas pressure sintering was successfully employed to achieve the in-situ formation of Si_(3)N_(4)-bonded MgO-C refractories.The primary objective was to investigate the influence of different gas pressures on ...Nitrogen gas pressure sintering was successfully employed to achieve the in-situ formation of Si_(3)N_(4)-bonded MgO-C refractories.The primary objective was to investigate the influence of different gas pressures on the mechanical properties and microstructure of MgO-C refractories.The results indicate that higher nitrogen pressure promotes the transformation of silicon nitride from theαphase to theβphase.This phase transition positively impacts the mechanical properties of Si_(3)N_(4)-bonded MgO-C refractories,leading to an enhancement in their overall strength.Notably,when the nitrogen pressure was set at 3 MPa,exceptional compressive strength of 109.7 MPa and an elastic modulus of 142.4 GPa were achieved by these prepared refractories.These findings highlight the great potential for utilizing gas pressure sintered Si_(3)N_(4)-MgO-C refractories.展开更多
The interaction of MgO-MgAl_(2)O_(4)-based and MgO-Cr_(2)O_(3)-based refractories with X70 molten steel was studied by immersion experiments at 1560℃.The effects of immersion time(30 and 60 min)on the contents of tot...The interaction of MgO-MgAl_(2)O_(4)-based and MgO-Cr_(2)O_(3)-based refractories with X70 molten steel was studied by immersion experiments at 1560℃.The effects of immersion time(30 and 60 min)on the contents of total oxygen(TO),Al,Nb,Si,Mn,and Cr as well as the composition,number density,and size distribution of inclusions in the molten steel were investigated.The influence of the penetration and erosion degree of the molten steel to the refractory on the steel-refractory interface layer was analyzed.The results show that,at 1560℃,the MgO-MgAl_(2)O_(4)-based refractory can better control the contents of TO and the composition of molten steel compared with the MgO-Cr_(2)O_(3)-based refractory.The TO content is only 16×10^(-4) wt.%in the molten steel after reacted with the Mg0-MgAl_(2)O_(4)-based refractory at the end point of refining,4 accounting for 11.5%of that reacted with the MgO-Cr_(2)O_(3)-based refractory(139×10^(-4) wt.%).The number density of inclusions is only 14 mm^(-2),and the average size ofinclusions is only 1.31μm,with thelargest proportion of inclusions in 1-2μm(70%).The Al_(2)O_(3)-MnS-CaO complex inclusions in the original steel changed to complex inclusions dominated by Cr-Nb-Mn-S-O and MgO.Al_(2)O_(3),corresponding to the MgO-Cr_(2)O_(3)-based and MgO-MgAl_(2)O_(4)-based refractories,respectively.The MgO.Al_(2)O_(3) layer was formed at the reaction interface between MgO-MgAl_(2)O_(4)-based refractory and molten steel,which is helpful to restrict the erosion of refractories and the pollution of molten steel.The damage mechanism of the MgO-Cr_(2)O_(3)-based refractory is mainly permeation and chemical reaction,while the damage of the MgO-MgAl_(2)O_(4)-based refractory is mainlyscouring erosion.展开更多
The service life of refractory brick in the slag tapping hole of gasifiers is a significant concern for long-term and stable operation.This study examined the damage mechanism of high chromia refractory of four commer...The service life of refractory brick in the slag tapping hole of gasifiers is a significant concern for long-term and stable operation.This study examined the damage mechanism of high chromia refractory of four commercial coal-water slurry gasifiers with their corresponding gasification coal samples and the corroded refractory bricks in the slag tapping hole of the gasifier.The slag characteristic,including crystallization and viscosity-temperature of four gasification coal samples were analyzed.The results revealed that the low viscosity slag could lead to more severe damage to refractory bricks.Given the risk of slag crystallization,it is recommended to establish a safe slag tapping temperature range should be set as tICT(initial crystallization temperature)−t_(2.5) when tICT is higher than t_(25).Upon examining interior morphology of these corroded refractory bricks,some cracks were observed within them.The chemical composition of molten slag was analyzed using SEM-EDS.However,XRD results found no spinel containing zirconium in these cracks.This suggests that the emergence of these cracks are mainly attributed to the molten slag penetration and the subsequent reaction with the refractory material.The difference in thermal expansion between the newly formed substances and refractory material is critical in forming these cracks.Furthermore,SEM-EDS analysis was also conducted on the slag-aggregate and the slag-matrix interface.The results reveal that the reduction in Cr_(2)O_(3) content is the earliest characteristic of damage in high chromia refractories.A proposed damage mechanism of refractory brick suggests that the matrix and aggregate of high chromia refractory are initially compromised because of the reduced Cr_(2)O_(3) content.Subsequently,the molten slag penetrates the interior of the refractory brick,forming new substances,leading to damage caused by the difference in thermal expansion between the new substances and the refractory brick.Understanding and preventing the reduction of Cr_(2)O_(3) content is vital to prolonging the service life of refractory brick in the slag tapping hole of the gasifier based on this damage mechanism.展开更多
Refractory metals,including tungsten(W),tantalum(Ta),molybdenum(Mo),and niobium(Nb),play a vital role in industries,such as nuclear energy and aerospace,owing to their exceptional melting temperatures,thermal durabili...Refractory metals,including tungsten(W),tantalum(Ta),molybdenum(Mo),and niobium(Nb),play a vital role in industries,such as nuclear energy and aerospace,owing to their exceptional melting temperatures,thermal durability,and corrosion resistance.These metals have body-centered cubic crystal structure,characterized by limited slip systems and impeded dislocation motion,resulting in significant low-temperature brittleness,which poses challenges for the conventional processing.Additive manufacturing technique provides an innovative approach,enabling the production of intricate parts without molds,which significantly improves the efficiency of material usage.This review provides a comprehensive overview of the advancements in additive manufacturing techniques for the production of refractory metals,such as W,Ta,Mo,and Nb,particularly the laser powder bed fusion.In this review,the influence mechanisms of key process parameters(laser power,scan strategy,and powder characteristics)on the evolution of material microstructure,the formation of metallurgical defects,and mechanical properties were discussed.Generally,optimizing powder characteristics,such as sphericity,implementing substrate preheating,and formulating alloying strategies can significantly improve the densification and crack resistance of manufactured parts.Meanwhile,strictly controlling the oxygen impurity content and optimizing the energy density input are also the key factors to achieve the simultaneous improvement in strength and ductility of refractory metals.Although additive manufacturing technique provides an innovative solution for processing refractory metals,critical issues,such as residual stress control,microstructure and performance anisotropy,and process stability,still need to be addressed.This review not only provides a theoretical basis for the additive manufacturing of high-performance refractory metals,but also proposes forward-looking directions for their industrial application.展开更多
Microwave roasting self-leaching is an innovative method for recovering gold from high-sulfur refractory gold concentrates,without using deadly toxic cyanide reagents.However,the mechanism of gold self-leaching,which ...Microwave roasting self-leaching is an innovative method for recovering gold from high-sulfur refractory gold concentrates,without using deadly toxic cyanide reagents.However,the mechanism of gold self-leaching,which relies on lixiviants prepared using volatilized sulfur obtained from roasting,has not been fully elucidated.This study employs the response surface methodology to optimize processing parameters,resulting in an increased gold extraction rate of 96.18%.Analytical factorization and the Tafel curve indicate that CuSO_(4) and NH_(3)·H_(2)O significantly influence the self-leaching process.Furthermore,X-ray photoelectron spectroscopy(XPS)analysis reveals that S^(2−),S_(2)^(2−),polysulfides(S_(n)^(2−)),and thiosulfate(S_(2)O_(3)^(2−))are involved in the gold leaching reaction,with S^(2−),S_(2)^(2−),and S_(n)^(2−) serving as primary ligands for gold complexation.The role of S_(2)O_(3)^(2−) in the early stages of the gold-leaching reaction is also noteworthy.The copper–ammonia complex catalyzes the self-leaching gold reaction;however,an improper addition ratio can lead to copper-sulfur compound precipitates,reducing the extraction rate.展开更多
MgO-C refractories with stainless steel fibers were prepared to investigate the effects of stainless steel fibers addition on the thermal shock resistance,oxidation resistance,and microstructure of MgO-C refractories,...MgO-C refractories with stainless steel fibers were prepared to investigate the effects of stainless steel fibers addition on the thermal shock resistance,oxidation resistance,and microstructure of MgO-C refractories,and the optimum amount of stainless steel fibers was determined.The results showed that adding stainless steel fiber in MgO-C refractories can increase flexural strength and thermal shock resistance,with an optimal addition of 2 wt.%,owing to the bridging effect and crack deflection toughening of stainless steel fibers inside the material.The formation of MgAl1.9Fe0.1O4 composite spinel,which was responsible for higher oxidation resistance,produced volume expansion and prevented the diffusion of oxygen.The strengthening mechanism is physical embedding at room temperature,while it is reaction bonding at high temperature.展开更多
To solve the problem of poor high-temperature service performance caused by low carbonization of MgO-C refractories,low-carbon MgO–C refractories with excellent thermal shock,oxidation and corrosion resistances were ...To solve the problem of poor high-temperature service performance caused by low carbonization of MgO-C refractories,low-carbon MgO–C refractories with excellent thermal shock,oxidation and corrosion resistances were successfully designed by using SiC whiskers as reinforcing phases and introducing micro-Al_(2)O_(3) powders as additives.The results indicated that the addition of micro-Al_(2)O_(3) powders optimized the internal structure of the material,like the columnar β-Si_(3)N_(4) with a stepped distribution and the mosaic structure formed between granular and flaky Mg_(2)SiO_(4),which synergistically strengthened and toughened the material and gave the material excellent mechanical properties and thermal shock resistance.Specifically,the cold modulus of rupture and cold crushing strength after thermal shock were increased by 4.1 and 20.3 MPa,respectively.Moreover,the addition of micro-Al_(2)O_(3) powders promoted the formation of fine particles of Mg_(2)SiO_(4),MgAl_(2)O_(4) and MgO,as well as a dense protective layer of Mg_(2)SiO_(4) in the material under high-temperature environment.Furthermore,spinel and high-temperature solid solution were formed in the corrosion environment.The oxidation and corrosion resistances were greatly improved by 41%and 15%,respectively.展开更多
Wetting phenomena between MgO C and CaO SiO2 slags were investigated by varying carbon content.A sessile drop technique was adopted to study the wetting phenomena in conjunction with a high speed camera for the observ...Wetting phenomena between MgO C and CaO SiO2 slags were investigated by varying carbon content.A sessile drop technique was adopted to study the wetting phenomena in conjunction with a high speed camera for the observation of intrinsic wetting phenomena.The results show that the high content of SiO2 and the presence of Al2O3 in slags enhance the diffusion of Mg2+,leading to the promotion of reactive wetting.The carbon in MgO C refractory impedes the penetration of slags by repelling the slag and slowing the diffusion of Mg2+.This accounts for the non-wetting behavior of the slag on MgO C refractory with 17% (mass fraction) carbon similar to that of graphite.展开更多
Al2O3-SiC composite was synthesized with pyrophyllite and natural graphite as raw materials by carbothermal reduction reaction under argon atmosphere. The effect of synthesis temperature on phase composition and micro...Al2O3-SiC composite was synthesized with pyrophyllite and natural graphite as raw materials by carbothermal reduction reaction under argon atmosphere. The effect of synthesis temperature on phase composition and microstructure was investigated. Low-carbon MgO-C refractories were prepared by using the synthesized Al2O3-SiC composite as additive. The effect of its addition on the slag penetration and corrosion resistance as well as oxidation resistance of the refractories was investigated, and the slag resistance and oxidation resistance mechanisms of the Al2O3-SiC composite were also discussed. The results show that the synthesis temperature has a great influence on preparation of Al2O3-SiC composite. The Al2O3-SiC composite can be synthesized at 1873-1973 K under argon atmosphere, with pyrophyllite and natural graphite as raw materials, and particle sizes of the composite synthesized at 1973 K are mainly distributed as 1-2 μm. The slag penetration and corrosion resistance of low-carbon M80-C refractories can be remarkably improved by adding the synthesized Al2O3-SiC composite, and the oxidation resistance has an improvement to some extent. The increase of slag viscosity and the formation of MgAl2O4 can effectively inhibit the slag penetration and corrosion for the refractories.展开更多
Al_(4)SiC_(4) was synthesized from Al powder, silicon carbide, and graphite by microwave sintering, and characterized by XRD and SEM. Then the synthesized material was added to the magnesia carbon refractory brick to ...Al_(4)SiC_(4) was synthesized from Al powder, silicon carbide, and graphite by microwave sintering, and characterized by XRD and SEM. Then the synthesized material was added to the magnesia carbon refractory brick to study its effect on the oxidation resistance, apparent porosity, bulk density, elastic modulus, and modulus of rupture. It is found that Al_(4)SiC_(4) can be synthesized by microwave sintering at 1 300 ℃ and the addition of Al_(4)SiC_(4)-containing material as an antioxidant can enhance the oxidation resistance of the magnesia carbon refractory brick.展开更多
Magnesiu-Calcia materials containing 22 -53 wt% CaO hare been investigated Jot refinery slag corrosion and penetration resistance by Scanning Electron Microscopy （ SEM） .nd XRD. The corrosion and penetration resista...Magnesiu-Calcia materials containing 22 -53 wt% CaO hare been investigated Jot refinery slag corrosion and penetration resistance by Scanning Electron Microscopy （ SEM） .nd XRD. The corrosion and penetration resistance of MgO-CaO materials is enhanced with the increase of CaO content in specimens. It can be explained that, with increase of CaO content, the specimens reacted will＋ slag form higher melting point minerals of C3S ant C2S, creating a dense surface layer, which stopped others from penetrating further. Thus , the corrosion and penetration resistame was improved. No matter what kinds of slag were chosen, the depth of penetration decreased will＋ increase of CaO con,tent.展开更多
Carbon nanotubes （CNTs） have been extensively studied over the last two decades since they possess excellent properties.CNTs have been considered as new promising reinforcements for carbon containing refractories （...Carbon nanotubes （CNTs） have been extensively studied over the last two decades since they possess excellent properties.CNTs have been considered as new promising reinforcements for carbon containing refractories （CCRs）.Current research progress of the CNT-reinforced MgO-C and Al2O3-C refractories was summarized in this mini-review,and the CNT-reinforced CCRs possess remarkable mechanical properties and superior thermal shock resistance compared to CCRs without CNTs.展开更多
An investigation on the oxidation mechanism of the graphite in the MgO-C refractory materials is helpful to improving both the quality of these materials and to preventing and/or lowering of the adverse effects of the...An investigation on the oxidation mechanism of the graphite in the MgO-C refractory materials is helpful to improving both the quality of these materials and to preventing and/or lowering of the adverse effects of the high-temperature oxidation. In this research, the oxidation behavior of the MgO-C refractories containing 5～20 wt% graphite was studied via weight-loss method. Atmospheric air was used for oxidation at temperatures ranging from 900℃ to 1300°C and the experimental data were compared with those obtained from the dimensionless kinetic equations of the shrinking core model, in order to determine the oxidation mechanisms of the refractories. The best fit was achieved with the porous layer diffusion control regime. Oxidation mechanism tends, however, to slightly deviate from pure pore diffusion control to pore diffusion-external gas transfer regime in the samples having more graphite contents (e.g. 20%).展开更多
The demand for low-carbon MgO–C refractories is ever growing to meet the development of advanced steelmaking technologies and efficient energy conservation.Meanwhile,to improve the oxidation resistance and inhibit th...The demand for low-carbon MgO–C refractories is ever growing to meet the development of advanced steelmaking technologies and efficient energy conservation.Meanwhile,to improve the oxidation resistance and inhibit the weakness of low-carbon MgO–C refractories,antioxidants are necessary.The application of ternary carbides that focused on improving the oxidation performance of MgO–C refractories has been explored,and the ternary carbides including Al_(4)O_(4)C,Al8B_(4)C_(7),Al_(4)SiC_(4),Ti_(2)AlC,Ti_(3)AlC_(2),and Ti_(3)SiC_(2)have been proved effective.The crystal structure,physical properties,oxidation behavior,and synthesis of these ternary carbides were summarized,and their oxidation mechanism in assisting antioxidation of MgO–C refractories was discussed.In addition,the potential aspects related to the usage and development of ternary carbides in low-carbon MgO–C refractories were proposed.展开更多
Corrosion resistance and penetration resistance of MgO-CaO materials with different CaO contents （22%, 42%, 49%, 53%, in mass）to refining AOD slag or VOD slag were investigated using static crucible technique by vis...Corrosion resistance and penetration resistance of MgO-CaO materials with different CaO contents （22%, 42%, 49%, 53%, in mass）to refining AOD slag or VOD slag were investigated using static crucible technique by visual observation, SEM and XRD. The corrosion resistance and penetration resistance of speci-mens decrease with the increase of CaO content. This may be caused by the formation of C3S and C2S during the reactions between specimens and the slag. The formed C3S and C2S can restrain the further penetration to the matrix. The higher the CaO content, the more the C2S or C3S formed, the lower the porosity of the speci-mens, and the lower the penetration depth and corrosion rate. The corrosion resistance to AOD slag is better than that to VOD slag, because the reaction between AOD slag and the matrix is slighter than that between VOD slag and the matrix.展开更多
基金the support from the National Key R&D Program(No.2023YFB3709900)the National Key R&D Program(No.2023YFB3709901)+2 种基金the National Natural Science Foundation of China(Grant No.U22A20171)the Hebei Natural Science Foundation(Grant No.52304340)the High Steel Center(HSC)at North China University of Technology.
文摘Laboratory experiments and thermodynamic calculations were performed to investigate the interfacial reactions between the MgO-C refractory and the steel with and without the lanthanum(La)addition.Following a reaction time of 50 min,a reaction layer comprised MgO and CaS with a thickness of 30μm was observed at the interface between the La-free steel and refractory.The MgO layer was observed in La-bearing steel after just 10 min of reaction.The addition of La to the steel accelerated the formation of the MgO layer.As the reaction time increased,a La-containing layer was formed at the La-bearing steel/refractory interface.This La-containing layer progressed through stages from La_(2)O_(2)S+La2O3→La-Ca-O-S→La-Ca-O→La-Ca-Al-O.Furthermore,the evolution of oxide inclusions in the La-free steel followed the sequence of MgO⋅Al_(2)O_(3),Ti-Ca-Al-O and Ti-Mg-Al-O→MgO·Al_(2)O_(3)and MgO with increasing the reaction time.In contrast,the sequence for the La-bearing steel was:La_(2)O_(2)S and La2O3→La_(2)O_(2)S and La-Ti-Al-Mg-O→La-Ti-Al-Mg-O,MgO and MgO·Al_(2)O_(3).The average penetration depth of the La-bearing steel into the refractory was notably lower than that of the La-free steel,revealing that the incorporation of rare earth element La in steel exhibits a significant inhibitory effect on the penetration of molten steel into the MgO-C refractory.
基金supported by the National Natural Science Foundation of China(51974017).
文摘The effect of Al content in molten steel on the interaction between SPHC steel(0.005-0.068 wt.%Al,and 19×10^(-4)-58×10^(-4)wt.%O)and MgO-C refractory(11.63 wt.%C)was investigated.Non-metallic inclusions in the steel were examined at various periods(0,5,15,30,45,and 60 min)as well as the MgO-C interface after 60 min of corrosion at 1600℃.The results show that when MgO-C refractory comes into contact with SPHC steel,the refractory interface consists of three layers arranged from the innermost to the outermost,including the original refractory layer,the dense MgO layer,and the iron infiltration layer.The carbon in the MgO-C refractories and the Al content in the molten steel undergo a reaction with the MgO in the refractories,resulting in an increase in Mg concentration in the steel.Increasing Al content in the molten steel from 0.005 to 0.068 wt.%causes a spinel layer to appear at the interface,and the disappearance time of Al_(2)O_(3) inclusions in the steel decreases from 60 to 30 min,while the average MgO content in inclusions increases.Therefore,controlling the Al content in the molten steel and the smelting duration can help regulate the formation of spinel inclusionsinthe steel.
基金Funded by the National Natural Science Foundation of China (No.50872125)
文摘In-situ magnesia-rich spinel fiber was formed resulting from the addition of ferrocene into MgO-C refractory matrixes. The formation of in-situ spinel fiber was detected to start at 1300 ℃. The amount, diameter and length of the fibers increased with rising temperature. Ferrocene may have catalytic effects on the growth of the fibers in two aspects. First, the reaction between MgO and C and the decomposition of Al4C3 may be catalyzed at high temperature. Suitable concentration gaseous phase is then created for vapor-vapor reaction which could result in the in-situ formation of fibers. Second, Fe nanoparticle produced from ferrocene can act as catalytic droplets and catalyze the growth of the fibers. The fibers are formed via the vapor-liquid-solid and vapor-solid mechanisms. In terms of chemical thermodynamics, the partial pressure of CO and Mg（g） are found to play an important role in the in-situ fibers formation. Different concentration of vapors affects the size, amount and composition of the fibers at different temperatures. The mechanical properties of MgO-C brick was found to be improved by ferrocene addition.
文摘Kinetics of oxidation of MgO-C refractories was investigated by shrinking core modeling of the gas-solid reactions taking place during heating the porous materials to the high temperatures. Samples containing 4.5-17 wt pct graphite were isothermally oxidized at 1000-1350℃. Weight loss data was compared with predictions of the model. A mixed 2-stage mechanism comprised of pore diffusion plus boundary layer gas transfer was shown to generally control the oxidation rate. Pore diffusion was however more effective, especially at graphite contents lower than 10 wt pct under forced convection blowing of the air. Model calculations showed that effective gas diffusion coefficients were in the range of 0.08 to 0.55 cm^2/s. These values can be utilized to determine the corresponding tortuosity factors of 6.85 to 2.22. Activation energies related to the pore diffusion mechanism appeared to be around （46.44±2） kJ/mol. The estimated intermolecular diffusion coefficients were shown to be independent of the graphite content, when the percentage of the graphite exceeded a marginal value of 10.
基金Project(2011-0030058) supported by the National Research Foundation of Korea(NRF)Project(20134030200220) supported by the Human Resources Development Program of the Korea Institute of Energy Technology Evaluation,Korea+1 种基金Project supported by the Planning (KETEP) Grant Funded by the Korea Government Ministry of Trade,Industry and Energy and POSCO 2012,KoreaProject(10043795) supported by the Technology Innovation Program of the Ministry of Knowledge Economy Korea
文摘Graphite, used as a carbon source in a conventional magnesia-carbon(MgO-C) refractory, was modified with an acid reagent, resulting in a negative charge on the surface of graphite, to enhance the coating efficiency of aluminum(Al) phase, which was compared to the pristine graphite through its dispersibity and oxidation behavior. The graphite particles with and without surface modification were added, respecticely, in an Al(NO3)3 suspension used as a coating reagent, and then filtered at room temperature. The modified graphite shows better disperbility than the pristine graphite, indicating that the coating efficiency of Al precursor is enhanced in the modified graphite. With respect to oxidation behavior, the modified graphite without the coating layer is totally reacted with oxygen at heat treatment of 900 °C in air. However, the Al-coated graphite starts to react with oxygen at heat treatment of 900 °C and fully reacted with oxygen at heat treatment of 1000 °C, showing the gray and white colors, respectively. It is verified that the Al layer is individually and uniformly formed on the surface of graphite and the oxidation resistance of graphite is enhanced owing to the increased coating efficiency of Al precursor.
基金the financial support from the National Natural Science Foundation of China(U21A2057 and 52402034)the Key Research and Development Program of Hubei Province(2023BAB106).
文摘Nitrogen gas pressure sintering was successfully employed to achieve the in-situ formation of Si_(3)N_(4)-bonded MgO-C refractories.The primary objective was to investigate the influence of different gas pressures on the mechanical properties and microstructure of MgO-C refractories.The results indicate that higher nitrogen pressure promotes the transformation of silicon nitride from theαphase to theβphase.This phase transition positively impacts the mechanical properties of Si_(3)N_(4)-bonded MgO-C refractories,leading to an enhancement in their overall strength.Notably,when the nitrogen pressure was set at 3 MPa,exceptional compressive strength of 109.7 MPa and an elastic modulus of 142.4 GPa were achieved by these prepared refractories.These findings highlight the great potential for utilizing gas pressure sintered Si_(3)N_(4)-MgO-C refractories.
基金support from the National Natural Science Foundation of China(Grant Nos.U1860205 and 52204352)Youth Project of Hubei Natural Science Foundation(Grant No.2022CFB593)+1 种基金Key R&D Project of Hubei Province(Grant No.2022BAA021)Guiding Project of Scientific Research Plan of Hubei Provincial Department of Education(Grant No.B2022019).
文摘The interaction of MgO-MgAl_(2)O_(4)-based and MgO-Cr_(2)O_(3)-based refractories with X70 molten steel was studied by immersion experiments at 1560℃.The effects of immersion time(30 and 60 min)on the contents of total oxygen(TO),Al,Nb,Si,Mn,and Cr as well as the composition,number density,and size distribution of inclusions in the molten steel were investigated.The influence of the penetration and erosion degree of the molten steel to the refractory on the steel-refractory interface layer was analyzed.The results show that,at 1560℃,the MgO-MgAl_(2)O_(4)-based refractory can better control the contents of TO and the composition of molten steel compared with the MgO-Cr_(2)O_(3)-based refractory.The TO content is only 16×10^(-4) wt.%in the molten steel after reacted with the Mg0-MgAl_(2)O_(4)-based refractory at the end point of refining,4 accounting for 11.5%of that reacted with the MgO-Cr_(2)O_(3)-based refractory(139×10^(-4) wt.%).The number density of inclusions is only 14 mm^(-2),and the average size ofinclusions is only 1.31μm,with thelargest proportion of inclusions in 1-2μm(70%).The Al_(2)O_(3)-MnS-CaO complex inclusions in the original steel changed to complex inclusions dominated by Cr-Nb-Mn-S-O and MgO.Al_(2)O_(3),corresponding to the MgO-Cr_(2)O_(3)-based and MgO-MgAl_(2)O_(4)-based refractories,respectively.The MgO.Al_(2)O_(3) layer was formed at the reaction interface between MgO-MgAl_(2)O_(4)-based refractory and molten steel,which is helpful to restrict the erosion of refractories and the pollution of molten steel.The damage mechanism of the MgO-Cr_(2)O_(3)-based refractory is mainly permeation and chemical reaction,while the damage of the MgO-MgAl_(2)O_(4)-based refractory is mainlyscouring erosion.
基金Supported by Carbon Neutrality and Energy System Transformation (CNEST) ProgramScience and Technology Innovation Project of CHN Energy (GJNY-24-26)。
文摘The service life of refractory brick in the slag tapping hole of gasifiers is a significant concern for long-term and stable operation.This study examined the damage mechanism of high chromia refractory of four commercial coal-water slurry gasifiers with their corresponding gasification coal samples and the corroded refractory bricks in the slag tapping hole of the gasifier.The slag characteristic,including crystallization and viscosity-temperature of four gasification coal samples were analyzed.The results revealed that the low viscosity slag could lead to more severe damage to refractory bricks.Given the risk of slag crystallization,it is recommended to establish a safe slag tapping temperature range should be set as tICT(initial crystallization temperature)−t_(2.5) when tICT is higher than t_(25).Upon examining interior morphology of these corroded refractory bricks,some cracks were observed within them.The chemical composition of molten slag was analyzed using SEM-EDS.However,XRD results found no spinel containing zirconium in these cracks.This suggests that the emergence of these cracks are mainly attributed to the molten slag penetration and the subsequent reaction with the refractory material.The difference in thermal expansion between the newly formed substances and refractory material is critical in forming these cracks.Furthermore,SEM-EDS analysis was also conducted on the slag-aggregate and the slag-matrix interface.The results reveal that the reduction in Cr_(2)O_(3) content is the earliest characteristic of damage in high chromia refractories.A proposed damage mechanism of refractory brick suggests that the matrix and aggregate of high chromia refractory are initially compromised because of the reduced Cr_(2)O_(3) content.Subsequently,the molten slag penetrates the interior of the refractory brick,forming new substances,leading to damage caused by the difference in thermal expansion between the new substances and the refractory brick.Understanding and preventing the reduction of Cr_(2)O_(3) content is vital to prolonging the service life of refractory brick in the slag tapping hole of the gasifier based on this damage mechanism.
基金National MCF Energy R&D Program(2024YFE03260300)。
文摘Refractory metals,including tungsten(W),tantalum(Ta),molybdenum(Mo),and niobium(Nb),play a vital role in industries,such as nuclear energy and aerospace,owing to their exceptional melting temperatures,thermal durability,and corrosion resistance.These metals have body-centered cubic crystal structure,characterized by limited slip systems and impeded dislocation motion,resulting in significant low-temperature brittleness,which poses challenges for the conventional processing.Additive manufacturing technique provides an innovative approach,enabling the production of intricate parts without molds,which significantly improves the efficiency of material usage.This review provides a comprehensive overview of the advancements in additive manufacturing techniques for the production of refractory metals,such as W,Ta,Mo,and Nb,particularly the laser powder bed fusion.In this review,the influence mechanisms of key process parameters(laser power,scan strategy,and powder characteristics)on the evolution of material microstructure,the formation of metallurgical defects,and mechanical properties were discussed.Generally,optimizing powder characteristics,such as sphericity,implementing substrate preheating,and formulating alloying strategies can significantly improve the densification and crack resistance of manufactured parts.Meanwhile,strictly controlling the oxygen impurity content and optimizing the energy density input are also the key factors to achieve the simultaneous improvement in strength and ductility of refractory metals.Although additive manufacturing technique provides an innovative solution for processing refractory metals,critical issues,such as residual stress control,microstructure and performance anisotropy,and process stability,still need to be addressed.This review not only provides a theoretical basis for the additive manufacturing of high-performance refractory metals,but also proposes forward-looking directions for their industrial application.
基金supported by the National Natural Science Foundation of China(No.51974016).
文摘Microwave roasting self-leaching is an innovative method for recovering gold from high-sulfur refractory gold concentrates,without using deadly toxic cyanide reagents.However,the mechanism of gold self-leaching,which relies on lixiviants prepared using volatilized sulfur obtained from roasting,has not been fully elucidated.This study employs the response surface methodology to optimize processing parameters,resulting in an increased gold extraction rate of 96.18%.Analytical factorization and the Tafel curve indicate that CuSO_(4) and NH_(3)·H_(2)O significantly influence the self-leaching process.Furthermore,X-ray photoelectron spectroscopy(XPS)analysis reveals that S^(2−),S_(2)^(2−),polysulfides(S_(n)^(2−)),and thiosulfate(S_(2)O_(3)^(2−))are involved in the gold leaching reaction,with S^(2−),S_(2)^(2−),and S_(n)^(2−) serving as primary ligands for gold complexation.The role of S_(2)O_(3)^(2−) in the early stages of the gold-leaching reaction is also noteworthy.The copper–ammonia complex catalyzes the self-leaching gold reaction;however,an improper addition ratio can lead to copper-sulfur compound precipitates,reducing the extraction rate.
基金supported by the Scientific and Technological Research Project of the Henan Provincial Department of Science and Technology of China(No.212102210579).
文摘MgO-C refractories with stainless steel fibers were prepared to investigate the effects of stainless steel fibers addition on the thermal shock resistance,oxidation resistance,and microstructure of MgO-C refractories,and the optimum amount of stainless steel fibers was determined.The results showed that adding stainless steel fiber in MgO-C refractories can increase flexural strength and thermal shock resistance,with an optimal addition of 2 wt.%,owing to the bridging effect and crack deflection toughening of stainless steel fibers inside the material.The formation of MgAl1.9Fe0.1O4 composite spinel,which was responsible for higher oxidation resistance,produced volume expansion and prevented the diffusion of oxygen.The strengthening mechanism is physical embedding at room temperature,while it is reaction bonding at high temperature.
基金the Scientific Research Fund of Hunan Provincial Education Department(22B0856)the Hengyang"Xiaohe"Science and Technology Talent Special Project([2023]45)+3 种基金the Guidance Plan Project of Hengyang City([2023]40)the National Natural Science Foundation of China(U20A20239)the College Students'Innovation and Entrepreneurship Training Project(S202311528055)the Characteristic Application Discipline of Material Science Engineering in Hunan Province([2022]351).
文摘To solve the problem of poor high-temperature service performance caused by low carbonization of MgO-C refractories,low-carbon MgO–C refractories with excellent thermal shock,oxidation and corrosion resistances were successfully designed by using SiC whiskers as reinforcing phases and introducing micro-Al_(2)O_(3) powders as additives.The results indicated that the addition of micro-Al_(2)O_(3) powders optimized the internal structure of the material,like the columnar β-Si_(3)N_(4) with a stepped distribution and the mosaic structure formed between granular and flaky Mg_(2)SiO_(4),which synergistically strengthened and toughened the material and gave the material excellent mechanical properties and thermal shock resistance.Specifically,the cold modulus of rupture and cold crushing strength after thermal shock were increased by 4.1 and 20.3 MPa,respectively.Moreover,the addition of micro-Al_(2)O_(3) powders promoted the formation of fine particles of Mg_(2)SiO_(4),MgAl_(2)O_(4) and MgO,as well as a dense protective layer of Mg_(2)SiO_(4) in the material under high-temperature environment.Furthermore,spinel and high-temperature solid solution were formed in the corrosion environment.The oxidation and corrosion resistances were greatly improved by 41%and 15%,respectively.
基金supported by the R&D Center for Valuable Recycling(Global-Top Environmental Technology Development Program)funded by the Ministry of Environment(Project No.:11-C22-ID)
文摘Wetting phenomena between MgO C and CaO SiO2 slags were investigated by varying carbon content.A sessile drop technique was adopted to study the wetting phenomena in conjunction with a high speed camera for the observation of intrinsic wetting phenomena.The results show that the high content of SiO2 and the presence of Al2O3 in slags enhance the diffusion of Mg2+,leading to the promotion of reactive wetting.The carbon in MgO C refractory impedes the penetration of slags by repelling the slag and slowing the diffusion of Mg2+.This accounts for the non-wetting behavior of the slag on MgO C refractory with 17% (mass fraction) carbon similar to that of graphite.
基金supported by the National Science and Technology Major Special Project (No.2009ZX04006-032)the National Natural Science Foundation of China (No.50274021) and Baoshan Iron and SteelCo.,Ltd.,China
文摘Al2O3-SiC composite was synthesized with pyrophyllite and natural graphite as raw materials by carbothermal reduction reaction under argon atmosphere. The effect of synthesis temperature on phase composition and microstructure was investigated. Low-carbon MgO-C refractories were prepared by using the synthesized Al2O3-SiC composite as additive. The effect of its addition on the slag penetration and corrosion resistance as well as oxidation resistance of the refractories was investigated, and the slag resistance and oxidation resistance mechanisms of the Al2O3-SiC composite were also discussed. The results show that the synthesis temperature has a great influence on preparation of Al2O3-SiC composite. The Al2O3-SiC composite can be synthesized at 1873-1973 K under argon atmosphere, with pyrophyllite and natural graphite as raw materials, and particle sizes of the composite synthesized at 1973 K are mainly distributed as 1-2 μm. The slag penetration and corrosion resistance of low-carbon M80-C refractories can be remarkably improved by adding the synthesized Al2O3-SiC composite, and the oxidation resistance has an improvement to some extent. The increase of slag viscosity and the formation of MgAl2O4 can effectively inhibit the slag penetration and corrosion for the refractories.
基金This work was funded by Luoyang Major Science and Technology Innovation Project(2301009A)Henan Province Key Research and Development Project(231111230200)。
文摘Al_(4)SiC_(4) was synthesized from Al powder, silicon carbide, and graphite by microwave sintering, and characterized by XRD and SEM. Then the synthesized material was added to the magnesia carbon refractory brick to study its effect on the oxidation resistance, apparent porosity, bulk density, elastic modulus, and modulus of rupture. It is found that Al_(4)SiC_(4) can be synthesized by microwave sintering at 1 300 ℃ and the addition of Al_(4)SiC_(4)-containing material as an antioxidant can enhance the oxidation resistance of the magnesia carbon refractory brick.
文摘Magnesiu-Calcia materials containing 22 -53 wt% CaO hare been investigated Jot refinery slag corrosion and penetration resistance by Scanning Electron Microscopy （ SEM） .nd XRD. The corrosion and penetration resistance of MgO-CaO materials is enhanced with the increase of CaO content in specimens. It can be explained that, with increase of CaO content, the specimens reacted will＋ slag form higher melting point minerals of C3S ant C2S, creating a dense surface layer, which stopped others from penetrating further. Thus , the corrosion and penetration resistame was improved. No matter what kinds of slag were chosen, the depth of penetration decreased will＋ increase of CaO con,tent.
基金financially supported by the National Natural Science Foundation of China ( General program,51272188, 51472184 and 51472185 )the Natural Science Foundation of Hubei Province,China ( Contract No. 2013CFA086 )Foreign Cooperation Projects in Science and Technology of Hubei Province,China ( Contract No. 2013BHE002)
文摘Carbon nanotubes （CNTs） have been extensively studied over the last two decades since they possess excellent properties.CNTs have been considered as new promising reinforcements for carbon containing refractories （CCRs）.Current research progress of the CNT-reinforced MgO-C and Al2O3-C refractories was summarized in this mini-review,and the CNT-reinforced CCRs possess remarkable mechanical properties and superior thermal shock resistance compared to CCRs without CNTs.
文摘An investigation on the oxidation mechanism of the graphite in the MgO-C refractory materials is helpful to improving both the quality of these materials and to preventing and/or lowering of the adverse effects of the high-temperature oxidation. In this research, the oxidation behavior of the MgO-C refractories containing 5～20 wt% graphite was studied via weight-loss method. Atmospheric air was used for oxidation at temperatures ranging from 900℃ to 1300°C and the experimental data were compared with those obtained from the dimensionless kinetic equations of the shrinking core model, in order to determine the oxidation mechanisms of the refractories. The best fit was achieved with the porous layer diffusion control regime. Oxidation mechanism tends, however, to slightly deviate from pure pore diffusion control to pore diffusion-external gas transfer regime in the samples having more graphite contents (e.g. 20%).
基金The authors acknowledge the financial support from the National Natural Science Foundation of China(U20A20239)Natural Science Foundation of Hubei Province(2020CFB692).
文摘The demand for low-carbon MgO–C refractories is ever growing to meet the development of advanced steelmaking technologies and efficient energy conservation.Meanwhile,to improve the oxidation resistance and inhibit the weakness of low-carbon MgO–C refractories,antioxidants are necessary.The application of ternary carbides that focused on improving the oxidation performance of MgO–C refractories has been explored,and the ternary carbides including Al_(4)O_(4)C,Al8B_(4)C_(7),Al_(4)SiC_(4),Ti_(2)AlC,Ti_(3)AlC_(2),and Ti_(3)SiC_(2)have been proved effective.The crystal structure,physical properties,oxidation behavior,and synthesis of these ternary carbides were summarized,and their oxidation mechanism in assisting antioxidation of MgO–C refractories was discussed.In addition,the potential aspects related to the usage and development of ternary carbides in low-carbon MgO–C refractories were proposed.
文摘Corrosion resistance and penetration resistance of MgO-CaO materials with different CaO contents （22%, 42%, 49%, 53%, in mass）to refining AOD slag or VOD slag were investigated using static crucible technique by visual observation, SEM and XRD. The corrosion resistance and penetration resistance of speci-mens decrease with the increase of CaO content. This may be caused by the formation of C3S and C2S during the reactions between specimens and the slag. The formed C3S and C2S can restrain the further penetration to the matrix. The higher the CaO content, the more the C2S or C3S formed, the lower the porosity of the speci-mens, and the lower the penetration depth and corrosion rate. The corrosion resistance to AOD slag is better than that to VOD slag, because the reaction between AOD slag and the matrix is slighter than that between VOD slag and the matrix.
