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
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
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
MgO-CaO(40 wt.%CaO)refractory aggregates were prepared using the calcined dolomite and light-burned magnesia fine powder as raw materials and TiO_(2) as additive.The effect of TiO_(2) on their phase composition,micros...MgO-CaO(40 wt.%CaO)refractory aggregates were prepared using the calcined dolomite and light-burned magnesia fine powder as raw materials and TiO_(2) as additive.The effect of TiO_(2) on their phase composition,microstructures and properties was investigated by X-ray diffraction and scanning electron microscopy.The properties such as bulk density,apparent porosity,relative aggregate tube strength and hydration resistance were also investigated.The results showed that the CaTiO_(3) generated by the reaction between CaO and TiO_(2) was distributed around the CaO grain boundaries and intermittently distributed with MgO,which formed an isolation layer around CaO and greatly improved the hydration resistance.Meanwhile,the introduction of TiO_(2) promoted sintering and increased the grain size,further improving the strengths and hydration resistance of the materials.In addition,the most significant enhancement in the hydration resistance and strengths of the samples was achieved when 1.0-2.0 wt.%TiO_(2) was added.In this case,the relative strength of aggregate increased from 33.3% to 37.3%-43.1%,and the mass gain after the hydration test decreased from 3.13% to 1.26%-1.45%.展开更多
In this study,biomass cokes from sunflower seed hull(SFSH)and wood pellets(WP)were added to a MgO-C batch(3 mass%C)to replace 1.1 mass%of graphite.After hardening and carbonizing the samples,the influence of the bioma...In this study,biomass cokes from sunflower seed hull(SFSH)and wood pellets(WP)were added to a MgO-C batch(3 mass%C)to replace 1.1 mass%of graphite.After hardening and carbonizing the samples,the influence of the biomass cokes on the microstructure and thermal shock resistance was investigated.The replacement of flaky graphite by carbonized WP and SFSH reduced the bulk density and increased the apparent porosity after pressing and carbonization,but the degree was only marginal.This was confirmed by SEM investigations,where the biomass-coke containing samples exhibited a microstructure with a higher amount of pores between the fine MgO grains.The thermal shock resistance of the porous wood pellet coke containing MgO-C is at the same level as the reference sample but not superior to it.展开更多
Refractory high/medium-entropy alloys(RH/MEAs)are known for their outstanding performance at el-evated temperatures;however,they usually exhibit poor room-temperature plasticity,which can be at-tributed to the non-uni...Refractory high/medium-entropy alloys(RH/MEAs)are known for their outstanding performance at el-evated temperatures;however,they usually exhibit poor room-temperature plasticity,which can be at-tributed to the non-uniform deformation that occurs at room temperature.Once cracks nucleate,they will rapidly propagate into vertical splitting cracks.Here,we introduce multiple phases including FCC and HCP phases into the NbMoTa RMEA via appropriate addition of carbon.The results show that multiple-phase synergy effectively suppresses non-uniform deformation,thereby delaying the onset of vertical splitting cracks.An optimal combination of compressive strength-plasticity is achieved by the(NbMoTa)_(92.5)C_(7.5) alloy.The significant improvement in room-temperature mechanical properties can be attributed to its hierarchical microstructure:in the mesoscale,the BCC matrix is divided by eutectic structures;while at the microscale,the BCC matrix is further refined by abundant lath-like FCC precipitates.The FCC precip-itates contain high-density stacking faults,acting as a dislocation source under compressive loading.The HCP phase in the eutectic microstructures,in turn,acts as a strong barrier to dislocation movement and simultaneously increases the dislocation storage capacity.These findings open a new route to tailor the microstructure and mechanical properties of RH/MEAs.展开更多
Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-depo...Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-deposited and remelted were developed to refine the microstructure and enhance the oxidation resistance of refractory high entropy alloy using electron beam freeform fabrication(EBF3).Finer and short-range ordering structures were observed in the remelted sample,whereas the Al-deposited sample showcased the formation of silicide and intermetallic phases.High-temperature cyclic and isothermal oxidation tests at 1000℃ were carried out.The total weight gain after 60 h of cyclic oxidation decreased by 17.49%and 30.46%for the remelted and deposited samples,respectively,compared to the as-cast state.Oxidation kinetics reveal an evident lower mass gain and oxidation rate in the treated samples.A multilayer oxide consisting of TiO_(2)+Al_(2)O_(3)+SiO_(2)+AlNbO_(4) was studied for its excellent oxidation resistance.The oxidation behavior of rutile,corundum and other oxides was analyzed using first principles calculations and chemical defect analysis.Overall,this research,which introduces novel treatments,offers promising insights for enhancing the inherent oxidation resistance of refractory high entropy alloys.展开更多
Grain boundary engineering plays a significant role in the improvement of strength and plasticity of alloys. However, in refractory high-entropy alloys, the susceptibility of grain boundaries to oxygen presents a bott...Grain boundary engineering plays a significant role in the improvement of strength and plasticity of alloys. However, in refractory high-entropy alloys, the susceptibility of grain boundaries to oxygen presents a bottleneck in achieving high mechanical performance. Creating a large number of clean grain boundaries in refractory high-entropy alloys is a challenge. In this study, an ultrafine-grained (UFG) NbMoTaW alloy with high grain-boundary cohesion was prepared by powder metallurgy, taking advantages of rapid hot-pressing sintering and full-process inert atmosphere protection from powder synthesis to sintering. By oxygen control and an increase in the proportion of grain boundaries, the segregation of oxygen and formation of oxides at grain boundaries were strongly mitigated, thus the intrinsic high cohesion of the interfaces was preserved. Compared to the coarse-grained alloys prepared by arc-melting and those sintered by traditional powder metallurgy methods, the UFG NbMoTaW alloy demonstrated simultaneously increased strength and plasticity at ambient temperature. The highly cohesive grain boundaries not only reduce brittle fractures effectively but also promote intragranular deformation. Consequently, the UFG NbMoTaW alloy achieved a high yield strength even at elevated temperatures, with a remarkable performance of 1117 MPa at 1200 ℃. This work provides a feasible solution for producing refractory high-entropy alloys with low impurity content, refined microstructure, and excellent mechanical performance.展开更多
Hydrogen-based mineral phase transformation(HMPT)technology has demonstrated its effectiveness in separating iron and enriching rare earths from Bayan Obo refractory ores.However,further research is needed to clarify ...Hydrogen-based mineral phase transformation(HMPT)technology has demonstrated its effectiveness in separating iron and enriching rare earths from Bayan Obo refractory ores.However,further research is needed to clarify the phase composition and floatability of rare earths obtained after HMPT owing to the associated phase transformations.This study explored the mineralogical characteristics and separation behavior of rare earths in HMPT-treated iron tailings.Process mineralogy studies conducted via BGRIMM process mineralogy analysis and X-ray diffraction revealed that the main valuable minerals in the tailings included rare-earth oxides(9.15wt%),monazite(5.31wt%),and fluorite(23.52wt%).The study also examined the impact of mineral liberation and gangue mineral intergrowth on flotation performance.Flotation tests achieved a rare-earth oxide(REO)grade of 74.12wt% with a recovery of 34.17% in open-circuit flotation,whereas closed-circuit flotation resulted in a REO grade of 60.27wt% with a recovery of 73%.Transmission electron microscopy and scanning electron microscopy coupled with energy-dispersive spectroscopy revealed that monazite remained stable during the HMPT process,while bastnaesite was transformed into Ce_(7)O_(12)and CeF_(3),leading to increased collector consumption.Nonetheless,the HMPT process did not significantly affect the flotation performance of rare earths.The enrichment of fluorite in the tailings highlighted its further recovery potential.The integration of HMPT with magnetic separation and flotation presents an efficient strategy for recovering rare earths,iron,and fluorite from Bayan Obo ores.展开更多
BACKGROUND A case study of multiple distinct levels of skipped thoracolumbar spine infection was reported in which 13 successful vacuum sealing drainage(VSD)surgeries were treated.CASE SUMMARY The patient underwent a ...BACKGROUND A case study of multiple distinct levels of skipped thoracolumbar spine infection was reported in which 13 successful vacuum sealing drainage(VSD)surgeries were treated.CASE SUMMARY The patient underwent a total of 13 procedures within our medical facility,including five performed under local anesthesia and eight performed under general anesthesia.The source of the ailment was ultimately identified as Enterobacter cloacae.After the last procedure,the patient's symptoms were alleviated,and the recovery process was satisfactory.Three months post-operation,the Japanese Orthopaedic Association scores had improved to 100%.Imageological examination revealed a satisfactory position of internal fixation,and the abnormal signals in the vertebral body and intervertebral space had been eliminated when compared to the pre-operative results.CONCLUSION The study demonstrates that the extreme lateral approach debridement combined with multiple VSD operations is a secure and successful method of treatment for recurrent spinal infection,providing an alternative to traditional surgery.展开更多
Introducing B2 ordering can effectively improve the mechanical properties of lightweight refractory high-entropy alloys(LRHEAs).However,(Zr,Al)-enriched B2 precipitates generally reduce the ductility because their ord...Introducing B2 ordering can effectively improve the mechanical properties of lightweight refractory high-entropy alloys(LRHEAs).However,(Zr,Al)-enriched B2 precipitates generally reduce the ductility because their ordering characteristic is destroyed after dislocation shearing.Meanwhile,the local chemical order(LCO)cannot provide an adequate strengthening effect due to its small size.展开更多
1 Production and Running Status of China’s Refractories Industry in 20241.1 Production and Running Status In 2024,according to the statistical data from The Association of China Refractories Industry,China’s refract...1 Production and Running Status of China’s Refractories Industry in 20241.1 Production and Running Status In 2024,according to the statistical data from The Association of China Refractories Industry,China’s refractories output was 22.0711million tons,decreasing by 3.73%YOY;in which the outputs of dense shaped refractory products,insulating refractory products and monolithic refractories were 11.3163 million tons decreasing by 6.07%YOY,83.77 thousand tons increasing by 11.17%YOY,and 9.9971 million tons decreasing by 2.07%YOY,respectively.The outputs of the main varieties are shown in Fig.1.展开更多
Henan refractories industry is a major refractory production base in China,which is also an advantage industry in Henan province.Recently,Henan provincial government has formulated relevant industrial and environmenta...Henan refractories industry is a major refractory production base in China,which is also an advantage industry in Henan province.Recently,Henan provincial government has formulated relevant industrial and environmental protection policies,and approved the construction of“Henan Province New Refractory Industry Cluster”.Henan’s main refractory enterprises have developed a series of green technologies,processes and products,and carried out automation and intelligent transformation,equipment upgrading,and the deep integration of information technology and refractory manufacturing through interconnection and digital empowerment.To promote the high-quality development of refractory industry,The Association of Henan Refractory Industry has established a series of standards and evaluation systems of refractories including air pollutant emission,energy consumption limits,carbon emission limits,green products,etc.The Association of Henan Refractory Industry also organized exchanges and mutual cooperation between enterprises inside and outside the region,and guided the development of specialization,refinement and innovation.This paper summarized the relevant works of refractories in Henan,and put forward some suggestions for solving the existing problems of refractories in Henan.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.
基金the Key Project of the National Natural Science Foundation of China(Grant Nos.U21A2058 and 51802235)the Hubei Science and Technology Innovation Talent Project(Grant No.2023DJC087).
文摘MgO-CaO(40 wt.%CaO)refractory aggregates were prepared using the calcined dolomite and light-burned magnesia fine powder as raw materials and TiO_(2) as additive.The effect of TiO_(2) on their phase composition,microstructures and properties was investigated by X-ray diffraction and scanning electron microscopy.The properties such as bulk density,apparent porosity,relative aggregate tube strength and hydration resistance were also investigated.The results showed that the CaTiO_(3) generated by the reaction between CaO and TiO_(2) was distributed around the CaO grain boundaries and intermittently distributed with MgO,which formed an isolation layer around CaO and greatly improved the hydration resistance.Meanwhile,the introduction of TiO_(2) promoted sintering and increased the grain size,further improving the strengths and hydration resistance of the materials.In addition,the most significant enhancement in the hydration resistance and strengths of the samples was achieved when 1.0-2.0 wt.%TiO_(2) was added.In this case,the relative strength of aggregate increased from 33.3% to 37.3%-43.1%,and the mass gain after the hydration test decreased from 3.13% to 1.26%-1.45%.
基金funded by the Deutsche Forschungsgemeinschaft(DFG,German Research Foundation),project number 461482547within the Research Training Group“GRK 2802:Refractory Recycling:A contribution for raw material-,energy-and climateefficiency in high temperature processes”The authors thankfully acknowledge the support of Dr.Gert Schmidt for the SEM/EDX investigations and Dr.Vânia Regina Salvini(Universidade Federal de São Carlos)for her inspiring input to conduct the thermal shock resistance investigation.
文摘In this study,biomass cokes from sunflower seed hull(SFSH)and wood pellets(WP)were added to a MgO-C batch(3 mass%C)to replace 1.1 mass%of graphite.After hardening and carbonizing the samples,the influence of the biomass cokes on the microstructure and thermal shock resistance was investigated.The replacement of flaky graphite by carbonized WP and SFSH reduced the bulk density and increased the apparent porosity after pressing and carbonization,but the degree was only marginal.This was confirmed by SEM investigations,where the biomass-coke containing samples exhibited a microstructure with a higher amount of pores between the fine MgO grains.The thermal shock resistance of the porous wood pellet coke containing MgO-C is at the same level as the reference sample but not superior to it.
基金financial support from the Na-tional Natural Science Foundation of China(No.52231006)National Key Research and Development Program of China(No.2017YFB0702003)the National Natural Science Foundation of China(No.51871217).
文摘Refractory high/medium-entropy alloys(RH/MEAs)are known for their outstanding performance at el-evated temperatures;however,they usually exhibit poor room-temperature plasticity,which can be at-tributed to the non-uniform deformation that occurs at room temperature.Once cracks nucleate,they will rapidly propagate into vertical splitting cracks.Here,we introduce multiple phases including FCC and HCP phases into the NbMoTa RMEA via appropriate addition of carbon.The results show that multiple-phase synergy effectively suppresses non-uniform deformation,thereby delaying the onset of vertical splitting cracks.An optimal combination of compressive strength-plasticity is achieved by the(NbMoTa)_(92.5)C_(7.5) alloy.The significant improvement in room-temperature mechanical properties can be attributed to its hierarchical microstructure:in the mesoscale,the BCC matrix is divided by eutectic structures;while at the microscale,the BCC matrix is further refined by abundant lath-like FCC precipitates.The FCC precip-itates contain high-density stacking faults,acting as a dislocation source under compressive loading.The HCP phase in the eutectic microstructures,in turn,acts as a strong barrier to dislocation movement and simultaneously increases the dislocation storage capacity.These findings open a new route to tailor the microstructure and mechanical properties of RH/MEAs.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFF0609000)National Natural Science Foundation of China(Grant Nos.52171034 and 52101037)Postdoctoral Fellowship Program of CPSFara(No.GZB20230944).
文摘Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-deposited and remelted were developed to refine the microstructure and enhance the oxidation resistance of refractory high entropy alloy using electron beam freeform fabrication(EBF3).Finer and short-range ordering structures were observed in the remelted sample,whereas the Al-deposited sample showcased the formation of silicide and intermetallic phases.High-temperature cyclic and isothermal oxidation tests at 1000℃ were carried out.The total weight gain after 60 h of cyclic oxidation decreased by 17.49%and 30.46%for the remelted and deposited samples,respectively,compared to the as-cast state.Oxidation kinetics reveal an evident lower mass gain and oxidation rate in the treated samples.A multilayer oxide consisting of TiO_(2)+Al_(2)O_(3)+SiO_(2)+AlNbO_(4) was studied for its excellent oxidation resistance.The oxidation behavior of rutile,corundum and other oxides was analyzed using first principles calculations and chemical defect analysis.Overall,this research,which introduces novel treatments,offers promising insights for enhancing the inherent oxidation resistance of refractory high entropy alloys.
基金supported by the National Natural Science Foundation of China(Nos.52371128,52304378,52101031 and 92163107).
文摘Grain boundary engineering plays a significant role in the improvement of strength and plasticity of alloys. However, in refractory high-entropy alloys, the susceptibility of grain boundaries to oxygen presents a bottleneck in achieving high mechanical performance. Creating a large number of clean grain boundaries in refractory high-entropy alloys is a challenge. In this study, an ultrafine-grained (UFG) NbMoTaW alloy with high grain-boundary cohesion was prepared by powder metallurgy, taking advantages of rapid hot-pressing sintering and full-process inert atmosphere protection from powder synthesis to sintering. By oxygen control and an increase in the proportion of grain boundaries, the segregation of oxygen and formation of oxides at grain boundaries were strongly mitigated, thus the intrinsic high cohesion of the interfaces was preserved. Compared to the coarse-grained alloys prepared by arc-melting and those sintered by traditional powder metallurgy methods, the UFG NbMoTaW alloy demonstrated simultaneously increased strength and plasticity at ambient temperature. The highly cohesive grain boundaries not only reduce brittle fractures effectively but also promote intragranular deformation. Consequently, the UFG NbMoTaW alloy achieved a high yield strength even at elevated temperatures, with a remarkable performance of 1117 MPa at 1200 ℃. This work provides a feasible solution for producing refractory high-entropy alloys with low impurity content, refined microstructure, and excellent mechanical performance.
基金the financial support received from the Key Program of National Natural Science Foundation of China(No.52130406)the National Key R&D Program of China(Nos.2021YFC2901000 and 2022YFC2905800)+1 种基金the General Program of National Natural Science Foundation of China(No.52274253)Natural Science Foundation Innovation Group Project of Hubei Province,China(No.2023AFA044)。
文摘Hydrogen-based mineral phase transformation(HMPT)technology has demonstrated its effectiveness in separating iron and enriching rare earths from Bayan Obo refractory ores.However,further research is needed to clarify the phase composition and floatability of rare earths obtained after HMPT owing to the associated phase transformations.This study explored the mineralogical characteristics and separation behavior of rare earths in HMPT-treated iron tailings.Process mineralogy studies conducted via BGRIMM process mineralogy analysis and X-ray diffraction revealed that the main valuable minerals in the tailings included rare-earth oxides(9.15wt%),monazite(5.31wt%),and fluorite(23.52wt%).The study also examined the impact of mineral liberation and gangue mineral intergrowth on flotation performance.Flotation tests achieved a rare-earth oxide(REO)grade of 74.12wt% with a recovery of 34.17% in open-circuit flotation,whereas closed-circuit flotation resulted in a REO grade of 60.27wt% with a recovery of 73%.Transmission electron microscopy and scanning electron microscopy coupled with energy-dispersive spectroscopy revealed that monazite remained stable during the HMPT process,while bastnaesite was transformed into Ce_(7)O_(12)and CeF_(3),leading to increased collector consumption.Nonetheless,the HMPT process did not significantly affect the flotation performance of rare earths.The enrichment of fluorite in the tailings highlighted its further recovery potential.The integration of HMPT with magnetic separation and flotation presents an efficient strategy for recovering rare earths,iron,and fluorite from Bayan Obo ores.
基金Supported by Natural Science Foundation of Shandong Province,No.ZR2023MH331.
文摘BACKGROUND A case study of multiple distinct levels of skipped thoracolumbar spine infection was reported in which 13 successful vacuum sealing drainage(VSD)surgeries were treated.CASE SUMMARY The patient underwent a total of 13 procedures within our medical facility,including five performed under local anesthesia and eight performed under general anesthesia.The source of the ailment was ultimately identified as Enterobacter cloacae.After the last procedure,the patient's symptoms were alleviated,and the recovery process was satisfactory.Three months post-operation,the Japanese Orthopaedic Association scores had improved to 100%.Imageological examination revealed a satisfactory position of internal fixation,and the abnormal signals in the vertebral body and intervertebral space had been eliminated when compared to the pre-operative results.CONCLUSION The study demonstrates that the extreme lateral approach debridement combined with multiple VSD operations is a secure and successful method of treatment for recurrent spinal infection,providing an alternative to traditional surgery.
基金supported by the National Natural Science Foundation of China(Nos.52171166 and U20A20231)the Natural Science Foundation of Hunan Province,China(Nos.2024JJ2060 and 2024JJ5406)+1 种基金the Key Laboratory of Materials in Dynamic Extremes of Sichuan Province(No.2023SCKT1102)the Postgraduate Scientific Research Innovation Project of National University of Defense Technology(No.XJJC2024065).
文摘Introducing B2 ordering can effectively improve the mechanical properties of lightweight refractory high-entropy alloys(LRHEAs).However,(Zr,Al)-enriched B2 precipitates generally reduce the ductility because their ordering characteristic is destroyed after dislocation shearing.Meanwhile,the local chemical order(LCO)cannot provide an adequate strengthening effect due to its small size.
文摘1 Production and Running Status of China’s Refractories Industry in 20241.1 Production and Running Status In 2024,according to the statistical data from The Association of China Refractories Industry,China’s refractories output was 22.0711million tons,decreasing by 3.73%YOY;in which the outputs of dense shaped refractory products,insulating refractory products and monolithic refractories were 11.3163 million tons decreasing by 6.07%YOY,83.77 thousand tons increasing by 11.17%YOY,and 9.9971 million tons decreasing by 2.07%YOY,respectively.The outputs of the main varieties are shown in Fig.1.
文摘Henan refractories industry is a major refractory production base in China,which is also an advantage industry in Henan province.Recently,Henan provincial government has formulated relevant industrial and environmental protection policies,and approved the construction of“Henan Province New Refractory Industry Cluster”.Henan’s main refractory enterprises have developed a series of green technologies,processes and products,and carried out automation and intelligent transformation,equipment upgrading,and the deep integration of information technology and refractory manufacturing through interconnection and digital empowerment.To promote the high-quality development of refractory industry,The Association of Henan Refractory Industry has established a series of standards and evaluation systems of refractories including air pollutant emission,energy consumption limits,carbon emission limits,green products,etc.The Association of Henan Refractory Industry also organized exchanges and mutual cooperation between enterprises inside and outside the region,and guided the development of specialization,refinement and innovation.This paper summarized the relevant works of refractories in Henan,and put forward some suggestions for solving the existing problems of refractories in Henan.
