The oxidation behavior of molybdenum disilicide （MoSi2） powders at 400, 500, and 600℃ for 12 h in air were investigated by using X-ray diffraction （XRD） and transmission electron microscopic （TEM） techniques. S...The oxidation behavior of molybdenum disilicide （MoSi2） powders at 400, 500, and 600℃ for 12 h in air were investigated by using X-ray diffraction （XRD） and transmission electron microscopic （TEM） techniques. Significant changes were observed in volume, mass, and color. Especially at 500℃, the volume expansion was found to be as high as 7-8 times, the color changed from black to yellow-white, and the mass gain was about 169.34% after 8 h, with SiO2 and MoO3 as main reaction products. The gains in volume and mass were less at 400 and 600℃ compared with those at 500℃, probably due to the less reaction rate at 400℃ and the formation of silica glass scale at 600℃, which would protect the matrix and restrain the diffusion of oxygen and molybdenum. Thus, the accelerated oxidation behavior of MoSi2 powder appeared at 500℃ and the volume expansion was the sign of accelerated oxidation.展开更多
TaB_(2)-SiC coating modified by different content of MoSi_(2) was fabricated on graphite substrate with SiC inner coating by liquid phase sintering to elevate the anti-oxidation capability of the TaB_(2)-SiC coatings....TaB_(2)-SiC coating modified by different content of MoSi_(2) was fabricated on graphite substrate with SiC inner coating by liquid phase sintering to elevate the anti-oxidation capability of the TaB_(2)-SiC coatings.As compared to the sample with the TaB_(2)-40wt% SiC coating,the coating sample modified with MoSi_(2) exhibited a weight gain trend at lower temperatures,the fastest weight loss rate went down by 76%,and the relative oxygen permeability value reduced from about 1% to near 0.More importantly,the large amount of SiO_(2) glass phase produced over the coating during oxidation was in contact with the modification of MoSi_(2),which was proved to be beneficial to the dispersion of Ta-oxides.A concomitantly formed continuous Ta-Si-O-B compound glass layer showed excellent capacity to prevent oxygen penetration.However,when the TaB_(2) content was sacrificed to increase the MoSi_(2) content,the relative oxygen permeability of the coating increased instead of decreased.Thus,on the basis of ample TaB_(2) content,increasing the MoSi_(2) content of the coating is conducive to reducing the relative oxygen permeability of the coatings in a broad temperature region.展开更多
New two-layer Ruddlesden-Popper(RP)oxide La_(0.25)Sr_(2.75)FeNiO_(7-δ)(LSFN)in the combination of Sr_(3)Fe_(2)O_(7-δ) and La_(3)Ni_(2)O_(7-δ) was successfully synthesized and studied as the potential active single-...New two-layer Ruddlesden-Popper(RP)oxide La_(0.25)Sr_(2.75)FeNiO_(7-δ)(LSFN)in the combination of Sr_(3)Fe_(2)O_(7-δ) and La_(3)Ni_(2)O_(7-δ) was successfully synthesized and studied as the potential active single-phase and composite cathode for protonic ceramics fuel cells(PCFCs).LSFN with the tetragonal symmetrical structure(IMmmm)is confinned,and the co-existence of Fe^(3+)/Fe^(4+) and Ni^(3+)/Ni^(2+) couples is demonstrated by X-ray photoelectron spectrometer(XPS)analysis.The LSFN conductivity is apparently enhanced after Ni doping in Fe-site,and nearly three times those of Sr_(3)Fe_(2)O_(7-δ),which is directly related to the carrier concentration and conductor mechanism.Importantly,anode supported PCFCs using LSFN-BaZr_(0.1)Ce_(0.7)Y_(0.2)O_(3-δ)(LSFN-BZCY)composite cathode achieved high power density(426 mW·cm^(-2) at 650℃)and low electrode interface polarization resistance(0.26Ω·cm^(2)).Besides,distribution of relaxation time(DRT)function technology was further used to analyse the electrode polarization processes.The observed three peaks(Pl,P2,and P3)separated by DRT shifted to the high frequency region with the decreasing temperature,suggesting that the charge transfer at the electrode-electrolyte interfaces becomes more difficult at reduced temperatures.Preliminary results demonstrate that new two-layer RP phase LSFN can be a promising cathode candidate for PCFCs.展开更多
To achieve high oxygen blocking structure of the ZrB_(2)-MoSi_(2) coating applied on carbon structural material,ZrB_(2)-MoSi_(2) coating was prepared by spark plasma sintering(SPS)method utilizing ZrB_(2)-MoSi_(2) com...To achieve high oxygen blocking structure of the ZrB_(2)-MoSi_(2) coating applied on carbon structural material,ZrB_(2)-MoSi_(2) coating was prepared by spark plasma sintering(SPS)method utilizing ZrB_(2)-MoSi_(2) composite powders synthesized by self-propagating high-temperature synthesis(SHS)technique as raw materials.The oxygen blocking mechanism of the ZrB_(2)-MoSi_(2) coatings at 1973 K was investigated.Compared with commercial powders,the coatings prepared by SHS powders exhibited superior density and inferior oxidation activity,which significantly heightened the structural oxygen blocking ability of the coatings in the active oxidation stage,thus characterizing higher oxidation protection efficiency.The rise of MoSi_(2) content facilitated the dispersion of transition metal oxide nanocrystals(5-20 nm)in the SiO_(2) glass layer and conduced to the increasing viscosity,thus strengthening the inerting impact of the compound glass layer in the inert oxidation stage.Nevertheless,the ZrB_(2)-40 vol% MoSi_(2) coating sample prepared by SHS powders presented the lowest oxygen permeability of 0.3% and carbon loss rate of 0.29×10^(6)g·cm^(-2)·s^(-1).Owing to the gradient oxygen partial pressure inside the coatings,the Si-depleted layer was developed under the compound glass layer,which brought about acute oxygen erosion.展开更多
Porous TiAl3 intermetallics were fabricated through vacuum reactive sintering from Ti-75A1 at.% elemental powder mixture.The phase compositions,expansion behaviors,pore characteristics and microstructure evolution of ...Porous TiAl3 intermetallics were fabricated through vacuum reactive sintering from Ti-75A1 at.% elemental powder mixture.The phase compositions,expansion behaviors,pore characteristics and microstructure evolution of TiAl3 intermetallics were investigated,and the pore formation mechanism was also proposed.It was found that the actual temperature of compacts showed an acute climb from 668 to 1244℃ in 166s,while the furnace temperature maintained the linear growth of 5℃/min,which indicated that an obvious thermal explosion（TE）reaction occurred during sintering,and only single-phase TiA13 intermetallic was synthesized in TE products.The open porosity increased from 22.2（green compact）to 32.8% after reactive diffusion sintering at 600℃ and rised to 58.7% after TE,then decreased to 51.2% after high-temperature homogenization at 1100℃.Therefore,TE reaction is the dominated pore formation mechanism of porous TiAl3 intermetallics.The pore evolution in porous TiAl3 intermetallics occurred by the following mechanisms：certain intergranular pores remained among powder particles of green compact,then low-temperature sintering resulted in a further increase in porosity due to the Kirkendall effect.Moreover,TE reaction gave rise to a dramatic volume expansion because of the rapid increase in temperature,and high-temperature sintering caused densification and a slight shrinkage.展开更多
There is keen interest in using Ti alloys as lightweight structural materials for aerospace and automotive industries.However,a long-standing problem for these materials is their poor oxidation resistance.Herein,we de...There is keen interest in using Ti alloys as lightweight structural materials for aerospace and automotive industries.However,a long-standing problem for these materials is their poor oxidation resistance.Herein,we designed and fabricated a Ti_(5)Si_(3) reinforced Ti-4(wt.%)Mo composite with two-scale network architecture by low energy milling and spark plasma sintering.It displays superior oxidation resistance at 800°C owing to the in-situ formation of a multi-component surface layer.This oxide layer has a dense grain size gradient structure that consists of an outer TiO_(2)layer and an inner SiO_(2)-padding-TiO_(2) layer,which has remarkable oxidation resistance and thermal stability.Furthermore,it was revealed that the hitherto unknown interaction between Ti_(5)Si_(3) reinforcement and nitrogen during oxidation would contribute to the formation of a TiN nano-twin interface layer,which accommodates the thermal mismatch strain between the oxide layer and matrix.This,along with high adhesion,confers excellent thermal cycling life with no cracking or spallation during long-term oxidation.In this regard,the secure operating temperature of this new composite can be increased to 800°C,which provides a design pathway for a new family of Ti matrix composites for high-temperature applications.展开更多
基金This work was financially supported by the National Natural Science Foundation of China (No.50025412)
文摘The oxidation behavior of molybdenum disilicide （MoSi2） powders at 400, 500, and 600℃ for 12 h in air were investigated by using X-ray diffraction （XRD） and transmission electron microscopic （TEM） techniques. Significant changes were observed in volume, mass, and color. Especially at 500℃, the volume expansion was found to be as high as 7-8 times, the color changed from black to yellow-white, and the mass gain was about 169.34% after 8 h, with SiO2 and MoO3 as main reaction products. The gains in volume and mass were less at 400 and 600℃ compared with those at 500℃, probably due to the less reaction rate at 400℃ and the formation of silica glass scale at 600℃, which would protect the matrix and restrain the diffusion of oxygen and molybdenum. Thus, the accelerated oxidation behavior of MoSi2 powder appeared at 500℃ and the volume expansion was the sign of accelerated oxidation.
基金supported by the Fundamental Research Funds for the Central Universities(No.2018GF14).
文摘TaB_(2)-SiC coating modified by different content of MoSi_(2) was fabricated on graphite substrate with SiC inner coating by liquid phase sintering to elevate the anti-oxidation capability of the TaB_(2)-SiC coatings.As compared to the sample with the TaB_(2)-40wt% SiC coating,the coating sample modified with MoSi_(2) exhibited a weight gain trend at lower temperatures,the fastest weight loss rate went down by 76%,and the relative oxygen permeability value reduced from about 1% to near 0.More importantly,the large amount of SiO_(2) glass phase produced over the coating during oxidation was in contact with the modification of MoSi_(2),which was proved to be beneficial to the dispersion of Ta-oxides.A concomitantly formed continuous Ta-Si-O-B compound glass layer showed excellent capacity to prevent oxygen penetration.However,when the TaB_(2) content was sacrificed to increase the MoSi_(2) content,the relative oxygen permeability of the coating increased instead of decreased.Thus,on the basis of ample TaB_(2) content,increasing the MoSi_(2) content of the coating is conducive to reducing the relative oxygen permeability of the coatings in a broad temperature region.
基金financially supported by the Fundamental Research Funds for the Central Universities(No.2019GF10).
文摘New two-layer Ruddlesden-Popper(RP)oxide La_(0.25)Sr_(2.75)FeNiO_(7-δ)(LSFN)in the combination of Sr_(3)Fe_(2)O_(7-δ) and La_(3)Ni_(2)O_(7-δ) was successfully synthesized and studied as the potential active single-phase and composite cathode for protonic ceramics fuel cells(PCFCs).LSFN with the tetragonal symmetrical structure(IMmmm)is confinned,and the co-existence of Fe^(3+)/Fe^(4+) and Ni^(3+)/Ni^(2+) couples is demonstrated by X-ray photoelectron spectrometer(XPS)analysis.The LSFN conductivity is apparently enhanced after Ni doping in Fe-site,and nearly three times those of Sr_(3)Fe_(2)O_(7-δ),which is directly related to the carrier concentration and conductor mechanism.Importantly,anode supported PCFCs using LSFN-BaZr_(0.1)Ce_(0.7)Y_(0.2)O_(3-δ)(LSFN-BZCY)composite cathode achieved high power density(426 mW·cm^(-2) at 650℃)and low electrode interface polarization resistance(0.26Ω·cm^(2)).Besides,distribution of relaxation time(DRT)function technology was further used to analyse the electrode polarization processes.The observed three peaks(Pl,P2,and P3)separated by DRT shifted to the high frequency region with the decreasing temperature,suggesting that the charge transfer at the electrode-electrolyte interfaces becomes more difficult at reduced temperatures.Preliminary results demonstrate that new two-layer RP phase LSFN can be a promising cathode candidate for PCFCs.
基金supported by the National Natural Science Foundation of China(Nos.51972338,51874305,and 51805533)the Fundamental Research Funds for the Central Universities(Nos.2021ZDPYYQ005 and 2019XKQYMS17)National Defense Basic Research Program(No.JCKYS2019607004-01).
文摘To achieve high oxygen blocking structure of the ZrB_(2)-MoSi_(2) coating applied on carbon structural material,ZrB_(2)-MoSi_(2) coating was prepared by spark plasma sintering(SPS)method utilizing ZrB_(2)-MoSi_(2) composite powders synthesized by self-propagating high-temperature synthesis(SHS)technique as raw materials.The oxygen blocking mechanism of the ZrB_(2)-MoSi_(2) coatings at 1973 K was investigated.Compared with commercial powders,the coatings prepared by SHS powders exhibited superior density and inferior oxidation activity,which significantly heightened the structural oxygen blocking ability of the coatings in the active oxidation stage,thus characterizing higher oxidation protection efficiency.The rise of MoSi_(2) content facilitated the dispersion of transition metal oxide nanocrystals(5-20 nm)in the SiO_(2) glass layer and conduced to the increasing viscosity,thus strengthening the inerting impact of the compound glass layer in the inert oxidation stage.Nevertheless,the ZrB_(2)-40 vol% MoSi_(2) coating sample prepared by SHS powders presented the lowest oxygen permeability of 0.3% and carbon loss rate of 0.29×10^(6)g·cm^(-2)·s^(-1).Owing to the gradient oxygen partial pressure inside the coatings,the Si-depleted layer was developed under the compound glass layer,which brought about acute oxygen erosion.
基金supported by the Fundamental Research Funds for the Central Universities(2017XKQY006)
文摘Porous TiAl3 intermetallics were fabricated through vacuum reactive sintering from Ti-75A1 at.% elemental powder mixture.The phase compositions,expansion behaviors,pore characteristics and microstructure evolution of TiAl3 intermetallics were investigated,and the pore formation mechanism was also proposed.It was found that the actual temperature of compacts showed an acute climb from 668 to 1244℃ in 166s,while the furnace temperature maintained the linear growth of 5℃/min,which indicated that an obvious thermal explosion（TE）reaction occurred during sintering,and only single-phase TiA13 intermetallic was synthesized in TE products.The open porosity increased from 22.2（green compact）to 32.8% after reactive diffusion sintering at 600℃ and rised to 58.7% after TE,then decreased to 51.2% after high-temperature homogenization at 1100℃.Therefore,TE reaction is the dominated pore formation mechanism of porous TiAl3 intermetallics.The pore evolution in porous TiAl3 intermetallics occurred by the following mechanisms：certain intergranular pores remained among powder particles of green compact,then low-temperature sintering resulted in a further increase in porosity due to the Kirkendall effect.Moreover,TE reaction gave rise to a dramatic volume expansion because of the rapid increase in temperature,and high-temperature sintering caused densification and a slight shrinkage.
基金financially supported by the National Natural Science Foundation of China(NSFC)[Grant No.51534009]National Key R&D Program of China[Grant No.2017YFB0306001]Natural Science Foundation of Hunan Province China(Grant No.2021JJ40750)。
文摘There is keen interest in using Ti alloys as lightweight structural materials for aerospace and automotive industries.However,a long-standing problem for these materials is their poor oxidation resistance.Herein,we designed and fabricated a Ti_(5)Si_(3) reinforced Ti-4(wt.%)Mo composite with two-scale network architecture by low energy milling and spark plasma sintering.It displays superior oxidation resistance at 800°C owing to the in-situ formation of a multi-component surface layer.This oxide layer has a dense grain size gradient structure that consists of an outer TiO_(2)layer and an inner SiO_(2)-padding-TiO_(2) layer,which has remarkable oxidation resistance and thermal stability.Furthermore,it was revealed that the hitherto unknown interaction between Ti_(5)Si_(3) reinforcement and nitrogen during oxidation would contribute to the formation of a TiN nano-twin interface layer,which accommodates the thermal mismatch strain between the oxide layer and matrix.This,along with high adhesion,confers excellent thermal cycling life with no cracking or spallation during long-term oxidation.In this regard,the secure operating temperature of this new composite can be increased to 800°C,which provides a design pathway for a new family of Ti matrix composites for high-temperature applications.
