Using boron powder as additive, the preparation of zirconium diboride(ZrB 2) by carbothermal reduction was investigated. The results show that the carbothermal reduction cannot be completely done until the temperature...Using boron powder as additive, the preparation of zirconium diboride(ZrB 2) by carbothermal reduction was investigated. The results show that the carbothermal reduction cannot be completely done until the temperature is more than 1900 ℃. The ZrB2 particles prepared without boron(B) additive at 1900 ℃ for 3 h are rodlike and show a preferential grain growth along [001] direction. B additive changes the heat effect of the raw materials. With B additive, the morphology of ZrB2 particles turns to be regular shape. The average particle size is about 3.6 μm with 2.5 wt% B additives. With more B additive, the shape of particles turns to be round like and the average particle size is decreased to 2.3 μm when 5 wt% B is added. The existence of oxides in grain boundary is a key factor to keep ZrB2 ceramic from deep densification. Using ZrB2 powder prepared with 5 wt% B additives, by controlling carbon content in ZrB2 powder, ZrB2 ceramic with 93%relative density is hot-pressed.展开更多
The oxidation behaviors of fused zirconium diboride and chemosynthetic zirconium diboride as well as morphology and composition of their oxidation products were researched by FESEM-EDS and XRD.The two kinds of zirconi...The oxidation behaviors of fused zirconium diboride and chemosynthetic zirconium diboride as well as morphology and composition of their oxidation products were researched by FESEM-EDS and XRD.The two kinds of zirconium diboride were heated at 700℃,900℃,1100℃and 1300℃for 3 h in air,respectively.The results show that Zr02 and B203(Ⅰ)are generated from the chemosynthetic zirconium diboride oxidized at 700℃for 3 h or the fused zirconium diboride oxidized at 800℃for 24 h;B203(Ⅰ)dissolves into water and then H3B03 crystallizes.展开更多
A single phase of zirconium diboride （ZrB2） powder was successfully synthesized by sol-gel method in Zr-B-C-O system, using zirconium oxychloride （ZrOC12 ~ 8H20）, nano-scale boron and suerose（C12H22011）as the st...A single phase of zirconium diboride （ZrB2） powder was successfully synthesized by sol-gel method in Zr-B-C-O system, using zirconium oxychloride （ZrOC12 ~ 8H20）, nano-scale boron and suerose（C12H22011）as the starting materials and propylene oxide （PO） as complexing agent at a low temperature. Simultaneously, the experimen- tal and theoretical studies of ZrB2 synthesized by boro/carbothermal reduction from novel sol-gel technology were discussed. The results indicated that the pure rod-like ZrB2 powder without residual ZrO2 phase could be obtained with a B/Zr molar ratio of 3.5 at 1 400~C in argon atmosphere. Besides, in this study, a kinetic model for the Zr-B-C-O sys- tem producing ZrB2 by boro/carbothermal reaction was established based on thermodynamic analysis. It was also ob- served that, with the increase of reaction temperature, the reaction which produced ZrB2 powders changed from the borothermal reaction to boro/carbothermal reaction in the Zr-B-C-O system.展开更多
Zirconium oxide （ZrO：） and boron carbide （B4C） were added to ZrB2 raw powders to prepare ZrB2 porous ceramics by reactive spark plasma sintering （RSPS）. The reactions between ZrO2 and B,C which produce ZrB2 and...Zirconium oxide （ZrO：） and boron carbide （B4C） were added to ZrB2 raw powders to prepare ZrB2 porous ceramics by reactive spark plasma sintering （RSPS）. The reactions between ZrO2 and B,C which produce ZrB2 and gas （such as CO and B2O3） result in pore formation. X-Ray Diffraction results indicated that the products phase was ZrB2 and the reaction was completed after the RSPS process. The porosity could be controlled by changing the ratio of synthesized ZrB2 to raw ZrB2 powders. The porosity of porous ceramics with 20 wt% and 40 wt% synthsized ZrB2 are 0.185 and 0.222, respectivly. And dense ZrB：SiC ceramic with a porosity of 0.057 was prepared under the same conditions for comparison. The pores were homogeneously distributed within the microstructure of the porous ceramics. The results indicate a promising method for preparing porous ZrB：based ceramics.展开更多
The present study focuses on the thermal response of carbon fiber-reinforced phenolic composites, where the matrix has been modified with different reinforcements. Two types of materials, multiwalled carbon nanotubes ...The present study focuses on the thermal response of carbon fiber-reinforced phenolic composites, where the matrix has been modified with different reinforcements. Two types of materials, multiwalled carbon nanotubes and zirconium diboride （ZrB2）, were used in a new design of mixture to produce the heat- resistant ablative composite system. The CNT/ZrB2/carbon/phenolic nanocomposite （Z/NT-CR） system corresponding to CNT/carbon/phenolic nanocomposite （NT-CR） showed a reasonable decrease in mass loss and the ablation rate as compared to carbon/phenolic composite （CR）. However, substantial drop in two factors was found for Z/NT-CR as compared to carbon/phenolic and NT-CR. Ablation mechanisms for all three composites were investigated by thermal gravimetric analysis in conjunction with micro- structural studies using a field emission scanning electron microscope. The microstructural studies revealed that CNTs acted as an ablation resistant phase for protection against 2000 ℃, and the conversion from ZrB2 to ZrO2 played an important role as an insulator in the performance of char layer in the ablation resistance.展开更多
Ultra-high temperature ceramics have been considered as good candidates for plasma facing materials due to their combination of high melting point,high strength and hardness,high thermal conductivity as well as good c...Ultra-high temperature ceramics have been considered as good candidates for plasma facing materials due to their combination of high melting point,high strength and hardness,high thermal conductivity as well as good chemical inertness.In this study,zirconium diboride has been chosen to investigate its irradiation damage behavior.Irradiated by 4 MeV Au^(2+)with a total fluence of 2.5×10^(16)cm^(-2),zirconium diboride ceramic shows substantial resilience to irradiation-induced damage with its structural integrity well maintained but mild damage at lattice level.Grazing incident X-ray diffraction evidences no change of the hexagonal structure in the irradiated region but its lattice parameter a increased and c decreased,giving a volume shrinkage of 0.46%.Density functional theory calculation shows that such lattice shrinkage corresponds to a non-stoichiometric compound as ZrB1.97.Electron energy-loss spectroscopy in a transmission electron microscope revealed an increase of valence electrons in zirconium,suggesting boron vacancies were indeed developed by the irradiation.Alo ng the irradiation depth,long dislocations were observed inside top layer with a depth of 750 nm where the implanted Au ions reached the peak concentration.Underneath the top layer,a high density of Frank dislocations is formed by the cascade collision down to a depth of 1150 nm.All the features show the potential of ZrB_(2) to be used as structural material in nuclear system.展开更多
ZrB2 ceramics were prepared by self-propagating high-temperature synthesis（SHS） and were sintered by hot pressing（HP）.The effects of the granularities and doses of raw materials in Zr-B2O3-Mgon SHS process and pro...ZrB2 ceramics were prepared by self-propagating high-temperature synthesis（SHS） and were sintered by hot pressing（HP）.The effects of the granularities and doses of raw materials in Zr-B2O3-Mgon SHS process and product were investigated.XRD and combustion temperature curves prove that the ideal SHS reactants of Zr-B2O3-Mg are 50μm Zr powder,75μm B2O3 powder and 400μm Mg powder with 45% excessive.The particle sizes of SHS product,acid-leached product,sintered product are 2-5μm,0.5-2μm,2-10μm respectively.Chemical analysis indicates that the acid-leached product consists of ZrB2（94.59%）,ZrO2（3.87%）,and H3BO3（1.54%）,The sintered product has a relative density of 95.4%.展开更多
LaB 6 ZrB 2 eutectic composites were fabricated using electric arc furnace and EBZM(electron beam zone melting) technique Orientated ZrB 2 fibers yielded in a LaB 6 matrix The average diameter of ZrB 2 fiber...LaB 6 ZrB 2 eutectic composites were fabricated using electric arc furnace and EBZM(electron beam zone melting) technique Orientated ZrB 2 fibers yielded in a LaB 6 matrix The average diameter of ZrB 2 fibers is about 0 2～1 2 μm, and the length can be up to 100 μm For the ingot solidified with planar growth, the orientation relation of the phases is: Growth direction: LaB 6 ∥ ZrB 2 , Interfacial plane: (110) LaB 6 ∥(110) ZrB 2展开更多
Carbon microspheres were firstly prepared using glucose （C6H12O6 ） as the starting materials by hydrotherreal carbonization. Then hollow ZrB2 spheres were successfully synthesized using zirconium oxychloride （ ZrCl...Carbon microspheres were firstly prepared using glucose （C6H12O6 ） as the starting materials by hydrotherreal carbonization. Then hollow ZrB2 spheres were successfully synthesized using zirconium oxychloride （ ZrClO2 · 8H2O）, boric acid （ H3BO3 ） by a combined solgel and boro/carbothermal reduction method, and the prepared carbon microspheres as the template. The effects of the reaction temperatures （1 200, 1 300, 1 400 and 1 500 ℃, respectively） and contents of carbon microspheres （ n （ C ） ： n （ ZrO2 ＋ B2O3） is 5. 0, 5. 5, 6. 0 and 6. 5, respectively） on the synthesis of hollow ZrB2 spheres were studied. The prepared carbon microspheres have smooth sugrace and good hollow structure by hydrothermal nitridation. Increase of reaction temperature and excessive carbon microspheres can greatly promote the formation of hollow ZrB2 spheres. The optimized reaction temperature and molar ratio of n （C）/ n （ ZrO2 ＋ B2O3 ） were 1 500 ℃ and 6.5, respectively.展开更多
The strong covalent bonding characters of zirconium diboride（ Zr B2） and hafnium diboride（ Hf B2） with natural hexagonal Al B2-type crystal structure give them high melting points（ 〉 3 200 ℃）, high bending str...The strong covalent bonding characters of zirconium diboride（ Zr B2） and hafnium diboride（ Hf B2） with natural hexagonal Al B2-type crystal structure give them high melting points（ 〉 3 200 ℃）, high bending strength, high elastic modulus and high hardness.Zr B2- and Hf B2-based ceramics are promising candidates for the thermal protection components of propulsion systems,rocket nozzles,sharp leading edges and nose cones. This paper introduces the recent research progress on Zr B2- and Hf B2-based ceramics,including the synthesis methods of the boride powders,the sintering methods of the boride-based ceramics and their properties.The advantages of different synthesis methods and sintering methods are compared. The influence factors on the mechanical properties,oxidation resistance and thermal shock resistance are summarized.展开更多
The thermal shock behavior of ZrB2-SiC ceramics was studied with water, air and methyl silicone oil as quenching media, respectively. The temperature of all coolants was room temperature （25℃） and the residual stre...The thermal shock behavior of ZrB2-SiC ceramics was studied with water, air and methyl silicone oil as quenching media, respectively. The temperature of all coolants was room temperature （25℃） and the residual strength of the ceramics after quenching was tested. The strength of the ceramics after water quenching had an obvious drop when the temperature difference, AT, was about 275℃, while the residual strength of the specimens quenched by air and silicone oil only varied a little and even increased slightly when the temperature difference was higher than 800℃. The different thermal conductive coefficient of the coolants and surface heat transfer coefficient resulted in the differences in the thermal shock behavior. The formation of oxidation layer was beneficial for improving the residual strength of the ceramics after quenching.展开更多
基金financially supported by the National Natural Science Foundation of China(No. 51674035)
文摘Using boron powder as additive, the preparation of zirconium diboride(ZrB 2) by carbothermal reduction was investigated. The results show that the carbothermal reduction cannot be completely done until the temperature is more than 1900 ℃. The ZrB2 particles prepared without boron(B) additive at 1900 ℃ for 3 h are rodlike and show a preferential grain growth along [001] direction. B additive changes the heat effect of the raw materials. With B additive, the morphology of ZrB2 particles turns to be regular shape. The average particle size is about 3.6 μm with 2.5 wt% B additives. With more B additive, the shape of particles turns to be round like and the average particle size is decreased to 2.3 μm when 5 wt% B is added. The existence of oxides in grain boundary is a key factor to keep ZrB2 ceramic from deep densification. Using ZrB2 powder prepared with 5 wt% B additives, by controlling carbon content in ZrB2 powder, ZrB2 ceramic with 93%relative density is hot-pressed.
文摘The oxidation behaviors of fused zirconium diboride and chemosynthetic zirconium diboride as well as morphology and composition of their oxidation products were researched by FESEM-EDS and XRD.The two kinds of zirconium diboride were heated at 700℃,900℃,1100℃and 1300℃for 3 h in air,respectively.The results show that Zr02 and B203(Ⅰ)are generated from the chemosynthetic zirconium diboride oxidized at 700℃for 3 h or the fused zirconium diboride oxidized at 800℃for 24 h;B203(Ⅰ)dissolves into water and then H3B03 crystallizes.
基金Supported by the Fund for the Self-dependent Innovation of Tianjin University(2014)
文摘A single phase of zirconium diboride （ZrB2） powder was successfully synthesized by sol-gel method in Zr-B-C-O system, using zirconium oxychloride （ZrOC12 ~ 8H20）, nano-scale boron and suerose（C12H22011）as the starting materials and propylene oxide （PO） as complexing agent at a low temperature. Simultaneously, the experimen- tal and theoretical studies of ZrB2 synthesized by boro/carbothermal reduction from novel sol-gel technology were discussed. The results indicated that the pure rod-like ZrB2 powder without residual ZrO2 phase could be obtained with a B/Zr molar ratio of 3.5 at 1 400~C in argon atmosphere. Besides, in this study, a kinetic model for the Zr-B-C-O sys- tem producing ZrB2 by boro/carbothermal reaction was established based on thermodynamic analysis. It was also ob- served that, with the increase of reaction temperature, the reaction which produced ZrB2 powders changed from the borothermal reaction to boro/carbothermal reaction in the Zr-B-C-O system.
基金Funded by the National Natural Science Foundation of China(No.51272190)the 111 Project(No.B13035)
文摘Zirconium oxide （ZrO：） and boron carbide （B4C） were added to ZrB2 raw powders to prepare ZrB2 porous ceramics by reactive spark plasma sintering （RSPS）. The reactions between ZrO2 and B,C which produce ZrB2 and gas （such as CO and B2O3） result in pore formation. X-Ray Diffraction results indicated that the products phase was ZrB2 and the reaction was completed after the RSPS process. The porosity could be controlled by changing the ratio of synthesized ZrB2 to raw ZrB2 powders. The porosity of porous ceramics with 20 wt% and 40 wt% synthsized ZrB2 are 0.185 and 0.222, respectivly. And dense ZrB：SiC ceramic with a porosity of 0.057 was prepared under the same conditions for comparison. The pores were homogeneously distributed within the microstructure of the porous ceramics. The results indicate a promising method for preparing porous ZrB：based ceramics.
文摘The present study focuses on the thermal response of carbon fiber-reinforced phenolic composites, where the matrix has been modified with different reinforcements. Two types of materials, multiwalled carbon nanotubes and zirconium diboride （ZrB2）, were used in a new design of mixture to produce the heat- resistant ablative composite system. The CNT/ZrB2/carbon/phenolic nanocomposite （Z/NT-CR） system corresponding to CNT/carbon/phenolic nanocomposite （NT-CR） showed a reasonable decrease in mass loss and the ablation rate as compared to carbon/phenolic composite （CR）. However, substantial drop in two factors was found for Z/NT-CR as compared to carbon/phenolic and NT-CR. Ablation mechanisms for all three composites were investigated by thermal gravimetric analysis in conjunction with micro- structural studies using a field emission scanning electron microscope. The microstructural studies revealed that CNTs acted as an ablation resistant phase for protection against 2000 ℃, and the conversion from ZrB2 to ZrO2 played an important role as an insulator in the performance of char layer in the ablation resistance.
基金financially supported by the National Natural Science Foundation of China(51532009)Science and Technology Commission of Shanghai Municipality(16DZ2260603,18ZR1401400)+1 种基金Shanghai Technical Platform for Testing and Characterization on Inorganic Materials(19DZ2290700)Loughborough University’s PhD studentship provided to SR。
文摘Ultra-high temperature ceramics have been considered as good candidates for plasma facing materials due to their combination of high melting point,high strength and hardness,high thermal conductivity as well as good chemical inertness.In this study,zirconium diboride has been chosen to investigate its irradiation damage behavior.Irradiated by 4 MeV Au^(2+)with a total fluence of 2.5×10^(16)cm^(-2),zirconium diboride ceramic shows substantial resilience to irradiation-induced damage with its structural integrity well maintained but mild damage at lattice level.Grazing incident X-ray diffraction evidences no change of the hexagonal structure in the irradiated region but its lattice parameter a increased and c decreased,giving a volume shrinkage of 0.46%.Density functional theory calculation shows that such lattice shrinkage corresponds to a non-stoichiometric compound as ZrB1.97.Electron energy-loss spectroscopy in a transmission electron microscope revealed an increase of valence electrons in zirconium,suggesting boron vacancies were indeed developed by the irradiation.Alo ng the irradiation depth,long dislocations were observed inside top layer with a depth of 750 nm where the implanted Au ions reached the peak concentration.Underneath the top layer,a high density of Frank dislocations is formed by the cascade collision down to a depth of 1150 nm.All the features show the potential of ZrB_(2) to be used as structural material in nuclear system.
文摘ZrB2 ceramics were prepared by self-propagating high-temperature synthesis（SHS） and were sintered by hot pressing（HP）.The effects of the granularities and doses of raw materials in Zr-B2O3-Mgon SHS process and product were investigated.XRD and combustion temperature curves prove that the ideal SHS reactants of Zr-B2O3-Mg are 50μm Zr powder,75μm B2O3 powder and 400μm Mg powder with 45% excessive.The particle sizes of SHS product,acid-leached product,sintered product are 2-5μm,0.5-2μm,2-10μm respectively.Chemical analysis indicates that the acid-leached product consists of ZrB2（94.59%）,ZrO2（3.87%）,and H3BO3（1.54%）,The sintered product has a relative density of 95.4%.
文摘LaB 6 ZrB 2 eutectic composites were fabricated using electric arc furnace and EBZM(electron beam zone melting) technique Orientated ZrB 2 fibers yielded in a LaB 6 matrix The average diameter of ZrB 2 fibers is about 0 2～1 2 μm, and the length can be up to 100 μm For the ingot solidified with planar growth, the orientation relation of the phases is: Growth direction: LaB 6 ∥ ZrB 2 , Interfacial plane: (110) LaB 6 ∥(110) ZrB 2
基金financially supported by National Natural Science Foundation of China(General program,51272188,51472184,51472185)State Basic Research Development Program of China(973 Program,2014CB660802)+1 种基金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 microspheres were firstly prepared using glucose （C6H12O6 ） as the starting materials by hydrotherreal carbonization. Then hollow ZrB2 spheres were successfully synthesized using zirconium oxychloride （ ZrClO2 · 8H2O）, boric acid （ H3BO3 ） by a combined solgel and boro/carbothermal reduction method, and the prepared carbon microspheres as the template. The effects of the reaction temperatures （1 200, 1 300, 1 400 and 1 500 ℃, respectively） and contents of carbon microspheres （ n （ C ） ： n （ ZrO2 ＋ B2O3） is 5. 0, 5. 5, 6. 0 and 6. 5, respectively） on the synthesis of hollow ZrB2 spheres were studied. The prepared carbon microspheres have smooth sugrace and good hollow structure by hydrothermal nitridation. Increase of reaction temperature and excessive carbon microspheres can greatly promote the formation of hollow ZrB2 spheres. The optimized reaction temperature and molar ratio of n （C）/ n （ ZrO2 ＋ B2O3 ） were 1 500 ℃ and 6.5, respectively.
基金Financial supports from the National Natural Science Foundation of China ( No. 51272266 )the Science and Technology Commission of Shanghai ( No. 15ZR1445200 )the State Key Laboratory of High Performance Ceramics and Superfine Microstructure
文摘The strong covalent bonding characters of zirconium diboride（ Zr B2） and hafnium diboride（ Hf B2） with natural hexagonal Al B2-type crystal structure give them high melting points（ 〉 3 200 ℃）, high bending strength, high elastic modulus and high hardness.Zr B2- and Hf B2-based ceramics are promising candidates for the thermal protection components of propulsion systems,rocket nozzles,sharp leading edges and nose cones. This paper introduces the recent research progress on Zr B2- and Hf B2-based ceramics,including the synthesis methods of the boride powders,the sintering methods of the boride-based ceramics and their properties.The advantages of different synthesis methods and sintering methods are compared. The influence factors on the mechanical properties,oxidation resistance and thermal shock resistance are summarized.
文摘The thermal shock behavior of ZrB2-SiC ceramics was studied with water, air and methyl silicone oil as quenching media, respectively. The temperature of all coolants was room temperature （25℃） and the residual strength of the ceramics after quenching was tested. The strength of the ceramics after water quenching had an obvious drop when the temperature difference, AT, was about 275℃, while the residual strength of the specimens quenched by air and silicone oil only varied a little and even increased slightly when the temperature difference was higher than 800℃. The different thermal conductive coefficient of the coolants and surface heat transfer coefficient resulted in the differences in the thermal shock behavior. The formation of oxidation layer was beneficial for improving the residual strength of the ceramics after quenching.
