Two polyborosiloxanes （PBSis） with char yield up to 74.13% at 800 ℃ were synthesized by the direct polycondensation of boric acid with phenyltrimethoxysilane in diglyme. The PBSis were characterized by gel permeati...Two polyborosiloxanes （PBSis） with char yield up to 74.13% at 800 ℃ were synthesized by the direct polycondensation of boric acid with phenyltrimethoxysilane in diglyme. The PBSis were characterized by gel permeation chromatography, IR spectroscopy as well as ^1H-, ^29Si- and ^11B-NMR. PBSi modified phenol-formaldehyde resins （PBSi/PFs） were prepared at different PBSi/PF mass ratios and were cured at 150 ℃. The PBSi/PFs were characterized by IR spectroscopy, scanning electron microscopy, thermogravimetric analysis and tensile test. The results revealed that the cured PBSi/PFs had sea-island morphology and higher char yield than the common PF. PBSi/PF blend with PBSi/PF mass ratio of 0.4：1 had char yield up to 70.83% at 800 ℃. The PBSi/PFs had tensile strength similar to PF. The ceramization of PBSi/PFs was also studied. The silicon boron oxycarbide （SiBOC） ceramics formed were characterized by IR spectroscopy and elemental analysis. This method provided a valuable way to prepare easily shapeable polymer blends as ceramic precursors.展开更多
A new kind of polytitanosilazane precursor PTSZ for Si/C/N/Ti-based ceramic was synthesized from the condensation reaction of silazane lithium salt and titanium tetrachloride (TiCl4). The results indicated that the c...A new kind of polytitanosilazane precursor PTSZ for Si/C/N/Ti-based ceramic was synthesized from the condensation reaction of silazane lithium salt and titanium tetrachloride (TiCl4). The results indicated that the ceramic yield of PTSZ was much higher than that of corresponding silazane oligomer.展开更多
The current generation of ultrahigh temperature ceramic precursors typically encounters obstacles in achieving high ceramic yields(<40 wt.%)due to the challenges in integrating significant amounts of boron,which ha...The current generation of ultrahigh temperature ceramic precursors typically encounters obstacles in achieving high ceramic yields(<40 wt.%)due to the challenges in integrating significant amounts of boron,which hampers their conversion into boride-based ultrahigh temperature ceramics.To tackle these challenges,a serious of pioneering liquid multi-component hafnium-containing ceramic SiHfCB precursors(with different Hf/Si ratios)have been developed.These novel precursors are featured with stable molec-ular structure and high ceramic yield which were successfully created through a novel one-pot polymer-ization process.They present in liquid form and their structure is characterized by C-C bonds forming its main chain with branched chains of O-Si-O,Si-O-Hf,Si-O-B,and B-O-Hf which have untapped advantages including uniform component dispersion,and excellent fluidity.The ceramic yield of SiHfCB precursor with Hf/Si of 0.2 is remarkably up to 68.6 wt.%at 1500℃,and their Hf content exceeded 50 wt.%.Of particular interest,the pyrolyzed product HfB_(2)-SiC nanopowders derived from the SiHfCB precursor with Hf/Si of 0.2,consist of nanopowders in the 40-60 nm range with a density of 5.23 g cm^(−3).Remarkably,this material demonstrates exceptional performance in ultrahigh temperature oxygen-containing environ-ments at 2500℃,showing near-zero ablation with a linear ablation rate of just 2.5×10^(−4) mm s^(−1).Post-ablation analysis of the microstructure reveals that the formation of a lava-like HfO_(2) and HfO_(2)-SiO_(2) oxide layer effectively blocks oxygen penetration and provides excellent oxidation resistance.The inno-vative SiHfCB hafnium-containing ceramic precursor offers a groundbreaking solution for the preparation of lightweight ultrahigh-temperature ceramics.This development is poised to provide robust technical support for the use of ultrahigh temperature ceramics in non-ablative thermal protective systems,partic-ularly in the construction of hypersonic vehicles,where ultrahigh temperature resilience is crucial.展开更多
A new kind of organometallic precursor for Si/Zr/C/N-based ceramics was synthesized from the amine exchangereaction of hexamethylcyclotrisilazane (D_3~N) and tetrakis(diethylamino) zirconium (Zr[NEt_2]_4). Pyrolysis w...A new kind of organometallic precursor for Si/Zr/C/N-based ceramics was synthesized from the amine exchangereaction of hexamethylcyclotrisilazane (D_3~N) and tetrakis(diethylamino) zirconium (Zr[NEt_2]_4). Pyrolysis was performedunder nitrogen at 800℃ in a tube furnace equipped with a temperature program controller. The highest pyrolytic yield was67.5%.展开更多
Nucleation behavior of amorphous Si–B–C–N ceramics derived from boron-modified polyvinylsilazane procusors was systematically investigated by transmission electron microscopy(TEM) combined with spatially-resolved e...Nucleation behavior of amorphous Si–B–C–N ceramics derived from boron-modified polyvinylsilazane procusors was systematically investigated by transmission electron microscopy(TEM) combined with spatially-resolved electron energy-loss spectroscopy(EELS) analysis. The ceramics were pyrolyzed at1000℃ followed by further annealing in N2, and SiC nano-crystallites start to emerge at 1200℃ and dominate at 1500℃. Observed by high-angle annular dark-field imaging, bright and dark clusters were revealed as universal nano-structured features in ceramic matrices before and after nucleation, and the growth of cluster size saturated before reaching 5 nm at 1400℃. EELS analysis demonstrated the gradual development of bonding structures successively into SiC, graphetic BNCxand Si3N4 phases, as well as a constant presence of unexpected oxygen in the matrices. Furthermore, EELS profiling revealed the bright SiC clusters and less bright Si3N4-like clusters at 1200–1400℃. Since the amorphous matrix has already phase separated into SiCN and carbon clusters, another phase separation of SiCN into SiC and Si3N4-like clusters might occur by annealing to accompany their nucleation and growth, albeit one crystallized and another remained in amorphous structure. Hinderance of the cluster growth and further crystallization was owing to the formation of BNCxlayers that developed between SiC and Si3N4-like clusters as well as from the excessive oxygen to form the stable SiO2.展开更多
This work investigated the structure and dielectric behavior of precursor-derived spark plasma sintered(SPS)hafnium dioxide(HfO_(2)).X-ray diffractograms confirmed the presence of monoclinic HfO_(2)(m-HfO_(2))and scan...This work investigated the structure and dielectric behavior of precursor-derived spark plasma sintered(SPS)hafnium dioxide(HfO_(2)).X-ray diffractograms confirmed the presence of monoclinic HfO_(2)(m-HfO_(2))and scanning electron micrographs revealed micron/nanosized grains and grain boundaries in SPS m-HfO_(2).The theoretical density of ceramics is 94%,and the porosity is very low.In the temperature interval of 25-200℃,the real part of the permittivity(ε')is almost frequency-and temperature-independent and the e'value is about 21 in the frequency range 10^(2)-10^(6)Hz.ε'of SPS ceramics is higher than that of traditionally sintered HfO_(2) ceramics.At temperatures above 225℃,there is a sharp increase in the permittivity and loss at low measuring frequencies.In order to comprehend the underlying conduction mechanisms,an analysis of the dispersion dependences of the dielectric response was undertaken.High permittivity values were attributed to the space charge polarization mechanism occurring at grain boundaries due to the thermally activated movement of oxygen vacancies.The DC conductivity of SPS m-HfO_(2) is thermally activated,and conductivity is determined by oxygen vacancies through hopping mechanism.展开更多
A highly branched polycarbosilane bearing allyl groups has been prepared by a one-pot synthesis with chloromethyltrichlorosilane, chloromethylmethyldichlorosilane and allyl chloride as the starting materials. The resu...A highly branched polycarbosilane bearing allyl groups has been prepared by a one-pot synthesis with chloromethyltrichlorosilane, chloromethylmethyldichlorosilane and allyl chloride as the starting materials. The resultant polymer, with the approximate formula [SiH1.2(CH3)0.71(CH2CHCH2)0.09CH2]n, has been characterized by 1H, 13C, and 29Si NMR, GPC, TG and elemental analysis. It could be cross-linked thermally at 170 °C in the absence of oxygen. Pyrolysis of the polymer gave a ceramic with a yield of about 70%.展开更多
A new kind of polyorganozircosilazane as Si/Zr/C/N-based ceramic precursor was synthesized from the condensation reaction of hexamethylcyclotrisilazane lithium salts (D3NLi) and zirconium tetrachloride (ZrCl4). In th...A new kind of polyorganozircosilazane as Si/Zr/C/N-based ceramic precursor was synthesized from the condensation reaction of hexamethylcyclotrisilazane lithium salts (D3NLi) and zirconium tetrachloride (ZrCl4). In the presence of N, N, N, N-tetramethyl ethylene diamine (TMEDA), polyorganozircosilazane was obtained in high yield.展开更多
Nd∶GGG ultrafine polycrystalline powders for transparent ceramics precursor powder were synthesized by sol-gel method, and sol-gel transformation mechanics was discussed. Nd∶GGG polycrystalline material was analyzed...Nd∶GGG ultrafine polycrystalline powders for transparent ceramics precursor powder were synthesized by sol-gel method, and sol-gel transformation mechanics was discussed. Nd∶GGG polycrystalline material was analyzed by XRD, SEM and fluorescence spectrum. XRD analysis shows that Nd∶GGG polycrystalline phase is formed at 1000 ℃, and the grain size increases with rising sintering temperature by SEM, and the particle size is about 100 nm. They are used as transparent ceramics precursor powder. Fluorescence spectrum test shows that the strongest fluorescence emission peak is 1061.45 nm for the Nd∶GGG polycrystalline precursor powder, which is the fluorescence-emission of Nd 3+ 4F_ 3/2—4I_ 11/2.展开更多
文摘Two polyborosiloxanes （PBSis） with char yield up to 74.13% at 800 ℃ were synthesized by the direct polycondensation of boric acid with phenyltrimethoxysilane in diglyme. The PBSis were characterized by gel permeation chromatography, IR spectroscopy as well as ^1H-, ^29Si- and ^11B-NMR. PBSi modified phenol-formaldehyde resins （PBSi/PFs） were prepared at different PBSi/PF mass ratios and were cured at 150 ℃. The PBSi/PFs were characterized by IR spectroscopy, scanning electron microscopy, thermogravimetric analysis and tensile test. The results revealed that the cured PBSi/PFs had sea-island morphology and higher char yield than the common PF. PBSi/PF blend with PBSi/PF mass ratio of 0.4：1 had char yield up to 70.83% at 800 ℃. The PBSi/PFs had tensile strength similar to PF. The ceramization of PBSi/PFs was also studied. The silicon boron oxycarbide （SiBOC） ceramics formed were characterized by IR spectroscopy and elemental analysis. This method provided a valuable way to prepare easily shapeable polymer blends as ceramic precursors.
基金support of the National Natural Science Foundation of China(No.50072033)the Chinese Academy of Sciences(CXJJ-10).
文摘A new kind of polytitanosilazane precursor PTSZ for Si/C/N/Ti-based ceramic was synthesized from the condensation reaction of silazane lithium salt and titanium tetrachloride (TiCl4). The results indicated that the ceramic yield of PTSZ was much higher than that of corresponding silazane oligomer.
基金supported by the Key Program of the National Natural Science Foundation of China(No.52032003)the Major Program of the National Natural Science Foundation of China(No.52293372)+2 种基金the National Natural Science Foundation of China(No.51972082)the National Natural Science Foundation of China(No.52102093)the National Natural Science Foundation of China(No.52172041)and the science foundation of national key laboratory of science and technology on advanced composites in special environments.
文摘The current generation of ultrahigh temperature ceramic precursors typically encounters obstacles in achieving high ceramic yields(<40 wt.%)due to the challenges in integrating significant amounts of boron,which hampers their conversion into boride-based ultrahigh temperature ceramics.To tackle these challenges,a serious of pioneering liquid multi-component hafnium-containing ceramic SiHfCB precursors(with different Hf/Si ratios)have been developed.These novel precursors are featured with stable molec-ular structure and high ceramic yield which were successfully created through a novel one-pot polymer-ization process.They present in liquid form and their structure is characterized by C-C bonds forming its main chain with branched chains of O-Si-O,Si-O-Hf,Si-O-B,and B-O-Hf which have untapped advantages including uniform component dispersion,and excellent fluidity.The ceramic yield of SiHfCB precursor with Hf/Si of 0.2 is remarkably up to 68.6 wt.%at 1500℃,and their Hf content exceeded 50 wt.%.Of particular interest,the pyrolyzed product HfB_(2)-SiC nanopowders derived from the SiHfCB precursor with Hf/Si of 0.2,consist of nanopowders in the 40-60 nm range with a density of 5.23 g cm^(−3).Remarkably,this material demonstrates exceptional performance in ultrahigh temperature oxygen-containing environ-ments at 2500℃,showing near-zero ablation with a linear ablation rate of just 2.5×10^(−4) mm s^(−1).Post-ablation analysis of the microstructure reveals that the formation of a lava-like HfO_(2) and HfO_(2)-SiO_(2) oxide layer effectively blocks oxygen penetration and provides excellent oxidation resistance.The inno-vative SiHfCB hafnium-containing ceramic precursor offers a groundbreaking solution for the preparation of lightweight ultrahigh-temperature ceramics.This development is poised to provide robust technical support for the use of ultrahigh temperature ceramics in non-ablative thermal protective systems,partic-ularly in the construction of hypersonic vehicles,where ultrahigh temperature resilience is crucial.
基金This work was supported by the National Natural Sciences Foundation of China (No. 50072033).
文摘A new kind of organometallic precursor for Si/Zr/C/N-based ceramics was synthesized from the amine exchangereaction of hexamethylcyclotrisilazane (D_3~N) and tetrakis(diethylamino) zirconium (Zr[NEt_2]_4). Pyrolysis was performedunder nitrogen at 800℃ in a tube furnace equipped with a temperature program controller. The highest pyrolytic yield was67.5%.
基金financially supported by National Natural Science Foundation of China (Grant Nos. 51172255 and 51532006)
文摘Nucleation behavior of amorphous Si–B–C–N ceramics derived from boron-modified polyvinylsilazane procusors was systematically investigated by transmission electron microscopy(TEM) combined with spatially-resolved electron energy-loss spectroscopy(EELS) analysis. The ceramics were pyrolyzed at1000℃ followed by further annealing in N2, and SiC nano-crystallites start to emerge at 1200℃ and dominate at 1500℃. Observed by high-angle annular dark-field imaging, bright and dark clusters were revealed as universal nano-structured features in ceramic matrices before and after nucleation, and the growth of cluster size saturated before reaching 5 nm at 1400℃. EELS analysis demonstrated the gradual development of bonding structures successively into SiC, graphetic BNCxand Si3N4 phases, as well as a constant presence of unexpected oxygen in the matrices. Furthermore, EELS profiling revealed the bright SiC clusters and less bright Si3N4-like clusters at 1200–1400℃. Since the amorphous matrix has already phase separated into SiCN and carbon clusters, another phase separation of SiCN into SiC and Si3N4-like clusters might occur by annealing to accompany their nucleation and growth, albeit one crystallized and another remained in amorphous structure. Hinderance of the cluster growth and further crystallization was owing to the formation of BNCxlayers that developed between SiC and Si3N4-like clusters as well as from the excessive oxygen to form the stable SiO2.
基金supported by the grant received from the Department of Science and Technology,Ministry of Science and Technology,Government of India(project no.DST/ICD/BRICS/Call-3/RaviKumar-PORMAT/2019)supported by the Ministry of Science and Higher Education of the Russian Federation within the State task FSEG-2023-0016.
文摘This work investigated the structure and dielectric behavior of precursor-derived spark plasma sintered(SPS)hafnium dioxide(HfO_(2)).X-ray diffractograms confirmed the presence of monoclinic HfO_(2)(m-HfO_(2))and scanning electron micrographs revealed micron/nanosized grains and grain boundaries in SPS m-HfO_(2).The theoretical density of ceramics is 94%,and the porosity is very low.In the temperature interval of 25-200℃,the real part of the permittivity(ε')is almost frequency-and temperature-independent and the e'value is about 21 in the frequency range 10^(2)-10^(6)Hz.ε'of SPS ceramics is higher than that of traditionally sintered HfO_(2) ceramics.At temperatures above 225℃,there is a sharp increase in the permittivity and loss at low measuring frequencies.In order to comprehend the underlying conduction mechanisms,an analysis of the dispersion dependences of the dielectric response was undertaken.High permittivity values were attributed to the space charge polarization mechanism occurring at grain boundaries due to the thermally activated movement of oxygen vacancies.The DC conductivity of SPS m-HfO_(2) is thermally activated,and conductivity is determined by oxygen vacancies through hopping mechanism.
文摘A highly branched polycarbosilane bearing allyl groups has been prepared by a one-pot synthesis with chloromethyltrichlorosilane, chloromethylmethyldichlorosilane and allyl chloride as the starting materials. The resultant polymer, with the approximate formula [SiH1.2(CH3)0.71(CH2CHCH2)0.09CH2]n, has been characterized by 1H, 13C, and 29Si NMR, GPC, TG and elemental analysis. It could be cross-linked thermally at 170 °C in the absence of oxygen. Pyrolysis of the polymer gave a ceramic with a yield of about 70%.
基金the National Natural Sciences Foundation of China(No.50072033)for the financial support
文摘A new kind of polyorganozircosilazane as Si/Zr/C/N-based ceramic precursor was synthesized from the condensation reaction of hexamethylcyclotrisilazane lithium salts (D3NLi) and zirconium tetrachloride (ZrCl4). In the presence of N, N, N, N-tetramethyl ethylene diamine (TMEDA), polyorganozircosilazane was obtained in high yield.
文摘Nd∶GGG ultrafine polycrystalline powders for transparent ceramics precursor powder were synthesized by sol-gel method, and sol-gel transformation mechanics was discussed. Nd∶GGG polycrystalline material was analyzed by XRD, SEM and fluorescence spectrum. XRD analysis shows that Nd∶GGG polycrystalline phase is formed at 1000 ℃, and the grain size increases with rising sintering temperature by SEM, and the particle size is about 100 nm. They are used as transparent ceramics precursor powder. Fluorescence spectrum test shows that the strongest fluorescence emission peak is 1061.45 nm for the Nd∶GGG polycrystalline precursor powder, which is the fluorescence-emission of Nd 3+ 4F_ 3/2—4I_ 11/2.
