Polymer-derived ceramics(PDCs) strategy shows a great deal of advantages for the fabrication of advanced ceramics. Organosilicon polymers facilitate the shaping process and different silicon-based ceramics with contro...Polymer-derived ceramics(PDCs) strategy shows a great deal of advantages for the fabrication of advanced ceramics. Organosilicon polymers facilitate the shaping process and different silicon-based ceramics with controllable components can be fabricated by modifying organosilicon polymers or adding fillers. It is worth noting that silicate ceramics can also be fabricated from organosilicon polymers by the introduction of active fillers, which could react with the produced silica during pyrolysis. The organosilicon polymer-derived ceramics show many unique properties, which have attracted many attentions in various fields. This review summarizes the typical organosilicon polymers and the processing of organosilicon polymers to fabricate silicon-based ceramics, especially highlights the three-dimensional(3 D) printing technique for shaping the organosilicon polymerderived ceramics, which makes the possibility to fabricate silicon-based ceramics with complex structure. More importantly, the recent studies on fabricating typical non-oxide and silicate ceramics derived from organosilicon polymers and their biomedical applications are highlighted.展开更多
In order to enhance dielectric properties of polymer-derived SiC ceramics,a novel single-source-precursor was synthesized by the reaction of an allylhydrido polycarbosilane(AHPCS)and divinyl benzene(DVB)to form carbon...In order to enhance dielectric properties of polymer-derived SiC ceramics,a novel single-source-precursor was synthesized by the reaction of an allylhydrido polycarbosilane(AHPCS)and divinyl benzene(DVB)to form carbon-rich SiC.As expected,the free carbon contents of resultant SiC ceramics annealed at 1600℃are significantly enhanced from 6.62 wt%to 44.67 wt%.After annealing at 900-1600℃,the obtained carbon-rich SiC ceramics undergo phase separation from amorphous to crystalline feature where superfine SiC nanocrystals and turbostratic carbon networks are dispersed in an amorphous SiC(O)matrix.The dielectric properties and electromagnetic(EM)absorption performance of as-synthesized carbon-rich SiC ceramics are significantly improved by increasing the structural order and content of free carbon.For the 1600℃ ceramics mixed with paraffin wax,the minimum reflection coefficient(RCmin)reaches-56.8 dB at 15.2 GHz with the thickness of 1.51 mm and a relatively broad effective bandwidth(the bandwidth of RC values lower than-10 dB)of 4.43 GHz,indicating the excellent EM absorption performance.The carbon-rich SiC ceramics have to be considered as harsh environmental EM absorbers with excellent chemical stability,high temperature,and oxidation and corrosion resistance.展开更多
Since the 1960s,a new class of Si-based advanced ceramics called polymer-derived ceramics(PDCs)has been widely reported because of their unique capabilities to produce various ceramic materials(e.g.,ceramic fibers,cer...Since the 1960s,a new class of Si-based advanced ceramics called polymer-derived ceramics(PDCs)has been widely reported because of their unique capabilities to produce various ceramic materials(e.g.,ceramic fibers,ceramic matrix composites,foams,films,and coatings)and their versatile applications.Particularly,due to their promising structural and functional properties for energy conversion and storage,the applications of PDCs in these fields have attracted much attention in recent years.This review highlights the recent progress in the PDC field with the focus on energy conversion and storage applications.Firstly,a brief introduction of the Si-based polymer-derived ceramics in terms of synthesis,processing,and microstructure characterization is provided,followed by a summary of PDCs used in energy conversion systems(mainly in gas turbine engines),including fundamentals and material issues,ceramic matrix composites,ceramic fibers,thermal and environmental barrier coatings,as well as high-temperature sensors.Subsequently,applications of PDCs in the field of energy storage are reviewed with a strong focus on anode materials for lithium and sodium ion batteries.The possible applications of the PDCs in Li–S batteries,supercapacitors,and fuel cells are discussed as well.Finally,a summary of the reported applications and perspectives for future research with PDCs are presented.展开更多
In this work,novel carbon nanotube(CNT)/CoSi/SiOC nanocomposite ceramics with in-situ formed multi-walled CNTs and core-shell structured CoSi@C nanoparticles were successfully prepared via a single-source-precursor de...In this work,novel carbon nanotube(CNT)/CoSi/SiOC nanocomposite ceramics with in-situ formed multi-walled CNTs and core-shell structured CoSi@C nanoparticles were successfully prepared via a single-source-precursor derived ceramic approach.Ppolymericprecursor characterization as well as phase evolution,microstructure,and electromagnetic wave(EMW)absorption properties of the ceramics were investigated in detail.The results show that the in-situ formed CNTs and magnetic CoSi@C nanoparticles provide a synergistic effect on both dielectric loss(tand:)and magnetic loss,leading to outstanding EMW absorption properties of the ceramics annealed at only 1100 C.(i)For the Co feeding of 6.25 wt%,the minimum reflection loss(RLmin)is-53.1 dB,and the effective absorption bandwidth(EAB)is 4.96 GHz(7.12-12.08 GHz)with a ceramic-paraffin hybrid sample thickness of 3.10 mm,achieving full X-band coverage;(i)for the Co feeding of 9.09 wt%,the RLmin value of-66.4 dB and the EAB value of 3.04 GHz(8.40-11.44 GHz)were achieved with a thickness of only 2.27 mm.Therefore,the present CNT/CoSi/SiOC nanocomposite ceramics have potential applications for thin,lightweight,and efficient EMW absorption in harsh environments.展开更多
Pressure measurement with excellent stability and long time durability is highly desired,especially at high temperature and harsh environments.A polymer-derived silicoboron carbonitride(SiBCN)ceramic pressure sensor w...Pressure measurement with excellent stability and long time durability is highly desired,especially at high temperature and harsh environments.A polymer-derived silicoboron carbonitride(SiBCN)ceramic pressure sensor with excellent stability,accuracy,and repeatability is designed based on the giant piezoresistivity of SiBCN ceramics.The SiBCN ceramic sensor was packaged in a stainless steel case and tested using half Wheatstone bridge with the uniaxial pressure up to 10 MPa.The SiBCN ceramic showed a remarkable piezoresistive effect with the gauge factor(K)as high as 5500.The output voltage of packed SiBCN ceramic sensor changes monotonically and smoothly versus external pressure.The as received SiBCN pressure sensor possesses features of short response time,excellent repeatability,stability,sensitivity,and accuracy.Taking the excellent high temperature thermo-mechanical properties of polymer-derived SiBCN ceramics(e.g.,high temperature stability,oxidation/corrosion resistance)into account,SiBCN ceramic sensor has significant potential for pressure measurement at high temperature and harsh environments.展开更多
The microstructure of polymer-derived ceramics(PDCs)was closely related to processing.This study demonstrated that SiCN matrix prepared by polymer infiltration and pyrolysis(PIP)at 900℃ inside a Si_(3)N_(4) whisker(S...The microstructure of polymer-derived ceramics(PDCs)was closely related to processing.This study demonstrated that SiCN matrix prepared by polymer infiltration and pyrolysis(PIP)at 900℃ inside a Si_(3)N_(4) whisker(Si_(3)N_(4w))preform with submicro-sized pores differed from its powder-consolidated analogue in both the content and structure of free carbon.Chemical analysis showed that PIP process had a higher free carbon yield.Raman spectroscopy and transmission electron microscopy(TEM)observation discovered a higher graphitization degree of free carbon and the existence of nanocrystalline graphite in SiCN matrix.Dielectric properties of Si_(3)N_(4w)/SiCN composites were greatly enhanced when volume fraction of SiCN matrix reached 24.5%due to dielectric percolation caused by highly-lossy free carbon.Reconsolidation of hydrocarbon released during pyrolysis by gas-state carbonization in Si_(3)N_(4) whisker preform was supposed to account for the high yield and graphitization degree of free carbon in PIP process.展开更多
Copper(Cu)-containing single-source precursors(SSPs)for the preparation of SiCuCN-based ceramic nanocomposites were successfully synthesized for the first time using polysilazane(PSZ),copper(II)acetate monohydrate(CuA...Copper(Cu)-containing single-source precursors(SSPs)for the preparation of SiCuCN-based ceramic nanocomposites were successfully synthesized for the first time using polysilazane(PSZ),copper(II)acetate monohydrate(CuAc),and 2-aminoethanol via nucleophilic substitution reactions at silicon(Si)centers of PSZ.The synthesis process,polymer-to-ceramic transformation,and high-temperature microstructural evolution of the prepared ceramics were characterized.Dielectric properties and electromagnetic wave(EMW)absorbing performance of the ceramics were investigated as well.The results show that the polymer-to-ceramic transformation finishes at ca.900 ℃,and Cu nanoparticles are homogeneously distributed in a SiCN matrix,forming a SiCN/Cu nanocomposite.After annealing at 1200 ℃,the Cu nanoparticles completely transform into copper silicide(CusSi).Interestingly,the thermal stability of the Cu nanoparticles can be strongly improved by increasing the free carbon content,so that a part of metallic Cu nanoparticles can be detected in the ceramics annealed even at 1300 ℃,forming a SiCN/Cu/Cu_(3)Si/C nanocomposite.Compared with SiCN,the SiCuCN-based nanocomposites exhibit strongly enhanced dielectric properties,which results in outstanding EMW absorbing performance.The minimum reflection coefficient(RC_(min))of the SiCN/Cu/Cu_(3)Si/C nanocomposites annealed at 1300 ℃ achieves-59.85 dB with a sample thickness of 1.55 mm,and the effective absorption bandwidth(EAB)broadens to 5.55 GHz at 1.45 mm.The enhanced EMW absorbing performance can be attributed to an in situ formed unique network,which was constructed with Cu and Cu_(3)Si nanoparticles connected by ring-like carbon ribbons within the SiCN matrix.展开更多
SiBN ceramics are widely considered to be the most promising material for microwavetransparent applications in harsh environments owing to its excellent thermal stability and low dielectric constant.This work focuses ...SiBN ceramics are widely considered to be the most promising material for microwavetransparent applications in harsh environments owing to its excellent thermal stability and low dielectric constant.This work focuses on the synthesis and ceramization of single-source precursors for the preparation of SiBN ceramics as well as the investigation of the corresponding microstructural evolution at high temperatures including molecular dynamic simulations.Carbon-and chlorine-free perhydropolysilazanes were reacted with borane dimethyl sulfide complex at different molar ratios to synthesize single-source precursors,which were subsequently pyrolyzed and annealed under N2 atmosphere(without ammonolysis)to prepare SiBN ceramics at 1100,1200,and 1300℃with high ceramic yield in contrast to previously widely-used ammonolysis synthesis process.The obtained amorphous SiBN ceramics were shown to have remarkably improved thermal stability and oxidation resistance compared to amorphous silicon nitride.Particularly,the experimental results have been combined with molecular dynamics simulation to further study the amorphous structure of SiBN and the atomic-scale diffusion behavior of Si,B,and N at 1300℃.Incorporation of boron into the Si–N network is found to suppress the crystallization of the formed amorphous silicon nitride and hence improves its thermal stability in N2 atmosphere.展开更多
基金support by grants from the National Natural Science Foundation of China(Grant No.51872185)the Science and Technology Commission of Shanghai Municipality(Grant No.17060502400)the University of Shanghai for Science and Technology(Grant No.2017KJFZ010).
文摘Polymer-derived ceramics(PDCs) strategy shows a great deal of advantages for the fabrication of advanced ceramics. Organosilicon polymers facilitate the shaping process and different silicon-based ceramics with controllable components can be fabricated by modifying organosilicon polymers or adding fillers. It is worth noting that silicate ceramics can also be fabricated from organosilicon polymers by the introduction of active fillers, which could react with the produced silica during pyrolysis. The organosilicon polymer-derived ceramics show many unique properties, which have attracted many attentions in various fields. This review summarizes the typical organosilicon polymers and the processing of organosilicon polymers to fabricate silicon-based ceramics, especially highlights the three-dimensional(3 D) printing technique for shaping the organosilicon polymerderived ceramics, which makes the possibility to fabricate silicon-based ceramics with complex structure. More importantly, the recent studies on fabricating typical non-oxide and silicate ceramics derived from organosilicon polymers and their biomedical applications are highlighted.
基金supported by the National Natural Science Foundation of China(No.51872246)Shenzhen Science and Technology Projects(JCYJ20180306172957494).
文摘In order to enhance dielectric properties of polymer-derived SiC ceramics,a novel single-source-precursor was synthesized by the reaction of an allylhydrido polycarbosilane(AHPCS)and divinyl benzene(DVB)to form carbon-rich SiC.As expected,the free carbon contents of resultant SiC ceramics annealed at 1600℃are significantly enhanced from 6.62 wt%to 44.67 wt%.After annealing at 900-1600℃,the obtained carbon-rich SiC ceramics undergo phase separation from amorphous to crystalline feature where superfine SiC nanocrystals and turbostratic carbon networks are dispersed in an amorphous SiC(O)matrix.The dielectric properties and electromagnetic(EM)absorption performance of as-synthesized carbon-rich SiC ceramics are significantly improved by increasing the structural order and content of free carbon.For the 1600℃ ceramics mixed with paraffin wax,the minimum reflection coefficient(RCmin)reaches-56.8 dB at 15.2 GHz with the thickness of 1.51 mm and a relatively broad effective bandwidth(the bandwidth of RC values lower than-10 dB)of 4.43 GHz,indicating the excellent EM absorption performance.The carbon-rich SiC ceramics have to be considered as harsh environmental EM absorbers with excellent chemical stability,high temperature,and oxidation and corrosion resistance.
基金Zhaoju Yu thanks the National Natural Science Foundation of China(Nos.51872246 and 52061135102)for financial supportQingbo Wen thanks the National Natural Science Foundation of China(No.52102085)+3 种基金the State Key Laboratory of Powder Metallurgy,Central South University,Changsha,China(No.621022117)Fangmu Qu acknowledges the financial support by the China Scholarship Council(CSC,No.201904910776)This review also originated from the Research Training Group at TU Darmstadt and Karlsruhe Institute of Technology(KIT)entitled“Materials Composites from Composite Materials”funded by the Deutsche Forschungsgemeinschaft(DFG,No.GRK 2561)Magdalena Graczyk-Zajac acknowledges DFG support in the frame of the project GR 4440/4-1.
文摘Since the 1960s,a new class of Si-based advanced ceramics called polymer-derived ceramics(PDCs)has been widely reported because of their unique capabilities to produce various ceramic materials(e.g.,ceramic fibers,ceramic matrix composites,foams,films,and coatings)and their versatile applications.Particularly,due to their promising structural and functional properties for energy conversion and storage,the applications of PDCs in these fields have attracted much attention in recent years.This review highlights the recent progress in the PDC field with the focus on energy conversion and storage applications.Firstly,a brief introduction of the Si-based polymer-derived ceramics in terms of synthesis,processing,and microstructure characterization is provided,followed by a summary of PDCs used in energy conversion systems(mainly in gas turbine engines),including fundamentals and material issues,ceramic matrix composites,ceramic fibers,thermal and environmental barrier coatings,as well as high-temperature sensors.Subsequently,applications of PDCs in the field of energy storage are reviewed with a strong focus on anode materials for lithium and sodium ion batteries.The possible applications of the PDCs in Li–S batteries,supercapacitors,and fuel cells are discussed as well.Finally,a summary of the reported applications and perspectives for future research with PDCs are presented.
基金the National Natural Science Foundation of China(Nos.51872246 and 52061135102)for financial support.
文摘In this work,novel carbon nanotube(CNT)/CoSi/SiOC nanocomposite ceramics with in-situ formed multi-walled CNTs and core-shell structured CoSi@C nanoparticles were successfully prepared via a single-source-precursor derived ceramic approach.Ppolymericprecursor characterization as well as phase evolution,microstructure,and electromagnetic wave(EMW)absorption properties of the ceramics were investigated in detail.The results show that the in-situ formed CNTs and magnetic CoSi@C nanoparticles provide a synergistic effect on both dielectric loss(tand:)and magnetic loss,leading to outstanding EMW absorption properties of the ceramics annealed at only 1100 C.(i)For the Co feeding of 6.25 wt%,the minimum reflection loss(RLmin)is-53.1 dB,and the effective absorption bandwidth(EAB)is 4.96 GHz(7.12-12.08 GHz)with a ceramic-paraffin hybrid sample thickness of 3.10 mm,achieving full X-band coverage;(i)for the Co feeding of 9.09 wt%,the RLmin value of-66.4 dB and the EAB value of 3.04 GHz(8.40-11.44 GHz)were achieved with a thickness of only 2.27 mm.Therefore,the present CNT/CoSi/SiOC nanocomposite ceramics have potential applications for thin,lightweight,and efficient EMW absorption in harsh environments.
基金The authors appreciate the financial support from the National Natural Science Foundation of China(No.U1904180)Key Scientific Research Projects of High Education Institutions of Henan province(No.19A430025).
文摘Pressure measurement with excellent stability and long time durability is highly desired,especially at high temperature and harsh environments.A polymer-derived silicoboron carbonitride(SiBCN)ceramic pressure sensor with excellent stability,accuracy,and repeatability is designed based on the giant piezoresistivity of SiBCN ceramics.The SiBCN ceramic sensor was packaged in a stainless steel case and tested using half Wheatstone bridge with the uniaxial pressure up to 10 MPa.The SiBCN ceramic showed a remarkable piezoresistive effect with the gauge factor(K)as high as 5500.The output voltage of packed SiBCN ceramic sensor changes monotonically and smoothly versus external pressure.The as received SiBCN pressure sensor possesses features of short response time,excellent repeatability,stability,sensitivity,and accuracy.Taking the excellent high temperature thermo-mechanical properties of polymer-derived SiBCN ceramics(e.g.,high temperature stability,oxidation/corrosion resistance)into account,SiBCN ceramic sensor has significant potential for pressure measurement at high temperature and harsh environments.
基金supported by the National Natural Science Foundation of China(Grant Nos.51632007,51872229,and 52072304)National Science and Technology Major Project(Grant No.2017-VI-0007-0077).
文摘The microstructure of polymer-derived ceramics(PDCs)was closely related to processing.This study demonstrated that SiCN matrix prepared by polymer infiltration and pyrolysis(PIP)at 900℃ inside a Si_(3)N_(4) whisker(Si_(3)N_(4w))preform with submicro-sized pores differed from its powder-consolidated analogue in both the content and structure of free carbon.Chemical analysis showed that PIP process had a higher free carbon yield.Raman spectroscopy and transmission electron microscopy(TEM)observation discovered a higher graphitization degree of free carbon and the existence of nanocrystalline graphite in SiCN matrix.Dielectric properties of Si_(3)N_(4w)/SiCN composites were greatly enhanced when volume fraction of SiCN matrix reached 24.5%due to dielectric percolation caused by highly-lossy free carbon.Reconsolidation of hydrocarbon released during pyrolysis by gas-state carbonization in Si_(3)N_(4) whisker preform was supposed to account for the high yield and graphitization degree of free carbon in PIP process.
基金Qingbo Wen thanks the National Natural Science Foundation of China(No.52102085)the National Science Fund for Excellent Young Scholars(Overseas)+1 种基金State Key Laboratory of Powder Metallurgy,Central South University(No.621022222)for financial supportXiang Xiong thanks the National Natural Science Foundation of China(No.52072410)for financial support.
文摘Copper(Cu)-containing single-source precursors(SSPs)for the preparation of SiCuCN-based ceramic nanocomposites were successfully synthesized for the first time using polysilazane(PSZ),copper(II)acetate monohydrate(CuAc),and 2-aminoethanol via nucleophilic substitution reactions at silicon(Si)centers of PSZ.The synthesis process,polymer-to-ceramic transformation,and high-temperature microstructural evolution of the prepared ceramics were characterized.Dielectric properties and electromagnetic wave(EMW)absorbing performance of the ceramics were investigated as well.The results show that the polymer-to-ceramic transformation finishes at ca.900 ℃,and Cu nanoparticles are homogeneously distributed in a SiCN matrix,forming a SiCN/Cu nanocomposite.After annealing at 1200 ℃,the Cu nanoparticles completely transform into copper silicide(CusSi).Interestingly,the thermal stability of the Cu nanoparticles can be strongly improved by increasing the free carbon content,so that a part of metallic Cu nanoparticles can be detected in the ceramics annealed even at 1300 ℃,forming a SiCN/Cu/Cu_(3)Si/C nanocomposite.Compared with SiCN,the SiCuCN-based nanocomposites exhibit strongly enhanced dielectric properties,which results in outstanding EMW absorbing performance.The minimum reflection coefficient(RC_(min))of the SiCN/Cu/Cu_(3)Si/C nanocomposites annealed at 1300 ℃ achieves-59.85 dB with a sample thickness of 1.55 mm,and the effective absorption bandwidth(EAB)broadens to 5.55 GHz at 1.45 mm.The enhanced EMW absorbing performance can be attributed to an in situ formed unique network,which was constructed with Cu and Cu_(3)Si nanoparticles connected by ring-like carbon ribbons within the SiCN matrix.
基金The authors would like to acknowledge Merck KGaA for the financial support of this research project.Wei Li acknowledges financial support from China Scholarship Council(No.201907040060)during his research at TU Darmstadt.Zhenghao Wu acknowledges the funding of Deutsche Forschungsgemeinschaft via the SFB-TRR 146“Multiscale Simulation Methods for Soft Matter Systems”,Project A8.
文摘SiBN ceramics are widely considered to be the most promising material for microwavetransparent applications in harsh environments owing to its excellent thermal stability and low dielectric constant.This work focuses on the synthesis and ceramization of single-source precursors for the preparation of SiBN ceramics as well as the investigation of the corresponding microstructural evolution at high temperatures including molecular dynamic simulations.Carbon-and chlorine-free perhydropolysilazanes were reacted with borane dimethyl sulfide complex at different molar ratios to synthesize single-source precursors,which were subsequently pyrolyzed and annealed under N2 atmosphere(without ammonolysis)to prepare SiBN ceramics at 1100,1200,and 1300℃with high ceramic yield in contrast to previously widely-used ammonolysis synthesis process.The obtained amorphous SiBN ceramics were shown to have remarkably improved thermal stability and oxidation resistance compared to amorphous silicon nitride.Particularly,the experimental results have been combined with molecular dynamics simulation to further study the amorphous structure of SiBN and the atomic-scale diffusion behavior of Si,B,and N at 1300℃.Incorporation of boron into the Si–N network is found to suppress the crystallization of the formed amorphous silicon nitride and hence improves its thermal stability in N2 atmosphere.