Numerical modeling of SiC by low-pressure chemical vapor deposition from methyltrichlorosilane

The development of functional relationships between the observed deposition rate and the experimental conditions is an important step toward understanding and optimizing low-pressure chemical vapor deposition(LPCVD)or low-pressure chemical vapor infiltration(LPCVI).In the field of ceramic matrix composites(CMCs),methyltrichlorosilane(CH3 SiCl3,MTS)is the most widely used source gas system for SiC,because stoichiometric SiC deposit can be facilitated at 900°C–1300°C.However,the reliability and accuracy of existing numerical models for these processing conditions are rarely reported.In this study,a comprehensive transport model was coupled with gas-phase and surface kinetics.The resulting gas-phase kinetics was confirmed via the measured concentration of gaseous species.The relationship between deposition rate and 24 gaseous species has been effectively evaluated by combining the special superiority of the novel extreme machine learning method and the conventional sticking coefficient method.Surface kinetics were then proposed and shown to reproduce the experimental results.The proposed simulation strategy can be used for different material systems.

Single-atom catalysts for CO oxidation,CO_(2) reduction,and O_(2) electrochemistry

CO_(x)(x=1,2)and O_(2) chemistry play key roles in tackling global severe environmental challenges and energy issues.To date,the efficient selective electrocatalytic transformations of COx-carbon chemicals,and O_(2)-hydrogenated products are still huge challenges.Single-atom catalysts(SACs)as atomic-scale novel catalysts in which only isolated metal atoms are dispersed on supports shed new insights in overcome these obstacles in CO_(x) and O_(2) chemistry,including CO oxidation,CO_(2) reduction reaction(CO_(2)RR),oxygen reduction reaction(ORR),and oxygen evolution reaction(OER).In this review,the unique features and advanced synthesis strategies of SACs from a viewpoint of fundamental synthesis design are first highlighted to guide future strategy design for controllable SAC synthesis.Then,the to-date reported CO_(2)RR,CO oxidation,OER,and ORR mechanism are included and summarized.More importantly,the design principles and design strategies of improving the intrinsic activity,selectivity,and stability are extensively discussed and the engineering strategy is classified as neighbor coordination engineering,metal-atom engineering,and substrate engineering.Via the comprehensive review and summary of state-of-the-art SACs,the synthesis–structure–property–mechanism–design principle relation can be revealed to shed lights into the structural construction of SACs.Finally,we present an outlook on current challenges and future directions for SACs in CO_(x) and O_(2) chemistry.

Atmosphere-free activation methodology for holey graphene/cellulose nanofiber-based film electrode with highly efficient capacitance performance

An efficient chamber-induced activation method was applied for the preparation of holey graphene/cellulose nanofiber-based film with high specific surface area(SSA)and multiple channels through the graphene nanosheets.With the cellulose nanofiber(CNF)simultaneously serving as“dispersing agent,”“spacer,”and“activating agent,”the graphene oxide(GO)nanosheets are perforated by the pyrolysis gas from CNF in the confined space inside the hybrid films,uniformly dispersed,and sandwiched between CNF networks with less agglomeration and restacking.Additionally,we have proved that H2O and H2 are primarily responsible for the activation and etching of GO/CNF film.As the CNF content increases,the mesoporosity of the activated reduced GO/CNF(A-RGO/CNF)film increases,and the graphene nanosheets show more nanopore perforations.Benefitting from the high SSA,high density,moderate mesoporosity,and abundant channels for ion diffusion through the graphene nanosheets,the A-RGO/CNF film exhibits the highest specific capacitance of 323(236)F g^(−1)(F cm^(−3))at 1Ag^(−1).For the A-RGO5/CNF5 film containing half CNF and half GO,an excellent comprehensive electrochemical performance including superior rate performance(208(160)F g^(−1)(F cm^(−3))at 60Ag^(−1))is exhibited.Moreover,the A-RGO5/CNF5 electrode in an all-solid-state flexible symmetric supercapacitor delivers a high specific capacitance of 250(193)F g^(−1)(F cm^(−3))at 1Ag^(−1).This study provides a novel idea for the preparation of holey graphene-based film for supercapacitor electrodes.The strategy of simultaneously employing CNF as“dispersing agent,”“spacer,”and“activating agent”also offers a new vision for the assembly of homogeneous nanohybrid material and the utilization of pyrolysis gas.

Evolution of microstructure and electromagnetic interference shielding performance during the ZrC precursor thermal decomposition process

A polymer-derived ZrC ceramic with excellent electromagnetic interference(EMI)shielding performance was developed to meet ultra-high temperature requirements.The thermal decomposition process of ZrC organic precursor was studied to reveal the evolution of phase composition,microstructure,and EMI shielding performance.Furthermore,the carbothermal reduction reaction occurred at 1300℃,and the transition from ZrO_(2) to ZrC was completed at 1700℃.With the increase in the annealing temperature,the tetragonal zirconia gradually transformed into monoclinic zirconia,and the transition was completed at the annealing temperature of 1500℃ due to the consumption of a large amount of the carbon phase.The average total shielding effectiveness values were 11.63,22.67,22.91,22.81,and 34.73 dB when the polymerderived ZrC was annealed at 900,1100,1300,1500,and 1700℃,respectively.During the thermal decomposition process,the graphitization degree and phase distribution of free carbon played a dominant role in the shielding performance.The typical core–shell structure composed of carbon and ZrC can be formed at the annealing temperature of 1700℃,which results in excellent shielding performance.

C/SiC Composites with a Self-healing SiBC Matrix Fabricated by Liquid Silicon Infiltration

Most researched continuous carbon fiber reinforced silicon carbide matrix composites(C/Si C)composites have porous matrix,which are fabricated by chemical vapor infiltration(CVI)or polymer infiltration and pyrolysis(PIP).The porous C/Si C composites exhibit higher fracture toughness,

Electromagnetic Wave Absorption Property of SiC NWs/GA-PDMS Composites

Ultralight graphene foam has triggered a new wave of discoveries.It is expected to be the most promising candidate for lightweight high performance microwave absorption(MA).Aligned-structured Si C nanowires(NWs)/graphene aerogel(GA)polydimethylsilox-ane(PDMS)composites are fabricated through a

Strengthened and toughened SiHfBCN-based hightemperature resistant adhesive with SiC NWs

To further improve the performance of binders,a SiHfBCN-based high-temperature resistant adhesive was successfully synthesized by Polymer-Derived Ceramics(PDC)route using TiB2,Polysiloxane(PSO)and short SiC nanowires as fillers.The effect of short SiC nanowires on the adhesive strength at room temperature and high temperature,as well as the reinforcing mechanism was studied.Compared with the adhesive without SiC nanowires,after curing(at 170℃)and pyrolysis(at 1000℃)in air,the appropriate adding of SiC nanowires upgrades the room temperature and high temperature(at 1000℃ in air)adhesive strength to(12.50±0.67)MPa(up by about 32%)and(13.11±0.79)MPa(up by about 106%),respectively.Attractively,under the synergistic impact of the nanowire bridging,nanowire breaking,nanowire drawing and crack deflection,the optimized adhesive exhibits multi-stage fracture,causing the increscent fracture displacement.

Preparation and properties of Ti_(3)SiC(2) -based corrosion mitigation coatings for SiC_(f) /SiC PWR accident tolerant fuel cladding

To enhance the resistance of SiC_(f)/SiC to hydrothermal corrosion in the pressurized water reactor(PWR)environment,structurally tunable Ti_(3)SiC(2)-based corrosion mitigation coatings for SiC_(f)/SiC were prepared using molten salt synthesis.The influence of various process parameters,such as Si/Ti molar ratio in raw materials,annealing time,and annealing temperature,on the phase composition and the structure of the coatings was explored.Through the process control,the fabricated coatings can be either Ti_(3)SiC(2) monolithic structure or TiC/Ti_(3)SiC(2) and TiC/Ti_(3)SiC(2)/Ti_(5)Si_(3)C_(x) multilayered structures.The coatings demonstrate strong bonding to the substrate due to in-situ reaction,exhibiting tensile and shear strength of at least 26.9 and 30.8 MPa,respectively.Incorporating TiC as a transition layer further enhances the tensile and shear strength to 41.3 and 51.4 MPa,respectively.Monolithic Ti_(3)SiC(2) coatings enhance the thermal conductivity of SiC_(f)/SiC by 10%–12%.Notably,Ti_(3)SiC(2) coatings effectively protect SiC_(f)/SiC from hydrothermal corrosion,demonstrating an 83%strength retention rate compared to 71%in the control group after corrosion.However,the Ti5Si3Cx layer exhibits unsatisfactory corrosion mitigation.The Ti_(3)SiC(2) monolithic coating has higher thermal conductivity,TiC/Ti_(3)SiC(2) multi-layered coating has higher bonding strength,and both have desirable resistance to the hydrothermal corrosion.

Application and structure of carbon nanotube and graphene-based flexible electrode materials and assembly modes of flexible lithium-ion batteries toward different functions

In recent years,the rapid development of portable/wearable electronics has created an urgent need for the development of flexible energy storage devices.Flexible lithium-ion batteries(FLIBs)have emerged as the most attractive and versatile flexible electronic storage devices available.Carbon nanotubes(CNTs)are hollow-structured tubular nanomaterials with high electrical conductivity,large specific surface area,and excellent mechanical properties.Graphene(G)is to some extent comparable to CNTs,because both have unlimited value in flexible electrodes.Herein,a systematic summary of the application of CNT and G in FLIBs electrodes is presented,including different functional applications and services at different temperatures.Furthermore,the effects of electrode structures,including powder,wire-shaped,and film-shaped structures,on electrochemical properties is highlighted.The assembly structures of the FLIBs consisting of CNT and G-based flexible electrodes to realize different functions,including bendability,stretchability,foldability,self-healing,and self-detecting,are systematically reviewed.The current challenges and development prospects of flexible CNT and G-based flexible electrodes and corresponding FLIBs are discussed.

Enhanced thermal conductivity and mechanical properties of 2D C_(f)/SiC composites modified by in-situ grown carbon nanotubes

In this work,the effects of carbon nanotubes(CNTs)on the microstructure evolution,thermal conductivity,and mechanical properties of C_(f)/SiC composites during chemical vapor infiltration(CVI)densification were investigated in detail.Compared with composites without CNTs,the thermal conductivity,flexural strength,flexural modulus,fracture toughness,interfacial shear strength,and proportional limit stress of specimens with CNTs of 4.94 wt%were improved by 117%,21.8%,67.4%,10.3%,36.4%,and 71.1%,respectively.This improvement was attributed to the role of CNTs in the division of inter-layer pores,which provided abundant vapor growth sites for the ceramic matrix and promoted densification of the whole composite.In addition,the high thermal conductivity network formed by the overlap of CNTs and the rivet strengthening effect of CNTs were beneficial for synergistic improvement of thermal conductivity and mechanical properties of the composites.Therefore,this study has practical significance for the development of thermal protection composite components with enhanced thermal conductivity and mechanical characteristics.

Mechanical and dielectric properties of porous and wave-transparent Si3N4–Si3N4 composite ceramics fabricated by 3D printing combined with chemical vapor infiltration

Porous Si3N4–Si3N4 composite ceramics were fabricated by 3D printing combined with low-pressure chemical vapor infiltration(CVI).This technique could effectively improve the designability of porous Si3N4 ceramics and optimize the mechanical and dielectric properties.The effects of process parameters including the deposition time and heat treatment on the microstructure and properties of porous Si3N4–Si3N4 composite ceramics were studied.The study highlights following:When CVI processing time was increased from 0 to 12 h,the porosity decreased from68.65%to 26.07%and the density increased from 0.99 to 2.02 g/cm3.At the same time,the dielectric constant gradually increased from 1.72 to 3.60;however,the dielectric loss always remained less than0.01,indicating the excellent electromagnetic(EM)wave-transparent performance of porous Si3N4–Si3N4 composite ceramics.The maximum flexural strength of 47±2 MPa was achieved when the deposition time attained 6 h.After heat treatment,the porosity increased from 26.07%to 36.02%and the dielectric constant got a slight increase from 3.60 to 3.70 with the dielectric loss still maintaining lower than 0.01.It has been demonstrated that the porous Si3N4–Si3N4 composite ceramics are a promising structural and EM wave-transparent material suitable for high temperature service.

Long-term ceramic matrix composite for aeroengine

Three strategies were proposed to prolong the service life of continuous fiber-reinforced silicon carbide ceramic matrix composite(CMC-SiC),which served as thermal-structure components of aeroengine at thermo-mechanical-oxygenic coupling environment.As for some thermal-structure components with low working stress,improving the degree of densification was crucial to prolong the service life,and the related process approaches were recited.If the thermal-structure components worked under moderate stress,the matrix cracking stress(σ^(mc))should be improved as far as possible.The fiber preform architecture,interface shear strength,residual thermal stress,and matrix strengthening were associated withσ_(mc)in this review.Introducing self-healing components was quite significant with the appearance of matrix microcracks when CMC-SiC worked at more severe environment for hundreds of hours.The damage can be sealed by glass phase originating from the reaction between self-healing components and oxygen.The effective self-healing temperature range of different self-healing components was first summarized and distinguished.The structure,composition,and preparation process of CMC-SiC should be systematically designed and optimized to achieve long duration target.

Enhanced mechanical property and tunable dielectric property of SiC_(f)/SiC-SiBCN composites by CVI combined with PIP

The SiBCN matrix via chemical vapor infiltration(CVI)or/and polymer infiltration pyrolysis(PIP)technologies was orderly introduced to SiC_(f)/SiC composites to optimize the mechanical property and electromagnetic(EM)shielding effectiveness simultaneously.The BN interface with the thickness of 350 nm was designed to obtain a little stronger interface bonding.The flexural strength of SiC_(f)/SiC-SiBCN composites reached 545.45±29.59 MPa thanks to the crack deflection between the CVI SiC and CVI SiBCN,as well as CVI SiBCN and PIP SiBCN matrix because of the modulus difference between them.The fracture toughness(KiC)with the value of 16.02±0.94 MPa·m^(1/2) was obtained owing to the extension of crack propagation path.The adverse effect of stronger interface bonding was eliminated by the design of matrix microstructure for SiC_(f)/SiC-SiBCN composites.The thermal conductivity in the thickness direction was 7.64 W·(m·K)^(-1) at 1200℃and the electric resistivity decreased to 1.53×10^(3) Ω·m.The tunable dielectric property was obtained with the coordination of wave-absorption CVI SiBCN matrix and impedance matching PIP SiBCN matrix,and the total shielding effectiveness(SE_(T))attained 30.01 dB.It indicates that the SiC_(f)/SiC-SiBCN composites have great potential to be applied as structural and functional materials.

Dielectric and Electromagnetic Wave Absorbing Properties of Two Types of SiC Fibres with Different Compositions

The dielectric and electromagnetic properties of two types of SiC fibres with different compositions were investigated. The permittivity and electromagnetic shielding effectiveness （SE） of SiC fibre bundles were measured in 8.2-12.4 GHz by waveguide method. The reflection coefficient （RC） of unidirectional SiC fibre laminates was determined in 8-18 GHz using naval research laboratory （NRL）-arc method. Results showed that the electromagnetic wave （EMW） absorbing properties of SiC fibres were correlated with their composition, microstructure and instinct performance of electrical resistance. SiC fibres with higher content and greater size of nano-scale H-SiC showed higher permittivity, conductivity, SE and lower RC, which resulted in their better EMW absorbing ability, Le. the lower reflection to EMW.

3D printing“wire-on-sphere”hierarchical SiC nanowires/SiC whiskers foam for efficient high-temperature electromagnetic wave absorption

Electromagnetic wave absorption(EWA)materials for use in extreme environments are of great interest.Herein,SiC nanowires/SiC whiskers(SiC_(nw)/SiC_(w))foam with unique“wire-on-sphere”hierarchical structure was developed for efficient high-temperature EWA.SiC_(w)were assembled to porous SiC_(w)spheres via spray drying and then SiC_(w)spheres were 3D printed to SiC_(w)foam.The catalyst-free precursor infiltration pyrolysis process was first developed to ensure that SiCnwcan intentionally grow in situ on the surface of SiC_(w)spheres,thereby achieving“wire-on-sphere”hierarchical structure foam.At room-temperature,the maximum electromagnetic wave effective absorption bandwidth(EAB_(max))and minimum electromagnetic wave reflection coefficient(RC_(min))of SiC_(nw)/SiC_(w)foam can reach 4 GHz and-57 dB,respectively.At600℃,the EAB_(max)and RC_(min) were 3 GHz and-15 dB,respectively.Furthermore,even oxidized at 1000-1500℃,SiC_(nw)/SiC_(w)foam can still retain EAB_(max)ranging from 2.7 to 3.9 GHz and RC_(min)ranging from-16 dB to-64 dB,because the formation of SiO_(2)layer with appropriate thickness can boost interfacial polarization and regulate impedance matching.The SiC_(nw)/SiC_(w)foam also shows the flexural strength as high as 17.05 MPa.All results demonstrate that the SiC nw/SiC_(w)foam is a promising EWA material for applications of harsh environments.And the material-independent“wire-on-sphere”hierarchical structure and its novel preparation process should find the widespread use in the design and fabrication of high-efficiency EWA micro-nano materials.

Failure behavior of interfacial domain in SiC-matrix based composites

In this work,the microstructure,failure behavior and interfacial properties with respective to the interfacial domain in SiCf/BN/SiC and C_(f)/PyC/SiC composites were studied via the fiber push-in test.The differences in the mechanical response of the interfacial domain were observed.During the fiber push-in test for SiCf/BN/SiC,the interface debonding accompanied with interphase fracture occurred,resulting in an obvious sign of the onset of debonding on loading-displacement(P-u)curves.While the good continuity of P-u curves can be observed for Cf/PyC/SiC,which is due to that the failure is in the form of interface debonding along with interphase lateral slipping caused by the extension of buckled carbon fiber,without any interphase fracture.The interfacial properties calculated from the fiber push-in test show that Cf/PyC/SiC possesses a weaker interfacial domain compared with SiC_(f)/BN/SiC.The interfacial shear stress of SiCf/BN/SiC and C_(f)/PyC/SiC composites amounts 94.2 and 48.1 MPa,respectively.

Proportional Limit Stress and Residual Thermal Stress of 3D SiC/SiC Composite

Proportional limit stress （PLS） and residual thermal stresses （RTS） of 3D SiC/SiC composite were investigated. PLS was obtained by four different methods from the monotonic stress-strain response curve to get a convincing value. RTS in the SiC matrix was quantified by solving the geometric intersection point of the regression lines of hysteresis loops from the periodical loading-unloading-reloading cycle test curve. Classical ACK model and analytical formulas were used to analytically calculate the PLS and RTS of 3D SiC/ SiC composite. Good agreement between the experimental results and the analytical calculation was observed. And relationship between the PLS and the RTS of 3D SiC/SiC was discussed.

Controllable synthesis of mesoporous carbon hollow microsphere twined by CNT for enhanced microwave absorption performance

The low dielectric loss of mesoporous carbon hollow microsphere(PCHM)requires high filler loading(higher than 20 wt%)when it is used as microwave absorbers.In order to decrease the filler loading of PCHM,a new strategy for synergistic increase of polarization and conductive loss was developed by twining PCHM with carbon nanotube(CNT)according to theoretic calculation.By the optimization of CNT content,the minimum reflection coefficient was -34.6 dB with a filler loading of only 10 wt%,which was much lower than -2.1 dB of PCHM.In addition,the effective absorption bandwidth was 3.6 GHz at X band with a thickness of 2.8 mm.The enhanced microwave absorption performance can be ascribed to the unique combination of hollow PCHM and one-dimensional CNT with higher graphitization degree,leading to increase of conductivity and heterogeneous interfaces.As a result,the conductive loss increased from 0.12 to 2.27 and polarization loss increased from 0.15 to 0.67,achieving the balance between attenuation ability and impedance match.

Oxidation behaviors of carbon fiber reinforced multilayer SiC–Si_(3)N_(4) matrix composites

Oxidation behaviors of carbon fiber reinforced SiC matrix composites(C/SiC)are one of the most noteworthy properties.For C/SiC,the oxidation behavior was controlled by matrix microcracks caused by the mismatch of coefficients of thermal expansion(CTEs)and elastic modulus between carbon fiber and SiC matrix.In order to improve the oxidation resistance,multilayer SiC–Si_(3)N_(4) matrices were fabricated by chemical vapor infiltration(CVI)to alleviate the above two kinds of mismatch and change the local stress distribution.For the oxidation of C/SiC with multilayer matrices,matrix microcracks would be deflected at the transition layer between different layers of multilayer SiC–Si_(3)N_(4) matrix to lengthen the oxygen diffusion channels,thereby improving the oxidation resistance of C/SiC,especially at 800 and 1000℃.The strength retention ratio was increased from 61.9%(C/SiC–SiC/SiC)to 75.7%(C/SiC–Si_(3)N_(4)/SiC/SiC)and 67.8%(C/SiC–SiC/Si_(3)N_(4)/SiC)after oxidation at 800℃for 10 h.