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1.
《Ceramics International》2019,45(10):12764-12772
On account of the excellent oxidation resistance of precursor-derived SiBCN ceramics, carbon-fiber-reinforced SiBCN (C/SiBCN) composites are increasingly being used in high-temperature aerospace applications. However, very few studies have investigated the high-temperature oxidation behavior of C/SiBCN composites for their application to high-heat engines. Herein, C/SiBCN composites prepared by precursor infiltration and pyrolysis were tested in static air up to an oxidation temperature of 1700 °C. The composites’ structural evolution after oxidation and their potential oxidation mechanisms were investigated in detail. The carbon fibers were preferentially oxidized at temperatures in the range of 1200–1500 °C and completely oxidized at 1500 °C. The oxidation of the fibers at 1500 °C resulted in the formation of abundant oxygen channels and consequently a high oxide scale growth rate of 5–7 μm2 h−1 and a large mass loss of 54.6 wt%. At elevated temperatures in the range of 1600–1700 °C, a dense SiO2 oxide layer was formed by the sacrificial oxidation of the SiBCN matrix. The oxidation rate of the composites was therefore controlled by the diffusion rate of oxygen through the protective SiO2 oxide layer and the weight loss of the composites decreased to 28.6% after oxidation at 1600 °C for 60 min. The structural integrity of the composites was maintained after long-term oxidation at 1600 °C.  相似文献   

2.
The high hardness, exceptional high temperature stability, and oxidation resistance of bulk Si–B–C–N ceramics have led to the expectation that these materials will be good candidates for superior coating materials in high-temperature applications. In this study, SiBCN films were prepared using ion beam assisted sputter (IBAS) deposition, and the mechanical properties and thermal stabilities of the films at 600, 700, and 800 °C in air were investigated. In particular, the effects of the ion beam assist on the properties of the SiBCN films were examined. The SiBCN films were deposited on Si plates by sputtering a target composed of Si + BN + C using a 2-keV Ar+ ion beam. A low-energy N2+ and Ar+ mixed ion beam irradiated the samples during the sputter deposition. The Si content in the SiBCN films was controlled by changing the Si/(BN + C) ratio of the target. BCN films were also deposited for comparison. The composition and chemical bonding structure of the prepared films were investigated by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. We found that c-BN bonds were formed in the ion-assisted BCN film. The oxide layer thickness on the SiBCN films after thermal annealing decreased due to the IBAS deposition and an increase in the Si content. Ion-assisted SiBCN films annealed at 800 °C showed the highest hardness of 20 GPa.  相似文献   

3.
Polyboronsilazane (PBSZ) precursors for SiBCN ceramics were prepared by using 9-borabicyclo-[1,3,3] nonane (9-BBN) and copolysilazanes (CPSZ) as starting materials, involving the hydroboration reaction between vinyl groups of PSZ and BH groups of 9-BBN under mild conditions. The as-synthesized PBSZ was obtained as a soluble liquid, which was characterized by FT IR and NMR. The polymer-to-ceramic conversion of PBSZ at a ceramic yield of 62.2–79.9% was investigated by means of FT IR and TGA. The crystallization behavior and microstructures of PBSZ-derived SiBCN ceramics were studied by XRD, SEM and HRTEM. The SiBCN ceramic began to crystallize at 1600 °C. Further heating at 1800 °C induced partial crystallization to give mixed XRD patterns for SiC, Si3N4, and BN(C). It is observed that the introduction of boron improves the thermal stability of SiBCN ceramics, especially under high temperatures of 1600–1800 °C. In addition, the introduction of boron significantly improves the ceramic density while inhibits the SiC crystallization.  相似文献   

4.
《Ceramics International》2023,49(16):26642-26653
The electromagnetic wave (EMW) absorbing materials are widely applied to attenuate the useless and harmful EMW generated from wireless communication and 5G networks, which could protect the human health and electronic device safety. In this study, La-doped SiBCN ceramics with broadband EMW absorption capability were prepared via generating abundance of heterointerfaces, as graphene were in-situ grown by La2O3 catalyzing. The graphene in-situ formed in the ceramics can be attributed to the La atom decreasing the potential energy of the free carbon ring nucleation from −760.9 Ha to −8984.3 Ha. Consequently, the electrical conductivity of the SiBCN ceramics improved from 12.360 S/m to 18.025 S/m, the minimum reflection loss (RLmin) obtained was −26.48 dB at 7.2 GHz and the effective absorption bandwidth (EAB) was 6.32 GHz (11.68–18.00 GHz) at a thickness of 1.7 mm. At 700 °C, the RLmin and EAB values reached −43.18 dB and 4.2 GHz, respectively. The enhanced EMW absorbing capability can be attributed to the rationally tailor the heterointerfaces to improve the polarization loss and conduction loss of the SiBCN ceramics. The interfaces between graphene and amorphous phases generate built-in electric fields and space chare regions to strengthen the interface polarization, while the electrons migrating rapidly in the graphene and other crystals improved the electrical conductivity. The positive effect of heterointerfaces regulation of graphene in-situ growth improved the dielectric loss capacity of the SiBCN ceramics; therefore, this study provides a feasible method to enhance the EMW absorption capability of polymer-derived ceramics.  相似文献   

5.
Quaternary siliconboron carbonitride (SiBCN) ceramics show excellent high-temperature stability and oxidation resistance, indicating great potential as high-temperature electromagnetic (EM) wave absorbing materials. In this contribution, an efficient and facile method was developed to prepare bulk iron-containing SiBCN (Fe–SiBCN) ceramics with remarkable EM wave absorption at high temperature by pyrolyzing boron and iron containing precursors (PSZV-B–Fe). The introduction of boron and iron not only improves the high-temperature stability but also influences the complex permittivity and EM wave absorption. The minimum reflection coefficient (RCmin) is −61.05 dB, and the effective bandwidth absorption (EAB) is 3.35 GHz (9.05–12.4 GHz). The RCmin will be decreased to −52.3 dB at 600°C as well as the EAB covers more than 67% of the X band (2.8 GHz). The high-temperature stable Fe–SiBCN ceramics with adjustable dielectric properties can be utilized as high-performance EM wave-absorbing materials in high-temperature and harsh environments.  相似文献   

6.
Polymer derived SiBCN ceramics (PDCs-SiBCN) were prepared from polyborosilazane and then annealed at 1200–1800 °C in N2. Effects of annealing temperature on the microstructure, phase composition, dielectric and wave-absorbing properties of ceramics were investigated. Results showed that nano-sized SiC grains were formed in amorphous SiBCN after annealing and the content and crystallization degree of SiC gradually intensified with annealing temperature increasing. The permittivity, dielectric loss and electrical conductivity of PDCs-SiBCN gradually increased as the temperature rose due to the formation of conductivity network of SiC grains and the increase of nano-grain boundary. The increased content of SiC (as the dipole) and interface between SiC nano-grains and amorphous SiBCN phase led to a higher polarization ability and higher dielectric loss. The RC gradually decreased with the annealing temperature increasing, demonstrating the annealed ceramics had the superior wave-absorbing ability and high annealing temperature was conducive to the improvement of wave-absorbing property.  相似文献   

7.
《Ceramics International》2020,46(11):18940-18947
In this study, NdAlO3 with perovskite structure was synthesized by the stearic acid method at relatively low temperature. The structural characteristics of the as-synthesized product were identified by TG–DSC, XRD, FT–IR, SEM, and TEM techniques. Using the powders as starting materials, NdAlO3 bulk microwave ceramics were prepared, and the corresponding densification process, microstructural and dielectric properties were studied. The XRD and FI–IR results confirmed that single phase NdAlO3 could be prepared at low temperature by the stearic acid method. A unique two-dimensional platelike morphology with an unevenly dispersed bubble shape structure was observed in the calcined powder. However, the TEM result revealed that the powder calcined at 800 °C had a good dispersity accompanied with narrow particle size distribution within a range of 20–35 nm. The average particle size of 27.3 nm was in accordance with that calculated from the XRD data. Using the powder calcined at 800 °C as raw materials, the as-obtained NdAlO3 ceramics sintered at 1500 °C for 4 h possessed the highest density and favorable combined microwave dielectric properties (i.e., εr = 23.02, Q × f = 65320 GHz, and τf = −32.4 ppm/°C). The present work developed a fast, energy-efficient approach to synthesize NdAlO3 powder used as promising raw materials of microwave dielectric ceramics.  相似文献   

8.
Tris(dichloromethylsilylethyl)borane is a compound containing a B–C bond and Cl and H elements. Herein, we propose a novel method to synthesize polyborosilazanes using tris(dichloromethylsilylethyl)borane and boron trichlorosilane as boron sources and hexamethyldisilazane as a nitrogen source. The microstructure and chemical composition of the as-synthesized polyborosilazanes and as-annealed SiBCN ceramics were investigated using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, Raman spectroscopy, scanning electron microscope, and transmission electron microscope methods. The organic precursors were converted entirely into inorganic ceramics at 800 °C, and the ceramic yield of the polyborosilazanes was 88% at 1000 °C. SiBCN ceramics with irregular shapes contained chemical bonds of B–N, Si–N, and Si–C at 1500 °C and retained an amorphous structure below 1600 °C. After the first cycle, the fabricated SiBCN ceramic anodes exhibited a reversible capacity of 261.3 mA h/g, which was 2.6 times that reported in the literature (101 mA h/g). The discharge capacity decreased to 157.6 mA h/g after 30 cycles. The satisfactory electrochemical performance of the resulting SiBCN ceramic anodes can be attributed to the formation of conductive carbon species favoring the transport properties of lithium ion.  相似文献   

9.
C/SiBCN composites with a density of 1.64 g/cm3 were prepared via precursor infiltration and pyrolysis and the bending strength and modulus at room temperature was 305 MPa and 53.5 GPa. The precursor derived SiBCN ceramics showed good thermal stability at 1600 °C and the SiC and Si3N4 crystals appeared above 1700 °C. The bending strength of the composites was 180 MPa after heat treatment at 1500 °C, and maintained at 40 MPa-50 MPa after heat treatment for 2 h at 1600 °C–1900 °C. In C/SiBCN composites, SiBCN matrix could retain amorphous up to 1500 °C and SiC grains appeared at 1600 °C but without Si3N4. The reason for no detection of Si3N4 was that the carbon fiber reacted with Si3N4 to form an interface layer (composed of SiC and unreacted C) and a polycrystalline transition layer (composed of B and C elements), leading to the degradation of the mechanical properties.  相似文献   

10.
《Ceramics International》2020,46(6):7001-7008
The SiBCN ceramic aerogel/graphene composites were synthesized by combining a simple sol-gel infiltration process with CO2 supercritical drying technology and polymer-derived ceramics route. In order to select the best preceramic sample for sintering, the micromorphology of PSNB aerogel/graphene composites fabricated with different graphene oxide solution concentrations were investigated. The microstructure evolution of the prepared SiBCN ceramic aerogel/graphene composites and phase composition were studied by SEM, TEM and XRD, the pore structure of the preceramic composites pyrolyzed at 1200 °C was tested by specific surface area and pore size analyzer. Furthermore, the compressive strain-stress curve and toughening mechanisms of composites were also investigated in detail. The results showed that all the preceramic composites and obtained ceramic aerogel composites possessed the mesoporous structure. The basic structure of SiBCN aerogel network changed from the initial spherical particles accumulation to the nanowires lapping with the sintering temperature increased from 800 °C to 1200 °C. After pyrolyzing at 1200 °C, the specific surface area and pore volume for the sample were 101.61 m2 g−1 and 1.43 cm3 g−1, respectively, and a small amount of β-SiC crystalline phases were formed in amorphous ceramic matrix and had an relatively uniform distribution. Moreover, the paepared ceramic aerogel composites possessed a certain degree of toughness, the toughening mechanisms of composite samples mainly included the crack deflection, graphene pull-out, graphene bridging and graphene crumpling.  相似文献   

11.
《Ceramics International》2020,46(6):7719-7732
In this account, RGO-SiCnw/SiBCN composite ceramics were fabricated using polymer derived ceramic (PDC) combined with chemical vapor infiltration (CVI) technology. Dielectric property of as-obtained RGO-SiCnw/SiBCN composite ceramics was significantly enhanced thanks to established conductive pathway through overlapped nanoscale SiCnw and micro-sized RGO. The minimum RC of composite ceramics with 0.5 wt% GO and 2.29 wt% SiCnw at thickness of 3.6 mm reached -42.02 dB with corresponding effective absorption bandwidth (EAB) of 4.2 GHz. As temperature rose from 25 to 400 °C, permittivity increased with enhanced charge carrier density and then it decreased due to oxidation process of RGO from 400 to 600 °C. The minimum reflection coefficient (RC) was recorded as -39.13 dB and EAB covered the entire X-band at 600 °C. EMW absorption ability was evaluated after high-temperature oxidation experiment under protective effect of wave-transparent Si3N4 coating. RGO-SiCnw/SiBCN composite ceramics maintained outstanding EMW absorption ability with minimum RC of -10.41 dB after oxidation at 900 °C, indicating RGO-SiCnw/SiBCN composite ceramics with excellent EMW absorption characteristic even at high temperatures and harsh environments.  相似文献   

12.
《Ceramics International》2015,41(7):8468-8474
This paper reports the dynamic compression behavior of ultrafine grained (Hf, Zr)B2–SiC composites, sintered using reactive spark plasma sintering at 1600 °C for 10 min. Dynamic strength of~2.3 GPa has been measured using Split Hopkinson Pressure Bar (SHPB) tests in a reproducible manner at strain rates of 800–1300 s−1. A comparison with competing boride based armor ceramics, in reference to the spectrum of properties evaluated, establishes the potential of (Hf, Zr)B2–SiC composites for armor applications.  相似文献   

13.
In this paper, Co2Si(Co)/SiCN composite ceramics were synthesized by simple precursor-derived ceramics method. The phase composition, morphology, and microwave absorption properties of Co2Si(Co)/SiCN composite ceramics at different pyrolysis temperatures (1000–1400°C) were studied. When pyrolysis temperature was 1300°C, carbon nanowires (CNWs), Co2Si, Si2N2O, SiC and Si3N4 were in situ generated and the best electromagnetic wave (EMW) absorption performance was obtained. The minimum reflection loss reached−50.04 dB at 4.81 mm, and the effective absorption bandwidth broadened to 3.48 GHz (14.52–18 GHz) at 1.31 mm. The excellent EMW absorption performance mainly comes from the coexistence of multiple loss mechanisms, including the magnetic loss of Co2Si, the conduction loss of CNWs, and the heterogeneous interfaces polarization between varieties of nanocrystals and amorphous ceramic matrix. By adjusting the sample thickness from 1 to 5 mm, the effective absorption of S1300 can cover the entire X and Ku bands, from 3.36 to 18 GHz. This study provides a simple way to synthesize high performance ceramic-based microwave absorbing materials.  相似文献   

14.
Terbium aluminum garnet (Tb3Al5O12, TAG) ceramics have become a promising magneto-optical material owing to the outstanding comprehensive performance, including the magneto-optical, thermal, and mechanical properties. Fine-grained TAG ceramics with high optical quality and mechanical properties have attracted much attention. In this study, TAG ceramics with fine grains and high optical quality are fabricated successfully by a two-step sintering method from co-precipitated nano-powders. After pre-sintered at 1525°C in vacuum and hot isostatic pressed at 1600°C, the in-line transmittance of TAG ceramics reaches 81.8% at 1064 nm, and the average grain size is 7.1 μm. The Verdet constant of TAG ceramics is −179.6 ± 4.8 rad T−1 m−1 at 633 nm and −52.1 ± 1.9 rad T−1 m−1 at 1064 nm, higher than that of commercial Tb3Ga5O12 crystals. The thermal conductivity of TAG ceramics is determined from 25 to 450°C, and the result is 5.12 W m−1 K−1 at 25°C and 3.61 W m−1 K−1 at 450°C. A comparison of mechanical properties between large- and fine-grained TAG ceramics fabricated under different conditions is conducted. The fine-grained TAG ceramics possess a bending strength of 226.3 ± 16.4 MPa, which is 9.7% higher than that of the large-grained ceramics. These results indicate that reducing the grain size on the premise of high optical quality helps improve the comprehensive performance of TAG ceramics.  相似文献   

15.
Fluorinated amorphous carbon (a–C:F) films have been deposited by electron cyclotron resonance chemical vapor deposition (ECR–CVD) at room temperature using C4F8 and CH4 as precursor gases. The chemical compositions and electrical properties of a–C:F films have been studied by X-ray photoelectron spectroscopy (XPS), capacitance–voltage (C–V) and current-voltage (IV) measurements. The results show that C–CFx and C–C species of a–C:F films increase and fluorine content decreases after annealing. The dielectric constant of the annealed a–C:F films increases as a result of enhancement of film density and reduction of electronic polarization. The densities of fixed charges and interface states decrease from 1.6 × 1010 cm 2 and (5–9) × 1011 eV 1 cm 2 to 3.2 × 109 cm 2 and (4–6) × 1011 eV 1 cm 2 respectively when a–C:F films are annealed at 300 °C. The magnitude of CV hysteresis decreases due to reduced dangling bonds at the a–C:F/Si interfaces after heat treatment. The conduction of a–C:F films shows ohmic behavior at lower electric fields and is explained by Poole–Frankel (PF) mechanism at higher electric fields. The PF current increases indicative of reduced trap energy when a–C:F films are subjected to higher annealing temperatures.  相似文献   

16.
Glass–ceramics based on the CaO–MgO–SiO2 system with limited amount of additives (B2O3, P2O5, Na2O and CaF2) were prepared. All the investigated compositions were melted at 1400 °C for 1 h and quenched in air or water to obtain transparent bulk or frit glass, respectively. Raman spectroscopy revealed that the main constituents of the glass network are the silicates Q1 and Q2 units. Scanning electron microscopy (SEM) analysis confirmed liquid–liquid phase separation and that the glasses are prone to surface crystallization. Glass–ceramics were produced via sintering and crystallization of glass-powder compacts made of milled glass-frit (mean particle size 11–15 μm). Densification started at 620–625 °C and was almost complete at 700 °C. Crystallization occurred at temperatures >700 °C. Highly dense and crystalline materials, predominantly composed of diopisde and wollastonite together with small amounts of akermanite and residual glassy phase, were obtained after heat treatment at 750 °C and 800 °C. The glass–ceramics prepared at 800 °C exhibited bending strength of 116–141 MPa, Vickers microhardness of 4.53–4.65 GPa and thermal expansion coefficient (100–500 °C) of 9.4–10.8 × 10−6 K−1.  相似文献   

17.
Polymer-derived ceramics (PDCs), such as SiOC, SiCN, SiBCN, and SiC are considered the best candidates for designing high-performance microwave absorber due to their controllable structure, homogeneous element composition at atom level, tunable electromagnetic and electrochemical properties. Herein, Fe ions doped silicon oxycarbide (Fe ions-SiOC) ceramics have been successfully fabricated via solvothermal method. The electromagnetic absorption performances of the nanocomposites prove to be controllable via tailoring Fe ion contents. The Fe ions effectively enhance both the interfacial polarization of amorphous SiOC, and the dielectric properties of the nanocomposites but barely effect magnetic properties of the nanocomposite. As for 0.16 mol/L-SiOC ceramics annealed at 1450°C, the effective absorption bandwidth as high as 2.00 GHz and reflection loss of −59.60 dB at 5.40 GHz with the thickness of 4.55 mm are obtained. Such work opens up a novel and simple route to scale up the PDC-based materials with broadband and excellent microwave absorbing performances.  相似文献   

18.
《Ceramics International》2021,47(21):30099-30105
The thermal behavior of pyrochlores composing of Bi1·5Mg0.75M1.5O6.75 (M = Nb, Ta) (sp. gr. Fd-3m:2) was studied using the high-temperature X-ray powder diffraction in a wide temperature range of 30–1200 °C. At a temperature above 1080 °C both compounds thermally dissociate forming one of the reaction products MgMO6 (M = Nb, Ta) whose reflexes are traced on X-ray diffraction patterns after cooling the sample down to room temperature. In the case of Bi1·5Mg0·75Nb1·5O6.75 orthoniobate α-BiNbO4 forms at about 800–1020 °C as admixture. The thermal expansion analysis of Bi1·5Mg0.75M1.5O6.75 (M = Nb, Ta) showed that the compounds studied belong to slightly or moderately expanding materials. Thermal expansion for both compounds is isotropic. With a rise in temperature the unit cell parameter a and the thermal expansion coefficient (TEC) are increased uniformly and slightly for M = Ta (Nb): from 10.52822 (10.55325) Å (30 °C) up to 10.59181 (10.62801) Å (1050 °C) and from 3.8 (30 °C) up to 7.4 (8.9) × 10−6 °С−1 at 800 °C respectively. The average TEC values in the range of 30–800 °C range are 5.6 (6.4) × 10−6 °C−1 for M = Ta (Nb) respectively. Bi1.5Mg0.75Nb1.5O6.75 is characterized with the highest thermal expansion that may be related to the longer bond-length of Nb(Bi)–O in the polyhedra.  相似文献   

19.
Composite ceramics made of two perovskite-type compounds, (La0.9Sr0.1)0.98Ga0.8Mg0.2O3−δ (LSGM) and La0.8Sr0.2Fe0.8Co0.2O3−δ (LSFC) mixed in the ratio 60:40 wt.%, possess relatively high oxygen permeability limited by both bulk ionic conduction and surface exchange at 700−950 °C. Sintering at elevated temperatures (1320–1410 °C) necessary to obtain dense materials leads to fast interdiffusion of the components, forming almost single perovskite phase ceramics with local inhomogeneities. This phase interaction decreases the oxygen ionic transport in the composites, where the level of ionic conductivity is intermediate between those of LSGM and LSFC. The scanning electron microscopy (SEM) suggests a presence of Ga-enriched domains, probably having a high ionic conductivity. The size and concentration of these domains can be increased by decreasing sintering temperature or using preliminary coarsened LSGM powders. The maximum oxygen permeability is thus observed for the composite prepared under minimum sintering conditions sufficient to obtain gas-tight ceramics, including the use of LSGM, preliminary passivated at 1150 °C, and sintered at 1320 °C. The activation energy values for total conductivity, which is predominantly p-type electronic and slightly decreases due to component interaction, vary in the narrow range from 24.0 to 26.2 kJ/mol at 25–575 °C. The average thermal expansion coefficients (TECs) of LSGM-LSFC composites, calculated from dilatometric data in air, are (12.4–13.5)×10−6 K−1 at 100–650 °C and (17.8–19.8)×10−6 K−1 at 650–1000 °C.  相似文献   

20.
《Ceramics International》2021,47(22):31130-31137
Partial/full replacement of traditional dense refractory aggregates (for furnace lining) with lightweight aggregates is considered to be an effective and promising strategy for energy saving and emission reduction. In this work, lightweight magnesia refractory ceramics with tailored closed porosity were prepared by one-step sintering at 1600 °C from high-purity magnesite added with silicon kerf waste in different ratios, with the emphasis on the evolution of their phase compositions, micromorphologies, and various properties. With the addition of additives, Mg2–xFexSiO4 solid solution was formed at the grain boundaries of the MgO matrix, and then the volumetric expansion effect (interfacial reaction) and activated sintering effect (vacancy defect) promote the decrease of apparent porosity and the increase of closed porosity, respectively. Consequently, MgO ceramics with apparent/closed porosity of 0.6%/6.5%, bulk density of 3.25 g cm−3, and lightweight index of 7.8% were successfully prepared, suitable for the working lining of metallurgical furnaces.  相似文献   

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