Effect of BN content on the structural,mechanical, and dielectric properties of PDCs-SiCN(BN) composite ceramics

Hexagonal boron nitride (h-BN) with low dielectric loss and high temperature resistance opens up new opportunities for the preparation of polymer-derived SiCN ceramics (PDCs-SiCN ceramics) with excellent mechanical and dielectric properties. BN-containing polymer-derived SiCN composite ceramics (PDCs-SiCN(BN) composite ceramics) with different BN content were prepared via a pyrolysis process of ball-milling-blended Polyvinylsilazane/boron nitride (PVSZ/BN) precursors. BN is stably embedded in the SiCN tissue and tightly bound with it. The appropriate content of BN greatly improves the mechanical properties of PDCs-SiCN ceramics, as BN reduces the number of pores and prevents crack expansion. Additionally, BN is also beneficial in lowering the dielectric loss of PDCs-SiCN ceramics because of the weakened polarization relaxation behavior. PDCs-SiCN (BN) composite ceramics have optimal mechanical and dielectric properties when the BN content is 1 wt%. The flexural strength, flexural modulus and compression strength of PDCs-SiCN(BN) composite ceramics with 1 wt% BN doping content were 189.37 MPa, 46.38 GPa, and 399.02 MPa, respectively. Its average dielectric loss (tanδ_ε) at 12.4-18 GHz is 0.0049.     

Hierarchical carbon nanowires network modified PDCs-SiCN with improved microwave absorption performance

In order to optimize the dielectric performance of polymer derived SiCN ceramics (PDCs-SiCN), carbon nanowires (CNW) were deposited in SiCN by catalytic chemical vapor deposition (CCVD). Microstructure evolutions, dielectric property and electromagnetic (EM) wave absorption capacity of CNW/SiCN were investigated. Results show that carbon nanowires had plentiful pits/defects on their roughened surface and formed hierarchical network in SiCN which benefited the impedance match and generated strong conductivity and polarization loss, enhancing the absorption ability of CNW/SiCN. When CNW accounted for 5.61 wt%, RC_min reached −51 dB with EAB of 3.0 GHz at 2.7 mm in thick, showing excellent microwave absorbing performance. The favorable microwave absorption ability could be ascribed to three aspects including enhanced conductivity loss derived from the excellent conductivity of CNW, polarization loss generated by defects, and multiple reflection loss enhanced by hierarchical network. By comparing the variation tendency between defect concentration and electrical conductivity in CNW/SiCN, it is rational to conclude that the conductivity loss dominated the dielectric loss while the polarization loss and repeated multi-reflection simultaneously worked. This work can be further extended to study regarding the effect of heat-treatment temperature since CNW have the potential to promote the crystallization process of amorphous PDCs thereby improving their dielectric properties.     

Dielectric and microwave absorption properties of polymer derived SiCN ceramics annealed in N2 atmosphere

Porous SiCN ceramics were successfully fabricated by pyrolysis of a kind of polysilazane. The effects of annealing temperature on the microstructure evolution, direct-current electrical conductivity, dielectric properties, and microwave absorption properties of SiCN in the frequency range 8.2–12.4 GHz (X-band) were investigated. With the increase of annealing temperature, SiC, Si₃N₄ and free carbon nanodomains are gradually formed in the SiCN. Both the SiC and free carbon nanodomains lead to the increases of the complex relative permittivity and loss tangent of SiCN. With the increase of the annealing temperature, the average real permittivity, imaginary permittivity and loss tangent increase from 4.4, 0.2 and 0.05 to 13.8, 6.3 and 0.46, respectively. The minimum reflection coefficient and the frequency bandwidth below −10 dB for SiCN annealed at 1500 °C are −53 dB and 3.02 GHz, indicating good microwave absorption properties.     

Microwave absorption performance of PDCs-SiCN(Fe) ceramics with negative imaginary permeability

PDCs-SiCN(Fe) ceramics were successfully fabricated with different content of ferric acetylacetonate (FA) by polymer-derived method. The effects of FA on the phase composition, microstructure, resistivity, dielectric properties, magnetic properties and microwave absorption properties of PDCs-SiCN(Fe) ceramics in the range of 2–18?GHz were investigated. The samples presented amorphous structure with a few crystalline phases of α-Fe and free carbon in the gaps, which were expected to be good soft magnetic materials. The average real permittivity and imaginary permittivity of PDCs-SiCN(Fe) ceramics with 50?wt% FA was about 14.1 and 5.3 respectively. Furthermore, the PDCs-SiCN(Fe) ceramics with 50?wt% FA addition content showed the broad absorption bandwidth in the 5.1–8.4?GHz with RL ≤??10?dB (>?90% absorption) at 4?mm.     

Dielectric properties of Si3N4–SiCN composite ceramics in X-band

Si₃N₄–SiCN composite ceramics were successfully fabricated through precursor infiltration pyrolysis (PIP) method using polysilazane as precursor and porous Si₃N₄ as preform. After annealed at temperatures varying from 900 °C to 1400 °C, the phase composition of SiCN ceramics, electrical conductivity and dielectric properties of Si₃N₄–SiCN composite ceramics over the frequency range of 8.2–12.4 GHz (X-band) were investigated. With the increase of annealing temperature, the content of amorphous SiCN decreases and that of N-doped SiC nano-crystals increases, which leads to the increase of electrical conductivity. After annealed at 1400 °C, the average real and imaginary permittivities of Si₃N₄–SiCN composite ceramics are increased from 3.7 and 4.68 × 10^?3 to 8.9 and 1.8, respectively. The permittivities of Si₃N₄–SiCN composite ceramics show a typical ternary polarization relaxation, which are ascribed to the electric dipole and grain boundary relaxation of N-doped SiC nano-crystals, and dielectric polarization relaxation of the in situ formed graphite. The Si₃N₄–SiCN composite ceramics exhibit a promising prospect as microwave absorbing materials.     

SiCN ceramics with controllable carbon nanomaterials for electromagnetic absorption performance

Different kinds of carbon nanomaterials, free carbon (C_free), graphene, and N-containing graphene (NG), in single-source-precursors-derived SiCN ceramics, were in situ generated by modifying polysilazane with divinylbenzene, dopamine hydrochloride and melamine, respectively. Adjusting the carbon source brings phase structure and electromagnetic wave absorption (EMA) properties differences of SiCN/C ceramics. In situ C_free enhances the EMA capacity of SiCN ceramics by improving their electrical conductivity of 9.2 × 10⁻⁴ S/cm. The electrical conductivity of SiCN ceramics with 2D graphene sheets balloons to 2.5 × 10⁻³ S/cm, causing poor impedance match thus leading to a worse EMA performance. In situ NG in SiCN ceramics has a low electrical conductivity of 5.6 × 10⁻⁸ S/cm, making for excellent impedance match. The corrugated NG boosts dielectric loss, interfacial, and dipole polarization. NG-SiCN nanocomposites possess an outstanding EMA performance with RL_min of −61.08 dB and effective absorption bandwidth of 4.05 GHz, which are ∼2.4 times lower and ∼4 times higher than those of SiCN, respectively.     

Enhanced high-temperature dielectric properties and microwave absorption of SiC nanofibers modified Si3N4 ceramics within the gigahertz range

Si₃N₄ ceramics modified with SiC nanofibers were prepared by gel casting aiming to enhance the dielectric and microwave absorption properties at temperatures ranging from 25?°C to 800?°C within X-band (8.2–12.4?GHz). The results indicate that the complex permittivity and dielectric loss are significantly increased with increased weight fraction of SiC nanofibers in the Si₃N₄ ceramics. Meanwhile, both complex permittivity and dielectric loss of SiC nanofibers modified Si₃N₄ ceramics are obviously temperature-dependent, and increase with the higher test temperatures. Increased charges mobility along conducting paths made of self-interconnected SiC nanofibers together with multi-scale net-shaped structure composed of SiC nanofibers, Si₃N₄ grains and micro-pores are the main reason for these enhancements in dielectric properties. Moreover, the calculated microwave absorption demonstrates that much enhanced microwave attenuation abilities can be achieved in the SiC nanofibers modified Si₃N₄ ceramics, and temperature has positive effects on the microwave absorption performance. The SiC nanofibers modified Si₃N₄ ceramics will be promising candidates as microwave absorbing materials for high-temperature applications.     

Improved dielectric and electromagnetic interference shielding properties of ferrocene-modified polycarbosilane derived SiC/C composite ceramics

In order to enhance the dielectric and electromagnetic interference shielding (EMI) properties, the SiC/C composite ceramics were fabricated by pyrolysis of ferrocene-modified polycarbosilane. The microstructure evolutions, dielectric properties, EMI and microwave absorption properties of SiC/C composite ceramics were investigated. The increases of both ferrocene contents and annealing temperatures led to the increases of crystallizations of SiC and carbons. Crystallized carbons including carbon nanowires, turbostratic carbons, onion-like carbons and graphene-like carbons were obtained in the materials. The carbon nanowires were longest when the 5 wt.% ferrocene-modified polycarbosilane was annealed at 1250 °C. These carbons played a more important role than SiC in the increases of dielectric and EMI properties. The average real and imaginary permittivities of materials increased from 4.4 and 0.7 to 38.9 and 39.6, respectively. The materials exhibited high total shielding effectiveness, high absorption shielding effectiveness and low reflection shielding effectiveness, which were 36.6, 30.1 and 6.5 dB, respectively.     

Tailoring microwave absorption bandwidth of SiCN based composite ceramic fibers by tuning the embedding ratio of Ni3Si

In order to expand the application prospects of SiCN ceramics in the field of microwave (MW) absorption materials, a series of Ni₃Si embedded SiCN ceramic fibers composites (NSF) were prepared by controlling Ni conversion rate through the electrospinning technique and polymer derivation, with the intention of improving the impedance matching degree, enhancing the conductivity and polarization, and further promoting the dielectric loss ability and MW absorption performance of ceramic materials. The microstructure, phase composition, conductivity, MW absorption properties and mechanism of the material were analyzed by a variety of characterization methods. The results show that NSF exhibited high dielectric loss efficiency and desirable effective absorption bandwidth (EAB) when the conversion rate of Ni was 0.5 wt%: The MW of the entire Ku band (12–18 GHz, 6 GHz) could be effectively absorbed by the sample with a thickness of 2.64 mm, and its EAB could cover 6–18 GHz by adjusting its thickness from 1 mm to 5 mm, so its performance is significantly superior to a number of similar SiCN based composite ceramic materials previously reported. To sum up, the NSF prepared in this work exhibits suitable impedance matching degree, good conductivity, obvious polarization effect, excellent dielectric loss ability, and gratifying EAB in MW, and it is expected to become a powerful candidate in the field of broadband MW absorption materials in the future.     

Enhanced electromagnetic wave absorption performance of SiCN(Fe) fibers by in-situ generated Fe3Si and CNTs

The SiCN(Fe) fibers with excellent one-dimensional microstructure and electromagnetic wave (EMW) absorption performance were synthesized by combining polymer-derived ceramics (PDCs) method and electrospinning. The in-situ generation of Fe₃Si and CNTs by adding ferric acetylacetonate (FA) into the raw materials effectively improved the dielectric properties, magnetic properties and the impedance matching performance of the SiCN(Fe) fibers. The EMW absorption performance of SiCN(Fe) fibers were mainly based on dipole polarization loss, interface polarization loss and eddy current loss. The RL_min value of SiCN(Fe) fibers reached ?47.64 dB at 1.38 mm and the effective absorption band (EAB, RL ≤ ?10 dB) reached 4.28 GHz (13.72–18 GHz, 1.35 mm).     

Polymer-derived Co2Si(Co)/SiCN composite ceramics with tunable microwave absorption properties

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.     

Design and fabrication of Al2O3f/SiCN composite with excellent microwave absorbing and mechanical properties

A new kind of structural and functional integration ceramic matrix composite material was prepared from high-performance alumina (Al₂O₃) fibers and absorbing silicon carbonitride (SiCN) ceramics via a combination of polymer infiltration pyrolysis (PIP) and chemical vapor infiltration (CVI) methods. The Al₂O₃ fiber annealed at its cracked temperature had enhanced permittivity, because the sizing agent on the Al₂O₃ fiber surface was cracked into pyrolysis carbon. For PIP + CVI Al₂O_3f/SiCN composites, PIP SiCN matrix with low conductivity was used as the matching phase, while CVI SiCN matrix with medium permittivity and dielectric loss was regarded as the reinforcing phase distributed in porous PIP SiCN matrix and inter-bundles of Al₂O₃ fiber to improve their mechanical and microwave absorption properties. The fracture toughness and flexural strength of Al₂O_3f/SiCN composite were determined to be 9.4 ± 0.5 MPa m^1/2 and 279 ± 28 MPa, respectively. Based on the design principles for impedance matching, the Al₂O_3f/SiCN composites before and after oxidation were used as loss and impedance layers, respectively. It was found that the optimized composite had the lowest reflection coefficient (RC) of −70 dB and the effective absorption bandwidth covering the whole X-band. In conclusion, Al₂O_3f/SiCN composite can serve as a high-temperature structural material with excellent microwave absorption properties for aerospace applications.     

Crystallization Mechanism of CVD Si3N4–SiCN Composite Ceramics Annealed in N2 Atmosphere and Their Excellent EMW Absorption Properties

To tailor a new electromagnetic wave (EMW) absorbing material with lower reflection coefficient (RC) and larger operating frequency band, the CVD Si₃N₄–SiCN composite ceramics were prepared from SiCl₄–NH₃–C₃H₆–H₂–Ar system and then annealed at the temperatures of 1400–1700°C in N₂ atmosphere. Effect of the annealing temperatures on the microstructure, phase composition, permittivity, and microwave‐absorbing properties of the ceramic were investigated. Results showed that the CVD Si₃N₄–SiCN ceramics gradually crystallized into nanosized SiC grains, Si₃N₄ grains and graphite (T ≤ 1600°C), and then the grains grew up at T = 1700°C. The permittivity, dielectric loss, and electrical conductivity of as‐annealed CVD Si₃N₄–SiCN ceramics (T ≤ 1600°C) increased firstly due to the formation of conductivity and polarity network and the increase in nanograin boundary, and then decreased at 1700°C because of the growth of nanograins and the disappearance of nanograin boundary. The minimal RC and effective absorption bandwidth of the as‐annealed CVD Si₃N₄–SiCN ceramic at 1600°C was ?41.67 dB at the thickness of 2.55 mm and 3.95 GHz at the thickness of 3.05 mm, respectively, demonstrating that the totally crystallized CVD Si₃N₄–SiCN ceramic (T = 1600°C) had the superior microwave‐absorbing ability.     

Enhanced electromagnetic wave absorption of Fe-doped silicon oxycarbide nanocomposites

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.     

Enhanced electromagnetic absorption properties of Fe-doped Sc2Si2O7 ceramics

Doping transition metal elements in a crystal causes distortion and defects in the lattice structure, which change the electronic structure and magnetic moment, thereby adjusting the electrical conductivity and electromagnetic properties of the material. Fe-doped Sc₂Si₂O₇ ceramics were synthesized using the sol-gel method for application to microwave absorption. The effect of Fe-doped content on the electromagnetic (EM) and microwave absorption properties was investigated in the Ku-band (12.4–18 GHz). As expected, the dielectric and magnetic properties improve substantially with increasing Fe content. Fe doping causes defects and impurity levels, which enhance polarization loss and conductance loss, respectively. Fe replaces Sc atoms in the ScO₆ octahedral structure, creating a difference in spin magnetic moments, which increases the magnetic moment. Moreover, the magnetic coupling of Fe and O atoms occurs at the Fermi level, which benefits magnetic loss. In particular, when the Fe content is 6%, the fabricated Fe-doped Sc₂Si₂O₇ ceramics show an absorption property with absorption peaks located at 14.5 GHz and a minimum reflection loss (RL_min) of ?12.8 dB. Therefore, Fe-doped Sc₂Si₂O₇ ceramics with anti-oxidation and good microwave absorption performance have a greater potential for application in high-temperature and water-vapor environments.     

The influence of Nd substitution in Ni–Zn ferrites for the improved microwave absorption properties

Nanocrystalline Ni–Zn ferrites with different neodymium contents (Ni_0.5Zn_0.5Nd_xFe_2-xO₄) were synthesized by sol-gel route combined with self-propagating combustion (SPC) method. The presence of surface functional groups, crystal structure and morphology of the samples were studied by FT-IR, XRD and SEM. The results show that the prepared samples are composed of spinel phase under the condition of low neodymium content, like the pure Ni–Zn ferrite. While neodymium oxide appears after the content of Nd³⁺ exceeds a certain limit (x > 0.04) and there exist two phases in the ferrite. The results of vibrating sample magnetometer (VSM) and vector network analyzer (VNA) show that adjusting the content of Nd is significant in improving the dielectric properties and microwave absorption capacity of the materials, specifically at low frequencies. When x < 0.04, the enhancement of dielectric loss ability of spinel ferrites by doping Nd³⁺ is the dominant factor affecting microwave absorption ability of samples. The secondary phase Nd₂O₃ hardly appears under this condition, thus the weakening effect of Nd³⁺ addition on magnetic loss ability is not obvious. When x = 0.04, the optimal absorption peak of the material reaches −20.8 dB at 4.4 GHz with a thickness of 8.5 mm and the effective absorption bandwidth (R_L < −10 dB) was 3.2 GHz. On the contrary, when x > 0.04, the magnetic loss ability decreases rapidly (e.g., Ms decreases from 82.47 emu/g to 59.77 emu/g). Meanwhile, the dielectric loss increases slowly and the microwave absorption capacity decreases.     

Si3N4-BN-SiCN ceramics with unique hetero-interfaces for enhancing microwave absorption properties

SiCN-based ceramics with broadband and strong microwave absorption properties are desired for the structural and functional integration of ceramic matrix composites. The elemental composition and thermal expansion coefficients of the ceramics matrix crucially affect its microstructure and electromagnetic wave (EMW) absorption properties. BN layer with lower electrical conductivity and higher specific area, exhibits both the impedance matching characteristic and EMW attenuation in the process of multiple reflections, electrical conductivity loss, dipole polarization and interfacial polarization. Therefore, Si₃N₄-BN-SiCN ceramics, which were synthesized using chemical vapor infiltration (CVI) method, construct unique hetero-interface of Si₃N₄-BN, Si₃N₄–SiCN and BN-SiCN. Therefore, the Si₃N₄-BN-SiCN ceramics have outstanding EMW absorption performance and realize an effective absorption bandwidth (EAB) that covers the whole X band and the minimum reflection coefficient (RC) reaches -18.43 dB at a thickness of 3.37 mm.     

A new BaB2O4 microwave dielectric ceramic for LTCC application

To satisfy the requirements of miniaturization and integration of microwave devices, microwave dielectric ceramics with low sintering temperatures and good microwave dielectric properties are particularly important for LTCC materials. In this study, low-cost BaB₂O₄ ceramics were prepared with different Ba/B ratios using a solid-phase method. Combined with the Raman spectra, the effects of the Raman shift and FWHM of the vibration peaks on the microwave dielectric properties were determined. As a novel microwave dielectric ceramic, BaB₂O₄ consists of a highly dense structure with optimal microwave dielectric properties (ε_r = 4.06, Q×f = 23845 GHz, and τ_f = −7.2 ppm/℃) at a low sintering temperature (840 ℃). In addition, BaB₂O₄ ceramic is chemically compatible with Ag, making it a promising candidate substrate for microwave communications.     

Preparation and properties of silicon nitride-phosphate composites for application in microwave furnace

Si₃N₄ ceramic is one of the most promising microwave metallurgy furnace materials because of the outstanding mechanical, relatively low dielectric properties and excellent thermal shock resistance. However, the difficult sintering of Si₃N₄ ceramics extremely restrict their large-scale application in the field of refractories for microwave metallurgy. In this work, silicon nitride-phosphate ceramics were fabricated by introducing aluminum phosphate or chromium phosphate aluminum into Si₃N₄ ceramics at 1500 °C. The effect of the amount of aluminum phosphate and chromium phosphate aluminum on sintering performance and dielectric properties was investigated. The results showed that the addition of aluminum phosphate or chromium phosphate aluminum could promote sintering, and the mechanical and dielectric properties of Si₃N₄ ceramics were efficiently improved. The Si₃N₄-aluminum phosphate composites exhibited better sintering performance (higher density and mechanical property) than that of Si₃N₄-chromium phosphate aluminum composites. Meanwhile, the dielectric constant and dielectric loss of Si₃N₄-chromium phosphate aluminum composites were better than Si₃N₄-chromium phosphate aluminum composites.     

Enhanced electromagnetic microwave absorption properties of SiCN(Fe) ceramics produced by additive manufacturing via in-situ reaction of ferrocene

SiCN(Fe) ceramics with excellent electromagnetic wave (EMW) absorption performance were successfully prepared from a preceramic polymer doped with ferrocene. Additive manufacturing (Digital Light Processing), providing enhanced structural design ability, was employed to fabricate samples with complex architectures. During pyrolysis, ferrocene catalyzed the in-situ formation of a large amount of turbostratic carbon, graphite and SiC nanosized phases, which formed carrier channels in the electromagnetic field and increased the conductivity loss. Meanwhile, it also increased the dipole polarization, interface polarization and the dielectric properties of the material, which finally enhanced the EMW absorption capacity of SiCN(Fe) ceramics. When containing 0.5 wt% ferrocene, the material showed good performance with EAB 4.57 GHz at 1.30 mm, and RL_min −61.34 dB at 2.22 mm. The RL_min of 3D-SiCN-0.5 ceramics was −6 dB, and the RL of the X-band was lower than −4 dB at 2 mm.