Adjustable iron-containing SiBCN ceramics with high-temperature microwave absorption and anti-oxidation properties

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 (RC_min) is −61.05 dB, and the effective bandwidth absorption (EAB) is 3.35 GHz (9.05–12.4 GHz). The RC_min 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.     

Effect of boron content on the microstructure and electromagnetic properties of SiBCN ceramics

Electromagnetic wave (EMW) absorbing materials have excellent potential for various applications in civil engineering and the military. In this study, siliconboron carbonitride (SiBCN) ceramics with excellent EMW absorption capability and oxidation resistance were obtained by adjusting the boron content. The results revealed that the graphite crystallite size in the SiBCN ceramics increased from 3.42 to 3.78 nm, whereas the thickness of the oxide layer decreased from 16.6 to 8.2 μm. The highest electrical conductivity and permittivity for the SiBCN ceramics were obtained when the boron content was 5%. The minimum reflection loss was ?35.25 dB at 10.57 GHz and a ceramic thickness of 2.0 mm. At a temperature of 600 °C, the SiBCN ceramic exhibited excellent EMW attenuation ability; particularly, the minimum reflection loss reached ?29.18 dB at 9.65 GHz and a ceramic thickness of 2.5 mm. The superior EMW absorption properties of the SiBCN ceramics at high temperatures can be ascribed to the synergistic effect of relaxation and conductivity. The results suggest that boron could enhance the transformation of amorphous carbon into crystalline graphite and increase the number of heterointerfaces and conductive paths. This work provides a method for obtaining SiBCN ceramics with excellent EMW absorption properties.     

Strong effect of atmosphere on the microstructure and microwave absorption properties of porous SiC ceramics

Excellent microwave absorption properties of porous SiC ceramics were successfully synthesized using SiC/camphene slurries with various polycarbosilane (PCS) contents related to the SiC powder. The compositions of the nanowires (NWs) growth in the pore channels of porous SiC ceramics strongly depended on the pyrolysis atmosphere, with N₂-generating Si₃N₄ NWs and Ar SiC NWs. With the increase of PCS content, the minimum reflection coefficient (RC) of porous SiC ceramics decreased from ?7.6 dB to ?67.4 dB in Ar and from ?10.9 dB to ?24.7 dB in N₂, respectively. The effective absorption bandwidth (EAB) of porous SiC ceramics could be up to 8.1 GHz in Ar and 4.5 GHz in N₂. The enhanced microwave absorption properties of porous SiC ceramics could be attributed to the formation of SiC nano-crystalline, nanosized carbon and the NWs, which would increase the amount of boundaries and defects, leading to the electronic dipole polarization and interfacial scattering.     

SiBCN ceramic aerogel/graphene composites prepared via sol-gel infiltration process and polymer-derived ceramics (PDCs) route

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.     

Flexible SiC-CNTs hybrid fiber mats for tunable and broadband microwave absorption

Flexible microwave absorbers with high stability are in increasing demand for the applications under harsh conditions. SiC as a functional ceramic material has the feature of high environmental tolerance and adjustable electromagnetic (EM) absorbing properties, making them suitable to be applied for harsh environments. However, the electrical property of SiC requires to be further enhanced to obtain qualified EM absorbing performance. In this work, multiwall carbon nanotubes (CNTs) were introduced to SiC to enhance the electrical properties. Flexible two-dimensional (2D) CNTs loaded SiC fiber mats were prepared as EM absorbers via electrospinning and polymer-derived-ceramic (PDC) methods. The CNTs inside the fibers can form conductive networks and act as reinforcement to ensure high flexibility and enhance the microwave absorption properties of SiC mats. Thus, a reflection loss of ?61 dB and an effective absorption band (EAB) of 2.9 GHz were obtained. More importantly, the EM absorption can be adjusted by tuning the content of CNTs and the EAB can cover the entire X-band by adjusting the material thickness. The work provided a facile strategy to fabricated flexible 2D ceramic mats with high environmental stability and tunable electrical properties, which may shed light on the production of reliable EM absorber for broadband EM absorption applications.     

The heterointerface of graphene in-situ growth for enhanced microwave attenuation properties in La-doped SiBCN ceramics

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 (RL_min) 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 RL_min 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.     

The dielectric and microwave absorption properties of polymer-derived SiCN ceramics

The polymer-derived SiCN ceramics were synthesized at different annealing temperature (900 ～ 1400 °C). The XRD, SEM, FT-IR, Raman and XPS were used to analyze the phase composition and microstructure. The result indicated that the crystallization degree and content of free carbon gradually improved with the increase of annealing temperature. The resistivity, dielectric and microwave absorption properties of the samples were studied at 2 ～ 18 GHz. The resistivity decreased gradually as the annealing temperature rose. The dielectric constant of sample decreased with the increase of frequency in 1 ～ 5 MHz. The existence of free carbon could improve the dielectric properties of polymer-derived SiCN ceramics at high frequency. The reflectance of the sample synthesized at 1100 °C was below ?10 dB (> 90% absorption) in a wide frequency range of 6 ～ 16 GHz and the maximum value of dielectric loss angle tangent was about 0.6 at 16 GHz.     

Bridged polysilsesquioxane-derived SiOCN ceramic aerogels for microwave absorption

The development of high-performance microwave absorption materials in harsh environment is highly desirable but challenging. Herein, lightweight silicon oxycarbonitride (SiOCN) ceramic aerogels were fabricated by the pyrolysis of bridged polysilsesquioxane aerogels, which was presynthesized by a sol–gel method followed by vacuum drying. The structural order and content of free carbon phase determined by pyrolysis temperature play a critical role in modulating the impedance matching and attenuation capacity. The as-prepared SiOCN aerogel pyrolyzed at 1000°C achieves a minimal reflection loss of −64.2 dB at 8.96 GHz and a broad bandwidth of 5.4 GHz at a low thickness of 2.15 mm. The hierarchical pore structure, abundant heterogeneous amorphous SiOCN/free carbon interfaces, and conductive free carbon phase benefit the superior absorption performance by forming good impedance matching, multiple scattering, interface polarization, and conduction losses. This work provides an insight for the rational design of polymer-derived ceramic aerogel-based microwave absorption materials for potential application under extreme conditions such as high-temperature and oxidation environments.     

Microstructure and electromagnetic wave absorption property of reduced graphene oxide-SiCnw/SiBCN composite ceramics

In this account, RGO-SiC_nw/SiBCN composite ceramics were fabricated using polymer derived ceramic (PDC) combined with chemical vapor infiltration (CVI) technology. Dielectric property of as-obtained RGO-SiC_nw/SiBCN composite ceramics was significantly enhanced thanks to established conductive pathway through overlapped nanoscale SiC_nw and micro-sized RGO. The minimum RC of composite ceramics with 0.5 wt% GO and 2.29 wt% SiC_nw 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-SiC_nw/SiBCN composite ceramics maintained outstanding EMW absorption ability with minimum RC of -10.41 dB after oxidation at 900 °C, indicating RGO-SiC_nw/SiBCN composite ceramics with excellent EMW absorption characteristic even at high temperatures and harsh environments.     

High performance X-band electromagnetic wave absorption of SiBCN metamaterials fabricated by direct pyrolysis

Electromagnetic wave (EMW)-absorbing ceramic metamaterials without doping absorbers were prepared by direct pyrolysis of polymer-derived SiBCN ceramics (PDC-SiBCN). The pyrolytic behavior of the ceramics, the effect of the pyrolysis temperature on the mechanical strength, and the EMW absorption properties of the metamaterials are discussed in detail. The mechanism of the enhanced EMW absorption by the metamaterials was further analyzed. The results indicated that PDC-SiBCN demonstrated the optimum impedance matching and absorption performance at a pyrolysis temperature of 1500 °C. The metamaterial can effectively absorb the full X-band when its thickness is in the range of 4.3–5.7 mm. When the thickness was adjusted to 4.7 mm, the minimum reflection coefficient (RC) reached − 26.6 dB. In addition, the flexural strength of the metamaterial was 31.2 MPa, and the compressive strength was 96.9 MPa, which is 60 times higher than that of the solid structure. This study provides a feasible guide for the simple fabrication of lightweight, high-strength, and high-performance EMW-absorbing materials.     

Preparation,dielectric property and microwave absorption property of Cu doped SiC nanopowder by combustion synthesis

Abstract

Cu doped SiC nanopowders have been prepared via combustion synthesis, using silicon powder and carbon black as the raw materials, copper powder as the doping source and polytetrafluoroethylene as the chemical activator respectively. The microstructure of prepared nanopowders has been characterised by X-ray diffraction and scanning electronic microscope. The electric permittivities of prepared SiC nanopowders in the frequency range of 8·2–12·4 GHz have been determined. Results show that prepared β-SiC nanopowders have fine spherical particles and narrow particle size distribution, and a quantity of SiC whisker increases with increasing Cu doping content. The Cu₃Si impurity has been generated when Cu content is up to 10%. The β-SiC doped with 10% Cu has the highest real part ?′ and dielectric loss tanδ values. The 5% Cu doped SiC nanopowder with matching thickness of 2 or 2·5 mm exhibits the best microwave absorption properties in the frequency range of 8·2–12·4 GHz.     

Dielectric and microwave absorption properties of divalent-doped Na3Zr2Si2PO12 ceramics

The work attempted to develop a new kind of high temperature microwave absorption material. Dense Na₃Zr_1.9M_0.1Si₂PO_11.9 (M?=?Ca²⁺, Ni²⁺, Mg²⁺, Co²⁺, Zn²⁺) and Na₃Zr_2-xZn_xSi₂PO_12-x (x?=?0.1, 0.2, 0.3, 0.4) ceramics were prepared by solid-state reactions for phase, microstructure characterization and dielectric properties, microwave absorption properties analysis. Results show that the complex permittivity increases in all the divalent-doped Na₃Zr₂Si₂PO₁₂ ceramics. Na₃Zr_1.8Zn_0.2Si₂PO_11.8 ceramic exhibits the highest complex permittivity and optimum microwave absorption performance. The lowest reflection loss is -28.1?dB at 9.88?GHz and the bandwidth is 4.14?GHz (8.26–12.4?GHz) with a thickness of 2.1?mm. It indicates that Na₃Zr₂Si₂PO₁₂ ceramic can be chosen as a potential candidate of microwave absorption material and the performance can be enhanced by divalent doping strategy.     

Method for fabricating microwave absorption ceramics with high thermal conductivity

In this work, a high-performance microwave absorption ceramic together with high thermal conductivity was proposed through the introduction of phenolic resin as the carbon source into AlN ceramic substrate. The phenolic resin was initially mixed with AlN powder and sintering additives in ethanol to form homogeneous slurries, followed by drying, pyrolysis, dry pressing and pressureless sintering to develop nano carbon in situ in AlN substrate. The well controlled microstructure with homogeneous distribution of nano sized carbon lead to the high thermal conductivity and excellent microwave absorption properties. by adjusting the phenolic resin content, the ceramic showed a minimal reflection coefficient of about ?30 dB with an effective bandwidth of about 2 GHz together with a high thermal conductivity of about 135.1 W/m K.     

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.     

Synthesis,microstructure and electromagnetic properties of Hf-based SiBCN ceramics

In this work, two kinds of ceramic polymers, polyborosilazane and polyhafnoxane, were mixed by a precursor blending method, followed by curing and pyrolysis to obtain Hf-based SiBCN ceramics. Through FTIR and NMR characterization of cured product, it can be found that the two precursors underwent cross-linking reaction during the curing process, resulting in the increase of crystallization temperature of HfO₂ and β-SiC, and the formation of new components (HfB₂ and HfN) during pyrolysis. When the pyrolysis temperature increases, the average values of the real part and imaginary part of the dielectric constant of Hf-based SiBCN ceramics increased from 7.2 to 4.9 to 9.0 and 6.6, respectively, resulting from the precipitation of HfB₂ and HfC(N) with high dielectric constants. The effective absorption width decreased from 3.4 to 2.5 GHz, and the minimum value of reflection coefficient increased from −14.9 to −12.2 dB, which is caused by poor impedance matching. After being oxidized at 500 °C for 50 h in air, the free carbon basically disappears, and the full X-band absorption can be realized for the Hf-based SiBCN ceramic pyrolyzed at 1500 °C with a thickness of 2.8 mm.     

Enhanced electromagnetic microwave absorption of SiC nanowire-reinforced PDC-SiC ceramics catalysed by rare earth

Rare earth elements can modulate the dielectric constant of materials and significantly improve their dielectric properties. Herein, SiCnws/SiC ceramics were prepared through polymer derived ceramics (PDCs) technology with rare earth Sc particles as the catalyst. The Sc particles promote the precipitation of SiC and C from the matrix. Furthermore, the SiCnws, grown via the vapour-liquid-solid (VLS) mechanism, construct the three dimensional (3D) network structure to improve impedance matching and loss characteristics. Remarkably, the SiCnws/SiC ceramics minimum reflection coefficient (RC_min) achieved a value of ?33.2 dB at 9.4 GHz with a thickness of 2.75 mm, and the effective absorption bandwidth (EAB) was 4.2 GHz covering the whole X band. When microwaves permeated into the SiCnws/SiC ceramics, those trapped in the 3D network structure underwent a variety of microwave energy dissipation processes, including multiple reflections, scattering, and interface and dipole polarisation. Consequently, SiCnws-reinforced PDC-SiC ceramics catalysed by rare earth emerge as a promising new approach to enhance electromagnetic (EM) wave absorption performance.     

Influence of different matrices on the mechanical and microwave absorption properties of SiC fiber-reinforced oxide matrix composites

Fiber-reinforced ceramic matrix composites have excellent mechanical and microwave absorption properties, but still present considerable challenges. We prepared a SiC_f/mullite-SiO₂ composite (composite A) and a SiC_f/Al₂O₃-SiO₂ composite (composite B) by a precursor infiltration and sintering (PIS) process. Compared with the composite B, the composite A was easily densified. The flexural strength of the composite A reached 216 MPa, whereas that of the composite B was 159 MPa. The imaginary part of permittivity for composites A and B, which was determined by the contents of matrix and porosity, varied in the range of 2.5–3.5 and 3.6–5, respectively. The microwave absorption properties of the composite A were significantly enhanced in the range of 8.2–12.4 GHz. The results indicate that an optimal reflection loss of ?44 dB was reached at 12 GHz with a thickness of 2.9 mm for the composite A. These SiC fiber-reinforced oxide matrix materials have promising applications in microwave absorption, especially at high temperatures.     

Synthesis,pyrolysis of a novel liquid SiBCN ceramic precursor and its application in ceramic matrix composites

SiBCN ceramic precursor, polyborosilazane, was synthesized through a novel method which used sodium borohydride as boron source. Vinyl silazane with SiCl was converted to vinyl silazane with SiH structure, followed by hydroboration reaction and subsequent high-temperature reaction to form soluble polyborosilazane liquid. The process of precursor-to-ceramic conversion was almost completed before 800 °C and the cross-linked polyborosilazane precursor exhibited higher ceramic yield 75.6% at 1200 °C. The SiBCN ceramic annealed at 1400 °C contained BN, SiN and SiC bonds with smooth and dense surface and still retained principally amorphous structure up to 1600 °C. In addition, the viscosity of the polyborosilazane was 65 mPa.s, which can efficiently prepare ceramic matrix composite by means of precursor infiltration and pyrolysis (PIP). The density of as-obtained ceramic matrix composite (CMC) was 1.82 g/cm³, and the average bending strength, bending modulus and tensile strength were 265.2 MPa, 37.5 GPa and 158.6 MPa, respectively.     

Construction of core-shell BaFe12O19@MnO2 composite for effectively enhancing microwave absorption performance

BaFe₁₂O₁₉, a traditional ferrite, has always been extensively investigated as a microwave absorption material because of the application value. Herein, the core-shell BaFe₁₂O₁₉@MnO₂ composite was designed and constructed successfully by a facile hydrothermal method. By introducing nanostructured MnO₂, a typical dielectric loss medium, the electromagnetic wave absorption performance is effectively enhanced. The core-shell structure contributes to high interface polarization, thereby promoting the attenuation of electromagnetic waves. In addition, the optimal temperature of the hydrothermal reaction was explored through the characterization of the morphology and the analysis of microwave absorption performance. The result exhibits that the maximum reflection loss of the prepared BaFe₁₂O₁₉@MnO₂-170 reaches -54.39 dB and the effective absorbing bandwidth reaches 4.64 GHz. The simple preparation method and attractive performance make BaFe₁₂O₁₉@MnO₂ a promising candidate as microwave absorbers.     

Electrical conductivity,dielectric and microwave absorption properties of graphene nanosheets/magnesia composites

Herein, a novel microwave absorbing material with Graphene nanosheets (GNSs) as microwave absorbing filler and magnesia (MgO) as matrix were prepared by hot-pressing sintering. The composites were highly dense with a homogeneous distribution of GNSs. Electrical conductivity, dielectric and microwave absorption properties in X-band were investigated. The results revealed that the electrical conductivity of the GNSs/MgO composites showed a typical percolation-type behavior with a percolation threshold of 3.34 vol%. With GNSs content increased to 3 vol%, the real permittivity, imaginary permittivity and dielectric loss tangent of the composites increased from ～9, ～0 and ～0 to 26–43, 23–28 and 0.55–0.96, respectively. By adjusting the GNSs content, thickness and frequency, the 2.5 vol% GNSs/MgO composite shows the minimum reflection loss of ?36.5 dB at 10.7 GHz and the reflection loss below ?10 dB (90% absorption) ranges from 9.4 to 11.4 GHz with 1.5 mm thickness, exhibiting excellent microwave absorption properties.