Microstructural evolution and microwave transmission/absorption transition in polymer-derived SiOC ceramics

Herein, we present the structural evolution of polymer-derived SiOC ceramics with the pyrolysis temperature and the corresponding change in their microwave dielectric properties. The structure of the SiOC ceramics pyrolyzed at a temperature lower than 1200 °C is amorphous, and the corresponding microwave complex permittivity is pretty low; thus, the ceramics exhibit wave transmission properties. The Structural arrangement of free carbon in the SiOC ceramics mainly happens in the temperature range of 1200 °C-1300 °C due to the separation from the Si–O–C network and graphitization, while the structural arrangement of the Si-based matrix mainly occurs in the range of 1300 °C-1400 °C owing to the separation of SiC₄ from the Si–O–C network to form nanocrystalline SiC. In pyrolysis temperature range of 1200 °C-1400 °C, the microwave permittivity of SiOC shows negligible change. At a pyrolysis temperature exceeding 1400 °C, the carbothermal reaction of free carbon and the Si–O backbone becomes significant, leading to the formation of crystalline SiC. The as-formed SiC and residual defective carbon improve the polarization loss of SiOC ceramics. In this case, the SiOC ceramics show significantly increased complex permittivity, exhibiting electromagnetic absorption characteristics. These characteristics promote the application of polymer-derived SiOC ceramics to high-temperature electromagnetic absorption materials.     

Enhanced electromagnetic wave absorption properties of a novel SiC nanowires reinforced SiO2/3Al2O3·2SiO2 porous ceramic

To realize the broad-bandwidth and high-efficiency absorption characteristics, a novel SiC nanowires reinforced SiO₂/3Al₂O₃·2SiO₂ porous ceramic was successfully fabricated by method of precursor infiltration pyrolysis (PIP). Polycarbosilane (PCS) and ferrocene (Fe(C₅H₅)₂) were used as the precursor and catalyst to incorporate SiC nanowires into the SiO₂/3Al₂O₃·2SiO₂ porous ceramic. The curvy SiC nanowires formed three-dimensional (3D) networks with a proper nanometer heterostructure, thereby consuming the microwave energies. The influence of SiC nanowires contents on the microwave absorption properties was investigated. The results indicate that the SiC nanowires contents can be tuned by controlling the PIP cycles, thereby modifying the dielectric properties of as-prepared composite ceramics. The dielectric and electromagnetic wave absorption performances are gradually enhanced with an increasing of SiC nanowires contents. The SiC nanowires reinforced SiO₂/3Al₂O₃·2SiO₂ composite ceramic exhibits excellent electromagnetic wave absorption abilities when the SiC nanowires content is 23.9% (PIP5). The minimum reflection coefficient (RC_min) of the composite ceramic is −30 dB at 10.0 GHz, corresponding to more than 99.9% of the electromagnetic wave consumption. The effective absorption bandwidth (EAB) can cover the frequency ranges of 8.2–12.4 GHz (the entire X-band) at the thickness of 5.0 mm. In general, the novel SiC nanowires reinforced SiO₂/3Al₂O₃·2SiO₂ composite ceramic can be considered as a promising electromagnetic wave absorbing material.     

Dielectric and microwave absorption properties of polymer-derived TiC/SiC/SiOC multiphase ceramics in X band

Polymer-derived TiC/SiC/SiOC ceramics were prepared using tetrabutyl titanate (TBT)-modified polysiloxane (PSO) as precursor. The effects of heat treatment temperature and TBT content in precursor on the microstructure, phase composition, and microwave absorbing properties of TiC/SiC/SiOC ceramics were investigated. The crystallinity of the ceramics increases with the increase of heat treatment temperature. With the increase of TBT content, the TiC content of the ceramics increases and the SiC content decreases. When the TBT content ranges from 1 to 5 wt.%, the increase of TBT content has little effect on the real part of the dielectric constant of TiC/SiC/SiOC ceramics. When the TBT content is 7 wt.%, the imaginary part of the dielectric constant of the ceramics changes. For TiC/SiC/SiOC ceramic obtained from the pyrolysis of PSO-TBT precursor with 7 wt.% TBT, the dielectric constant is within the target electromagnetic parameters. Therefore, it has an effective absorption bandwidth of 4.2 GHz, covering the entire X band, showing an excellent microwave absorbing performance.     

Enhanced microwave absorption properties of Fe-doped SiOC ceramics by the magnetic-dielectric loss properties

The combination of multiple loss characteristics is an effective approach to achieve broadband microwave wave absorption performance. The Fe-doped SiOC ceramics were synthesized by polymer derived ceramics (PDCs) method at 1500 °C, and their dielectric and magnetic properties were investigated at 2–18 GHz. The results showed that adding Fe content effectively controlled the composition and content of multiphase products (such as Fe₃Si, SiC, SiO₂ and turbostratic carbon). Meanwhile, the Fe promoted the change of the grain size. The Fe₃Si enhanced the magnetic loss, and the SiC and turbostratic carbon generated by PDCs process significantly increased the polarization and conductance loss. Besides, the magnetic particles Fe₃Si and dielectric particles SiO₂ improved the impedance matching, which was beneficial to EM wave absorption properties. Impressively, the Fe-doped SiOC ceramics (with Fe addition of 3 wt %) presented the minimum reflection coefficient (RC_min) of ?20.5 dB at 10.8 GHz with 2.8 mm. The effective absorption bandwidth (EAB, RC < ?10 dB) covered a wide frequency range from 5 GHz to 18 GHz (covered the C, X and Ku-band) when the absorbent thickness increased from 2 mm to 5 mm. Therefore, this research opens up another strategy for exploring novel SiOC ceramics to design the good EM wave-absorbing materials with broad absorption bandwidth and thin thickness.     

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.     

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.     

Lightweight and resilient SiOC/SiC foam with efficient electromagnetic wave absorption and high-temperature stability

Integrating multiple functions such as high electromagnetic (EM) wave absorption, thermal insulation, and resilience into one material is critical, especially for applications in harsh environment. SiC ceramic has received considerable attention as high-temperature wave absorber, but its applications are limited by common wave absorption performance and brittleness of ceramics. Here by incorporating SiO₂ with SiC in a unique three-dimensional network structure, SiOC/SiC foam consisting of abundant SiOC thin flakes interconnected by numerous long interweaving SiC nanowires have been prepared. The foam shows high EM wave absorption with minimum reflection loss of −30.23 dB, broad effective absorption bandwidth of 5.4 GHz, and a nearly complete compressive resilience from 10% strain. Besides, the foam displays high-temperature resistance up to 1400°C in air and good thermal insulation performance. Such multifunctional material is promising for applications in advanced aerospace industry under extreme conditions.     

Improved dielectric properties of PDCs-SiCN by in-situ fabricated nano-structured carbons

In order to enhance dielectric properties of polymer derived SiCN ceramics (PDCs-SiCN), nano-structured carbons were in-situ fabricated in PDCs-SiCN by pyrolysis of ferrocene-modified polysilazane. Microstructure evolutions, dielectric and microwave absorption properties of PDCs-SiCN decorated with nano-structured carbons were investigated. Nano-structured PDCs-SiCN ceramics are composed of carbon nanowires as well as interpenetrating graphene-like free carbons, SiC nano-crystals, Si₃N₄ nano-crystals and amorphous SiCN. Relative complex permittivities of nano-structured PDCs-SiCN increase with increasing ferrocene contents and annealing temperatures. Free carbons in PDCs-SiCN play a dominating role on the improved dielectric properties. Polarization loss is the primary dielectric loss. Loss tangent of PDCs-SiCN exceeding 0.7 is obtained when free carbons are only 2.57% in weight. Nano-structured PDCs-SiCN exhibit good microwave absorption property. The reflectivity is smaller than −14 dB in the whole X band when material is composed of both impedance and microwave absorption materials.     

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.     

Multifunction properties of SiOC reinforced with carbon fiber and in-situ SiC nanowires

Herein, the SiC nanowires were successfully fabricated via chemical vapor infiltration (CVI) into carbon fiber felts (CFs) and then the SiOC/SiCnws/CFs composites were synthesized by precursor infiltration and pyrolysis (PIP) processes. Results indicated that the lightweight composites possessed enhanced mechanical performance, low thermal conductivity, and excellent electromagnetic wave absorption properties. Detailedly, the compressive strength reached to 22.0 MPa and 9.6 MPa after two PIP processes cycles in z and x/y directions, respectively. Meanwhile, the composites exhibited tailored electromagnetic wave absorption performance with the effective absorption bandwidth of 3.06 GHz, and the minimum reflection loss (RL_min) was -48.2 dB with a thickness of 3.6 mm. The present work has a guidance to prepare and design multifunction properties for application in harsh environment.     

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.     

Enhanced microwave-absorption properties of polymer-derived SiC/SiOC composite ceramics modified by carbon nanowires

Novel microwave-absorbing SiOC composite ceramics with dual nanowires (carbon nanowires (CNWs) and SiC nanowires) with high performances were fabricated by using the polymer-derivation method and heat treatment in Ar atmosphere. The introduction of CNWs in the amorphous SiOC ceramics promotes the ceramic crystallization into SiC nanoparticles and SiC nanowires at lower annealing temperatures, which leads to multi-phases and multiple nano heterogeneous interfaces. The distinctive architectures largely increase the interfacial and dipole polarizations of the composite ceramics. The CNWs/SiC/SiOC composite ceramics exhibit excellent microwave-absorption properties in the Ku band (12.4–18 GHz). The minimum reflection coefficient (RC) is -24.5 dB at a thickness of 1.8 mm, while the maximum effective absorption bandwidth (EAB, the corresponding frequency band in which RC is smaller than -10 dB) is 4.8 GHz at a thickness of 1.9 mm, which make the CNWs/SiC/SiOC composite ceramics promising electromagnetic-wave-absorbing materials.     

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.     

Preparation of Micro‐/Mesoporous SiOC Bulk Ceramics

Micro‐/mesoporous SiOC bulk ceramics with high surface area and bimodal pore size distribution were prepared by pyrolysis of polysiloxane in argon atmosphere at 1100°C–1400°C followed by etching in hydrofluoric acid solution. Their thermal behaviors, phase compositions, and microstructures at different nano‐SiO₂ filler contents and pyrolysis temperatures were investigated by XRD, SEM, DSC, and BET. The SiO₂ fillers and SiO₂‐rich clusters in the SiOC matrix act as pore‐forming sites and can be etched away by HF. At the same time, the SiO₂ filler promotes SiOC phase separation during the pyrolysis. The filler content and pyrolysis temperature have important effects on phase compositions and microstructures of porous SiOC ceramics. The resulting porous SiOC bulk ceramic has a maximum specific surface area of 822.7 m²/g and an average pore size of 2.61 nm, and consists of free carbon, silicon carbide, and silicon oxycarbide phases.     

Microwave-absorption properties of SiOC ceramics derived from novel hyperbranched ferrocene-containing polysiloxane

In this contribution, we design a novel strategy to synthesize SiOC ceramics by pyrolysis of hyperbranched ferrocene-containing polysiloxane (HBPSO-VF) which are synthesized by the reaction of polysiloxane (PSO) with 1,1′-Bis(dimethylvinylsilyl)ferrocene (VF). This SiOC ceramics show much lower crystallization temperature because of the capability of HBPSO-VF to incorporate metallic iron into the backbone of PSO. The usage of HBPSO-VF offers enhanced ceramic yield of 83 wt% at 1200 °C due to the deep cross-linking of hydrosilylation. Nano-sized SiC and turbostratic carbons are separated from amorphous SiOC phase when it is annealed at 1100 °C, while crystallization temperature is 1400 °C when PSO is used as polymer precursors. The minimum reflection coefficient (RC_min) of this nanocrystal-containing ceramic reaches −46 dB, exhibiting a promising prospect as a kind of electromagnetic wave (EMW) absorbing materials. This method also can be further extended to develop other functional Si-based polymer derived ceramic (PDC) systems for EMW absorption and shielding applications.     

5G array antenna substrate for electromagnetic beam splitting via cobalt-substituted zinc molybdate low temperature co-fired ceramics

A novel Zn_1-xCo_xMoO₄ (ZCMO) (x = 0.03) ceramic with low-dielectric constant, low-loss, and low-sintering temperature for 5G electromagnetic beam splitting is developed by solid-state reaction method. This ceramic exhibits excellent microwave dielectric properties with ε_r = 8.0, Q × f = 57682 GHz, τ_f = ? 54.9 ppm/°C at a sintering temperature of 825 °C. An array antenna for electromagnetic beam splitting at 5.4 GHz is designed by using this ceramic for the first time. The highest efficiency and the best electromagnetic beam splitting effect can be jointly controlled by the dielectric constant and dielectric loss of the ceramic. The normalized reflection amplitude of each array unit cell is above 98 %, and the reflection phase covers 360°. The function of electromagnetic beam splitting is verified by the far-field pattern of the electric field. This work helps to promote the development of LTCC and broaden the application scope of microwave dielectric ceramics.     

A nanocomposite of dual-phase Fe/TiCN wrapped in nitrogen-doped carbon with magnetic and dielectric characters for superior microwave absorption

A careful approach to the optimization of magnetic and dielectric losses in nanomaterials can improve the electromagnetic wave absorption loss performance for certain microwave absorption applications. In this study we prepared dual core (Fe/TiCN) coated with nitrogen (N) doped carbon shell nanocomposite by arc-discharge method under mix atmospheres of working gases and with varying elemental compositions. Among all nanocomposites, (Fe/TiC_0.7N_0.3)@N–C dual-core@ N- doped shell nanocomposite exhibits enhanced microwave absorption. Owing to the novel dual-core@ N-doped shell structure and numerous defects induced by doping N in carbon shells, an improved dielectric relaxation in composite is observed and the minimum reflection loss was reached −44.36 dB at 5.3 GHz for 4.8 mm thickness.     

Multiscale SiCnw and carbon fiber reinforced SiOC ceramic with enhanced mechanical and microwave absorption properties

The hierarchical SiOC/SiCnws/CF composites (A/B/C structure) were designed via precursor infiltration and pyrolysis process. The SiOC ceramics served as the wave-transparent characteristic materials to adjust the impedance matching. Herein, the in situ growth of SiCnws not only was used for the absorber but served as the reinforcement of SiOC matrix composites. In detail, the SiOC/SiCnws/CF-1200°C-2 exhibits excellent electromagnetic absorption performance with minimum reflection loss of −46 dB at 14.4 GHz with the thickness of 1.6 mm, and its effective absorption band reaches 4.3 GHz. Its compressive strength reaches 8.69 and 16.41 MPa in z and x/y directions, separately. This contribution has a guidance for the application of carbon fiber/ceramics matrix composites in harsh environment.     

Impact of blending with polystyrene on the microstructural and electrochemical properties of SiOC ceramic

In this work, we present the electrochemical behavior and microstructural analysis of silicon oxycarbide (SiOC) ceramics influenced by an addition of polystyrene (PS). Polymer-derived ceramics were obtained by pyrolysis (1000°C, Ar atmosphere) of different polysiloxanes prepared by sol–gel synthesis. This method is very effective to obtain desired composition of final ceramic. Two alkoxysilanes phenylthriethoxysilane and diphenyldimethoxysilane were used as precursors. Before pyrolysis polysiloxanes were mixed with PS using toluene as a solvent. Blending with PS affects the microstructure and free carbon content in the final ceramic material. Free carbon phase has been confirmed to be a major lithium storage host. Nevertheless, we demonstrate here that capacity does not increase linearly with increasing carbon content. We show that the amount of SiO₄ units in the SiOC microstructure increases the initial capacity but decreases the cycling stability and rate capability of the material. Furthermore, the microstructure of the free carbon influences the electrochemical performance of the ceramic: More ordered graphitic clusters favor better rate capability performance.     

Nano-SiC-decorated Y2Si2O7 ceramic for enhancing electromagnetic waves absorption performance

To improve the electromagnetic (EM) wave absorption performance of rare earth silicate in harsh environments, this work synthesized dense SiC–Y₂Si₂O₇ composite ceramics with excellent EM wave absorption properties by using the polymer permeation pyrolysis (PIP) process, which introduced carbon and SiC into a porous Y₂Si₂O₇ matrix to form novel composite ceramics. SiC–Y₂Si₂O₇ composite ceramics with different numbers of PIP cycles were tested and analysed. The results show that the as-prepared composites exhibit different microstructures, porosities, dielectric properties and EM wave absorption properties. On the whole, the SiC–Y₂Si₂O₇ composite ceramics (with a SiC/C content of 29.88 wt%) show superior microwave absorption properties. The minimum reflection loss (RL_min) reaches ?16.1 dB when the thickness is 3.9 mm at 9.8 GHz. Moreover, the effective absorption bandwidth (EAB) included a broad frequency from 8.2 GHz to 12.4 GHz as the absorbent thickness varied from 3.15 mm to 4.6 mm. In addition, the EM wave absorption mechanism was analysed profoundly, which ascribed to the multiple mediums of nanocrystalline, amorphous phases and turbostratic carbon distributed in the Y₂Si₂O₇ matrix. Therefore, SiC–Y₂Si₂O₇ composite ceramics with high-efficiency EM wave absorption performance promise to be a novel wave absorbing material for applications in harsh environments.