Polymer precursor synthesis of novel ZrC–SiC ultrahigh-temperature ceramics and modulation of their molecular structure

In this study, ZrC–SiC composite ceramics were prepared with varying Zr/Si molar ratios using sol–gel method. Composites were characterized by Fourier-transform infrared spectroscopy (FT–IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, and energy-dispersive X-ray spectroscopy (EDS). FT–IR analysis confirmed macromolecular network structure of composites, in which the precursor is composed of polyvinyl butyral (PVB) as main chain, silane molecules are interlinked via –OH moieties in PVB side chains, and Zr atoms are crosslinked with Si in corresponding proportion. Ceramic precursor begins to decompose at a temperature exceeding 1300 °C and is completely transformed into ZrC–SiC composite ceramics with corresponding Zr/Si molar ratio at 1600 °C. Raman spectroscopy and TEM results reveal that after annealing at 1600 °C, ZrC powder uniformly covers surface of SiC ceramics, and high-crystallinity graphite carbon covers ZrC powder.     

In situ toughened two-phase B12(C,Si, B)3–SiC ceramics fabricated via liquid silicon infiltration

In situ toughened B₁₂(C, Si, B)₃–SiC ceramics were successfully fabricated via the liquid silicon infiltration process. Two types of B₁₂(C, Si, B)₃ phases, with high and low Si contents, respectively, and plate-like SiC particles were formed by the reaction between B₄C and Si. The in situ toughening mechanism involved two effects: the multiple crack deflections caused by the increased grain boundaries, and the pullout and rupture of a significant amount of plate-like SiC particles. Block ceramics with a high fracture toughness of 6.5 ± 0.5 MPa·m^1/2 were fabricated via the in situ toughening mechanism. A strong interface bond was present between the high- and low-B₄C-content layers in the laminated ceramics, which led to residual compressive stress inside the materials. As a result, the laminated structural design enhanced the fracture toughness to 7.5 ± 0.5 MPa·m^1/2.     

Preparation,microstructure and ion-irradiation damage behavior of Al4SiC4-added SiC ceramics

Single-phase Al₄SiC₄ powder with a low neutron absorption cross section was synthesized and mixed with SiC powder to fabricate highly densified SiC ceramics by hot pressing. The densification of SiC ceramics was greatly improved by the decomposition of Al₄SiC₄ and the formation of aluminosilicate liquid phase during the sintering process. The resulting SiC ceramics were composed of fine equiaxed grains with an average grain size of 2.0 μm and exhibited excellent mechanical properties in terms of a high flexure strength of 593 ± 55 MPa and a fracture toughness of 6.9 ± 0.2 MPa m^1/2. Furthermore, the ion-irradiation damage in SiC ceramics was investigated by irradiating with 1.2 MeV Si⁵⁺ ions at 650 °C using a fluence of 1.1 × 10¹⁶ ions/cm², which corresponds to 6.3 displacements per atom (dpa). The evolution of the microstructure was investigated by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The breaking of Si–C bonds and the segregation of C elements on the irradiated surface was revealed by XPS, whereas the formation of Si–Si and C–C homonuclear bonds within the Si–C network of SiC grains was detected by Raman spectroscopy.     

Polymer precursor‐derived HfC–SiC ultrahigh‐temperature ceramic nanocomposites

Due to poor mechanical properties and antioxidation properties, etc of single phase ultrahigh‐temperature ceramics (UHTCs), the second phase such as SiC was usually introduced for improving those properties. Herein, a novel stratagem for synthesis of binary HfC–SiC ceramics has been presented. A Hf–O–Hf polymer as a HfO₂ precursor has been synthesized for preparing soluble HfC–SiC precursors with high solid content and low viscosity solutions without additional organic solvents. The structure of PHO was characterized by FTIR and ¹H‐NMR, the crystalline behavior and morphologies of polymer‐derived ceramics were identified by XRD, SEM‐EDS, and TEM. It was shown that PHO firstly transformed into HfO₂, and then reacted with in situ carbon derived from DVB and PCS thus producing cubic HfC through carbothermal reduction. In addition, the obtained HfC–SiC nanopowders exhibited spherical morphology with a diameter less than 100 nm, while the Hf, Si, and C are homogeneously distributed.     

Synthesis,densification, and microstructure of TaC‐TaB2‐SiC ceramics

The usual way to prepare TaC‐TaB₂ ceramics by adding B₄C to TaC leads to formation of residual C, which degrades samples’ mechanical properties. To eliminate the residual C, we suggest incorporating Si together with B₄C into TaC ceramics, resulting in new ultrahigh‐temperature ceramics (TaC‐TaB₂‐SiC). Dense ceramics (>99%) with SiC volume fraction ranging from 15.86% to 41.04% were fabricated by reactive spark plasma sintering at 1900°C for 5 minutes. The formation of SiO₂‐based transient liquid phase was evidenced by the “film” in intermediate products, which can promote densification. The fine‐grained microstructure in final products was found to be associated with the in situ formed SiC, which impeded TaC and TaB₂ grains from coarsening by the pinning effect. Besides, ultrafine TaB₂ grains (~100 nm) produced during the reaction and then rearranged in liquid also contributed to grain refinement. Compared to TaC‐TaB₂(‐C) ceramics prepared from TaC and B₄C, the acquired composites exhibit better mechanical properties, due to their fine‐grained microstructures and the elimination of residual C.     

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.     

Physical,thermal and ablative performance of CVI densified urethane-mimetic SiC preforms containing in situ grown Si3N4 whiskers

A two-step process has been developed for silicon carbide (SiC) coated polyurethane mimetic SiC preform containing silicon nitride (Si₃N₄) whiskers. SiC/Si₃N₄ preforms were prepared by pyrolysis/siliconization treatment at 1600 °C, of powder compacts containing rigid polyurethane, novolac and Si, forming a porous body with in situ grown Si₃N₄ whiskers. The properties were controlled by varying Si/C mole ratios such as 1–2.5. After densification using a chemical vapour infiltration, the resulting SiC/Si₃N₄/SiC composites showed excellent oxidation resistance, thermal conductivity of 4.32–6.62 Wm⁻¹ K⁻¹, ablation rate of 2.38 × 10⁻³ − 3.24 × 10⁻³ g cm⁻² s and a flexural strength 43.12–55.33 MPa for a final density of 1.39–1.62 gcm⁻³. The presence of a Si₃N₄ phase reduced the thermal expansion mismatch resulting in relatively small cracks and well-bonded layers even after ablation testing. This innovative two-step processing can provide opportunities for expanded design for using SiC/Si₃N₄/SiC composites being lightweight, inexpensive, homogeneous and isotropic for various high temperature applications.     

Synthesis and pyrolysis of non-oxide precursors for ZrC/SiC and HfC/SiC composite ceramics

Multiphase ceramics like ZrC/SiC are promising candidates as ultra-high temperature ceramics for applications in extreme environments. In this work, non-oxide precursors for ZrC/SiC and HfC/SiC composite ceramics were synthesized by a one-pot reaction of three components – metal source, silicon source, and activating reagent. Molecular structures of the precursors were identified by ¹H NMR and FTIR. Transformation process of the precursors to the ZrC/SiC ceramics was investigated via XRD and SEM. After heat-treatment at 1600 °C under argon, the obtained ZrC/SiC and HfC/SiC ceramics features a particle size of 100–200 nm and high metal content without excess carbon. The elemental composition of pyrolyzed ceramics can be tuned by varying the ratio of the reagents in the synthesis of precursors. This strategy also inspires a facile fabrication of composite ceramics with other elemental compositions.     

Effect of carbon content on electrical,thermal, and mechanical properties of porous SiC ceramics with B4C and C additives

The electrical, thermal, and mechanical properties of porous SiC ceramics with B₄C-C additives were investigated as functions of C content and sintering temperature. The electrical resistivity of porous SiC ceramics decreased with increases in C content and sintering temperature. A minimal electrical resistivity of 4.6 × 10^?2 Ω·cm was obtained in porous SiC ceramics with 1 wt% B₄C and 10 wt% C. The thermal conductivity and flexural strength increased with increasing sintering temperature and showed maxima at 4 wt% C addition when sintered at 2000 °C and 2100 °C. The thermal conductivity and flexural strength of porous SiC ceramics can be tuned independently from the porosity by controlling C content and sintering temperature. Typical electrical resistivity, thermal conductivity, and flexural strength of porous SiC ceramics with 1 wt% B₄C-4 wt% C sintered at 2100 °C were 1.3 × 10^?1 Ω·cm, 76.0 W/(m·K), and 110.3 MPa, respectively.     

Microstructure and properties of B4C-SiC composites prepared by polycarbosilane-coating/B4C powder route

B₄C-SiC composites with fine grains were fabricated with hot-pressing pyrolyzed mixtures of polycarbosilane-coated B₄C powder without or with the addition of Si at 1950 °C for 1 h under the pressure of 30 MPa. SiC derived from PCS promoted the densification of B₄C effectively and enhanced the fracture toughness of the composites. The sinterability and mechanical properties of the composites could be further improved by the addition of Si due to the formation of liquid Si and the elimination of free carbon during sintering. The relative density, Vickers hardness and fracture toughness of the composites prepared with PCS and 8 wt% Si reached 99.1%, 33.5 GPa, and 5.57 MPa m^1/2, respectively. A number of layered structures and dislocations were observed in the B₄C-SiC composites. The complicated microstructure and crack bridging by homogeneously dispersed SiC grains as well as crack deflection by SiC nanoparticles may be responsible for the improvement in toughness.     

Dielectric and electromagnetic properties of amorphous PDCs-Si(Al)CNO with different Al contents in X-band

Amorphous polymer-derived Si(Al)CNO ceramics with different Al contents were successfully prepared using polyvinylsilazane (PVSZ) doped with different mass fractions (0 to 15 wt%) of aluminum tri-sec-butoxide (ASB) as the precursors. The thermogravimetric, crystal morphology, microstructure, electrical conductivity and dielectric properties of Si(Al)CNO ceramics were characterized and tested, respectively. The results show that the porosity of Si(Al)CNO ceramics first decreased and then increased with the increase of ASB doping content. The electrical conductivity of SiAlCNO-5, SiAlCNO-10 and SiAlCNO-15 ceramics gradually decreased from 2.80 × 10^-9 to 0.89 × 10^-9 (Ω cm)^-1. Their conductivity was related to free carbon in the ceramics based on Raman spectroscopy. The average permittivity of SiCNO, SiAlCNO-5, SiAlCNO-10 and SiAlCNO-15 ceramics gradually increased from 3.63 to 3.93 with the increase of ASB doping content in X-band. The dielectric loss of SiAlCNO ceramics doped with ASB was smaller than that of SiCNO ceramics. But with the continuous increase of ASB doping content, the dielectric loss of SiAlCNO ceramics also increased. The permittivity and dielectric loss of Si(Al)CNO ceramics were related to their porosity and electrical conductivity. The average absorption coefficient of Si(Al)CNO ceramics were less than 0.020, while their transmission coefficient were greater than 0.500. It was found that the amorphous Si(Al)CNO ceramics exhibit good electromagnetic wave transmission properties.     

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.     

Pore structure and thermal oxidation curing behavior of porous polymer derived ceramics with superhigh porosity fabricated by freeze casting

Porous ceramics with porosity up to 92.5 % have been successfully fabricated by freeze casting of polycarbosilane (PCS) solution. The effect of PCS concentration and thermal oxidation curing on the pore structure and compressive properties was investigated. Curing mechanism and thermodynamics were illuminated through analyzing the molecular structure, curing activation energy, and curing degree. Porous ceramics, mainly composed of SiC and a small amount of SiO₂, have dendritic pore structure which well replicates the solidification morphology of camphene solvent. Results of FT-IR and Gaussian computation of PCS electron density show that Si–H and Si–CH₃ bonds play a dominant role in thermal oxidation curing reaction. Both curing degree and ceramic yield increase with the increase in curing temperature and time. The curing degree of Si–H bond is close to 52 % and the corresponding ceramic yield is about 83 % when the porous PCS was cured at 200 °C for 90 min. Both polymer concentration and curing time have influences on the compressive strength of porous ceramics.     

In situ pressureless sintering of SiC/MoSi2 composites

SiC-reinforced MoSi₂ composites have been successfully prepared by in situ pressureless sintering from elemental powders of Mo, Si and C. Meanwhile, the evolutions of the samples’ microstructure and phase at different temperatures were investigated by using X-ray diffraction (XRD) and scanning electron microscopy (SEM) with an energy dispersive X-ray spectrometer (EDS). It can be seen that at the temperature of 1100 °C, the main phases were Mo and Si, accompanying with a small amount of rich molybdenum products Mo₅Si₃ and Mo₃Si. Then the main phases changed to MoSi₂ and SiC when the sintering temperature reached 1300 °C. Finally we obtained MoSi₂/SiC composites with well-dispersed SiC particles after sintering at the temperature of 1550 °C for 120 min. The evolution of porosity in these composites fits the porosity reduction model well developed by Pines and Bruck, which revealed the particle agglomeration in the composites. The flexural strength and fracture toughness of 10% SiC/MoSi₂ composites were up to 274.5 MPa and 5.5 MPa m^1/2, increased by approximately 40.8% and 30.6% compared with those of monolithic MoSi₂, respectively.     

Effect of co-addition of SiC and WC on the densification behaviour and microstructural evolution of TiC-based composites

In the present study, the effect of simultaneous incorporation of SiC and WC additives on the densification behaviour and microstructural development of TiC-based composites is studied. Four different TiC-SiC-WC (TSW) composites with varying SiC and WC content were synthesized by ultrasonic wet milling followed by spark plasma sintering (SPS) at 1750 °C for 5 min under 40 MPa external pressure. The average particle size of the ultrasonic wet-milled mixture underwent an appreciable refinement from 2.48 μm (un-milled powder) to between 0.9 and 1.25 μm. The sintered compacts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and thermodynamic assessment. All TSW sintered specimens exhibited a relative density of greater than 98% with TiC +10 wt% SiC +15 wt% WC reaching the highest value of 99.2%. The XRD analysis and microstructural evaluation confirmed the in-situ formation of Ti₃SiC₂ compound for specimens TiC +15 wt% SiC +10 wt% WC and TiC +20 wt% SiC +5 wt% WC as suggested by the thermodynamic evaluation. Besides, except for specimen TiC +20 wt% SiC +5 wt% WC, some of the SiC grains with unclean grain boundaries were found to be dissolved partially within the (Ti, W) C solid solution, thereby indicating the formation of (Ti, W, Si) C solid solutions as confirmed by the SEM/EDS analysis. The optimum hardness and indentation fracture toughness of 22.43 GPa and 6.54 MPa m^½ were obtained for the samples TS10W15 and TS15W10, respectively. Crack deflection, branching, and bridging induced by the untwine SiC grains, partly un-dissolved WC particles, and (Ti, W) C solid solution phase are among the main toughening mechanisms responsible for improving the fracture toughness of the co-reinforced specimens besides the break of intertwining SiC grains.     

Microstructural,electrical, and mechanical properties of conductive SiC ceramics fabricated by spark plasma sintering

Nitrogen (N)-doped conductive silicon carbide (SiC) of various electrical resistivity grades can satisfy diverse requirements in engineering applications. To understand the mechanisms that determine the electrical resistivity of N-doped conductive SiC ceramics during the fast spark plasma sintering (SPS) process, SiC ceramics were synthesized using SPS in an N₂ atmosphere with SiC powder and traditional Al₂O₃–Y₂O₃ additive as raw materials at a sintering temperature of 1850–2000°C for 1–10 min. The electrical resistivity was successfully varied over a wide range of 10⁻³–10¹ Ω cm by modifying the sintering conditions. The SPS-SiC ceramics consisted of mainly Y–Al–Si–O–C–N glass phase and N-doped SiC. The Y–Al–Si–O–C–N glass phase decomposed to an Si-rich phase and N-doped Y_xSi_yC_z at 2000°C. The Vickers hardness, elastic modulus, and fracture toughness of the SPS-SiC ceramics varied within the ranges of 14.35–25.12 GPa, 310.97–400.12 GPa, and 2.46–5.39 MPa m^1/2, respectively. The electrical resistivity of the obtained SPS-SiC ceramics was primarily determined by their carrier mobility.     

Microstructural characterization using orientation imaging microscopy of cellular Si/SiC ceramics synthesized by replication of Indian dicotyledonous plants

Woods from three dicotyledonous plants of local origin (mango Mangifera indica), jackfruit (Artocarpus integrifolia) and teak (Tectona grandis) were transformed by pyrolysis into carbonaceous preforms and subsequently converted into cellular Si/SiC ceramics by liquid Si-infiltration and reaction. The pyrolyzed mango, jackfruit and teak were characterized in terms of pyrolysis weight loss, shrinkages, bulk density and microstructures. The Si-infiltrated pyrolyzed woods were found to have densities and porosities in the range of 2.46–2.60 gm cm⁻³ and 1.5–3.6 vol.% respectively. SEM imaging confirmed the preservation of microcellular tissue anatomy of the precursor wood structure in the morphologies of final ceramics. The end ceramics were investigated for the phases present and for crystallographic microtexture. A combination of XPS (X-ray photoelectron spectroscopy), XRD (X-ray diffraction) and OIM (orientation imaging microscopy) was used to establish the presence and the relative locations of silicon (Si), silicon carbide (SiC) and graphite (C). Fine SiC grains did typically surround coarse crystals of Si – the latter had significant presence of Σ3 twin boundaries. Graphite was primarily present in the regions containing SiC and was more textured than the SiC. Distinct orientation relationship could be established between the graphite crystals and the Si grains containing them.     

Fabrication of porous silicon carbide ceramics with high porosity and high strength

Unique porous SiC ceramics with a honeycomb structure were fabricated by a sintering-decarburization process. In this new process, first a SiC ceramic bonded carbon (SiC/CBC) is sintered in vacuum by spark plasma sintering, and then carbon particles in SiC/CBC are volatized by heating in air at 1000 °C without shrinkage. The honeycomb structure has at least two different sizes of pores; ∼20 μm in size resulting from carbon removal; and smaller open pores of 2.1 μm remaining in the sintered SiC shell. The total porosity is around 70% and the bulk density is 0.93 mg/m³. The bending and compressive strengths are 26 MPa, and 105 MPa, respectively.     

Microstructure and properties of porous SiC ceramics with AlN–RE2O3 (RE = Sc,Y, Lu) additives

The intrinsic microstructure and crystalline phases of porous SiC ceramics with 5 vol% AlN–RE₂O₃ (RE = Sc, Y, Lu) additives were characterized by high-resolution transmission microscopy with energy-dispersive spectroscopy and X-ray diffraction. The homophase (SiC/SiC) and heterophase (SiC/junction) boundaries were found to be clean; that is, amorphous films were not observed in the specimens. In addition, ScN, YN, and LuN were formed as secondary phases. The flexural strength and thermal conductivity of the ceramics were successfully tuned using different additive compositions. The flexural strength of the ceramics improved by a factor of ~3, from 11.7 MPa for the specimen containing Y₂O₃ to 34.2 MPa for that containing Sc₂O₃, owing to the formation of a wide necking area between SiC grains. For the same reason, the thermal conductivity improved by ~56%, from 9.2 W·m^?1·K^?1 for the specimen containing Lu₂O₃ to 14.4 W·m^?1·K^?1 for that containing Sc₂O₃.     

Densification,microstructure, and mechanical properties of ZrC–SiC ceramics

ZrC–SiC ceramics were fabricated by high-energy ball milling and reactive hot pressing of ZrH₂, carbon black, and varying amounts of SiC. The ceramics were composed of nominally pure ZrC containing 0 to 30 vol% SiC particles. The relative density increased as SiC content increased, from 96.8% for nominally pure ZrC to 99.3% for ZrC-30 vol% SiC. As SiC content increased from 0 to 30 vol%, Young's modulus increased from 404 ± 11 to 420 ± 9 GPa and Vickers hardness increased from 18.5 ± 0.7 to 23.0 ± 0.5 GPa due to a combination of the higher relative density of ceramics with higher SiC content and the higher Young's modulus and hardness of SiC compared to ZrC. Flexure strength was 308 ± 11 MPa for pure ZrC, but increased to 576 ± 49 MPa for a SiC content of 30 vol%. Fracture toughness was 2.3 ± 0.2 MPa·m^1/2 for pure ZrC and increased to about 3.0 ± 0.1 MPa·m^1/2 for compositions containing SiC additions. The combination of high-energy ball milling and reactive hot pressing was able to produce ZrC–SiC ceramics with sub-micron grain sizes and high relative densities with higher strengths than previously reported for similar materials.