Search Results (21)

Precursor-derived silicon carbide (SiC) ceramics have been widely used as absorbing materials, but the residual carbon sink produced by ceramicization limits their application under high-temperature and oxygen-containing conditions, such as the nozzle or jet vane of high-speed aircraft. In this paper, a novel molybdenum carbide/silicon carbide (Mo₂C/SiC) microwave-absorbing ceramic with a two-dimensional sheet structure was obtained through the pyrolysis of polycarbosilane-coated molybdenum sulfide (PCS@MoS₂). The results indicate that addition of an appropriate amount of MoS₂ can react with the free carbon generated during the pyrolysis of PCS, thereby reducing the material’s carbon content and forming Mo₂C. Concurrently, the layered structural characteristics of MoS₂ are utilized to create a two-dimensional composite structure within the material, which enhances the material’s absorption vastly. The as-prepared Mo₂C/SiC ceramics sintered at 1300 °C exhibit a minimum reflection loss (RL_min) of −46.49 dB at 8.96 GHz with a thickness of 2.6 mm. Additionally, the effective absorption bandwidth (EAB) of Mo₂C/SiC spans the entire X-band (8–12 GHz) due to the combined effect of multiple loss mechanisms. Full article

The microwave heating of silicon carbide is induced at a specific frequency of 2.45 GHz, leading to rapid heating within a temperature range of several hundred degrees Celsius. In this study, a mechanochemical curing process using iodine was employed to cure polycarbosilane (PCS), followed by the addition of carbon nanotubes (CNTs) to produce mixed polymer powders. The effects of the CNT addition on the microstructure, crystalline structure, and microwave heating properties were investigated. The findings indicated that the incorporation of CNTs generally led to a reduction in the number of micropores; however, when the CNT concentration exceeded 10 wt%, the aggregation of CNTs became evident. In terms of microwave heating properties, the sample containing 0.1 wt% CNTs achieved the highest temperature, whereas samples with a higher CNT content demonstrated a heating limit of approximately 500 °C. Remarkably, post-processing of the specimens with 10 wt% CNTs enabled rapid heating to approximately 1800 °C within 4 s of microwave exposure. Full article

The direct ink writing (DIW) process has been successfully used to prepare SiC-based composites from preceramic polymers due to the porous light weight, lower sintering temperature, and tailored design. However, it still presents challenges in improving the mechanical properties of composites and endowing them with multifunctionality. In this study, we present a 3D-printing strategy for preparing a graphene/SiC_p/SiC composite using the DIW process. A polycarbosilane (PCS)-based slurry containing graphene/SiC_p composite powder was developed and 3D-printed into scaffolds with a lattice structure, which were then pyrolyzed at 1500 °C to obtain a graphene/SiC_p/SiC composite. The weight loss, viscosity, and printability of the graphene/SiC_p/PCS slurry were evaluated, and it was determined that the slurry after 4 h of magnetic stirring was suitable for the DIW process. When heat-treated at above 800 °C in an N₂ atmosphere, PCS was first reacted with SiC_xO_y, which was further transformed into β-SiC and pyrocarbon. The 3D-printed lattice structure achieved porosity and low density, while the SiC_p reduced defects caused by large shrinkage during pyrolysis of PCS. Meanwhile, GNPs provided the composites with better conductivity and lower density. The density was as low as 1.08 g/cm³, the conductivity reached 670 S·m⁻¹, and the compressive strength was 4.3 MPa. Thus, a lightweight and porous SiC-based composite with high conductivity and strength can be prepared. Full article

Silicon carbide (SiC) has excellent mechanical and chemical properties and is used in a wide range of applications. It has the characteristic of rapidly heating up to several hundred degrees within one minute when irradiated with microwave radiation at 2.45 GHz. In this study, we investigated the oxidation curing process and microwave heating properties of polycarbosilane (PCS). A PCS disk-shaped green body was fabricated via uniaxial pressure molding. Silicon carbide was prepared by varying the pyrolysis temperature, and the heating characteristics of the microwaves were evaluated. The results showed that the samples pyrolyzed at 1300 °C after oxidation curing for 2 h at 180 °C rapidly heated up to 802 °C within 1 min, and the temperature remained constant for 120 min. The maximum temperature of the samples pyrolyzed at 1500 °C was relatively low, but the rate of heating was the highest. The microstructures and crystal structures of the microwaves as a function of the pyrolysis temperature were investigated. Full article

The thermal decomposition product of magnesium hydroxide (MH) is magnesium oxide (MgO), which serves as the foundational material for fireproof layer construction in the condensed phase. However, the weak interaction force between particles of MgO generated by thermal decomposition leads to the insufficient strength and poor adhesion ability of the fireproof layer. The fireproof layer was easily damaged and detached in this study, resulting in the low flame-retardant efficiency of MH. In this work, polycarbosilane (PCS) and divinyl benzene (DVB) were used to modify MH, and EVA/MH/PCS/DVB composites were made via melt blending. The flame-retardant properties of EVA/MH/PCS/DVB were evaluated using the limiting oxygen index (LOI), vertical combustion (UL-94), and a cone calorimeter (CONE). The thermal stability of the composites and flame retardants was analyzed using a thermogravimetric analyzer. The char layer structure was observed and analyzed using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The results indicate that the LOI of the EVA/MH/PCS/DVB with 50 wt.% flame retardants in total was as high as 65.1, which increased by 160% in comparison with EVA/MH. Furthermore, the total smoke production (TSP) of the EVA/MH/PCS/DVB composite decreased by 22.7% compared to EVA/MH/PCS; the thermal stability of the MH/PCS/DVB and EVA/MH/PCS/DVB improved to some extent; and the compact residual char after the combustion of EVA/MH/PCS/DVB had fewer cracks due to the adhesive effect induced by PCS/DVB. Full article

In the field of non-oxide ceramics, the polymer-derived ceramic (PDC) approach appears to be very promising, especially for obtaining easily shaped and homogeneous materials in terms of structure and composition. However, in order to reach a suitable form during the process, it is often necessary to study the rheology of preceramic polymers while they are modified during polymerisation or crosslinking reactions. Given this need in the understanding of the real-time rheology of macromolecules during their synthesis, a rheometer coupled with both an infrared spectrometer and a Raman probe is described as a powerful tool for monitoring in situ synthesised polycarbosilanes. Indeed, this original device allows one to control the viscosity of a hyberbranched polycarbosilane from defined difunctional and tetrafunctional monomers. Meanwhile, it links this evolution to structural modifications in the macromolecular structure (molar masses, dispersity and conformation), based on SEC-MALS analyses, synchronised by the monomer conversion determined by using Raman and infrared spectroscopies, a common denominator of the aforementioned instrumental platform. Full article

Continuous SiC fiber is a kind of high–performance ceramic fiber that combines many advantages, such as high strength, high modulus, high hardness and low density. It has excellent mechanical properties, high–temperature and oxidation resistance, which could be applied as essential reinforcement in advanced ceramic matrix composites (CMCs) in the fields of aerospace and advanced weaponry. Melt–spinnable polytitanocarbosilane (PTCS) is an important precursor, which can be used to prepare continuous SiC fibers through a precursor–derived method. In this work, low–softening–point polycarbosilane (LPCS) and tetrabutyl titanate were used to prepare polytitanocarbosilane with a ceramic yield of 67.5 wt% at 1000 °C. FT–IR, TGA, GPC, ¹H NMR, ²⁹Si NMR, and elemental analysis were used to analyze the composition and structure of the PTCS precursor. Finally, Si–C–Ti–B fibers with an average tensile strength of 1.93 GPa were successfully prepared by melt spinning, pre–oxidation, pyrolysis, and high–temperature sintering of the PTCS precursor. The strength retention rates were 71.5% and 79.8% after heat treatment at 1900 °C and 2000 °C under an argon atmosphere for 1 h, respectively. The strength retention rates of Si–C–Ti–B fibers are higher than those of commercial Hi–Nicalon fibers, Tyranno ZMI fibers and Hi–Nicalon S fibers. This work can lay a theoretical foundation and technical support for developing high-performance SiC ceramic fibers containing titanium and their ceramic matrix composites. Full article

Development of the organomorphic ceramic-matrix composites (CMCs), where the reinforcing preform is built using polymer fibers subject essentially to hot pressing, was motivated by a desire to obtain much higher structural uniformity as well as to reduce the number of the process steps involved in the production of CMCs. This paper addresses the peculiarities of the organomorphic silicon carbide preform formation process. Using X-ray phase analysis, tomography, mass and IR spectroscopy, and thermomechanical and X-ray microanalysis, both the properties of the initial fibers of polycarbosilane (PCS)—the silicon carbide fiber precursor—and their transformation in the preform while heated to 1250 °C under constant pressing at 10–100 kPa were studied. Analysis of the data obtained showed the organomorphic SiC preform relative density at a level of 0.3–0.4 to be ensured by self-bonding of the silicon carbide preform, resulting from the fact that during the low-temperature part of pyrolysis, easily polymerizing substances are released leaving a high coke residue, thus cementing the preform. Another possible factor of SiC framework self-bonding is the destruction of the polymer fibers during pyrolysis of various PCS preforms differing in their methylsilane composition (for example, dimethylsilane), where deposition of silicon carbide on the contacting fibers starts as early as at 450–500 °C. Full article

The rheological properties of macromolecules represent one of the fundamental features of polymer systems which expand the possibilities of using and developing new materials based on them. In this work, we studied the shear-stress relaxation of the second generation PAMAM and PPI dendrimer melts by atomistic molecular dynamics simulation. The time dependences of relaxation modulus G(t) and the frequency dependences of the storage G′(ω) and loss G″(ω) moduli were obtained. The results were compared with the similar dependences for the polycarbosilane (PCS) dendrimer of the same generation. The chemical structure of the dendrimer segments has been found to strongly influence their mechanical relaxation. In particular, it has been shown that hydrogen bonding in PAMAM dendrimers leads to an entanglement of macromolecules and the region is observed where G′(ω) > G″(ω). This slows down the mechanical relaxation and rotational diffusion of macromolecules. We believe that our comprehensive research contributes to the systematization of knowledge about the rheological properties of dendrimers. Full article

A polymer ceramic precursor material—polycarbosilane (PCS)—was used as a synergistic additive with magnesium hydroxide (MH) in flame-retardant ethylene–vinyl acetate copolymer (EVA) composites via the melt-blending method. The flame-retardant properties of EVA/MH/PCS were evaluated by the limiting oxygen index (LOI) and a cone calorimeter (CONE). The results revealed a dramatic synergistic effect between PCS and MH, showing a 114% increase in the LOI value and a 46% decrease in the peak heat release rate (pHRR) with the addition of 2 wt.% PCS to the EVA/MH composite. Further study of the residual char by scanning electron microscopy (SEM) proved that a cohesive and compact char formed due to the ceramization of PCS and close packing of spherical magnesium oxide particles. Thermogravimetric analysis coupled with Fourier-transform infrared spectrometry (TG–FTIR) and pyrolysis–gas chromatography coupled with mass spectrometry (Py–GC/MS) were applied to investigate the flame-retardant mechanism of EVA/MH/PCS. The synergistic effect between PCS and MH exerted an impact on the thermal degradation products of EVA/MH/PCS, and acetic products were inhibited in the gas phase. Full article

Boron nitride (BN) ceramic fibers containing amounts of silicon nitride (Si₃N₄) were prepared using hybrid precursors of poly(tri(methylamino)borazine) (PBN) and polycarbosilane (PCS) via melt-spinning, curing, decarburization under NH₃ to 1000 °C and pyrolysis up to 1600 °C under N₂. The effect of Si₃N₄ contents on the microstructure of the BN/Si₃N₄ composite ceramics was investigated. Series of the BN/Si₃N₄ composite fibers containing various amounts of Si₃N₄ from 5 wt% to 25 wt% were fabricated. It was found that the crystallization of Si₃N₄ could be totally restrained when its content was below 25 wt% in the BN/Si₃N₄ composite ceramics at 1600 °C, and the amorphous BN/Si₃N₄ composite ceramic could be obtained with a certain ratio. The mean tensile strength and Young’s modulus of the composite fibers correlated positively with the Si₃N₄ mass content, while an obvious BN (shell)/Si₃N₄ (core) was formed only when the Si₃N₄ content reached 25 wt%. Full article

In the field of non-oxide ceramic composites, and by using the polymer-derived ceramic route, understanding the relationship between the thermal behaviour of the preceramic polymers and their structure, leading to the mechanisms involved, is crucial. To investigate the role of Zr on the fabrication of ZrC–SiC composites, linear or hyperbranched polycarbosilanes and polyzirconocarbosilanes were synthesised through either “click-chemistry” or hydrosilylation reactions. Then, the thermal behaviours of these polymeric structures were considered, notably to understand the impact of Zr on the thermal path going to the composites. The inorganic materials were characterised by thermogravimetry-mass spectrometry (TG-MS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). To link the macromolecular structure to the organisation involved during the ceramisation process, eight temperature domains were highlighted on the TG analyses, and a four-step mechanism was proposed for the polymers synthesised by a hydrosilylation reaction, as they displayed better ceramic yields. Globally, the introduction of Zr in the polymer had several effects on the temperature fragmentation mechanisms of the organometallic polymeric structures: (i) instead of stepwise mass losses, continuous fragment release prevailed; (ii) the stability of preceramic polymers was impacted, with relatively good ceramic yields; (iii) it modulated the chemical composition of the generated composites as it led, inter alia, to the consumption of free carbon. Full article

Carbon nanotubes (CNTs) coated with SiC coating was successfully prepared by pyrolysis of polycarbosilane (PCS) used as a precursor. The function of pyrolysis temperature on the oxidation resistance and the dielectric properties of CNTs/SiC were studied in X-band. The results demonstrate that the obtained dense SiC film can prevent the oxidation of CNTs when the pyrolysis temperature reaches 600 °C. Correspondingly, after heat treatment is at 400 °C for 200 h, the mass loss of P-600 is less than 1.86%, and the real and imaginary parts of the dielectric constant nearly keep constant (ε′ from 14.2 to 14, and ε″ from 5.7 to 5.5). SiC-coated CNTs have a better oxidation resistance than pristine CNTs. Therefore, this work, with a facile preparation process, enhances the oxidation resistance of CNTs at high temperature for a long time and maintains a stable dielectric property, which means CNTs/SiC composites can be good candidates for applications in the field of high-temperature absorbers. Full article

A series of carbosilane dendrimers of the 4th, 6th, and 7th generations with a terminal trimethylsilylsiloxane layer was synthesized. Theoretical models of these dendrimers were developed, and equilibrium dendrimer conformations obtained via molecular dynamics simulations were in a good agreement with experimental small-angle X-ray scattering (SAXS) data demonstrating molecule monodispersity and an almost spherical shape. It was confirmed that the glass transition temperature is independent of the dendrimer generation, but is greatly affected by the chemical nature of the dendrimer terminal groups. A sharp increase in the zero-shear viscosity of dendrimer melts was found between the 5th and the 7th dendrimer generations, which was qualitatively identical to that previously reported for polycarbosilane dendrimers with butyl terminal groups. The viscoelastic properties of high-generation dendrimers seem to follow some general trends with an increase in the generation number, which are determined by the regular branching structure of dendrimers. Full article

In this work, a (SiC-AlN)/ZrB₂ composite with outstanding mechanical properties was prepared by using polymer-derived ceramics (PDCs) and hot-pressing technique. Flexural strength reached up to 460 ± 41 MPa, while AlN and ZrB₂ contents were 10 wt%, and 15 wt%, respectively, under a hot-pressing temperature of 2000 °C. XRD pattern-evidenced SiC generated by pyrolysis of polycarbosilane (PCS) was mainly composed by 2H-SiC and 4H-SiC, both belonging to α-SiC. Micron-level ZrB₂ secondary phase was observed inside the (SiC-AlN)/ZrB₂ composite, while the mean grain size (MGS) of SiC-AlN matrix was approximately 97 nm. This unique nano-micron hybrid microstructure enhanced the mechanical properties. The present investigation provided a feasible tactic for strengthening ceramics from PDCs raw materials. Full article