Polyborosilazane with Broadly Tunable Boron Content for SiBCN Ceramics.

The high-temperature durability of SiBCN ceramics is significantly influenced by the boron concentration and synthesis methods. Although single-source synthetic routes allow one to obtain homogeneous ceramics at the atomic level, the content of the boron element therein is limited by borane (BH3). In this study, the synthesis of carborane-substituted polyborosilazanes was performed via a simple one-pot reaction of polysilazanes with alkyne bonds on the main chain and decaborododecahydrodiacetonitrile complexes with different molar ratios. This enabled one to vary the boron content from ∼0 to 40.00 wt %. The ceramic yields were in the range of 50.92-90.81 wt %. Independently of the borane concentration, SiBCN ceramics started to crystallize at 1200 °C, and B4C appeared as a new crystalline phase with increasing boron content. The introduction of boron inhibited the crystallization of Si3N4 and increased the crystallization temperature of SiC. The presence of the B4C phase improved both thermal stability and functional properties such as neutron-shielding characteristics of the ceramics. Therefore, this research opens up new prospects for the design of novel polyborosilanzes with great application potential.

Structural Evolution in Glassy Carbon Investigated Based on the Temperature Dependence of Young's Modulus.

As a non-graphitized carbon material, possessing exceptional hardness and chemical inertness, glassy carbon (GC) is often synthesized through the pyrolysis method, which includes a compression procedure of powdered precursor materials, thus increasing the costs for production of glassy carbon at an industrial scale. Direct preparation of GC via pyrolysis of bulk precursors is a low-cost approach but encounters challenges arising from an insufficient knowledge of carbon structure formation. In order to solve this problem, a new analysis of the temperature-dependent variation in Young's modulus of GC obtained by the pyrolysis of phenolic resin at 1000 °C, utilizing the impulse excitation technique (IET), was performed. Our findings demonstrate that there is a critical temperature range of 500-600 °C where pyrolysis leads to the most significant density change and GC is formed as a result. When GC samples are heated again, a significant structural reformation occurs in the same temperature range. It causes a decrease in stiffness, especially at heating rates >3 °C/min, and an interesting restorative effect-increase in stiffness when a GC sample is annealed at temperatures of 500-550 °C. These results bring important implications for the direct formation of large amounts of glassy carbon using bulk precursors.

Polyborosilazanes with Controllable B/N Ratio for Si-B-C-N Ceramics.

Polyborosilazanes with controllable B/N ratio were synthesized using high-boron-content m-carborane, dichloromethylsilane, and hexamethydisilazane. After high-temperature pyrolysis, Si-B-C-N quaternary ceramics with SiC and B4C as the main phases were obtained. The B/N ratio in the precursors corresponded to the change in the feeding ratio of carborane and dichloromethylsilane. The effects of boron content and B/N ratio on the ceramic precursors and microphase structure in Si-B-C-N quaternary ceramics were explored in detail through a series of analytical characterization methods. A high boron content results in a significant increase in the ceramic yield (up to 71 wt%) of polyborosilazanes, and at the same time, the B/N molar ratio was regulated from 28.4:1 to 1.62:1. The appearance of the B4C structure in the Si-B-C-N quaternary ceramics through the regulation of the B/N ratio, has rarely been reported.