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.     

Dimethylaminoborane-modified copolysilazane as a novel precursor for high-temperature resistant SiBCN ceramics

A novel polyborosilazane (PBSZ) precursor was synthesized by the reaction of copolysilazane (CPSZ) with dimethylaminoborane (DMAB). The resultant PBSZs were characterized by FT-IR and NMR spectroscopy. It was found that both, BH and NH bonds of DMAB, react with CPSZ leading to boron containing copolysilazanes. The polyborosilazanes were pyrolyzed at 900 °C in argon and the precursor-to-ceramic transformation was studied by TG-MS and FT-IR spectroscopy. The modification of CPSZ with DMAB enhances the cross-linking of the resulting PBSZ, which increases the final ceramic yield from 57.8% to 77.5–80.0%. Finally, the ceramics obtained at 900 °C were subsequently annealed at different temperatures ranging from 1200 to 1800 °C. The heat-treated products were characterized by X-ray powder diffraction and electron microscopy. Accordingly, the resulting SiBCN ceramics exhibit significantly enhanced high-temperature-resistance with respect to decomposition and crystallization as compared with boron-free CPSZ-derived SiCN ceramics. TEM results support that the thermal stability is due to the segregation of a BN(C) phase as interlayer between Si₃N₄ nanocrystals formed during heat-treatment of SiBCN at T > 1500 °C.     

Synthesis and pyrolysis mechanism of a novel polymeric precursor for SiBN ternary ceramic fibers

A novel polymeric precursor polyborosilazane (PBSZ) for SiBN ternary ceramic fibers was successfully synthesized from trichlorosilane (HSiCl₃), boron trichloride (BCl₃) and hexamethyldisilazane (HDMZ) by a simple one step reaction process. The chemical structures and ceramic yield of the PBSZ precursors were investigated by NMR spectroscopy, FT-IR and TGA. The preparation of PBSZ fibers was conducted in a lab-scale melt-spinning equipment at a spinning speed of 130 m/min. SiBN ternary ceramic fibers were obtained after the non-fusible treatment and pyrolysis of PBSZ fibers in an NH₃ atmosphere. The pyrolysis mechanism, high-temperature behavior and morphologies of the SiBN ternary ceramic fibers were investigated by NMR, XRD, TEM and SEM. The obtained SiBN ternary ceramic fibers had good flexibility, and possessed a tensile strength of 0.84 GPa with a diameter of ∼18 μm. Furthermore, these SiBN ceramic fibers exhibited excellent thermal stability, and maintained the amorphous state up to 1600 °C.     

Synthesis,characterization and ceramization of a novel vinyl-rich liquid precursor for Si(O)C ceramic

Polymethylsilane (PMS) was partially modified with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane ([CH₃(CH₂åCH)SiO]₄, D4Vi) via conventional hydrosilylation. The as-synthesized vinyl-rich liquid precursor (V-PMS) was characterized by the viscosity test, gel-permeation chromatography, Fourier-transform infrared spectroscopy, nuclear magnetic resonances spectroscopy. The results indicate that the obtained precursor is well soluble in common solvents and exhibits a controllable viscosity of 326.9–714.6 mPa s at room temperature. The thermal properties of V-PMS were investigated by differential scanning calorimetry and thermogravimetric analysis. The V-PMS can be cured readily at 150 °C in inert atomosphere. The ceramic yield of V-PMS reaches 81% at 1200 °C, 38% higher than that of PMS. The final pyrolytic residue is hard, dense monolithic up to 1400 °C under Ar atmospheres. The controllable viscosity, excellent thermal curability and high ceramic yield enable the liquid precursor a promising material to shape various Si(O)C ceramic materials for high-temperature application.     

Synthesis and thermal performance of polymer precursor for ZrC ceramic

A novel ZrC preceramic precursor (PZC) was compounded via liquid phase chemical reaction without any organic solvent choosing ZrOCl₂·8H₂O and polyvinyl alcohol as Zr source and C source, respectively. The composition and structure of ZrC precursor were analysed through XRD, FT-IR, XPS and SEM. The results showed both Zr-O-C bonds and Zr-O bonds existed in the precursor. The results observed by SEM showed that many irregular particles were generated, whose particle sizes were mainly in the range of 0.2–3 μm. In addition, particle aggregation can be easily observed. Besides, the thermal property and pyrolysis process of PZC were studied. In accordance with XRD, the initial temperature of the earliest detection of ZrC in pyrolysis products of PZC was 1300 °C. Monoclinic ZrO₂ and tetragonal ZrO₂ can be observed at this temperature as well. Ulteriorly, when the pyrolysis temperature was risen up to 1500 °C, only ZrC ceramic can be found.     

Simple and low-cost synthetic route for SiBCN ceramic powder from a boron-modified cyclotrisilazane

This study reports a simple and low-cost synthetic route for preparing SiBCN ceramic powder via pyrolysis of boron-modified cyclotrisilazane (BCTS). BCTS resins were synthesized by reacting boric acid with 1, 3, 5-trimethyl-1′, 3′, 5′-trivinylcyclotrisilazane (CTS) in the molar ratio of 1:1, 1:3, and 1:5. The boron modification in CTS resin resulted in optimum properties for preceramic polymers such as solubility in common solvents, processable viscosity (<20 cps) and high ceramic yield (>80 wt. %). The polymer to ceramic conversion was carried out at 1450 and 1650°C under a nitrogen atmosphere. The study demonstrated that the changes in CTS concentration and pyrolysis temperature significantly affected the evolution of ceramic phases, morphology, and elemental composition which were thoroughly investigated through XRD, SEM, and HRTEM techniques. The results revealed the formation of β-SiC, β-Si₃N₄, and oxide ceramic phases with BCTS in the molar ratio of 1:1 and 1:3; whereas, β-SiC, β-Si₃N₄, and turbostratic BN(C) ceramic phases were obtained with BCTS in the molar ratio of 1:5.     

Design and synthesis of a novel spinnable polyborazine precursor with high ceramic yield via one-pot copolymerization

Synthesis of spinnable precursors with high ceramic yield is a crucial issue in BN fibers manufacturing by polymer-derived ceramics (PDCs) route. Spinnability and high ceramic yield are the basis of precursor processability, formability, and mechanical properties. Herein, based on DFT simulation, we designed and synthesized a novel polymer precursor poly[2-propylamino-4,6-bis(methylamino) borazine-co-tri(methylamino) borazine] (PPMAB) via a facile one-pot copolymerization strategy. The random copolymerization model of condensations was obtained through DFT calculation. The molecular chain structure, molecular weight, and molecular weight distribution were optimized by adjusting the synthesis conditions. The precursor PPMAB-1:1 with a high ceramic yield of 62.43% and concentrated molecular weight distribution (PDI < 1.3) was obtained. Rheological performance research revealed the excellent and stable spinnability of PPMAB-1:1 by the tunable viscosity and low flow activation energy (23.61 kJ/mol). As a demonstration of spinnability, continuous BN fiber with a fine diameter (>10 km, 7.60 ± 1.13 μm, and 1.6 GPa) was obtained after melt spinning. The present work effectively improved the ceramic yield and spinnability of polyborazine precursors. Simultaneously, it can be used extensively as a universal method to prepare multifunctional copolymers with precise structure control.     

Synthesis and nitrosation of processible copolymers from pyrrole and ethylaniline

A series of copolymers were prepared by an oxidative polymerization of pyrrole (PY) and 2-ethylaniline (EA) in HCl. The polymerization process was followed by tracking open-circuit potential and temperature of the reaction solutions. The fine particles of the PY/EA copolymers obtained in situ were further N-nitrosated for the first time in order to improve their solubility. The size, structure, and properties of the fine particles and their N-nitroso products were systematically characterized by laser particle size analyzer, FTIR, UV-vis, GPC, solution casting, and TG techniques. It is found that both the open-circuit potential and temperature of the solutions exhibit a maximum during the copolymerization, while the particle size of the copolymers will decrease monotonically with prolongating polymerization time or doping. Both the polymerization yield and molecular weight of the copolymers exhibit a minimum with PY/EA ratio, indicating a mutual retarding effect between the PY and EA monomers. The top potential and top temperature of the copolymerization as well as the particle size and its distribution, solubility, film-forming ability, electroconductivity, and thermostability of the copolymers all depend significantly on the PY/EA ratio. The PY/EA copolymers have good solubility in the solvents with the solubility parameter from 23 to 27 J^1/2/cm^3/2, dielectric constant greater than 12 and polarity index from 6.4 to 7.4 and their solubility becomes further better with increasing EA content. The N-nitrosation of copolymers can also improve their solubility in polar solvents furthermore. The copolymers with PY content of less than 30 mol% in NMP and THF exhibit good thin-film formability. The copolymer films become smoother and tougher with increasing EA content and by N-nitrosation. With increasing PY content, the decomposition temperature, maximum decomposition rate, char yield at 500 °C, and activation energy all decrease but decomposition order increases. The temperature at the maximum weight-loss rate of the copolymers has a maximum at the PY/EA molar ratio of 30/70. These results suggest that the polymer obtained is a real copolymer containing two comonomer units.     

B4C/SiC ceramic hollow microspheres prepared by slurry-coating and precursor conversion method

In this work, a new approach to fabricate B₄C/SiC ceramic hollow microsphere was established through combination of slurry-coating and precursor conversion method. Firstly, different slurries were prepared using modified B₄C powder with addition of PCS and LPCS. Subsequently, slurry was coated on a POM microsphere, followed by crosslinking, POM decomposition and heat-treatment at 1100 °C. Finally, the B₄C/SiC hollow microspheres with average diameter of 1.6–1.9 mm and thickness of 10–60 μm were obtained. The roughness (Ra) of outer surface was as low as 40.3 nm with high sphericity of 99.6%. Deoxidation was also explored by heat treatment at 1700 °C. The oxygen content was decreased from 11.06 wt.% to 0.37 wt.%, and crush load was promoted from 1.73 N to 4.50 N. The preparative method of B₄C/SiC ceramic hollow microspheres in this work can be easily extended for large-scale production.     

Preparation of novel carborane-containing boron carbide precursor and its derived ceramic hollow microsphere

High melting point and hardness of boron carbide make it extremely difficult to be directly prepared as hollow microsphere. However, precursor derived method is an effective approach to prepare ceramic materials with complex shape. Therefore, in this work a novel boron carbide precursor, poly[1,7-bis(4-chlorophenyl)-m-carborane] (P4CB), was synthesized. The ceramic yield of the precursor P4CB reached as high as 90.25% at 900 °C in nitrogen. Oxidation of P4CB in air was barely observed below 500 °C, and a passive oxidation was exhibited beyond 700 °C. The P4CB/PAN slurry was prepared and coated on a polyoxymethylene (POM) ball substrate. After air crosslinking, substrate decomposition and heat-treatment at 1100 °C in Ar atmosphere, boron carbide hollow microsphere with diameter of approximate 1.34 mm and average shell thickness of 30 μm was finally obtained. The novel precursor could be also utilized to fabricate boron carbide ceramics with different shapes due to its high ceramic yield.     

Synthesis of a novel benzoxazine precursor containing phenol hydroxyl groups and its polymer

A novel benzoxazine precursor containing phenol hydroxyl groups was synthesized from bisphenol A, 4,4′‐diaminodiphenyl methane, and formaldehyde with a molar ratio of 2:1:4. The benzoxazine precursor was characterized with Fourier transform infrared, proton nuclear magnetic resonance, and size exclusion chromatography. The curing reaction was monitored by the gel time, differential scanning calorimetry, and Fourier transform infrared. The obtained polybenzoxazine showed high thermal stability and a high glass‐transition temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Selection of a scheme for ceramic precursor synthesis

Three schemes of synthesis of precursors for barium-titanate ceramics are considered. Water-hydrochloric acid media with application of isopropyl and butyl alcohols and water-hydrochloric acid media with introduction of hydrogen peroxide and subsequent ammonia hydrolysis are investigated. Methods of synthesis are discussed. The processes are monitored with the pH-meter method. The experimental results are processed according to probability theory and the random processes method. Predictions of the interdependence of the ingredients and their effect on the course of synthesis are made. Consumption of chemical reagents is optimized. Translated from Steklo i Keramika, No. 5, pp. 20 – 24, May, 1998.     

Synthesis and polymer‐to‐ceramic conversion of tailorable copolysilazanes

Tailorable copolysilazanes (CPSZs) with variable chemical structure and molecular weights were prepared by coammonolysis of dichloromethylsilane, dichloromethylvinylsilane, and trichloromethylsilane. The as‐synthesized CPSZ was characterized by gel permeation chromatography, Fourier transformed infrared (FTIR) spectroscopy, and nuclear magnetic resonance spectroscopy. The CPSZ could be cured in an inert atmosphere at 180°C for 24 h. Pyrolysis behavior and structure evolution of the cured CPSZ were studied by means of thermal gravimetric analysis and FTIR. Hydrosilylation, transamination, dehydrogenation, and demethanation reactions were involved in the polymer‐to‐ceramic conversion of CPSZ. The ceramization process was complete at 900°C with a ceramic yield of 81–84%. Elemental analysis indicated that the compositions of final ceramics can be tailored by controlling the feed ratios of the starting chlorosilanes. Moreover, the microstructural evolution of the resultant Si? C? N ceramics was further investigated by X‐ray diffraction, Raman spectroscopy, and transmission electron microscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Theoretical study on a kind of cyclization mechanism of boron trichloride and hexamethyldisilazane to form the borazine ring for SiBCN ceramics precursor

Borazine rings act as a pivotal part in siliconboroncarbonitride ceramics (SiBCN) for high-temperature stability and great resistance to crystallization. A detailed investigation of the ring formation mechanism will guide the design and synthesis of SiBCN to meet application requirements under extreme conditions. Boron trichloride (BCl₃) and hexamethyldisilazane (HN(SiMe₃)₂) are common raw materials for the synthesis of precursors for SiBCN. In this paper, quantum chemical calculation was used to study the cyclization reaction mechanism between BCl₃ and HN(SiMe₃)₂ to form trichloroborazine (TCBZ) at the MP2/6-31G (d,p) level of theory. We discussed the structure properties, reaction pathways, energy barriers, reaction rates, and other aspects in detail. The results show that BCl₃ and HN(SiMe₃)₂ alternately participate in the reaction process, accompanied by the release of trimethylchlorosilane (TMCS), and that the entire reaction shows an absolute advantage in terms of energy. In the Step by step reaction, lower reaction barriers are formed due to the introduction of BCl₃ with more heat released compared to that for the introduction of HN(SiMe₃)₂. The final single-molecule cyclization and TMCS elimination steps are found to be faster compared to all previous bimolecular reactions.     

High-temperature electrical properties of polymer-derived ceramic SiBCN thin films fabricated by direct writing

The in situ temperature monitoring of hot components in harsh environments remains a challenging task. In this study, SiBCN thin-film resistance grids with thicknesses of 1.8 μm were fabricated on alumina substrates via direct writing. Owing to their dense microscopic morphology and extremely high graphitisation level, the produced SiBCN films exhibited large high-temperature oxidation resistance and electrical conductivity. The resistance–temperature, stability, and repeatability characteristics of these films were examined in an aerobic environment at temperatures up to 800 °C. The obtained results revealed that the thermistor resistance decreased monotonously with increasing temperature from room temperature to 800 °C. The SiBCN film resistance variations observed during repeated temperature cycling in the regions of 505–620 °C and 610–720 °C were 0.09% and 1.7%, respectively. The high cyclability and stability of the SiBCN thin film thermistor suggested its potential applicability for the in situ temperature monitoring of hot components in harsh environments.     

Synthesis of processible doped polyaniline‐polyacrylic acid composites

Processible composites of emeraldine salt form of polyaniline (PANI) with polyacrylic acid (PAA) are synthesized and studied for their structural, electrical, mechanical, thermal, and electrochemical properties. The processible conducting composites of various weight percentage from 20 wt % to 90 wt % (of PANI) have been prepared by mixing the PANI and PAA under vigorous stirring and sonication conditions. Self‐standing films of electroactive homogeneous composites are obtained by solution casting method. A significant improvement in processibility, crystallinity, and thermal stability is observed in the composites; however, the electrical conductivity decreased remarkably as the percentage of PANI is decreased in the composites. The 60 wt % PANI‐PAA composite showed crystalline structural property with orthorhombic crystal system and cell parameters as a = 5.93Å, b = 7.57Å, and c = 10.11Å. The 60 wt % PANI‐PAA composite also showed better thermal stability and highest capacitance amongst all the composites and used as an active material for development of electrochemical capacitors (parallel plate assembly). The processible composites based electrochemical capacitors using 0.5 M NaClO₄‐Acetonitril electrolyte showed super capacitance with ease in fabrication and cost effectiveness in comparison to other similar materials based capacitors. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

Synthesis and pyrolysis of single-source precursor for HfCxN1-x-SiC ceramic with different SiC contents

A novel single-source precursor was synthesized to prepare HfC_xN_1-x/SiC multiphase ceramics by using hafnium chloride (HfCl₄), diallylamine (DAA) and polycarbosilane (PCS). We conducted an investigation of the synthesis process, polymer-to-ceramic conversion, as well as the microstructure and phase evolution of HfC_xN_1-x/SiC multiphase ceramics with different levels of SiC content. The results showed that the core-shell particles of HfC_xN_1-x-carbon were embedded homogeneously in the β-SiC matrix which is beneficial for preventing grain growth and improving oxidation resistance. Based on data from oxidation tests, the ceramics improved the oxidation temperature and remained stable at a high temperature (1500 °C) with oxidation layer formation on the surface. Due to the highly cross-linked structure without oxygen, high ceramic yield, homogeneous composition and excellent oxidation resistance of the pyrolysis product, the as-prepared precursor is a promising material for making high-performance composite ceramics.     

聚合物先驱体转化法制备陶瓷MEMS器件

简述了聚合物先驱体转化陶瓷(PDC)法在制备陶瓷纤维、陶瓷涂层和陶瓷粘接等方面的应用,重点介绍了PDC法在微机电系统(MEMS)器件制造中的发展概况。耐高温MEMS的发展面临两大挑战:高温材料的选择和发展合适的微加工技术。指出了传统加工技术制备陶瓷MEMS的不足,着重介绍了PDC法制备陶瓷MEMS的优缺点。以国外采用PDC法制备陶瓷MEMS的几种典型器件为例,指出该方法在制备陶瓷MEMS器件中存在的问题和未来的发展方向。     

Preparation of self-healing Cf/SiBCN(O) composite using a novel polyborosilazane

In this study, novel polyborosilazane-derived SiBCN(O) ceramic was used as self-healing component in self-healing C_f/SiBCN(O) composite, which was prepared by polymer infiltration and pyrolysis (PIP) process. Molecular-level structure design of boron-containing ceramic precursors was utilized to achieve uniform dispersion of boron-containing self-healing components in prepared composites. No elemental diffusion was observed at the interface of ceramic matrix and carbon fibers, which resulted in stable SiBCN(O) structure. In addition, boron was uniformly distributed in C_f/SiBCN(O) composite ceramic matrix, which was beneficial for self-healing of cracks. Cracks and indentations were able to heal at high temperatures in air. The best crack-healing behavior occurred in air atmosphere at 1000 °C, with nearly complete crack healing. This excellent self-healing behavior was achieved because silicon and boron atoms in SiBCN(O) ceramic reacted with available oxygen at high temperatures to form SiO₂(l), B₂O₃(l), and B₂O₃·xSiO₂ liquid phases, which effectively filled cracks. In general, as-prepared C_f/SiBCN(O) composite exhibited excellent self-healing properties and shows great application potential in high-temperature environment applications such as aviation, aerospace, and nuclear power.