A Novel Polymeric Precursor for Boron Nitride Ceramics: Synthesis,Characterization, and Ceramic Conversion

A new polymeric boron nitride (BN) precursor poly[(phenylamino)borazine] (PPAB) with good melt‐processing performance was successfully synthesized by reaction of B‐trichloroborazine (TCB), aniline, and N‐methylaniline under mild conditions. The as‐synthesized PPAB as well as its structural evolution during the ceramic conversion was studied by means of various complementary techniques. The effect of process parameters including monomer ratio, reaction time, and reaction temperature on the properties of polymers was investigated, and the optimized parameters were obtained. Gel permeation chromatography (GPC) analysis of typical PPAB revealed that the number‐average molecular weight (M_n) was 30,520 Da and the polymerization degree was 319. The polymer could be converted to BN ceramics under ammonia atmosphere at 1200°C with carbon content as low as 0.9wt%. The PPAB polymer could be melt‐spun into continuous polymer fibers by hand drawing, which could be further transformed into BN ceramic fibers with good quality. The PPAB polymer is promising for applications that require BN precursor with stable melt processability.     

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.     

三氯环硼氮烷及其衍生物的制备与表征

以三氯化硼和氯化铵为原料,以氯苯为溶剂,采用Schlenk技术合成并提纯出高纯度三氯环硼氮烷(TCB)晶体,利用二甲胺与TCB进行反应,得到TCB的衍生物烷基胺环硼氮烷,为获得高质量BN材料作了原料准备. 采用NMR以及单晶衍射方法对合成样品进行了分析,对反应条件、反应装置及反应路线进行了考察. 研究结果表明,合成反应为均液相反应,加入催化剂Hg, TCB产率可达89%以上;不加催化剂,适当延长反应时间,TCB产率可达87%以上. 在提纯TCB的步骤中,精馏塔理论塔板数为6时较佳. 采用B3LYP/6-31G*计算水平对取代反应过程进行模拟计算,结果表明,取代反应过渡态包含Cl-B-N-HCl四元环结构,通过计算推测反应有可能生成几种取代衍生物的混合物.     

Gas phase reaction kinetics in boron fibre production

In the production of boron fibres using the chemical vapor deposition (CVD) technique, boron deposition and dichloroborane formation reactions occurs simultaneously. Boron deposition reaction occurs at the surface, whereas the formation of dichloroborane is the result of both gas phase and surface reactions. A continuous stirred tank reactor (CSTR) type of reactor was designed to investigate the reaction kinetics and kinetic parameters in the gas phase reactions of boron trichloride and hydrogen. It was concluded that reaction rate of the product increased with an increase in the inlet concentration of both reactants (BCl₃ and H₂) and with an increase in the reactor temperature. While reaction order with respect to BCl₃ was almost constant at about 0.5 at each temperature, reaction order with respect to hydrogen increased significantly at temperatures lower than 350°C. A general rate expression was derived for BHCl₂ formation from BCl₃ and hydrogen. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Novel processable precursor for BN by the polymer-derived ceramics route

Novel precursors polymerized from (alkylamino)borazines (AAB) were synthesized and transformation of processable poly-AAB to boron nitride (BN) was researched. The AAB monomers of the type (BNH)₃(NHR)₃ were synthesized via ammolysis of 2,4,6-trichloroborazine (TCB) with different propylamines under mild conditions. The specially designed monomers served as molecular precursors for BN by the polymer-derived ceramics route. The processability of the polymeric precursors varied with propylamino-groups of AAB linked with boron atoms on (BNH)₃. The good processability of the poly[2,4,6-tris(iso-propylamino)borazine] (PTPⁱAB) was proven by melt-spinning it into polymer fiber. Furthermore, the PTPⁱAB gave a ceramic yield of about 53 wt% in Ar at 1200 °C by TGA. Based on FTIR, Raman, XRD, XPS and elemental analysis, the pyrolytic product of PTPⁱAB showed a composition of BN_1.07. In addition, the BN illustrated excellent oxygen resistance in air.     

Preceramic polymer for Si?B?N?C fiber via one‐step condensation of silane,BCl3, and silazane

A preceramic polymer for Si? B? N? C fiber, polyborosilazane, has been synthesized by one‐step condensation reaction of dichloromethylsilane, BCl₃, and hexamethyldisilazane with high yield. The reaction mainly involves the condensation of Si? Cl and B? Cl with N? SiMe₃ followed by SiMe₃Cl evaporation and dehydrogenation between N? H and Si? H. The resulted polymer is a soluble colorless transparent solid with melting point of 70°C and molecular weight of 10,800. The backbone of the polymer is mainly composed of ? Si? N? B‐bridge with some borazine rings. The polymer exhibits good processability and flexible polymer fibers with diameter of 15–20 μm were obtained by melt spinning. Pyrolysis of the as‐synthesized polymer to 1000°C under nitrogen atmosphere results in a ceramic yield of 63 wt %, and the obtained Si? B? N? C ceramic remains fully amorphous up to 1700°C, and only small amount of poorly crystallized BN, Si₃N₄, and SiC phases were observed upon heating at 1850°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

氮化硼纤维先驱体聚合物的合成及其表征

以三氯化硼与氯化铵为基础原料合成了三氯环硼氮烷（TCB）,然后将TCB和三氯化硼分别与甲胺反应制得TCB的衍生物（CH3NH）3N3B3H3和B（NHCH3）3单体,将这些衍生物混合后在一定条件下进行缩合反应得到氮化硼先驱体。从合成方法、反应机理及其产物的结构性能表征等方面研究了氮化硼陶瓷纤维的先驱体,并且用IR、NMR、EA．XRD及DSC等表征方法对先驱体的结构、成分及性能进行了分析。结果表明：先驱体中含有B、C、N、H元素,存在CH3、B-N、N—H、G—H、BN六元环等结构单元。最后,对此先驱体进行了试纺丝,并用扫描电镜观察了所得纤维的形态。     

Influence of hydrogen on growth and microstructure of boron nitride coatings obtained from BCl3–NH3–H2 system by chemical vapor infiltration

Hexagonal boron nitride (h-BN) interfacial coatings were prepared by chemical vapor infiltration (CVI) process from BCl₃–NH₃–H₂ system with different hydrogen contents for improving the toughness of ceramic matrix composites. In this study, the yield of BN was found to be 94.90% without hydrogen present in the reactant system as calculated via FactSage, while it reached 99.95% at the [H₂]/[BCl₃] ratio of 10 and the [NH₃]/[BCl₃] ratio of 1, when chemical equilibrium was reached. BN interfacial coatings containing mixture of hexagonal and turbostratic phases were obtained. The deposition rate of coating increased from 18.2 ± 0.4 nm min⁻¹ (β = 0) to 23.0 ± 0.4 nm min⁻¹ (β = 5) with the increase of hydrogen content in reactants, then it significantly decreased when β was 10. Owing to different nucleation amounts on the surface of fibers, samples S2 (β = 2) and S3 (β = 5) exhibited particles with circular shapes and smooth surfaces, while the other coatings presented particles with polygonal shapes and rough surfaces. Moreover, the onset temperature of weight gain of sample S2 was 102 °C higher than that of sample S4, thus indicating the enhancement of the high-temperature oxidation resistance of BN coating.     

Silicon nitride/boron nitride ceramic composites fabricated by reactive pressureless sintering

Using Si and BN powders as raw materials, silicon nitride/hexagonal boron nitride (Si₃N₄/BN) ceramic composites were fabricated at a relatively low temperature of 1450 °C by using the reaction bonding technology. The density and the nitridation rate, as well as the dimensional changes of the specimens before and after nitridation were discussed based on weight and dimension measurements. Phase analysis by X-ray diffraction (XRD) indicated that BN could promote the nitridation process of silicon powder. Morphologies of the fracture surfaces observed by scanning electron microscopy (SEM) revealed the fracture mode for Si₃N₄/BN ceramic composites to be intergranular. The flexural strength and Young's modulus decreased with the increasing BN content. The reaction-bonded Si₃N₄/BN ceramic composites showed better machinability compared with RBSN ceramics without BN addition.     

Influence of pressure on chemical vapor deposition of boron nitride from BCl3/NH3/H2 gas mixtures

Boron nitride (BN) was synthesized from BCl₃/NH₃/H₂ precursor mixtures via chemical vapor deposition, with a focus on the influence of the total partial pressure of BCl₃, NH₃, and H₂ (p_BCl3+NH3+H2) on the surface deposition rate. The surface deposition rate of BN initially increased and then decreased with increasing p_BCl3+NH3+H2, implying that the deposition process transitioned from surface reaction control to mass transfer control. BN deposition from BCl₃ and NH₃ was mainly attributable to several intermediate gaseous products containing B, N, Cl, and H, such as Cl₂BNH₂, ClB(NH₂)₂, and B(NH₂)₃. The microstructures of BN coatings deposited on SiC fibers were also analyzed. The BN coatings were uniformly and evenly deposited on the SiC fiber surfaces at low p_BCl3+NH3+H2 values, whereas excessive p_BCl3+NH3+H2 values afforded coatings containing large grains. The as-prepared BN coatings were stoichiometric but amorphous. Heat treatment substantially improved the texture and crystallinity to afford hexagonal BN.     

Effect of temperature on the growth of boron nitride interfacial coatings on SiC fibers by chemical vapor infiltration

In order to improve bonding property between SiC fibers and matrix of SiC_f/SiC composites, boron nitride (BN) interfacial coatings were synthesized by chemical vapor infiltration. BN coatings were fabricated from BCl₃–NH₃ gaseous mixtures at four different temperatures (843 °C, 900 °C, 950 °C and 1050 °C) with different deposition times. Growth kinetics, nucleation and growth processes, microstructure and chemical composition of boron nitride coatings were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Raman spectrometry. Results showed that deposition rate increased as the temperature increased from 843 °C to 950 °C. However, deposition rate decreased slightly from 23.10 ± 0.85 nm/min (950 °C) to 21.39 ± 0.67 nm/min when the temperature was increased further to 1050 °C. It could be due to the nucleation occurring in the gas and the consumption of a large amount of BCl₃ and NH₃. When deposition temperature was 843 °C, BN grains deposited on top layer of the coating could not completely cross Ehrlich-Schwoebel barrier and grew in island growth mode. On the other hand, the deposition pattern followed a layer-by-layer growth mode when deposition temperature was 1050 °C. Deposition temperature significantly affected the microstructure of as-deposited BN coatings. At 843 °C, 950 °C and 1050 °C, the coatings presented amorphous, polycrystalline and hexagonal structures, respectively.     

A simple and efficient method for the synthesis of SiBNC ceramics with different Si/B atomic ratios

The high-temperature durability of SiBNC ceramics is significantly influenced by Si/B ratios and the synthetic procedures. Single-source synthetic routes can yield homogeneous ceramics at the atomic level, but the Si/B ratio cannot be efficiently adjusted. In this paper, a simple and efficient method for the synthesis of SiBNC precursor polyborosilazanes (PBSZs) with different Si/B ratios has been established via a one-pot reaction involving boron trichloride, dichloromethylsilane and hexamethyldisilazane in different molar ratios. The Si/B ratios of the derived SiBNC ceramics were consistent with that of the precursor PBSZs. When pyrolysed at 1000 °C, PBSZs with 0.52, 0.94 and 2.12 Si/B ratios transformed into SiB_2.6N₅C_2.2, SiB_0.9N_2.7C_1.3 and Si₂BN₃C_1.4 ceramics respectively. The polymer-to-ceramic process was also studied and featured ceramic yields of 43.2 wt%, 50.1 wt% and 62.2 wt%, respectively. The derived ceramic SiB_0.9N_2.7C_1.3 resisted crystallization up until 1700 °C, whereas the SiB_2.6N₅C_2.2 and Si₂BN₃C_1.4 could remain amorphous up to 1600 °C only. Using the precursor with 0.94 Si/B ratio, the SiBNC ceramic fibres were also obtained.     

Mechanism studies on CVD of boron carbide from a gas mixture of BCL3, CH4, and H2 in a dual impinging‐jet reactor

Nearly pure boron carbide free from impurities was produced on a tungsten substrate in a dual impinging‐jet chemical vapor deposition reactor from a BCl₃, CH₄, and H₂ mixture. The Fourier Transform Infrared (FTIR) analysis proved the formation of reaction intermediate BHCl₂, which is proposed to occur mainly in the gaseous boundary layer next to the substrate surface. Among a large number of reaction mechanisms proposed only the ones considering the molecular adsorption of boron carbide on the substrate surface gave reasonable fits. In the proposed mechanism dichloroborane is formed in the gas phase only as a by‐product. Boron carbide, on the other hand, is formed through a series of surface reactions involving adsorbed boron trichloride, adsorbed methane and gas phase hydrogen. The simultaneous fit of the experimental rate data to the model expressions gave correlation coefficient values of 0.977 and 0.948, in predicting the B₄C and BHCl₂ formation rates, respectively. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Properties of Porous Si3N4/BN Composites Fabricated by RBSN Technique

Reaction bonding of silicon nitride (RBSN) technique combined with slip-casting shaping process was used to fabricate porous Si₃N₄/BN ceramic composites. Si/BN slurry with chemical stability, good dispersibility, and viscosity was prepared using glycerol trioleate (GTO) covering on Si surface and poly(acrylic acid) (PAA) as dispersant. The hydrolysis of Si was strongly prevented by GTO coating. The dispersibility of covered Si and BN suspensions were improved by PAA dispersant. Twenty volume percent covered Si/BN slurries with low viscosity were successfully casted. The cast bodies were dried at room temperature, debindered at 750°C and nitrided below 1450°C. The nitrided samples mainly consist of α-Si₃N₄, β-Si₃N₄, and h-BN. The composites exhibit homogeneous microstructure consisting of faceted particles, α-Si₃N₄ nanowires and a large amount of pores. The porosity is 52.64% and the pore size is in the range of 60–300 nm. The composites show compressive strength of 16.6±1.5 MPa. The dielectric constant of the composite is about 3.1 and the dielectric loss is below 0.5% under different frequencies.     

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.     

Microstructural and microtextural investigations of boron nitride deposited from BCl3–NH3–H2 gas mixtures

The structural, morphological and textural characteristics of BN coatings processed by CVD from (BCl₃, NH₃, H₂) gas mixtures, at low pressure (P=1.3 kPa) and low temperature (T=800 °C), with different Q_NH3/Q_BCl3 gas flow rate ratios, have been investigated. Whereas the as-processed coatings are amorphous, a high degree of crystallisation can be achieved after a post-deposition heat treatment. The sole post-elaboration heat treatment does not allow the improvement of the crystallisation degree of the boron nitride. The presence of a small amount of oxygen, resulting from a simple exposure of the coating to a controlled atmosphere (temperature, moisture rate), is also necessary. For given temperature and pressure, a wide range of microstructures of the heat-treated BN coatings, from isotropic to anisotropic, can be observed by varying the Q_NH3/Q_BCl3 ratio.     

In-situ formation of BN layers by nitriding boron powders in BN/Si3N4-based composite ceramics

Boron nitride/silicon nitride (BN/Si₃N₄) composite ceramics were fabricated via the in-situ nitridation of boron (B) and silicon (Si) powders in forming gas (95%N₂/5%H₂) at 1390?°C. The effect of the B content on the phase composition, microstructure, density/porosity, machinability as well as mechanical properties of nitridized BN/Si₃N₄ composite ceramics was investigated. The addition of B slightly increased the nitridation degree of the Si and B powders mixture, and improved the ratio of the β-Si₃N₄ phase significantly at low B contents. B powders may have acted as a nucleating agent to promote the formation of β-Si₃N₄ crystals. A core-shell Si₃N₄/BN structure was revealed by the TEM technique, and the number of BN layers increased with the increase of the B content. The in-situ BN formed by the nitridation of B played a similar role with the BN directly added in enhancing the machinability of the BN/Si₃N₄ composite ceramics. The method of the in-situ nitridation of B is also effective to prepare SiC fiber-reforced BN/Si₃N₄ ceramic matrix composites.     

Synthesis and ceramic conversion of a novel processible polyboronsilazane precursor to SiBCN ceramic

Polyboronsilazane (PBSZ) precursors for SiBCN ceramics were prepared by using 9-borabicyclo-[1,3,3] nonane (9-BBN) and copolysilazanes (CPSZ) as starting materials, involving the hydroboration reaction between vinyl groups of PSZ and BH groups of 9-BBN under mild conditions. The as-synthesized PBSZ was obtained as a soluble liquid, which was characterized by FT IR and NMR. The polymer-to-ceramic conversion of PBSZ at a ceramic yield of 62.2–79.9% was investigated by means of FT IR and TGA. The crystallization behavior and microstructures of PBSZ-derived SiBCN ceramics were studied by XRD, SEM and HRTEM. The SiBCN ceramic began to crystallize at 1600 °C. Further heating at 1800 °C induced partial crystallization to give mixed XRD patterns for SiC, Si₃N₄, and BN(C). It is observed that the introduction of boron improves the thermal stability of SiBCN ceramics, especially under high temperatures of 1600–1800 °C. In addition, the introduction of boron significantly improves the ceramic density while inhibits the SiC crystallization.     

Transamination Reactivity of Ti(NMe2)4 and Zr(NMe2)4 with 1,3,4,5,6-Pentamethyl-2-aminoborazine and Aryl Amines. Model Chemistry for the Formation of Metalloborazine Preceramic Polymers and MN/BN (M?=?Ti, Zr) Ceramic Composites

The transamination reactions between Ti(NMe₂)₄ and 1,3,4,5,6-pentamethyl-2-aminoborazine, (Me)₃N₃(Me)₂B₃(NH₂), and diphenylamine (Ph₂NH) and between [Zr(NMe₂)₄]₂ and 1,3,4,5,6-pentamethyl-2-aminoborazine, aniline (PhNH₂) and diphenylamine have been studied and the molecular product species have been isolated, spectroscopically characterized and single crystal X-ray structure analyses completed. The results of these studies have been used to interpret the outcome of reactions of Ti(NMe₂)₄ and Zr(NMe₂)₄ with borazinylamine preceramic polymers that, upon pyrolysis, produce TiN/BN, ZrN/BN and ZrH_0.6N/BN composite powders. The transamination reactivity of a two-point poly(borazinylamine) oligomer having terminal –NH₂ amino groups with Ti(NMe₂)₄ and Zr(NMe₂)₄ has been used to obtain metallated preceramic oligomers that, upon pyrolysis, give TiN/BN and ZrN/ZrH_0.6N/BN nanocomposites. Model reactions of 1,3,4,5,6-pentamethyl-2-amino borazine, aniline and Ph₂NH₂ with Ti(NMe₂)₄ and Zr(NMe₂)₄ are also described as models for the formation of the metallated oligomers. Molecular structure determinations for the metal amides are presented. We dedicate this paper to Professor Christopher W. Allen in recognition of his distinguished career and his accomplishments in inorganic ring and polymer chemistry.     

Evaluation of poly(methylsilane‐carbosilane) synthesized from methyl‐dichlorosilane and chloromethyldichloromethylsilane as a precursor for SiC

A new poly(methylsilane‐carbosilane) (PMSCS) for silicon carbide precursor was synthesized by Wurtz‐type copolycondensation of methyldichlorosilane (MeHSiCl₂) with chloromethyldichloromethylsilane (ClCH₂MeSiCl₂) and terminated with vinylmagnesium chloride (ViMgCl). The use of insufficient sodium made the reaction more economic and safe. By changing the ratios of two monomers and the end‐block agent, the properties of the obtained PMSCS and the C/Si ratio of its derived ceramic could be tuned. Upon pyrolysis at 1000 °C under argon, silicon carbide with nearly stoichiometric C/Si ratio and low oxygen content was obtained in 64% of ceramic yield. PMSCS showed high potential as an economical SiC ceramic precursor for the fabrication of SiC matrix, coating, and adhesives. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46610.