Fabrication of SiC and Si3N4 Whiskers under Pressurized Ar and N2 Atmosphere through High‐Energy Ball Milling

SiO_{2 (activated or mesoporous silica)}/Mg_{(magnesiothermic or metal sintering aid)}/C_{(activated or polymeric carbon)}/N_{2 (atmosphere)} systems were used in the one‐step synthesis of β‐SiC and β‐Si₃N₄ whiskers. In this study, a mixture of the active precursors was allowed to react via a self‐sustaining reaction (high‐energy ball milling process). Scanning electron micrographs and X‐ray diffraction (XRD ) analysis showed that the rod‐like SiC whiskers (~800 µm) were synthesized in situ by the direct carbothermal reduction of silicon nitride (or silicon) with activated carbon in N₂ (or Ar) atmosphere. The results show that β‐Si₃N₄ (without β‐SiC ) was fully formed after 5 h of milling with four different morphologies, namely whisker tip (droplet/no droplet) and nonuniform whiskers (short hexagonal/rhombohedral/rod‐like) with a length of 0.1–400 µm. By adding metal sintering aids, the liquid phase Mg–Si–O–N and the rate of carbothermal reduction increased (enhanced densification via particle rearrangement) and their hexagonal whiskers tended to assume a rod‐like shape. The effect of the concentration of CO (reduction of α‐Fe₂O₃ to Fe by CO ) on the whisker synthesis suggests that, in addition to the concentration of CO , the nature of the family of mesoporous silica/carbon template is an important factor in the synthesis of β‐SiC and β‐Si₃N₄ whiskers. The possible chemical reactions were investigated by studying the unwanted phases (MgO , Si, SiC , Fe₂O₃ , Fe₃O₄ , FeO , Fe, Fe₃C , MgCO₃ ) of comparable XRD graphs.     

Effect of Modifying Additives on the Sintering and Properties of SiC/SiC<Subscript>w</Subscript> Ceramic Composite Material

Spark plasma sintering and hot compaction methods were used to obtain experimental samples of a composite material of the SiC?SiC_w system with various modifying additives (AlN, B₄C, HfB₂, Y₂O₃, Al₂O₃, Si₃N₄). The effect of the modifying additives on the sintering process, physicomechanical, and thermal properties of the ceramic composite material was examined. The introduction of the modifying additives lowered the sintering temperature of silicon carbide produced by the hot compaction method by 200°C and that formed with spark plasma spark sintering by 300?450°C as compared with the sintering temperature of silicon carbide without additives.     

Chemical Vapor Deposition of Silicon Carbide and Silicon Nitride—Chemistry's Contribution to Modern Silicon Ceramics

Pure silicon carbide and silicon nitride have valuable properties in bulk pore-free form; however, their industrial exploitation has hardly been possible so far. Neither compound can be melted or sintered in pure form; hot pressing or sintering at normal pressure requires the presence of additives; and the reaction-sintering process in which only Si and C or Si and N are employed as additives affords porous materials.–The novel process of chemical vapor deposition has partly overcome the drawbacks of the previous methods. In the new process SiC is produced, e.g., by pyrolysis of CH₃SiCl₃, and Si₃N₄ by reaction of SiCl₄ with NH₃. This technique can also be used for pore filling in objects made of SiC and Si₃N₄ (gas phase impregnation) and for producing extremely fine SiC and Si₃N₄ (gas phase impregnation) and for producing extremely fine SiC and Si₃N₄ powder and SiC monofilaments suitable as components for SiC composites. Moreover, gas phase impregnation can also give fiber composites.     

The morphology of ceramic phases in BxC-SiC-Si infiltrated composites

The present communication is concerned with the effect of the carbon source on the morphology of reaction bonded boron carbide (B₄C). Molten silicon reacts strongly and rapidly with free carbon to form large, faceted, regular polygon-shaped SiC particles, usually embedded in residual silicon pools. In the absence of free carbon, the formation of SiC relies on carbon that originates from within the boron carbide particles. Examination of the reaction bonded boron carbide revealed a core-rim microstructure consisting of boron carbide particles surrounded by secondary boron carbide containing some dissolved silicon. This microstructure is generated as the outcome of a dissolution-precipitation process. In the course of the infiltration process molten Si dissolves some boron carbide until its saturation with B and C. Subsequently, precipitation of secondary boron carbide enriched with boron and silicon takes place. In parallel, elongated, strongly twinned, faceted SiC particles are generated by rapid growth along preferred crystallographic directions. This sequence of events is supported by X-ray diffraction and microcompositional analysis and well accounted for by the thermodynamic analysis of the ternary B-C-Si system.     

Preparation of Boron Carbide from BF<Subscript>3</Subscript> and BCl<Subscript>3</Subscript> in Hydrogen Plasma of Arc RF Discharge

A comparative study was carried out of the process of plasma chemical deposition of boron carbide from hydrogen plasma containing the mixtures of BF₃ + CH₄ and BCl₃ + CH₄ sustained by RF arc (13.56 MHz) discharge. It was shown that in the case of synthesis of B₄C from a mixture of BF₃ + CH₄, carbon and complex coordination compound [X₃B]^?H⁺ (R₃B·FH) are formed as the by-products of condensed products. In the case of synthesis of B₄C from the BCl₃ + CH₄ mixture, the only condensed product is carbon. Mechanisms for the formation of boron carbide on the surface of heated electrodes are proposed. The main feature of these mechanisms is the preliminary deposition of a graphite layer from CH₄ and then the precipitation of boron with the participation of the radicals BF₂, BF and BCl. B₄C samples were obtained and the impurity composition, morphology and structure of bulk boron carbide samples obtained using both of its halides were studied. It was found that in both cases a carbon phase is present in boron carbide samples. The main impurities entering the B₄C, in the case of using a mixture of BF₃ + CH₄, is silicon, and in the case of a mixture of BCl₃ + CH₄, is tungsten.     

Solid‐State NMR Investigations on the Amorphous Network of Precursor‐Derived Si2B2N5C4 Ceramics

Employing a multitude of modern solid state NMR techniques including ¹³C{¹⁵N}REDOR NMR, ¹H–¹³C CP NMR, ¹¹B MQMAS NMR spectroscopic experiments, the structural organization of Si₂B₂N₅C₄ ceramic has been studied. The experiments were executed on double isotope enriched (¹³C, ¹⁵N) and natural isotope abundance Si₂B₂N₅C₄ ceramics. The materials were synthesized by aminolysis and subsequent pyrolysis of intermediate pre‐ceramic polymers that were obtained from the single source precursor TSDE, 1‐(trichlorosilyl)‐1‐(dichloroboryl)ethane (Cl₃Si–CH(CH₃)–BCl₂). The result of the ¹³C{¹⁵N} REDOR NMR spectroscopic experiment shows that carbon atoms are incorporated into the network by bridging to nitrogen, which already occurs during the polymerization step. Furthermore, the combined results of ¹¹B NMR and ¹¹B MQMAS NMR indicate that boron atoms may also be connected to carbon in addition to nitrogen.     

Heat shield materials

Some properties and applications in the aerospace industry of high-temperature whiskers (SiC, Si₃N₄, AlN) and fibers (SiO₂, A1₂O₃) are described     

An In Situ Carbonization–Replication Method to Synthesize Mesostructured WO3/C Composite as Nonprecious‐Metal Anode Catalyst in PEMFC

A meostructured WO₃/C composite with crystalline framework and high electric conductivity has been synthesized by a new in situ carbonization–replication route using the block copolymer (poly(ethylene glycol)‐block‐poly(propylene glycol)‐block‐poly(ethylene glycol)) present in situ in the pore channels of mesoporous silica template as carbon source. X‐ray diffraction, X‐ray photoelectron spectroscopy, transmission electron microscopy, thermogravimetry differential thermal analysis, and N₂ adsorption techniques were adopted for the structural characterization. Cyclic voltammetry, chronoamperometry, and single‐cell test for hydrogen electrochemical oxidation were adopted to characterize the electrochemical activities of the mesoporous WO₃/C composite. The carbon content and consequent electric conductivity of these high‐surface‐area (108–130 m² g^?1) mesostructured WO₃/C composite materials can be tuned by variation of the duration of heat treatment, and the composites exhibited high and stable electrochemical catalytic activity. The single‐cell test results indicated that the mesostructured WO₃/C composites showed clear electrochemical catalytic activity toward hydrogen oxidation at 25 °C, which makes them potential non‐precious‐metal anode catalysts in proton exchange membrane fuel cell.     

Fully Borylated Methane and Ethane by Ruthenium‐Mediated Cleavage and Coupling of CO

Many transition‐metal complexes and some metal‐free compounds are able to bind carbon monoxide, a molecule which has the strongest chemical bond in nature. However, very few of them have been shown to induce the cleavage of its C?O bond and even fewer are those that are able to transform CO into organic reagents with potential in organic synthesis. This work shows that bis(pinacolato)diboron, B₂pin₂, reacts with ruthenium carbonyl to give metallic complexes containing borylmethylidyne (CBpin) and diborylethyne (pinBC≡CBpin) ligands and also metal‐free perborylated C₁ and C₂ products, such as C(Bpin)₄ and C₂(Bpin)₆, respectively, which have great potential as building blocks for Suzuki–Miyaura cross‐coupling and other reactions. The use of ¹³CO‐enriched ruthenium carbonyl has demonstrated that the boron‐bound carbon atoms of all of these reaction products arise from CO ligands.     

Superlubricity behaviors of Si3N4/DLC Films under PAO oil with nano boron nitride additive lubrication

The tribological properties of Si₃N₄ ball sliding against diamond‐like carbon (DLC) films were investigated using a ball‐on‐disc tribometer under dry friction and oil lubrications, respectively. The influence of nano boron nitride particle as lubricant additive in poly‐α‐olefin (PAO) oil on the tribological properties of Si₃N₄/DLC films was evaluated. The microstructure of DLC films was measured by Raman spectroscopy and X‐ray photoelectron spectroscopy. The experimental results show coefficient of friction (COF) of Si₃N₄/DLC films was as low as 0.035 due to the formation of graphite‐like transfer films under dry friction condition. It also indicates that the tribological properties of Si₃N₄/DLC films were influenced significantly by the viscosity of oil and the content of nano boron nitride particle in PAO oil. COF increases with the viscosity of PAO oil increasing. Si₃N₄/DLC films exhibit the superlubricity behaviors (μ=0.001 and nonmeasurable wear) under PAO 6 oil with 1.0 wt% nano boron nitride particle lubrication, indicating that the improved boundary lubrication behaviors have indeed been responsible for the significantly reduced friction. Nano boron nitride additive is used as solid lubricant‐like nano scale ball bearing to the pointlike contact and a soft phase bond with the weak van der Waals interaction force on the contact surface to improve the lubrication behaviors of Si₃N₄/DLC films. The potential usefulness of nano boron nitride as lubricant additive in PAO oil for Si₃N₄/DLC films has been demonstrated under oil lubrication conditions. The present work will extend the wide application of nano particle additive and introduce a new approach to superlubricity under boundary lubrication in future technological areas. Copyright © 2013 John Wiley & Sons, Ltd.     

Geometry,stability, and isomerization of BnN2 (n = 1−6) isomers

We perform a systematic study on the geometry, stability, nature of bonding, and potential energy surface of low‐lying isomers of planar and cyclic B_nN₂ (n = 1?6) at the CCSD(T)/6‐311+G(d)//B3LYP/6‐311+G(d) level. B_nN₂ (n = 2?4) clusters are structurally similar to pure boron clusters. The evolution of the binding energy per atom, incremental binding energy, and second‐order difference of total energy with the size of B_nN₂ reveals that the lowest energy isomer of B₃N₂ has high stability. B₅N₂ and B₆N₂ possess π‐aromaticity according to Hückel (4n + 2) rule. The aromaticity of some isomers of B₄N₂ and B₆N₂ is examined based on their valence molecular orbitals. At the CCSD(T)/6‐311+G(d)//B3LYP/6‐311+G(d) level, several B₂N₂, B₃N₂, B₄N₂, and B₅N₂ isomers are predicted to be stable both thermodynamically and kinetically, and detectable in future experiments. © 2013 Wiley Periodicals, Inc.     

Electron probe microanalysis of chemical gradients in gas pressure sintered silicon nitride

During gas pressure sintering of silicon nitride (Si₃N₄) — which normally contains oxide additives such as SiO₂, Al₂O₃ and Y₂O₃ — in a resistance heated graphite furnace, a reduction of the Si₃N₄ sample takes place. At high temperatures (>1800°C) this effect is accompanied by decomposition reactions of Si₃N₄. Both lead to chemical gradients in larger components which influence the strength of the sintered article. Electron probe microanalysis (EPMA) has been carried out in order to study the influence of the crucible material [graphite (C), boron nitride (BN)] and the quantity of filling on the gradient formation.     

Reactions of Tri‐tert‐butylazadiboriridine NB2R3 with Carbonyl and Similar Species

The carbonyl group of X(R')CO is added to the B—B bond of the three‐membered ring compound NB₂R₃ ( 1 ; R = tBu) to give the five‐membered rings [—BR—NR—BR—X(Rapos;)C—O—] ( 2a — d ; Rapos;/X = tBu/H, Ph/Ph, H/OMe, H/NMe₂). The tetraazoniatetraboratatricyclo[6.2.0.0^{3, 6}]deca‐2, 4, 7, 9‐tetraenes N₄B₄C₂R₆Rapos;₂ ( 4a , b ; Rapos; = Me, Et), known products from the reaction of 1 with isonitriles CNRapos;, undergo a rearrangement to give the corresponding deca‐1, 4, 6, 9‐tetraenes 6a , b by the migration of two tBu groups from boron to carbon on photolysis; the structure of 6a is confirmed by X‐ray analysis. The reaction of CO, generated from carbonylmetal complexes (photolytically from [Cr(CO)₆] or [Cp₂Fe₂(CO)₄]; thermally from [Fe₂(CO)₉] or [Co₂(CO)₈]), with 1 gives the 3, 7‐dioxonia‐1, 5‐diazonia‐2, 4, 6, 8‐tetraboratanaphtalene O₂N₂C₂B₄R₆ ( 7 ), as has been known from the reaction of [Fe(CO)₅] and 1 . The product 7 is also obtained from the isomeric dispiro compound 5 , the known product from the reaction of 1 with gaseous CO at —78 °C, by standing in solution at room temperature. Surprisingly, the reaction of 1 with CO from the photolysis of [CpMn(CO)₃] gives a naphthalene‐type isomer of 7 , the 1, 5‐dioxonia‐3, 7‐diazonia species 8 , the crystal structure of which is reported.     

Preparation, microstructure and mechanical properties of SiC-SiC and B4C-B4C laminates

Silicon carbide and boron carbide are high hardness materials with a low density but, like most ceramics, with a low toughness, that limits their use in various applications. One approach to reinforce ceramic materials consists in using crack deflection by weakening the interfaces in laminar materials. In our study, ceramic layers of different compositions were prepared by tape casting and stacked in predefined sequences. Different weak layers were tested: porous layers made with different pore forming agents for SiC; porous layers made with pore forming agent or by varying the quantity of sintering aid and weak interfaces made with graphite spray for B₄C. After debinding, SiC (Al₂O₃, Y₂O₃ additions) and B₄C (C addition) were pressureless sintered. For evaluation of the sintered parts, firstly the macrostructure and microstructure were characterized. Then, mechanical properties of multi-layered materials, obtained by stacking dense and porous layers that should contain enough porosity to initiate crack deflection, according to the models, were evaluated.     

Prediction of Boron–Boron Triple‐Bond Polymers Stabilized by Janus‐Type Bis(N‐heterocyclic) Carbenes

A class of polymeric compounds containing boron–boron triple bonds stabilized by N‐heterocyclic biscarbenes is proposed. Since a triply bonded B₂ is related to its third excited state, the predicted macromolecule would be composed by several units of an electronically excited first‐row homonuclear dimer. Moreover, it is shown that the replacement of biscarbene with N₂ or CO as spacers could change the bonding profile of the boron–boron units to a cumulene‐like structure. Based on these results, different types of diboryne polymers are proposed, which could lead to an unprecedented set of boron materials with distinct physical properties. The novel diboryne macromolecules could be synthesized by the reaction of Janus‐type biscarbenes with tetrabromodiborane, B₂Br₄, and sodium naphthalenide, [Na(C₁₀H₈)], similarly to Braunschweig’s work on the room temperature stable boron–boron triple bond compounds (Science, 2012 , 336, 1420).     

Estimation of the upper limit of carbon concentration in boron carbide crystals

The existence of a boron carbide phase with ∼25 at % carbon was proven experimentally. To evaluate the maximum possible concentration of C atoms in boron carbide (B_{12 − x} C _x )(BC₂) crystals, we performed quantum-chemical calculations of (B_{12 − x} C _x )(BH₂)₆(CH₃)₆ model compounds (x = 0–4; the goal of calculations was to determine the upper limiting number of C atoms in the B_{12 − x} C _x icosahedron) by the density functional theory method (B3LYP, 6-31G** basis set, full geometry optimization). A comparison of the experimental and calculated data showed that the calculations of the model compounds reproduced the experimental dependences of the structural parameters of the icosahedron (mean bond length and volume) on the number of C atoms in it. The icosahedra were found to be stable at x ≤ 3. According to the results of the quantum-chemical calculations, the maximum carbon concentration in boron carbide was 33 at %, which corresponded to the composition B₁₀C₅ and the structural formula (B₉C₃)(BC₂).     

Thermal stability of high surface area silicon carbide materials

The synthesis of mesoporous silicon carbide by chemical vapor infiltration of dimethyl dichlorosilane into mesoporous silica SBA-15 and subsequent dissolution of the silica matrix with HF was investigated. The influence of the synthesis parameters of the composite material (SiC/SBA-15) on the final product (mesoporous SiC) was determined. Depending on the preparation conditions, materials with specific surface areas from 410 to 830 m² g⁻¹ and pore sizes between 2 and 10 nm with high mesopore volume (0.31-0.96 cm³ g⁻¹) were prepared. Additionally, the thermal stability of mesoporous silicon carbide at 1573 K in an inert atmosphere (argon) was investigated, and compared to that of SBA-15 and ordered mesoporous carbon (CMK-1). Mesoporous SiC has a much higher thermal textural stability as compared to SBA-15, but a lower stability than ordered mesoporous carbon CMK-1.     

Silicon Boron Nitrides: Hypothetical Polymorphs of Si3B3N7

A simple construction principle is provided for the generation of Si-B-N structures. With this protocol, for example, starting from α-Si₃N₄ ( 1 ) a nitrogen atom is removed (→ 2 ), three silicon atoms are replaced by boron (→ 3 ), and the structure is relaxed to give 4 (Si: large empty circles, N: small empty circles, B: small filled circles). For Si₃B₃N₇ over 100 structures were derived in this way, whose geometries and energies were determined by density functional calculations. Two likely candidates for crystalline Si₃B₃N₇ were found.     

Synthesis of highly dispersed vanadium diboride with the use of nanofibrous carbon

Reduction of vanadium(III) oxide with boron carbide and nanofibrous carbon in an induction furnace in argon was used to obtain a highly dispersed vanadium diboride powder. The characteristics of vanadium diboride powders were studied by various analytical methods. It was found that the material obtained contains only a single phase, vanadium diboride, with powder particles mostly aggregated, the average size of particles and aggregates being 9.8 μm at a wide particle size distribution. The optimal synthesis parameters were determined: V₂O₃: B₄C: C ratio corresponding to the stoichiometry, temperature 1700°C, and keeping time 20 min.     

A Bis(silylene)‐Substituted ortho‐Carborane as a Superior Ligand in the Nickel‐Catalyzed Amination of Arenes

The synthesis and structure of the first 1,2‐bis(NHSi)‐substituted ortho‐carborane [(LSi:)C]₂B₁₀H₁₀ (termed SiCCSi) is reported (NHSi=N‐heterocyclic silylene; L=PhC(NtBu)₂). Its suitability to serve as a reliable bis(silylene) chelating ligand for transition metals is demonstrated by the formation of [SiCCSi]NiBr₂ and [SiCCSi]Ni(CO)₂ complexes. The CO stretching vibration modes of the latter indicate that the Si^II atoms in the SiCCSi ligand are even stronger σ donors than the P^III atoms in phosphines and C^II atoms in N‐heterocyclic carbene (NHC) ligands. Moreover, the strong donor character of the [SiCCSi] ligand enables [SiCCSi]NiBr₂ to act as an outstanding precatalyst (0.5 mol % loading) in the catalytic aminations of arenes, surpassing the activity of previously known molecular Ni‐based precatalysts (1–10 mol %).