Preparation of tungsten borides by combustion synthesis involving borothermic reduction of WO3

An experimental study on the preparation of two tungsten borides, WB and W₂B₅, was conducted by self-propagating high-temperature synthesis (SHS), during which borothermic reduction of WO₃ and elemental interaction of W with boron proceeded concurrently. Powder mixtures with two series of molar proportions of WO₃:B:W = 1:5.5:x (with x = 1.16–2.5) and 1:7.5:y (with y = 0.5–1.33) were adopted to fabricate WB and W₂B₅, respectively. The starting stoichiometry of the reactant compact substantially affected the combustion behavior and the phase composition of the final product. The increase of metallic tungsten and boron reduced the overall reaction exothermicity, leading to a decrease in both combustion temperature and reaction front velocity. The initial composition of the reactant compact was optimized for the synthesis of WB and W₂B₅. In addition to small amounts of W₂B and W₂B₅, the powder compact of WO₃ + 5.5B + 2 W produced WB dominantly. Optimum formation of W₂B₅ was observed in the sample of WO₃ + 7.5B + 0.85W. Experimental evidence indicates that an excess amount of boron about 10–13% is favorable for the formation of WB and W₂B₅.     

Improvement of high-temperature stability of PIP SiCf/SiC material through in situ grown BNNTs

In this paper, the effect of in situ grown boron nitride nanotubes (BNNTs) and preparation temperature on mechanical behavior of PIP (Precursor Infiltration and Pyrolysis) SiC_f/SiC minicomposites under monotonic and compliance tensile is investigated. In situ BNNTs are grown on the surface of SiC fibers using ball milling–annealing process. Composite elastic modulus, tensile strength, fracture strain, tangent modulus, and loading/unloading inverse tangent modulus (ITM) are obtained and adopted to characterize the mechanical properties of the composites. Microstructures of in situ grown BNNTs and tensile fracture surfaces are observed under scanning electronic microscopic (SEM). For SiC_f/SiC minicomposites with BNNTs, the elastic modulus, tensile strength, and fracture strain are all lower than those of SiC_f/SiC minicomposites without BNNTs, mainly due to high preparation temperature and the oxidation of the PyC interphase during the annealing process. Tensile stress–strain curves of SiC_f/SiC minicomposites with and without BNNTs are predicted using the developed micromechanical constitutive model. The predicted results agreed with experimental data. This work will provide guidance for predicting the service life of SiC_f/SiC composite materials and may enable these materials to become a backbone for thermal structure systems in aerospace applications.     

Synthesis of poly(borazinylamine)

1,3,5-Trichloroborazine (TCB) was prepared from the reaction of ammonia chloride with boron trichloride. TCB along with hexamethyldisilazane and boron trichloride were used to synthesize boron nitride (BN) preceramic polymer poly(borazinylamine). This study showed that, the lower the reaction temperature, the higher the synthetic yield. Poly(borazinylamine)'s solubility mainly depended on the ratio of TCB, (Me₃Si)₂NH, and BCl₃. The solvent used in the reaction had a large effect on the ceramic yield of poly(borazinylamine). A soluble poly(borazinylamine) with good synthesis and ceramic yields was obtained when the reaction temperature was −15°C, cyclohexane was the solvent, and the ratio of TCB : (Me₃Si)₂NH : BCl₃ was 1 : 6 : 1. By means of infrared and mass spectroscopy analyses, the structure of the poly(borazinylamine) was identified. Thermal decomposition of the poly(borazinylamine) precursor to hydrolyzed BN was also examined. Hydrolyzed BN was obtained at 1000°C, where the ceramic yield was 35–45%. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 863–868, 1999     

New insights into synthesis of nanocrystalline hexagonal BN

Uncovering the mechanism behind nanocrystalline hexagonal boron nitride (h-BN) formation at relatively low temperatures is of great scientific and practical interest. Herein, the sequence of phase transformations occurring during the interaction of boric acid with ammonia in a temperature range of 25–1000 °C has been studied in detail by means of thermo-gravimetric analysis, X-ray diffraction, infrared spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The results indicate that at room temperature boric acid reacts with ammonia to form an ammonium borate hydrate (NH₄)₂B₄O₇x4H₂O. Its interaction with ammonia upon further heating at 550 °C for 1 h leads to the formation of turbostratic BN. Nanocrystalline h-BN is obtained either during heating in ammonia at 550 °C for 24 h or at 1000 °C for 1 h. This result is important for the development of novel cost-effective and scalable syntheses of h-BN nanostructures, such as nanosheets, nanoparticles, nanofibers, and nanofilms, as well as for sintering h-BN ceramic materials.     

Thermal properties and formation mechanism of h‐BN nanoneedles synthesized via carbothermic reduction reaction

Hexagonal boron nitride (BN) was synthesized through the carbothermic reduction reaction (CRR) of boric acid using lactose as a carbon source under the nitrogen atmosphere at 1500^°C for 3 hours. The boron/carbon (B/C) molar ratio was controlled during the CRR, and the produced samples were investigated by XRD diffraction pattern, FTIR analysis, and Raman spectra. Boron carbide (B₄C) was formed in samples that have a higher carbon content, in addition to boron nitride. While boron nitride pure sample was produced from lower carbon content samples. Formation of B₄C was found to depend on the B/C molar ratio. The morphology of the produced powder was also investigated by SEM and TEM, which revealed that the samples consist of nanoneedles of BN and hexagonal particles of B₄C. The vapor‐solid (VS) reaction mechanism was processed greatly with increasing boron amount, producing boron nitride nanoneedles, which compete with the liquid‐solid (LS) reaction mechanism. The physicochemical properties of the produced samples were studied by DTA, UV, PL, and AC impedance measurements, and revealed that the samples are promising to many proper applications.     

A comparative study on combustion synthesis of Ta-B compounds

A comparative study on the preparation of various tantalum borides (including Ta₂B, Ta₃B₂, TaB, Ta₅B₆, Ta₃B₄, and TaB₂) in the Ta-B system was experimentally conducted by self-propagating high-temperature synthesis (SHS) from the elemental powder compacts of their corresponding stoichiometries. Both combustion temperature and reaction front velocity increased and then decreased with increasing boron content in the powder mixture. The fastest flame front with a reaction temperature of 1732 °C and a propagation rate of 11.2 mm/s was observed in the sample of Ta:B = 1:1. The combustion temperature (1205 °C) and flame-front velocity (3.82 mm/s) for the powder compact of Ta:B = 2:1 were the lowest. According to the XRD analysis, single-phase TaB and TaB₂ were produced from the samples of Ta:B = 1:1 and 1:2, respectively. However, multiphase products were synthesized from the samples of other stoichiometries. In the final products from Ta-rich samples of Ta:B = 2:1 and 3:2, two boride phases, Ta₂B and TaB, along with a large amount of residual Ta were detected. The products yielded from boron-rich reactants of Ta:B = 5:6 and 3:4 were composed of TaB, Ta₃B₄, and TaB₂. Based upon the temperature dependence of combustion wave velocity, the activation energies associated with the formation of TaB and TaB₂ by solid state combustion were determined to be 131.1 and 181.4 kJ/mol, respectively.     

B NMR of boron-doped graphite as the negative electrode of a lithium secondary battery

Boron-doped graphite used as a negative electrode for a lithium rechargeable battery is known to have higher discharge capacity than undoped graphite. Herein, the graphites were mixed with 1, 2.5, 5, and 7 wt.% of boron carbide during the graphitizing process. The structural states of boron in those boron-doped graphites were successfully identified by solid-state ¹¹B NMR spectroscopy. For 1 wt.% sample, all boron atoms were at substitutional sites, as evident by the second-order quadrupole broadened ¹¹B NMR line having a quadrupole coupling constant, Q_CC=3.36(2) MHz. The NMR results show evidence of excess boron atoms recrystallizing as boron carbide during the graphitizing process which is in agreement with XRD data. Agreement of experimental results with computer simulated data indicate that the substitutional sites in boron-doped graphites were observed for the first time.     

Production of titanium-containing metal-ceramic composites based on boron carbide in the nanocrystalline state

ABSTRACT

The results of the study of the production technology, phase composition, structure and physico-mechanical properties of metal-ceramic materials based on boron carbide and their components are presented. Boron carbide was obtained by direct synthesis from chemical elements using amorphous boron and carbon black. By mechanical dispersion, solid reagents were converted into an ultrafine state. Using a chemical method, nanoscale (70–80?nm) boron carbide was synthesised from suspension solutions of amorphous boron and liquid hydrocarbons. Boron carbide-based metal-ceramic composite powder B₄C–(Co–Ni–Ti) was obtained by mechanical dispersion of the constituent components. Based on results of studying of the temperature-dependence of wetting angle of boron carbide with Co–Ni–Ti metallic alloy, the compacting modes of metal-ceramic composite powders by plasma-spark sintering and hot pressing have been developed. The influence of the component content of the binder metal (alloy) on some physico-mechanical properties (linear expansion coefficient, hardness, and bending strength) of hardmetal-ceramic materials based on boron carbide was studied. It was found that the optimum content of the metal component in the composite is ～ 25?wt-%. In the temperature range 300–600°C, the materials obtained are characterised by stable dimensional factors, since in this temperature range the thermal conductivity coefficient does not depend much on temperature. At room temperature, their bending strength is about 1?GPa. A new method of chemical synthesis of nanocrystalline ceramic compositions of boron carbide and titanium diboride using suspension solutions for the preparation of powders and their spark plasma sintering was also developed to obtain a compacted material of composition B₄C+30?wt-%TiB₂, which has a high hardness of 95 HRA (with maximum microhardness 45.6?GPa) and sufficient strength (with a bending strength of 834?MPa).     

Role of boron addition on phase composition,microstructural evolution and mechanical properties of nanocrystalline SiBCN monoliths

Nanocrystalline SiBCN monoliths with the same Si/C/N mole ratio and various boron additions ranged from 0 to 3.0 mol were prepared by mechanical alloying plus reactive hot pressing methods. Correction of boron content and microstructural/morphological evolution was investigated in detail by XRD, SEM, TEM and STEM-EDX structure characterization. Except for SiC and BN(C), boron addition contributes to B_xC formation. Besides, boron addition promotes the crystallization of SiC, leading to the formation of poor crystallinity of spherical structures in inner SiC. Furthermore, boron addition significantly promotes the grain growth of SiC and B_xC and therefore increases the relative volume ratios of B_xC/BN(C) and B_xC/SiC. Amorphous-like BN(C) changes to belt-like structures as boron addition increases. The new formed B_xC effectively contributes to the improvement of Vicker’s hardness while pull-out of BN(C) belt-like structures benefits the fracture toughness.     

Synthesis and NMR studies of the polymer membranes based on poly(4-vinylbenzylboronic acid) and phosphoric acid

Proton conduction in novel anhydrous membranes based on host polymer, poly(4-vinylbenzylboronic acid), (P4VBBA) and phosphoric acid, (H₃PO₄) as proton solvent was studied. The materials were prepared by the insertion of the proton solvent into P4VBBA at different stoichiometric ratios to get P4VBBA·xH₃PO₄ composite electrolytes. Homopolymer and the composite materials were characterized by FT-IR, ¹¹B MAS NMR and ³¹P MAS NMR. ¹¹B MAS NMR results suggested that acid doping favors or leads to a four-coordinated boron arrangement. ³¹P MAS NMR results illustrated the immobilization of phosphoric acid to the polymer through condensation with boron functional groups (B-O-P and/or B-O-P-O-B). Thermogravimetric analysis (TGA) showed that the condensation of composite materials starts approximately at 140 °C. An exponential weight loss above this temperature was attributed to intermolecular condensation of acidic units forming cross-linked polymer. The insertion of phosphoric acid into the matrix softened the materials shifting T_g to lower temperatures. The temperature dependence of the proton conductivity was modeled with Arrhenius relation. P4VBBA·2H₃PO₄ has a maximum proton conductivity of 0.0013 S/cm at RT and 0.005 S/cm at 80 °C.     

Static and dynamic mechanical properties of boron carbide processed by spark plasma sintering

Spark plasma sintering (SPS) has become a popular technique for the densification of covalent ceramics. The present investigation is focused on the static mechanical properties and dynamic compressive behavior of SPS consolidated boron carbide powder without any sintering additives. Fully dense boron carbide bodies were obtained by a short high temperature SPS treatment. The mechanical properties of the SPS-processed material, namely hardness (32 GPa), Young modulus (470 GPa), fracture toughness K_C (3.9–4.9 MPa m^0.5), flexural strength (430 MPa) and Hugoniot elastic limit (17–19 GPa) are close or even better than those of hot-pressed boron carbide.     

Effect of boron on crystallization,microstructure and dielectric properties of CBS glass-ceramics

Herein, we demonstrate the preparation of CBS glass-ceramics by using chemically pure CaO, SiO₂ and B₂O₃ as raw materials. Differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrical measurements have been carried out to explore the effect of boron addition on crystallization, microstructure and dielectric properties of CBS glass-ceramics. Furthermore, the influence of sintering temperature and sintering schemes has been systematically investigated. Results show that the increase of boron content reduces crystallization temperature of CBS glass-ceramics. For instance, with the increase of boron oxide from 10.8?wt% to 19.4?wt%, crystallization temperature decreased by 130?°C. However, excessive boron affects the precipitation of wollastonite crystal phase, destroys crystal structure and damages close arrangement of crystal grains. Moreover, higher boron content weakens dielectric properties of CBS glass-ceramics. In this study, the best molar ratio of ingredients, meeting the ideal target material, is n(Ca): n(Si): n(B) =?1:1:0.6. After optimal sintering procedure, dielectric constant of the best sample was 6 (1?MHz), 6 (10?MHz), and dielectric loss was 2.27?×?10^?3 (1?MHz) and 3.37?×?10^?3 (10?MHz). We demonstrate that the optimal boron content and sintering procedure is required to attain desired dielectric properties of CBS glass-ceramics.     

Correlation of boron content and high temperature stability in Si–B–C–N ceramics

The preparation and characterization of precursor derived Si–B–C–N ceramics with similar Si/C/N ratios but variable boron content are reported. The polymeric precursors were prepared via hydroboration of poly(methylvinylsilazane) using different BH₃·SMe₂/polymer stoichiometries. High temperature thermogravimetric analysis of as-pyrolysed ceramics as well as XRD studies of post-annealed samples display a retarding effect of boron on both crystallization of SiC and Si₃N₄ and stabilization of crystalline β-Si₃N₄.     

Effect of calcination conditions on the species formed and the reduction behavior of the cobalt–magnesia catalysts

The structural characteristics and the reduction behavior of the Co/MgO catalysts were investigated using temperature‐programmed reduction (TPR) and X‐ray diffraction (XRD). The variables investigated included the preparation method and the heat treatment conditions (calcination temperature and time). Depending on these factors, one, two or three of the following Co‐containing species, Co₃O₄, MgCo₂O₄ and (Co, Mg)O (solid solution of CoO and MgO) were identified. The extent of solid solution formation increased as the calcination temperature and calcination time increased. A much lower calcination temperature was needed to form a solid solution in the impregnated catalysts than in the physically mixed ones. The formation of a solid solution rendered the catalyst less reducible. Finally, the decomposition of CH₄, as a probe reaction, was performed and it was found that the amount of carbon deposited decreased with increasing extent of solid solution formation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Controllable preparation of boron nitride microspheres and their epoxy-based thermoconductive composites

How to prepare spherical boron nitride (BN) particle with different size is an extremely challenging work. In this paper, the controllable preparation of spherical BN particle from nanospheres to microsphere was realized by changing the synthesis temperature of trimethyl borate (B(OMe)₃) and ammonia. The spherical precursor (SP) with high oxygen content was obtained first, and then it was heated under flowing ammonia atmosphere to form stable boron nitride microspheres (BNMS). The BNMS exhibits onion-like cavitation structure with a diameter of 0.8–3.4 μm. The effects of the lower reaction temperature (700–825 °C) and gas flow rate on the spherical precursor are discussed. A possible mechanism is proposed to explain the formation of precursors and the appearance of onion-like structure. It is believed that the formation of microsphere is due to the deposition and growth of BO species during the flow process of nanosphere. In addition, the effect of the addition of BNMS on the thermal conductivity of epoxy resin (EP) composites was investigated.     

The effect of B4C addition to MnO2 in a cathode material for battery applications

Boron carbide (B₄C) added manganese dioxide (MnO₂) used as a cathode material for a Zn-MnO₂ battery using aqueous lithium hydroxide (LiOH) as the electrolyte is known to have higher discharge capacity but with a lower average discharge voltage than pure MnO₂ (additive free). The performance is reversed when using potassium hydroxide (KOH) as the electrolyte. Herein, the MnO₂ was mixed with 0, 5, 7 and 10 wt.% of boron carbide during the electrode preparation. The discharge performance of the Zn|LiOH|MnO₂ battery was improved by the addition of 5-7 wt.% boron carbide in MnO₂ cathode as compared with the pure MnO₂. However, increasing the additive to 10 wt.% causes a decrease in the discharge capacity. The performance of the Zn|KOH|MnO₂ battery was retarded by the boron carbide additive. Transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy analysis (EDS) results show evidence of crystalline MnO₂ particles during discharging in LiOH electrolyte, whereas, manganese oxide particles with different oxygen and manganese counts leading to mixture of phases is observed for KOH electrolyte which is in agreement with X-ray diffraction (XRD) data. The enhanced discharge capacity indicates that boron atoms promote lithium intercalation during the electrochemical process and improved the performance of the Zn|LiOH|MnO₂ battery. This observed improvement may be a consequence of B₄C suppressing the formation of undesirable Mn(III) phases, which in turn leads to enhanced lithium intercalation. Too much boron carbide hinders the charge carrier which inhibits the discharge capacity.     

Boron removal by means of chemical precipitation with calcium hydroxide and calcium borate formation

Boron removal was investigated by chemical precipitation from aqueous solutions containing boron using calcium hydroxide. pH, initial boron concentration, amount of Ca(OH)₂, stirring speed and solution temperature were selected as operational parameters in a batch system. The highest boron removal efficiency was reached at pH 1.0. Increasing initial boron concentration and amount of calcium hydroxide raised to boron removal efficiency. Boron removal efficiency was highest at a stirring speed of 150 rpm. The most important parameter affecting boron removal efficiency was solution temperature. Increasing solution temperature increased importantly boron removal. XRD analysis showed that CaB₃O₃(OH)₅·4H₂O, which is a borate mineral called inyoite, occurred between Ca(OH)₂ and borate ions. As a result of the obtained experimental data, when the optimum operational conditions were selected, over 96% of boron removal efficiency was reached by this method.     

Effect of boron‐containing materials on the flammability and thermal degradation of polyamide 6 composites containing melamine

Three different boron‐containing substances—zinc borate (ZnB), borophosphate (BPO₄), and a boron‐ and silicon‐containing oligomer (BSi)—were used to improve the flame retardancy of melamine in a polyamide 6 (PA‐6) matrix. The combustion and thermal degradation characteristics of PA‐6 composites were investigated with the limiting oxygen index (LOI), the UL‐94 standard, thermogravimetric analysis (TGA)/Fourier transform infrared (FTIR) spectroscopy, and differential scanning calorimetry (DSC). A slight increase was seen in the LOI values of a sample containing BSi (1 wt %). BPO₄ at high loadings showed a V0 rating (indicating the best flame retardancy) and slightly lower LOI values in comparison with samples with only melamine. For ZnB and BSi, glassy film and char formation decreased the dripping rate and sublimation of melamine, and this led to low LOIs. According to the TGA–FTIR results, the addition of boron compounds did not change the decomposition product distribution of melamine and PA‐6. The addition of boron compounds affected the flame retardancy by physical means. The TGA data showed that boron compounds and melamine reduced the decomposition temperature of PA‐6. According to the DSC data, the inclusion of boron compounds increased the onset temperature of sublimation of melamine and also affected the flame retardancy negatively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Theoretical prediction on structure evolution and optimal properties of silicon modified hexagonal boron nitride as interphase in SiCf/SiC composite

To predict the effects of Si doping on hexagonal boron nitride (h-BN) and to achieve a balance between mechanical and oxidation properties for the interphase modification in SiC_f/SiC composites, we herein calculate and analyze the crystal structures and mechanical properties of (BN)₆₄Si_x (x = 4, 8, 16, 32) models by means of density functional theory (DFT) calculations and ab initio molecular dynamics (aiMD) simulations. The possible trends of crack deflection and self-healing ability are discussed. The modeling shows an obvious transition of (BN)₆₄Si_x from the layered crystal structure and anisotropic mechanical property to amorphous structure and isotropic mechanical property as the Si doping content up to 36.1 wt%. Regarding to the application of interphase in SiC_f/SiC composites, (BN)₆₄Si₁₆ model structure possess the highest debonding potential according to Cook and Gordon’s criteria and illustrates the higher self-healing capacity at elevated temperature.     

Synthesis of nanocrystalline boron carbide by sucrose precursor method-optimization of process conditions

Nanocrystalline boron carbide powder was synthesized by a precursor method using B₂O₃ as the source of boron and sucrose as the source of carbon. Precursor was prepared at different temperatures ranging from 300 to 800 °C. The optimum temperature for the precursor preparation was found to be 600 °C. All the precursors were heat treated at different temperatures from 1000 to 1600 °C for different duration of heating, ranging from 5 to 240 min under vacuum. The products thus obtained after heat treatment were characterized using X-ray diffraction. The boron carbide obtained was nanocrystalline and the average X-ray crystallite size was found to be ~ 33 nm. Boron, total carbon and free carbon contents also were determined. The free carbon content was found to be less than 3% for samples heated at 1600 °C for 10 min. Effect of heat treatment temperature on the morphology of the synthesized product was studied using scanning electron microscope.