Morphological evolution of boron carbide particles: Sol-gel synthesis of nano/micro B4C fibers

Herein we present a novel non-catalytic sol-gel route to synthesize nano/micro boron carbide fibers. By in-situ decoration of the precursor surface with boric acid crystals during the thermal decomposition stage, the growth kinetics of boron carbide particles was manipulated. Therefore, the formation of anisotropic crystals instead of polyhedral-equiaxed ones was successfully enabled. The results indicated that highly crystalline boron carbide (B₄C) particles with a low amount (<1 ± 5 wt%) of free carbon were obtained. The SEM and HR-FESEM micrographs revealed that B₄C particles with fully polyhedral-equiaxed morphology were obtained from the precursors, which were thermally decomposed with 2 h holding time at 675 °C. As a result of increased thermal decomposition duration of precursor, B₄C particles with various morphologies, such as rhomboid-plate, nanobelt, and fiber were formed beside the polyhedral-equiaxed particles. The yield of boron carbide fiber formation was increased, and polyhedral-equiaxed particles were decreased in the final products by tailoring the structure of the preceramic precursor. The products containing at least 50% of boron carbide fiber were achieved using 12 h of thermally decomposed precursors. The formation and growth mechanisms of boron carbide particles were speculated and comprehensively discussed.     

Processing and properties of boron carbide (B4C) reinforced LDPE composites for radiation shielding

In the present work, boron carbide (B₄C) particles were synthesized with sol-gel technique following with heat treatment at 1500 °C in an argon atmosphere. 3-(Triethoxysilyl)-propylamine, a silane coupling agent, was doped on to the surface of synthesized B₄C particles. The surface modified B₄C particles were embedded in LDPE matrix in order to obtain flexible, lightweight and environmentally friendly shielding materials. The effect of surface functionalization and concentration of boron carbide on its distribution characteristics in the polymer matrix and its effects on the mechanical and neutron shielding properties of the composites are examined. The results showed that high purity-fully crystalline B₄C powders with polyhedral-equiaxed morphology in the size range of 20 nm–500 nm were produced. It was found that even the very low amount (0.6–1.7 wt%) of incorporated nano/sub-micron B₄C particles in LDPE matrix improved the neutron shielding (up to 39%), tensile strength (9.3%) and impact resistance (8%) of the composites.     

Combustion synthesis of hexagonal boron nitride nanoplates with high aspect ratio

High crystalline hexagonal boron nitride nanoplates with high aspect ratio of ~400 have been synthesized by combustion synthesis method through magnesiothermic reduction reaction between B₂O₃ and Mg in N₂ pressure. The synthesized hexagonal boron nitride nanoplates were about 50 nm in thickness and larger than 20 μm in lateral size. The six-fold symmetric spots electron diffraction pattern of transmission electron microscopy shows that the nanoplate is well crystallized. Hexagonal boron nitride nanoplates grow via an Oswald ripening process and have larger lateral size when it was prepared with larger magnesium particles. High temperature liquid magnesium provides an important environment for the growth and crystallization of boron nitride. This work provides an effective way to achieve low-cost and large-scale preparation of high-quality boron nitride nanoplates.     

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.     

Effect of boron carbide nano particles in CuSi4Zn14 silicone bronze nanocomposites on matrix powder surface morphology and structural evolution via mechanical alloying

In the present research work, [82Cu4Si14Zn]_100-x – x wt% B₄C (x?=?0, 3, 6, 9, and 12) nanocomposite powders had synthesized by mechanical alloying (MA). The MA process had carried out in a single vial high-energy planetary ball mill with the ball-to-powder ratio of 10:1 for 20?h. The results had revealed that the addition of B₄C nano-ceramic particles had contributed more reduction on Cu-Zn-Si matrix powder particle size, changes in shapes, and structural refinement. The synthesized nanocomposite powders had characterized by advanced microscopes. The calculated average nanocomposite powder particle size was 13?±?1.2?µm, 9?±?0.8?µm, 5?±?0.65?µm, 3?±?0.4?µm, and 1?±?0.25?µm for 0, 3, 6, 9, and 12?wt% B₄C reinforced nanocomposite powders respectively. Further, an average nanocrystallite size of 84?nm had obtained for [CuSi4Zn14]-0% B₄C sample whereas 13?nm had achieved for [CuSi4Zn14]-12% B₄C sample. This had attributed by variation in repeated cold welding, severe plastic deformation, and fragmentation of mechanical collisions with the function of boron carbide (B₄C) nano-ceramic particles in Cu-Zn-Si matrix. In addition, the laser powder particle size (diameter, μm) and its distribution at D₁₀₀, D₁₀, D₅, D₁, D_0.1, and D_0.01 with the function of the percentage of B₄C ceramic particles had also studied and investigated.     

High pressure synthesis of new heterodiamond phase

New heterodiamond phase (structure type of cubic boron nitride) with boron and nitrogen atoms partially substituted by carbon has been synthesized by using high pressure-high temperature treatment of the mixture of boron and C₃N₄ carbon nitride powders. This phase consisted of up to 5 micron-sized individual crystals. The composition of new phase was established with the help of microanalysis and structure refinement.     

Synthesis of sub-micro sized high purity zirconium diboride powder through carbothermal and borothermal reduction method

Sub-micro sized zirconium diboride (ZrB₂) powders were successfully prepared via the boro/carbothermal reduction method using zirconium oxide and boron carbide as the primary raw materials. The prepared mixtures were thermally reacted at 1250 °C for 1 h. The optimized composition range containing the lowest oxide and carbide impurity, which was 0.14% of oxygen and 0.3% of carbon contents, was determined using crystallographic and elemental analysis. The particle size was reduced from 5 µm to 245 nm by the addition of B₄C as a reductant within a composition range that maintained the highest purity. The morphology changed from faceted to angular hexagonal bar-like with a simultaneous growth in particle size. Changes in the particle structure were a result of the existing liquid B₂O₃ phase during the reaction. The 245-nm particles contained 12.1% oxygen content and 16.2% oxygen content for the 5-μm particle in the circumstance in which limited oxides could be produced.     

Preparation of submicron boron carbide powder through gas-solid reaction method

Boron carbide submicron powder was synthesized with boron oxide and graphene as starting materials by gas-solid reaction method using two different apparatuses. The effects of calcination temperature and holding time, apparatus type and B₂O₃/C ratio of the starting materials on the phase composition and morphology of the synthesized powders were evaluated. A newly formed residual carbon morphology distinct from original graphene were present in samples synthesized at a higher B₂O₃/C ratio or temperature. The synthesis temperature of ∼1500 °C was found to be more suitable to obtain boron carbide powder without the existence of residual carbon. The new type of apparatus enabled the synthesis of boron carbide phase at a relatively lower temperature, due to its more efficient use of B₂O₃ vapor.     

Bulk boron carbide nanostructured ceramics by reactive spark plasma sintering

Bulk boron carbide (B₄C) ceramics was fabricated from a boron and carbon mixture by use of one-step reactive spark plasma sintering (RSPS). It was also demonstrated that preliminary high-energy ball milling (HEBM) of the B+C powder mixture leads to the formation of B/C composite particles with enhanced reactivity. Using these reactive composites in RSPS permits tuning of synthesized B₄C ceramic microstructure. Optimization of HEBM + RSPS conditions allows rapid (less than 30 min of SPS) fabrication of B₄C ceramics with porosity less than 2%, hardness of ~35 GPa and fracture toughness of ~ 4.5 MPa m ^1/2     

Optical characterization of boron carbide powders synthesized with varying B-to-C ratios

Boron carbide powders were synthesized from elemental powders and studied using X-ray diffraction (XRD) and UV–visible diffuse reflectance, Raman, and diffuse reflectance IR spectroscopies. Following reaction at 1400°C for 6 h, synthesized powders exhibited possible faulting as suggested by XRD patterns. B₃C, B_4.3C, and B₅C powders contained graphitic carbon whereas the boron carbides with higher B/C ratios contained no residual carbon, suggesting that the carbon rich phase boundary is likely temperature dependent. Analysis by Raman and IR spectroscopy suggested that Raman spectra are influenced by excitation frequency due to resonance. We suggest that measurement of boron carbides with resonant Raman lifts the selection rules to allow measurement of Raman silent modes that are present in the IR spectra. Optical reflectance of the boron carbide powders revealed that the B/C ratio governed the indirect and direct optical band gaps of the faulted powders. B₃C and B_4.3C powders were light gray in spite of the presence of the carbon, whereas B₅C, B_6.5C, B₁₀C, and B₁₂C were gray, green, brown, and dark brown, respectively. Increasing carbon content increased the optical indirect band gap from 1.3 eV for B₁₂C to 3.2 eV for B₃C, causing the observed color changes.     

Effects of reactants proportions on features of in-situ magnesiothermic self-propagating high temperature synthesized boron carbide powder

The effects of reactant proportions were investigated on features (phase composition, micromorphology and crystal development) of B₄C (boron carbide) powder synthesized by in-situ magnesiothermic SHS (self-propagating high temperature synthesis) method, which was based on the perspective of thermodynamic design. The results showed that the reactant proportions were the fundamental reasons affecting the phase composition of the products during the reaction process. Mg addition could decrease the Mg₃B₂O₆/MgO mass ratio of the SHS products. Moreover, C addition would increase the C/B mass ratio of the leached products. When the C molar ratio was 0.2, free boron appeared in the leached products, and the composition of boron carbide was B₁₃C₂. When the C molar ratio ≥0.6, the composition of boron carbide changed into B₄C, while free carbon began to appear. The lattice parameters a and c of boron carbide crystal dropped with the increase of the C/B mass ratio from 0.1 to 0.3. Meanwhile, carbon atoms gradually entered the boron carbide unit cell. When the C/B mass ratio exceeds 0.3, the lattice parameters tended to be constants of a = 5.608 Å, c = 12.039 Å, while free carbon began to appear in the leached products.     

Construction of hexagonal boron nitride@polystyrene nanocomposite with high thermal conductivity for thermal management application

Hexagonal boron nitride (BN) hold great promise as emerging building blocks for thermal interface materials owing to their outstanding heat transfer performance. Herein, we report a carboxylated polystyrene-coated hydroxylated BN (BN–OH@PS-COOH) nanocomposite with highly thermal conductivity (TC) and extraordinary mechanical properties for thermal management. The exfoliated BN-OH nanosheets were obtained via molten alkali hydroxide pretreatment and sonication. Subsequently, PS-COOH nanospheres were grew on the surface of BN-OH nanosheets by in situ polymerization. Noncovalent interactions between PS-COOH and BN-OH are favor to reduce interfacial thermal resistance, which contributes to accelerate heat transport. As a result, the TC of the resultant BN-OH@PS-COOH nanocomposite with 12 wt% BN-OH addition is 1.131 W/mK, which is much higher than that of neat PS (0.186 W/mK) and BN/PS blend nanocomposite (0.312 W/mK). Moreover, the BN-OH@PS-COOH nanocomposite exhibits outstanding mechanical properties. Our study may stimulate novel perspectives on the design of high-performance polymer-based thermal interface materials.     

Investigation on mechanochemical synthesis of Al2O3/BN nanocomposite by aluminothermic reaction

Alpha-alumina–boron nitride (α-Al₂O₃–BN) nanocomposite was synthesized using mixtures of aluminum nitride, boron oxide and pure aluminum as raw materials via mechanochemical process under a low pressure of nitrogen gas (0.5 MPa). The phase transformation and structural evaluation during mechanochemical process were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential thermal analysis (DTA) techniques. The results indicated that high exothermic reaction of Al–B₂O₃ systems under the nitrogen pressure produced alumina, aluminum nitride (AlN), and aluminum oxynitride (Al₅O₆N) depending on the Al value and milling time, but no trace of boron nitride (BN) phases could be identified. On the other hand, AlN addition as a solid nitrogen source was effective in fabricating in-situ BN phase after 4 h milling process. In Al–B₂O₃–AlN system, the aluminothermic reaction provided sufficient heat for activating reaction between B₂O₃ and AlN to form BN compound. DTA analysis results showed that by increasing the activation time to 3 h, the temperature of both thermite and synthesis reactions significantly decreased and occurred as a one-step reaction. SEM and TEM observations confirmed that the range of particle size was within 100 nm.     

Conical Boron Nitride Nanorods Synthesized Via the Ball-Milling and Annealing Method

A boron nitride (BN) nanostructure, conical BN nanorod, has been synthesized in a large quantity on Si substrates for the first time via the ball-milling and annealing method. Nitridation of milled boron carbide (B₄C) powders was performed in nitrogen gas at 1300°C on the surface of the substrates to form the BN nanorods. The highly crystallized nanorods consist of conical BN basal layers stacked along the nanorod axis. Ball milling of the B₄C powders can significantly enhance the nitridation of the powders and thus facilitate the formation of nanorods during the annealing process.     

Effect of mono and hybrid ceramic reinforcement particles on the tribological behavior of the AZ31 matrix surface composites developed by friction stir processing

The effects of the size and morphology of the reinforcement particles on hardness and tribological behaviors of the AZ31 Mg alloy matrix composites were studied. Different ceramic compounds, including boron carbide (B₄C), tungsten carbide (WC), and Zirconia (ZrO₂) were selected as the reinforcement materials for developing mono composites. The average sizes of the B₄C, WC, and ZrO₂ particles were about 150 μm, 5 μm, and 35 nm, respectively. Besides, hybrid reinforcements composed of the B₄C + ZrO₂ and WC + ZrO₂ powders were employed to develop hybrid composites. All the composite were fabricated using the friction stir processing (FSP) technique. Investigating the microstructure of the composites by secondary electron microscopy (SEM) analysis showed a homogenous distribution of the reinforcement particles in the AZ31 Mg alloy matrix. Microhardness measurements revealed that the hardness of AZ31/ZrO₂ nanocomposite is about 120% higher than that of AZ31 base metal. According to the results of the dry sliding wear tests, the AZ31/B₄C and AZ31/ZrO₂ composites had a maximum wear resistance and a minimum friction coefficient average, respectively. Combining the B₄C and WC reinforcements with the ZrO₂ nanoparticles caused an improvement in wear resistance and friction performances of the hybrid composites. SEM observations of the worn surfaces and debris resulted from wearing of the samples after 500 m sliding distance under the normal load of 10 N, revealed that the severe and mild abrasive mechanisms are dominant.     

Processing factors influencing the free carbon contents in boron carbide powder by rapid carbothermal reduction

High quality boron carbide powder without free carbon is desired for many applications. In this study, the factors that influence free carbon content in boron carbide powders synthesized by rapid carbothermal reduction reaction were evaluated. The dominant factors affecting free carbon contents in boron carbide powder were reaction temperature, precursor homogeneity, the particle size of reactants, and excess boron reactant amount. The reaction temperature at 1850 °C was sufficient to synthesize boron carbide with low free carbon content. Depending on process conditions, precursor homogeneity was also affected by the calcination temperature and time. Smaller particle size of reactants contributed to less carbon content and more uniformity in synthesized boron carbide. Excess boric acid effectively compensated for B₂O₃ volatilization. In the optimal sample, using 80 mol% excess nano boric acid and calcined at 500 °C, the free carbon in the synthesized boron carbide was negligible (0.048 wt.%).     

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.     

Effect of BN or B4C content on physical and tribological properties of copper-clad laminates reinforced with carbon fiber and epoxy resin

Plasma treatment was used to improve the surface roughness of copper foil. The copper-clad laminates reinforced with carbon fiber, boron nitride (BN), or boron carbide (B₄C), and epoxy resin were prepared by hot pressing. The effect of BN or B₄C content on the physical properties and tribological properties of copper-clad laminates reinforced with carbon fiber and epoxy resin were studied. The resulting copper-clad laminate exhibited desirable properties, such as dielectric constant, peel strength, oxygen index, and arc resistance, which were influenced by the concentration of BN or B₄C particles. Additionally, the wear and friction properties of the laminate were evaluated, revealing the effects of load, sliding speed, and particle content on weight loss, specific wear rate, and coefficient of friction. SEM analysis of worn surfaces provided insight into the stages of wear, highlighting the importance of an oxide layer in reducing wear and protecting the copper surface.     

Sol-Gel synthesis and characterization of SiC–B4C nano powder

In the present research, SiC–B₄C nano powders were synthesized through sol–gel process in water–solvent–catalyst–dispersant system. In order to evaluate the formation mechanism of the product during sol-gel process, TEM, SEM, DTA/TG, BET, XRD, FTIR and DLS analysis methods were employed. The nanometric size of precursor was controlled by dispersing agents and controlling pH inside the sol. DLS analysis revealed that the particles of the precursor inside the sol were below 10 nm. FTIR results indicated that the (Si–O–B) bonds were formed in the dried gel powder, due to hydrolysis and condensation reactions. DTA analysis confirmed that the synthesis temperature was lower than 1400 °C. XRD results implied the presence of cubic β-SiC and the rhombohedral B₄C phases, which were formed simultaneously in the SiC–B₄C nanopowder. BET analysis indicated a high surface area for the particles of about 171.42 m²/g, and that the surfaces of these particles were meso porous. SEM analysis exhibited that SiC– B₄C particle size was in the range of 20–40 nm with homogenous morphology. Ultimately, the TEM/EDS microstructural analysis showed that B₄C and SiC particles were formed simultaneously and uniformly in the final product.     

Effects of boron oxide composition,structure, and morphology on B4C formation via the SHS process in the B2O3–Mg – C ternary system

This study investigates the formation of B₄C in the B₂O₃–Mg–C ternary system via a magnesiothermic reduction process using two kinds of boron oxide (B₂O₃) ‒ the commercial B₂O₃ and that synthesized from boric acid via the coupled chemical-thermal process. In addition to the raw materials, the products were subjected to XRD, FTIR, SEM, and FESEM analyses to determine the effects of microstructural and morphological properties of boron oxide as an important raw material, on B₄C formation in the combustion synthesis process. For this purpose, powder mixtures of B₂O₃:Mg:C were prepared at a stoichiometric molar ratio of 2:6:1 and compacted into pellets using a uniaxial hydraulic press, which were subsequently subjected to the combustion synthesis process based on the self-propagating high-temperature synthesis (SHS). Finally, the samples thus obtained were leached in an aqueous hydrochloric acid solution. Analysis of the commercial B₂O₃ revealed the presence of large amounts of such by-products as magnesium borate (Mg₃B₂O₆) and magnesium oxide (MgO) along with relatively small amounts of boron carbide after the leaching process, while those obtained for the chemically-thermally synthesized B₂O₃ showed a relatively large amount of B₄C (from micron-sized particles to nanoparticles) together with a remaining carbon phase and very small amounts of magnesium borate as by-products. It can be, therefore, concluded that the changes in chemical composition and introduction of a hydrous HBO₂ phase in the boron oxide in the B₂O₃–Mg–C mixture as well as its varied microstructure, morphology, and particle size have significant effects on the efficiency of B₄C production through the SHS process.