Van der Waals epitaxy and characterization of hexagonal boron nitride nanosheets on graphene

Graphene is highly sensitive to environmental influences, and thus, it is worthwhile to deposit protective layers on graphene without impairing its excellent properties. Hexagonal boron nitride (h-BN), a well-known dielectric material, may afford the necessary protection. In this research, we demonstrated the van der Waals epitaxy of h-BN nanosheets on mechanically exfoliated graphene by chemical vapor deposition, using borazine as the precursor to h-BN. The h-BN nanosheets had a triangular morphology on a narrow graphene belt but a polygonal morphology on a larger graphene film. The h-BN nanosheets on graphene were highly crystalline, except for various in-plane lattice orientations. Interestingly, the h-BN nanosheets preferred to grow on graphene than on SiO₂/Si under the chosen experimental conditions, and this selective growth spoke of potential promise for application to the preparation of graphene/h-BN superlattice structures fabricated on SiO₂/Si.     

Modification of hexagonal boron nitride nanoparticles with fluorosilane

Surfaces of hexagonal boron nitride (hBN) nanoparticles were modified with perfluorooctyl-triethoxysilane (FTS). Experiments were performed for 40–120 min in 70–150 °C range with FTS/hBN weight ratio in the range of 0.5–1.5. The products were analyzed by FT-IR, TGA, FESEM, HRTEM and EDX. Results of FT-IR analyses indicated that modification takes place in 80 min at 150 °C under reflux with a FTS/hBN ratio of 1.5. Presence of FTS on hBN nanoparticles was confirmed by the weight losses in TGA, and by TEM, TEM-EDX analyses.     

Evaluation of antibacterial and catalytic potential of copper-doped chemically exfoliated boron nitride nanosheets

Boron nitride (BN) nanosheets were prepared by chemical exfoliation method and incorporation of Cu as a dopant was achieved using hydrothermal route. Hexagonal phase of BN (h-BN) was detected using x-ray difractometer (XRD). Functional group analysis with fourier transform infrared spectroscope (FTIR) was employed to identify the chemicals used in the process, which was then further confirmed with energy dispersive x-ray spectroscopy (EDS) coupled with FESEM. Optical analysis undertaken with UV–vis. spectroscopy indicated absorption at UV region. Raman spectroscopy was used to acquire molecular fingerprints of BN molecules. Photoluminescence (PL) spectroscopy was carried out to study the exciton behaviour of samples in order to elucidate the electron migration and transfer rate. Field emission scanning electron microscope (FESEM) and high resolution transmission electron microscope (HRTEM) were employed to examine the morphology and structure of materials. The experimental results indicate that Cu-doped BN nanosheets possess excellent catalytic potential and superior antibacterial activity.     

Excellent electrical conductivity of the exfoliated and fluorinated hexagonal boron nitride nanosheets

The insulator characteristic of hexagonal boron nitride limits its applications in microelectronics. In this paper, the fluorinated hexagonal boron nitride nanosheets were prepared by doping fluorine into the boron nitride nanosheets exfoliated from the bulk boron nitride in isopropanol via a facile chemical solution method with fluoboric acid; interestingly, these boron nitride nanosheets demonstrate a typical semiconductor characteristic which were studied on a new scanning tunneling microscope-transmission electron microscope holder. Since this property changes from an insulator to a semiconductor of the boron nitride, these nanosheets will be able to extend their applications in designing and fabricating electronic nanodevices.     

Physical and mechanical properties of hexagonal boron nitride ceramic fabricated by pressureless sintering without additive

Hexagonal boron nitride hBN ceramic was successfully fabricated by pressureless sintering at 2100C using submicrometre hBN powders without any sintering additive. The as-prepared hBN ceramic showed a room temperature flexural strength of 30.7MPa. Its flexural strength increased with the increment of temperature in N₂ atmosphere, and it retained a strength of 57.2MPa nearly two times of the room temperature strength at 1600C due to clean grain boundaries with no glassy phase. Additionally, the as-prepared hBN ceramic showed a high thermal conductivity of 31.76Wm¹k¹ and a good thermal shock resistance, which retained a relatively high residual flexural strength of 22.6MPa 73.5 of the original flexural strength at T800C. The as-prepared hBN ceramic presents a good application prospect at high temperature.     

Correlations between microstructure and dielectric properties of hexagonal boron nitride

Hexagonal boron nitride is a material with a unique combination of mechanical, chemical, and electrical properties and therefore of considerable technical and commercial interest. Nevertheless, there exists only very limited knowledge concerning the correlation of microstructure and electrical and dielectrical properties of such materials. In this work, the microstructure, dielectric breakdown resistance (dielectric strength), and low permittivity of different BN ceramics and composites were investigated. Besides exhibiting a very high specific electrical resistivity of 10¹³–10¹⁵ Ω cm, the materials had excellent dielectric strengths (up to 53 kV/mm) and low electrical permeability (4.1). The dielectric strength depended strongly on the porosity and to a lesser extent on the content of secondary phases, whereas the permittivity was influenced by the secondary phases. The aging of the materials in humid air did not significantly alter these values. The permittivity was found to be independent of frequency between 0.1 MHz and 10 MHz and temperature up to 300 °C.     

Band-edge luminescence of deformed hexagonal boron nitride single crystals

We studied deformation effects on band-edge luminescence of pure hexagonal boron nitride single crystals. After simple deformation of the single crystals at room temperature, the band-edge luminescence showed a dramatic change, originating from stacking disorder, in the peak wavelength. It changed from 215 nm in a free exciton band to 227 nm in a bound exciton band. This 227-nm bound exciton luminescence has a fast radiative decay time (below a few ns).     

Highly thermally conductive hexagonal boron nitride/alumina composite made from commercial hexagonal boron nitride

Hexagonal BN is an unusual material in that it is both highly thermally conductive as well as an electrical insulator. Additionally, hBN is also thermally stable in air. This unusual combination of properties makes hBN of significant interest for thermal management. Unfortunately, hBN is not easily consolidated into substrates without the addition of second phases which generally result in poorer thermal performance. This research investigates the potential to utilize this material to dissipate heat from high‐voltage, high‐power electrical devices. Specifically, a process to coat individual platelets of commercial hexagonal BN powder with a layer of amorphous aluminum oxide was developed. The coated hexagonal BN was then hot‐pressed to form a highly thermally conductive substrate. The process to coat hexagonal BN platelets with aluminum oxide was accomplished by mixing hexagonal BN with AlCl₃ containing some water, then evaporation of excess AlCl₃ to form a Al, Cl, and O layer on hexagonal BN. This product was then heated in air to convert the surface layer into aluminum oxide. Following hot pressing to 1950°C and 10 ksi, the consolidated composite has through‐plane and in‐plane thermal conductivity of 14 and 157 W·(m·K)^?1, respectively, at room temperature.     

Structure,morphology and dielectric properties of hexagonal boron nitride nanoparticles reinforced biopolymer nanocomposites

Hexagonal boron nitride nanoparticles (h-BNNPs)/Chitosan (CS)/Hydroxypropyl methylcellulose (HPMC) based ternary nanocomposites were prepared using solution casting method and characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analyses (TGA), Scanning electron microscopy (SEM) and Atomic force microscopy (AFM). The dielectric properties of CS/HPMC/h-BNNP nanocomposite films were also investigated as a function of frequency and temperature and a maximum dielectric constant of ~1200 was achieved at 5 wt % of h-BNNP loading in CS/HPMC blend matrix. The results from the structural, morphological and thermal studies revealed good interactions between h-BNNPs, CS and HPMC.     

Catalytic effect of potassium carbonate on carbothermic production of hexagonal boron nitride

Effect of potassium carbonate addition on the carbothermic formation of hexagonal boron nitride (hBN) was investigated by keeping the K₂CO₃ added B₂O₃+C mixtures in nitrogen atmosphere at 1400 °C for 40–160 min. K₂CO₃ amount was varied in the range of 10–60 wt% of the B₂O₃+C mixture. Products were subjected to XRD and quantitative analyses, SEM and TEM observations, and particle size measurement. Amount of hBN increased considerably with K₂CO₃ addition; also particle size and crystallinity improved. Catalytic role of K₂CO₃ was suggested as forming a potassium borate melt in which hBN particles form, in addition to carbothermic formation reaction. Effect of K₂CO₃ on increasing the hBN amount decreased when it was used over 40%. This was attributed to the rapid evaporation of the formed potassium borate liquid.     

Thermal conductivity and mechanical properties of thermally conductive composites based on multifunctional epoxyorganosiloxanes and hexagonal boron nitride

As electronics become portable and compact with concomitant thermal issues, the demand for high-performance thermal interface materials has increased. However, the low thermal conductivity of polymers and the poor dispersion of fillers impede the realization of high filler loading composites, and this in turn limits the increase in thermal conductivity. To overcome this, multifunctional epoxyorganosiloxanes (MEOSs) were synthesized and used to fabricate thermally conductive composites in this study. In the first part of this study, the effect of the molecular weights of MEOSs on the curing behaviors of the MEOSs/trimethylolpropane tris(3-mercaptopropioante)/1-methyl imidazole systems was investigated by a DSC analysis. Both the nonisothermal and isothermal curing of the epoxy compositions (ECs) verified that the reaction rate of EC-1 containing MEOS-1 with lower molecular weight was faster than that of EC-2. In addition, mechanical properties of the cured EC-1 were superior to those of its counterpart because of a higher density in crosslinking. In the second part, EC-1 was admixed with h-BN to fabricate thermally conductive (TC) composites. Owing to the low viscosity (1.6 Pa s at 0.1 Hz) of EC-1, a TC-3 composite containing 45 wt% h-BN fillers was obtained, and the in-plane and through-plane thermal conductivity of the cured TC-3 composite reached 3.55 ± 0.29 Wm^?1K^?1 and 1.08 ± 0.08 Wm^?1K^?1, respectively. Furthermore, the tensile modulus of the cured TC-3 was measured as 76.3 ± 6.1 MPa, which was 9.1 times higher than that of the cured EC-1. Both the high thermal conductivity and good mechanical properties of the cured TC-3 composite were ascribed to the percolation of h-BN networks stemming from the high filler loading.     

Hexagonal boron nitride nanosheets as metal-free electrochemical catalysts for oxygen reduction reactions

A high-performance ball milling technique was developed for synthesizing hexagonal boron nitride (h-BN) carbon paper (CP) electrodes as metal-free catalyst for the oxygen reduction reaction (ORR) and hydrogen storage (electrochemically) in acidic media. The h-BN nanosheets were functionalized with glycine to enhance the number of active sites and to boost the catalytic activity. The ball-milled h-BN catalytic electrodes demonstrated ultra-high catalytic activity toward electrochemical hydrogen adsorption/desorption (～3.5 times higher than pristine electrodes) as well as ORR in acidic electrolytes. Furthermore, in-situ durability analysis of the h-BN electrodes was performed via conducting a long-duration cycling experiment (>200 cycles). A mechanistic reaction pathway (sequential) including chemisorption and charge transfer reactions (four-electron and two-electron pathways) was also proposed for the ORR. Considering superior catalytic activity of as-prepared h-BN/CP electrodes, this class of metal-free nanostructured materials can be employed as inexpensive catalysts for the electrochemical H-storage and ORR within various energy storage/conversion devices (e.g., batteries, electrolyzers, and fuel cells).     

Scalable production of boron nitride nanosheets in ionic liquids by shear-assisted thermal treatment

Due to their intriguing properties, boron nitride nanosheets (BNNSs) with large lateral size and high crystallinity have great promise for many applications. However, the quantitative exfoliation of hexagonal boron nitride (h-BN) into good quality BNNSs still remains a key challenge. Herein, we report a scalable method to exfoliate BNNSs in ionic liquids (ILs) via shear-assisted thermal treatment. Few-layer BNNSs with well-preserved structural integrity are successfully prepared by this method. The synergistic effects of strong physical adsorption and intercalation of IL molecules, chemical interactions between hydrogen fluoride (HF) and h-BN, activation energy provided by heat treatment, and shear forces generated by repetitive stirring effect contribute to the exfoliation of BNNSs.     

Large-scale synthesis and growth mechanism of boron nitride nanocomposite assembled by nanosheets and nanotubes

Boron nitride nanocomposites assembled by nanosheets and nanotubes can exert multi-dimensional synergistic toughening and strengthening effects. This material is expected to be a high-efficiency reinforcement additive in advanced structural ceramics. In this study, we designed a universal method for synthesizing gram-scale boron nitride nanocomposites by annealing the precursor containing catalyst in chemical vapor deposition equipment under flowing ammonia, and a combined growth mechanism of surface-diffusion and solid-liquid-solid is proposed. The boron nitride nanosheets were initially formed by a surface-diffusion reaction between boron trioxide and ammonia at 1300°C. At elevated temperatures (1400°C-1500°C), the boron nitride nanotubes grew in-situ from the nanosheets in the presence of catalysts through a solid-liquid-solid mechanism, forming the desired boron nitride nanocomposite.     

Effect of hexagonal boron nitride on the coefficient of frictions of organic-inorganic hybrid polymer thin films for metal surface coatings

Abstract

Organic-inorganic hybrid coatings were developed via a sol-gel method using hexagonal boron nitride (h-BN) as a ceramic filler material incorporated into a polymeric matrix. To investigate the effects of h-BN on the properties of polymer-based coatings, parameters such as hardness, coefficient of friction, and hydrophobicity were investigated. Colloidal silica (CS), methyltrimethoxysilane (MTMS), water, and acid catalyst containing coatings were prepared by varying the content of h-BN from 10% to 25%. All the coatings were prepared with the same experimental procedure and coated on 1050 aluminum alloy plates. The compensating contents of MTMS and colloidal silica with a fixed molar ratio of MTMS and CS were set to be 1:1.2, and a specific amount of the catalyst was utilized. Coatings were examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), and energy-dispersive X-ray spectroscopy (EDS). The most promising physical properties were determined to be the pencil hardness of 8B, adhesion strength of 5B, coefficient of friction of 0.332?N, and water contact angle of 114.75°. Therefore, it can be concluded that the h-BN improves the physical properties of polymeric coatings. In addition, this study demonstrates the effect of h-BN on the adherence of polymer matrix-based hybrid coatings.     

Electrical and Electromagnetic Interference (EMI) shielding properties of hexagonal boron nitride nanoparticles reinforced polyvinylidene fluoride nanocomposite films

The hexagonal boron nitride nanoparticles (h-BNNPs) reinforced flexible polyvinylidene fluoride (PVDF) nanocomposite films were prepared via a simple and versatile solution casting method. The morphological, thermal and electrical properties of h-BNNPs/PVDF nanocomposite films were elucidated. The electromagnetic interference (EMI) shielding properties of prepared nanocomposite films were investigated in the X-band frequency regime (8–12 GHz). The EMI shielding effectiveness (SE) was increased from 1 dB for the PVDF film to 11.21 dB for the h-BNNPs/PVDF nanocomposite film containing 25 wt% h-BNNPs loading. The results suggest that h-BNNPs/PVDF nanocomposite films can be used as lightweight and low-cost EMI shielding materials.     

The effect of boron nitride nanosheets on the mechanical and thermal properties of aluminum nitride ceramics

The boron nitride nanosheets (BNNSs)/aluminum nitride (AlN) composites were prepared by hot press sintering at 1600°C. The microstructure, mechanical properties, and thermal conductivity of the samples were measured, and the effect of adding BNNSs to AlN ceramics on the properties was studied. It is found that the addition of BNNSs can effectively improve the mechanical properties of AlN. When the additional amount is 1 wt%, the bending strength of the sample reaches the maximum value of 456.6 MPa, which is 23.1% higher than that of the AlN sample without BNNSs. The fracture toughness of the sample is 4.47 MPa m^1/2, a 68.7% improvement over the sample without BNNSs. The composites obtained in the experiment have brilliant mechanical properties.     

Synthesis and characterization of polyimide/hexagonal boron nitride composite

Polyimide (PI)/hexagonal boron nitride (h‐BN) composites were produced via the thermal imidization procedure from solution mixtures of a polyamicacid, which is prepared from 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride and 3,3′‐diaminodiphenyl sulfone (DADPS) in N‐methyl‐2‐pyrrolidone (NMP), and alkoxysilane functionalized h‐BN. The structure, thermostability, thermal behavior, and surface properties of the resulting materials were characterized by means of Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM). The thermal characteristics of PI/h‐BN films were better than the pure PIs. The physical and mechanical properties of the films were evaluated by various techniques such as contact angle, chemical resistance, and tensile tests. The flame retardancy of the composite materials was also examined by the limiting oxygen index (LOI). The experiments showed that the LOI values of PIs increased from 32 to 43 for the materials containing hexagonal boron nitride. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of Na2CO3 on hexagonal boron nitride prepared from urea and boric acid

Formation of hexagonal boron nitride (hBN) from a precursor obtained by the reaction of urea and boric acid was studied in nitrogen, ammonia and argon atmospheres in 700-1200 °C temperature range. Effect of sodium carbonate (Na₂CO₃) addition on this process was investigated. Reaction products were subjected to X-ray diffraction, particle size distribution, gravimetric and Fourier transformed infrared spectroscopy analyses. Particle size and crystallite thickness of the formed hBN were seen to increase from about 60 nm and 5 nm at 700 °C to 230 nm and 19 nm at 1200 °C, respectively in NH₃ atmosphere with Na₂CO₃ addition. Highest conversion of boron in the precursor into hBN was achieved as 73.6% when Na₂CO₃ added precursor was reacted at 1200 °C in NH₃. hBN powder with high yield and relatively large particle size was obtained at low temperature such as 1200 °C with Na₂CO₃ addition. Role of Na₂CO₃ addition was suggested to be formation of a sodium borate melt from which hBN crystallized via the reaction of borate and nitrogen ions in the melt. Obtained hBN has the potential for utilization as a clean starting material for synthesis of B or N containing compounds.     

先驱体法制备氮化硼纤维的研究

以三聚氰胺和硼酸为原料,用有机化学法合成先驱体,制备氮化硼纤维。采用中和滴定法、红外吸收光谱、X射线衍射及扫描电镜进行氮化硼纤维的氮含量的测定及结构分析。结果表明:合成的先驱体是结晶体,晶体发育良好;制得的氮化硼纤维具有B-N键、B-N六元环的特征吸收;随着氮化处理温度的提高, 氮化硼纤维的氮含量增加;用扫描电镜观察1 700℃制得的氮化硼纤维的直径为2-5μm,长径比为20- 100,氮含量为53．46％。