Shear-Assisted Production of Few-Layer Boron Nitride Nanosheets by Supercritical CO2 Exfoliation and Its Use for Thermally Conductive Epoxy Composites.
ABSTRACT: Boron nitride nanosheets (BNNS) hold the similar two-dimensional structure as graphene and unique properties complementary to graphene, which makes it attractive in application ranging from electronics to energy storage. The exfoliation of boron nitride (BN) still remains challenge and hinders the applications of BNNS. In this work, the preparation of BNNS has been realized by a shear-assisted supercritical CO2 exfoliation process, during which supercritical CO2 intercalates and diffuses between boron nitride layers, and then the exfoliation of BN layers is obtained in the rapid depressurization process by overcoming the van der Waals forces. Our results indicate that the bulk boron nitride has been successfully exfoliated into thin nanosheets with an average 6 layers. It is found that the produced BNNS is well-dispersed in isopropyl alcohol (IPA) with a higher extinction coefficient compared with the bulk BN. Moreover, the BNNS/epoxy composite used as thermal interface materials has been prepared. The introduction of BNNS results in a 313% enhancement in thermal conductivity. Our results demonstrate that BNNS produced by supercritical CO2 exfoliation show great potential applications for heat dissipation of high efficiency electronics.
Project description:A green approach to prepare exfoliated hexagonal boron nitride nanosheets (h-BNNS) from commercially pristine h-BN involving a two-step procedure was investigated. The first step involves the dispersion of pristine h-BN within an aqueous solution containing gelatin and potassium or zinc chloride using a sonication method. The second involves the removal of larger exfoliated h-BNNS through a centrifugation procedure. The exfoliation was caused not only by the sonication effect but also by intercalation of K? and Zn<sup>2+</sup> ions. Transmission electronic microscopy, X-ray diffraction and Raman spectroscopy techniques show that the obtained h-BNNS generally display a thickness of about a few (2?3) layers with an exfoliation efficiency as high as 16.3 ± 0.4%.
Project description:Layered materials present attractive and important properties due to their two-dimensional (2D) structure, allowing potential applications including electronics, optoelectronics, and catalysis. However, fully exploiting the outstanding properties will require a method for their efficient exfoliation. Here we present that a series of layered materials can be successfully exfoliated into single- and few-layer nanosheets using the driving forces coming from the phase inversion, i.e., from micelles to reverse micelles in the emulsion microenvironment built by supercritical carbon dioxide (SC CO2). The effect of variable experimental parameters including CO2 pressure, ethanol/water ratio, and initial concentration of bulk materials on the exfoliation yield have been investigated. Moreover, we demonstrate that the exfoliated 2D nanosheets have their worthwhile applications, for example, graphene can be used to prepare conductive paper, MoS2 can be used as fluorescent label to perform cellular labelling, and BN can effectively reinforce polymers leading to the promising mechanical properties.
Project description:Hexagonal boron nitride nanosheets (h-BNNS) have been proposed as an ideal substrate for graphene-based electronic devices, but the synthesis of large and homogeneous h-BNNS is still challenging. In this contribution, we report a facile synthesis of few-layer h-BNNS on melted copper via an atmospheric pressure chemical vapor deposition process. Comparative studies confirm the advantage of using melted copper over solid copper as a catalyst substrate. The former leads to the formation of single crystalline h-BNNS that is several microns in size and mostly in mono- and bi-layer forms, in contrast to the polycrystalline and mixed multiple layers (1-10) yielded by the latter. This difference is likely to be due to the significantly reduced and uniformly distributed nucleation sites on the smooth melted surface, in contrast to the large amounts of unevenly distributed nucleation sites that are associated with grain boundaries and other defects on the solid surface. This synthesis is expected to contribute to the development of large-scale manufacturing of h-BNNS/graphene-based electronics.
Project description:Polymer-based nanodielectrics have been intensively investigated for their potential application as energy storage capacitors. However, their relatively low energy density (Ue) and discharging efficiency (η) may greatly limit their practical usage. In present work, high insulating two-dimensional boron nitride nanosheets (BNNS), were introduced into a linear dielectric polymer (P(VDF-TrFE-CTFE)-g-PMMA) matrix to enhance the energy storage performance of the composite. Thanks to the surface coating of polydopamine (PDA) on BN nanosheets, the composite filled with 6 wt% coated BNNS (mBNNS) exhibits significantly improved breakdown strength (Eb) of 540 MV/m and an energy density (Ue) of 11 J/cm³, which are increased by 23% and 100%, respectively as compared with the composite filled with the same content of pristine BNNS. Meanwhile, η of both composites is well retained at around 70% even under a high voltage of 400 MV/m, which is superior to most of the reported composites. This work suggests that complexing polymer matrix with linear dielectric properties with surface coated BNNS fillers with high insulating 2D structure might be a facile strategy to achieve composite dielectrics with simultaneously high energy density and high discharging efficiency.
Project description:Although tailored wet ball milling can be an efficient method to produce a large quantity of two-dimensional nanomaterials, such as boron nitride (BN) nanosheets, milling parameters including milling speed, ball-to-powder ratio, milling ball size and milling agent, are important for optimization of exfoliation efficiency and production yield. In this report, we systematically investigate the effects of different milling parameters on the production of BN nanosheets with benzyl benzoate being used as the milling agent. It is found that small balls of 0.1-0.2 mm in diameter are much more effective in exfoliating BN particles to BN nanosheets. Under the optimum condition, the production yield can be as high as 13.8% and the BN nanosheets are 0.5-1.5 ?m in diameter and a few nanometers thick and of relative high crystallinity and chemical purity. The lubrication properties of the BN nanosheets in base oil have also been studied. The tribological tests show that the BN nanosheets can greatly reduce the friction coefficient and wear scar diameter of the base oil.
Project description:A strategy was reported to prepare boron nitride nanosheets (BNNSs) by a molten hydroxide assisted liquid exfoliation from hexagonal boron nitride (h-BN) powder. BNNSs with an average thickness of 3?nm were obtained by a facile, low-cost, and scalable exfoliation method. Highly thermally conductive polyimide (PI) composite films with BNNSs filler were prepared by solution-casting process. The in-plane thermal conductivity of PI composite films with 7?wt% BNNSs is up to 2.95?W/mK, which increased by 1,080% compared to the neat PI. In contrast, the out-of plane thermal conductivity of the composites is 0.44?W/mK, with an increase by only 76%. The high anisotropy of thermal conductivity was verified to be due to the high alignment of the BNNSs. The PI/BNNSs composite films are attractive for the thermal management applications in the field of next-generation electronic devices.
Project description:The highly thermo-conductive but electrically insulating film, with desirable mechanical performances, is extremely demanded for thermal management of portable and wearable electronics. The integration of boron nitride nanosheets (BNNSs) with regenerated cellulose (RC) is a sustainable strategy to satisfy these requirements, while its practical application is still restricted by the brittle fracture and loss of toughness of the composite films especially at the high BNNS addition. Herein, a dual-crosslinked strategy accompanied with uniaxial pre-stretching treatment was introduced to engineer the artificial RC/BNNS film, in which partial chemical bonding interactions enable the effective interfiber slippage and prevent any mechanical fracture, while non-covalent hydrogen bonding interactions serve as the sacrifice bonds to dissipate the stress energy, resulting in a simultaneous high mechanical strength (103.4 MPa) and toughness (10.2 MJ/m3) at the BNNS content of 45 wt%. More importantly, attributed to the highly anisotropic configuration of BNNS, the RC/BNNS composite film also behaves as an extraordinary in-plane thermal conductivity of 15.2 W/m·K. Along with additional favorable water resistance and bending tolerance, this tactfully engineered film ensures promised applications for heat dissipation in powerful electronic devices.
Project description:Thermal management has become a critical challenge in electronics and portable devices. To address this issue, polymer composites with high thermal conductivity (TC) and low dielectric property are urgently needed. In this work, we fabricated perfluoroalkoxy (PFA) composite with high anisotropic TC and low dielectric constant by aligning boron nitride nanosheets (BNNs) via hot pressing. We characterized the thermal stability, microstructure, in-plane and through-plane TCs, heat dissipation capability, and dielectric property of the composites. The results indicate that the BNNs-PFA composites possessed good thermal stability. When the BNNs content was higher than 10 wt %, the BNNs were well layer aligned in the PFA matrix, and the composites showed obvious anisotropic TC. The in-plane TC and through-plane TCs of 30 wt % BNNs-PFA composite were 4.65 and 1.94 W m-1 K-1, respectively. By using the composite in thermal management of high-power LED, we found that alignment of BNNs in composite significantly improves the heat dissipation capability of composite. In addition, the composites exhibited a low dielectric property. This study shows that hot pressing is a facile and low-cost method to fabricate bulk composite with anisotropic TC, which has wide applications in electronic packaging.
Project description:Atomically thin boron nitride (BN) nanosheets are important two-dimensional nanomaterials with many unique properties distinct from those of graphene, but investigation into their mechanical properties remains incomplete. Here we report that high-quality single-crystalline mono- and few-layer BN nanosheets are one of the strongest electrically insulating materials. More intriguingly, few-layer BN shows mechanical behaviours quite different from those of few-layer graphene under indentation. In striking contrast to graphene, whose strength decreases by more than 30% when the number of layers increases from 1 to 8, the mechanical strength of BN nanosheets is not sensitive to increasing thickness. We attribute this difference to the distinct interlayer interactions and hence sliding tendencies in these two materials under indentation. The significantly better interlayer integrity of BN nanosheets makes them a more attractive candidate than graphene for several applications, for example, as mechanical reinforcements.
Project description:High-intensity ultrasound exfoliation of a bulk-layered material is an attractive route for large-scale preparation of monolayers. The monolayer slices could potentially be prepared with a high yield (up to 100%) in a few minutes. Exfoliation of natural minerals (such as tungstenite and molybdenite) or bulk synthetic materials (including hexagonal boron nitride (h-BN), hexagonal boron carbon nitride (h-BCN), and graphitic carbon nitride (g-C3N4)) in liquids leads to the breakdown of the 3D graphitic structure into a 2D structure; the efficiency of this process is highly dependent upon the physical effects of the ultrasound. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) were employed to verify the quality of the exfoliation. Herein, this new method of exfoliation with ultrasound assistance for application to mono- and bilayered materials in hydrophobic and hydrophilic environments is presented.