Lightweight high-density polyethylene (HDPE)-graphene nanoplatelet (GnP) composite foams were fabricated via a supercritical-fluid (SCF) treatment and physical foaming in an injection-molding process. We demonstrated that the introduction of a microcellular structure can substantially increase the electrical conductivity and can decrease the percolation threshold of the polymer-GnP composites. The nanocomposite foams had a significantly higher electrical conductivity, a higher dielectric constant, a higher electromagnetic interference (EMI) shielding effectiveness (SE), and a lower percolation threshold compared to their regular injection-molded counterparts. The SCF treatment and foaming exfoliated the GnPs in situ during the fabrication process. This process also changed the GnP's flow-induced arrangement by reducing the melt viscosity and cellular growth. Moreover, the generation of a cellular structure rearranged the GnPs to be mainly perpendicular to the radial direction of the bubble growth. This enhanced the GnP's interconnectivity and produced a unique GnP arrangement around the cells. Therefore, the through-plane conductivity increased up to a maximum of 9 orders of magnitude and the percolation threshold decreased by up to 62%. The lightweight injection-molded nanocomposite foams of 9.8 vol % GnP exhibited a real permittivity of ε' = 106.4, which was superior to that of their regular injection-molded (ε' = 6.2). A maximum K-band EMI SE of 31.6 dB was achieved in HDPE-19 vol % GnP composite foams, which was 45% higher than that of the solid counterpart. In addition, the physical foaming reduced the density of the HDPE-GnP foams by up to 26%. Therefore, the fabricated polymer-GnP nanocomposite foams in this study pointed toward the further development of lightweight and conductive polymer-GnP composites with tailored properties.
Dielectric polymer nanocomposites with high dielectric constant (ε') and low dielectric loss (tan δ) are extremely desirable in the electronics industry. Percolative polymer-graphene nanoplatelet (GnP) composites have shown great promise as dielectric materials for high-performance capacitors. Herein, an industrially-viable technique for manufacturing a new class of ultralight polymer composite foams using commercial GnPs with excellent dielectric performance is presented. Using this method, the high-density polyethylene (HDPE)-GnPs composites with a microcellular structure were fabricated by melt-mixing. This was followed by supercritical fluid (SCF) treatment and physical foaming in an extrusion process, which added an extra layer of design flexibility. The SCF treatment effectively in situ exfoliated the GnPs in the polymer matrix. Moreover, the generation of a microcellular structure produced numerous parallel-plate nanocapacitors consisting of GnP pairs as electrodes with insulating polymer as nanodielectrics. This significantly increased the real permittivity and decreased the dielectric loss. The ultralight extruded HDPE-1.08 vol % GnP composite foams, with a 0.15 g·cm density, had an excellent combination of dielectric properties (ε' = 77.5, tan δ = 0.003 at 1 × 10 Hz), which were superior to their compression-molded counterparts (ε' = 19.9, tan δ = 0.15 and density of = 1.2 g·cm) and to those reported in the literature. This dramatic improvement resulted from in situ GnP's exfoliation and dispersion, as well as a unique GnP parallel-plate arrangement around the cells. Thus, this facile method provides a scalable method to produce ultralight dielectric polymer nanocomposites, with a microscopically tailored microstructure for use in electronic devices.
Graphene nanoplatelets (GN) produced on a large scale by mechanochemical exfoliation of graphite are incorporated in a co‐continuous ethylene‐vinyl acetate/linear low‐density polyethylene (EVA/LLDPE) blend. Two different processing routes are chosen to selectively place GN in the EVA phase or force its migration to the EVA/LLDPE interface. The results show a drastic decrease in the electrical percolation threshold when the blends are compared to the respective single‐polymer composites. Even with the presence of agglomerates, GN particles are able to migrate to the blend interface and stabilize the morphology and hence the electrical properties. Annealing the insulating samples at processing temperatures causes a drastic increase in conductivity due to continued GN migration and blend morphology coarsening. Semi‐conductive samples, in which a more robust GN network is already established during processing, present no change in morphology but a slight increase in conductivity during annealing. The mechanical performance of the materials is also evaluated and some of the blends with GN present similar elongation at break as pure EVA, but with increased tensile modulus and tensile strength. The electrical performance at different working temperatures shows that the EVA/LLDPE/GN composites are good candidates to act as a semi‐conductive screen material in power cables or as anti‐static materials in electronic devices.
Economically viable high‐density polyethylene (HDPE)/graphene nanocomposites were produced using mass produced graphene powder and an industrial twin‐screw melt‐compounding machine. Rheological and electrical properties were investigated and scanning electron microscopy was carried out to investigate graphene dispersion and its network formation in the matrix. Mechanical properties of the nanocomposites were evaluated using tensile, flexural and impact tests. Differential scanning calorimetry analysis indicated that the crystalline structure of the polymer might be affected by high loadings of graphene. SEM evaluation revealed reasonable graphene dispersion in the matrix. In addition, the amount of graphene required to form a percolated network was similar for both rheological and electrical networks. The nanocomposites exhibited a significant increase in Young's and flexural moduli without a notable reduction in impact strength up to 14 wt% graphene loading. In these experiments, compounding graphene powder with HDPE produced a clear and distinct improvement in mechanical properties at an industrially suitable low cost. POLYM. ENG. SCI., 59:675–682, 2019. © 2018 Society of Plastics Engineers
Ideal dielectric materials for microelectronic devices should have high directionally tailored thermoconductivity with low dielectric constant and loss. Hexagonal boron nitride (hBN) with excellent thermal and dielectric properties shows a promise for the fabrication of thermoconductive dielectric polymer composites. Herein, a simple method for the fabrication of lightweight polymer/hBN composites with high directionally tailored thermoconductivity and excellent dielectric properties is presented. The solid polymer/hBN composites are manufactured by melt-compounding and injection molding. The porous composites are successfully manufactured in an injection molding process through supercritical fluid (SCF) foaming. X-ray tomography provides direct visualization of the internal microstructure and hBN orientation, leading to an in-depth understanding of the directionally dependent thermoconductivity of the polymer/hBN composite. Shear-induced orientation of hBN platelets in the solid HDPE/hBN composites leads to a significant anisotropic thermal conductivity. The solid HDPE/23.2 vol % hBN composites show an in-plane thermoconductivity as high as 10.1 W m–1 K–1, whereas the through-plane thermoconductivity is limited to 0.28 W m–1 K–1. However, the generation of a porous structure via SCF foaming imparts in situ exfoliation, random orientation, and interconnectivity of hBN platelets within the polymer matrix. This results in highly isotropic thermoconductivity with higher bulk thermal conductivity in the lightweight porous composites as compared to their solid counterparts. Furthermore, the electrically insulating composites developed in this study exhibit low dielectric constant and ultralow dielectric loss. Thus, this study presents a simple fabrication method to develop lightweight dielectric materials with tailored thermal conductivity for modern electronics.
Graphene, the newest member of the carbon’s family, has proven its efficiency in improving polymers’ resistance against photodegradation, even at low loadings equal to 1 wt% or lower. This protective role involves a multitude of complementary mechanisms associated with graphene’s unique geometry and chemistry. In this review, these mechanisms, taking place during both the initiation and propagation steps of photodegradation, are discussed concerning graphene and graphene derivatives, i.e., graphene oxide (GO) and reduced graphene oxide (rGO). In particular, graphene displays important UV absorption, free radical scavenging, and quenching capabilities thanks to the abundant π-bonds and sp2 carbon sites in its hexagonal lattice structure. The free radical scavenging effect is also partially linked with functional hydroxyl groups on the surface. However, the sp2 sites remain the predominant player, which makes graphene’s antioxidant effect potentially stronger than rGO and GO. Besides, UV screening and oxygen barriers are active protective mechanisms attributed to graphene’s high surface area and 2D geometry. Moreover, the way that graphene, as a nucleating agent, can improve the photostability of polymers, have been explored as well. These include the potential effect of graphene on increasing polymer’s glass transition temperature and crystallinity.
Polyester nanocomposites reinforced with graphene nanoplatelets (GnPs) with two different lateral sizes are prepared by high shear mixing, followed by compression molding. The effects of the size and concentration of GnP, as well as of the processing method, on the electrical conductivity and electromagnetic interference (EMI) shielding behavior of these nanocomposites are experimentally investigated. The in-plane electrical conductivity of the nanocomposites with larger-size GnPs is approximately one order of magnitude higher than the cross-plane volume conductivity. According to the SEM images, the compression-induced alignments of GnPs is found to be responsible for this anisotropic behavior. The orientation of the small size GnPs in the composite is not influenced by the compression process as strongly, and consequently, the electrical conductivity of these nanocomposites exhibits only a slight anisotropy. The maximum EMI shielding effectiveness (SE) of 27 dB (reduction of 99.8% of the incident radiation) is achieved at 25 wt.% of the smaller-size GnP loading. Experimental results show that the EMI shielding mechanism of these composites has a strong dependency on the lateral dimension of GnPs. The non-aligned smaller-size GnPs are leveraged to obtain a relatively high absorption coefficient (≈40%). This absorption coefficient is superior to the existing single-filler bulk polymer composite with a similar thickness.
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