Key Laboratory of Engineering Dielectrics and Its Application, Ministry of Education, Harbin University of Science and Technology, Harbin 150080, China
Dr. Jiaming Yang
Key Laboratory of Engineering Dielectrics and Its Application, Ministry of Education, Harbin University of Science and Technology, Harbin 150080, China
Compared to cross-linked polyethylene, polypropylene has a thermoplastic property and the advantage of recycling. However, the poor impact resistance at low temperature and the corresponding space charge problem restrict the application of polypropylene with the extruded high voltage direct current (HVDC) cable. Sufficient introduction of the β form of the polypropylene crystal can significantly improve impact resistance at low temperatures. Although it has been widely applied in insulation engineering, the effect of β-crystal on the space charge characteristics of polypropylene has rarely been researched until now. In this paper, a rare earth nucleating agent of β-crystal is employed to modify the performance of polypropylene to investigate the effects of nucleating agent content on β-crystalline, mechanical relaxation, trap, and space charge characteristics of polypropylene. The results of differential scanning calorimeter (DSC) and X-ray diffraction (XRD) tests indicate that the relative content of β-crystal in modified polypropylene increases gradually with the increasing concentration of the nucleating agent, approaching 43.5% when the nucleating agent content has been raised to 0.2 wt %, suggesting appreciable efficiency of the nucleating agent utilized in our research. Scanning electron microscopy (SEM) is utilized to characterize the morphology of β-crystal spherulites, which illustrates that the β-spherulites are in bunchy shape, and the lamellar crystals are parallel to each other without an obvious boundary between them. The results of the space charge test demonstrate that the modified polypropylene can substantially suppress space charge accumulation, which is attributed to an increment of β-crystal content by adopting a rare earth nucleating agent. It is indicated from dynamic mechanical analysis (DMA) measurements that the enhancement of β-crystalline in modified polypropylene can distinctly increase and decrease the β and α relaxation losses, respectively, which proves that the defects in β-crystal and amorphous regions are reduced and increased respectively. Thermally stimulated depolarization current tests further confirm that the number of traps caused by defects in the β-form of polypropylene crystal declines definitely, which dominantly accounts for the suppression of space charge accumulation.
Compared with traditional insulation materials, such as cross-linked polyethylene (XLPE), polypropylene (PP) is famous for its better recyclable and thermal properties, as well as its good electrical performance. However, the problem of poor impact strength has restricted the application of pure PP in high-voltage, direct current (HVDC) cables. In this paper, styrene-ethylene-butylene-styrene block copolymer (SEBS) was used as a toughening filler, and nano-SiO2 was expected to improve the electric properties of the nano-composite. By controlling the masterbatch system, the dispersion characteristics of nano-SiO2 in the ternary composite system were changed. When PP/SiO2 was used as the masterbatch and then blended with SEBS, nano-SiO2 tended to disperse in the PP phase, and the number of nano-particles in the SEBS phase was lower. When PP/SEBS was used as the masterbatch, nano-SiO2 was distributed in both the PP phase and the SEBS phase. When SEBS/SiO2 was used as the masterbatch, nano-SiO2 tended to be dispersed in the SEBS phase. The different dispersion characteristics of nano-SiO2 changed the crystallization and mechanical properties of the ternary composite system and produced different electrical performance improvement effects. The results of our experiment revealed that the space charge suppression capability was positively correlated with the direct current (DC) breakdown strength improvement effect. Compared with the DC performance of 500 kV commercial XLPE materials, the self-made PP-based ternary composite system has better space charge suppression effects and higher DC breakdown strength. When nano-SiO2 was more dispersed in the PP phase, the space charge improvement effect was best. When the nano-SiO2 particles were more dispersed in the SEBS phase, the expected electrical property improvement was not obtained. Scanning electron microscopy showed that the nano-SiO2 particles in the SEBS phase were more dispersed at the interface than in the SEBS matrix, indicating that the nano-particles were poorly dispersed, which may be a reason why the electrical properties of the composite system were not significantly improved.
Acetophenone can significantly improve the dielectric properties of polyethylene (PE) insulation materials. However, it easily migrates from the PE due to its poor compatibility with the material, which limits its application. In this paper, the functional units of acetophenone were modified in polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) by an acetylation reaction, and SEBS was used as the carrier to inhibit the migration of acetophenone. The number of functional units in the acetylated SEBS (Ac-SEBS) was measured by 1H NMR and the effect of the acetylation degree of SEBS on its compatibility with PE was studied. Meanwhile, the effects of Ac-SEBS on PE’s direct current (DC) breakdown strength and space charge accumulation characteristics were investigated. It is demonstrated that Ac-SEBS can significantly improve the field strength of the DC breakdown and inhibit the accumulation of space charge in the PE matrix. This work provides a new approach for the application of aromatic compounds as voltage stabilizers in DC insulation cable materials.
In order to achieve both high toughness and favorable dielectric properties of polypropylene materials, a styrene–butadiene–styrene block copolymer (SEBS) was employed as a toughening filler, in addition to a copolymerized polypropylene grafted by maleic anhydride (cPP-g-MAH) as a compatibilization modifier, to develop a novel isotactic polypropylene (iPP) composite (cPP-g-MAH/iPP/SEBS composite) with significantly improved direct-current (DC) dielectric performance and tenacity. The underlying physical and chemical mechanisms of modifying electric insulation were studied utilizing micro-structure characterization methods in combination with multiple thermal–mechanic–electric tests. The SEBS phase islands are uniformly distributed in the PP matrix with evidently improved dispersion due to cPP-g-MAH compatibilization. Compared with iPP, the elastic modulus of cPP-g-MAH/iPP/SEBS composites can be reduced by 58% with doubled thermal elongation, which is still superior to that of cross-linked polyethylene (XLPE), implying that the composites are qualified in terms of mechanical properties for use as power cables. The space charge accumulation and electric conduction are considerably suppressed in comparison with pure iPP and the iPP/SEBS composite. In the interest of charge-trapping characteristics modified by chemically grafting MAH, the deep traps introduced into polypropylene by grafting MAH were measured with a thermal stimulation current experiment to be 1.2 and 1.6 eV of energy level in trapping depth, verified through the first-principles electronic structure calculations with an all-electron numerical orbital scheme. It was concluded that the acquired high density of deep traps can effectively restrict the carrier transport and suppress the injection of space charge, resulting in a remarkable improvement of DC dielectric properties for the MAH grafted composites. The present work demonstrates that the cPP-g-MAH/iPP/SEBS composites are eligible to be applied to polypropylene-based high-voltage DC cables due to their excellent DC insulation performance, together with the appropriate mechanical properties.
Nanocomposite dielectrics show a great potential application in high voltage direct current cables for their obvious improvements in electrical properties. In the present manuscript, nanocomposite composed of low-density polyethylene and nanoscale polystyrene particles is studied by using low-density polyethylene grafted with polystyrene molecule. Fourier-transform infrared spectra reveal successful grafting of the polystyrene molecule onto the low-density polyethylene chain and the scanning electron microscope image shows the homogeneously dispersed nanoscale polystyrene particles. The presence of the polystyrene nanoparticles obviously improves the dielectric properties, such as the direct current breakdown strength and space charge inhibition. The conductivity and thermally stimulated current characteristics imply the deep traps in the composite increase obviously. Density functional theory calculation reveals that the grafted polystyrene can accommodate both shallow and deep electron carriers, and the depth of the hole traps are as deep as 2.07 eV.
To achieve exceptional recyclable DC cable insulation material using thermoplastic polypropylene (PP), we have introduced the organic polar molecule styrene-maleic anhydride copolymer (SMA) into PP-based insulation materials following the principles of deep trap modification. PP, PP/SMA, PP/ethylene-octene copolymer (POE), and PP/POE/SMA insulating samples were prepared, and their meso-morphology, crystalline morphology, and molecular structure were comprehensively characterized. The results indicate that SMA can be uniformly dispersed in PP with minimal impact on the crystalline morphology of PP. The DC electrical properties of the materials were tested at temperatures of 30, 50, and 70 °C. The findings demonstrate that the introduction of SMA can improve the DC properties of the material in both PP and PP/POE. The thermal stimulated depolarization current results reveal that SMA can introduce deep traps into the material, thereby improving its DC properties, which is in agreement with the quantum chemical calculation results. Subsequently, a bipolar carrier transport model was employed for coaxial cables to simulate the space charge distribution in the insulation layer of the four sets of insulation samples as well as the actual cable in service. The results highlight that SMA can significantly suppress space charge in PP and PP/POE systems, and it exhibits excellent electric field distortion resistance. In summary, the results illustrate that SMA is expected to be used as an organic deep trap modifier in PP-based cable insulation materials.