Modified crosslinked polyethylene (XLPE) with appreciably enhanced DC electrical insulation properties has been developed by chemical modification of grafting chloroacetic acid allyl ester (CAAE), exploring the trapping mechanism of charge transport inhibition. The bound state traps deriving from grafted molecule are analyzed by first-principles calculations, in combination with the electrical DC conductivity and dielectric breakdown strength experiments to study the underlying mechanism of improving the electrical insulation properties. In contrast to pure XLPE, the XLPE-graft-CAAE represents significantly suppressed space charge accumulation, increased breakdown strength, and reduced conductivity. The substantial deep traps are generated in XLPE-graft-CAAE molecules by polar group of grafted CAAE and accordingly decrease charge mobility and raise charge injection barrier, consequently suppressing space charge accumulation and charge carrier transport. The well agreement of experiments and quantum mechanics calculations suggests a prospective material modification strategy for achieving high-voltage polymer dielectric materials without nanotechnology difficulties as for nanodielectrics.
Space charge characteristics of cross-linked polyethylene (XLPE) at elevated temperatures have been evidently improved by the graft modifications with ultraviolet (UV) initiation technique, which can be efficiently utilized in industrial cable manufactures. Maleic anhydride (MAH) of representative cyclic anhydride has been successfully grafted onto polyethylene molecules through UV irradiation process. Thermal stimulation currents and space charge characteristics at the elevated temperatures are coordinately analyzed to elucidate the trapping behavior of blocking charge injection and impeding carrier transport which is caused by grafting MAH. It is also verified from the first-principles calculations that the bound states as charge carrier traps can be introduced by grafting MAH onto polyethylene molecules. Compared with pure XLPE, the remarkably suppressed space charge accumulations at high temperatures have been achieved in XLPE-g-MAH. The polar groups on the grafted MAH can provide deep traps in XLPE-g-MAH, which will increase charge injection barrier by forming a charged layer of Coulomb-potential screening near electrodes and simultaneously reduce the electrical mobility of charge carriers by trap-carrier scattering, resulting in an appreciable suppression of space charge accumulations inside material. The exact consistence of experimental results with the quantum mechanics calculations demonstrates a promising routine for the modification strategy of grafting polar molecules with UV initiation technique in the development of high-voltage DC cable materials.
Direct current (DC) electrical performances of crosslinked polyethylene (XLPE) have been evidently improved by developing graft modification technique with ultraviolet (UV) photon-initiation. Maleic anhydride (MAH) molecules with characteristic cyclic anhydride were successfully grafted to polyethylene molecules under UV irradiation, which can be efficiently realized in industrial cable production. The complying laws of electrical current varying with electric field and the Weibull statistics of dielectric breakdown strength at altered temperature for cable operation were analyzed to study the underlying mechanism of improving electrical insulation performances. Compared with pure XLPE, the appreciably decreased electrical conductivity and enhanced breakdown strength were achieved in XLPE-graft-MAH. The critical electric fields of the electrical conduction altering from ohm conductance to trap-limited mechanism significantly decrease with the increased testing temperature, which, however, can be remarkably raised by grafting MAH. At elevated temperatures, the dominant carrier transport mechanism of pure XLPE alters from Poole–Frenkel effect to Schottky injection, while and XLPE-graft-MAH materials persist in the electrical conductance dominated by Poole–Frenkel effect. The polar group of grafted MAH renders deep traps for charge carriers in XLPE-graft-MAH, and accordingly elevate the charge injection barrier and reduce charge mobility, resulting in the suppression of DC electrical conductance and the remarkable amelioration of insulation strength. The well agreement of experimental results with the quantum mechanics calculations suggests a prospective strategy of UV initiation for polar-molecule-grafting modification in the development of high-voltage DC cable materials.
In order to achieve high quality electrical materials for cable terminations, the crosslinked ethylene-propylene-diene monomer (EPDM) materials, with adequate breakdown strength, appropriately increased conductivity and are developed by employing auxiliary crosslinker and ultraviolet (UV) photoinitiated crosslinking technique. The characteristic cyclic anhydrides with coupled carbonyl groups are utilized as auxiliary crosslinkers to promote crosslinking efficiency and provide polar-groups to EPDM molecules in UV-initiated crosslinking processes, which can be effectively fulfilled in industrial cable production. The results of infrared spectroscopy show that the auxiliary crosslinkers have been successfully grated to EPDM molecules through UV initiation process. The conductivity of EPDM increases after individually utilizing three auxiliary crosslinkers to EPDM at various temperatures of cable operations, by which the highest conductivity has been acquired by grafting N.N-m-phenylene dimaleimide. The first-principles calculations demonstrate that some occupied local electronic-states have been introduced in the band-gap of the EPDM crosslinked by N.N-m-phenylene dimaleimide (EPDM-HAV2), which can be thermally excited from valence band to conduction band at lower temperature or in higher density, leading to augmentation in electrical conductivity. Meanwhile, the breakdown strength achieves a significant improvement in consistency with the theoretical estimation that deeper hole-traps can be introduced by auxiliary-crosslinking modification, and will consequently increase breakdown strength through the trapping mechanism of space charge suppression. in relation to the appropriately increased conductivity, in combination with persistent breakdown strength, the finite element simulations of the electric field distribution in EPDM cable terminations suggest that the effectively homogenized electric field at the root of stress cone will be realized for EPDM-HAV2. The present study offers a fundamental strategy to ameliorate EPDM materials in the application of insulated cable accessories.
Given the high interest in promoting crosslinking efficiency of ultraviolet-initiated crosslinking technique and ameliorating electrical resistance of crosslinked polyethylene (XLPE) materials, we have developed the funcionalized-SiO2/XLPE nanocomposites by chemically grafting auxiliary crosslinkers onto nanosilica surfaces. Trimethylolpropane triacrylate (TMPTA) as an effective auxiliary crosslinker for polyethylene is grafted successfully on nanosilica surfaces through thiolene-click chemical reactions with coupling agents of sulfur silanes and 3-mercaptopropyl trimethoxy silane (MPTMS), as characterized by nuclear magnetic resonance and Fourier transform infrared spectroscopy. The functionalized SiO2 nanoparticles could be dispersively filled into polyethylene matrix even at a high filling content that would generally produce agglomerations of neat SiO2 nanofillers. Ultraviolet-initiated polyethylene crosslinking reactions are efficiently stimulated by TMPTA grafted onto surfaces of SiO2 nanofillers, averting thermal migrations out of polyethylene matrix. Electrical-tree pathways and growth mechanism are specifically investigated by elucidating the microscopic tree-morphology with fractal dimension and simulating electric field distributions with finite-element method. Near nano-interfaces where the shielded-out electric fluxlines concentrate, the highly enhanced electric fields will stimulate partial discharging and thus lead to the electrical-trees being able to propagate along the routes between nanofillers. Surface-modified SiO2 nanofillers evidently elongate the circuitous routes of electrical-tree growth to be restricted from directly developing toward ground electrode, which accounts for the larger fractal dimension and shorter length of electrical-trees in the functionlized-SiO2/XLPE nanocomposite compared with XLPE and neat-SiO2/XLPE nanocomposite. Polar-groups on the modified nanosilica surfaces inhibit electrical-tree growth and simultaneously introduce deep traps impeding charge injections, accounting for the significant improvements of electrical-tree resistance and dielectric breakdown strength. Combining surface functionalization and nanodielectric technology, we propose a strategy to develop XLPE materials with high electrical resistance.
The water-resistant characteristics of ultraviolet crosslinked polyethylene (UV-XLPE) are investigated specially for the dependence on the hydrophilicities of auxiliary crosslinkers, which is significant to develop high-voltage insulating cable materials. As auxiliary crosslinking agents of polyethylene, triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMPTMA), and N,N′-m-phenylenedimaleimide (HAV2) are individually adopted to prepared XLPE materials with the UV-initiation crosslinking technique, for the study of water-tree resistance through the accelerating aging experiments with water blade electrode. The stress–strain characteristics and dynamic viscoelastic properties of UV-XLPE are tested by the electronic tension machine and dynamic thermomechanical analyzer. Monte Carlo molecular simulation is used to calculate the interaction parameters and mixing energy of crosslinker/water binary systems to analyze the compatibility between water and crosslinker molecules. Water-tree experiments verify that XLPE-TAIC represents the highest ability to inhibit the growth of water-trees, while XLPE-HAV2 shows the lowest resistance to water-trees. The stress–strain and viscoelastic properties show that the concentration of molecular chains connecting the adjacent lamellae in amorphous phase of XLPE-HAV2 is significantly higher than that of XLPE-TAIC and XLPE-TMPTMA. The molecular simulation results demonstrate that TAIC/water and TMPTMA/water binary systems possess a higher hydrophilicity than that of HAV2/water, as manifested by their lower interaction parameters and mixing free energies. The auxiliary crosslinkers can not only increase the molecular density of amorphous polyethylene between lamellae to inhibit water-tree growth, but also prevent water molecules at insulation defects from agglomerating into micro-water beads by increasing the hydrophilicity of auxiliary crosslinkers, which will evidently reduce the damage of micro-water beads on the amorphous phase in UV-XLPE. The better compatibility of TAIC and water molecules is the dominant reason accounting for the excellent water resistance of XLPE-TAIC.
In order to inhibit the outward-migrations of photo-initiator molecules in the ultraviolet-initiated crosslinking process and simultaneously improve the crosslinking degree and dielectric properties of crosslinked polyethylene (XLPE) materials, we have specifically developed surface-modified-SiO2/XLPE nanocomposites with the silica nanofillers that have been functionalized through chemical surface modifications. With the sulfur-containing silanes and 3-mercaptopropyl trimethoxy silane (MPTMS), the functional monomers of auxiliary crosslinker triallyl isocyanurate (TAIC) have been successfully grafted on the silica surface through thiol–ene click chemistry reactions. The grafted functional groups are verified by molecular characterizations of Fourier transform infrared spectra and nuclear magnetic resonance hydrogen spectra. Scanning electronic microscopy (SEM) indicates that the functionalized silica nanoparticles have been filled into polyethylene matrix with remarkably increased dispersivity compared with the neat silica nanoparticles. Under ultraviolet (UV) irradiation, the high efficient crosslinking reactions of polyethylene molecules are facilitated by the auxiliary crosslinkers that have been grafted onto the surfaces of silica nanofillers in polyethylene matrix. With the UV-initiated crosslinking technique, the crosslinking degree, insulation performance, and space charge characteristics of SiO2/XLPE nanocomposites are investigated in comparison with the XLPE material. Due to the combined effects of the high dispersion of nanofillers and the polar-groups of TAIC grafted on the surfaces of SiO2 nanofillers, the functionlized-SiO2/XLPE nanocomposite with an appropriate filling content represents the most preferable crosslinking degree with multiple improvements in the space charge characteristics and direct current dielectric breakdown strength. Simultaneously employing nanodielectric technology and functional-group surface modification, this study promises a modification strategy for developing XLPE nanocomposites with high mechanical and dielectric performances.
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