The effect of water absorption on the dielectric properties of epoxy nanocomposites

In this research, the influence of water absorption on the dielectric properties of epoxy resin and epoxy micro-composites and nano-composites filled with silica has been studied. Nanocomposites were found to absorb significantly more water than unfilled epoxy. However, the microcomposite absorbed less water than unfilled epoxy: corresponding to reduced proportion of the epoxy in this composite. The glass transition temperatures of all the samples were measured by both differential scanning calorimetry and dielectric spectroscopy. The Tg decreased as the water absorption increased and, in all cases, corresponded to a drop of approximately 20K as the humidity was increased from 0% to 100%. This implied that for all the samples, the amount of water in the resin component of the composites was almost identical. It was concluded that the extra water found in the nanocomposites was located around the surface of the nanoparticles. This was confirmed by measuring the water uptake, and the swelling and density change, as a function of humidity as water was absorbed. The water shell model, originally proposed by Lewis and developed by Tanaka, has been further developed to explain low frequency dielectric spectroscopy results in which percolation of charge carriers through overlapping water shells was shown to occur. This has been discussed in terms of a percolation model. At 100% relative humidity, water is believed to surround the nanoparticles to a depth of approximately 5 monolayers. A second layer of water is proposed that is dispersed by sufficiently concentrated to be conductive; this may extend for approximately 25 nm. If all the water had existed in a single layer surrounding a nanoparticle, this layer would have been approximately 3 to 4 nm thick at 100%. This "characteristic thickness" of water surrounding a given size of nanoparticle appeared to be independent of the concentration of nanoparticles but approximately proportional to water uptake. Filler particles that have surfaces that are functionalized to be hydrophobic considerably reduce the amount of water absorbed in nanocomposites under the same conditions of humidity. Comments are made on the possible effect on electrical aging

A "water shell" model for the dielectric properties of hydrated silica-filled epoxy nano-composites

The electrical properties of epoxy resin have been studied as a function of hydration. The epoxy was studied in an un-filled state, filled with 40 µm SiO2 particles, and filled with 50 nm SiO2 particles. The relative humidity was controlled by saturated salt solutions at ambient temperatures from 298-353 K. Measurements were made using dielectric spectroscopy over the frequency range 10-3-105 Hz. The hydration isotherm (i.e. the mass uptake of water) was established by measuring the mass as a function of relative humidity (RH). It was found that the nanocomposites absorb up to 60% more water than the unfilled and micro-filled epoxies. Dielectric spectroscopy shows different conduction and quasi-DC behaviours at very low frequencies (<10-2 Hz) with activation energies dependent on the hydration and temperature. These observations have led to the development of a “water shell” model to explain this phenomenon

“Mirror Image Effect” Space Charge Distribution in XLPE Power Cable under Opposite Stressing Voltage Polarity

The paper presents space charge distributions under opposite voltage polarities in full size cross-linked polyethylene power cables using the pulsed electro-acoustic technique. Under both positive and negative polarities, space charge distributions possess similar profiles but opposite polarities. A similar phenomenon had been reported previously in plaque samples and was termed the “mirror image effect”. By comparing the results between cables treated by degassing under different conditions, the paper concludes that the “mirror image” charge distribution is mainly attributed to a bulk effect within the volume of the insulation, whilst electron transfer by tunneling through an electrode/insulator interface contributes to the generation of homo “mirror image” close to the electrodes

Improving the Dielectric Properties of Polymers by Incorporating Nano-particles.

The paper presents a brief review of the promise of nanotechnology applied to polymeric insulation materials and discusses the electrical properties found. For a variety of nanocomposites, the dielectric behaviour has shown that the interface between the embedded particles and host matrix holds the key to the understanding of the bulk phenomena being observed. Dielectric spectroscopy verified the motion of carriers through the interaction zones that surround the particles. The obvious improvements in endurance and breakdown strength of nanocomposites may be due to a reduction of charge accumulation. PEA space charge tests confirm this charge dissipation. By examining the onset field of space charge accumulation, it may be possible to determine whether a system is likely to be useful

The Influence of Water on Dielectric Behavior of Silica-filled Epoxy Nano-composites and Percolation Phenomenon

The dielectric properties of epoxy resin were studied as a function of hydration by dielectric spectroscopy. The dielectric spectroscopy measurements show different conduction and quasi-DC behaviors at very low frequencies (<10-2 Hz) with activation energies dependent on the hydration. These observations lead to the development of a model in which a “water shell” is formed around the nano-particles. The multiple shell model, originally proposed by Lewis and developed by Tanaka, has been further developed to explain low frequency dielectric spectroscopy results in which percolation of charge carriers through overlapping water shells was shown to occur. At 100% relative humidity, water is believed to surround the nanoparticles to a depth of approximately 10 monolayers as the first layer. A second layer of water is proposed that is dispersed by sufficiently concentrated to be conductive. If all the water had existed in a single layer surrounding a nanoparticle, this layer would have been approximately 5 nm thick at 100% RH. Filler particles that have surfaces that are functionalized to be hydrophobic considerably reduce the amount of water absorbed in nanocomposites under the same conditions of humidity. PEA results show that the wetted epoxy specimens have a higher threshold field of space charge accumulation than such dry specimens since water enhances charge decay

Influence of absorbed water on the dielectric properties and glass-transition temperature of silica-filled epoxy nanocomposites

Work on dielectric spectroscopy of epoxy resin filled with nano-SiO2 at different relative humidities and temperatures is reported. Above the glass-transition temperature (Tg), dc-like imperfect charge transport (QDC or LFD) dominates the low frequency dielectric spectrum. Another mid-frequency relaxation process was found in the non-dried composites. Water also induces glass-transition temperature decreases, which can be measured both by dielectric spectroscopy and DSC. Both theory and experiment demonstrated that a higher water content could exist in nanocomposites than unfilled epoxy suggesting a bigger free volume when nanostructured. In our system, the hydrophilic surface of silica is likely to cause water to surround and lead to delamination of the epoxy from SiO2. This is a potential mechanical and dielectric weakness in the nanocomposites, which may lead to an ageing phenomenon. Hydrophobic surface group may reduce the water adsorption in nanocomposites

The Influence of Material Modification and Residues on Space Charge Accumulation in XLPE for DC Power Cable Application

The effects of material modification and cross-linking by-products (residues) quantity on space charge accumulation and decay in XLPE have been investigated using the pulsed electro-acoustic technique. The threshold stress for space charge generation during voltage-ramping was found to show considerable variation and to depend upon the material and the amount of residue present. However, the modified XLPE material was found to exhibit a higher threshold for space charge accumulation than the reference XLPE whatever the conditions. De-gassed samples were found to exhibit the highest threshold stress, with that of the modified de-gassed XLPE accumulating no space charge at all even after 24 hours stressing at 70kV. In general heterocharge regions were formed when the residues were present and homocharge or no charge was formed when the residues were removed by degassing. Differences were also found in the space charge decay following short-circuit (volts-off), with the decay of heterocharge being rapid, whereas that of homocharge was slow. A tentative explanation is offered to explain these features

The influence of physical and chemical linkage on the properties of nanocomposites

It has been shown by several groups that the mechanical and electrical behavior of composites changes quite substantially, and often beneficially, when the filler particle size is less than 100 nm in diameter. There is also good reason to believe that the interface between the embedded particulates and the polymer matrix holds the key to understanding the bulk phenomena observed. Materials based on an SiO2-polyolefin system have been formulated with functionalized particulates so as to affect the physical and chemical linkages. The agents used to achieve this include amino-silane, hexamethyl-disilazane and triethoxyvinylsilane. The emerging picture of the interface is supported by detailed dielectric spectroscopy and internal space charge assessment. The nature of the internal structure has been related to the bulk properties observed such as the breakdown strength, voltage endurance, and the measurement of internal charges resulting from interfacial polarization

Electroluminescence excitation mechanisms in an epoxy resin under divergent and uniform field

Electroluminescence excitation mechanisms have been investigated in epoxy resin under divergent and uniform field situations. Metallic wires embedded in the resin were used to produce field divergence whereas film samples were metallised to obtain a uniform field. Electroluminescence under divergent field was stimulated by an impulse voltage. Light was emitted on the positive and negative fronts of the square pulses when the field exceeded 20 kV/mm at the wire surface, with equal intensity and without polarity dependence. There was evidence of space charge accumulation around the wires in multiple-pulse experiments. Charge injection and extraction occurring at both fronts of the pulse provide the condition for EL excitation. Further excitation of the EL during the plateau of the voltage pulse is prevented by the opposite field of the trapped charge. Field computation with and without space charge supports the proposed interpretation. A DC voltage was used for the uniform field experiments. A continuous level of electroluminescence is found at 175 kV/mm. Charging/discharging current measurements and space charge profile analyses using the pulsed electro-acoustic (PEA) technique were performed at different fields up to the EL level. Dipolar orientation generates a long lasting transient current that prevents the conduction level being reached within the experimental protocol (one hour poling time). The continuous EL emission is nevertheless associated with a regime where the conduction becomes dominant over the orientational polarization. Polarization and space charge contribute to the PEA charge profiles. Homo-charge injection at anode and cathode is seen at 20 kV/mm and a penetration of positive space charge in the bulk is detected above 100 kV/mm, suggesting an excitation of the continuous EL by bipolar charge recombination

Space charge induced luminescence in epoxy resin

Dielectric breakdown of epoxies is preceded by a light emission from the solid state material, so-called electroluminescence. Very little is known however on the luminescence properties of epoxy. The aim of this paper is to derive information that can be used as a basis to understand the nature of the excited states and their involvement in electrical degradation processes