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

Application of thermoelectric aging models to polymeric insulation in cable geometry

The life expressions of models of insulation ageing are functions of temperature and field as well as material parameters. A methodology is presented that allows these models to be applied to a cable geometry in which there is a radial variation of both field and temperature. In this way material parameters can be extracted from cable data. The methodology is illustrated using one such model and the parameters deduced from cable failure distributions are compared with those obtained for thin films. This comparison allows conclusions to be drawn about how the ageing process affects specimens of the same material with different volumes

Influence of water absorption in flexible epoxy resins on the space charge behaviour

The aim of the current work is to achieve a better understanding of the influence of water uptake in flexible epoxy resins on the space charge dynamics at high electric fields. The space charge behaviour was studied using pulsed electroacoustic (PEA) technique. The samples were prepared from Araldite CY1311, which is a bisphenol-A epoxy resin. This particular resin was chosen because its glass transition is 0°C and hence it is in a flexible state at room temperature. All samples were conditioned in containers with saturated salt solutions or de-ionised water so that various water uptake levels were obtained. It was found that the space charge dynamics was correlated with the amount of absorbed water in the samples and this is consistent with the dielectric measurements made on the same material where ion transport was identified as the main charge transport process from the observed QDC behaviour

Limitations of Kramers-Kronig transform for calculation of the DC conductance magnitude from dielectric measurements

The Kramers-Kronig (K-K) transform relates the real and imaginary parts of the complex susceptibility as a consequence of the principle of causality. It is a special case of the Hilbert transform and it is often used for estimation of the DC conductance from dielectric measurements. In this work, the practical limitations of a numerical implementation of the Kramers-Kronig transform was investigated in the case of materials that exhibit both DC conductance and quasi-DC (QDC) charge transport processes such as epoxy resins. The characteristic feature of a QDC process is that the real and imaginary parts of susceptibility (permittivity) follow fractional power law dependences with frequency with the low frequency exponent approaching -1. Dipolar relaxation in solids on the other hand has a lower frequency exponent <1. The computational procedure proposed by Jonscher for calculation of the K-K transform involves extrapolation and truncation of the data to low frequencies so that convergence of the integrals is ensured. The validity of the analysis is demonstrated by performing K-K transformation on real experimental data and on theoretical data generated using the Dissado-Hill function. It has been found that the algorithm works well for dielectric relaxation responses but it is apparent that it does not work in the case of a low frequency power law in which the low frequency exponent approaches -1, i.e. in the case of QDC responses. In this case convergence can only be guaranteed by extrapolating the low frequency power law over many decades towards zero frequency

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

Discharge-generated electrical fields and electrical tree structures

The discharge-avalanche (D-A) model for electrical tree propagation in polymers is founded entirely upon basic physical concepts. Electrical discharges in an existing tree structure are taken to raise the electrical field in the polymer both along the discharge path and particularly at the tree tips. As a result of the field increase, electron multiplication avalanches occur within the polymer causing damage, possibly through ionisation of polymer molecules, which is accumulated over a period of thousands (or more) cycles and eventually leads to a tree extension of limited size. The assumption that the damage produced in an avalanche is proportional to the number of ionisations allows the model to be expressed quantitatively in terms of material properties: such as the ionisation potential, I; the impact-ionisation length parameter λ; the critical number of ionisations for tree extension Nc; discharge features such as the number of 1-electron initiated avalanches per half cycle, Nb ; and the potential difference ΔV between the start and end of the avalanche over a distance Lb

Application of polymer ageing models to power cables

Ageing models have been developed to predict the lifetime of polymeric insulation subject to electro-thermal stresses. We present here a method for applying the models to situations in which the field is not constant over the whole specimen, as for cable geometry. The method has been applied to characteristic lifetime data from AC ageing experiments on cables. The results are presented, and the effect of insulation volume upon the model parameters is discussed

Temperature dependance of charge packet velocity in XLPE Cable peelings

The generation and transit of charge packets in 150μm thick peelings from the insulation of Medium Voltage Cables manufactured using the same XLPE batch have been investigated at a number of different temperatures. Charge packet motion was investigated in peelings taken from cables that have been electro-thermally stressed at T= 90 degrees C for 5000 hours with a Laplacian field E ≈ 20kV/mm at the location of the samples. It was found that charge packets were generated by an applied field of 120kV/mm when the internal space charge field reached 140-150kV/mm. Measurements were made in three controlled temperature environments and it was found that the transit time fitted an Arrhenius behaviour with an activation energy of ~1.2 eV. This value is similar to estimates made for the deepest traps (>1.1eV) made from the decay of space charge accumulated at lower fields of 46.67kVmm. It is also close to the activation energy for the conductivity (~1.25 eV) obtained from the dielectric spectroscopy of unpeeled cable sections at Erms ≈ 0.41 V/mm, and ~1.15eV from the dielectric spectroscopy of the peelings (E = 40V/mm). It is therefore concluded that the transit of the charge packet is associated with the trap-to-trap transport of charge carriers located in the deepest traps available. The implications of these results for the mechanism of charge packet generation is discussed

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