Copoly(2-nonyl-2-oxazoline)-stat-poly(2-dec-9′enyl-2-oxazoline)s can be crosslinked by the thiol-ene reaction with glycol dimercaptoacetate. The copoly(2-oxazoline)-stat-copolyester is tested as dielectric for high-voltage applications, either as unfilled resin or as composite with nanoscaled fillers of silica, alumina, and hexagonal boron nitride. During AC voltage tests, all materials have an average breakdown strength of 45–50 kV mm−1. For DC voltage tests, samples with SiO2 (hBN) have an average breakdown strength of ≈100 (80) kV mm−1, while the unfilled copoly(2-oxazoline) has an average breakdown strength of ≈60 kV mm−1. Permittivity measurements at 20 °C and 50 Hz reveal that all nanocomposites are dielectrics (D = 0.06–0.08), while the unfilled copoly(2-oxazoline)s has a high loss factor of D = 8.43. This phenomenon can be retraced to the phase separation in the crosslinked copolymer, the M-OH functionality of silica and alumina particles, and models of polymer–particle interactions such as the Tanaka model, revealing that the nanofillers reduce the interfacial and dipolar polarizability.@en

Five types of nanofillers, namely, silica, surface-silylated silica, alumina, surface-silylated alumina, and boron nitride, were tested in this study. Nanocomposites composed of an epoxy/amine resin and one of the five types of nanoparticles were tested as dielectrics with a focus on (i) the surface functionalization of the nanoparticles and (ii) the water absorption by the materials. The dispersability of the nanoparticles in the resin correlated with the composition (OH content) of their surfaces. The interfacial polarization of the thoroughly dried samples was found to increase at lowered frequencies and increased temperatures. The β relaxation, unlike the interfacial polarization, was not significantly increased at elevated temperatures (below the glass-transition temperature). Upon the absorption of water under ambient conditions, the interfacial polarization increased significantly, and the insulating properties decreased or even deteriorated. This effect was most pronounced in the nanocomposite containing silica, and occurred as well in the nanocomposites containing silylated silica or non-functionalized alumina. The alternating current (AC) breakdown strength of all specimens was in the range of 30 to 35 kV·mm−1. In direct current (DC) breakdown tests, the epoxy resin exhibited the lowest strength of 110 kV·mm−1; the nanocomposite containing surface-silylated alumina had a strength of 170 kV·mm−1. In summary, water absorption had the most relevant impact on the dielectric properties of nanocomposites containing nanoparticles, the surfaces of which interacted with the water molecules. Nanocomposites containing silylated alumina particles or boron nitride showed the best dielectric properties in this study.@en

The emergence of nano dielectrics for specialized high voltage applications sparked off a variety of research activities, which proved that nano-fillers are capable of improving the electrical, thermal and mechanical properties of polymers. This paper primarily investigates the effect of addition of hBN (hexagonal boron nitride) nanoparticles into an epoxy polymer base by increasing fill-grade, from 0.2 to 5 % by volume, from two different standpoints: (a) characterizing the electrical space charge (S.C.) accumulation threshold under DC electrical fields, and, (b) demonstrating the alterations in material properties of the modified polymeric materials, from the unfilled polymer. Objective (a) is experimentally investigated by the pulsed electro-acoustic (PEA) technique, well known for determining spatial charge distribution in dielectrics. Objective (b) is investigated by determining the ultrasonic velocity response of the modified composites and unfilled polymer. The obtained results suggest a relation between electrical threshold fields for S.C. accumulation fill-grades, as well as the fact that incorporating stiff filler materials into brittle polymer bases leads to a tougher composite (capable of withstanding greater breaking stress levels), but with reduced ductility.

@en

Many researchers have reported an improvement of the properties of polymer dielectrics by introducing nanofillers. However, the influence of ambient conditions and sample storage under different conditions are often not taken into account. The epoxy matrix itself is a polar polymer susceptible to water absorption, and the presence of hydrophilic nanofillers such as silica will enhance the uptake of moisture from the environment. The dielectric response both of neat epoxy resin and an epoxy-based nanocomposite under an electrical stress greatly depends on the amount of absorbed water. This study investigates the effect of water absorbance on the dielectric spectrum of epoxy-silica nanocomposites containing different concentrations of nanoparticles.

@en

The addition of microsized fillers to polymers, in order to tailor their properties, has been extensively used in many industrial applications since the 1960s. The same approach applies to the field of electrical insulation. Epoxy resin is a widely used polymer in the electrical power sector, but it is usually loaded with microsized fillers, such as aluminum oxide and silicon dioxide, mainly to increase its thermal conductivity, improve its mechanical properties, and to decrease cost. Polymers with microsized fillers are called microcomposites. In the mid-1990s, a new type of polymeric composites for high voltage applications, the so-called nanocomposites, emerged. The main characteristic of these composites is the small filler size, which is smaller than 100 nm at least in one dimension. Since then, there has been a growing interest in the performance of polymeric nanocomposites for high voltage applications, including epoxy nanocomposites. The performance of nanocomposites is mainly related to the tremendous effective internal surface area of these materials because of the high surface-tovolume ratio of nanofillers. After 20 years of research, a significant amount of data has been generated which reflects the potential of nanodielectrics. It has been shown that nanofillers are capable of contributing to the improvement of both the thermal and electrical properties of polymers. However, the laboratory performance of nanocomposites is inconsistent and unpredictable. These are the main factors which inhibit the applicability of nanodielectrics. Important challenges in the field of epoxy nanocomposites should be overcome before nanodielectrics can be produced on an industrial level. The most important challenge is related to the dubious reproducibility of the nanocomposite performance which is closely related to sample homogeneity. Thus, the effectiveness of separating the nanoparticles from each other and the homogeneous incorporation of them into the polymer matrix are expected to affect the performance of nanocomposites. However, the extent to which the behavior of nanocomposites is influenced by sample homogeneity is not well defined. In this thesis, a number of epoxy nanocomposites and mesocomposites were synthesized aiming at the analysis of the parameters which influence their thermal and electrical properties. The analysis includes the thermal and electrical conductivity, dielectric response, and breakdown strength under both AC and DC electric fields. The experimental results demonstrate the important role of interfaces in the behavior of epoxy nanocomposites. Based on the experimental results, important parameters for determining the performance of nanocomposites are suggested to be the polymer re-organization and water uptake. The former is related to the influence of nanofillers on the polymer structure, i.e., the areas in the vicinity of nanofillers are assumed to exhibita different behavior from the rest of the polymer matrix. The uptake of water is related mainly to the hydrophilic nature of nanofillers and plays a significant role in the electrical performance of nanocomposites. Apart from the aforementioned mechanisms, the presence of structural imperfections should not be neglected as they affect both the thermal and electrical properties of epoxy nanocomposites. Additionally to the experimental part, models were developed for both the relative permittivity and thermal conductivity of nanocomposites. The models are based on the two aforementioned parameters; polymer re-organization in the vicinity of nanofillers and water uptake due to the hydrophilicity of nanofillers. The main characteristic of both models is the use of the same structure which strengthens the validity of the assumptions. The experimental results are in good agreement with the model results. Also, a large part of the thesis is devoted to the evaluation of the influence of sample homogeneity on the performance of nanocomposites. For this purpose, nanocomposites with different synthesis techniques were fabricated. The results suggest that the thermal conductivity, dielectric response, and breakdown strength (AC and DC) of epoxy nanocomposites are not significantly influenced by the nanoparticle distribution. This observation suggests that high levels of reproducibility can be achieved when the particles are similarly dispersed and differently distributed. Finally, hybrid composites which combine both microsized and nanosized fillers were fabricated, tested, and analyzed. This type of composites is more likely to be employed in industry as epoxy resin in its pure form is rarely used for high voltage applications. It is usually reinforced with high loadings of microparticles. Microcomposites reinforced only with a small amount of nanofillers, i.e., less than 1 % by volume, show a significant thermal and electrical improvement.@en

Poly(2-nonyl-2-oxazoline)80-stat-poly(2-dec-9′-enyl-2-oxazoline)20 and poly(2-dec-9′-enyl-2-oxazoline)100 can be synthesized from the cationic ring-opening polymerization of monomers that can be derived from fatty acids from renewable resources. These (co)poly(2-oxazoline)s can be crosslinked with di- and trifunctional mercapto compounds using the UV-induced thiol-ene reaction. The complex permittivity of the corresponding networks increases with the temperature and decreases with the network density. In a frequency range from 10−2 to 106 Hz and at temperatures ranging from −20 to 40 °C, the changes of the real part of the complex permittivity as well as the loss factor can be explained by interfacial polarization within the material. At a temperature of 20 °C and a frequency of 50 Hz, the permittivity of the crosslinked (co)poly(2-oxazoline)s covers a range from 4.29 to 4.97, and the loss factors are in the range from 0.030 to 0.093. The electrical conductivities of these polymer networks span a range from 5 × 10−12 to 8 × 10−9 S/m, classifying these materials as medium insulators. Notably, the values for the permittivity, loss factor and conductivity of these copoly(2-oxazoline)s are in the same range as for polyamides, and, hence, these copoly(2-oxazoline)-based networks may be referred to as “green” alternatives for polyamides as insulators in electronic applications.@en