Yoshimichi Ohki

Surface degradation of polyamide nanocomposites caused by partial discharges using IEC (b) electrodes

Partial discharge (PD) degradation of polyamide both without nanoscale fillers (nanofillers) and with 2,4 and 5 wt% additions of nanofillers was investigated. Such materials were subjected to PDs using the IEC (b) electrodes for evaluation. Comparisons were made as to the surface roughness observed by scanning electron microscopy and atomic force microscopy. It was found that the change in the surface roughness is far smaller in specimens with nanofillers than those without nanofillers, and that the 2 wt% addition is sufficient for improvement of the surface roughness. Furthermore, it was elucidated that the difference of surface roughness of the degraded area due to PDs among the specimens originates from the difference in their crystalline structures. These results indicate that polyamide nanocomposite is more resistance to PDs than polyamide without nanofillers.

Various types of nonbridging oxygen hole center in high‐purity silica glass

Optical absorption measurements of the 2.0‐eV band and photoluminescence measurements of the 1.9‐eV emission, excited by various excitation bands, were carried out on high‐purity silica glasses subjected to γ‐ray irradiation. Two, and possibly three, different forms of nonbridging oxygen hole centers were deconvoluted from the results of the isochronal annealing experiments. The difference in the peak wavelength of the 2.0‐eV absorption and 1.9‐eV luminescence bands among various forms of nonbridging oxygen hole centers is reported.

Enhanced partial discharge resistance of epoxy/clay nanocomposite prepared by newly developed organic modification and solubilization methods

Frequency accelerated partial discharge (PD) aging of epoxy nanocomposite with 5 wt % additions of clay was investigated in comparison with that of epoxy without clay in terms of PD erosion depth. It was found that the change in the erosion depth is far smaller in specimens with clay than those without clay. The newly developed organic modification and solubilization methods give comparable PD resistance characteristics. The latter would be more resistant to PDs than the former, if specimens were prepared properly. It was clarified that nano-micro mixed composites were superior to the single nanocomposite. Nano segmentation with some interaction zone effect is proposed as a mechanism of improvement in PD resistance.

Plasma-enhanced chemical vapor deposition and characterization of high-permittivity hafnium and zirconium silicate films

Deposition of hafnium silicate films with various hafnium contents was tried by plasma-enhanced chemical vapor deposition using tetraethoxysilane and a hafnium alkoxide. From x-ray photoelectron spectroscopy, the deposited films are confirmed to be silicate with Hf–O–Si bonds but without any Hf–Si bonds. The permittivity calculated from the capacitance of the accumulation layer increases monotonically with an increase in the hafnium content, whereas the optical band gap energy estimated from vacuum ultraviolet absorption spectra decreases. Similar results were obtained from zirconium silicate films deposited using tetraethoxysilane and a zirconium alkoxide. If we compare the films with the same hafnium or zirconium content, the hafnium silicate exhibits a higher permittivity and a larger band gap energy than the zirconium silicate.

Visible photoluminescence from Si clusters in γ-irradiated amorphous SiO2

Visible photoluminescence (PL) bands around 2 eV were studied in 60Co γ‐irradiated (dose<1 MGy) oxygen‐deficient‐type amorphous SiO2 (a‐SiO2) excited by 2–4 eV photons. In addition to the well‐known 1.9 eV PL band due to nonbridging oxygen hole centers, another PL band was observed at 2.2 eV when excited by 3.8 eV photons. The intensity of the 2.2 eV band increases with decreasing oxygen partial pressure during the sample preparation. Electron‐spin‐resonance measurements show that the intensity of the 2.2 eV band is correlated with the concentration of the Eδ′ center, a paramagnetic state of a cluster of silicons. After much higher γ irradiation with a dose up to 10 MGy, a new PL band was induced at 1.75 eV under excitation by 2.5 eV photons, as well as the 1.9 and 2.2 eV PL bands. By comparing its spectral shape and excitation energy with known PL band in Si‐implanted a‐SiO2, it is suggested that the 1.75 eV band is associated with Si nanocrystals formed from Si clusters in a‐SiO2 by the high‐dose γ irra...

Defects and optical absorption bands induced by surplus oxygen in high-purity synthetic silica

The nature of excess oxygen in as‐manufactured and γ‐irradiated high‐purity synthetic silicas is investigated. Electron‐spin‐resonance measurements suggest that peroxy radicals ( 3/4 SiOO⋅) could be produced either by the cleavage of peroxy linkages ( 3/4 SiOOSi 3/4 ) or by the reaction of E’centers ( 3/4 Si⋅) with oxygen molecules. The excess oxygen is found to exist in the glass in two forms: as peroxy linkages and as interstitial molecular oxygen. The peroxy linkage is shown to be the cause of optical absorption at 3.8 eV. Heat treatment at 900–1000 °C results in the growth of the 3.8‐eV band, that is, the peroxy linkages, through the reaction of oxygen vacancies and interstitial dioxygen molecules. These results indicate that the 5.0‐ and 3.8‐eV bands (which are characteristic of ‘‘oxygen‐deficient’’ and ‘‘oxygen‐surplus’’ silica, respectively) can coexist in a glass, depending on the synthesis conditions.

Dielectric properties of water and water/ethylene glycol mixtures for use in pulsed power system design

One class of modern pulse power generators use deionized water as an energy storage, switching and transmission dielectric. Water is chosen for its high dielectric constant and relatively high resistivity, which allows reasonably sized and efficient low-impedance high-voltage pulse lines where pulse durations are less than 100 µs. Water/ethylene glycol mixtures are being researched, so that rotating machinery, rather than the usual Marx generator, can be used as the primary energy store. The high resistivity and high dielectric constant of these mixtures at low temperature permit low-loss operation on millisecond time scales. Simple design criteria linking load parameters and charging circuit characteristics to the liquid dielectric are developed which show that the dielectric constant, breakdown strength, and relaxation time are the primary properties of interest to the pulse power engineer. On time scales greater than 100 µs, injection of space charge, with density q and mobility µ, affects the charging and discharging circuit characteristics, introduces the time constant of the time of flight for injected charge to migrate between electrodes, and increases the effective ohmic conductivity σ to σ + qµ. A drift-dominated conduction model is used to describe measured space-charge effects. Kerr electrooptic field mapping measurements show strong space-charge effects with significant distortions in the electric field distribution a few hundred microseconds after high voltage is applied. The injected charge magnitude and sign depends on the electrode material. Thus by appropriate choice of electrode material combinations and voltage polarity, it is possible to have uncharged liquid, unipolar-charged negative or positive, or bipolar-charged liquid. An important case is that of bipolar injection, which has allowed up to a 40 percent higher applied voltage without breakdown than with no charge injection, and thus a doubling of stored energy due to the space-charge shielding which lowers the electric field strengths at both electrodes. Although injected space charge increases the stored electric energy over the capacitive space-charge-free energy, (1/2)CV2, more energy is required from a source during charging and the energy delivered to a resistive load is reduced because of internal dissipation in the capacitor as the charge is conducted to the electrodes. However, it appears that this extra dissipation due to injected charge can be made negligibly small and well worth the price if the space charge allows higher voltage operation for long charging time or repetitively operated machines.

Effects of nano-filler addition on partial discharge resistance and dielectric breakdown strength of Micro-Al 2 O 3 Epoxy composite

It is often observed that the insulation structure for an insulated gate bipolar transistor (IGBT) suffers from dielectric failure, when the insulation is made of epoxy resin to which micro fillers with a high thermal conductivity were added. In order to reveal the above phenomena and to clarify the breakdown (BD) mechanism, we have carried out experiments using an MB-PWB (metal-base printed wiring board) insulation simulated structure. As a result, it was clarified that the IGBT insulation breaks down after successive partial discharges (PDs). It was also elucidated that BD strength becomes lower, when epoxy resin was loaded with high content of micro-fillers. A trial was made to raise the once-lowered BD strength by adding nano-Al2O3 fillers. Three kinds of experiments were carried out, i.e. an MB-PWB insulation simulated structure for dielectric failure, a rod-to-plane electrode for PD erosion resistance, and a sphere-to-sphere electrode for BD strength for four kinds of insulation samples, i.e. neat epoxy, 5-wt% nano- Al2O3/epoxy composite, 60-wt% micro-Al2O3/epoxy composite, and combined 2-wt% nano- and 60-wt% micro-Al2O3/epoxy composite. It was clarified that the nano-micro-composite is higher in both BD strength and PD resistance than the micro-composite. It should be noted that the addition of nano-fillers would provide an excellent approach that can increase the dielectric BD strength and time of micro-filled epoxy composites.

Possible mechanisms of superior resistance of polyamide nanocomposites to partial discharges and plasmas

Degradation profiles induced by partial discharges and those induced by oxygen plasmas are compared for polyamide/mica nanocomposites. Both the resistances to partial discharges and to plasmas improve with an increase in nanofiller content. On the other hand, the partial discharge resistance is not improved if mum-sized glass fibers are added to polyamide. In order to investigate these phenomena, the superior resistance mechanism of nanocomposites is discussed, focusing on the effects of the nanofillers on the bulk and surface structures of the resin. It was revealed from X-ray diffraction and permittivity measurements that the nanofiller loading increases crystallinity of the resin and restricts the molecular motion. This should enhance the resistance to degradation. Furthermore, observation results by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction revealed that the nanofillers had piled up themselves to form a layered structure on the sample surface in an early stage of degradation. Such a structure acts as a barrier against impact of charged particles and diffusion of gases such as oxygen, which should contribute to the improvement of resistance to degradation as its direct effect and also as its indirect effect by suppressing the oxidation of resin. Moreover, it was also revealed from scanning electron microscopy that the nanofillers impede the growth of surface cavities by partial discharges drastically.

Development of epoxy/BN composites with high thermal conductivity and sufficient dielectric breakdown strength partI - sample preparations and thermal conductivity

The aim of this research is to find a way to achieve the epoxy composites with both high thermal conductivity and acceptable dielectric breakdown (BD) strength. As high thermal conductivity, low permittivity and low thermal expansion coefficient of filler can endow composite with higher thermal conductivity, higher BD strength and lower thermal expansion coefficient respectively, BN (boron nitride) with high thermal conductivity, low permittivity and low thermal expansion coefficient was adopted as main filler in the research. Thermal conductivity was investigated in this part. The BD strength of samples will be discussed in Part II. Neat epoxy and other 25 kinds of epoxy/BN composites were prepared by a hot press method. Most of BN fillers were surface modified with silane coupling agent through ethanol/water reflux method to improve thermal conductivity. The values of 2.91 W/m·K, 3.95 W/m·K and 10.1 W/m·K as thermal conductivity were obtained for the composites that was single-loaded with h-BN(hexagonal boron nitride), c-BN (cubic boron nitride) or conglomerated h-BN, respectively. They were further improved to 5.26 W/m·K, 5.94 W/m·K and 12.3 W/m·K, respectively, by adding extra smaller A1N (aluminum nitride) to fill the voids in sample. Thermal conductivity of samples changes with the ratio of c-BN and h-BN when c-BN and h-BN were co-loaded. A value of 5.74 W/m·K as maximum was obtained at their ratio of 1 to 1 when total filler content is 80 wt%. A much higher value of 7.69 W/m·K was obtained by adding extra AIN. From the experiment data, it is concluded that the filler orientation in vertical direction of sample surface and the decrease of voids in sample are very important to obtain high thermal conductivity, and that the filler surface modification is also necessary to improve thermal conductivity especially for epoxy/c-BN composites, and addition of nano silica in small amount can also increase thermal conductivity if sample is prepared appropriately.