Acid catalyzed ageing of oil impregnated kraft paper has been studied experimentally. Five different carboxylic acids (formic, acetic, laevulinic, stearic and naphtenic acid) have been added to mineral oil to arrive at a neutralization value of 0,4 mg KOH/g. Thereafter, kraft paper of two different humidities has been allowed to equilibrate with the oil. The results show that the lower the molecular weight of the carboxylic acids is the more is absorbed by the paper. Furthermore, a clear synergy for the paper ageing rates between moisture and the lower molecular weight acids is found, while for the higher molecular weight acids almost no effects were found. It is concluded that present techniques for measuring acidity of oils do not reflect these detailed conditions. It is suggested to introduce a new measuring technique for neutralization value where water rinsing is used to identify the content of low molecular weight, water soluble acids.

A simulation model for second mode positive streamers in dielectric liquids is presented. Initiation and propagation is modeled by an electron-avalanche mechanism and the Townsend-Meek criterion. The electric breakdown is simulated in a point-plane gap, using cyclohexane as a model liquid. Electrons move in a Laplacian electric field arising from the electrodes and streamer structure, and turn into electron avalanches in high-field regions. The Townsend-Meek criterion determines when an avalanche is regarded as a part of the streamer structure. The results show that an avalanche-driven breakdown is possible, however, the inception voltage is relatively high. Parameter variations are included to investigate how the parameter values affect the model. visible light [3], re-illuminations, from one or more of its branches. Above the breakdown voltage, streamers may change between the 2nd, the 3rd, and the 4th mode during propagation. There are usually more reilluminations in the 3rd mode than the 2nd mode. The inception of the 4th mode is associated with a drastic increase in speed and fewer, more luminous, branches [2].There are numerous mechanisms that can be involved in the streamer phenomena, the challenge is identifying their importance during initiation and propagation. Applying a potential to a needle can cause charge injection, giving a space-charge limited current [16] causing Joule heating [16], which in turn can cause bubble nucleation [17]. A breakdown in the gas bubble can then propagate the needle potential, and the process may repeat. This is one way to explain 1st mode propagation. Electric fields can also cause electrohydrodynamic flow, which could cause streamer formation through cavitation [18]. Electrostatic cracking has also been proposed as a cavitation mechanism [19]. A main topic of discussion is whether a lowering of the liquid density is needed before charge generation can occur. Electron avalanches are important in gas discharge, but their importance in liquid breakdown is still disputed. In water, strong scattering could prevent electrons from forming avalanches in the liquid phase [20]. Therefore, discharges in micro-bubbles can be important for charge generation [10,14,20]. The same mechanism was also proposed for non-polar liquids [19], however, the relative permittivity is about 80 in water and about 2 in a typical oil, and this difference can prove important since the field enhancement within a bubble in oil is much lower than in water. Contrary to water, there are indications of electron avalanches in non-polar liquids [16,21,22], furthermore, while the initiation and the propagation length of 2nd mode streamers are dependent on the pressure, their propagation velocity is not pressure dependent [16,23]. This implies that the mechanism responsible for propagation occurs in the liquid phase and that the gaseous channel follows as a consequence. In very high electric fields, field-ionization can occur [24,25], and this mechanism has been proposed for the fast 3rd and 4th propagation mode...

High-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopic study of the two lowest electronic states of the ozone cation O 3 + Rotationally resolved pulsed field ionization photoelectron study of CO + (X 2 Σ + ,v + =0-42) in the energy range of 13.98-21.92 eVThe aim is to improve the understanding of high-field phenomena (such as preinception currents/conduction, streamer initiation and propagation) in insulating materials in terms of the molecular properties of the substances involved. In high electric fields, ionization is a likely process, and in all such processes, the ionization potential is an important parameter. A fundamental question is how these processes depend on the electric field, and therefore, based on the interaction between a negative point charge and a molecular cation as modeled by density functional theory, a field-dependent model for the ionization potential is developed. In addition, the first excitation energies as a function of the electric field are calculated using time-dependent density functional theory. It is demonstrated that empirical high-field conduction models for cyclohexane and n-tridecane can be explained in terms of the difference between the ionization potential and the first excitation energy. It is also suggested that the reduction of the ionization potential with electric fields, can help explain how fast-mode streamers propagate.

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The electric-field dependence of the molecular ionization potential and excitation energies is investigated by density-functional theory calculations. It is demonstrated that the ionization potential has a strong field dependence and decreases with increasing field. The excitation energies depend weakly on the field and the number of available excited states decreases with increasing field since the ionization potential has a stronger field dependence. Above a specific field, different for each molecule, a two-state model is obtained consisting of the electronic ground state and the ionized state. Implications for streamer propagation and electrically insulating materials are discussed.

In this letter, we experimentally demonstrate that the lightning impulse breakdown characteristics of natural ester liquids can be significantly enhanced by dispersing molecular additives possessing lower values of both the ionization potential and 1st excitation energies as compared to the base liquid. One such additive contributed to an increase in the breakdown and acceleration voltage of the base liquid by 32% and 90%, respectively. Apart from the expected influence of the low ionization potential of the additives, results also indicate a positive effect of lower value of 1st excitation energy.

Hydrolysis of transformer insulating Kraft paper is experimentally investigated. Paper moisture content was varied and five different acids -representative of what may be found in an aging transformer -were added to the oil. The low molecular weight acids were to a large degree absorbed by the paper, contrary to the high molecular acids that remained in the oil. The three low molecular acids accelerated the aging of the paper, and a clear synergy between these acids and water content was found. The high molecular acids did not influence the paper aging significantly. The results support a theory explaining the hydrolysis as governed by acid catalysis. Examples from measurements on real transformers are shown. It is concluded that low molecular acids constitute an important aging factor for transformer windings and should be included in diagnostic schemes, and when estimating the pay-back from maintenance actions.