Against the background of environmental compatibility and unrestricted technical usability, synthetic, and natural transformer oils are critically compared in long‐term tests under high voltage using electrical and instrumental analytical methods. Synthetic alkyl esters of pentaerythrol appear to be sustainable and sometimes superior substitutes for mineral oils in terms of chemical stability, viscosity, permittivity, and heat transport. Natural esters of unsaturated fatty acids are found to be unsuitable for equipment exposed to moist air. Adsorbed water appears to be a general problem in transformer oils. The aging mechanisms and molecular changes during long‐term operation include radical reactions, and the formation, isomerization and cleavage of CC bonds. Extensive material data are provided.

Insulation materials are critical for the reliability and performance of electrical power systems, particularly in high-voltage rotating machines. While failures can arise from thermal, mechanical, or electrical stress, they predominantly manifest as electrical breakdowns. Prior research has primarily concentrated on aging in straight winding sections, despite evidence indicating that failures frequently occur in the bending regions of turn insulation. This study explores the influence of high-frequency pulsed electrical stress on the lifetime behavior of Type II insulation systems used in high-voltage rotating machines. Practical samples, designed with geometric configurations and technology akin to that in rotating machines, were tested under conditions characterized by voltage slew rates (dv/dt) exceeding 10 kV/μs, with variations in frequency and waveform shape. The findings reveal that the rate of electrical aging remains consistent across differing pulse widths, risetimes, and polarities, displaying a similar lifetime exponent. Nonetheless, insulation durability is markedly more compromised under pulsed conditions. At the identical times-to-failure, the sinusoidal waveform necessitated nearly twice the applied peak voltage as the bipolar pulse waveform. This finding clearly suggests that pulsed excitation exacerbates insulation degradation more effectively due to the sharp rise times and high (dv/dt) rates imposing substantial electrical stress on dielectric materials.