New materials are currently being developed for applications in transformer design. With the useful life of transformers now determined by solid insulation conditions, a better understanding of aging kinetics is important in order to improve electrical system management and planning from the technical and economic points of view. This paper summarizes an investigation of the effects of impregnating aramid and cellulose/aramid papers (Nomex 410 and 910) with insulation fluids (Nynas Polaris and Luminol Tri) at thermally accelerated conditions (170 degrees C) on their mechanical properties. It was found that Nomex 410 (100% aramid) showed only a small change in tensile strength (similar to 5% decrease) after accelerated aging (around 7500 h). However, its elongation capacity was significantly reduced (similar to 45-70% decrease for dry and wet Nomex 410, respectively) by the end of the aging process, probably due to hydrolysis. In addition, the interaction between water and aramid hydrogen bonds at high temperatures produced the rupture and then, the randomly rebuilt of these bonds in meta-aramid fibres, thereby reducing its plastic deformation capacity. In the case of Nomex 910 (aramid enhanced cellulose), its mechanical properties were maintained for a longer time than those of thermally upgraded Kraft paper (TUK), as measured by the retained percentage of tensile index. However, when the tensile index was used instead of the retained percentage, TUK showed a higher tensile index value than Nomex 910 during the initial stage, while the values for both papers became similar during the second stage. It is only at the end of the aging process that Nomex 910 presented an advantage over TUK paper due to the addition of the aramid fibres. It was also found that the inception fractures in Nomex 910, as a fibrous layered composite paper, start in the weakest part of the composite, probably in the central cellulose layer. The fracture line follows the weakest path, avoiding the aramid fibres. The results presented in this paper can be used as a benchmark for improving our understanding of aging and changes in the mechanical properties of these relatively new materials used in the solid insulation of power transformers. A better understanding of the aging characteristics (thermal degradation) of aramid-based papers should help better assess the condition of the new generation of power transformer fleets.

This manuscript presents a comprehensive literature review with the aim to provide readers a reference document with up-to-date information on the field of methanol use as a chemical marker. It has been a little more than a decade since methanol was first introduced as a marker for assessing solid insulation condition in power transformers. It all started when methanol was identified in the laboratory during thermal ageing tests carried out with oil-immersed insulating papers and was subsequently also identified in transformer field samples. The first publication on the subject was released in 2007 by our research group. This review covers the methanol fundamentals such as the analytical methods for its determination in transformer oil, which is generally performed by headspace gas chromatography with mass spectrometry or flame ionization as a detector. Current standardization efforts for its determination include ASTM working group 30948 and IEC TC10. Kinetic studies have confirmed the relationship between methanol generation, the number of broken 1,4-β-glycosidic bonds of cellulose and changes in mechanical properties. Laboratory tests have confirmed its stability at different accelerated ageing temperatures. Several utilities have identified methanol during field measurements, case studies on power and some distribution transformers are presented, as well as transformer postmortem investigations. These field-testing results demonstrate its utility in monitoring cellulosic insulation degradation. Recently, a model of methanol interpretation has become available that allows for evaluation of the average degree of polymerization of core type transformer cellulose winding. Methanol has a role as an indicator of cellulosic solid insulation ageing in transformer mineral oil, and it is expected that in the future it will be in routine use by utilities.

To go further in our assessment of methanol for the monitoring of the cellulosic insulation condition in electrical transformers, two of the paper/oil systems [one comprising a standard wood Kraft paper and the other, a thermally-upgraded Kraft paper (TU paper)] discussed in Parts 1 and 2 (Gilbert et al. in Cellulose 16:327–338. doi: 10.1007/s10570-008-9261-1, 2009; Cellulose 17:253–269. doi: 10.1007/s10570-009-9365-2, 2010) were reinvestigated under accelerated ageing conditions (T between 130 and 210 °C). The experimental data were tracked by testing two mathematical models, one that takes into account the inhomogeneous nature of the polymer by decreasing with time a pseudo-zero rate constant by a first-order process and the other, by simultaneously operating a separate first-order law for the three main categories of 1,4-β-glycosidic bonds in the polymer structure. These additional results provide evidence that the degradation proceeds via a random opening of these bonds in both the amorphous and crystalline regions, with the influence of a pyrolysis-like mechanism even at relatively low temperatures. Very good dependence with the temperature (lnk vs 1/T) is noted for the rate constants of the production of chain-end groups and the formation of methanol, confirming the importance of carrying out the ageing tests beyond the LODP of the specimens (leveling-off value of the degree of polymerization). The grouping of some of these data with those published in Part 2 for an identical system reveals that the degradation is governed by a single reaction pattern over 70–210 °C. The Arrhenius law applied to this data grouping shows an activation energy of 95 ± 4 kJ mol−1 with a frequency factor (lnAa) of 22 ± 1 for the depolymerization, while for the formation of CH3OH, the respective values are 122 ± 6 kJ mol−1 and 33 ± 2. Finally, the kinetic parameters obtained under accelerated ageing conditions over 150–210 °C show that the stabilizing substances of the TU-Kraft paper modify the bond opening mechanism by blocking the effect of the acid and water generated by the oil decomposition. When they are present in the fibrous structure, the activation energy of the reaction goes up to 148 ± 14 kJ mol−1 with a frequency factor of 33 ± 4 for the depolymerization and 133 ± 11 kJ mol−1 with a frequency factor of 33 ± 3 for the formation of CH3OH.

Recently, the existence of a relation between the rupture of 1,4-β-glycosidic bonds in the cellulose during thermal-ageing of paper/oil systems and the detection of methanol in the oil has been reported for the first time in this journal (Jalbert et al. 2007). The present study addresses the rate constants of the reaction for standard wood kraft papers, two immersed in inhibited naphthenic oil under air (paper/oil weight–volume ratio of 1:18) and one in non-inhibited paraffinic oil under nitrogen (paper/oil weight–volume ratio of 1:30). The isotherms in the range of 60–130 °C show that the initial rate of methanol production markedly increases with temperature and to a lesser extent with the moisture of the specimens (initially between 0.5 and 2.25% (w/w)), similarly to what is noted for the depolymerization through the Ekenstam’s pseudo-zero order model. The Arrhenius expression of the rate constants reveals linear relationships that confirm the dominance of a given mechanism in both cases. A very good agreement is also noted for the activation energy over the entirely paper/oil systems studied (106.9 ± 4.3 and 103.5 ± 3.7 kJ mol−1 for methanol and scissions, respectively). Furthermore, a comparison of the rate constants \( \left( {k_{{{\text{CH}}_{ 3} {\text{OH}}}} /k_{\text{scissions}} } \right) \) shows approximately constant values indicating an apparent yield for the methanol of about one-third molecule per every scission for the tests under air (0.27 ± 0.04 for Clupak HD75 and 0.37 ± 0.14 for Munksjö TH70) and even lower for the ones under N2 (0.12 ± 0.03 for Munksjö E.G.). As expected from a pseudo-zero order model, these values were shown to be consistent with a similar comparison of the amount of CH3OH and chain-end groups produced under specific time–temperature ageing conditions (168 h at 120 °C). Finally, an additional test carried out with unaged cellulose in contact with a fresh solution of methanol in oil (cellulose/oil weight–volume ratio of 1:18) shows that at equilibrium, over 58% of the species is lost from the solution due to penetration into the fibres. Such results reveal the importance of the species partitioning in establishing the true correspondence between the molecules of CH3OH produced and the scissions.

In order to go further in demonstrating that methanol can be used as a universal cellulose degradation indicator in power transformers, the ageing study of standard wood kraft specimens in oil in the range of 60–130 °C (Gilbert et al. in Cellulose 16:327–338, 2009) has been extended to thermally-upgraded (TU) papers. The kinetic model that best tracks the ageing patterns was shown to be a function that can accelerate or decelerate the pseudo-zero kinetics by the adjustment of a free parameter. The results showed a non-negligible contribution of 1,4-β-glycosidic bond breaking in the crystalline regions suggesting that the degradation at this level is not necessary occurring through a quantum mode mechanism. The results also showed a significant error in the determination of the rate constants when obtained from isotherms of varying degree of depolymerization. In the case of TU papers, provided that there is a sufficient amount of stabilizers in the fibrous structure, not only could the self-catalyzing nature of the cellulose ageing process as well as the effect of an external supply of catalysts be lost but the chain-breaking could decrease to nearly zero for an undetermined period well before reaching the levelling-off degree of polymerization. The initial rate constants (k 1o) for the depolymerization and methanol formation of these papers were found to be very near those of standard cellulose (giving about the same activation energy), which indicates that they are obtained from the ageing patterns well before the retardant action has fully taken place. The life extension of TU papers is achieved by a reduction with time of the frequency at which the bonds are ruptured. Moreover, the production of methanol and chain-end groups showed about the same value for the frequency factor, which introduces the possibility that the rate of production of CH3OH from chopped chains is much higher than the rate of depolymerization, so that the latter becomes the rate determining step of the overall reaction. On the other hand, the apparent yield of CH3OH molecules per scission is seen to increase substantially with the amount of stabilizers (from ~0.4 to 0.8 and to 1.4 for a paper containing 0 to 1.15 and to 3.9% (w/w) N2) and to a lesser extent, with the moisture in the specimens. However, these variations could either be attributed to a modification of the CH3OH paper/oil partitioning by the stabilizers and moisture in fibrous structure. Finally, pre-aged systems (130 °C for 168 h) conditioned at 20 °C for variable lengths of time provided further evidence that O2 is not necessarily involved in CH3OH production.

In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded (TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with 2-furfuraldehyde, which is the current reference in the domain.