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Ageing phenomena of cellulose/oil

insulation in natural ester and mineral oil

C. Perrier*, M-L. Coulibaly, (Alstom Grid - France)
J. Lukic, V. Vasovic, (Institute Nikola Tesla - Serbia)

Abstract
Degradation of electrical insulation due to ageing by were performed using copper, paper, pressboard and
combination of thermal, oxidative and hydrolytic processes insulating oils in proportions close to real design. Hermetic
is one of the main factors that affect power transformer systems were used and oxygen content in the oil was
service life. A better understanding of ageing phenomena is adjusted to simulate conditions of sealed transformers
of great importance for transformer condition assessment. (not free breathing). It was found that in conditions of
This enables reliable operation and affords application of particular ageing test, thermal degradation, i.e. oil pyrolysis
adequate mitigation action to slow down the degradation was dominant degradation mechanism, while oxidation
process of insulating materials and extend transformer and hydrolysis were minor processes. This was confirmed
service life. This issue is all the more important when by low to moderate rate of antioxidants depletion in
new insulating liquids as natural esters are being applied both, natural ester and inhibited mineral oil. Stability and
in growing number in transformer industry. For these performance of natural ester were found to be very good,
reasons, this paper is focused on the ageing phenomena of especially regarding the impact on solid insulation. Indeed,
cellulosic materials (paper and pressboard) impregnated degradation of solid insulation was present at lowest rate, in
with different insulating liquids as natural ester, inhibited comparison with mineral oils, on the basis of highest degree
and uninhibited mineral oils. of polymerization values at the end of ageing.

A first part is dedicated to moisture equilibrium in
impregnated paper and pressboard systems in order to give 1. Introduction
some guidelines on the evaluation of cellulose humidity
through the oil. Moisture equilibrium isotherms were created Power transformers are one of the vital and expensive
for temperatures from 40 to 120°C and for water content elements in the industry of electrical energy, having
in paper and pressboard from 0.5 to 5%. Differences in essential functions in power transmission and generation.
distribution of water within cellulose/oil insulation between Although transformers are very reliable devices, there
natural ester and mineral oil were observed and discussed. remains one inevitable type of failure called “end of life”
Natural esters have higher water solubility and therefore, for failure mode. Most, if not all, organic materials used within
the same water content in cellulose, at same temperature, the transformer are subject to aging processes which lead
water content in the oil was considerably higher in natural to the gradual degradation of their physical, chemical and
ester oil than in mineral oil. It was also found that water electrical properties. The most important of these organic
distribution between paper and pressboard in mineral and materials is the composite insulation system, i.e. cellulosic
ester oils is quite different. Established isotherms constitute materials (mainly paper and pressboard) impregnated with
a useful tool for the condition assessment of green power insulating liquid (mainly mineral and ester oils). Three
transformers [1]. main processes drive the aging of cellulose/oil insulation
systems. First one, pyrolysis is initiated by the temperature
A second part is dedicated to thermal ageing at 140°C up to as the main driving force behind the chemical reactions that
120 days in order to evaluate ageing profile and long term cause ageing. The other processes are hydrolysis, initiated
stability of different oils and solids. Ageing experiments by the presence od water and oxidation, initiated by the

*christophe.perrier@alstom.com

KEYWORDS
Cellulosic insulation, Mineral oil, Moisture equilibrium, Natural ester, Thermal ageing

Cigre Science & Engineering • N°1 February 2015
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Proper condition monitoring of ageing the life of the transformer. Since it is not possible to remove parameters for evaluation of the condition of insulation paper samples from the active windings of a transformer system can improve replacement planning in order to under operation and measure water content of the paper. The chemical method is this property is the degree of polymerization (DPv). end of life is reached when DPv is below 250. Water is also recognized as the “enemy Since the cellulose insulation is more hygroscopic than the number one” of liquid-filled transformers [2] because it oil it contains most of the water in paper/oil system and can has detrimental effect to the dielectric properties of the constitute several percentages by weight of the total mass of insulation system as well as its mechanical characteristics. In order to avoid premature degradation of the cellulosic insulation.presence of oxygen. avoid the consequences of a sudden and untimely failure of indirect measurements were developed as the assessment transformer. or dielectric by the mechanical strength and best measurement to assess response measurements [5]. the water content of the cellulose is cellulose can be maximized through careful monitoring about 0. 8]. solid insulation. Since it is not possible to monitor showing moisture in cellulose insulation versus water DPv values of transformers in service. and pressboard (see table 1) were taken in can introduce the risk of bubble formation during overload specified mass ratios (90% of oil. The mechanical life of the transformer insulation is halved for each doubling in the water content [3]. corresponding to actual ratios in transformers. After reaching equilibrium. 4% of paper and 6% of [4]. moisture equilibrium insulating fluids. In addition. reduces dielectric breakdown and mechanical strength and also Oil. the water is distributed between the paper and pressboard insulation. this paper 2.1 Condition assessment equilibrium isotherms were created for temperatures from 40 to 120OC and for water content in paper and pressboard Moisture in oil/cellulose insulation can affect the life of from 0. It is generally not known simulating ageing of paper/oil insulation in accelerated if the equilibrium curves were obtained from experiments conditions enables a feasible way to analyze the effect of using paper and pressboard insulation in mass ratios different oils and key ageing parameters: temperature. Oil. Moisture 2. Although the end of life failure is inevitable. transformers by leading to significant reductions in both dielectric and mechanical properties. More precisely. paper. the water must be kept to a minimum value. End of life of cellulose insulation is determined through the oil humidity (chemical method).1 Test conditions increases the ageing rate and the dielectric losses. 7. monitoring techniques and test methods for evaluation of cellulosic insulation condition. filtered under vacuum oven. such as natural esters (vegetable oils) charts become necessary tool to evaluate water content instead of mineral oils. paper and pressboard isotherms were performed by Karl-Fisher titration. Moisture equilibrium specified temperature. For this reason. Kraft paper and pressboard immersed in mineral insulating oil and natural ester oil. laboratory models content in mineral oil [6. and how oxygen and water on cellulose ageing kinetics. the paper and pressboard samples were dried and water in the solid insulation after manufacturing process. the life of the In a new transformer. paper under equilibrium conditions. This procedure was followed Cigre Science & Engineering • N°1 February 2015 7 . due to increased applications of With the growing interest to use alternative liquids as natural ester oils in transformers. direct measurements of moisture in the oil. paper and pressboard were heated in 50 ml sealed vials with butyl septa at the 2.5% and is expected to gradually increase during and maintenance. water 2. To achieve the initial low water is present due to moisture ingress from outside and retained content. in insulation systems impregnated with natural ester it becomes important to evaluate the applicability of current insulating liquids. corresponding to approximate mass ratios in materials.5 to 5 %. but major amount of water in cellulose materials actual power transformers. for some transformer applications.2. Various researchers this being the minimum strength considered necessary to had experimentally derived moisture equilibrium charts withstand a short circuit. Water is one of the degradation products of cellulosic pressboard).2 Experimental study will be focused in a first part on experimental studies related to humidity equilibrium curves and in a second part Moisture equilibrium charts were created for conventional on ageing stability of composite oil/cellulose system. From based on moisture partitioning curves between oil and literature data.

which was extended slightly to verify the state of level in the oils was kept below 10000 ppm. inhibited IEC 62770 Paper Thickness 0. Initial water contents in the paper and pressboard at selected moisture levels of 0. taking into consideration higher viscosity of ester oil. non inhibited IEC 60296 Natural ester Triester. equilibration time was longer with ester the air space above the oil level. Equilibrium was certain time at specified temperature and humidity [4. The water content 0 C and for an equilibration time that was taken from the in the mineral oil and ester oil used for impregnation was literature. and pressboard specimens were placed low moisture contents. they were heated oil. pressboard. taking into consideration the material type and respectively up to 5 ppm and 30 ppm. 9].3 g/cm3 IEC 60641-3-2 Pressboard Thickness 1mm. Then. leaving same temperature.2-1. were analyzed by the test method described in IEC 60814.0 %. paper. Density 1-1. Density 1. reached at longer times for low temperatures as well as for Prepared oils.25mm.2 g/cm3 IEC 60641-3-1 Table 1: Tested materials by impregnation with dried and degassed oil.5 to 5. are presented on figure 1. All preparation procedures were made in a glove box with argon atmosphere. The moisture levels were considered contents of paper. were achieved by Different equilibrium times obtained for each oil with paper placing the impregnated specimens in a wet chamber for and pressboard. for 24 h. Figure 1: Equilibrium times as a function of temperature and water content in the paper and pressboard samples impregnated with mineral oil and natural ester Cigre Science & Engineering • N°1 February 2015 8 . Materials Type Standard Mineral oil Naphtenic. at in an oven at specified temperatures between 40 and 120 700C for mineral oil and 90°C for ester oil. For the same moisture level and the together in 50 ml vials crimped with butyl septa. and the insulating liquids as reached when last three measurements matched closely. The moisture equilibrium [10-11]. and the oxygen thickness.

for the same moisture content in the cellulosic materials. together. the estimated moisture in the paper can be underestimated. Wcpaper is the moisture content in the paper (%mass). and 3 % water in cellulosic insulation. was done using the following equation: Figure 2: Perrier-Lukic equilibrium curves for paper/pressboard in mineral and natural ester oils Where Wcc is the total moisture content in the cellulose materials (%mass). The use of equilibrium charts for paper and pressboard together enables greater precision in estimating the moisture content and likely closer to those expected from electrical tests. natural ester and mineral oil are presented for absolute moisture content. paper and pressboard together. This is why these curves are even more important. For example. Comparative analyses of the moisture distribution between cellulose. Indeed. as well as to evaluate cumulative moisture content in both cellulosic materials. i. the expected water content in natural ester oil is significantly higher than in mineral oil. Wcpress is the moisture content in the pressboard (% mass) and mpress is the mass of the pressboard (g).2. water content in natural ester oil is around 10 times higher than in mineral oil. The observed differences with moisture distribution paper and pressboard impregnated with natural esters can have an important role in estimating the moisture content in transformer insulation based on electrical measurements (FDS). Figure 4: Perrier-Lukic equilibrium curves for paper and pressboard in natural ester Cigre Science & Engineering • N°1 February 2015 9 . as they can be used to evaluate water content in the paper and pressboard separately. for equilibrium at 60OC.e.2 Experimental results The developed charts are referred to in this article as the “Perrier-Lukic” equilibrium curves. Separate equilibrium curves for paper. Due to the higher solubility of moisture in natural ester compared to mineral oil. Distribution of humidity pressboard in mineral oil between paper and pressboard in mineral oil is relatively equivalent. the moisture equilibrium curves are significantly moved on the right with natural ester oil (figure 2). Therefore.2. in both oil types are Figure 3: Perrier-Lukic equilibrium curves for paper and presented in Figures 3 and 4. mpaper is the mass of the paper (g). Note that calculation of the total moisture content in paper and pressboard. whereas uneven distribution. pressboard. lower water contents in pressboard and higher water contents in the paper were obtained in ester oil.

the transformer is at risk from the mechanical ratio: 30%.2 Experimental study and maintenance regime. based on Temperature. as end 2-FAL content (IEC 61198).1 Test conditions that cause ageing. copper. viscosity at 40OC (ISO 3104). and less heavily loaded transformers restricted oxygen ingress (initial oxygen content < 10 can last 40-60 years and even longer [12]. inhibited IEC 62770 Paper Thickness 0. affecting the ageing of the cellulose/oil insulation system. the increase of dielectric dissipation factor. impregnation was around 5ppm and 25ppm for natural ester oil. Materials Type Standard Mineral oil Naphtenic. independent vials were heated at forces arising under short circuit or even during normal 140°C during different periods: 10. a comparative ageing study versus mineral oil was done at laboratory scale under accelerated ageing conditions. The presence of oxygen is particularly detrimental to ageing of transformer oil.5%. can be deposited on the windings and 60450). Ageing stability With the emergence of new insulating liquids as natural 3. The exact life of a transformer is not a fixed period and depends on many factors. Density 1. with heat energy being the main driving force behind the chemical reactions 3. In this paper. and with lifespan of 20-25years. For each oil.1 Ageing of transformer insulation ester. the design and materials used. non inhibited IEC 60296 Natural ester (VOR) Triester. we 000 ppm). 60. For each period.25mm.2-1. while the presence Cellulose materials have been dried in deep vacuum at of water predominately speeds up ageing of solid insulation 60°C during 24h and immediately thereafter impregnated by causing a cleavage of cellulose macromolecule chain. following measurements were increase the concentration of polar compounds and cause performed: water content in oil and cellulose (IEC 60814). Water content of mineral oils used for strength of the insulation system. acidity (IEC 62021) and antioxidants content (IEC 60666). 120 days at 140°C are equivalent to around 40 years at 98°C. pour point (ISO 3016). and to a certain extent.3 g/cm3 IEC 60641-3-2 Pressboard Thickness 1mm. crimped with silicone septa. with respective dried and degassed oil during 48 h at 90 Water is also the main factor which affects the dielectric °C in deep vacuum. Initial water content in kraft paper and pressboard The most critical aspect of the ageing process of solid was around 0. days.2. high grade IEC 60296 (MOHG) Mineral oil (MOSG) Naphtenic. decreases heat transfer by blocking cooling ducts. Density 1-1. esters. Sludge. inhibited. water and oxygen are three main factors Arrhenius law and IEC 60076-7 standard (loading guide). The test temperature was chosen at 140°C (for 120 days) to simulate an accelerated ageing. Once and surface ratios close to real design: paper/oil mass ratio: the cellulose has fallen below a critical level of mechanical 4 %.2 g/cm3 IEC 60641-3-1 Table 2: Tested materials Cigre Science & Engineering • N°1 February 2015 10 . degree of polymerization (IEC product of oil ageing. paper and pressboard were aged in 50 ml Experiences show that heavily loaded transformers have a headspace vials. 100 and 120 operation. These factors include the operating 3. All materials (table 2) were taken in mass insulation is reduction of its mechanical strength. Acids produced during oil ageing can increase paper pressboard and bare copper (“II exp”). 20. duplicate vials were used for heating oil alone (“I exp”) and for heating oil in presence of paper. Decomposition products (from cellulose and oil itself) will Prior and after ageing. degradation and attack metallic parts in the transformer. pressboard/oil mass ratio: 6 % and copper /oil mass strength. Indeed. the characteristics of the network. The critical parameter is temperature.3. 40. The aim of this test set-up is to simulate sealed are only focused on the ageing performance of insulating transformer conditions as it is requested for the use of natural materials. Oil.

This can be explained by higher thermal stability the consequence of water migration from cellulose materials of ester oil and the fact that high temperature-low oxygen into the oil. The increase and decrease the level of additive at the end of ageing in mineral oil of water was more significant in ester oil VOR. Figure 6: Inhibitor consumption (left) and 2-FAL evolution (right) in mineral oils and natural ester Cigre Science & Engineering • N°1 February 2015 11 . pressboard and copper. As shown on figure 5. increase of water content in the oil was significant after 10 days Consumption of detected antioxidants (figure 6) is more of ageing in all investigated oils. as shown on figure 7. Nevertheless. “I exp” means results on oil alone since they do not degrade cellulose insulation significantly and “II exp” means results on oil in presence of paper. This peak was (VOR). but then decrease was pronounced in mineral oil (MOHG) than in natural ester observed in all ageing periods for both oils. [15]. These results are quite encouraging for ester oil (figure 5) is correlated with water consumption and the use of natural ester in power transformers in sealed can be explained by hydrolysis reaction. (oil with still remained acceptable (IEC 60422). These acids seem not to be aggressive for solid insulation and should be of high molecular nature. 14]. pressboard and copper).2 Experimental results studies [13. Water content in the cellulose decreased over testing conditions suited better for ester oil. as shown by other applications. Low to acceptable paper. Note that for all graphics. whole ageing period in both oils. Important increase of acidity in during ageing.2. Figure 5: Evolution of acidity (left) and humidity (right) in mineral oils and natural ester 3. due to higher rate of water decrease of inhibitor content can be explained by low migration from cellulose materials to ester oil which has concentration of oxygen and reduced oxidation process higher water solubility.

with negligible and pressboard) and insulating oils (mineral and natural difference in respect to different oil quality and presence of ester) have shown that natural ester oil has higher capacity antioxidant in inhibited oil. Figure 7: Evolution of degree of polymerization (DPv) of pressboard (left) and paper (right) Degradation of paper and pressboard aged with ester Kinematic viscosity of mineral oils did not change during oil (VOR) was observed to be of slightly lower rate in whole period of ageing whereas small increase was detected comparison to mineral oils (figure 7). paper and pressboard Moisture distribution between cellulose materials (paper reached end of life in both mineral oils. natural ester oil in sealed units. pour point of all three oils was not affected during whole period of ageing. to dissolve water comparing to mineral oils. This may be attributed to lower solubility of furans 4. thus confirming the possibility of using [16]. and this was observed in other studies concentration [17]. It was interested to observe that after 120 days of ageing at 140ºC. as chemical Figure 8: Evolution of oil viscosity (left) and pour point (right) in mineral oil and natural ester Cigre Science & Engineering • N°1 February 2015 12 . Note that. This increase remains acceptable degree of polymerization can be correlated to lower 2-FAL in comparison with previous studies under higher oxygen values (figure 6). the difference in 2-FAL values between oil seemed to be more significant than the difference between DP values. Higher values of with ester oil (figure 8). Conclusion in ester oil than in mineral oil. However.

[11] J. 6.137. IEEE TDEI.. IEEE Elec. pp. Minutes of the fifty-fith annual International conference of Doble clients. pp. 6-9 June. [3] Y. A. an alternative to mineral oil for power transformers – experimental study of paper aging in vegetable oil versus mineral oil” IEEE Mag. 2002. Griffin. Chicago. 2008. December. Achieved results related to ageing of solid insulation and Ageing mechanism was predominantly pyrolytic (low natural esters are quite encouraging for the use of natural oxygen. No. C. Thompson. Perrier. and pressboard was observed in ester oil. 2013. [5] Cigre brochure n°414. August 2008. Bruce. [14] M-L. system.. 1995. A. M. J. significantly during ageing and it seems that some amount more water is dissolved in the oil in comparison with of water in the oil was spent in hydrolysis reactions and mineral oil. Lundgaard & al. Vol. [17] C. PDC). Rungis. “Vegetable oils. V. Proceedings of the 18th International Conference on Large Electric Systems. 873-878. 10-9. No. 2011. A. “Moisture equilibrium in paper-oil system”. Martin. Insul. Acidity of natural ester oil increased equilibrium in natural ester oil is moved towards the oil. pp..composition of natural ester is more polar nature. “Moiture equilibrium and moisture migration within transformer insulation systems”. Mag. “Aging of pressboard in different insulating liquids”. Fabre. October 1983. at 140ºC) and was found to have more significant ester in power transformers in low oxygen environment impact on degradation of solid insulation impregnated (sealed units). Sec. G. Oct. Behavior of mineral oils paper. C 57. Cigre Science & Engineering • N°1 February 2015 13 . June 2008. 6. “Transformer paper in oil water diffusion time constant”. Uneven distribution of water between paper degraded significantly in the presence of high acid content. M. Flow properties were acceptable at the end of and pressboard separately and together enables greater ageing for mineral oils and also for ester oil with acceptable precision in estimating the moisture content in insulation viscosity increase of 15% from the initial value. Beroual. Pichon. Vol. solid insulation was not in the paper. with mineral insulating oils than on solid insulation filled References [1] H. p. [15] L. Oommen. No. 2011. 1972-1976. November/December. 26. S. 15. P. “Deterioratiion processes and products of paper in oil”. Zhou. However. [12] Areva T&D book. M. Ester. Martins. Zahn. and Silicone Oils”. A. This may cause underestimation of water content in related to paper ageing was similar regardless of difference the paper when evaluation is done using electrical methods in oil quality and presence of antioxidant in inhibited (FDS. 540-546. Krause. The use of equilibrium charts for paper mineral oil. “Aging of Kraft paper by acid catalyzed hydrolysis”. J. 2007. 1. [2] A.1. 1. Lashbrook and R. Coulibaly. 2010. IEEE TDEI. 2008. Vol. [16] M. Sierota. 2009. Dolata. [6] J. [4] Cigre brochure n°323. C. CIRED conference. “Moisture equilibrium in transformer paper-oil Systems”. Mag. Lesieutre. C.. Moisture with natural ester oil. 6. J. ICDL conference. Perrier. 25. Vol. “New and innovative Smart and green transformer technologies”.106 WG. IEEE TDEI Vol. pp. IEEE Elec. 1960 [7] T. Christie. C. Du. “Comparison of water equilibrium in silicone and mineral oil transformers”. No. 8-20. 2 – Expertise”. F. RVM. 3. pp. Vol. M. B. Perrier and A. 1988. “Electrical insulating oils-Part 1: characterization and pre-treatment of new transformers oils”. ‘‘Experimental Investigations on Insulating Liquids for Power Transformers: Mineral. 11-20. 15. 1999. No. pp. Lindgren. 26-30 June. C. presented at the IEEE Insulating fluids Subcommittee. J. [8] P. IEEE Electrical Insulation Magazine. “Ageing of cellulose in mineral-oil insulated transformers”. Vol. lower values were It seems that chemical composition of acids is more measured in pressboard and higher water contents in the important than its total amount. Devaux. 20. Beroual. ‘‘Aging behavior of cellulosic materials in presence of mineral oil and ester liquids under various conditions”. [9] CIGRE brochure n°349.nsformer windings”. R. 15. [13] H. “Modeling of transient moisture equilibrium in Oil-Paper Insulation”. No. November/December. at the same temperature and water content formation of fatty acids. 6 – 13. Electrical Electronics Conference. “Power transformers – Vol. D. April 2010. B. Apr. 11. Fink. especially for natural ester. [10] L. pp. 2. Insul. No. “Dielectric response diagnoses for tra. Gasser. Marugan and A. 7-13. Mamishev.

department for mineral insulating oil testing. D1) & IEC (TC 10). He is member of of CIGRE WG A2. diagnostics. In 2008. determination of viscosimetric degree of polymerization of paper for electrotechnical purposes. Chemical Engineering at Faculty of Chemical transformers.40: “Copper sulphide long-term CIGRE (A2. in Alstom representative in IEC TC 10 Committee and co-liaison of Grid. He is currently with Alstom Grid . Since 2012. D degree in Jelena Lukic. PhD in Chemical Engineering is Head of insulating materials in 2005 from the Ecole Centrale de Laboratory for insulating oil and paper testing. she is in the course of PhD studies. Coulometry. Mitigation and Risk Assessment”. department Lyon (France). Main field of her expertise are oil to optimize power transformers reliability. Serbia.Biographies Christophe Perrier obtained his Ph. Currently Groups. He is member of CIGRE and IEC Working engeenering.TICC Massy and etc. Cigre Science & Engineering • N°1 February 2015 14 . corrosion phenomena induced by corrosive (Massy) where he developed a laboratory and activities sulphur and for oil treatment processes. France. acts as IEC TC 10 for CIGRE SC A2. She is Serbia NC dedicated to insulating materials. She is engaged in different technical expert on insulating liquids and is Eco-design IEC TC 10 and CIGRE working groups and is a convenor coordinator for Power Transformers.Sc. Karl Fisher Areva T&D in 2009. University of Belgrade. Mamadou-Lamine Coulibaly has joined the Technology. analysis. In 2006. Infrared Spectrofotometry. France after receiving the Ph. in Laboratory for Testing and (TICC) of Areva T&D (presently Alstom Grid) at Massy. He started his career in the R&D center for Electrical Measurements of Electrical Engineering of Areva T&D (Villeurbanne) on insulating liquids Institute Nikola Tesla.D degree in Electrical at the position of associate research engineer. Valentina Vasovic is working in Electrical Engineering Innovation and Competence Development Centre Institute «Nikola Tesla». she took a university degree involving solids and mixed solids/liquids for power B. Her main Engineering (Dielectric Materials and High Voltage) field of work is oil analyses. he is in charge of R&D projects on materials. She is engaged in research activities in the field of works on R&D projects linked to insulating materials natural ester oils. High-performance liquid from the Ecole Centrale de Lyon in collaboration with chromatography. Calibration. degradation phenomena of paper/ he moved to the R&D Center on Power Transformers oil insulation.