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Aging of Cellulose at Transformer Service Temperatures. Part 1: Influence of Type of Oil and Air on the Degree of Polymerization of Pressboard, Dissolved Gases, and Furanic Compounds in Oil
Key Words: Power Transformers, pressboard insulation, tranformer oil, dissolved gas analysis, thermal aging
Introduction
power transformer is expected to operate up to 40 years. With current cost-benefit calculations, the user is forced to perform maintenance that will bring a further extension of the transformer life. The maintenance can only be based on on-site and off-site monitoring with extended analytical and electrical tests, which can define the service condition of the transformer and predict its further life expectancy. The investment boom of the 1970s determines, to a large extent, the age distribution of transformers in service, and the percentage of transformers older than 30 years is increasing in both the utilities and industry. Highly loaded generator and furnace transformers show a more accelerated aging in comparison to grid units. It is not unusual that older transformers have 3 to 4% humidity in the solid insulation. The life of a transformer is mainly dependent on the life of its solid insulation, and the life-limit is determined by the thermal degradation of the winding paper. The Kraft paper decreases in tensile strength with the progress of aging and, at some point, can no longer withstand the short circuit stresses. A traditional and significant parameter of paper degradation is the degree of polymerization (DP). The mechanism of paper degradation is complex and strongly dependent on the operating conditions. Degradation occurs by the cleavage of the 1,4-glycoside bond between two glucose monomers. These chain scissions result in the lowering of the DP and a decrease in tensile strength. Typical byproducts that are detectable in oil are also formed; these are

A. J. Kachler, I. Hhlein
Siemens Transformer Factory, Nuremberg, Germany

The monitoring of the complex permittivity of transformer oils, as a function of frequency and temperature, may provide information concerning the state of the insulation.

carbon monoxide, carbon dioxide, detectable by gas-in-oil analysis, as well as furane compounds. There are several detailed literature surveys on cellulosic aging [1] [8], [11]. Most experiments, however, have been carried out at temperatures >100C because of the shorter reaction times under laboratory conditions. The aging products, as a result of typical operating transformer temperatures, have not been investigated in detail. Furthermore, the development of aging is quite different in open and closed systems. Closed systems do

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not allow the escape of moisture and other byproducts. It is likely that even a free-breathing transformer follows closer the behavior of closed, rather than that of open, systems, especially in respect to moisture. The aging is strongly influenced by temperature, moisture, air, and electrical stress [10]. It is well known that the aging of thermally upgraded paper is different from the aging of normal Kraft paper [5].

Experimental Procedures
In this article, we show the influence of air and oil type (inhibited, non-inhibited) on the aging of pressboard under the influence of a considerable amount of moisture. (At an initial content of 3.9% moisture, the solid insulation of a transformer would be classified as wet.) The rate of the degree of polymerization, the development of furanic compounds, as well as the gas-in-oil analysis in comparison with the aging of the pure oil under the same conditions have been investigated. The aging test object consisted of pressboard with a thickness of 1 mm in closed headspace vessels, with a ratio of oil:pressboard equal to 1:10. The moisture content of the pressboard was 3.9%, and the moisture content of the oil at 20C was 20 to 25 ppm. Two different types of oil have been used: Oil A (naphthenic type, non-inhibited) and Oil B [naphthenic type, inhibited; the inhibitor content (DBPC) was 0.3%]. The following conditions have been investigated by measuring the degree of polymerization of the pressboard, furanic content in the oil, and gas-in-oil analysis with time. Aging has been carried out in a temperature-controlled oven at 85C constant temperature: 1) 2) 3) 4) 5) 6) Oil A, pressboard in air Oil B, pressboard in air Oil A, pressboard in inert gas Oil A in air Oil B in air Oil A in inert gas

Fig. 1. Development of hydrogen as a function of time in the presence of air at 85C. Solid line - pressboard/oil A, dotted line - oil A only.

Fig. 2. Development of hydrogen as a function of time in the presence of air at 85C. Solid line - pressboard/oil B, dotted line - oil B only.

The analysis has been carried out as follows: Dissolved Gas Analysis (DGA) - with the headspace method according to IEC 60567 Furane - according to IEC 61198 DP - according to IEC 60450

Results
A. Gas-in-Oil Analysis of Pressboard Oil System Hydrogen
The oil-pressboard system developed more hydrogen compared to the pure oil system at the beginning of the aging as can be seen in Figs. 1-3. With the further aging the hydrogen values were similar for both the oil-pressboard and the pure oil systems. The development of hydrogen may be influenced by humidity.

Fig.3. Development of hydrogen with time in the absence of air at 85C. Solid line pressboard/oil A, dotted line oil A only.

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Palavanpour et al. [9] reported experiments under dry conditions with no detectable hydrogen evolution at 85C.

Methane
The same effect, even more pronounced is observed for methane as shown in Figs. 4-6. While the methane amounts in the case of oil A/pressboard/air rose initially and then decreased, the produced methane amounts of oil A-air, oil A-inert gas remained nearly the same during the aging period. Fig.4. Development of methane as a function of time in the presence of air at 85C. Solid line pressboard/oil A, dotted line oil A only.

Carbon monoxide
It is well known, that carbon monoxide is generated by pure oil aging, as well as by aging of oil/cellulosic systems. The experimental results confirm this finding as shown in Figs. 7 - 9. Furthermore, the development of carbon monoxide in oil, as well as in the mixed insulation is triggered by oxygen. It is obvious, that in a low oxygen medium, the amount of carbon monoxide generated remains much lower than in the corresponding oxygen-containing systems. This is probably due to a cleavage of unstable bonds. Furthermore a residual amount of air, allowing this reaction is always present. The moisture present is also a source of oxygen.

Carbon Dioxide
The development of carbon dioxide in pure oil systems is much lower than its development in a cellulosic/oil system under the conditions investigated as can be seen in Figs. 10 - 12. Wet pressboard-oil insulation with uninhibited oil under air produces a large amount of carbon dioxide, which remains constant for a long period of time, see Fig. 10. The presence of an inhibited oil shortens the period of strong production of carbon dioxide, probably through deactivating the dissolved oxygen in oil, see Fig. 11. In an inert gas, a period of strong carbon dioxide production is also observed. It is, however, in comparison to the other ex-

Fig. 5. Development of methane as a function of time in the presence of air at 85C. Solid line - pressboard/oil B, dotted line - oil B only.

Fig.6. Development of methane as a function of time in the absence of air at 85C. Solid line pressboard/oil A, dotted line oil A only.

Fig.7. Development of carbon monoxide as a function of time in the presence of air at 85C. Solid line pressboard/oil A, dotted line oil A only.

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Fig. 8. Development of carbon monoxide with time in the presence of air at 85C. Solid line - pressboard/oil A, dotted line - oil A only.

Fig.10. Development of carbon dioxide as a function of time in the presence of air at 85C. Solid line pressboard/oil A, dotted line oil A only.

perimental conditions time limited, so that the absolute amount (area) is smaller, as shown in Fig. 12.

Development of CO2 against consumption of air

The plotting of carbon dioxide production against oxygen consumption from the headspace phase shows that the carbon dioxide production in air-rich systems is always supported by consumption of oxygen, see Fig. 13 and Fig. 14. Oxygen in the air is consumed very quickly, that is why the increase of CO and CO2 in air is immediate. This phenomenon is often observed in free-breathing transformers with aged insulation. In the system with a low oxygen content, Fig. 15, the development of carbon dioxide cannot be correlated with oxygen consumption. We believe that in this case hydrolysis, caused by moisture, plays a decisive role. Moisture, present in the solid insulation, is a second source of oxygen, which takes some time to migrate out of the insulation and react.

B. Effect on DP
The Emsley and Stevens model [1] for the decrease in the degree of polymerization has been assumed, Eq. 1:

Fig. 11. Development of carbon dioxide as a function of time in the presence of air at 85C. Solid line pressboard/oil B, dotted line oil B only.

Fig.9. Development of carbon monoxide as a function of time in the absence of air at 85C. Solid line pressboard/oil A, dotted line oil A only.

Fig.12. Development of carbon dioxide as a function of time in the absence of air at 85C. Solid line pressboard/oil A, dotted line oil A only.

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Fig.13. Development of carbon dioxide and consumption of oxygen as a function of time at 85C (pressboard/oil A/air). Solid line CO2, dotted line O2.

Fig.15. Development of carbon dioxide and consumption of oxygen as a function of time at 85C (pressboard/oil A/ exclusion of air). Solid line CO2, dotted line O2.

(1) Where DPt is the degree of polymerization at time t, DPo is the initial DP, and k10 and k2 are constants. If k2 is small, Eq. 1 can be reduced to Eq 2:

inhibited oil exerts a certain protective influence under air and decreases the rate by 1.5 times compared to uninhibited oil. Substituting the values for initial DPo of 1000 and final DPt of 200, the expected life time is given by: Life = 0.004/k i.e. under the investigated conditions 3.9% moisture in the solid insulation at 85C - in air, the life expectancy is 1.1 years. In air with inhibited oil the life is 1.66 years. Without oxygen the life is 3.3 years.

(2) with k = k10 Plotting of 1/DP against the aging time gives the reaction rate k shown in Fig. 16. Under these conditions oxygen leads to an acceleration of the aging rate up to 3 times compared with a system without oxygen. Similar results are reported in [12]. An

C. Furane Production
The difference in the rate of furanic production at the three different experimental procedures is even more pronounced, than the difference in 1/DP with time as can be seen in Fig. 17. Oxygen has a very strong trigger effect on the production of furane compounds. The basic derivative is 2-FAL.

Fig. 14. Development of carbon dioxide and consumption of oxygen as a function of time at 85C (pressboard/oil B/air). Solid line CO2, dotted line O2.

Fig. 16. Rate of Depolymerization at 85C. Solid line air, oil A, dotted line air, oil B, dashed line absence of air, oil A.

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Fig. 17. Development of 2-FAL with time at 85C. Solid line air, oil A, dotted line air, oil B, dashed line absence of air, oil A

Under the investigated conditions (85C, 3.9% moisture) the change of DP in air systems is more sensitive to 2-FAL development than in air-free systems, see Fig. 18. It is likely that the rate of furane development is more important than the absolute values. The comparison with a preanalysis is inevitable, but it requires exact knowledge of humidity, operating temperature, type of oil and paper, and design.

The exclusion of oxygen decreases the rate of aging up to 3 fold in comparison to an oxygen-rich atmosphere. The application of inhibited oils in air has a certain protective influence on the solid insulation and retards aging to some extent. Under the investigated conditions (85C, 3.9% moisture) the change of DP in air systems is more sensitive to 2-FAL development than in air-free systems. The absolute correlation of 2-FAL to DP is more complicated and is dependent on humidity, operating temperature, type of oil and paper, and design. A general (for all cases) dependence 2-FAL/DP is not likely to exist, but it is dependent on the test conditions. At defined and steady conditions, there is a dependence between 2-FAL and DP. The absolute value of 2-FAL can vary from transformer to transformer. In order to identify a failure (or a condition change) it is more important to evaluate the increase in the rates, rather than the absolute values. Further research on the dependency of 2-FAL on moisture and temperature is necessary.

References
[1] A. M. Emsley, and G. C. Stevens, Review of Chemical Indicators of Degradation of Cellulosic Electrical Paper Insulation in Oil-Filled transformers, IEE Proc.-Sci. Meas. Technol., Vol. 141, No. 5, pp. 324-334, September 1994. [2] A. M. Emsley, X. Xiao, R. J. Heywood, and M. Ali, Degradation of Cellulosic Insulation in Power Transformers. Part 3: Effects on Oxygen and Water on Aging in Oil, IEE Proc-Sci. Meas. Technol., 147, No. 3, pp. 115-119, May 2000. [3] A.M. Emsley, R. J. Heywood, M. Ali, and X. Xiao, Degradation of Cellulosic Insulation in Power Transformers. Part 4. Effects of Aging on the Tensile Strength of Paper, IEE Proc. Sci. Meas. Technol., Vol. 147, No. 6, pp. 285-290, May 2000. [4] A. M. Emsley, X. Xiao, R. J. Heywood, and M. Ali, Degradation of cellulosic insulation in power Transformers. Part 2: Formation of furan products in insulating oil, IEE Proc. Sci. Meas. Technol., Vol. 147, No. 3, pp 110-115, May 2000. [5] L. Lundgaard, W. Hansen, D. Linhjell, and T. Painter, Aging of Oil-Impregnated paper in Power transformers, IEEE Trans Pow. Del. Vol. 19, No. 1, pp. 230 -239, 2004. [6] D. H. Shroff, C. Eng, and A. W. Stannet, A Review of Paper Aging in Power Transformers, IEE Proceedings, Vol. 132, Pt. C, No. 6, pp. 312-219, 1985. [7] B. Bouvier, Nouveax criteres pour caracteriser la degradation thermique dune isolation a base de papier, Rev. Gen. Elec., Vol. 79, pp 489-496, 1970. [8] H. P. Moser, V. And Dahinden in Transformerboard II, H. Weidmann AG, Rapperswill, 1987, pp. 140-216. [9] B. Pahlavanpour, M. A. Martins, and A. De Pablo, Thermal degradation of Insulating Oil and paper Under Experimental Conditions, Private communication. [10] I. Hhlein, H. Ltke, A. and J. Kachler, Transformer Aging Research on Furanic Compounds Dissolved in Insulating Oil, CIGRE, Paper 15-302, CIGRE session 2002, Paris. [11] A. De Pablo, and B. Pahlavanpour, Furanic Compounds Analysis: A Tool for Predictive Maintenance of Oil-Filled Electrical Equipment, Electra, Nr. 175, pp 9-18. [12] J. Fabre, andA. Pichon, Deteriorating Processes and Products of Paper in Oil. Application to Transformers, CIGRE, Paper 137, (Paris), 1960.

Conclusions
The DGA of oil/cellulosic insulation systems depends on the absence or presence of oxygen. It is also dependent on the moisture content of the cellulose. These observations require further investigations under different moisture contents. The detection of degradation of cellulose by DGA is mainly due to the formation of carbon dioxide from the mixed insulation.

Fig. 18. DP as a function of 2-FAL under the different investigated conditions. Solid line air, oil A, dotted line air, oil B, dashed line absence of air, oil A. Trend line : D/air DP = -100 ln(2-FAL) + 709 DX/air DP = -100 ln(2-FAL) + 649 D/Argon DP = -77 ln(2-FAL) + 674

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Dr. h. c. Adolf J. Kachler, Dipl. Ing./ MSE, High Voltage Engineering from Technical University of Munich (1965). Doctor Honoris Causa from Technical University of Graz, Austria (2003). He has been a member of IEEE since 1969 and has been a Senior Member of IEEE since 1998. Since 1994, he has been a member of CIGRE. He has served on more than 25 working groups within IEEE/ CIGRE/IEC, CENELEC, and DKE. He has served more than 10 years as Chairman of the Germany Transformer Committee (DKE K 321) and more than 10 years as German Speaker of IEC TC 14 and CENELEC TC14. Since 1994, he has been German Expert to CIGRE A2 and D1. From 1972 to 2000 (28 years), he was a Germany member of TC 42/DKE 124. Since October 2003, he has been a consultant to all PT and DT Siemens factories for Quality and Diagnostics.

Ivanka Hhlein, Dipl. Chem, Ph. D. Univ. of Sofia 1985. Head of Material Testing Laboratory Siemens, PTD T, Nuremberg. Main topics of interest: Aging of solid and liquid insulation in transformers, gas-in-oil analysis, material testing. Member of CIGRE, Member of CIGRE WG Aging of Paper.

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