IEEE Transactions on Dielectrics and Electrical Insulation Vol. 19, No.

6; December 2012 1999

Ageing Rate of Paper Insulation used in Power Transformers

Part 1: Oil/paper System with Low Oxygen Concentration
Nick Lelekakis, Daniel Martin and Jaury Wijaya
Monash University
Wellington road
Clayton, Vic 3800, Australia

ABSTRACT
A substantial quantity of testing has been performed on the degradation of paper
insulation over the decades. The aim being to better educate the electrical industry on
how to best operate expensive assets, such as transformers. The longevity of paper
insulation is frequently tested using accelerated ageing experiments, where the effects
of temperature and the chemical environment on paper lifespan can be studied. Such
research has resulted in paper life expectancy curves being published by the IEEE and
the IEC. The investigations tend to use sealed vessels. However, the disadvantage of
using this method is that the water content of the paper changes during the ageing
process which then changes the ageing rate. In these ageing experiments the water and
oxygen content was controlled using a special test rig to compare the ageing rate to
previous work and to determine the ageing effect of paper by combining temperature,
water content of paper and oxygen content of the oil. We found that the rate of paper
ageing can be more accurately determined by controlling the water and oxygen during
the experiment which then produced noticeable changes in predicting life expectancy.
Index Terms - Ageing, cellulose, hydrolysis, paper insulation, oil-paper, power
transformer.

CH2OH
1 INTRODUCTION H OH

THE continued operation of a transformer is dependent on the H

C C C O O
H H
condition of its paper insulation. The condition of paper is H
C OH H C C C + H2O
quantified by its degree of polymerization (DP), or the average H OH H
H
number of glucose links per macromolecule. The DP of the paper O C O O C C
within a new, unused, transformer is usually around 1000. The
end of usable life for the paper is recommended to be around HOCH2 H OH
200. At this point the paper becomes brittle and loses its
mechanical strength [1]. Acid catalyst
Temperature, water, oxygen and mineral oil acids degrade the
paper over time [1]. It is therefore necessary to investigate how
CH2OH
these parameters determine the operating life of the transformer. H OH
A utility can then make various decisions to extend the life of a C O O
C C
transformer, such as use an online dry-out procedure [2], install H H H
OH H H
air sealing bags or de-rate the transformer. C C + C C
H OH H
Several research groups over the years have studied the effects H
of different chemical environments on the degradation of paper O C O OH HO C C
insulation. McNutt et al related paper degradation to three H OH
HOCH2
processes, hydrolysis (water), oxidation (oxygen) and pyrolysis Figure 1. Hydrolytic degradation reaction of cellulose.
(heat) [3]. The life of paper is influenced by all three reactions.
Hydrolysis is a reaction that involves water and acids which The hydrolysis of paper with different wetness in mineral oil
break the cellulose polymer chain (Figure 1). This reaction with low oxygen content has been studied [4, 5]. The ageing rate
produces free glucose molecules which decompose further to of paper insulation has traditionally been studied in sealed
form furans and water. The water then permits further hydrolysis. vessels at elevated temperatures. In these experiments the water
content of the paper does not remain constant over the ageing
Manuscript received on 18 March 2012, in final form 25 September 2012. period. The water content of the paper either increases since

1070-9878/12/$25.00 © 2012 IEEE

2000 N. Lelekakis et al.: Ageing Rate of Paper Insulation used in Power Transformers. Part 1: Oil/paper System

water is a degradation product of ageing or decreases if it is which has to be found in order to correctly apply the equation.
consumed in other reactions or from leaks in the sealing system. The A-value is dependent on the chemical environment of the
When water is consumed or produced in a sealed vessel this will paper such as the water, oxygen and acids.
result in a slower or higher ageing rate of the paper compared to In order to compare the reaction rates, A and E values to
an experiment where the water is restored. previous researches the pseudo zero-order Ekenstam’s
In this study, moisture probes were fitted to the ageing vessel relationship was used to obtain the reaction rate constants
to monitor and control the water content of the paper to be able to under different temperature and water in low oxygen
then compare with the ageing rates of the paper determined using conditions.
sealed vessels.
1.2 CALCULATING PAPER END OF LIFE
1.1 REACTION RATE For predicting end of life, Emsley substituted equation (3)
Emsley and Stevens reported in their review [6] that most into equation (1) and obtained the following:
reported data on cellulose ageing can be modelled by a  Ea
1 1 (4)
pseudo-zero order rate law (i.e. the rate is not dependent on   A  ageing period  e RT
DPageing DPstart
the bonds that are not yet ruptured) represented by the period

Ekenstam equation (1) [7]. Emsley then rearranged this equation to calculate end of life
1

1
 kt (1) at a given temperature shown in equation (5).
DPt DP0 1 1
 Ea
where, DP is the average degree of polymerisation per Expected Life ( years) 
DPend DPstart
 e RT (5)
molecular chain. The subscripts o and t refer to the initial DP A  24  365
value and at any time, t. Thus the ageing rate, k can be However, in a transformer the A-value is not constant for
determined from the gradient of 1/DPt – 1/DPo versus time. its entire life. Reactions take place which generate water and
This equation assumes that the rate of cellulose degradation is acids so the A-value increases. In order to produce a dynamic
constant. model to calculate remaining life of the paper insulation A-
Emsley later noted that k is not constant, but decreases with values should be determined for all water and oxygen
ageing time as the paper severely deteriorates below a DP of 200 conditions of the paper.
[4]. He modelled the data using a first-order reaction law (2).
1 1 k  ( k t )  (2) 1.3 PREVIOUSLY REPORTED A AND E VALUES
  1o 1  e 2 
DPt DP0 k2   The activation energy (Ea) is dependent on the type of
Emsley suggested that the reduction in the ageing rate is cellulose and chemical reaction. The activation energy is
caused by a reduction in the reagents and the molecular calculated by graphically plotting the natural logarithm of the
weight of the cellulose. In this study we investigated whether rate of reaction, k, against the inverse of the absolute
maintaining the paper water content in low oxygen would temperature and finding the gradient. The gradient is equal to
produce a constant rate of degradation for Kraft and thermally -Ea/R. Equation 6 is derived from equation (3).
upgraded Kraft paper.  Ea 1 (6)
ln ( k )    ln ( A)
Emsley also related the rate, k to temperature via the R T
Arrhenius relationship (3). In 1994 Emsley reviewed existing literature and concluded
 Ea from a variety of experimental conditions that the activation
k  A  e RT (3) energy for Kraft paper is 111 kJ/mol and is the same for
where, Ea is the activation energy required for the reaction in hydrolysis and oxidation [8].
J/mol, T is the temperature of the paper in K, R is the gas In 2004 Lundgaard used an activation energy of 111 kJ/mol
constant (8.314 J/mol/K) and A is the pre-exponential factor and calculated A-values from experimentally determined
in h-1. reaction rates to compare them to Emsley [5]. The results are
The advantage of this equation is that it relates ageing to shown in Table 1.
physical processes, taking into account activation energy and Figure 2 combines Emsley’s and Lundgaard’s A-values for
the molar gas constant, R. There is however one parameter, A, Kraft paper.

Table 1. Previously reported A-values (h-1) based on an activation energy of 111 kJ/mol.
Emsley’s data Lundgaard’s data
Test Condition Kraft paper 95 % conf. bounds Kraft paper Thermally upgraded paper (Insuldur)
Ea = 111 kJ/mol Ea=111 kJ/mol Ea = 111 kJ/mol
Dry & clean 1.1E+08 (0.2-4.7)E+08 (2.0±0.5)E+08 (0.7±0.1)E+08

0.7 % water (1.1±0.5)E+08

1 % water 3.5E+08 (0.8-15)E+08
1.5 % water (6.2±2.9)E+08
2 % water 7.8E+08 (1.8-33)E+08
3 % water (paper in air) (2.6±1.7)E+08
4 % water (paper in oxygen) 35E+08 (7.7-157)E+08
4.1 % water (21.0±7.8)E+08
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 19, No. 6; December 2012 2001

conical flask with a 1-litre rubber bag was used as a conservator

for when the oil expands. The conservator was placed outside the
oven and the rubber bag was purged with dry argon.

Figure 2. A-values reported by Emsley and Lundgaard for Kraft paper based
on an activation energy of 111 kJ/mol.

Currently there exists uncertainty in the A-value above 2.0 %

water content of paper so a straight line extrapolation from 0 to
2.0 % has been used in [9]. Figure 3. Vessel used for paper ageing experiments.
In 2009 Lundgaard showed that the activation energy for
hydrolysis and oxidation differ for each process and type of The mineral oil (Shell Diala AX) was dried and degassed
paper [9]. The A and E values for Kraft and thermally upgraded overnight using vacuum and 60 °C while being stirred. The
paper (Insuldur) reported are shown in Table 2 and Table 3. vacuum was released using dry argon gas. The antioxidant
concentration of the oil was 0.19 % and remained unchanged after
Table 2. Reported A and E values for hydrolysis of Kraft paper.
oil processing.
Parameter Dry, no oxygen 1.5 % water 3.5 % water
hydrolysis The two types of paper which were used in this study were Kraft
Ea-value (kJ/mol) 128 128 128 paper (K) and thermally upgraded Kraft paper (TUK), supplied by
A-value (h-1) 4.1E+10 1.5E+11 4.5E+11 Weidmann. About 30 strips of each type of paper were fixed on
separate paper sample holders. Both types of paper were made of
Table 3. Reported A and E values for hydrolysis of thermally upgraded paper
100 % sulphate wood pulp but the TUK paper has been chemically
(Insuldur).
Parameter Clean system 1.5 % water 3.5 % water modified to reduce the rate of degradation. The properties of the
hydrolysis paper (as per the material data sheets) are listed in Table 4.
Ea-value (kJ/mol) 86 86 86
A-value (h-1) 1.6E+04 3.0E+04 6.1E+04 Table 4. Properties of the paper samples used (tests performed according to
IEC Standard 60641-2).
presspaper Grade thermally upgraded
It can be seen that if water is present, its level up to 3.5 %
K Grade K
does not affect the activation energy. Thickness (mm) 0.127 0.127
In this investigation we set out to determine whether Sample size (mm) 150 x 11 150 x 11
maintaining the paper water content and oxygen levels produced Tensile strength (machine 94 115
significantly different A-values and activation energies for Kraft direction) (MPa)
and thermally upgraded Kraft paper. Elongation (machine 1.7 2.0
direction) (%)
Nitrogen content (%) - 1.8
2 INVESTIGATION
The previous investigations to determine the effect of water
The initial water content of the system was obtained by
on paper ageing have only considered initial water levels.
conditioning two lengths of type K pressboard (3 m length x 30
Cellulose hydrolysis will consume water while thermal and
mm width x 1 mm thickness) to the desired water content. The
oxidative degradation of the paper will produce water, therefore,
pressboards were formed into a coil, dried in the oven for 3 h and
we wished to investigate whether maintaining paper wetness at
then placed on a laboratory balance. The pressboard absorbed
a given level provides significantly different rates of ageing.
moisture from the air and when the water content of the pressboard
2.1 METHOD reached the desired level for the experiment the pressboard was
The paper samples were aged in 5-litre glass vessels shown in immersed in the oil. Water would then be exchanged between the
Figure 3. The lid was manufactured from stainless steel and pressboard, oil and paper samples until equilibrium was achieved.
included paper sample holders, a temperature and moisture The paper samples were not conditioned before use so that their DP
probe, ports for adding water and oxygen. A magnetic stirrer was remains unchanged. Several strips of pressboard with a 0.5 mm
used to circulate the oil within the vessel. The vessel was placed thickness (type TUK) were also attached to the paper sample
in an air circulating oven set to the desired temperature. A 2-litre holders for Karl-Fischer measurements.
2002 N. Lelekakis et al.: Ageing Rate of Paper Insulation used in Power Transformers. Part 1: Oil/paper System

The water content of the paper in each experiment was

controlled by maintaining a relative saturation in the oil that is 1200
0.5%, 140°C
equivalent to the desired water content of paper. A moisture probe 0.5%, 160°C
was used to measure the relative saturation of the oil. At constant 1000
1.6%, 120°C
1.6%, 130°C
temperature, thermodynamic equilibrium exists between the oil and 1.6%, 140°C
800
paper so the Fessler equation was used to calculate the water 2.7%, 100°C

DP value
2.7%, 120°C
content of the paper from the relative saturation of the oil [2, 10, 600 2.7%, 140°C
11]. The water content of the paper was also occasionally measured
directly using Karl-Fischer for comparison. The relative saturation 400
of the oil was continuously monitored and adjusted to maintain a
constant level. Measured quantities of water were added to 200

experiments which consumed water. For experiments which

0 1000 2000 3000 4000 5000 6000 7000
produced water, either vacuum was used to lower the water content Ageing time (hours)
of the oil (and thus the paper), or the pressboard coils were Figure 5. DP of thermally upgraded Kraft paper insulation as a function of
replaced with new reconditioned pressboards. temperature and insulation wetness for low oxygen (<6,000 ppm).
The oxygen concentration of the oil was measured using a
gas chromatograph according to ASTM D3612 [12]. cellulose as one water molecule is consumed per cellulose
The DP of the paper samples was measured according to split [14]. The changes in water content of paper for all the
standard ASTM D4243 [13]. The data was processed using experiments is summarised in Table 5.
software packages Microsoft Excel and Microcal Origin 6.0. For experiments in which the water content of the paper
decreased, water was added to the oil to return the water
3 RESULTS content of the paper to the desired level. For the 0.5 %
Paper ageing experiments were conducted in low oxygen experiments which showed an increase in the water content of
(<6,000 ppm). The water content of the paper was controlled at the paper, the pressboard coils were replaced with dry ones.
three levels, either 0.5 %, 1.6 % or 2.7 %. Experiments were
conducted at temperatures between 100 and 160 ºC. The changes
in paper DP as a function of temperature and paper water content
for low oxygen are shown in Figure 4 for Kraft paper and in Figure
5 for thermally upgraded Kraft paper.
The DP trends in Figure 4 and Figure 5 for low oxygen agree
with previous data [4] that increasing water and temperature
increase the rate of cellulose degradation for Kraft and TUK paper.

1200

0.5%, 140°C
1000
0.5%, 160°C
1.6%, 120°C
800 1.6%, 130°C
1.6%, 140°C
DP value

2.7%, 100°C
600 2.7%, 120°C Figure 6. Water content of paper maintained at 0.5 %, 140 °C with low
2.7%, 140°C
oxygen.
400

200

0
0 1000 2000 3000 4000 5000 6000 7000
Ageing time (hours)

Figure 4. DP of Kraft paper insulation as a function of temperature and

insulation wetness for low oxygen (<6,000 ppm).

3.1 CHANGES IN WATER CONTENT OF PAPER

The water content of the paper increased when the initial
water content was 0.5 % at 140 °C (e.g. Figure 6) and 160 °C.
At high temperature the increase in water content is likely to
be attributed to pyrolysis of the cellulose. A small amount of
water may also be produced from the oxidation of the oil [14,
15]. The water content of paper decreased when the initial
water content was 1.6 % (e.g. Figure 7) and 2.7 % (e.g. Figure Figure 7. Water content of paper maintained at 1.6 %, 120 °C with low
8). This decrease is likely to be a result of hydrolysis of the oxygen.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 19, No. 6; December 2012 2003

measurement. The Karl-Fischer results of pressboard

measured at the end of the experiment at 1.6 %, 130°C in low
oxygen is shown in Figure 9. The water content at the surface
of the pressboard sample was measured by removing a thin
slice from the surface using a scalpel.

3.2 OXYGEN CONTROL

The oxygen concentration of the oil was measured using
gas chromatography to ensure a low oxygen content. The
oxygen in the oil at the beginning was consumed by oxidation
of oil and paper (e.g. Figure 10) and then remained low for the
remainder of the test.

Figure 8. Water content of paper maintained at 2.7 %, 120 °C with low

oxygen.

Table 5. Summary of changes in water content, as measured by moisture

probe, of experiments performed at different temperatures and water contents
with low oxygen.
0.5 % 1.6 % 2.7 %
100 °C Decrease
120 °C Decrease Decrease
130 °C Decrease
140 °C Increase Decrease Decrease
160 °C Increase

Although it is obvious that changes in the water content of
the paper are occurring it is not simple to quantify the
change due to the ageing of the paper since some could have
been attributed to small leaks in the system and some could
also be attributed to the hydrolysis and oxidation of the
pressboard.
The water content of the paper and pressboard was
occasionally measured directly by Karl-Fischer. The water
content of the 0.127 mm paper samples was lower
than the pressboard, presumably due to evaporation during
Figure 9. Water content of 0.5 and 1 mm pressboard measured by Karl-
Fischer compared to calculated values using the Fessler equation at the end of
the experiment at 1.6 %, 130 °C with low oxygen.
Figure 10. The oxygen concentration of the oil remains low during the
experiment at 100°C and 2.7 % water content of paper.
4 KINETICS OF DEPOLYMERISATION
4.1 PSEUDO-ZERO ORDER KINETIC MODELING
Emsley and Lundgaard reported that the isotherms are
linear in the region (1/DPt – 1/DPo) x 1000 < 5 (i.e. DP
>200) [4, 5]. Emsley suggested that the reduction in the
ageing rate, when the DP is less than 200 is caused by a
reduction in the molecular weight of the cellulose and a
reduction in the reagents. By maintaining the experimental
conditions, contrary to a sealed vessel, we found that most
of the isotherms in Figure 11 and Figure 12 are non linear
meaning the Ekenstam zero-order kinetic approach cannot
be used for precise modelling of each reaction. However, a
linear extrapolation of the data was used to compare A and
E values obtained from these reaction rates to those reported
by Emsley and Lundgaard. The reaction rates determined
from the 1/DPt – 1/DPo versus time relationships are given in
Table 6. In Table 6 we can compare the ageing rates for
Kraft and thermally upgraded paper and we can see that the
thermally upgraded paper has a lower ageing rate than Kraft
paper when aged in low oxygen at the temperatures and
water content of paper studied.
The degree of polymerization expressed as 1/DPt – 1/DPo
versus time are shown in Figure 11 and Figure 12.
2004 N. Lelekakis et al.: Ageing Rate of Paper Insulation used in Power Transformers. Part 1: Oil/paper System

5 4

(1/DPTUK(t)-1/DPTUK(0)) x 1000
(1/DPK(t)-1/DPK(0)) x 1000

4
3

3
K 0.5%, 140°C TUK 0.5%, 140°C
K 0.5%, 160°C 2
TUK 0.5%, 160°C
2
K 1.6%, 120°C TUK 1.6%, 120°C
K 1.6%, 130°C TUK 1.6%, 130°C
K 1.6%, 140°C 1 TUK 1.6%, 140°C
1 K 2.7%, 100°C TUK 2.7%, 100°C
K 2.7%, 120°C TUK 2.7%, 120°C
K 2.7%, 140°C TUK 2.7%, 140°C
0 0
0 1000 2000 3000 4000 5000 6000 7000 0 1000 2000 3000 4000 5000 6000 7000
Ageing time (hours) Ageing time (hours)
Figure 11. 1/DPt – 1/DPo versus time relationship for Kraft paper in Shell Figure 12. 1/DPt – 1/DPo versus time relationship for thermally upgraded
Diala AX with low oxygen (<6,000 ppm). Kraft paper in Shell Diala AX with low oxygen (<6,000 ppm).

Table 6. Pseudo-zero order reaction rates determined from 1/DPt – 1/DPo versus time relationships for Kraft and thermally upgraded Kraft paper in low oxygen (<6,000 ppm).
% (w/w) H2O
0.5 1.6 2.7
T (°C) Kraft TUK Kraft TUK Kraft TUK
100 0.62E-06 0.44E-06
120 1.48E-06 0.50E-06 2.40E-06 1.43E-06
130 2.32E-06 0.80E-06
140 1.21E-06 0.56E-06 5.79E-06 2.77E-06 12.84E-06 6.73E-06
160 6.18E-06 3.12E-06

Table 7. First-order reaction rates determined from 1/DPt – 1/DPo versus time relationships for Kraft and thermally upgraded Kraft paper in low oxygen (<6,000 ppm).
% (w/w) H2O
0.5 1.6 2.7
T (°C) Kraft TUK Kraft TUK Kraft TUK
k1o k2 k1o k2 k1o k2 k1o k2 k1o k2 k1o k2
100 1.36E-06 3.30E-04 9.30E-07 3.10E-04
120 2.75E-06 1.17E-03 8.00E-07 6.10E-04 4.91E-06 9.60E-04 2.81E-06 7.00E-04
130 4.55E-06 8.40E-04 1.59E-06 3.10E-04
140 2.58E-06 6.60E-04 6.10E-07 3.00E-05 8.14E-06 1.31E-03 2.96E-06 1.60E-04 2.37E-05 4.32E-03 9.64E-06 1.88E-03
160 1.47E-05 3.59E-03 3.62E-06 2.90E-04

4.2 FIRST-ORDER KINETIC MODELING

The first-order kinetic coefficients for equation 2 were
calculated using Origin 6.0. The reaction rate constants for
k1o and k2 are given in Table 7. The dotted lines in Figure
11 and Figure 12 are calculated using the first-order kinetic
equation (2).

5 ANALYSIS OF PAPER AGEING IN LOW

OXYGEN
5.1 CALCULATION OF ACTIVATION ENERGY IN
LOW OXYGEN
The activation energies were determined using pseudo
zero-order reaction rates from Table 6 by plotting the ln(k)
against the inverse of temperature (equation 6). The results
of tests in low oxygen are plotted in Figure 13 for Kraft and
Figure 13. Plot of reaction rate constant, k, against the inverse of
Figure 14 for TUK. The activation energy is found by temperature in Kelvin as a function of cellulose water content for Kraft
multiplying the gradient by 8.314 (the molar gas constant). paper (K) in low oxygen.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 19, No. 6; December 2012 2005

Figure 14. Plot of reaction rate constant, k, against the inverse of Figure 15. Monash A-values compared to those reported by Emsley and
temperature in Kelvin as a function of cellulose water content for thermally Lundgaard for Kraft paper based on an activation energy of 111 kJ/mol.
upgraded Kraft paper (TUK) in low oxygen.

The activation energies calculated from Figure 13 and 5.3 COMBINING THE A-VALUES FROM MONASH,
Figure 14 are given in Table 8. The average activation EMSLEY AND LUNDGAARD FOR LOW OXYGEN
energy for both Kraft and thermally upgraded Kraft paper The A-values determined by Monash at 0.5 %, 1.6 % and
are close to 111 kJ/mol reported by Emsley. 2.7 % in low oxygen are compared to those determined by
Emsley and Lundgaard in Figure 15.
Table 8. Activation energies and A-values determined for different paper Part 2 of this study [15] has shown that the A-value is
water content and low oxygen.
dependent on the oxygen content of the oil. Thus, Emsley’s
Ea (kJ/mol) A-value (h-1) Recalculated
A-values A-values at 4.0 % conducted in oxygen and 2.0 %
based on Ea= conducted in air are removed from Figure 15 to obtain
111 kJ/mol Figure 16. We found that a polynomial best fits the
Kraft 0.5 % 121 2.58E+09 1.42E+08 remaining data with R2= 0.9742.
Kraft 1.6 % 92 2.19E+06 6.80E+08
Kraft 2.7 % 97 1.99E+07 1.65E+09
Average Ea for Kraft 103
(kJ/mol)
TUK 0.5 % 127 6.93E+09 6.92E+07
TUK 1.6 % 115 8.01E+08 2.61E+08
TUK 2.7 % 87 6.52E+05 1.03E+09
Average Ea for TUK 110
(kJ/mol)

5.2 CALCULATION OF A-VALUES IN LOW

OXYGEN
The A-values were calculated from the y-intercept
according to equation (6).
The A-values determined from the data for Kraft and
thermally upgraded Kraft paper are given in Table 8.
In order to compare the A-values to those reported by
Emsley and Lundgaard the A-values were recalculated
using the reaction rates determined from the experimental
data and an activation energy of 111 kJ/mol. The values are
given in Table 8 and presented graphically in Figure 15.
The recalculated A values for paper with <2.0 % water are
of the same magnitude as the previous researchers. The new
A-value for paper with 2.7 % clarifies the uncertainty that
previously existed above 2.0 %. This value also proves that
the correlation between A-value and water content of paper
is non-linear.
Figure 16. A-values for Kraft paper in low oxygen by Monash, Emsley
and Lundgaard based on an activation energy of 111 kJ/mol. Emsley’s A-
values at 4.0 % conducted in oxygen and 2.0 % conducted in air are
removed.
If Lundgaard’s A-value at 4.0 % is kept and the A value
from Monash at 2.7 % is removed a polynomial best fits the
data with R2=0.9963. However, if Lundgaard’s A-values at
0.3 % and 4.0 % are removed and the A-value from
Monash at 2.7 % is kept a polynomial best fits the data with
R2=1.0 (Figure 17). It seems that the experimental style in
maintaining the paper wetness has improved the accuracy
in calculating A and E values.
2006 N. Lelekakis et al.: Ageing Rate of Paper Insulation used in Power Transformers. Part 1: Oil/paper System
Figure 17. A-values for Kraft paper in low oxygen by Monash, Emsley
and Lundgaard based on an activation energy of 111 kJ/mol. Removing
Lundgaard’s A-value at 4.0 % gives the best fit of remaining data.
Thus the A-value for any paper wetness in low oxygen
can be determined from the polynomial equation (7):
y = (1.78E+12)x2 + (1.10E+10)x + 5.28E+07 (7)
where, y = A-value and x = water content of paper.
The A-values for thermally upgraded Kraft paper in low
oxygen are compared to those determined by Lundgaard in
Figure 18.
Figure 18. Comparison of A-values from Monash and Lundgaard for
thermally upgraded Kraft paper in low oxygen based on an activation
energy of 111 kJ/mol.
The A-values found for thermally upgraded Kraft paper
above 1.0 % water are significantly different to those
determined by Lundgaard. However, Lundgaard focussed
on a different type of thermally upgraded paper, Insuldur.
Liland and co-authors reported that there are different
grades of thermally upgraded paper with varying nitrogen
content [16]. They found that Insuldur thermally upgraded
paper had the highest nitrogen content (2.7%) and
resistance to hydrolysis. This could explain the difference
in the A-values found for the thermally upgraded Kraft
paper used in this study with a nitrogen content of 1.8 %.
6 LIFE CURVES FOR LOW OXYGEN
These curves show the time (in years) it would take for
the paper to degrade from an initial DP of 1000 to 200.
They relate temperature and water content of paper (in
percentage) in oil with a low oxygen concentration (<6,000
ppm).
6.1 LIFE CURVES FOR KRAFT PAPER IN LOW
OXYGEN
The life curves for Kraft paper in low oxygen published
by Lundgaard (Figure 19) were built using a combination
of A-values determined from Emsley and himself. The A-
values for dry, 1.0 %, 3.0 % (interpolated) and 4.0 % water
content of paper were from Emsley. The A-values at 1.5 %
and 2.0 % (interpolated) water content of paper were from
Lundgaard.
The life curves for low oxygen were redrawn
incorporating A-values from Monash (Figure 20). The
curves are built using Emsley's A-values at 0.3 % and 1.0
%, Lundgaard's A-value at 1.5 % and Monash A-values at
0.5 %, 1.6 % and 2.7 % water content of paper. The
polynomial regression (7) was used to determine A-values
at 0.5 %, 1.0 %, 1.5 %, 2.0 %, 3.0 % and 4.0 % water
content of paper (Table 9).
Figure 19. Life curves for Kraft paper of different water content in low
oxygen using A-values from Emsley and Lundgaard and an activation
energy of 111 kJ/mol.
Table 9. A-values recalculated using an activation energy of 111kJ/mol
determined from a polynomial regression using data from Emsley,
Lundgaard and Monash for Kraft paper in low oxygen.
Water content of Kraft paper (%) A-value (h-1)
0.5 % 1.52E+08
1.0 % 3.41E+08
1.5 % 6.19E+08
2.0 % 9.86E+08
3.0 % 1.99E+09
4.0 % 3.35E+09
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 19, No. 6; December 2012 2007

Figure 20. Life curves for Kraft paper with different water content in low Figure 21. Life curves for TUK paper in low oxygen using A-values from
oxygen by combining the A-values from Emsley, Lundgaard and Monash Monash with an activation energy of 111 kJ/mol.
with an activation energy of 111 kJ/mol.

The difference in estimated life between the existing life 7 CONCLUSIONS

curves (Figure 19) and the new (Figure 20) is shown in
- The water content of paper in these experiments
Table 10.
was controlled, contrary to paper ageing
experiments conducted using sealed vessels.
Table 10. Difference in estimated life between Figure 18 and Figure 19 for New ageing rates and life expectancy curves
Kraft paper in low oxygen. were determined for Kraft and thermally
Tem 1.0 % 1.5 % 2.0 % 3.0 % 4.0 % upgraded Kraft paper using this new method.
(°C) - The ageing rate of TUK paper is lower than Kraft
50 30.3 years 1.1 years 15.6 24.4 4.4 years paper in mineral oil with low oxygen content
years years between 0.5 % and 2.7 %.
60 8.8 years 0.3 years 4.5 years 7.1 years 1.3 years - The average activation energy (Ea ) for Kraft and
70 2.7 years 36.1 days 1.4 years 2.2 years 0.4 years
TUK paper in low oxygen (i.e. for hydrolysis)
was found to be 103 and 110 kJ/mol
80 0.90 years 12.0 days 0.5 years 0.7 years 47.8 days
respectively.
90 116.5 days 4.2 days 59.9 days 93.7 days 16.9 days - The ageing rate, k is not constant when the water
100 43.5 days 1.6 days 22.4 days 34.9 days 6.3 days content of the paper was maintained. The ageing
110 17.1 days 14.9 8.8 days 13.7 days 2.5 days isotherms are non-linear in the region (1/DPt –
hours 1/DP o) x 1000 < 5 (i.e. DP >200). Pseudo-order
120 7.0 days 6.1 hours 3.6 days 5.7 days 1.0 days reaction rate constants were used to compare to
130 3.0 days 2.6 hours 1.6 days 2.4 days 10.5 previous data however the first-order kinetic
hours model best fits the ageing data.
140 1.4 days 1.2 hours 16.8 1.1 days 4.7 hours - The correlation between pre-exponential factor (A-
hours value) and the water content of the paper is non-
linear. The A-value dependency on water content
of paper was developed for Kraft and TUK paper
We found that the life curves have shifted up resulting in aged in mineral oil with a low oxygen content.
an increase in the life expectancy of the paper at low - Thus the A and E values differ with paper type.
temperature. - Maintaining the water content of the paper during
the accelerated ageing experiments has resulted in
6.2 LIFE CURVES FOR THERMALLY UPGRADED an increase in the life expectancy of the paper.
KRAFT PAPER IN LOW OXYGEN - Life curves for thermally upgraded Kraft paper,
The life curves for TUK paper using the A-values with a thickness of 0.127 mm and a nitrogen
determined by Monash are shown in Figure 21. content of 1.8 %, aged in oil with a low oxygen
From these life curves we can see that thermally content were developed.
upgraded paper has a higher life expectancy than Kraft - The life expectancy of TUK paper exceeds that of
paper however the difference in life expectancy is greatly Kraft paper, however when the water content of
reduced as the water content of the paper increases to 4.0 TUK paper reached 3 % and above (in low
%. At 4.0 % the life expectancy of TUK paper is less than oxygen) the life expectancy was less than Kraft
Kraft paper. paper.
2008 N. Lelekakis et al.: Ageing Rate of Paper Insulation used in Power Transformers. Part 1: Oil/paper System
ACKNOWLEDGMENT
The authors wish to thank EPRI for funding this project.
The authors express their appreciation to the staff of
Monash University who supported this project, in particular
Arthur Lowery, Pam Dickinson, Martin Linzner, David
Morgan, Valery Davydov and Andrew Reykherdt. We
thank Yuriy Odarenko, of Wilson Transformer Company,
for the many interesting discussions we had with him on
modelling DP and the practical considerations of
investigating paper degradation from a manufacturer’s
viewpoint. We thank Weidmann for supplying the paper for
testing. Finally, we would like to thank the anonymous
reviewers for a very thorough review which has helped
improve the article.
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Nick Lelekakis was born in Melbourne, Australia
in 1971. He received the B.Sc. degree (with
Honors) in chemistry from Monash University in
1995. He has worked at Monash University on
transformer related projects since his graduation.
He has over 15 years experience in transformer
monitoring and diagnostics. He has studied
dissolved gas analysis methods using gas
chromatography, moisture dynamics in paper/oil
systems using Karl-Fischer, moisture probes and
dielectric response analysis. He has performed extensive paper ageing
studies measuring the degree of polymerization of various types of
cellulose.
Daniel Martin received the B.Eng. degree (with
Honors) in electrical and electronic engineering,
with study abroad in Germany, from the
University of Brighton, UK in 2000. He joined
Racal Electronics, which became the
international electronics company Thales,
working on communication and aircraft systems.
He left Thales in 2004 to pursue his Ph.D.
degree in electrical insulation at the University
of Manchester, UK. He investigated the
possibility of using vegetable oils and synthetic esters as substitutes
for mineral oil within large power transformers, and graduated in 2008.
After his Ph.D. degree he was employed as a research fellow at
Monash University investigating into condition monitoring of
transformer insulation. At the beginning of 2011 he was promoted to
the head of the transformer research centre at Monash, where he also
lectures.
Jaury Wijaya was born in Baubau, Indonesia.
He received the B.Eng. degree in electrical
engineering from Petra Christian University,
Surabaya, Indonesia, in 1999 and the M.Eng.Sc.
degree in electrical engineering from Monash
University, Australia. He was a technical
officer in the Department of Electrical and
Computer Systems Engineering at Monash from
August 2004 to March 2009, and is currently
pursuing the Ph.D. degree in that department.
He is a member of Cigre Working Group A2.38 transformer thermal.