I
Review of chemical indicators of degradation of
cellulosic electrical paper insulation in oil-filled
transformers
A.M. Emsley
G.C.Stevens
Indexing terms: Chemical indicators, Condition monitoring, Degradation, Electrical insulation, L$e prediction, Power transformers, Z-jiuraldehyde
Abstract: Chemical and thermal degradation of
electrical insulation in oil-filled transformers,
mechanisms of failure and methods of condition
monitoring and of life prediction are reviewed. An
insulation life prediction model is developed and
estimates of insulation life are presented under a
variety of oil/paper conditions. Systematic meas-
urements of the concentration of chemical indica-
tors in transformer oil are used to demonstrate
that furaldehyde and related products can be used
to detect high rates of paper degradation. Simi-
larly, phenol and related products indicate electri-
cal degradation in phenol-formaldehyde resins.
1 Introduction
Power transformer conductor windings are insulated by
paper impregnated with insulating oil, which is expected
to last the life of the transformer (25 years minimum at
an operating temperature of 65-95°C). A typical trans-
former contains 10-12 t of paper, 30-120pm thick
(density 0.7-0.8 kg/m3), and 45 t of oil. Heat, water and
oxygen degrade (depolymerise) the cellulose, reducing the
polymer molecular chain length and with it the mechan-
ical strength of the material. Local mechanical failure
could lead to shorted turns or paper fragments or fibres
in the oil ducts and hence to dielectric or thermal failure
of the insulation system. Changes in the compliance and
tension of the windings with time may result in distortion
and an increased susceptibility to short-circuit force
failure of the aged insulation or even of the winding itself.
Water is a product of ageing. Its presence in the insula-
tion increases conductivity and the likelihood of gas
bubble formation, reducing the thermal stability of the
insulation system during overload conditions.
Insulation grade paper is made by the delignification
of wood pulp by the Kraft process. It contains about
90% cellulose, 6-7% lignin and the balance is pentosans.
The natural humidity of paper is 4-5% by weight and the
insulation is dried after winding to less than 0.5%. The
dried paper is impregnated with insulating oil, which
increases its dielectric strength and also serves to cool the
0IEE, 1994
Paper 9957A (S2), first received 12th February and in revised form 29th
July 1993
A.M. Emsley is with the Department of Chemistry, University of
Surrey, Guildford, Surrey, G U 2 5XH, United Kingdom
G.C. Stevens is with National Power Research and Technology, Cleeve
Road, Leatherhead, Surrey, KT22 7SE, United Kingdom
324
windings 111. The major constituent of paper is cellulose,
which is a natural polymer of glucose. The monomer
units are combined in long straight chains, with an
average chain length or degree of polymerisation (DP) in
excess of 20000 monomer units, in the natural state.
Paper derives its mechanical strength from its fibrous
nature, which arises from intramolecular and inter-
molecular hydrogen bonding within and between cellu-
lose chains and the formation of a micro crystalline
structure. Aggregation of crystallites into elementary
fibrils 3-20 nm long and interlinking of the fibrils creates
the fibres that constitute the paper structure [2, 31.
The strength of paper is critically dependent on the
D P of the cellulose. After manufacture, the D P of the
paper is between 1000 and 1300 [4, 51. Drying the trans-
former reduces this to around 950 [SI and ageing in
service reduces it further. At DPs from 950 to 500, the
strength of paper is virtually constant but, in the range
500 to 200, it decreases in direct proportion to D P [SI.
The rate of loss of strength is temperature dependent
with an energy of activation very similar to that for
depolymerisation of cellulose [SI. At a D P of 150, the
strength is reduced to 20% of its initial value and below
150 paper has no strength at all [4-81.
Degradation of cellulose in electrical insulating paper
occurs via complex sequences of low temperature chem-
ical reactions, which are not yet fully understood. The
processes involve chain scission (depolymerisation) and
the release of breakdown products such as hydrogen,
short chain hydrocarbons, carbon monoxide, carbon
dioxide and water. They dissolve in the oil, where their
concentrations can be used to predict transformer condi-
tion through empirically established Rodgers ratios [SI.
Degradation also releases larger molecules such as 2-
furfuraldehyde (furfural) which can also be detected in the
oil and could give a more specific indication of the condi-
tion of the paper [ S , 10, 111. The kinetics and mechan-
isms of cellulose degradation and of furfural formation
are discussed in more detail in a separate paper [3].
The scope of this paper is to present a critical review
of our current knowledge of the chemical and thermal
degradation of electrical insulation in oil-filled trans-
formers, with particular reference to paper. This is then
developed into an insulation life prediction model. The
This work is published by permission of National
Power plc. The authors would like to thank
Messrs Fairholme and Fuller of the former CEGB
Midland Region SSD for providing the systematic
analyses of furfural, etc in transformer oils.
I E E Proc.-Sei. Meas. Technol., Vol. 141, No. 5, September 1994
 use of chemical indicators such as furaldehyde is also or oil. This suggests severe overheating and/or electrical
reviewed, and some specific examples of their systematic discharge activity.
use to monitor degradation of paper and of phenol-
formaldehyde resins in operational transformers are
given. ,
metallic particles ,n?g;yp1
2 Age profiles of transformer populations and
and fibres
discharge
processes
\
\ /I oxygen. water
oxidotive degrodotionctu
ri:;-1;7
/;\I
failure of paper insulation

2.1 Population age profiles and failure statistics

A large number of power stations and power transmis-
sion plant were built in the 1960s and many of the trans-
formers installed then are still in use. Kovacs et al. [12]
reported on transformer ages and failures in Hungary in
the ten years to 1981. They found that over 1800 of the
units in service were over 15 years old and over 200 of
those were over 20 years old. They recorded 35 catastro-
phic failures in the 10 year period, caused by gas build-up
as a result of the degradation of oil or paper.
In a review of transformer experience in the UK prior
to privatisation, the CEGB found that 50% of 650 MVA
power transformers would reach their expected life (25
years) by the year 2000, and 30% of 275 and 400 MVA
transformers will have attained 90% of life (40 years).
They found an average failure rate of 1.2 per year in 570-
660 MVA generator transformers in the 10 years to 1988
(2.7 x lo-' per generator transformer per year) and
some evidence that the rate of failure may be increasing.
15 failures in 275 and 400 kV transformers were studied
in detail. Less than a third could be directly attributed to
failure of the paper insulation, although some units were
refurbished with new insulation anyway.
The transformer population is ageing in all countries.
France, for instance, has 10-20% older than 30 years and
some over 50 y old (Guinnic, private communication). It
is therefore important to understand the processes of
insulation ageing and failure in transformers.
2.2 Failure mechanisms
Cellulose degradation reduces the degree of polymeris-
ation, destroys interfibre bonding and causes loss of
mechanical strength, leading to tearing and defibrillation.
In contrast, the dielectric strength is not greatly affected.
Many processes contribute to degradation and failure,
and some of them are shown in Fig. 1.
Gas evolution is a common mode of failure. The gas
released initially is water, but as the temperature rises
above about 90"C,CO and CO, are also formed. Gas
bubble formation occurs in paper/oil systems at tem-
peratures as low as 150°C [13]. The greatest danger
exists during the early stages of an overload condition,
when a sudden temperature rise can cause rapid evolu-
tion of moisture from the insulation. Gas bubble forma-
tion in the oil may also be sustained by a partial
discharge, which may lead to bubble growth and even-
tually to a flashover.
Other mechanisms of failure involving paper might
include: increased conductivity of both paper and oil as a
result of accumulation of degradation products [13-15);
thermal instability in the paper, as a result of decreased
resistivity and increased dielectric loss, due to build-up of
moisture; fibrous material in the oil tends to align itself
with the local electric fields, and can provide a short-
circuit, or a weak dielectric pathway between conductors,
particularly if wet [l].
The catastrophic failures reported by Kovac et al. [12]
clearly resulted from ignition of large amounts of hydro-
gen or hydrocarbon gas, accumulated in the top head-
space, following excessive rates of degradation of paper
IEE Proc.-Sei. Meas. Technol., Vol. 141, No. 5, September 1994
sparks
OrCS Ond
4
*/ water, oxygen
oil degradation paper ageing
solubility. portition
acidification decomposition woter formation
carbon dioxide
hydrogen and
hydrocarbon
gases
dissolved gas furfuroldehyde
analysis onolysis
Fig. 1 Factors influencing performance and degradation of trans-
former oillpaper insulation and resulting breakdown mechanisms
e.g. mechanical damage as result of embrittlement, moisture formation, fibre for-
mation
3 Condition monitoring
Methods employed in the UK for condition monitoring
such as partial discharge, loss tangent, DC resistance, oil
acidity, oil moisture content, dissolved gas in oil analysis
(DGA) and furfural in oil analysis have recently been
reviewed [16-181 and only the latter two are discussed
further. Other references to condition monitoring tech-
niques list alternatives such as:
(i) polarisation spectrum and recovery voltage of the
insulation after a long DC charge and a short discharge.
Specific areas of the polarisation spectrum are analysed
selectively [19,20] and in one case [20] correlations with
D P have been obtained;
(ii) electrical dissipation factor of the oil, but this is
more susceptible to degradation of the oil than the paper
BI;
(iii) relative humidity of the oil and low voltage
impulse measurements [l5, 221;
(iv) particle counting in, and atomic absorption spec-
troscopy or ferrography of, the oil. However, it was con-
cluded that DGA was more useful [23];
(v) degree of polymerisation of the paper by removing
samples from the accessible regions of the transformers,
near the oil outflow [24]. However, it is diflicult to see
how top samples could be representative of the bulk of
the paper and how they would cater for the possibility of
local overheating;
(vi) yield of levo-glucosan (a degradation product of
paper during pyrolysis of paper at 300°C) has been sug-
gested as a possible means of monitoring paper condition
~251;
(vii) evolution of CO + CO2 can be directly related to
the remaining strength of the paper [8, 26-30]; however,
the scatter of measurements made on service trans-
formers is so large that service lives can only be estimated
to within +/- 10 years [26].
325

I
It has been suggested that systematic rewinding of all
transformers over 15 years old should be carried out,
before the paper deteriorates to a critical condition [12].
However, most utilities prefer to use diagnostic condition
monitoring methods to avoid unnecessary outages. The
most widely used is dissolved gas in oil (DGA), which is
briefly described below.
3.1 Dissolved gas in oil analysis ( D G A )
The DGA technique and in situ monitoring of gases such
as hydrogen have been extensively reviewed elsewhere
[9, 31-41] and only the salient points will be discussed
here.
A healthy transformer should have less than 0.05 ml of
combustible gases (hydrogen and short chain hydrocar-
bons: methane, ethane, ethylene, acetylene) per 100 ml of
oil and insignificant levels of higher hydrocarbon gases
(greater than C, [31]). Measurements on free-breathing
+
transformers show average CO COz levels of 0.4 ml/
100 ml of oil after 15 years [26]. Unpublished measure-
ments made by the CEGB have shown that the
concentrations of dissolved gases normally increase
approximately parabolically with time. The rates are
different for each component so the ratios of gases in the
oil vary slightly with the age of the transformer.
Oxygen in the oil promotes the evolution of CO and
CO2 from both oil and paper and moisture has a signifi-
cant effect on the evolution of these gases, when present
in the paper [9, 311. Normal gas levels in power trans-
formers are given in Table 1, which also shows the
normal ratios of the concentrations of different hydrocar-
bons in the oil (Rodger’s ratios). Monitoring changes in
these ratios provides an early indication of overheating
132-34, 421. Corresponding concentrations in the gas
above the oil were not quoted, but measurements, made
by the CEGB, of hydrogen levels in Buchholz relays,
indicate a normal concentration less than 0.1%. A con-
centration of greater than 0.5% is taken to indicate a
fault condition and, under extreme discharge conditions,
the level can rise to 50%.
Table 1 : Normal gas levels and concentration ratios
(Rodgers ratios) in a healthy transformer
Gas concentration Normal gas concentration
in the oil pl/l ratios in the oil
hydrogen 75-200 methane/hydrogen >0.1 and tl
carbon 500-1000 ethanelmethane tl
monoxide
methane 25-100 ethylene/ethane <1
ethane 15-250 acetylene/ethylene <0.5
ethylene 10-30
acetvlene 10-1 5
Under partial discharge conditions the hydrogen level
increases (to up to 4% in the oil, 0.5 to 50% in the gas).
Under continuous discharge, the ethylene and acetylene
levels also increase. Methane and ethane levels increase
when the transformer overheats generally and high levels
of CO indicate thermal ageing of cellulose [9, 421. High
rates of paper degradation are also indicated when the
ethylene concentration increases strongly and the
CO,/CO ratio decreases below a ratio of about 6. At
COz/CO ratios less than 2, the probability of failure
increases significantly when the combustible gas concen-
trations exceed about 200 ppm [SI.
A major disadvantage of DGA analysis is that the
results refer mainly to gas evolution from degradation of
the oil and are not specific to paper degradation. Local
326
overheating of structural elements in the tank causes
evolution of high levels of hydrogen, methane and ethane.
It has been suggested that acceptable limits to local over
temperatures of the metal are 130-140°C over an area of
12 m2 or 160°C over 0.1 m2. This limits the increase in
degradation rate of the oil to less than a factor of 2 for an
average oil temperature of 110°C [43].
3.2 Analysis of furaldehyde in insulating oil
A number of studies of cellulose degradation have re-
ported furans, particularly 2-furaldehyde and 5-methyl-2-
furfural as products [lo, 44-47]. Both products have
been detected in transformer oil in laboratory degrada-
tion experiments [lo, 47, 481 and in operating trans-
formers [lo, 481 and are potentially unique monitors of
paper degradation.
Burton et al. [lo] and others [48] have demonstrated
methods of analysis based on high performance liquid
chromatography (HPLC) of extracts from the oil, which
could be used for routine condition monitoring. Burton
et al. [lo] have also devised a means of detecting degra-
dation at hotspots by combining DGA, which can be
used to estimate the temperature of the gas source, and
furfural measurements. They also demonstrated that the
temperature dependence of product formation may be
different for each indicator and hence the temperature
distribution of products may vary. In laboratory experi-
ments, Shroff and Stannett [SI and Burton et al. [lo]
demonstrated an empirical, inverse relationship between
log (DP of cellulose) and furfural concentration. This
implies that the possibility exists of establishing a
relationship between the cumulative concentration of fur-
fural in transformer oil and the condition of its paper
insulation.
It has been estimated that new paper, under normal
running conditions will generate furfural at the rate of
1.7 ng/g of paper/h. The rate of production increases with
increasing degree of degradation and a total yield of
0.5 mg of furfural/g of paper is expected in 100000 h of
running (15-20 years). Elevated temperatures, or the
presence of oxygen or water, will increase this rate. The
limits of detection of furfural are about 0.02 mg/l of oil,
or 800 mg in a typical 40000 1 oil loading. Levels of 1 to
10 mgjl have been detected in old, badly cooled trans-
formers. It is estimated that the overheating of a hotspot
at 250°C could be detected if the mass of paper involved
was greater than 1.1 kg [lo], but current analytical
improvements might reduce this to <0.5 kg. Further
work is required on the mechanism and kinetics of fur-
fural production, its partition between the paper and the
oil and its removal by conversion or trapping in trans-
formers, before it can be used as a reliable monitor of
condition.
4 Insulation life prediction
No satisfactory life prediction assessment for paper insu-
lation and transformer windings has yet been formulated.
There is even disagreement on what constitutes an
end-of-life criterion. It is generally agreed that the paper
insulation condition is the life determining factor and
50% loss of mechanical strength is often quoted as the
limiting condition [26, 491. It is also accepted that a
55°C rise in temperature halves the life expectancy [ 13.
Early estimates [SO] were 8°C. Fabre and Pichon [Sl]
quoted 10°C and evolved the empirical ‘ten degree rule’
to estimate the effects of temperature change on trans-
former life. This concept is arrived at from an argument
I E E Pror.-Sci. Meas. Technol., Vol. 141. No. 5, September 1994
 based on the Arrhenius theory of kinetic reactions [52].
It ignores the actual kinetics and the accelerative effects
of oxygen and water, which are discussed in more detail
later.
4.1 Paper strength and the degree of polymerisation
Many workers [4, 7, 26, 51, 53-57] have attempted to
relate paper strength to its D P and to define a limiting
acceptable value. The latter is usually in the range 150-
350 [4, 5, 24, 51, 541, and values as low as 150 have been
found in operating transformers [4, 24, 51, 561. Measure-
ments on laboratory aged samples confirm that paper
loses all its mechanical strength below a D P of about 150
[5, 51, 561. Insulation from operating and failed trans-
formers has been shown to decrease to an average D P of
about 200 and about 50% of its original strength in, at
best, 40 years and, in the worst cases, just 20 years [26].
Early experimental studies by Fabre and Pichon [Sl]
assumed a limiting D P of 150 and an initial D P of 1OOO.
Predicted insulation lifetimes from their data are given in
Table 2. Later Fallou [4] and Bouvier [54] extended the
theory and introduced a degradation factor, related to
Table 2: Lifetime oredictions from Fabre and Pichon 1511
Conditions Temperature Lifetime
"C
y
Paper under vacuum and 80 1200
containing 0.5% water 90 350
100 95
110 26
A free-breathing transformer 80 480
maintained in contact with 90 140
perfectly dry air 100 40
A free-breathing transformer with 80 67
50 ppm water in the oil 90 30
inn 15
the number of bonds broken. From an Arrhenius
analysis of the data, they calculated an activation energy
of 85 kJ/mole. They also demonstrated that the rate con-
stant for degradation could be related to the moisture
content of the paper by the following equation
In k , = In a + /IH
where a and /I are constants and
H = the percentage moisture content of the paper.
/I is quoted as 0.4, a is not quoted [54].
Life estimates from these figures are subject to error in
several respects
(i) The degradation factor (@) did not always vary lin-
early with time. In some cases, corresponding to values of
@ < 0.8, an initial period of rapid degradation was
observed before the linear relationship was established
~41.
(ii) Fabre and Pichon [Sl] point out that the rate of
degradation of the paper is a function of its age. Acker
[52] has shown that the practice of some transformer
manufacturers of providing data on fractional loss of life
per unit time can lead to erroneous lifetime predictions,
because the rate of degradation changes with age.
(iii) The choice of the end-of-life criterion and the limit-
ing value for the DP. Increasing the acceptable D P limit
to, for instance, 260, as suggested by some workers [SI,
halves the predicted life.
Other suggestions for the lowest acceptable level of deg-
radation are: reduction of the initial tensile strength to
50% of its initial value [26, 49, 581; reduction of D P to
20% [24] or 25% of its initial value [57].
I E E Proc.-Sci. Meas. Technol., Vol. 141, No. 5, September 1994
I
However, relative measures such as these do not take
into account differences in initial values and absolute
limits are preferable [56]. Such uncertainties over the
specific end-of-life criterion, together with a wide variety
of methods of calculation, have produced life predictions
of between 15 years and 50 years for typical service con-
ditions.
4.1.1 Advantages and disadvantages of life prediction
from DP measurements: The advantages of using D P
measurements to predict insulation life are: measure-
ments are relatively easy to make; D P can be empirically
related to insulation condition. However, using D P
values for life prediction presents a number of problems.
(i) The mechanisms and kinetics of the process are ill
defined, because a number of different reactions could be
operating simultaneously [7]. Examples of the processes
involved are discussed elsewhere [3,45,46, 59, 601.
(ii) The rate of degradation depends on the type of
paper and also on its final chemical treatment [SI.
(iii) The rate of degradation appears to increase dis-
continuously with increasing temperature above about
140°C [4, 26, 29, 30, 54, 611. From measurements of CO
+ CO2 formation, Hino and Suganuma [29, 301 predict
an increase in activation energy from 105 to 150 kJ/mole.
However, we would argue that it is the pre-exponential
factor that increases not the activation energy [3].
(iv) The rates of hydrolytic and oxidative degradation
of paper depend on accessibility of the reactants to the
interior of the insulation. It has been demonstrated that
the rate of degradation varies across the thickness [24]
and is greatest in the inner and outer layers [62-641.
(v) The strength of paper is not linearly dependent on
its DP except over a limited range of about 200 to 500. It
is worth noting that paper strength has been shown to
bear a linear relationship to the total volume of carbon
monoxide plus carbon dioxide evolved during degrada-
tion [8, 26, 29, 301. The correlation between D P and
strength is also independent of ageing conditions [4].
4.2 Effects of temperature,water and oxygen on
(1) insulation life
The low temperature thermal and hydrolytic degradation
kinetics and mechanisms are discussed in more detail in a
separate paper [3], but here we concentrate on those fea-
tures appropriate to transformer insulation ageing.
4.2.1 Effects of temperature: It was recognised long ago
that the degradation process is a chemical reaction and
as such should obey the Arrhenius theory of reaction
kinetics (see References 52, 65 and 66 for a detailed dis-
cussion of the application to transformer life prediction).
Values for the activation energy of degradation of cellu-
lose in oil, quoted in the literature, range from of the
order of 85 kJ/mole (which is close to the values quoted
for the thermal degradation reaction [4, 7, 541) to 120
kJ/mole [7] (close to those quoted for the hydrolytic
degradation reaction). Above about 140"C, some workers
have suggested that the rate of degradation increases
significantly implying either a change in the activation
energy or in the pre-exponential factor [26,29,30, 54,611.
4.2.2 Effects of oxygen: According to Fabre and Pichon
[Sl], oxygen increases the rate of degradation of paper
containing 0.3 to 5% moisture in oil by a factor of 2.5.
The effects on predicted insulation life are shown in
Table 2. Fallou [4] pointed out that, in an actual trans-
former, restricted oxygen access reduces the true value of
327
 the oxygen factor closer to 1.6 (see also [67]). In a model
transformer experiment [67], it was found that the
oxygen level in the oil increased initially, as the paper
outgassed, but then fell slowly as it was consumed by
reaction with the paper and oil. If the dissolved oxygen
level is maintained below 2000 ppm, the rate of oxidation
of the oil is reduced substantially. Maintaining the level
below 300 ppm can further reduce the acceleration due to
oxygen to a sixteenth of that at saturation (30000ppm)
[67, 681. The detrimental effects of oxygen on the paper
are to some degree ameliorated by the presence of
copper, which promotes the oxidation of the oil and thus
preferentially getters the oxygen [8].
4.2.3 Effects of water; Early studies [51] indicated that
the rate of degradation of paper increased in direct pro-
portion to the water content and predicted insulation life
estimates are given in Table 2. However, more detailed
studies [54] later concluded that, during the later stages
of degradation the logarithm of the rate is proportional
to the moisture level.
Water is a product of degradation and so the moisture
level in the paper increases with ageing [ 5 , 22, 691, by
0.5% every time the D P of the cellulose is halved by
degradation [66], resulting in a decrease in electrical
strength [57] i.e.
According to Fabre and Pichon [Sl] the equilibrium
humidity of clean oil is the same as that of the air in
contact with it. The relative levels of water in the paper
and the oil at ambient temperature is approximately
1000 : 1 but decreases with increasing temperature. Thus
the moisture content of paper in contact with oil of 50%
humidity, or greater, decreases from 9% by weight at
20°C to less than 1% above 80°C [4]. The predicted
water levels in the paper in a transformer at the end of
life at 80, 90 and 100°C are 5, 1.4 and 0.8% respectively.
Franklin [70] has shown that the relative humidity of oil
decreases from 0.8% at 12°C to 0.1% at 80°C. The
corresponding water content of paper in contact with it
decreases from 6% to 1.5%'$y weight, in agreement with
the figures of Fabre and Pichon [Sl] quoted above.
Water is released rapidly when the insulation tem-
perature rises during an overload. Computer programs
have also been developed to enable calculation of rates of
diffusion of water through the transformer and their
effects on the integrity of the insulation [71].
Calculations of the amount of water generated by
degradation of paper indicate an approximate rate of
2.5 ng/g of paper per hour. In thick layers of paper, diffu-
sion to the surface will inhibit release of this moisture
and enhanced degradation rates can occur [72]. In prac-
tice, moisture levels in paper insulation have been
observed to increase from <0.5% to, in extreme cases,
4-8% over their lifetime. Since the rate of degradation at
4% moisture in the paper is 20 times greater than at
OS%, at normal service temperatures, moisture accumu-
lation will have a significant effect on insulation life [4].
4.3 Results of model transformer experiments
A number of model experiments have been carried out in
an attempt to assess actual transformer ageing rates in a
way that can be scaled up to a true assessment of insula-
tion life. However, they all suffer from a lack of a funda-
328
1--
mental knowledge of the factors controlling ageing in real
transformers, which makes it impossible to realistically
scale up. Some of the problems, related to the measure-
ment of ageing rates, highlighted by such experiments,
are :
(i) more rapid rates of paper degradation are measured
in small units than in full-sized systems due to the accel-
erating effects of autocatalytic products (e.g. water) and
the proximity of walls (i.e. kinetic and diffusive effects
C731);
(ii) acid products of oil degradation accelerate paper
ageing [63,74];
(iii) antioxidants in the oil reduce paper ageing by
reducing the rate of acidification [73,75];
(iv) electric fields accelerate ageing, possibly by
increasing the precipitation of acid products of oil degra-
dation on to paper surfaces [63];
(v) in mixed insulation systems such as paper over
PTFE, undefined interactions between the paper and
PTFE reportedly accelerate ageing [49];
(vi) copper, iron, sodium and chloride ions in the
paper accelerate ageing [76]. However, copper also pro-
motes oxidation of the oil, thus reducing the oxygen level
PI;
(vii) different paper manufacturing treatments (e.g.
thermal upgrading, affect the rate of ageing).
While all these effects should be small compared to the
influence of temperature, water and oxygen, combined
together, they add to the uncertainty of transformer life
estimates. Further work is required on understanding the
basic mechanisms of degradation before accurate predic-
tions of insulation life can be made. Detailed forensic
studies on failed transformers will help in this respect.
5 Recent developments in insulation condition
monitoring and life prediction
Transformer operators would like to know the present
aged condition of their plant and be able to estimate life
expectancy so that replacement can be managed. Defin-
itive answers to these questions cannot be obtained at
present, but progress in the development of both chem-
ical and physical condition monitoring indicate that it
will be possible in the future.
5.1 Insulation life prediction from cellulose
degradation kinetics
The detailed kinetics and mechanisms of degradation of
paper are reviewed elsewhere [3], where we have shown
that a mechanism of random chain scission, widely used
to describe the degradation of cellulose, can be extended
to degradation under oil. The approach is similar to that
adopted by Fallou [4] and Bouvier [54]. The reaction
rate at any time is assumed to be proportional to the
number of unbroken polymer chain bonds available and
analysis reveals an equation of the form
-_-=
kt (3)
DP, DP,
where
DP, = D P at time t
DP, = initial D P
and
k = constant.
IEE Pr0c.-Sci. Meas. Technol., Vol. 141, No.5, September 1994
Shroff and Stannett [SI originally reported their paper shows their data replotted according to the above equa-
ageing data in the form of log (DP) vs. time, which was tion. It can be seen that the data are now essentially
linear over about 80% of the reaction, but did not linear throughout and extrapolate through the origin.
extrapolate through the initial conditions. Fig. 2u-e Similar results are obtained for most reported degrada-
tion data for cellulose under a wide range of experimental
conditions. This includes the data of the Fabre and
Pichon [Sl], Fallou [4] and Bouvier [54], which were
also nonlinear when plotted in their original form [3].
For predictive purposes, it is useful to relate k to tem-
perature via the Arrhenius relationship. A collation of all
120 oc available data (replotted according to eqn. 3 where
necessary) is represented schematically in Fig. 3. It_ can
_ be
E
-2
4000
time, h
0
8000 12 000

-4b\ 0
X

time, h
b
Fig. 3 Analysis of covariance offirst order rates of degradation of cel-
lulosefrom DP measurements as function of 'potential for oxidation'
1. V thermally upgrade paper in dry oil
g5
04[ y160 OC
2. A Kraft paper in dry oil
3. 0 paperlcotton in vacuo or nitrogen; or Kraft paper and I-2% H,O in vacuo
Kraft paper and I-2% H,O in oil; or paper/cotton in air

i l k
4.
140 O C 5. 0 Kraft paper and 4% H,O in oil or in uacuo; or cotton/paper in oxygen
x cotton in acid or alkali solution

61 seen that the slope of the plot remains constant under a

120 oc
E00 4000 8000 12 000 variety of experimental conditions. This yields a constant
activation energy of 111 kJ/mole, with 95% confidence
time, h limits on the mean of 105 and 117 kJ/mole. In contrast,
C the intercept (the pre-exponential of the Arrhenius
relationship) increases with increasing severity of reaction
0
all w d c a i r
conditions and increasing susceptibility of the paper to
degradation [3].
O all wood paper
I
The equations of the lines are given by

;2tY
e, I (4)

O@
where
0 T = temperature in Celsius
R = the gas constant = 8.314 J/mole/K
Values of A (including confidence limits) are given in
5r
I

Table 3 and are dependent on operating conditions.

Table 3: Praexponential facto-
of dearadation ratas
Data set
all wood paper
from analysis of covariance
Pre- 95% confidence
exDonential limits

E Upgraded paper in oil 3.65x 10' 7.93x lo* 1.68x 10'

Dry Kraft paper in oil 1.07x 1 O8 2.41 x lo7 4.71 x 1 Os
0 4000 8000 12 000
Kraft paper + 1 % H,O 3.50x 10' 8.41 x lo' 1.46x 10'
time, h in oil (or paper or
e cotton in vacuum)
Kraft paper + 2% H,O 7.78x 1 O8 1.83x 1 O8 3.30x 1 Os
Fig. 2 Reassessment of data of Shroflet al. [S, 6.71 in oil (or paper or
Effect of temperature on cotton in air)
a all wood Kraft paper Kraft paper + 4% moisture 3.47 x los 7.66x 1 OB 1.57x 10"
b all wood Kraft paper loaded with 4% water in oil H,O in oil
c thermally upgraded, all wood paper (or paper or cotton
d effect of air and copper
e effect of water loadings of I, 2 and 4%on Kraft paper at 120°C
in oxvoen)

I E E Proc.-Sci. Meas. Technol., Vol. 141, No. 5, September I994 329

5.1.I Extrapolating the data to transformer rem-
peratures: Fig. 3, Table 3 and eqn. 4 currently provide
the best available source of data for predicting the life of
paper insulation in transformers, because the large size of
the data set (some 80 datum points) reduces the statistical
errors. The data can be extrapolated to transformer oper-
ating temperatures using the equation
life is plotted against final D P values in the range 150 to
250. The dashed lines represent + 2 standard deviations
from the mean values at 1300 (upper line) and 900 (lower
line).
The errors in predicting life at normal operating tem-
peratures for any tightly defined environmental condi-
500r

Substituting the value for k from eqn. 4, and using initial

and final D P values of 1000 and 200, respectively, this
simplifies to

temperature. OC
Fig. 4a-e shows insulation life predictions obtained from a
eqn. 6 under a number of constant operating conditions.
The detrimental effects of water (Fig. 4d and e) and
oxygen (Fig. 4c) can be seen clearly and the possible
benefits of thermally upgraded paper, at least at tem-
peratures below 100"C, can be seen in Fig. 4a. The
dashed lines are two standard deviations about the mean.
5.1.2 Comparison with other data: The activation
energy obtained from the data of Fabre and Pichon [5l] Ob I I i

and Bouvier [54] are low compared to the average value 80 85 90 95 100 105 110
temperature, O C
quoted above [3]. Life estimates from their data will b
therefore be high at temperatures below about 100°C and 60
low above. On the other hand, the Shroff and Stannett * 501,
[5] activation energy for dry, all-wood paper is high rela-
tive to the mean. Rate estimates below 100°C will be low,
and life predictions high. Comparisons between Shroff
and Stannett and current predictions can be made (see
Table 4). L
a
lo
Table 4: Life estimate comparison
80 85 90 95 100 105 110
Temperature Conditions Predicted life Predicted life temperature. O C
(Shroff and (Current work)
Stannett)

90°C Dry all-wood paper 38 years 35 i 8

in dry oil
90°C All-wood paper plus 1.9 years 4.8 f 1.4
2% water in oil U
"
5.2 Limitations to insulation life prediction
The life estimates of Fig. 4 are based on a theoretical
model derived under idealised accelerated reaction condi- 80 85 90 95 100 105 110
tions and as such are subject to the following limitations. temperature, OC

(i) The kinetics and mechanisms of degradation are the d

same in transformers as in model laboratory experiments. 5K
This is not necessarily valid, and detailed studies are still
required to elucidate the chemistry of degradation.
(ii) Operating conditions remain constant. This cannot
be the case, so it would be important to have detailed
information about past and present operating conditions .v
U
2
if a realistic assessment is to be made.
(iii) The initial paper D P is known.
(iv) Some assumption is made about the minimum
80 85 90 95 100 105 110
acceptable D P below which the transformer is considered temperature, OC
to be at risk of failure. e
Fig. 4 Insulation life predictions for degradation of cellulose paper
Errors introduced in the assumptions regarding choice of from DP of 1000 to one of 200
the initial and final values of the D P are shown in Fig. 5 Dashed lines indicate i Istandard deviation
for dry paper in dry insulating oil at a temperature of a upgraded Kraft paper in dry oil
90°C. The initial D P is varied from 1300 (as quoted by b dry Kraft paper in dry oil
c dry Kraft paper in dry oil plus oxygen
Fabre and Pichon [52]), down to 900 as quoted by d Kraft paper containing 1-2% water in initially oil
Shroff and Stannett [5] (solid lines). Estimated predicted e Kraft paper containing 4% water in initially oil or in vmuo

330 IEE Proc.-Sri. Meas. Technol., Vol. 141, No. 5, September 1994
tion, and precisely known initial and final DP values, are
less than *20% of the mean value. However, summing
the errors over all possible environmental conditions and
taking into account variations in the initial and final DP
transformer. Fig. 7b shows a transformer that twice failed
with a flashover fault in the LV winding. The traces are
similar except for a small sharp rise in m-cresol immedi-
ately before each failure (indicated by an arrow). Note
that frequent sampling is required to detect this type of
fault. Fig. 7c shows the higher levels of all components,
but particularly furfural, found in a transformer known
to operate near the top of its allowable temperature
range, due to problems with the oil cooling circuit. Fig.
7d demonstrates the effect of abnormal overheating, as
occurred in this case when the oil cooler circuit failed.

!:p
The concentration of all components increased sharply,

0
L

n20' Id0 ,A0 2

o; 2o: 210
final DP value
Fig. 5 Variation of predicted insulation life with choice offinal DP c
I
valuesfor dry Krafi paper in dry oil at 90°C
Starting DPs of (1) 1300, (2) 1100 and (3) 900; dashed lines indicate i 2 standard
deviations on extreme mean values
-8
P4
values, this figure increases to *200%. This highlights r
0
the need for more accurate experimental data, and an 2 0
0 1000 2000 3000
ageing model which takes all factors into account in the time, h
extrapolation. a
It is interesting to note that a change in environmental
conditions, particularly a change in water levels, would
have a major effect on degradation rates and might
explain some of the rate changes reported in the liter-
ature. The possibilities are discussed in more detail else-
where [3]. Under transformer operating conditions, the
rate of degradation is likely to increase continuously as 8
water accumulates in the paper. Future kinetic models - 4
will need to allow for a time-dependent variation of reac-
e
120 o c
tion rate. 110 o c
- 0 1000 2000 3000
time, h
5.3 Furfural and related compounds as chemical b
indicators of insulation condition
5.3.1 Furfural formation in model experiments
revisited: Measurements of furfural and related com-
pounds in insulating oil are not yet sufficiently developed
to enable cumulative concentrations to be related to
paper condition. However, some useful conclusions can
be drawn from the previously unreported results of
Shroff and Stannett [ 5 ] and of Gibbons and Shroff
(unreported data); the data are summarised in Fig. 6a-d.
For 6 a shows the results of static experiments in which
:41D#
-
1 0
8

0 1000
,
2000
,
3000
the water level in the system was allowed to build up.
time, h
There is considerable variability in the results, which may C
be associated with uncontrolled levels of water. More
consistent, lower, results were obtained when the oil was
purged with nitrogen (Fig. 6b) or air (Fig. 6c). Fig. 6d
shows a dramatic increase in furfural production when

!:L
the paper is preloaded with water. It is interesting to note
that air purging apparently reduces the amount of fur-
fural formed, even though DP measurements on the
papers clearly showed increased rates of degradation. We
now believe that this arises as a result of forced evapo- e
ration of the products. 2
+ 00 1000 2000 3000

5.3.2 Furfural formation in operating transformers: We time, h

have found evidence, from a systematic HPLC study of d
oil in the former CEGB transformers, that certain types Fig. 6 Variation of furaldehyde concentration in laboratory experi-
of faults can be identified. Fig. 7 a shows the levels of six ments ageing all wood Kraft paper in transformer oil
chemical indicators: 2-furaldehyde (furfural), 5-methyl-2- LI in static oil at 120°C
b in oil Rushed with nitrogen at 110-140°C
furaldehyde, 2-acetyl furan (from paper) and phenol, c in oil flushed with oil at 120°C
m-cresol, xylene (from the resin), in a typical 20 year old d in static oil plus 2% water at 120°C

I E E Proc.-Sci. Meas. Technol., Vol. 141, No. 5, September I994 331

particularly furfural and m-cresol. It is interesting to note stant for the reaction is quoted as
that all the levels fell back near to their original value
after the fault was corrected (the oil was filtered and
degassed during the repair). This implies a dynamic equi-
k = (69 + 9.2 x lo3 x lop")exp - - ( 4;y) (7)

Extrapolating back to transformer conditions, an

approximate estimate of the half life of furfural at 100°C
and a pH of 6 is 125 hours. To maintain a steady-state
concentration of furfural of, say, 1 mg/l in 4OOOO 1 of oil
(see estimates in Burton et al. [lo]) would require a pro-
duction rate of approximately 0.35 g/h. If production
proceeds via glucose, approximately twice the weight of
cellulose is destroyed, equivalent to 0.7 g of paper per
hour (i.e. the 10-12 t of paper would disappear com-
pletely in 1.4 x lo7 h (1600 y)). In practice, the source of
-3 LVfJlure furfural would not be uniformly distributed through the
paper. If only 1% was the source, the life of paper at a
hotspot of 100°C would be 1.4 x lo5 h, which represents
15 years' continuous operation. Thus, as predicted
empirically by Burton et al. [lo], there should only be
cause for concern at furfural levels greater than 1 mg/l in
8
m
1985 1986 1987
.I .Z *f.
1988 1989
the oil. Fig. 7 indicates normal levels of furfural of 1-
2 mg/l.
No statistical data were given by Baugh et al. [77] so
it is impossible to estimate the errors in these figures.
They are very crude, and the initial extrapolation on
which they are based is far beyond the original data con-
ditions. Nevertheless, the values obtained are credible
and seem to agree well with empirical measurements.
Further work is required to establish the kinetics of fur-
fural decomposition in the oil and its partition coefficient

01 - - ' A
1985 1986
- c l -
7
!
9
1
21 -
1988
I c
1989
I
with the paper, and it should aim to provide accurate
data at realistic temperatures and environmental condi-
tions.

6 Conclusions

(i) The life expectancy of transformer paper insulation,

Fig. 7 Chemical indicators of paper ageing~intransforrk-oil
a typical levels during normal operation of225 MVA unit
b example of LV flashover failure in 600 MVA unit
c typical results of extended high temperature operation (close to normal
maximum limits) of600 MVA unit
d short-term overheating in 600 MVA unit
furfural
H aatylfuran
A methyl furfural
0 phenol
0 n-cresol
A xylene
librium in the oil between the production and loss of fur-
fural and other indicators (see below).
5.3.3 Furfural loss in transformers: In a transformer,
furfural will be lost from the oil as a result of thermal or
hydrolytic decomposition and absorption or adsorption
by the paper or elsewhere. Both paper and furfural are
relatively polar compared to the oil, so partition of fur-
fural between paper and oil should tend to favour reten-
tion in the paper; however, no information is currently
available on partitioning behaviour.
Baugh and McCarty [77] have measured furfural
decomposition rates in acid solutions of pH 2 to 4 at
temperatures of 190-230°C. A pseudo first order rate con-
332
at normal operating temperatures, can be calculated from
laboratory ageing experiments with statistical errors,
which are, at best, +20% of the estimated life.
(ii) Such an accuracy requires that: the initial degree of
polymerisation (DP) of the paper is accurately known; a
satisfactory assumption is made about the final DP value
limiting useful life; the operational history and environ-
mental condition of the transformer are known and
invariant.
(iii) The systematic use of furfural and related com-
pounds to monitor paper insulation condition promises a
useful complementary technique to dissolved gas analysis
and other monitoring techniques.
(iv) Measurement of phenol, m-cresol and xylene in the
oil may indicate that electrical and thermal degradation
of phenol formaldehyde resin insulation is occurring.
(v) Reliable insulation lifetime prediction from labor-
atory measurements and condition monitoring from
chemical indicators in insulating oil requires the estab-
lishment of: the detailed chemistry of degradation of
cellulose and modelling of the chemical and physical pro-
cesses involved; information about failure mechanisms
within a transformer (for instance, from forensic analyses
of old or failed transformers) and how this translates to a
probability for failure; knowledge of the kinetics and
mechanisms of loss of chemical indicators in a trans-
former (e.g. decomposition and absorption/partition on
the paper); a model relating the cumulative concentra-
tions in the oil to insulation condition (i.e. degree of pol-
ymerisation and strength of the paper) to failure
mechanisms and probability of failure.
I E E Proc.-Sci. Meas. Technol., Vol. 141, No. 5, September 1994
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