FURFURAL AND AGEING: HOW ARE THEY RELATED

Alfonso de Pablo
ASINEL, Spain

Introduction

In the past few years, furanic compounds analysis has demonstrated, as a complement of
the well establish dissolved gas analysis technique, t o be a powetful tool for diagnostic
and maintenance of electrical equipment insulated by cellulosic paper - mineral oil
impregnated systems.

However, a basic philosophy for monitoring says that monitored quantities "must be
measurable and must be directly correlated to (performance and operating) life of the
components".

By following this basic concept, furanic compounds analysis should only be useful for
electrical equipment condition monitoring if the measured amount can be related t o
operating conditions of the machine.

Thermal ageing of cellulosic papers

Paper is a mat of cellulose fibres, extracted from wood and other vegetable sources, which
also contain variable amounts of other chemical compounds such as lignin and
hemicelluloses (pentosanes).

Cellulose is a linear condensation polymer consisting of D-anhydroglucopyranose units

joined together by P-1.4-glycosidic bonds, as it is shown in Figure 1. X-ray diffraction
studies show that cellulose has both inter- and intra-molecular hydrogen bonds. A number
of cellulose chains are held together by the hydrogen bonds, in which the hydroxyl groups
are involved, to form a single cellulose fibre.

7-F- 0 Cy OH

Figure 1.- Chemical composition of cellulose

Cellulose degradation i s a complex process which is accelerated by the combined effect of

temperature, water and oxygen, all of them available t o the cellulose in the environment
of the transformer.

Several mechanisms for the thermal degradation of cellulose have been proposed.
depending on whether the predominant step is pyrolysis or hydrolysis of the glucose
units"'. In the first case, pyrolysis of glucose, the reaction proceeds via levoglucosan (1,6-
anhydro-J3-D-glucopyranose) a dehydrated sugar which, after a series of bond
rearrangements and further losses of water and formaldehyde (or hydrogen plus carbon
monoxide) yield furfuraldehyde among other products. The hydrolysis of glucose units
proceeds through the formation of an epoxide or an enol followed by internal re-

5/1
arrangements and further dehydration and elimination of formaldehyde t o yield
furfuraldehyde and other products.

It is noteworthy that water and carbon dioxide are the main by-products of the thermal
degradation of cellulose. Furans and carbonyl derivatives are the second major
degradation products, whereas alcohols, acids and aromatic and aliphatic hydrocarbons
are minor productsQ'.

Once degradation starts, all properties deteriorate; however, the mechanical properties
deteriorate faster than the electrical ones, thus they require a more stringent control.

The connection between the deterioration i n the material properties and the formation of
ageing products is the degree of polymerisation, the number of anhydroglucose units in
the cellulose chain. The degree of polymerisation proves t o be the most informative
parameter for assessing the ageing or the progress of ageing of cellulose"'. During
degradation, chain scissions take place leading t o the lowering of degree of
polymerisation. This results i n the depletion of the mechanical properties of the material,
i. e. tensile strength, elongation a t break, modulus of elasticity, bending strength and so
on and, on the other hand, the formation of decomposition products, namely water,
carbon monoxide, carbon dioxide, furans and others.

Figure 2 shows de evolution of degree of polymerisation and furfural formation during

the ageing of an insulating cellulosic paper sample in mineral insulating oil under well
controlled laboratory conditions.

1400 - 700
I
1200 - L 600

1000 - 1 500 N
71

800 ~ 1 400
e
600 - 1 300

400 - 1 200

200 - 1100

o w - , , , , , , , , ' , I " . ' / ' ' , I , ' . '

- 0
0 10 20 30 40 50 60
Days

Figure 2 - Evolution of degree of polymerisation (DP) and furfural (2FAL) during paper
ageing

The readion which takes place during the thermal degradation of cellulosic papers, can be
written as follows:

Cellulose --z Intermediate products (levoglucosane) --f Furfural

The first attempts t o correlate the amount of furfural dissolved in the oil and the degree
of polymerisation o f the paper were based on empirical formulas (models of Burton,
Vuarchex and Chendong). These have been derived from both laboratory experiments and
field measurements.

512
Based on a different approach, De Pab10'~'developed a degradation model based on a
common programme of research carried out by CIGRE Task Force 15.01.03. This model has
been improved later by Serena'".

In a series of experiments carried out in a number of European laboratories represented in

ClGRE Task Force 15.01.03. it was determined that the overall yield of the above reaction is
roughly 30 %, that means every 3 cellulose chain scissions give 1 furfural molecule.

From this laboratory experimental data, it can be shown that the amount of furfural
dissolved in the oil is defined by formula:

1o6
ZFAL (pg/g paper) = x N x 96x 0,3 = 222 x N (1)
162 x DP,

where DP, is the initial degree of polymerisation (800).162 is the molecular weight of the
glucose units constituting the cellulose, N is the number of chain scissions, 96 i s the
molecular weight of furfural and 0.3 i s the reaction yield.

Assuming a ratio (R) oil t o paper of 25, equation (1) can be written:

222 x N
ZFAL (mglkg oil) = - = 8,88 X N
R
N,the average number of bond scissions, is defined by formula:

Combination of formulas (2) and (3) gives:

8,88x DP, - 7100

DP = (4)
8,SS + 2FAL - 8,88 + 2FAL

which i s a formula which allows t o correlate the amount of furfural (ZFAL), expressed in
mg/ kg of oil, analysed in a transformer in service, with the degree of polymerisation (DP)
of the cellulosic paper in the windings of such transformer.

It has been shown that the minimum value for DP which may reach cellulose is about 180
t o 200 units. Then, the maximum amount of furfural which may be found dissolved in the
oil, calculated by formula (4) is about 30 mglkg which is quite consistent with the data
reported by CIGRE Task Force 15.01.03 members.

However, it is unlikely that all winding paper degrade with the same extension, as n o t all
the paper i s subjected t o the same conditions (i.e. the innermost layers of paper around
the conductors are subjected t o higher temperatures than the outermost, the transformer
may have a localised hot spot, etc.). Then, formula (2) should be modified on the basis of
the transformer operating conditions.

For instance, in a normal operating transformer it can be assumed that 20% of winding
conductor insulation (the innermost layers) degrade twice as fast as the rest of it, thus
accounting for 33% of total furfural. Then, the maximum level of degradation should be:

Nmax.= 2FAL 0733 = 0,186~2FAL (5)

8,88 x 02
and

800
DPmin. =
(0,186 x 2FAL) + 1

Also, the range of degradation of remaining winding insulation, assuming a variation of

C50% from the average, should be:

N=O,5x-
467 2FAL
to
067
12x-x-
2FAL
X
- (7)
0,s 8,88 0,s 8,88

and

800 800
DP = to DP= (8)
0,141 x 2FAL+1 0,047 x 2FAL+ 1

Under different operating conditions, i.e. overload of the machine, suspected hot spots,
etc., formulas 5, 6 and 7 may be changed by estimating the relative amount of cellulosic
paper involved in the process.

From this data it seems that the concentration of furanic compounds dissolved in the
transformer oil may be used t o monitor the insulation condition. However, thorough
engineering judgement must be exercised in all cases before adopting any action on the
transformer.

References

1.- Emsley, A. M., The kinetics and mechanisms o f degradation of cellulosic insulation in
power transformers, Polym. Deg. Stab.A.4 (1994) 343.

2.- Soares, S., Camino, G. and Levchik, S., Comparative study of the thermal decomposition
of pure cellulose and pulp paper. Polym. Deg. Stab., 49 (1995) 275.

3.- Moser, H. P. and Dahinden, V., Transformerboard II. H. Weidmann AG, CH-8640
Rapperswil, 1988.

4.- A. De Pablo and B. Pahlavanpour, Furanic compounds analysis: a tool for predictive
maintenance of oil-filled electrical equipment. Electra, 8-32,175.(1997).

5.-E. Serena. Degradation of transformers insulation. ClGRE TF 15-01-05 meeting, Turin

(1997).

0 1999 The Instiition of Elecbical Engineers.

5J4 Printed and published by the IEE, Savoy Place, London WCPR OBL