2014 Electrical Insulation Conference, Philadelphia, Pennsylvania, USA, 8 to 11 June 2014
The Degree of Polymerization of
Cellulosic Insulation: Review of Measuring
Technologies and its Significance on Equipment
Ch. Krause, L. Dreier, A. Fehlmann
WEIDMANN Electrical Technology AG
Rapperswil, Switzerland
christoph.krause@wicor.com
Abstract—In this paper, at first the term and the technical
significance of the degree of polymerization (DP) of cellulose
insulation is explained. Factors influencing the DP of new,
unused insulation products are detailed. An overview of
commonly used DP measuring techniques and standards is given.
Depending on the method, the measured DP value of cellulose
insulation can vary considerably. The DP loss at transformer
drying in the factory is examined and the correlation of the DP
with functional properties and lifetime of solid insulation is
detailed. The issue of minimum DP requirement of insulation of
new transformers is discussed, considering the assessed loss-of-
life due to transformer drying.
Keywords—DP; cellulose; transformer; insulation; lifetime;
drying; loss-of-life, degree of polymerization.
I. INTRODUCTION
The solid insulation materials that are traditionally used in
oil-cooled power transformers are presspaper and pressboard
[1]. These cellulose materials, made from wood pulp, are
immersed in mineral oil and they are exposed to elevated
temperatures in service of up to 100 °C and more, which
steadily degrade the insulation over time. The status of aging is
often determined and expressed by the degree of
polymerization (DP), which is a measure of the average length
of the cellulose macromolecules. In its virgin condition, the DP
value of the insulation is highest, and will decrease due to
aging – which is in fact a consequence of continuous
shortening of the cellulose molecules by chain scission.
It is common sense that new apparatuses are built with new,
unaged insulation. It is also commonly understood and
postulated that new apparatuses shall be completely dry when
shipped after successful testing. Yet, the high temperatures (up
to 130 °C) and lengthy exposure times (several days) required
for efficient drying by the transformer manufacturer will to
some extent entail an "early aging" phenomenon. This
premature aging effect – technically inevitable – is not
desirable if it has a significant impact on the lifetime of the
transformer insulation.
II. DP OF NEW, UNAGED CELLULOSE INSULATION
Mainly unbleached softwood kraft pulp is used for
manufacturing paper and pressboard for electrical
978-1-4799-2789-0/14/$31.00 ©2014 IEEE
J. Cross
WEIDMANN Electrical Technology Inc.
St. Johnsbury, VT, USA
james.cross@wicor.com
insulation [2]. The cellulose is refined chemically from
softwood trees (pine, spruce, fir). After processing, the typical
composition of unbleached Kraft pulp is 78-80 % cellulose,
10-20 % hemicellulose1 and 2-6 % lignin. Cellulose is a linear
condensation polymer consisting of anhydroglucose joined
together by glycosidic bonds, Fig. 1. The cellulose molecules
will organize in both crystalline and amorphous regions and the
DP value represents the average number (n) of glycosidic rings
in a cellulose macromolecule. It is typically in the range
1200-1400 for new unbleached softwood kraft pulp.
Fig. 1 Structural formula of cellulose
There are several factors having impact on the DP number
of new presspaper and pressboard:
• pulp source: type of trees
• climate condition of the trees (harvest, vintage)
• chemical treatment of the wood: extracting resins and
the majority of lignin
• paper and pressboard manufacturing process: origin
and blend of the used pulp, drying etc.
The above list explains why in practice, the DP of new
insulation products can vary over quite a wide range, typically
from 1100-1350, which is somewhat lower than new pulp.
The specific mechanical strength of the insulation cannot be
directly related to the DP alone. Apart from the molecule
length, the strength depends on other parameters: for instance
the build of fibers (thickness), the manufacturing process (in
particular degree of refining (freeness), the fibers' orientation,
the drying, impurities, the gravimetric density, etc.
1
Hemicellulose, in contrast to crystalline cellulose, has a random,
amorphous structure with little strength.
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 III. DP MEASURING TECHNIQUES AND STANDARDS Note that
DPw
Each family of wood polysaccharides exists as a spectrum Polydispersity = >1 (1)
of closely related polymers differing subtly in DP, degree of DPn
branching (if branched), the ratio of constituent sugars in the
case of heteropolymers, and in many other properties. There are many different chemical assay techniques
In understanding the measurement of DP, it is important to (laboratory analytical methods) for measuring or estimating DP
recognize that within any cellulosic material, there is a and each yields a unique figure. Different assay techniques
distribution of molecular weights (i.e. DP values) rather than measure different types (statistical analyses) of DP. Available
there being a single value. The latter would imply that all the assay techniques are shown in Table I.
cellulose macromolecules have exactly the same chain length TABLE I. Assey techniques and different measures of DP that they produce
with respect to the number of glycosidic rings. In reality, there
is a spectrum of molecular weights of the cellulose ASSAY TECHNIQUE MEASURES
macromolecules. The distribution is referred to by the term
Size Exclusion Chromatography
polydispersity. DPw
(Gel Permeation Chromatography)
There are a number of statistical means of characterizing
Scattering Methods: Light DPw
the distribution of molecular weights of a polymeric substance
such as cellulose. In particular, there are four types of Scattering Methods: X-Ray DPw
molecular weight averages that are commonly used in
characterizing DP (Fig. 2): Scattering Methods: Nuclear particles DPw

• Number-average degree of polymerization “DPn” -the Osmosis DPn

weighted mean of mole fraction.
• Weight-average degree of polymerization “DPw” - the
weighted mean of weight fraction.
• Z-Average molecular weight “DPz” – the average
weight where macromolecules become distributed
according to their size in a gravimetric separation when
in thermodynamic equilibrium.
• Volume-average molecular size “DPv” – average
“volume” or size of macromolecules of a polymer in a
dilute solution measured by viscometry.
Fig. 2 shows a typical distribution of molecular weight for
unbleached softwood kraft pulp, as determined by size
exclusion chromatography, for two different dynamic
viscosities of cellulose dissolved in solvent (22 mPa·s [blue
curve] and 36 mPa·s [red curve]). In both cases, the
relationship between DPz, DPw, DPv, and DPn is shown to be
consistent.
Fig. 2 Distribution of molecular weight in a typical cellulose material [3]
Ultracentrifuge (Gravimetric Separation) DPz
Diffusion DPa
Viscosity DPv
Reducing-End Determination DPn
Strictly speaking, one must show the resultant DP estimate
as DPx since all assay methods produce an estimate of an
average molecular weight.
Arguably the scientifically most appropriate method for
measuring DP is Size Exclusion Chromatography, which
estimates DPw. This test and some other advanced methods
like X-Ray or nuclear scattering require very specialized
instruments and are quite labor-intensive and time-consuming
to perform, and therefore expensive.
Primarily for reasons of cost and speed, the test usually
performed to determine DP for cellulosic insulation is
viscometry, which produces a result for DPv (subscript
denoting DP is related to the volume or size of the
macromolecule). Conceptually, viscometry works on the basis
that when a polymer (such as cellulose) is dissolved in a
suitable solvent, the specific viscosity of the solution is
proportional to the volume (size) of the macromolecules as
well as the concentration. Viscosity increases with the average
chain length of the polymer molecules because larger
molecules considerably impede the flow of a liquid.
The basis of viscometry as a means of estimating DPv
comes from the fact that many properties of a solution
containing macromolecules depend on the size of the dissolved
particles, not only the mass concentration of solute. Einstein [4]
showed that in a solution containing large particles the relative
increase in viscosity is proportional to the total volume of the
dispersed phase,. (2) and (3).

268
 η solution − η solvent V tube must be sized to the expected viscosity i.e. efflux times
η sp = = ƒ solute (2)
η solvent Vsolution
lim η sp ƒ 2.5
c→0
= = (3)
c d d he
where ηsp is the specific viscosity; V is the volume; f is a
viscosity factor (f = 2.5 for solid spherical particles); c is the
mass concentration of solute per volume of solution; d is the
density of dispersed particles; dhe is the density of a hydro-
dynamically equivalent sphere.
Consider such a specific property Pspecific as defined in (4),
which is a function of mass concentration c and molecular
mass M:
P − Psolvent
Pspecific = = f (c; M )
c ⋅ Psolvent
(4)
lim c →0 Pspecific = f ( M )
By measuring the property (in this case viscosity) for
several different solutions of different concentrations and
extrapolating the specific property thus derived to zero
concentration, a value is obtained which is an explicit measure
of molecular mass of the solute.
Viscometric assay techniques involve dissolving the
cellulose polymer in a suitable solvent - usually
bis(ethylenediamine)copper(II)hydroxide (known as CED or
CUEN): Cu(H2NCH2CH2NH2)2(OH)2. The viscosity of the
solution increases with the average chain length of the cellulose
molecule. The solution is allowed to flow through a calibrated
viscometer and the efflux time is measured.
The intrinsic viscosity value is derived by extrapolation of a
series of measurements at concentrations high enough to obtain
reliable data, but low enough to find a linear dependence on
concentration in order to be able to extrapolate the data to zero
concentration. In practice, an “optimum” concentration of
cellulose is selected to be dissolved in CUEN and a single-
point measurement and regression is utilized using an assumed
slope (k is usually taken to be 0.14 for cellulose) to determine
ηintrinsic.
From these measurements, the instrinsic viscosity (or
limiting viscosity number) of the solution is obtained using
Martin’s empirical formula (5) and the DPv is obtained from
this value using a mathematical conversion (the Mark-
Houwink equation).
ηspecific = ηintrinsic · c · 10(K · ηintrinsic· c) (5)
where “K” is the Martin coefficient = 0.14 for cellulose.
It should be pointed out that while viscometry is simple
conceptually, large variations in DPv estimates can result from
seemingly innocuous factors (e.g. temperature changes during
test) and very minor changes to key factors. To avoid thermal
kinetic energy effects and non-Newtonian flow, the viscometer
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must fall within a certain range. In short, accurate viscometry
depends on very precise analytical work in the lab, and
immaculate sample collection and handling in the field.
Even within the narrower field of viscometry techniques for
estimating DP, there are several test standards. In particular,
there are four test standards in common use for measuring DPv
of cellulose materials – two for pulps and two for electrical
insulating materials:
• ISO 5351 (2nd Edition: 2010-2-15) “Pulps –
Determination of limiting viscosity number in
cupriethylenediamine (CED) solution.” (formerly
SCAN 13:88)
• TAPPI T230 om-04 (revised 2004) – “Viscosity of
pulp (capillary viscometer method).”
• IEC 60450, Ed. 2 – “Measurement of average
viscometric degree of polymerization of new and aged
cellulosic electrically insulating materials.”
• ASTM D4243-99 (Re-approved 2004) – “Standard
Test Method for Measurement of Average Viscometric
Degree of Polymerization of New and Aged Electrical
Papers and Boards.”
For DPv values to be relevant, the test method used must be
identified as there are differences in technique - and, to some
extent, the results. In particular, note that the TAPPI T230
standard commonly used by pulp producers measures dynamic
viscosity, not intrinsic viscosity. There is no direct conversion
from a dynamic viscosity as measured in accordance with
TAPPI T230 to intrinsic viscosity, although a correlation was
established by Godsay [5].
There are several mathematical correlations that have been
established between intrinsic viscosity and DPv based on
research. Because of variability between these correlations,
DPv values are only valid if the means used to correlate the
values are included in the test report or if the test standard
followed in performing the test is referenced. Currently, this
practice is not common in the industry.
IV. THE EFFECT OF INSULATION DRYING ON DP:
EXPERIMENTAL INVESTIGATION
It is essential to dry cellulose insulation completely before
testing and commission, for two main reasons:
a) The dielectric strength of the insulation system is
strongly dependent on moisture. Semi-wet insulation may
cause partial discharges, surface creepage discharges along
pressboard/oil interfaces, or puncture in the worst case [6-10].
In most cases, wet insulation will be detected during the
partial-discharge test and/or insulation resistance testing or
power factor measurement in the case of large power
transformers. Moisture in smaller units that are only subjected
to voltage withstand test may be unrecognized at testing, but
may fail prematurely in operation.
b) As widely reported in literature, water in the paper/oil
insulation system acts as a strong aging accelerator, e.g. [2].
Transformers with incomplete dry-out will age fast and will
reach end-of-life early, which is not in the interest of the
transformer user.
(6)
In this study, the impact of vacuum was investigated at
three different drying temperatures (105, 120 and 140 °C).
High density pressboard (IEC 60641-3-1 B3.1) sheet samples In the following example, the impact of the initial DP0 on
of 1 mm thickness of initially 6 % water content were oven lifetime is shown, Fig. 4. Equation (6) is brought to linear time
dried and the impact of temperature and time was determined scale, and the vertical axis is the DP as it decreases with time.
by cutting small pressboard pieces from the sheets for A constant aging temperature of 85 °C is assumed; the solid
subsequent DP measuring. One oven was operated with red curve depicts the DP course with an initial DP0 value of
circulating air (oxygen access), the other oven with vacuum (no 1200. This results in a lifespan of about 37.5 years, assuming
oxygen, p < 1 mbar), Fig, 3. DP 200 as the end-of-life situation. In comparison, the case of
pre-maturely aged insulation with an initial DP of 1000 is
The loss of DP during drying in air was significant, even at investigated – this corresponds to a calculated “lifetime DP”
the lowest temperature of 105 °C. Under vacuum condition, the reduction of 20 % when compared with 1200. As can be seen
DP decrease was remarkably slower because of the absence of from the dashed black line in Fig. 4, the loss of life of the pre-
oxygen and because water was more quickly extracted from the aged insulation is only 1.5 years, which is just 4 %.
samples. Note that thin pressboard of 1 mm thickness reached
low water content < 0.5 % after a few hours in all cases, thus
hydrolysis was predominant only at the very beginning of the
drying experiment. In fact, with no oxygen present (i.e. under
vacuum), the DP remained almost unchanged at 105 °C, even
after 14 days of exposure. Yet, the DP decrease at 140 °C was
still pronounced even with vacuum, which indicates increasing
pyrolysis decomposition of cellulose at elevated temperature as
detailed in [2].

Fig. 4 Comparison of the DP decrease with time at 85 °C. Red solid line:
DP0 1200, dotted black line: DP0 1000.

Fig. 5 shows the calculated remaining lifetime as a function

of any initial DP0 value lower than 1200 and the assumption of
DP 200 as end-of-life. Even considering an allegedly heavily
pre-aged DP0 of 800, it can be seen that the loss of life is only
10 percent.
100
Fig. 3 DP of high density pressboard, 1 mm thick, initial water content 6 %,
90
subjected to drying in a hot air circulation oven (solid lines) and
under vacuum (dashed lines). 80
Service life (%)

70
From this experiment, it can be concluded that vacuum is
60
essential for smooth drying, but its "DP-preserving" effect is
reduced at high temperature, despite the absence of oxygen. At 50

vacuum drying temperatures above 120 °C, (premature) aging 40

of cellulosic insulation has to be taken into account. In practice, 30

care must be taken in the factories when insulation is pre-dried, 20

which is sometimes necessary in order to obtain the final 10
shrunk dimensions of certain cellulosic insulation components, 0
e.g. winding cylinders. Oxygen-free conditions have 1200 1000 800 600 400 200
considerably better “DP-preserving" effect at temperatures of Initial degree of polymerization

120 °C and below.

Fig. 5 Relative lifetime as a function of the initial DP0 and the end-of-life
criterion reached with DP 200.
V. DISCUSSION
Depending on the assumption of the end-of-life criterion,
A commonly used formula expressing the change of the lifetime can be expected to be different. Fig. 6 depicts the
degree of polymerization DPt as a function of time t is given in calculated relative change, with DP0 of 1200.
(6) [11]. DP0 is the initial DP value, A is a constant, EA is the
activation energy, R (8.314 J·K-1·mole-1) is the universal gas
constant and T the absolute temperature.

270
 250
the trees, the chemical treatment of the wood as well as
the paper and board manufacturing process.
200
Life expectancy (%)

• There are various definitions of the DP. Therefore, a

150
DP number depends on the used definition, respectively
the measuring method, and in consequence the DP
100
number will defer significantly. Most commonly, the
transformer industry uses the viscometric methods
according to IEC or ASTM.
50
• The impact of drying new pressboard on the DP is
investigated. Care must be taken to avoid premature
0
400 350 300 250 200 150 100 50 0
aging. Vacuum drying (absence of oxygen) provides
End degree of polymerization less DP loss at drying; yet, at temperatures around
140 °C and above, the aging process is presumed to be
Fig. 6 Relative life expectancy as a function of the end-of-life DP noticeably pyrolysis based and thus DP loss is
definition. Basis of the calculation is DP0 = 1200 significant even under vacuum.
It is important to recognize that insulation end-of-life as • A contribution to the discussion of acceptable initial DP
marked by imminent transformer failure is not reached at a numbers is given. It is demonstrated that pre-aged
particular DP value; this arbitrary DP value is a insulation, with an initial DP value as low as 800, still
mathematical convenience only. In fact, the mechanical has a remaining lifetime of approximately 90 % of that
properties of kraft paper are non-linear with DP, as can be of virgin insulation with DP 1200.
clearly identified for elongation and for tensile strength in
Fig. 7.

REFERENCES

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Fig. 7 Correlation between the degree of polymerization and the
mechanical characteristics of creped kraft paper. After [12]
VI. CONCLUSION
This paper discusses various topics around the degree of
polymerization of cellulosic insulation and its importance on
lifetime of power transformers.
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