On the degradation evolution equations of cellulose

H. -Z. Ding Z. D. Wang

Received: 18 January 2007 / Accepted: 9 August 2007 / Published online: 7 October 2007
Springer Science+Business Media B.V. 2007
Abstract Cellulose degradation is usually charac-
terized in terms of either the chain scission number or
the scission fraction of cellulose unit as a function of
degree of polymerisation (DP) and cellulose degra-
dation evolution equation is most commonly
described by the well known Ekenstam equations.
In this paper we show that cellulose degradation can
be best characterized either in terms of the percentage
DP loss or in terms of the percentage tensile strength
(TS) loss. We present a new cellulose degradation
evolution equation expressed in terms of the percent-
age DP loss and apply it for having a quantitative
comparison with six sets of experimental data. We
develop a new kinetic equation for the percentage TS
loss of cellulose and test it with four sets of
experimental data. It turns out that the proposed
cellulose degradation evolution equations are able to
explain the real experimental data of different
cellulose materials carried out under a variety of
experimental conditions, particularly the prolonged
autocatalytic degradation in sealed vessels. We also
develop a new method for predicting the degree of
degradation of cellulose at ambient conditions by
combining the master equation representing the
kinetics of either percentage DP loss or percentage
TS loss at the lowest experimental temperature with
Arrhenius shift factor function.
Keywords Cellulose Degradation
Kinetics Modelling Degree of polymerisation
Tensile strength Percentage loss
Timetemperature superposition
Arrhenius activation energy
Introduction
Cellulose is the main raw material in paper industry
and has been widely used as storage paper in books
and documents, and as insulating paper/pressboard in
high-voltage oil-lled power cables and transformers.
In all applications, methods of characterizing cellu-
lose degradation and kinetics of cellulose degradation
evolution are important, because they not only govern
the long-term performance of the paper products but
also ultimately determine the useful life of books,
documents, power cables and transformers. The
research into the characterization of cellulose degra-
dation and the kinetics of cellulose degradation
evolution has been a topic for decades and has made
considerable progress. Briey, there are three steps in
analysing the kinetics of cellulose degradation. The
rst step is to characterize the degradation (i.e., to
dene the degradation variable) because degradation
is not a quantity that can be directly measured. The
second step is to describe the evolution equation of
H. -Z. Ding (&) Z. D. Wang
School of Electrical and Electronic Engineering, The
University of Manchester, P O Box 88, Sackville Street,
Manchester M60 1QD, UK
e-mail: hongzhi.ding@manchester.ac.uk
1 3
Cellulose (2008) 15:205224
DOI 10.1007/s10570-007-9166-4
degradation variable, which shows how the stressing
conditions lead to new degradation in the cellulose.
These rst two steps essentially establish the consti-
tutive relationship of cellulose with defects. The third
step is to use the established constitutive relationship
in the kinetics analysis to predict the degree of
degradation of cellulose at ambient conditions and
the result regarding when the cellulose will fail.
Characterization of cellulose degradation
The characterization of the degradation includes
choosing a proper variable to describe the defects
of the cellulose at the molecular level, and to nd out
how these defects affect the macroscopic behaviours
of the cellulose. It is well recognized today that all
thermal, hydrolytic, photolytic, photochemical and
enzymatic degradation of cellulose are essentially
due to the scission of polymeric chains (a number of
the b-glucosidic bonds being broken). The method
most commonly used in the literature for character-
izing cellulose degradation involves the
determination of either the Chain Scission Number
(CSN) or the Scission Fraction of Cellulose Unit
(SFCU) as a function of degree of polymerisation
(DP). DP can be determined from the measured
change of the intrinsic viscosity using the Mark
Houwink equation.
The CSN, which represents the average number of
chain scissions per cellulose chain unit during the
time course of degradation, can be calculated using
the following equation (Hon 1985; Moser and
Dahinden 1987; Johansson et al. 2000; Bouchard
et al. 2006; Calvini and Gorassini 2006)
CSN =
DP
0
DP
1 (1)
where DP
0
and DP are the degree of polymerisation
before and after the degradation.
The SFCU, which represents the ratio of broken
glucose units to the total glucose units of a cellulose
chain, can be calculated using the following equation
(Hon 1985; Chen and Lucia 2003)
SFCU =
CSN
DP
0
=
1
DP

1
DP
0
(2)
Multiplying the SFCU by a factor of 100 gives the
percentage of the initial bonds that have been broken.
The evolution equations of cellulose degradation
The method most usually used in the literature for
following the kinetics of cellulose degradation
involves the determination of the SFCU as a function
of ageing time (t), which assumed a random rst-order
chain scission reaction relationship and showed (Eken-
stam 1936; Sharples 1971; Emsley and Stevens 1994)
ln 1
1
DP
0

ln 1
1
DP

= kt (3)
If DP
0
and DP are large, then Eq. 3 reduces to
1
DP

1
DP
0
= kt (4a)
This approximation is identical with the expression
obtained by assuming a zero-order reaction. Here k is
the reaction rate constant. Equation 4a is derived for
a homogeneous cellulose system. In a heterogeneous
cellulose system, the effect of physical structure on
hydrolysis degradation has to be taken into account,
and the generally approach involves the introduction
of the accessible fraction of bonds (a) in a practical
cellulose system in the determination of the rate of
bond scission, then (Sharples 1954, 1971)
1
DP

1
DP
0
= akt (4b)
Equations 3 and 4a are named as Ekenstam
equations in the literature. The important point in
Eq. 4a, as was argued by Sharples (1971), is that a
rectilinear plot is obtained if the reciprocal of DP is
plotted as a function of the time; while the direct plot
of DP as a function of time takes the form of a
rectangular hyperbola which is considered to be
obviously misleading. Equation 4a has been widely
used to describe various cellulose degradation such as
acidic degradation, light ageing, dry or moist thermal
ageing in ovens (Krassig and Kitchen 1961; Fung
1969; Shazadeh and Bradbury 1979; Zou et al. 1994,
1996; Testa et al. 1994). Emsley and Stevens (1994)
have shown that Eq. 4a holds for the majority of the
accelerated ageing data available in the literature for
thermal degradation of Kraft paper under a variety of
experimental conditions (in vacuo, in nitrogen, air
and oxygen, and in transformer oil). Zou et al. (1996)
have arrived to the same Eq. 4a without any
assumptions about the reaction order, by assuming a
constant bond breaking rate.
206 Cellulose (2008) 15:205224
1 3
While the traditional ethos of the subject has been
to assume that the kinetics of cellulose degradation
can be described by Ekenstam equation (4a), a
considerable number of studies have demonstrated
that when plotting the SFCU vs. degradation time, the
deviations from Ekenstam equation (4a) can result in
a downward curvature of the kinetic plot of the
measured DP data, so that two or three distinct
degradation phases with differing chain-scission rates
can be distinguished (Daruwalla and Narsian 1966;
Feller et al. 1986; Strlic et al. 2001); and when the
DP approaches the levelling-off degree of polymer-
isation (LODP), Ekenstam equation (4a) becomes
fairly invalid (Emsley et al. 1997; Heywood et al.
1999). In a letter to the Editor published in a previous
issue of Cellulose, Emsley and Heywood (1997) have
rst proposed that the reaction rate k in Eq. 4a should
not be a constant but decrease with the ageing time;
and the measured DP data is better represented by a
degradation rate equation:
1
DP

1
DP
0
=
k
10
k
2
[1 exp(k
2
t)[ (5)
where k
10
and k
2
are constants. More recently, Zervos
and Moropoulou (2005) have proposed a kinetic
model that describes the autocatalytic depolymerisa-
tion of pure cotton cellulose in sealed vessels as
1
DP

1
DP
0

100 = a[2
kt
1[ (6)
where k and a are constants. It has been shown by
Zervos and Moropoulou (2005) that Eq. 6 can t the
accelerated ageing data of Whatman (No. 2) lter
paper in sealed glass jars of 761% relative humidity
at 80 C up to 150 days.
The kinetic models described so far in the
literature, only deal with the extent of cellulose
degradation in terms of the SFCU, i.e., the difference
between two reciprocal values of DP, and as a
consequence, as has been pointed out by Calvini and
Gorassini (2006), every experimental uncertainty
about the actual values of DP
0
and DP is amplied
in the determination of the extent of cellulose
degradation. Recognizing this critical point and for
the purpose of minimizing the sources of errors,
Calvini and Gorassini (2006) have proposed that a
ratio between the values of DP should be introduced
into the rate equation of cellulose degradation, and
they use CSN developing a rate equation of cellulose
degradation as
DP
0
DP
1

=
DP
0
LODP
1

+ 1 e
kt

(7)
However, the CSN concept is suitable only when the
degree of polymerisation of the celluloses is the same
value; it is not suitable for characterizing the chain
scission activity of cellulose. This is because the CSN
of cellulose with a high DP value is greater than that
of cellulose with a low DP value when the chain
scission activity of cellulose is the same (Chen and
Lucia 2003).
To summarize our current understanding of both
characterizing the cellulose degradation and devel-
oping the cellulose degradation evolution equations,
although the methods developed are successful in
different respects, quantitative understanding is still
limited, which obviously can be attributed to the
complexity of the cellulose degradation problem
itself.
The aim of the present study is to develop an
alternative approach to characterizing cellulose deg-
radation. A new degradation evolution equation of
cellulose expressed in terms of the percentage DP
loss will be developed and its validity and universal-
ity will be tested by comparing with the data
available in the literature for degradation of different
cellulose materials carried out under a variety of
experimental conditions. Further, correlation between
the proposed degradation evolution equation and
Ekenstam equations (3) and (4a) as well as the
percentage TS loss will be addressed. Finally, by
applying timetemperature superposition method the
Arrhenius activation energy value for each set of
experimental data will be determined and compared
with existing published data.
Characterization of cellulose degradation in terms
of the percentage DP loss
Any scheme for characterization of cellulose degra-
dation should satisfy two requirements. One is to
include the essential physical aspects of degradation
process and another is that its mathematical structure
must be amenable to the desired analysis. This in our
case means that a description of cellulose degradation
Cellulose (2008) 15:205224 207
1 3
that produces consistent relationships between deg-
radation and material response and allows
representation of degradation evolution rates is
needed.
The idea to characterize cellulose degradation in
terms of the percentage DP loss is based on the
essential degradation mechanism in cellulose. Cellu-
lose consists of linear, polymeric chains of cyclic, b-
D-glucopyranosyl units, and the number of such units
per chain is called the degree of polymerisation. The
chains of cellulose associate in both crystalline and
amorphous regions to form micro-brils, and nally
form bres. Thus, the depolymerisation and the
increase in the number of chain scissions is the
essential mechanism of cellulose degradation, and the
irreversibility is caused by the energy dissipation
associated with acid-hydrolysis, oxidation and pyro-
lysis. A basic unit or entity of cellulose degradation
process is a chain scission. In view of the fact that
there is a well-documented connection between the
decrease of DP and the severity of cellulose degra-
dation, without loss of generality, we can introduce a
continuous scalar variable d and call it percentage
retention of DP:
d =
DP
DP
0
(8)
where DP
0
denotes the initial degree of polymerisa-
tion and DP the real degree of polymerisation,
decreased as a result of deterioration due to degra-
dation of cellulose. The variable d starts from d = 1
and decreases to d = 0 (or LODP results in a certain
value d
c
); the last value denotes total failure.
Degradation variable of cellulose can then be
dened in terms of the percentage DP loss as
x
DP
= 1 d = 1
DP
DP
0
(9)
where x
DP
is the accumulated DP loss of cellulose.
Using Eq. 9 the extent of cellulose degradation can
be quantied by measuring the DP of the cellulose; it
starts from x
DP
= 0, which corresponds to virgin
cellulose and the 100% retention of DP, ending with
x
DP
= 1, which corresponds to total failure of
cellulose. It should be noted here that for the failure
state of cellulose, the accumulated degradation may
be not necessary to reach the theoretical maximal
value of x
DP
, namely x
DP
= 1, but a certain smaller
value of x
DPcr
depending on specic experimental
conditions. It is generally accepted that when the DP
has decreased to an average DP of about 200 the
cellulose paper will lose all its mechanical strength; if
DP
0
= 1,200, then d
c
= 0.1667, and the accumulated
degradation critical value x
DPcr
= 0.8333.
As a method of expressing the rate of cellulose
degradation, the percentage DP loss is calculated
from the ratio between the values of DP. With this
method, the expression of degradation is not only
mathematically convenient but also more accurate
than the usual SFCU or CSN method. Further,
according to the present denition of cellulose
degradation by Eq. 9, the physical meaning of the
degradation variable x
DP
is the extent of progression
towards a maximum tolerable value, and the nature of
ageing in cellulose is that degradation accumulates
gradually in the course of stressing time and failure
occurs when these reaches a critical level.
Degradation evolution equation of cellulose
expressed in terms of the percentage DP loss
Degradation evolution equation of cellulose at a
molecular level
We begin our theoretical analysis by discussing chain
scission degradation of polymer at a molecular level.
Experimental and analytical investigations have
demonstrated that degradation of cellulose is due to
thermally activated polymeric chain scissions. Thus,
chemical reaction rate theory has been widely
employed to model cellulose degradation processes.
The exact mechanisms that lead to failure of cellulose
materials, however, are not known a priori. As a
consequence, various hypotheses have to be proposed
and sophisticated models with unknown parameters
have to be developed. Whatever the exact mecha-
nisms may be, it appears that degradation evolution
equations based on chemical reaction rate theory
describe the kinetics of cellulose degradation reason-
ably well, although certain modications may be
necessary to account for experimental observations.
On the other hand, there is now a great deal of
experimental evidence in polymers that chain scis-
sion occurs during the degradation and failure of
polymers and particularly, although the concentration
of chain scissions is a time function of the degrada-
tion, the total accumulation of chain scissions at
208 Cellulose (2008) 15:205224
1 3
failure for a given polymer is, to a good approxima-
tion, independent of the loading conditions
(Kukensko and Tamuzs 1981). The chain scission
concentration N of a polymer thereby represents a
logical scalar parameter with which to characterize
degradation within the material.
In order to quantitatively model the kinetic process
of cellulose degradation, it is assumed that on the
molecular level degradation is the result of chain
scission and, there exists, at time equals zero, a
certain number of potentially weak bonds denoted by
N
T
, which will be available for the degradation.
Therefore, according to chemical reaction rate theory,
the rst-order reaction kinetics of degradation can be
written as
dN
dt
= k N
T
N ( ); N(t = 0) = 0 (10)
The above differential equation relates the time rate
of change of the accumulated chain scission concen-
tration to the number of weak bonds available times
the chain scission reaction rate. Here k is the chain
scission reaction rate constant, and the initial condi-
tion implies that the material has undergone no
previous chain scission.
The general solution to Eq. 10 is given by
N(t) =
Z
t
0
N
T
k(x) exp
Z
t
x
k(y)dy

dx (11)
But for a constant reaction rate k the exact solution
may be written in the form
N = N
T
(1 e
kt
) (12)
If N -- N
T
; then
N N
T
kt (13)
This expression is identical with a zero-order approx-
imation solution of Eq. 10. As was noticed by Calvini
(2005), it is not difcult to verify that Ekenstam
equations (3) and (4a) can be derived from the above
Eqs. 12 and 13, respectively, if we consider that
N = SFCU = (1/DP1/DP
0
) and N
T
= (11/DP
0
).
Also, it is easy to verify that Eq. 7 can be derived
from Eq. 12, if we consider that N = CSN = (DP
0
/
DP1) and N
T
= (DP
0
/LODP1) (Calvini and Goras-
sini 2006).
Bear in mind that the chain scission concentration
in polymers at failure N
F
is approximately a constant.
We can therefore introduce a normalized chain
scission degradation variable of the form
n(t) =
N(t)
N
F
(14)
Based on this denition, we can quantify the degree of
degradation at a molecular level as follows: (1) n = 0
corresponds to no degradation; (2) n = 1 corresponds
to failure; and (3) 0 \n \1 implies that the material
has undergone some permanent chain scission degra-
dation. In terms of the normalized chain scission
degradation variable, Eq. 10 becomes
dn
dt
= k(n
+
n); n(t = 0) = 0 (15)
where n
*
= N
T
/N
F
represents the capacity of the chain
scission reservoir. For a constant reaction rate k the
time-evolution equation of the normalized chain
scission degradation variable n(t) obeys
n = n
+
(1 e
kt
) (16)
Equations 15 and 16 stand for the evolution rules of
cellulose degradation at a molecular level. We note
that expressions similar to Eqs. 15 and 16 have been
reported in the literature for describing the kinetics of
mechanochemical scission of the main chains of
polymer molecules (Zhurkov and Korsukov 1974;
Petrov 1984; Hansen and Baker-Jarvis 1990).
A new degradation evolution equation for
cellulose
In view of the similarity between two denitions of
degradation state variable, n at a molecular level and
x
DP
at a macroscopic level, without loss of gener-
ality, we can assume that the differential equation
governing the time dependence of x
DP
at a macro-
scopic level has exactly the same form as that of n at
a molecular level. Thus, analogous to Eq. 15, the
degradation evolution equation governing the time
dependence of x
DP
for cellulose assumes the form
dx
DP
dt
= k
DP
(x
+
DP
x
DP
); x
DP
(t = 0) = 0 (17)
Equation 17 relates the time rate of change of the
accumulated DP degradation of cellulose, dx
DP
/dt, to
the residual DP level available for the degradation,
Cellulose (2008) 15:205224 209
1 3
(x
DP
*
x
DP
), times the DP degradation reaction rate
k
DP
. The initial condition, x
DP
(t = 0) = 0, implies
that the cellulose has undergone no previous degra-
dation. For a constant reaction rate k
DP
the exact
solution of Eq. 17 reads
x
DP
= 1
DP
DP
0
= x
+
DP
(1 e
k
DP
t
) (18)
This is a new degradation evolution equation for
cellulose. We call parameter x
DP
*
of Eq. 18 the
capacity of the DP degradation reservoir. The value
of parameter x
DP
*
can be determined by introducing
the constraint condition x
DP
(t = t
f
) = 1, t
f
is the time
to failure.
A model equation and its parameters can be
accepted if, and only if a reasonable t can be
achieved by data from several experiments carried
out at different experimental conditions. The follow-
ing section will discuss how well the new cellulose
degradation evolution equation (18) ts with the data
available in the literature for degradation of different
cellulose materials under a variety of experimental
conditions.
Verication of the model equation (18) with
experimental data
Six sets of experimental data are used here to
demonstrate the application of the proposed cellulose
degradation evolution equation (18) in real cellulose
samples.
Ageing data of BBSP handsheets in completely
seal vessels and 75% RH
Figure 1 shows plots of the degree of degradation
change during accelerated ageing of bleached bisul-
te pulp (BBSP) handsheets in completely sealed
glass jars, together with the corresponding model
predictions using Eq. 18. The paper ageing data are
originally reported by Zou et al. (1996) in the form of
DP vs. accelerated ageing time. The BBSP samples
were those of bleached softwood bisulte pulp
originating from various Canadian mills and formed
into standard handsheets (60 g/m
2
, DP
0
= 1,336).
Ageing experiments were conducted at temperatures
ranging from 60 to 100 C and a relative humidity of
75% (a saturated NaCl solution was placed in the jar
to obtain a desired relative humidity). After acceler-
ated aging treatment, the samples were conditioned at
23 C and 50% RH for at least 24 h, and then tested.
The estimated values of the parameters for each curve
tting are given in Table 1, with the values of all the
regression coefcients R
2
[0.990. Note that herein-
after all nonlinear regression analyses were
preformed using Origin 6.0 software and a minimum
chi-square (Chi
2
) algorithm to obtain best-t param-
eters for Eq. 18.
Ageing data of Kraft paper in air
Figure 2 shows plots of the degree of degradation
change during accelerated ageing of Kraft pulp paper
in air, together with the corresponding predictions by
0 20 40 60 80 100 120
0.0
0.2
0.4
0.6
0.8
1.0
data of 60
o
C
data of 70
o
C
data of 80
o
C
data of 90
o
C
data of 100
o
C
fitting curves by Eq.(18)
fitting curves by Eq.(21)
D

f
o

e
e
r
g
e
,
n
o
i
t
a
d
a
r
g
e
d

P
D
Ageing time (days)
Fig. 1 Degree of degradation change during thermal ageing of
bleached bisulte pulp handsheets in completely sealed glass
jars of 75% relative humidity; experimental data of DP are
after Zou et al. (1996)
Table 1 Calculated parameters for tting equations (18) and
(21) to the data in Fig. 1
T (C) Equation 18 Equation 21
x
DP
*
k
DP
(1/day)
R
2
k ( 10
5
,
1/day)
R
2
60 0.5422 0.0083 0.9917 0.3338 0.9910
70 0.6359 0.0206 0.9930 1.0195 0.9931
80 0.7407 0.0378 0.9970 2.4469 0.9967
90 0.7686 0.1180 0.9982 8.2545 0.9993
100 0.8364 0.1846 0.9904 15.060 0.9760
210 Cellulose (2008) 15:205224
1 3
Eq. 18. The paper ageing data are originally reported
by Soares et al. (2001) in the form of DP vs. ageing
time. The paper samples were made by Mukyuo in
Sweden for transformer grade (774 kg/m
3
, DP
0
=
1,183). Ageing experiments were conducted in air
for up to 140 h in the temperature range 70120 C.
The estimated values of the parameters for each curve
tting are given in Table 2, with the values of all the
regression coefcients R
2
[0.996.
Ageing data of Kraft paper in transformer mineral
oil at high water/oxygen level
Figure 3 shows plots of the degree of degradation
change during thermal ageing of Kraft pulp paper
(774 kg/m
3
, DP
0
= 1,183) in mineral transformer oil,
together with the corresponding predictions using
Eq. 18. The ageing data are originally reported by
Soares et al. (2001) in the form of DP vs. ageing
time. The transformer oil for ageing experiments was
Texaco grade DNC 3230 standard mineral oil, used
as received. Ageing experiments were conducted in
transformer oil for up to 3,500 h in the temperature
range 65120 C. Air was not excluded during the
varying period of ageing. The estimated values of the
parameters for each curve tting are given in Table 3,
with the values of all the regression coefcients
R
2
[0.974.
Ageing data of Kraft paper in transformer mineral
oil at low water/oxygen level
Figure 4 shows plots of the degree of degradation
change during thermal ageing of Kraft insulation
paper (DP
0
= 1,250) in mineral transformer oil at
low-water/low oxygen levels, together with the
corresponding predictions using Eq. 18. The DP data
are originally reported by Emsley et al. (2000a).
Before starting the ageing experiments, the Kraft
paper (from Tullis Russell) samples were dried in a
pot overnight at 115 C under vacuum, and the
transformer oil was degassed at 60 C overnight in a
vacuum. The water in the paper was measured to be
less than 0.1% and the oxygen in the oil less than
400 ppm. Ageing experiments were conducted in
degassed transformer oil for up to 12,000 h in the
temperature range 120160 C. The estimated values
of the parameters for each curve tting are given in
0 20 40 60 80 100 120 140
0.0
0.2
0.4
0.6
0.8
1.0
data of 70
o
C
data of 80
o
C
data of 90
o
C
data of 105
o
C
data of 120
o
C
fitting curves by Eq.(18)
fitting curves by Eq.(21)

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

P
D
Ageing time (hours)
Fig. 2 Degree of degradation change during thermal ageing of
Kraft paper in air; experimental data of DP are after Soares
et al. (2001)
Table 2 Calculated parameters for tting equations (18) and
(21) to the data in Fig. 2
T (C) Equation 18 Equation 21
x
DP
*
k
DP
(1/h) R
2
k ( 10
6
, 1/h) R
2
70 0.1952 0.0227 0.9968 1.9189 0.8613
80 0.2796 0.0199 0.9987 2.8741 0.9212
90 0.4149 0.0248 0.9969 5.7227 0.9260
105 0.4357 0.0294 0.9995 6.7625 0.9084
120 0.5015 0.0351 0.9959 9.5182 0.9131
0 500 1000 1500 2000 2500 3000 3500
0.0
0.2
0.4
0.6
0.8
1.0

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

P
D
Ageing time (hours)
data of 65
o
C
data of 80
o
C
data of 120
o
C
fitting curves by Eq.(18)
fitting curves by Eq.(21)
Fig. 3 Degree of degradation change during thermal ageing of
Kraft paper in transformer mineral oil; experimental data of DP
are after Soares et al. (2001)
Cellulose (2008) 15:205224 211
1 3
Table 4, and the minimum value of the regression
coefcient for the data at 120 C is R
2
= 0.9167.
Ageing data of pure cotton cellulose in sealed
vessels at 80 C and 75% RH
Figure 5 shows plots of the degree of polymerisation
and the degree of degradation change during thermal
ageing of pure cotton cellulose in sealed vessels,
together with the corresponding predictions using
Eq. 18. Application of Eq. 6 has also been included
in Fig. 5 for comparison. The experimental data are
originally reported by Zervos and Moropoulou (2005)
in the form of viscosity-average DP
v
vs. ageing time.
The pure cotton cellulose samples were Whatman
(No. 2) lter papers (DP
v
0
= 1; 810; cut in test-strips
of 15 mm width). Ageing experiments were con-
ducted in sealed glass jars of 761% relative
humidity at 80 C up to 240 days. The estimated
values of the parameters for curve tting are given in
Table 5, and the value of the regression coefcient is
R
2
= 0.9954.
Ageing data of thermally upgraded Kraft paper in
sealed vessels with mineral transformer oil and
natural ester respectively
Figure 6 shows plots of the degree of degradation
change during thermal ageing of thermally upgraded
Kraft insulation paper in sealed metallic tubes at
160 C with mineral transformer oil and natural ester
(vegetable oil) dielectric uid, respectively, together
with the corresponding predictions using Eq. 18. The
experimental data of DP are originally reported by
McShane et al. (2003). Sealed steel ageing vessels
with a nitrogen headspace of 17% by volume
Table 3 Calculated parameters for tting equations (18) and
(21) to the data in Fig. 3
T (C) Equation 18 Equation 21
x
DP
*
k
DP
(1/h) R
2
k ( 10
6
, 1/h) R
2
65 0.3032 0.0005 0.9740 0.1014 0.9351
80 0.6983 0.0018 0.9931 1.0059 0.9377
120 0.7554 0.0032 0.9971 1.8681 0.8972
0 2000 4000 6000 8000 10000 12000
0.0
0.2
0.4
0.6
0.8
1.0
g
e
D
r
o

e
e
f
g
e
d

t
a
d
a
r
,
n
o
i

P
D
Ageing time (hours)
data of 120
o
C
data of 140
o
C
data of 160
o
C
fitting curves by Eq. (18)
fitting curves by Eq. (21)
Fig. 4 Degree of degradation change during thermal ageing of
Kraft paper in transformer mineral oil at low-water/low oxygen
levels; experimental data of DP are after Emsley et al. (2000a)
0 40 80 120 160 200 240 280
0.0
0.2
0.4
0.6
0.8
1.0

DP
data at 80
o
C
fitting curve by Eq. (18)
fitting curve by Eq. (21)
,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

P
D
Ageing time (days)
0.0
0.2
0.4
0.6
0.8
1.0
DP data at 80
o
C
fitting curve by Eq. (6)
P
D
/
1
-
P
D
/
1
(
0
0
0
1
x
)
Fig. 5 Degree of degradation change during thermal ageing of
pure cotton cellulose in sealed vessels; experimental data of DP
are after Zervos and Moropoulou (2005)
Table 4 Calculated parameters for tting equations (18) and
(21) to the data in Fig. 4
T (C) Equation 18 Equation 21
x
DP
*
k
DP
(1/h) R
2
k ( 10
6
, 1/h) R
2
120 0.6600 0.0008 0.9167 0.3200 0.8199
140 0.9000 0.0018 0.9719 2.0080 0.9865
160 0.9500 0.0063 0.9796 8.0000 0.9673
Table 5 Calculated parameters for tting equations (18) and
(21) to the data in Fig. 5
T (C) Equation 18 Equation 21
x
DP
*
k
DP
(1/day)
R
2
k ( 10
5
,
1/day)
R
2
80 1.0100 0.0137 0.9954 1.5503 0.9458
212 Cellulose (2008) 15:205224
1 3
containing thermally upgraded 0.255 mm Kraft paper
(26 g), dielectric uid (mineral transformer oil or
natural ester 350 mL), aluminium metal strip
(106 cm
2
) copper metal strip (76 cm
2
) and the mild
steel inner surface of the tube (323 cm
2
) were aged at
160 C for 250, 500, 750, 1,000, 1,500, and 3,000 h.
The paper was dried to approximately 0.5 wt.% water
content and the insulating uids were dried and
degassed. The initial DP values at 20 C are 1,152 in
mineral oil and 1,148 in natural ester, respectively.
The estimated values of the parameters for curve
tting are given in Table 6, and the values of the
regression coefcient are R
2
= 0.9970 for the data in
mineral oil and R
2
= 0.9985 for the data in natural
ester, respectively.
In summary, as shown clearly in Figs. 16 and
Tables 16, the present cellulose degradation evolu-
tion equation (18) has explained the real experimental
data of different cellulose materials carried out under
a variety of experimental conditions. The validation
and universality of the cellulose degradation evolu-
tion equation (18) expressed in terms of the
percentage DP loss can therefore be made.
Discussions
As has been mentioned in the introduction, it is well
recognized now that when take into account the effect
of cellulose structure on hydrolysis degradation, the
entire course of heterogeneous hydrolysis (depoly-
merisation) of cellulose cannot be described by a
single rst-order chain scission reaction kinetic equa-
tion but can be best represented by two or three rates
of reaction. The reason is that there is a mass transfer
difference between crystalline and amorphous struc-
ture, and when the amorphous regions are hydrolysed
which corresponds to fast kinetics of initial depoly-
merisation, and when the crystalline structure (LODP)
is depolymerised which corresponds to very slow
penetration rate and hydrolysis rate. Thus, it is
remarkable to observe that the present cellulose
degradation evolution equation (18) is able to explain
the real experimental data involving all depolymer-
isation processes of different cellulose materials
carried out under a variety of experimental conditions,
particularly the prolonged autocatalytic degradation
in sealed glass vessels with 761% relative humidity
at 80 C up to 240 days (Fig. 5 and Table 5), and in
sealed metallic tubes at 160 C with mineral trans-
former oil and natural ester (vegetable oil) dielectric
uid, respectively, up to 3,000 h (Fig. 6 and Table 6).
Although Eq. 18 gives a good quantitative t to
the calculated variation of degree of degradation with
ageing time over a wide temperature range and varied
experimental conditions, it is not derived from the
rigorous application of the relationship between the
number-average DP and the number of bond avail-
able for the degradation. Thus, further study about the
physical basis of Eq. 18 is needed.
Investigation into a possible correlation between
degradation evolution equation (18) and
Ekenstam equations (3) and (4a)
Starting fromEkenstamequation (3), which is the exact
rst-order relationship between the number-average DP
0 500 1000 1500 2000 2500 3000 3500
0.0
0.2
0.4
0.6
0.8
1.0

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

P
D
Ageing time (hours)
data in mineral oil
data in natural ester
fitting curves by Eq. (18)
fitting curves by Eq. (21)
Fig. 6 Degree of degradation change during thermal ageing of
thermally upgraded Kraft insulation paper in sealed metallic
tubes at 160 C with mineral transformer oil and natural ester,
respectively; experimental data of DP are after McShane et al.
(2003)
Table 6 Calculated parameters for tting equations (18) and
(21) to the data in Fig. 6
T = 160 C Equation 18 Equation 21
x
DP
*
k
DP
(1/h)
R
2
k ( 10
6
,
1/h)
R
2
In mineral oil 0.9963 0.0011 0.9970 1.8924 0.9692
In natural ester 0.7076 0.0013 0.9985 0.8624 0.9845
Cellulose (2008) 15:205224 213
1 3
and the number of bond available for the degradation,
simply by making a rearrangement in Eq. 3 it is not
difcult to have the following form
1
DP
DP
0
=
(DP
0
1)
1 (DP
0
1)(1 e
kt
)
(1 e
kt
)
(19)
We call Eq. 19 a modied Ekenstam equation, which
is exactly identical to Eq. 3.
It is interesting to observe that the new cellulose
degradation evolution equation (18) looks exactly the
same as Eq. 19 if we can assume that k
DP
is equal to k
and
x
+
DP
=
(DP
0
1)
1 (DP
0
1)(1 e
kt
)
(20)
It is important to realize that x
DP
*
in Eq. 18 is
independent of time but according to Eq. 20 is a
function of degradation time. However, this obser-
vation has interesting potential for further study.
According to Eq. 20, the minima of x
DP
*
is (11/
DP
0
); i.e., we will always have x
DP
*
[11/DP
0
.
Applying this result for six sets of experimental data
plotted in Figs. 16 and it is easy to show that
x
DP
*
[11/DP
0
means x
DP
*
[0.9990 for all exper-
imental data. However, the preceding analysis of the
experimental data according to Eq. 18 has resulted
in the evaluation of x
DP
*
, as shown in Tables 16.
Nearly all values of x
DP
*
in Tables 16 are smaller
than (11/DP
0
) except the value x
DP
*
= 1.01 in
Table 5. The larger value of x
DP
*
= 1.01 in Table 5
was attributed obviously to the fact that the
degradation process was a prolonged autocatalytic
reaction process, which in our opinion, means a
promoted number of effective chains taking part in
scission so that the required chain scission number
at failure under such an autocatalytic reaction
condition is less than the available number of
potentially weak bonds.
Due to its complex expression, the modied
Ekenstam equation (19) is mathematically not con-
venient to be utilized in explaining real experimental
data. When both DP
0
and DP are large (i.e., the extent
of DP degradation reaction is small), using the
approximation as same as in the Ekenstams
approaches in obtaining Eq. 4a, the modied Eken-
stam equation (19) can be simplied as
1
DP
DP
0
=
DP
0
kt
1 DP
0
kt
(21)
This equation is exactly identical to the widely used
Ekenstam equation (4a). Application of Eq. 21 and
comparison with real experimental results of cellu-
lose degradation have been included in Figs. 16 and
Tables 16.
To this end, a simple but far-reaching statement
can now be made. In short, some experimental data
can be described equally well with both Eqs. 18 and
21. However, this does not mean that all data that can
be described by Eq. 18 can also be described by
Eq. 21. For example, in Figs. 2, 5, such experimental
data can hardly be described by Eq. 21. Bear also in
mind that the constraint of x
DP
*
[11/DP
0
according
to Eq. 20 does not apply for Eq. 18. In these senses
Ekenstam equations (3) and (4a) or (19) and (21) can
be considered (roughly) as a special case of Eq. 18.
Investigation into a possible correlation between
degradation evolution equation (18) and tensile
strength
No attempt is made, in this paper, to include a
detailed study on the possible correlation between the
kinetics of cellulose degradation and the changes in a
wide range of macroscopic properties. In what
follows, we show how the concept of degradation
accumulation in terms of the percentage DP loss
developed in the present study can be used to derive a
kinetic equation for loss of tensile strength of
cellulose and paper.
Bear in mind that the main feature of tensile
strength loss of cellulose and paper is the successive
chain scission in cellulose bre. Accelerated ageing
test of pure cellulose papers in air (Zou et al. 1994)
and Kraft papers in transformer oil (Emsley et al.
2000b) have demonstrated that the loss of tensile
strength during the degradation is due to a decrease in
bre strength and not bond strength loss; and the
decrease in bre strength is due to depolymerisation
of the cellulose caused by acid-catalysed hydrolysis.
Hence, similar to the denition of degradation of
cellulose in terms of the percentage DP loss by Eq. 9,
we can introduce a new degradation variable x
TS
which is dened as the percentage TS loss, from an
214 Cellulose (2008) 15:205224
1 3
initial value of the tensile strength TS
0
to the current
tensile strength TS:
x
TS
= 1
TS
TS
0
(22)
Using the similar arguments as described in the
previous section in deriving the generalized cellulose
degradation equation (18), a new kinetic equation for
loss of tensile strength of cellulose, which is analo-
gous to Eq. 18, can be obtained as
x
TS
= 1
TS
TS
0
= x
+
TS
(1 e
k
TS
t
) (23)
where k
TS
is the TS degradation rate constant and x
TS
*
is the capacity of the TS degradation reservoir. The
value of x
TS
*
can be determined by introducing the
constraint condition: x
TS
(t = t
f
) = 1, t
f
is the time to
failure.
Let us now attempt to reconcile the above Eq. 23
with four specic experimental data reported in the
literature. Figure 7 shows the zero-span tensile
strength loss of Whatman lter paper (II) and cotton
linter sheets during thermal ageing at 90 C and
relative humidity 80% and corresponding regression
analysis t of Eq. 23. The ageing data are originally
reported by Zou et al. (1994). The values of the
parameters for each curve tting are given in Table 7,
and the values of the regression coefcient are
R
2
= 0.9767 for the data of Whatman lter paper
and R
2
= 0.9832 for the data of cotton linter sheets,
respectively.
Figure 8 shows plots of the tensile strength loss vs.
accelerated ageing time for results of thermally
upgraded insulation paper aged in closed, air-tight
system with mineral transformer oil at 120, 135 and
150 C, together with the corresponding predictions
using Eq. 23. The ageing data of TS are originally
reported by Gasser et al. (1999). As reported, the oil
was dried and degassed mineral oil Shell Diala D;
and copper and iron were loaded on to the frames as
catalysts. The weight ratio of Oil:Paper:Cu:Fe in the
ageing experiments was 100:2.5:0.45:0.33. The val-
ues of the parameters for each curve tting are given
in Table 8, with the minimum value of all the
regression coefcients is R
2
= 0.9869.
Figure 9 shows plots of the tensile strength loss vs.
accelerated ageing time for results of thermally
upgraded Kraft paper sealed tube aged at 160 C in
mineral transformer oil and natural ester obtained
from McShane et al. (2003) along with the corre-
sponding regression analysis t made with Eq. 23.
The values of the parameters for each curve tting are
0 5 10 15 20 25
0.0
0.2
0.4
0.6
0.8
1.0

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

S
T
Ageing time (days)
Data of Cotton linter sheets
Data of Whatman filter paper
fitting curves by Eq. (23)
fitting curves by Eq. (25)
Fig. 7 Zero-span tensile strength loss of Whatman lter paper
(II) and cotton linter sheets during thermal ageing at 90 C and
relative humidity 80%; experimental data of TS are after Zou
et al. (1994)
Table 7 Calculated parameters for tting equations (23) and
(25) to the data in Fig. 7
90 C, 80% RH Equation 23 Equation 25
x
TS
*
k
TS
(1/day)
R
2
C
TS
(1/day)
R
2
Cotton linter
sheets
0.3693 0.0851 0.9832 0.0214 0.9205
Whatman lter
paper (II)
0.6983 0.1214 0.9767 0.0644 0.9372
0 50 100 150 200 250 300 350 400
0.0
0.2
0.4
0.6
0.8
1.0

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

S
T
Ageing time (days)
Data of 120
o
C
Data of 130
o
C
Data of 150
o
C
fitting curves by Eq. (23)
fitting curves by Eq. (25)
Fig. 8 Tensile strength loss of thermally upgraded insulation
paper aged in mineral transformer oil; experimental data of TS
are after Gasser et al. (1999)
Cellulose (2008) 15:205224 215
1 3
given in Table 9, and the values of the regression
coefcient are R
2
= 0.9786 for the data in mineral oil
and R
2
= 0.9613 for the data in natural ester,
respectively.
Figure 10 shows plots of the tensile strength loss
vs. accelerated ageing time for results of Kraft
insulation paper aged in dried and degassed trans-
former oil (Shell Diala B) in the temperature range
129166 C under vacuum, together with the corre-
sponding predictions using Eq. 23. The TS data are
originally reported by Hill et al. (1995) in the form of
TS vs. ageing time. The values of the parameters for
each curve tting are given in Table 10, with the
minimum value of all the regression coefcients is
R
2
= 0.9827.
In summary, as shown clearly in Figs. 710 and
Tables 710, the good agreement between the pre-
dictions by Eq. 23 expressed in terms of the
percentage TS loss and experimental data appears
to be justied in principle even with limited data.
It is interesting to note that the good agreement
observed on Figs. 710 was obtained according to
Eq. 23 with two tting parameters, that is much less
than in Emsley and Heywood model (1997) which
have ve tting parameters. Starting from Eq. 5,
Emsley and Heywood (1997) had studied the
correlation between the kinetics of cellulose degra-
dation and the tensile strength loss, and derived a
relationship for loss of tensile strength with time as
follows
Table 8 Calculated parameters for tting equations (23) and
(25) to the data in Fig. 8
T (C) Equation 23 Equation 25
x
TS
*
k
TS
(1/day) R
2
C
TS
(1/day) R
2
120 0.5869 0.0028 0.9958 0.0014 0.9873
130 0.9430 0.0034 0.9869 0.0031 0.9868
150 0.5761 0.0335 0.9978 0.0115 0.9119
0 500 1000 1500 2000 2500 3000 3500
0.0
0.2
0.4
0.6
0.8
1.0
D

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e

S
T
Ageing time (hours)
TS data in mineral oil
TS data in natural ester
fitting curves by Eq. (23)
fitting curves by Eq. (25)
Fig. 9 Tensile strength loss of thermally upgraded Kraft
insulation paper in sealed metallic tubes at 160 C with
mineral transformer oil and natural ester respectively; exper-
imental data of TS are after McShane et al. (2003)
Table 9 Calculated parameters for tting equations (23) and
(25) to the data in Fig. 9
160 C Equation 23 Equation 25
x
TS
*
k
TS
(1/h) R
2
C
TS
(1/h) R
2
In natural
ester
0.3990 0.0008 0.9613 0.0002 0.8460
In mineral
oil
4.7800 0.0001 0.9786 0.0006 0.9027
0 5 10 15 20 25 30
0.0
0.2
0.4
0.6
0.8
1.0
D

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e

S
T
Ageing time (days)
Data of 129
o
C
Data of 138
o
C
Data of 153
o
C
Data of 166
o
C
fitting curves by Eq. (23)
fitting curves by Eq. (25)
Fig. 10 Tensile strength loss of Kraft insulation paper aged in
dried and degassed transformer oil; experimental data of TS are
after Hill et al. (1995)
Table 10 Calculated parameters for tting equations (23) and
(25) to the data in Fig. 10
T (C) Equation 23 Equation 25
x
TS
*
k
TS
(1/day)
R
2
C
TS
(1/day)
R
2
129 1.0000 0.0153 0.9827 0.0153 0.9827
138 0.6419 0.0396 0.9913 0.0211 0.9856
153 0.9537 0.0526 0.9972 0.0490 0.9971
166 0.8030 0.1987 0.9962 0.1118 0.9434
216 Cellulose (2008) 15:205224
1 3
TS TS
0
= K
1
e
k
2
t
K
2
(ln(e
k
2
t
K
3
)) K
4
(24)
where k
2
, K
1
, K
2
, K
3
and K
4
are constants, and TS
0
is
the tensile strength value at the initial. Note that
Eq. 24 was initially developed using air-aged results
of Kraft insulation paper (Emsley et al. 1997) and
had been applied equally to mineral transformer oil-
aged Kraft paper (Emsley et al. 2000b). One dif-
culty with the Emsley and Heywood model Eq. 24 to
make practical estimates from limited ageing exper-
imental data is the relative complexity of tensile
strength loss with time.
It is also noted that one of the earliest kinetic
models for loss of tensile strength of paper in the
literature was formulated empirically by researchers
at Weidmann
1
and reported in their Transformer-
board II (Moser and Dahinden 1987; also Gasser
et al. 1999) as follows:
TS = TS
0
e
C
TS
t
(25a)
where TS
0
and TS are the tensile strength values
before and after an ageing time, respectively, C
TS
is
the coefcient of ageing rate by 1/days and t is the
duration of ageing by days. This kinetic expression
has the advantage of requiring fewer data points, but
can only be applied to long-term ageing of paper. Hill
et al. (1995) have derived the same Eq. 25a with
assumptions that the chain scission reaction can be
represented by a zero-order kinetic but the relation-
ship between the tensile strength and bond scission is
rst-order kinetic model. According to Hill et al.
(1995), the parameter C
TS
in Eq. 25a is a zero-order
rate constant for chain scission. Simply by making a
rearrangement in Eq. 25a it is easy to have the
following form
1
TS
TS
0
= 1 e
C
TS
t
(25b)
This expression is exactly a special case of Eq. 23
when set parameter x
TS
*
= 1. Application of equation
(25b) and quantitative comparison with four sets of
experimental data have been included in Figs. 710
and Tables 710, which show that Eq. 25b can also
t the data approximately, but the values of the
regression coefcient R
2
are always smaller than
those of new kinetic equation (23).
It is interesting to observe that nearly all values
of x
TS
*
in Tables 710 are, similar to the values of
x
DP
*
in Tables 16, smaller than (11/DP
0
) except the
value x
TS
*
= 4.78 in Table 9 and x
TS
*
= 1 in
Table 10. The larger value of x
TS
*
= 4.78 for thermal
ageing of thermally upgraded Kraft insulation paper
in sealed metallic tubes in Table 9 was again
attributed obviously to the fact that the degradation
process was a prolonged autocatalytic reaction pro-
cess particularly with the presence of metallic
catalysts. This is essentially because the required
chain scission number at failure under such a
prolonged autocatalytic reaction condition is well
less than the available number of potentially weak
bonds. As a matter of fact, the effect of metals on
cellulose degradation is well recognized in the
literature (Williams et al. 1977; McCrady 1996 and
references; Baranski et al. 2006), and it is also well
known that both hydrolytic and oxidative processes
may occur simultaneously in the ageing of paper
(Arney and Noval 1982; Margutti et al. 2001). With
these in mind, it is reasonably to believe that
degradation of thermally upgraded Kraft insulation
paper in sealed metallic tubes in Fig. 9 and Table 9 is
caused by at least two processesacid-catalysed
hydrolysis and metal-catalysed oxidation. From this
point, it is remarkable that Eq. 23 holds even in the
mixed hydrolytic and oxidative processes of cellulose
degradation.
We point out that the similarity of mathematical
expression between Eqs. 23 and 18 does not neces-
sary to suggest a linear relationship between the
tensile strength and the degree of polymerisation.
This is not only because different values of the
degradation rate constants k
TS
and k
DP
but also
because different values of the parameters x
TS
*
and
x
DP
*
, even for the same ageing experiment of the
same cellulose sample. This point is shown clearly in
Figs. 6, 9 and Tables 6, 9.
Determination of Arrhenius activation energy
Throughout this work we have considered cellulose
degradation is a gradual change of state and property
that usually leads to a degree of degradation. The
primal process in all cases is that the cellulose chain
are repeatedly broken and reformed in new cong-
urations. Cellulose degradation is chemical kinetics.
It is now necessary to consider the energies associ-
ated with the degradation of the DP and the TS and
Cellulose (2008) 15:205224 217
1 3
how they might affect the evolution kinetics
described above.
The traditional use of the Arrhenius equation to
describe the degradation reaction rate is profound.
Suppose now both the degradation reaction rate con-
stants k
DP
and k
TS
have the empirical Arrhenius form
k
DP
= A
DP
exp
E
DPa
RT

(26a)
k
TS
= A
TS
exp
E
TSa
RT

(26b)
where E
DPa
and E
TSa
are the Arrhenius activation
energy (J/mol) that represent the effective activation
energy for the overall chemical kinetic expression
governing the degradation of DP and TS, respec-
tively; R is the gas constant (8.314 J/mol/K), T is the
absolute temperature and A
DP
and A
TS
represent the
pre-exponential factors, respectively. If a log-plot of
the failure time (1/k) vs. the inverse absolute
temperature is a straight line, the Arrhenius equation
is said to be valid and activation energy is then
determined from the slope of the plot using Eq. 26.
The Arrhenius activation energy determined by this
method for all the results of Figs. 14, 8, 10/
Tables 14, 8, 10 are summarized in Table 11. These
gures for energy of activation are however some-
what below the reported activation energy of about
1116 kJ/mol for Kraft paper in literature (Emsley
and Stevens 1994), with the exception of the two TS
data sets of Gasser et al. (1999) and Hill et al. (1995)
at 120 and 91 kJ/mol, respectively. Particularly, the
two data sets of Soares et al. (2001) in Figs. 2, 3/
Tables 2, 3 yield activation energy values of 11.47
and 33.69 kJ/mol, which are far below the excepted
norm of activation energy in the literature. This may
due not only to the complex nature of the cellulose
degradation kinetics and the likely changes in the
rate-determining parameters, but also to the method
which use only one experimental data point from
each temperature curve and eliminating most of the
experimental points from analysis.
To determine the activation energy using all of the
experimental data, we can employ the timetemper-
ature superposition (TTSP) method (Ding and Wang
2007) to shift the raw data of degree of degradation to
the lowest experimental temperature (T
ref
). This is
accomplished by multiplying the degradation times
appropriate to experiments at temperature (T) by a
shift factor (a
T
). The shift factors are chosen empir-
ically to give the best superposition of the data by
yielding an approximately smooth master curve. If
the data adhere to an Arrhenius relationship, the set of
shift factors a
T
will be related to the Arrhenius
activation energy by the following form
a
TDP
= exp
E
DPa
R
1
T
ref

1
T

(27a)
a
TTS
= exp
E
TSa
R
1
T
ref

1
T

(27b)
We call Eq. 27 Arrhenius shift factor function.
The best superposition of the data of degree of
degradation for Figs. 14, 8, 10 are shown in
Table 11 Comparison of Arrhenius activation energy values determined by the Arrhenius equation (26) and by timetemperature
superposition method
Experimental Activation energy determined
by Arrhenius equation (26)
Activation energy determined
by TTSP method
Notes
Bleached bisulte pulp in
sealed glass jars, 75% RH
E
DPa
= 82.15 kJ/mol E
DPa
= 104 kJ/mol Fig. 17
Kraft paper in air E
DPa
= 11.47 kJ/mol E
DPa
= 42.77 kJ/mol (E
DPa1
= 90.11 kJ/mol,
E
DPa2
= 35.10 kJ/mol)
Fig. 18
Kraft paper in mineral oil E
DPa
= 33.69 kJ/mol E
DPa
= 35.63 kJ/mol (E
DPa1
= 120 kJ/mol,
E
DPa2
= 27.62 kJ/mol)
Fig. 19
Kraft paper in mineral oil at
low water/oxygen level
E
DPa
= 72.68 kJ/mol E
DPa
= 115 kJ/mol Fig. 20
Thermally upgraded paper in
mineral oil
E
TSa
= 120.38 kJ/mol E
TSa
= 111.34 kJ/mol Fig. 21
Kraft paper in dried and
degassed transformer oil
E
TSa
= 91.33 kJ/mol E
TSa
= 97.92 kJ/mol Fig. 22
218 Cellulose (2008) 15:205224
1 3
Figs. 1116; and the corresponding Arrhenius plots
of the associated empirical shift factor values are
shown in Figs. 1722, respectively. Because of the
large differences in experimental temperature condi-
tions, the data for each condition are plotted
separately for the sake of visual clarity. The Arrhe-
nius activation energy determined by the TTSP
method for all the results of Figs. 1116 are also
summarized in Table 11. Obviously, all these gures
for energy of activation are now in good agreement
with the reported activation energy of 1116 kJ/mol
for Kraft paper in literature (Emsley and Stevens
1994), excepting for the two data sets of Soares et al.
(2001) at 42.77 and 35.63 kJ/mol, respectively,
which are still well below the excepted norm of
activation energy in the literature.
Further studies in Figs. 18 and 19 have found
that for the experimental data obtained in air, at
temperatures of 90 C and below the activation
energy value is equal to approximately 90 kJ/mol,
and the data above 90 C seems to imply a
curvature to a smaller activation energy value of
35.10 kJ/mol; and for the experimental data
obtained in mineral oil, at temperatures of 80 C
and below the activation energy value is equal to
approximately 120 kJ/mol, and the data above
80 C seems to imply a curvature to a smaller
activation energy value of 27.62 kJ/mol. The
downward curvature in the Arrhenius plots
observed for both the experimental data obtained
in air (Fig. 18) and the experimental data obtained
in mineral oil (Fig. 19) indicates that a change in
the mix of DP degradation reactions is occurring
with degradation temperature for the Kraft paper
studied. Generally speaking, such curvature implies
that certain higher activation energy processes are
becoming less important at higher degradation
temperatures. This is the evidence of non-Arrhenius
behaviour, and similar phenomena have been
reported in the literature for some polymers (Gillen
et al. 2005a, b).
Towards a new method for the prediction of
cellulose degradation at ambient conditions
All master curves in Figs. 1114 can be further tted
by Eq. 18 to yield corresponding master equation
representing the kinetics of percentage DP loss as
follows.
(1) For the DP data of BBSP handsheets aged in
seal vessels and 75% RH in Fig. 11:
1
DP
DP
0
= 0:780 1 e
0:0043a
TDP
t
T

(28a)
a
TDP
= exp 12; 509
1
273 60

1
273 T

(28b)
where t
T
is the degradation time by days at the
temperature T in Celsius.
(2) For the DP data of Kraft paper aged in air
Fig. 12:
1
DP
DP
0
= 0:480 1 e
0:0032a
TDP
t
T

(29a)
a
TDP
= exp 10; 838
1
273 70

1
273 T

(29b)
where t
T
is the degradation time by hours at the
temperature T in Celsius.
(3) For the DP data of Kraft paper aged in mineral
oil at high water/oxygen level in Fig. 13:
1
DP
DP
0
= 0:750 1 e
0:0002a
TDP
t
T

(30a)
0 100 200 300 400 500 600 700 800
0.0
0.2
0.4
0.6
0.8
1.0
TTSP master curve
R
2
= 0.9872

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

P
D
Shift time (=a
T
* ageing time) at 60
o
C, days
Temperature a
T
60
o
C 1
70
o
C 3.3
80
o
C 8.4
90
o
C 26
100
o
C 54
Fig. 11 Timetemperature superposition of the degree of
degradation data from Fig. 1 at 60 C using the shift factors
as shown in the gure
Cellulose (2008) 15:205224 219
1 3
a
TDP
= exp 14433:49
1
273 65

1
273 T

(30b)
where t
T
is the degradation time by hours at the
temperature T in Celsius.
(4) For the DP data of Kraft paper aged in mineral
oil at low water/oxygen level in Fig. 14:
1
DP
DP
0
= 0:900 1 e
0:0003a
TDP
t
T

(31a)
a
TDP
= exp 13; 832
1
273 120

1
273 T

(31b)
where t
T
is the degradation time by hours at the
temperature T in Celsius.
Similarly, master curves in Figs. 15, 16 can be
further tted by Eq. 23 to produce corresponding
master equation representing the kinetics of percent-
age TS loss as follows.
(5) For the TS data of thermally upgraded insula-
tion paper aged in closed system with mineral
oil in Fig. 15:
0 500 1000 1500 2000
0.0
0.2
0.4
0.6
0.8
1.0
TTSP master curve
R
2
=0.9524
Temperature a
T
70
o
C 1
80
o
C 2.4
90
o
C 5.6
105
o
C 8
120
o
C 13
D
e

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g

P
D
Shift time (= a
T
* ageing time) at 70
o
C, hours
Fig. 12 Timetemperature superposition of the degree of
degradation data from Fig. 2 at 70 C using the shift factors
as shown in the gure
0 20000 40000 60000
0.0
0.2
0.4
0.6
0.8
1.0
TTSP master curve
R
2
= 0.9648

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

P
D
Shift time (=a
T
* ageing time) at 65
o
C, hours
Temperature a
T
65
o
C 1
80
o
C 6.4
120
o
C 16
Fig. 13 Timetemperature superposition of the degree of
degradation data from Fig. 3 at 65 C using the shift factors
as shown in the gure
0 20000 40000 60000 80000 100000
0.0
0.2
0.4
0.6
0.8
1.0
TTSP master curve
R
2
=0.9616

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

P
D
Shift time (=a
T
* ageing time) at 120
o
C, hours
Temperature a
T
120
o
C 1
140
o
C 5.50
160
o
C 25.83
Fig. 14 Timetemperature superposition of the degree of
degradation data from Fig. 4 at 120 C using the shift factors
as shown in the gure
0 200 400 600 800 1000 1200
0.0
0.2
0.4
0.6
0.8
1.0
TTSP master curve
R
2
=0.9874

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

S
T
Shift time (=a
T
* ageing time) at 120
o
C, days
Temperature a
T
120
o
C 1
130
o
C 2.3
150
o
C 11.1
Fig. 15 Timetemperature superposition of the degree of
degradation data from Fig. 8 at 120 C using the shift factors
as shown in the gure
220 Cellulose (2008) 15:205224
1 3
1
TS
TS
0
= 0:594 1 e
0:0028a
TTS
t
T

(32a)
a
TTS
= exp 13391:87
1
273 120

1
273 T

(32b)
where t
T
is the degradation time by days at the
temperature T in Celsius.
(6) For the TS data of Kraft insulation paper aged in
dried and degassed transformer oil in Fig. 16:
1
TS
TS
0
= 0:810 1 e
0:0153a
TTS
t
T

(33a)
a
TTS
= exp 11777:72
1
273 129

1
273 T

(33b)
where t
T
is the degradation time by days at the
temperature T in Celsius.
According to master equations (28)(33), it
becomes possible to quantitatively predict the degree
of degradation of cellulose at ambient operating
conditions. Let us look at two examples. According to
Eq. 28, the extrapolated shift factor a
TDP
will be
a
TDP
= 0.0091 at 23 C, which implies that with
same relative humidity of 75%, the time required to
reach a given level of degree of degradation at 23 C
will be 110 times that required at the reference
temperature of 60 C; and the degree of degradation
of BBSP paper in terms of the percentage DP loss
0 50 100 150 200 250 300
0.0
0.2
0.4
0.6
0.8
1.0
TTSP master curve
R
2
=0.9703

,
n
o
i
t
a
d
a
r
g
e
d

f
o

e
e
r
g
e
D

S
T
Shift time (=a
T
* ageing time), days
Temperature a
T
129
o
C 1
138
o
C 1.9
153
o
C 5.2
166
o
C 11.8
Fig. 16 Timetemperature superposition of the degree of
degradation data from Fig. 10 at 129 C using the shift factors
as shown in the gure
2.6 2.8 3.0 3.2
10
-1
10
0
10
1
10
2
E DPa
=
8
2
.1
5
k
J
/m
o
l,
R
2
=
0
.9
9
4
0
Empirical shift factor a
T
/
1
(
n
l
k
P
D
)
E
D
P
a =
1
0
4
k
J
/m
o
l,
R 2
=
0
.9
9
0
7
p
m
E
i
h
s

l
a
c
i
r
i
a

,
r
o
t
c
a
f

t
f
T
1000/T, K
-1
1
2
3
4
5
6
7
DP degradation rate k
DP
Fig. 17 Arrhenius plots for the DP degradation rate k
DP
data
in Table 1 and for the empirical values of the shift factors a
T
used to superpose degree of degradation data from Fig. 11
2.40 2.55 2.70 2.85 3.00
10
-1
10
0
10
1
10
2
E
DPa2
=
. 5 3
1 kJ/mol, R
2
=
. 0 9
5 0 9
Empirical shift factor a
T
E
DPa
= 11.47 k / J mol, R
2
= 0.9149
/
1
(
n
l
k
P
D
) E
DPa
=
42.77 kJ/mol, R
2
=
0.9719
E
D
Pa1 =
9
0
.1
1
k
J
/m
o
l,
R 2
=
1
i
h
s

l
a
c
i
r
i
p
m
E
a

,
r
o
t
c
a
f

t
f
T
1000/T, K
-1
3
4
5
6
DP degradation rate k
DP
Fig. 18 Arrhenius plots for the DP degradation rate k
DP
data
in Table 2 and for the empirical values of the shift factors a
T
used to superpose degree of degradation data from Fig. 12
2.40 2.55 2.70 2.85 3.00
10
-1
10
0
10
1
10
2
Empirical shift factor a
T
E
DPa
= 33.69 kJ/mol, R
2
= 0.9052
E
DPa = 35.63 kJ/mol, R
2
=0.9558
E
D a P 2
= 27.62 kJ/mol, R
2
= 1
E
P
D
a1 =
2
1
0
k
J
m /
, l
o
R 2
1
=
m
E
r
i
p
i
l
a
c
a
f

t
f
i
h
s

a

,
r
o
t
c
T
1000/T, K
-1
6
8
10
12
14
DP degradation rate k
DP
/
1
(
n
l
k
P
D
)
Fig. 19 Arrhenius plots for the DP degradation rate k
DP
data
in Table 3 and for the empirical values of the shift factors a
T
used to superpose degree of degradation data from Fig. 13
Cellulose (2008) 15:205224 221
1 3
will reach 39.8% after 10 years, 59.3% after
100 years and 77.9% after 500 years. According to
Eq. 32, the extrapolated shift factor a
TTS
will be
a
TTS
= 0.0070 at 70 C (normal transformer opera-
tion temperature), which implies that with same
experimental conditions, the degree of degradation of
thermally upgraded insulation paper in terms of
percentage TS loss will reach 4.1% after 10 years,
17.86% after 50 years and 30.35% after 100 years.
Admittedly, these are approximate values. However,
the results described above illustrate a new method
for prediction of cellulose degradation at ambient
conditions.
Conclusions
The present study investigates the degradation evo-
lution equation of cellulose. From the results obtained
in the present study the following conclusions are
drawn.
(1) Cellulose degradation can be best characterized
in terms of the percentage DP loss. The
degradation variable x
DP
can be calculated
through the measured degree of polymerisation
of a cellulose, DP
0
, and the effective degree of
polymerisation after degradation occurred, DP,
in terms of the denition x
DP
: 1DP/DP
0
.
Different values of the degradation variable
correspond to different states of the cellulose as
(a) x
DP
= 0 corresponds to the undegraded
state; (b) x
DP
= 1 corresponds to the fully-
degraded state (i.e., failure); and (c) 0 \x
DP
\
1 corresponds to the degraded state.
(2) A new cellulose degradation evolution equation
expressed in terms of the percentage DP loss has
been presented and applied to have a quantita-
tive comparison with six sets of experimental
results. The results show that the new cellulose
degradation evolution equation (18) is able to
explain the real experimental data of different
cellulose materials under a variety of experi-
mental conditions, particularly the prolonged
autocatalytic degradation in sealed vessels.
(3) Cellulose degradation can be best characterized
also in terms of the percentage TS loss. The
degradation variable x
TS
can be calculated
through the measured tensile strength of a
2.2 2.3 2.4 2.5 2.6
10
0
10
1
10
2
/
1
(
n
l
k
P
D
)

,
r
o
t
c
a
f

t
f
i
h
s

l
a
c
i
r
i
p
m
E
a
T
E DPa
=
7
2
.6
8
k
J
/m
o
l,R
2
=
0
.9
8
8
6
Empirical shift factor a
T
E
D
Pa =
1
1
5
k
J
/m
o
l,
R 2
=
1
1000/T, K
-1
4
5
6
7
8
DP degradation rate k
DP
Fig. 20 Arrhenius plots for the DP degradation rate k
DP
data
in Table 4 and for the empirical values of the shift factors a
T
used to superpose degree of degradation data from Fig. 14
2.3 2.4 2.5 2.6
10
0
10
1
10
2
/
1
(
n
l
k
S
T
)
E TSa
=
1
2
0
.3
8
k
J
/m
o
l,
R
2
=
0
.9
6
0
6
Empirical shift factor a
T
E
TSa =
1
1
1
3 .
4
k
J
m /
o
l,
R 2
=
1
p
m
E
i
h
s

l
a
c
i
r
i
a

,
r
o
t
c
a
f

t
f
T
1000/T, K
-1
3
4
5
6
7
TS degradation rate k
TS
Fig. 21 Arrhenius plots for the TS degradation rate k
TS
data in
Table 8 and for the empirical values of the shift factors a
T
used
to superpose degree of degradation data from Fig. 15
2.2 2.3 2.4 2.5 2.6
10
-1
10
0
10
1
10
2
E TSa
=
9
1
3 .
3
k
J
m /
o
l
R ,
2
=
0
9 .
6
0
4
Empirical shift factor a
T
/
1
(
n
l
k
S
T
)
E
TSa =
97.92
kJ/m
ol, R 2
=
1
p
m
E
i
h
s

l
a
c
i
r
i
a

,
r
o
t
c
a
f

t
f
T
1000/T, K
-1
1
2
3
4
5
6
TS degradation rate k
TS
Fig. 22 Arrhenius plots for the TS degradation rate k
TS
data in
Table 10 and for the empirical values of the shift factors a
T
used to superpose degree of degradation data from Fig. 16
222 Cellulose (2008) 15:205224
1 3
cellulose, TS
0
, and the effective tensile strength
after degradation occurred, TS, in terms of the
denition x
TS
: 1TS/TS
0
. A new kinetic
equation (23) for loss of tensile strength of
cellulose, which is analogous to the new cellu-
lose degradation evolution equation (18), has
been presented and applied to explain four sets
of experimental data of tensile strength. The
results show that the good agreement between
the predictions and experimental data appears to
be justied in principle.
(4) A new method for prediction of cellulose
degradation at ambient conditions has been
developed by combining the master equation
representing the kinetics of either percentage
DP loss or percentage TS loss at the lowest
experimental temperature with Arrhenius shift
factor function.
(5) It is critical to model the cellulose degradation
evolution kinetics accurately for degradation
prediction. The proposed degradation evolution
equations expressed in terms of either the
percentage DP loss or the percentage TS loss
appear to accomplish this with good accuracy
for the experimental data considered. However,
additional theoretical and experimental studies
are suggested to conrm the proposed cellulose
degradation evolution equations (18) and (23).
Acknowledgements We would like to thank all anonymous
reviewers for some very valuable suggestions. We would also
like to thank Professor Wolfgang Glasser (Editor in Chief) for
encouragement. The research was partly supported by the
EPSRC-SUPERGEN V-AMPerES (Asset Management and
Performance of Energy Systems).
References
Arney JS, Noval CL (1982) Accelerated aging of paper. The
inuence of acidity on the relative contribution of oxygen-
independent and oxygen-dependent processes. Tappi J
65:113115
Baranski A, agan JM, ojewski T (2006) The concept of
mixed-control mechanisms and its applicability to paper
degradation studies. e-PS 3:14
Bouchard J, Methot M, Jordan B (2006) The effects of ionizing
radiation on the cellulose of woodfree paper. Cellulose
13:601610
Calvini P (2005) The inuence of levelling-off degree of
polymerisation on the kinetics of cellulose degradation.
Cellulose 12:445447
Calvini P, Gorassini A (2006) On the rate of paper degradation:
lessons from the past. Restaurator 27(4):275290
Chen SL, Lucia LA (2003) Improved method for evaluation of
cellulose degradation. J Wood Sci 49:285288
Daruwalla EH, Narsian MG (1966) Detection and identication
of acid-sensitive linkages in cellulose ber substances.
Tappi J 49(3):106111
Ding H-Z, Wang ZD (2007) Timetemperature superposition
method for predicting the permanence of paper by
extrapolating accelerated ageing data to ambient condi-
tions. Cellulose 14:171181
Ekenstam A (1936) The behaviour of cellulose in mineral acid
solutions: kinetic study of the decomposition of cellulose
in acid solutions. BER 69:540553
Emsley AM, Stevens GC (1994) Kinetics and mechanisms of
the low temperature degradation of cellulose. Cellulose
1:2656
Emsley AM, Heywood RJ, Ali M, Eley CM (1997) On the
kinetics of degradation of cellulose. Cellulose 4:15
Emsley AM, Xiao X, Heywood RJ, Ali M (2000a) Degradation
of cellulosic insulation in power transformers. Part 3:
effects of oxygen and water on ageing in oil. IEE Proc Sci
Meas Technol 147(3):115119
Emsley AM, Heywood RJ, Ali M, Xiao X (2000b) Degradation
of cellulosic insulation in power transformers. Part 4:
effects of ageing on the tensile strength of paper. IEE Proc
Sci Meas Technol 147(6):285290
Feller RL, Lee SB, Bogaard J (1986) The kinetics of cellulose
deterioration. In: Needles HL, Zeronian SH (eds) Historic
textile and paper materials: conservation and character-
ization. Advances in chemistry series 212. American
Chemical Society, Philadelphia, USA, pp 329346
Fung DPC (1969) Kinetics and mechanism of the thermal
degradation of cellulose. Tappi J 52:319321
Gasser HP, Huser J, Krause C, Dahinden V, Emsley AM
(1999) Determining the ageing parameters of cellulosic
insulation in a transformer. In: Eleventh international
symposium on high voltage engineering (IEE Conf. Publ.
No. 467), London, 2327 August 1999, pp 4.1434.147
Gillen KT, Bernstein R, Derzon DK (2005a) Evidence of non-
Arrhenius behaviour from laboratory aging and 24-years
eld aging of polychloroprene rubber materials. Poly Deg
Stab 87:5767
Gillen KT, Bernstein R, Celina M (2005b) Non-Arrhenius
behavior for oxidative degradation of chlorosulfonated
polyethylene materials. Poly Deg Stab 87:335346
Hansen AC, Baker-Jarvis J (1990) A rate-dependent kinetic
theory of fracture for polymers. Inter J Fracture 44:221
231
Heywood RJ, Stevens GC, Ferguson C, Emsley AM (1999)
Life assessment of cable paper using slow thermal ramp
method. Thermochim Acta 332:189195
Hill DJT, Le TT, Darveniza M, Saha T (1995) A study of
degradation of cellulosic insulation materials in a power
transformer. Part 2: tensile strength of cellulose insulation
paper. Polym Deg Stab 49:429435
Hon DNS (1985) Mechanochemistry of cellulosic materials. In:
Kennedy JF, Phillips GO, Wedlock DJ, Williams PA (eds)
Cellulose and its derivatives: chemistry, biochemistry and
applications, chapter 6. Ellis Horwood Limited, Chiches-
ter, UK, pp 7186
Cellulose (2008) 15:205224 223
1 3
Johansson EE, Lind J, Ljunggren S (2000) Aspects of the
chemistry of cellulose degradation and the effect of eth-
ylene glycol during ozone delignication of Kraft pulps. J
Pulp Pap Sci 26:239244
Krassig H, Kitchen W (1961) Factors inuencing tensile
properties of cellulose bers. J Polym Sci 51:123172
Kukensko VS, Tamuzs VP (1981) Fracture micromechanics of
polymer materials. Martinus Nijhoff Publishers, Boston, MA
Margutti S, Conio G, Calvini P, Pedemonte E (2001) Hydrolytic
and oxidative degradation of paper. Restaurator 22:6783
McCrady E (1996) Effect of metals on paper: a literature
review. Alkaline Paper Advocate, vol 9(1), May
McShane CP, Corkran JL, Rapp KJ, Luksich J (2003) Aging of
paper insulation retrolled with natural ester dielectric
uid. IEEE2003 annual report conf. on electrical insulation
and dielectric phenomena. Albuquerque, USA, pp 124127
Moser HP, Dahinden V (1987) Transformerboard II. H. We-
idmann AG, CH-8640 Rapperswil
Petrov VA (1984) Lifetime-under-load of solid subjected to
stresses below the breaking value. Sov Phys Solid State
26:12831284
Shazadeh F, Bradbury AGW (1979) Thermal degradation of
cellulose in air and nitrogen at low temperatures. J Appl
Polym Sci 23:14311442
Sharples A (1954) The hydrolysis of cellulose. Part 1. The ne
structure of Egyptian cotton. J Polym Sci 13:393401
Sharples A (1971) Degradation of cellulose and its derivatives.
A. Acid hydrolysis and alcoholysis. In: Bikales NM, Segal
L (eds) Cellulose and cellulose derivatives, vol V, Pt V.
Wiley-Interscience, New York, pp 9911006
Soares S, Ricardo N, Heatley F, Rodrigues E (2001) Low
temperature thermal degradation of cellulosic insulating
paper in air and transformer oil. Polym Int 50:303308
Strlic M, Kolar J, Pihlar B, Rychly J, Matisova-Rychla L
(2001) Initial degradation process of cellulose at elevated
temperatures revisited-chemiluminescence evidence.
Polym Deg Stab 72:157162
Testa G, Sardella A, Rossi E, Bozzi C, Seves A (1994) The
kinetics of cellulose ber degradation and correlation with
some tensile properties. Acta Polymer 45:4749
Williams JC, Fowler CS, Lyon MS, Merrill TL (1977) Metallic
catalysts in the oxidative degradation of paper. Advances
in chemistry series, ACS 164, pp 3761
Zervos S, Moropoulou A (2005) Cotton cellulose ageing in
sealed vessels. Kinetic model of autocatalytic depoly-
merization. Cellulose 12:485496
Zhurkov SN, Korsukov VE (1974) Atomic mechanism of
fracture of solid polymers. J Polym Sci: Polym Phys
12:385398
Zou X, Gurnagul N, Uesaka T, Bouchard J (1994) Accelerated
ageing of papers of pure cellulose: mechanism of cellu-
lose degradation and paper embrittlement. Polym Deg
Stab 43:393402
Zou X, Uesaka T, Gurnagul N (1996) Prediction of paper
permanence by accelerated ageing: Part 1 kinetic analysis
of the aging process. Cellulose 3:243267
224 Cellulose (2008) 15:205224
1 3