Some Electrical Properties of Wood Pulp

S. BOUTROS and A. A. HANNA, National Research Centre, Dokki, Cairo,

Egypt
Synopsis
The variation with temperature and frequency of the dielectric constant c' and the dielectric loss
for sheet wood pulp and ground wood pulp were measured. Also, the effect of the relative humidity
on the dielectric behavior was measured for the ground sample a t 25C. For the dry ground wood
pulp, the dielectric constant is larger than that for the dry sheet sample. This may be a result of
the increase in the surface area, of the decrease in the size of crystals and/or of the decrease in the
degree of crystallinity on grinding of the sheet sample. The variation of e'' with frequency passes
through a maximum. From the shift of this maximum with temperature, it is found that the apparent
activation energy LMfor this relaxation is equal to 7.06 kcal/mole and i t is attributed to the polar-.
ization of the OH groups in the cellulose molecule. From the relation between the dielectric constant
and the specific resistivity R,, the dissociation energy UOfor the ground wood pulp was calculated.
UOfor this sample below and above 52%RH is 0.315 and 5.13 X
erg, respectively. Also, the
dissociation energy of Egyptian Ashmouny cotton was calculated. The variation of the electrical
conductivity u with humidity for different types of cellulosic materials is represented graphically.
6'

INTRODUCTION
The dielectric properties of wood have been investigated by many authors.1-8
In a previous publication, the authors reported on the variation of the dielectric
properties with temperature, frequency, and relative humidity (RH) for Egyptian
Ashmouny cottong and British cotton.lOJ1 It was observed that both the dielectric constant and the dielectric loss increased with increasing temperature
and RH. The increase with temperature was attributed to an increase in the
rotation of the polarized groups in the cellulose molecules, while the increase with
the RH was attributed to the freeing of ions and groups in the cellulose as well
as to the ionization of some water molecules, especially at high relative humidity.
For the British cotton, the authors found that the dissociation energy Uo was
0.318 and 5.46 X
erg, respectively below and above 52% RH.
The present work is concerned with a further study of the dependence of the
dielectric properties for the cellulosic materials upon the relative humidity. Also,
a comparison between the dielectric behavior of sheet and ground wood pulp is
discussed. From the relation between the dielectric constant and specific resistivity the dissociation energy is calculated.

EXPERIMENTAL
The starting material was wood pulp sheets supplied by Elof Hansson, Goteborg, Sweden, and containing 91.3% cellulose. Two types of the wood pulp
samples were studied: a number of sheets as received from the supplier and a
ground wood pulp prepared from such sheets. To obtain the ground wood pulp,
some of the sheets were cut into small pieces and ground in a hardened steel vessel
containing two steel balls. The vessel was fitted to a Spex-Mixer mill which was
Journal of Polymer Science: Polymer Chemistry Edition, Vol. 16,1443-1448 (1978)
0 1978 John Wiley & Sons, Inc.
0360-6376/78/0016-1443$01.00

BOUTROS AND HANNA

1444

rotated for a sufficient time. The obtained powder was sieved through 0.2
standard mesh.
To study the dependence of the dielectric constant and the dielectric loss on
the relative humidity, four disks of a ground wood pulp were exposed to 35,52,
76, and 92%RH at 25OC. The RH of the disk was followed by using a previously
described technique.ll
A multidekameter WTW, type DK06, having frequency band from 0.1 to 12
MHz/sec and cell of the MFM5T type were used.9

RESULTS AND DISCUSSION

The variation of the dielectric constant t' with temperature at various
frequencies for the sheet and the ground samples is shown in Figure 1. From
the curves it is observed that the dielectric constant increases with increasing
temperature at all frequencies; this may be due to the decrease in the effect of
environment. The variation of the dielectric loss d' with log f passes through
a maximum (Fig. 2).
The dielectric constant and the dielectric loss are tabulated in Table I. It is
clear that both the dielectric constant and the dielectric loss increase with increasing the RH. Also, it is observed that the change in the dielectric loss with
RH is more considerable at RH above 52%. This behavior was observed and
discussed in detail previously for the Egyptian cotton9 and British cotton,ll but
the value of the dielectric constant of thk wood pulp is smaller than that value
for the Egyptian cotton, which contains 96.5% cellulose (Table 11). This may
result from the presence of some lignin in the wood pulp (91.3% cellulose).
Moreover, as the lignin compound has a relativity low dielectric constant, the
polarization of the OH groups in the cellulose molecule is reduced.
From Figure 1,it is observed that the dielectric constant 'for the ground sample

-20

20

LO

60

80 -20

20

LO

60

80

PC

Fig. 1. Variation of the dielectric constant with temperature at different frequencies for sheet
and ground wood pulp.

ELECTRICAL PROPERTIES OF WOOD PULP

1445

TABLE I
Variation of Dielectric Constant t and Dielectric Loss 6 for Ground Wood Pulp with RH For
Different Frequencies at 25C
____.__

35% RH

(Mhd
sec)

0.2
0.5
1
2
5
10

3.35
3.26
3.20
3.13
2.96
2.81

0.188
0.196
0.213
0.221
0.217
0.230

4.91
4.80
4.70
4.61
4.40
4.20

O%RH

CI

0.199
0.203
0.217
0.224
0.225
0.231

52% RH
f

5.71
5.52
5.40
5.34
5.12
4.84

0.241
0.241
0.242
0.242
0.242
0.243

76% RH
c

6.97
6.81
6.62
6.48
6.04
5.50

0.831
0.681
0.592
0.470
0.421
0.391

92% RH
c

8.31
7.80
7.01
6.66
6.42
5.56

3.02
1.70
1.21
1.04
0.96
0.78

TABLE I1
Variation of Dielectric Constant f and Dielectric Loss t for Egyptian Cotton with RH for
Different Frequencies at 25C

f
(MHd
sec)

O%RH
f

35% RH

0.2
0.5
1
2
5
10

2.82
2.76
2.73
2.67
2.57
2.46

0.102
0.134
0.131
0.165
0.185
0.207

3.78
3.69
3.63
3.55
3.39
3.22

f!

0.220
0.215
0.222
0.258
0.292
0.315

52% RH
d
f
4.36
4.22
4.14
4.03
3.82
3.61

0.343
0.309
0.310
0.326
0.329
0.367

76% RH
d
c
5.49
5.06
4.85
4.59
4.20
3.89

1.584
1.032
0.820
0.691
0.591
0.571

92% RH
t

8.97
7.70
6.62
5.47
4.21
3.90

13.600
6.330
3.550
2.518
1.900
1.400

is greater than that for the sheet. This behavior can be explained by assuming
the dielectric constant of cellulose is that of a two-component system, one
component being the crystalline fraction and the other the amorphous fraction.12
For the crystalline fraction, the dielectric constant depends to some extent upon
the size of crystals; more properly, it depends upon the surface area to volume
ratio of the crystals. This would be expected because the surface molecules will
have some polar groups that are not bonded in the crystal lattice, and therefore
have greater freedom of movement. Accordingly, the dielectric constant of very
small crystals should be somewhat larger than that of large crystals by an amount
corresponding to the polarization of the unbonded groups. For the amorphous
fraction, the dielectric constant would appear to be influenced considerably by
proximity and configuration of adjacent molecules, so that the decrease in
crystallinity results in a greater chance for the amorphous chains to achieve
random disorder, and therefore a higher dielectric constant value.
By grinding the wood pulp sheets, the ratio between the surface area to the
volume increases, the size of the crystals and the degree of crystallinity decrease,
and the polarization of the molecules increases, hence the dielectric constant
increases.13
Figure 2 shows that there is a flat loss maximum which shifts towards a
higher frequency with less broadening when the temperature is increased. The
shift of the maximum loss with temperature for the ground wood pulp proceeds
as follows: t = -2OoC, log f m , 5.58; OC, 6.03; 2OoC, 6.44; 4OoC, 6.80.
In general, two loss regions have been found in the high polymers in the solid

BOUTROS AND HANNA

1446

Log f

Fig. 2. Variation of the dielectric loss with frequencyat differenttemperatures for sheet and ground
wood pulp.

statel4-I6: the a relaxation which is characterized by a loss peak located at

temperature above the glass-transition point and the /3 relaxation characterized
by a flat loss maximum extending over a wide temperature range below the
transition point. The primary or a relaxation, which has been characterized
by a high apparent activation energy (70 kcal/mole) has been attributed to
large-scale conformational rearrangements of the main chains. The secondary
or p relaxation, whose activation energy is equal to 10 kcal/mole, has been attributed to the motion of the polar side groups, to chain twisting, or to small
unit motion of chain.17
In order to calculate the apparent activation energy for the relaxation process
AH, log f , is plotted against reciprocal temperature according to the equation18:

AH=

2.303 Rd log f,

d(l/T)
The resulting AH value is equal to 7.06 kcal/mole for ground wood pulp. This
value is in agreement with the activation energy obtained for Egyptian c ~ t t o n , ~
which was attributed to the polarization of the OH groups according to Ishidel8
and Thurn.lg
For the moist samples, the electrical conductivity u and the specific resistivity
R, were calculated by using the dielectric loss data11,20721for Ashmouny Egyptian
cotton, British cotton,ll and ground wood pulp (Table 111). From the relation
between the electrical conductivity and the relative humidity (Fig. 3 ) , it is obTABLE I11
Variation of Conductivity u, Specific Resistivity R,, and Dissociation Energy UOfor Ground
Wood P u b and EevDtian Cotton with RH at 25OC
Ground wood pulp

RH
(%)

0
35
52
76
92

x 107
0.0611
0.0777
0.0944

0.5126
2.2990

log Rs
8.2138
8.0821
8.0253
7.2900
6.6835

Egyptian cotton

uo x 102
(erg)
0.315

5.13

uo x 102
x 107

log Rs

0.0833
0.1100
0.1390
1.0501
13.6000

8.0792
7.9580
7.870
7.0210
5.8630

(erg)
0.310

3.510

ELECTRICAL PROPERTIES OF WOOD PULP

1447

- 6.0

- 6.5
-7.0

A
m

s -?.=
-8.0

-8.5

- 9.0
0

20

60

60
R H 'lo

80

100

Fig. 3. Variation of the electrical conductivity u with relative humidity: (- - -) Egyptian cotton;
British cotton; (--)
ground wood pulp.

(-.-)

served that as the relative humidity increases, the electrical conductivity increases. This increase may be due to the increase in the number of ions available
for conduction. At RH below 52%, the water was used in softening the cellulose
molecules and then facilitated the polarization of the OH groups in the cellulose
molecules, so that the dielectric constant increases markedly and the electrical
conductivity increases slightly. Above 52% RH, the added water was ionized
and the number of ions will increase, and hence the electrical conductivity increased markedly (Fig. 3).
The dissociation energy Uowas calculated from the following equation22:

A = Uolog e / 2 k T ,
where A is the slope of the line which represents the relation between log R , and
l l d (t' measured at 0.2 MHz/sec), e is the electronic charge, k is the Boltzmann
constant, and T is the absolute temperature (298'K).
and 5.13 X
The obtained value for the ground wood pulp is 0.315 X
erg below and above 52% RH, respectively (Table 111). These values are in good
agreement with values obtained for British cellulose,l1 also they are of the same
order of magnitude as the values obtained by other authors.22
In the same manner the dissociation energy was calculated for the Egyptian
and 3.51 X
erg.
cottong (Table 111). It is found that Uo is 0.310 X
From the two values for the dissociation energy and the variation of the electrical conductivity (Fig. 3) for Egyptian cotton, British cotton, and ground wood
pulp, it can be concluded that the effect of absorbed water on the electrical
properties depends not only on the polarity of the polar groups in the cellulosic
materials but also on the number of the ions resulting from the ionization of the
water molecules.

1448

BOUTROS AND HANNA

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Received March 18,1977