Colloids and Surfaces A: Physicochem. Eng.

Aspects 236 (2004) 39–44

Pulp charge determination by different methods:

effect of beating/refining
Nishi K. Bhardwaj, Tuan D. Duong, Kien L. Nguyen∗
Department of Chemical Engineering, Australian Pulp and paper Institute, Monash University, Clayton VIC 3800, Australia

Received 2 May 2003; accepted 29 January 2004

Abstract

Total and surface charge of unbleached and bleached softwood kraft pulps of different levels of freeness were determined using three
different techniques—potentiometric titrations, conductometric titrations (with NaOH and NaHCO3 separately) and polyelectrolyte titrations
using a particle charge detector (PCD). Each method gave different charge values but the relative levels were similar for each pulp. The surface
charge as determined by titration with poly-DADMAC was highly dependent on the degree of beating but the total fibre charge as given
by potentiometric titration or conductometric titration with NaOH remained constant after beating. Conductometric titration with sodium
hydroxide gave a slightly higher value for total charge than the potentiometric titration. Conductometric titrations with 0.05 M NaOH gave
higher values of pulp charge than similar titrations with 0.05 M NaHCO3 .
© 2004 Elsevier B.V. All rights reserved.

Keywords: Surface charge; Carboxyl groups; Kraft pulps; Beating; Refining

1. Introduction can be defined as the repeated passage of pulp through zones

Cellulosic fibres, the major portion of the papermaking
furnish, carry a charge when suspended in water due to the
ionization of acidic groups in the hemicellulose and lignin.
The water-soluble hemicelluloses include significant levels
of negatively charged polymers, such as glucuronoxylans in
hardwoods and galacto/arabino-glucuronomannans in soft-
woods. There are further contributions from fatty and resin
acids and from pectins (polymers of galacturonic acid). The
number of charged groups depends on the origin of the fi-
bre, and on the chemical treatment during pulping, bleach-
ing and refining.
The strength properties of a sheet of paper depend on
original qualities and strength of the fibres and to the extent
of bonding between the fibres that make up the sheet. A pa-
per sheet made from virgin pulp without beating/refining is
characterized by low strength, bulkiness and rough surface.
These undesirable characteristics can be changed to a large
extent by treating the pulp mechanically. This mechanical
treatment of fibres in water is termed beating/refining. This
∗Corresponding author. Fax: +61-3-990-53444-13.
E-mail address: loi.nguyen@eng.monash.edu.au (K.L. Nguyen).
of compression and shearing. Beating or refining of pulp is
an essential process of paper manufacture and is carried out
to a greater or lesser degree in all paper and board mills.
The refining of any fibrous raw material is a complex
process and the most influential of all of the papermaking
processes. Mechanical treatment of chemical pulps has been
reviewed by Fahey [1]. Many structural changes to the fi-
bres are attributed to beating, increased fibre swelling, fibre
shortening, internal and external fibrillation, etc. [2,3]. Apart
from improving fibre properties, it has the greatest influence
on product quality. Refining of pulp significantly contributes
to papermaking process by affecting not only the quality
of end product but also the runnability of the stock. A cor-
rect approach towards refining treatment is very essential for
product with desired properties. The old adage that ‘Paper
is made in the beater (now refiner)’ holds true for every pa-
per product. The effects of refining are most often evaluated
by freeness tests. This practice is somewhat an indirect way
of measuring the effects of refining, since the reduction in
drainage of the pulp, as measured by freeness, is not desir-
able in paper making process where high drainage is prefer-
able. The three main actions of beating/refining are: internal
fibrillation caused by the breakdown of fibre walls into sep-
arate lamellas which increases the flexibility of fibres so that

0927-7757/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.01.024
40 N.K. Bhardwaj et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 236 (2004) 39–44
during sheet formation the fibres conform to and around one
another producing large areas of intimate contact; external
fibrillation described as the creation and/or exposure of fib-
rils on the surface of the fibres; and generation of fines from
fibres when these are no longer able to sustain compressive
and/or shear forces during the treatment.
The sub-division of fibres into fibrils and the consequent
holding of water in fiber and more numerous capillary pas-
sages bring about a change in fibres that makes them more
reluctant to allow the drainage of water from or through
them. The fines in the furnish, often produced during the
refining process, tend to dominate the observed changes in
freeness as pulp is refined. Because of increased surface and
flexibility of pulp fibre in this condition, a greater degree of
bonding takes place when the sheet is dried. Kraft fibres in
particular are known to become more water-swollen during
beating/refining, and there is often a high correlation be-
tween water retention value and inter-fibre bond strength.
Refining develops various fibre properties in different ways
and the purpose is to achieve maximum desirable effects
with minimum undesirable effects [4].
In papermaking, the fibre surfaces are deliberately en-
larged by beating to improve bonding and develop optimum
strength properties. As fibre surfaces are peeled off during
beating/refining, increasing amounts of charged fines are
also formed. The primary fines consisting of parenchyma
cells tend to contribute bulk and some opacity to a sheet of
paper whereas the secondary fines produced by delaminating
the outer layers of fibre during beating/refining tend to be
slender and flexible—ideal for bonding. Theoretically, as the
surface is enlarged, the chemical components become more
easily accessible and lignin and hemicelluloses are redis-
tributed between pulp and water under the beating/refining
action. It is well known that fibre fines tend to have more
surface area per unit mass, compared to the fibres.
If increased surface area due to mechanical action leads to
more adsorption capacity in direct proportion to the increase
in surface area, then as beating opens up the fibre surface, the
fibre surface charge should increase with increased beating.
This fibre surface charge is also shown to greatly influence
the fibre swelling and paper strength properties [5,6].
In the present study, the effect of beating/refining (at dif-
ferent freeness levels) on surface and total charge of un-
bleached and bleached softwood kraft has been investigated.
2. Experimental
2.1. Chemicals
The analytical grades of NaOH, HCl, NaCl and NaHCO3
were used in the experiments. Polydiallyldimethyl am-
monium chloride (poly-DADMAC, molecular weight
150–200,000 g/mol) and sodium-polyethylenesulphate
(PES-Na) were reagent grades (ATA Scientific Pty. Ltd.).
These chemicals were diluted with deionised water with a
conductivity of 8×10−4 mS/cm to the desired concentration
before use. Nitrogen was used to prevent the absorption of
carbon dioxide into the test samples during potentiometric
and conductometric titrations.
2.2. Sources and preparation of pulps
The unbleached softwood kraft pulp (kappa number 103)
from ‘Pinus Radiata’ received from Visy’s Tumut mill was
in a never dried condition whereas bleached commercial
pulp (BSK) was supplied in dry sheet form. These two pulps
were beaten in a Valley beater after dilution with distilled
and deionised water to different freeness levels following
Tappi test method T 200 sp-96. The beaten pulps were fil-
tered on a Buchner funnel using a laboratory vacuum pump
to form a wet fibre pad and the filtrate recirculated once to
avoid loss of fines. Pulp freeness was measured using stan-
dard Tappi test method T 227 om-99 for the determination
of Canadian Standard Freeness. All the pulp samples were
stored in refrigerator at 4 ◦ C in the form of wet fibre pad at
dry content of about 30 ± 2%.
Before the charge measurements were undertaken, the
pulp samples were converted to their fully protonated form
by soaking the redispersed pulp pad at 1% consistency in
0.01 M hydrochloric acid for 16 h as suggested by a previous
researcher [7]. The pulp pH after 16 h of soaking was close
to 2.2. The pulp was then vacuum filtered using a Buchner
funnel and washed several times with deionised water until
the pH of the water filtrate was close to 6.0. The vacuum was
maintained until no more water could be extracted from the
pulp mat. After each titration, the amount of fibre in each
sample was determined gravimetrically by filtering the pulp
on pre-weighed filter paper and drying in an oven at 105 ◦ C
until a constant weight was obtained.
2.3. Determination of charge
2.3.1. Potentiometric titrations
The potentiometric titrations were performed using a high
precision, microprocessor controlled titrator (Metrohm—
718 STAT Titrino) and data logger. The pH of the slurry
was determined by using a combined pH glass electrode.
The electrode was calibrated using buffer solutions of pH
4, 7 and 9.2. During the titrations, a magnetic stirrer with
teflon rod was used to mix the pulp suspension. The rate of
titrant addition was controlled at 0.3 ml/min. The data were
recorded every 30 s by the data logger and transferred to a
computer. All the potentiometric titrations were performed
with pulp suspension at 0.5% consistency in 0.005 M HCl
in 1 mM NaCl and at 25 ◦ C. A blank titration curve was
generated by titrating 100 ml of 0.005 M HCl in 1 mM NaCl
against 0.05 M NaOH in 1 mM NaCl. The charge of the
fibre was calculated by the formula below:
c
So = 1000V
w
 N.K. Bhardwaj et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 236 (2004) 39–44 41

where So is the surface charge (mmol/kg), V the titre differ-

Conductance, mS/cm

0.26
ence (ml), c the titrant concentration (mol/l), w the weight 0.24
of dry pulp (g). 0.22
0.20
0.18
2.3.2. Conductometric titrations
0.16
The conductometric titration has been outlined by Katz 0.14
et al. [8] and is based on changes in conductance of the 0 0.3 0.6 0.9 1.2 1.5 1.8 2.1
suspension, which in turn is related to the concentration 0.05M NaOH added, ml
of the most highly conducting ions, i.e. the hydrogen and
hydroxyl ions. Approximately, 0.5 g of the acid washed Fig. 1. Experimental data from a conductometric titration of kraft pulp
pulp was dispersed in 1 mM sodium chloride (100 ml) and plotted as conductance vs. added volume of NaOH.
addition of 0.5 ml of 0.05 M HCl was made before the
12
start of titration. The titration was performed with two 11
10
titrants, 0.05 M NaOH and 0.05 M NaHCO3 , at 25 ◦ C us- 9
8
pH

ing the 718 STAT Titrino from Metrohm and a LC-81 7

6
conductivity meter from TPS Pty. Ltd. Conductivity mea- 5
4
surements were made every 1 min after 0.1 ml of alkali 3
9 9.5 10 10.5 11 11.5 12
solution addition except near the point of inflection where
readings were taken after every 0.05 ml of alkali. The 0.05M NaOH added, ml

conductivity decreased until excess acid was neutralized. Fig. 2. Experimental data from a potentiometric titration of kraft pulp
Further additions of alkali reacted with the acid groups plotted as pH vs. added volume of NaOH.
bound to the pulp and did not change the conductivity.
Excess alkali again raised the conductivity. The titration 800
gave the conductivity of the suspension as a function of 600
the volume of alkali added, and the carboxylic acid con- 400
mV

tent was given by the additional volume of alkali needed 200

to reach the second inflection point after the first inflection 0
point. -200 0 2 4 6 8 10

0.001N PES-Na added, ml

2.3.3. Polyelectrolyte titrations
The polyelectrolyte titrations were performed using a
MUTEK particle charge detector (PCD-02).
The pulp sample (0.5 g) was diluted with 100 g of
0.001N Poly-DADMAC and stirred by a magnetic stir-
rer for 2 h. During this time the cationic polyelectrolyte
completely neutralized the anionic charge in the pulp. The
solid content of the pulp was removed on a nylon sieve
and 10 ml of the filtrate was pipetted into the cell of
PCD-02 (MUTEK) and titrated with 0.001N PES-Na to
the endpoint where the streaming potential reached 0 mV.
The rate of titration was controlled at 0.3 ml/min. In
addition 10 ml of Poly-DADMAC solution was titrated
with PES-Na to the neutral point to determine the blank
value. In this investigation all charge determinations were
made at a 0.01 M NaCl concentration. The specific charge
density of the sample was calculated by the formula
below:
Fig. 3. Experimental data from a polyelectrolyte titration of kraft pulp
plotted as streaming potential (mV) vs. added volume of PES-Na.
3. Results and discussion
The shapes of typical titration curves for conductometric,
potentiometric and polyelectrolyte titrations are shown in
Figs. 1–3, respectively.
An experiment was carried out to check whether a 5 min
time lag between the titrant addition and pH measurement
in the potentiometric titrations was sufficient to reach equili-
bration of the system. The variation of pH in potentiometric
titration of unbleached softwood kraft pulp (kappa number
103) with holding time of about 5 min at different pH levels
is shown in Fig. 4. Up to neutral pH 7.0, the change in pH
11 10.16 - 10.19
10 9 01 - 9 15
9 7.90 - 8.00
8 7 13 - 7 18
pH

7
(Vp − Vb ) × c × 1000
6 31 - 6 35
6
q= 5 4.69 - 4.70

w 4
3
3.76 - 3.77

0.0 20.0 40.0 60.0 80.0

where q is the specific charge density (mmol/kg), Vp the Time, min

volume of titrant used for pulp (ml), Vb the volume of titrant Fig. 4. Variation of pH in potentiometric titration of kraft pulp with
used for blank (ml), c the concentration of titrant (mol/l), w holding time of about 5 min at different pH levels (no titrant was added
the solid content of pulp (g). during holding time).
42 N.K. Bhardwaj et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 236 (2004) 39–44
Fig. 5. Effect of different acid pre-treatment times on charge of unbleached
softwood kraft pulps as determined by poly-DADMAC adsorption in
0.01 M NaCl.
during 5 min holding was insignificant (less than 0.05 U). At
a pH of about 9.1, the variation increased to 0.14 U but then
decreased again to 0.03 U at pH 10.2. This suggested that a
holding time of longer than 5 min was not essential.
The effect of soaking time in the acid pre-treatment to
convert the anionic groups to the protonated form was de-
termined by comparing the charge given by polyelectrolyte
titration (PCD-02) after 16 h and 45 min soaking of two un-
bleached kraft pulps (Fig. 5). This figure shows that pulp
charge was higher after 16 h soak, so this treatment time was
used in this study.
The repeatability of each technique was determined by
performing three or four measurements on each pulp sam-
ple. Figs. 6 and 7 show the average value obtained by each
method plotted against pulp freeness with the error bars rep-
resenting one standard deviation on either side of the mean.
3.1. Effect of pulp beating on pulp charge
Variable results have been obtained from earlier studies
of the effect of beating/refining on electrokinetic properties
200
160
Charge mmol/kg
120
80
Potentiometric Tit. Conductometric Tit. (NaOH)
Conductometric Tit. (NaHCO3) Polyelectrolyte Tit.
40
0
750 640 560 460
Freeness, ml CSF
Fig. 6. Charge of the unbleached kraft pulp at various freeness levels as
determined by different methods.
60
Charge mmol/kg
40
20 Potentiometric Tit.
Conductometric Tit. (NaOH)
Polyelectrolyte Tit.
0
675 510 425 355 260
Freeness, ml CSF
Fig. 7. Charge of the bleached kraft pulp at various freeness levels as
determined by different methods.
of kraft pulps [9–16]. Goulet and Stratton [9] found that in-
creasing the level of refining did not appreciably affect the
weak acid content or the average electrophoretic mobility
of spruce kraft fibre fines. However, the cationic demand of
bleached sulfite [10] and softwood kraft [11] pulps as de-
termined by electrophoretic mobility has been reported to
increase with increased degree of beating. Miyanishi [12]
and Penniman [13] also reported similar results using the
streaming potential method for softwood kraft pulp. Her-
rington and Petzold [14] did not observe any change in total
charge, as measured by potentiometric titrations, during re-
fining of various previously dried bleached eucalyptus kraft
pulps. Gill [15] also found no effect of refining on surface
charge of bleached hardwood and softwood kraft pulps when
charge was determined by polyelectrolyte titration. The lack
of correlation of surface charge with the degree of refining
could not be explained. Carrasco et al. [16] reported an in-
crease in total cationic demand of industrial bleached hard-
wood kraft pulp on refining using colloidal titration with the
cationic polymer methylglycochitosan. To further compli-
cate matters, these researchers suggested that the fixation on
cellulosic fibres is attained through two mechanisms: ionic
exchange and adsorption by hydrogen bonds and van der
Waals forces.
The results of the beating treatment of unbleached soft-
wood kraft pulp are shown in Fig. 6. As beating opens up
the fibre surface, the fibre surface charge should increase
with increased beating. The polyelectrolyte titrations with
poly-DADMAC give the surface charge of pulp as only the
accessible charge on the surface of the fibres is able to be
neutralised by the poly-DADMAC. Only the polyelectrolyte
titrations give consistent increase in pulp charge with in-
creased beating. The pulp charge as determined by other
methods remained relatively constant as freeness was re-
370
duced due to increased beating.
The conductometric titrations with NaOH gave higher
pulp charge values compared to those obtained with
NaHCO3 because during the titration with sodium hydrox-
ide some of the lignin phenolic hydroxyl groups become
 N.K. Bhardwaj et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 236 (2004) 39–44 43

0.8 0.80
Charge ratio PCD/Pot. Tit.
Charge ratio PCD/Cond. Tit. (NaOH)

0.70
0.7

0.60

0.6
0.50

0.40
0.5 750 640 560 460 370
Freeness, ml CSF
Fig. 9. Relation of surface charge to total charge (Pot. Tit.) with pulp
freeness (unbleached softwood kraft pulp).
0.4
750 640 560 460 370

Freeness, ml CSF
0.80
Fig. 8. Relation of surface charge to total charge (Cond. Tit.) with pulp
freeness (unbleached softwood kraft pulp).
Charge ratio PCD/Pot. Tit.

y = 0.0058x
0.70 R 2 = 0.9472

ionised due to high pH towards the end of the titration and

consume the alkaline reagent [7].
The effects on the fibre charge from beating the bleached 0.60
softwood kraft pulp are shown in Fig. 7. Although the con-
ductometric titration gave slightly higher charge values than
the potentiometric titration for this pulp, the general trends 0.50
were similar to those shown by the unbleached pulp. Re- 80.00 100.00 120.00 140.00
cently, Fardim et al. [17], who compared different methods Charge (PCD)

for determining the total charge of pulp fibres, also observed Fig. 10. Relationship between surface charge and total charge of un-
the small differences between the results obtained from these bleached kraft pulp at various freeness levels.
two titration methods. It appears that within normal prac-
tical range of refining the total charge, which depends on
the chemical composition of fibre, does not change, which
supports the earlier observation reported by Herrington and 1.30

Petzold [14].
The ratio of surface charge to the total charge, as de-
termined by either conductometric titration using NaOH or
Charge ratio PCD/Pot. Tit.

1.10
potentiometric titration of pulps, is shown as a function of
freeness in Figs. 8 and 9, respectively. These curves show
two rather well differentiated sections: refining down to a y = 0.0313x
2
freeness of 560 CSF the ratio increases rapidly but then re- 0.90
R = 0.9732
mains relatively constant on refining to below this level.
The increase in the ratio at higher freeness levels (light
refining) can be interpreted in terms of accessibility of car-
boxylic groups. It may be recalled that the refining of pulp 0.70
not only increases both the outer and inner fibrillation but
also cuts the fibres. These actions increase surface accessibil-
ity and facilitate greater interaction between the carboxylic
groups and the polymer. This result agrees with previous 0.50
10.00 20.00 30.00 40.00
measurement where the amount of cationic polymer fixed
Charge (PCD)
by the pulp as a function of freeness was shown to increase
in similar fashion [16]. Similar trends were obtained with Fig. 11. Relationship between surface charge and total charge of bleached
bleached softwood kraft pulp. kraft pulp at various freeness levels.
44 N.K. Bhardwaj et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 236 (2004) 39–44
For both, unbleached and bleached pulps, a linear rela-
tionship was also obtained between the surface charge as
measured by polyelectrolyte titrations and ratio of surface
to total charge as determined by potentiometric titrations
(Figs. 10 and 11). This linear relationship confirms that only
fibre surface charge, as determined by the PCD method,
increased with the degree of beating, while the total fibre
charge did not change.
Similar linear relations were obtained between the surface
charge as measured by polyelectrolyte titrations and ratio
of surface to total charge as determined by conductometric
titrations using NaOH.
4. Conclusions
Conductometric titrations of the pulps with 0.05 M NaOH
resulted in higher values of pulp charge in comparison to
the same titrations with 0.05 M NaHCO3 due to ionization
of lignin phenolic hydroxyl groups at high pH. The sodium
hydroxide titrations gave values closer to the total charge as
determined by potentiometric titration.
Total charge of the fibres remained constant as refining
was increased but surface charge as determined by polyelec-
trolyte titration with poly-DADMAC increased as the degree
of refining increased.
Acknowledgements
The authors would like to thank staff at Visy’s Tumut mill
who provided the pulp samples. Nishi acknowledges the De-
partment of Chemical Engineering, Monash University and
Tuan acknowledges the Ministry of Education & Training
of Vietnam for the award of scholarships.
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