PEER-REVIEWED SIZING

Influence of wet-end variables on the sizing

efficiency of ASA on fine papers produced
with Eucalyptus globulus kraft pulps
SUSANA FERNANDES AND ANA PAULA DUARTE

ABSTRACT: The purpose of paper sizing is to make paper more resistant to liquid penetration.
Alkenyl succinic anhydride (ASA) is a synthetic sizing agent usually used in alkaline papermaking. ASA has
a fast curing size, but it can lose its ability if it is in contact with water. This work studies the influence of
dissolved Ca2+ and HCO3¯ ions in the papermaking stock, the effect of precipitated calcium carbonate (PCC),
and the influence of pH and temperature on ASA sizing efficiency using bleached Eucalyptus globulus kraft
pulps. Two different types of ASA (designated P and UP) and three different emulsions of ASA were used:
starch + ASA P, starch + ASA UP, and starch + ASA UP + surfactant. We concluded that a high concentra-
tion of dissolved Ca2+ ions in furnish diminished the sizing efficiency of ASA. Depending on the type of
ASA, concentrations below 300 or 500 ppm did not reduce the sizing efficiency. The amount of dissolved
HCO3¯ ions in furnish does not determine the sizing degree of ASA. According to our results, it is possible
to work with relatively high PCC loading levels. If it is necessary work with high filler loading levels, how-
ever, it is better to increase the ASA concentration in stock. The pH and temperature are the limiting vari-
ables of the process; high temperature with high pH reduces the sizing performance of ASA.
Application: This study describes the influence of wet-end variables on the internal sizing efficiency
of ASA. The results can be used by papermakers to better select and control paper chemistry.

A lkenyl succinic anhydride (ASA) is a cellulose-reactive siz-

ing agent that can impart different degrees of liquid repel-
lence to paper by decreasing the wettability of the cellulose
fibers. This synthetic sizing agent is known for its rapid on-
machine cure.ASA develops sizing in the sheet faster than oth-
ers sizing agents,such as alkyl ketene dimers (AKD).However,
in the presence of water, or if the furnish conditions are not
carefully controlled, ASA undergoes hydrolysis [1,2]. Usually,
this sizing agent is used for papers with low resistance to liq-
uids, such as fine paper grades [3].
The synthesis of ASA structures involves the reaction of
an alkene (or mixture of alkenes) with maleic anhydride.The 1. Formation of a covalent ester linkage between a cel-
number of carbon atoms in the alkene chain typically ranges lulose hydroxyl group and ASA4.
from 14 to 20, but the C16 and C18 structures are the most
effective.The anhydride function in the ASA molecule reacts must be prepared to add the ASA to the aqueous papermak-
with the cellulose hydroxy groups to give the corresponding ing suspension, and uniformly dispersed into it [4].The emul-
ester and carboxylic acid moieties. The latter is sterically sion is typically prepared with ASA,a cationic starch (or a syn-
shielded by the long hydrocarbon chain (Fig. 1), which pro- thetic cationic polymer),and a small amount of surfactant.The
vides hydrophobicity to the fibers [1,2]. starch-to-ASA ratio is usually in the range of 2:4 [1].The pa-
The undesired competitive reaction is the hydrolysis of rameters affecting the quality and stability of the emulsion are
the ASA anhydride function in the presence of water, which • the pH (3.5 to 4.5);
generates the corresponding dicarboxylic acid to the detri- • the temperature (room temperature);
ment of the sizing efficiency [1]. • the viscosity of the ASA sample;
ASA is a yellow, oily product that is insoluble in water, but • the contact time between the emulsion and the stock;
chemically sensitive to it.Therefore, an aqueous emulsion • the emulsion particle size (0.5-2 µm); and
VOL. 5: NO. 12 TAPPI JOURNAL 17
SIZING

2. Influence of additional Ca2+ ions on the ASA sizing 4. Influence of additional HCO3¯ ions on the ASA sizing
process using the three emulsions ASA P, ASA UP, and process using the three emulsions ASA P, ASA UP, and
ASA UP+S (2% of the fiber mass) (50ºC and pH 8) ASA UP+S (2% of the fiber mass) (50ºC and pH 8)
determined by Cobb60 analysis. determined by Cobb60 analysis.

• the time lag between the prepara- The rate of esterification during the threefold:
tion and use,which should be as short as on-machine cure is also affected by some • to study the factors affecting the ASA siz-
possible [4,5]. wet-end variables,including the stock pH ing of the fine papers produced with Por-
The emulsion process must be adjust- and temperature, the calcium and bicar- tuguese Eucalyptus globulus kraft pulps;
ed according to the type of ASA used [1]. bonate ion concentration, the type and • to show papermakers the benefits of
amount of filler particles present,and the ASA sizing, which only in the past few
first-pass retention levels on the machine years has gained some acceptance in Eu-
[1,2].Wasser [5] studied the effects of pH rope;and
and temperature in the cure rate of ASA. • to confirm ASA’s rapid on-machine cure.
The study showed that the cure rates de- To do that,we examined the effects
creased as the pH was lowered, and the of the wet-end variables in the ASA siz-
time to develop sizing was considerably ing process by producing paper sheets
reduced as a function of increasing tem- from industrial bleached kraft pulp
perature.According to Savolainen [6], a (100% E. globulus) in an M/K Systems
high concentration of soluble calcium former.The sizing efficiency was evalu-
ions reduces the sizing efficiency of ASA, ated by a set of techniques, as previ-
but a moderate concentration of bicar- ously suggested [8].
bonate ions improves it.This author also
found that the filler,which was precipitat- EXPERIMENTAL
ed calcium carbonate (PCC), influenced Preparation of the emulsions
the sizing by surface adsorption of the siz- The commercial ASA products used to
ing agents, making them unavailable for prepare the aqueous emulsions were
fiber sizing, and by reacting with the siz- supplied by Portuguese industries.
ing components. Fillers with a high spe- Their specifications (provided by the
cific surface area showed a higher ten- suppliers) are given in Table I. The
dency for chemical adsorption [7]. role of cationic starch is to stabilize the
The purpose of our investigation was ASA emulsion. It is used to control the

SAMPLE PROPERTIES VISCOSITY PURITY

Cationic starch DS — 82%
0.027-0.032
25% C16 +
3. Influence of additional Ca2+ ions
ASA P 65% C18 <225 mPa s* 90%
on the ASA sizing process using
non-ionic
the three emulsions ASA P, ASA UP,
ASA UP 100% C18 <200 mPa s* >95%
and ASA UP+S (2% of the fiber Non-ionic
mass) (50ºC and pH 8) determined
Surfactant — — —
by contact angle method at 0.5, 1,
*Measured in laboratory.
and 10 s following contact of the
drop of water with the paper. I. Properties of materials used in the production of emulsions.

18 TAPPI JOURNAL DECEMBER 2006

 SIZING
viscosity and fiber retention.The sur- PCC was the filler used in this study.
factant facilitates the emulsification and The pulp was disintegrated and then
enhances the ASA spreading [9]. beaten in a Valley beater (ISO 5264-1) to
Three different emulsions were pre- 25-30 ºSR, according to ISO 5267-1.The
pared, namely cationic starch + ASA P; suspensions were prepared in the differ-
cationic starch + ASA UP; and cationic ent conditions previously defined, and
starch + ASA UP + surfactant (ASA UP+S). test sheets of 80 g/m2 were fabricated in
The emulsions were prepared in batches an automatic MK 9000 former.This paper
at 30ºC using a commercial laboratory machine gives rise to ready-to-use paper
blender (Waring,model 7010S).The ASA P sheets.It comprises a suspension mixing
was blended at 22,000 rpm for 3.5 min., and sheet formation section, a press, and
the ASA UP and ASA UP+S were blended a drying station (~110°C).
at 18,000 rpm for 1.5 min.The ratio of We studied the effects of dissolved
cationic starch to ASA was 4:1 w/w. Ca2+ and HCO3¯ ions resulting from dif-
The suspension (500 g) of potato ferent additions of CaCl2 and NaHCO3 in
cationic starch (degree of substitution = the stock, respectively.The furnish tem-
0.027-0.032) at 3% (w/w), was cooked perature was 50ºC,the pH 8,the ASA ad-
for 30 min. at 95 ± 5ºC with continuous dition level 0.2% of the fiber mass, and
mechanical agitation following the the ionic concentration ranged from 50
methods of the TAPPI T 491-94 water to 2000 ppm for Ca2+ and from 100 to
immersion test of paperboard. 2000 ppm for HCO3¯.The levels of Ca2+
The emulsion particle size was in the stock were confirmed by atomic
measured in a Horiba model LA-300 an- absorption spectrophotometry.
alyzer and found to be consistently ~1 The influence of the PCC filler in
µm, as required in this context.The use the ASA sizing process was analyzed at
of the three ASA emulsions was limited 50ºC and pH 8 at 0.2% ASA addition
to 3-4 h at room temperature with me- level and the filler content was in the 5. Influence of additional HCO3¯
chanical agitation, during which no hy- range of 0% to 30% of the sheet weight. ions on the ASA sizing process
drolysis or increases in particle size A supplementary study was carried out using the three emulsions ASA P,
were detected. Given that a negligible with 20% PCC and 50, 300, or 500 ppm ASA UP, and ASA UP+S (2% of the
amount of ASA (if any) was hydrolyzed of calcium ions added, depending on fiber mass) (50ºC and pH 8) deter-
in all the experiment, this parameter the ASA emulsion used. mined by contact angle method at
was not taken into account. The study of the effect of stock pH 0.5, 1, and 10 s following contact of
Preparation of paper sheets and temperature at different ASA addi- the drop of water with the paper.
The test sheets used in this study were tion levels (0.1%, 0.2%, and 0.3% of the
prepared with a bleached kraft pulp fiber mass) on paper sizing was also on 15 samples of each ASA-sized sheet,
(100% E.globulus).The fine papers were carried out.The pH of the paper furnish according to the ISO 535 method,using
prepared in neutral/alkaline wet-end con- was adjusted to 5, 8, and 11. In the case deionized water on the wire side. Con-
ditions. They had a basis weight of 80 of pH 8 and 11, PCC was used as filler tact angles (five determinations per
g/m2 and a Cobb60 value of 28 g/m2. at a concentration of 20%.The temper- sample) were measured with a Data-
Table II lists the additives used in the atures in the stock were adjusted to Physics model OCAH 200 at 0.5, 1, and
preparation of the paper furnish and their 40ºC, 50ºC, and 60ºC. 10 s following the contact of the drop
dry weights,as provided by the suppliers. The order of component addition to of water with the paper (TAPPI T 458
the suspension was PCC,starch,ASA emul- om-94, surface wettability of paper).
PRODUCT DRY WEIGHT
sion (40 s in contact with the suspension), The filler retention on the test
Bleached kraft pulp 92% and finally the retention agents.For pH ad- sheets was determined by measuring
Cationic starch 82% justments of the stock, aqueous solutions the ash content of the paper, according
Precipitated calcium of HCl and NaOH were used. to the ISO 1762 standard method.
carbonate (PCC) 19.5% Sheets testing
Retention agent A 85%-90% The dried sheets were stored in a room RESULTS AND DISCUSSION
Retention agent B 90%-100% with controlled humidity and tempera- Effect of the dissolved
ture (50% RH and 23ºC, according to calcium ions
II. Properties of the additives used ISO 187) for 30 min. before characteri- Figure 2 shows the influence of Ca2+
in the preparation of the test zation. Cobb60 values were determined ions on the sizing efficiency, as deter-
sheets.
VOL. 5: NO. 12 TAPPI JOURNAL 19
SIZING

6. Effect of PCC addition level and dissolved Ca2+ ions 8. Effect of PCC addition level and dissolved Ca2+ ions
on paper sizing with ASA P (0.2% of the fiber mass) at on paper sizing with ASA UP+S (0.2% of the fiber
50ºC and pH 8 determined by Cobb60 and contact mass) at 50ºC and pH 8 determined by Cobb60 and
angle method. contact angle method.

9. Filler retention under different PCC concentrations

and dissolved Ca2+ ions additions for the three emul-
sions: ASA P, ASA UP, and ASA UP+S.

mined by Cobb60, for the ASA P,ASA UP, and ASA UP+S emul-
sions.With 500 ppm of Ca2+ ions, the Cobb60 value was the
same (20 g/m2) for both ASA UP and ASA UP+S,but lower for
the ASA P emulsion.This study verified that the upper limit
of Ca2+ ion concentration to be used with ASA P, without
harming sizing quality, was about 300 ppm.
Similar results were obtained with the contact angle deter-
minations (Fig. 3).These results indicated that high amounts of
7. Effect of PCC addition level and dissolved Ca2+ ions dissolved calcium ions in the stock were detrimental to the ASA
on paper sizing with ASA UP (0.2% of the fiber mass) sizing process,as emphasized by the contact angle values for the
at 50ºC and pH 8 determined by Cobb60 and contact ASA P with 1000 ppm of Ca2+.The contact angles were about 90º
angle method. for the first second following the drop contact with the paper,

20 TAPPI JOURNAL DECEMBER 2006

 SIZING
and decreased to ~70º within 10 s.When the Ca2+ concentration
was raised to 2000 ppm,it became impossible to determine the
contact angle after ~1 s because the water drop had already been
adsorbed by the paper sheet.
The importance of the study of the influence of the cal-
cium ion on the efficiency of ASA sizing is related to the char-
acteristics of the white water that is used in the alkaline pa-
permaking (the calcium ions are recycled with the water and
returned to the stock) and to the strong dependence of the
concentration of calcium ions on the pH of the furnish.A de-
crease of the wet-end process pH gives rise to an increase in
the calcium ion concentration.
The dissolved Ca2+ ions probably adsorb onto the surface of
the ASA droplets and prevent their uniform distribution on the
fibers’surface,consequently limiting the formation of ester link-
ages.The low concentration of Ca2+ ions does not limit the ef-
ficiency of ASA sizing. It is important, however, to control the
pH of the stock (pH = 7-8) to maintain a low dissolved calcium
ion concentration.
Effect of the bicarbonate ions
Figures 4 and 5 clearly show that the Cobb60 values (20-23
g/m2) and the contact angle (115°-120º) for the three emulsions
and for all the studied conditions were close to each other.This
seems to indicate that the degree of sizing was not affected by
the different bicarbonate ion concentrations of HCO3¯ at 50ºC
at pH 8.In other words,concentrations of 100-2000 ppm were
not harmful to the sizing efficiency of the ASA process.
The presence of HCO3¯ ions is essential for AKD to func-
tion as a sizing agent.Normally,papermakers add NaHCO3 and
Na2CO3 to increase the concentration of bicarbonate on the
paper furnish. Probably these ions improve the retention of
the AKD particles on the fiber surface [2].Our results with ASA
indicate a different behavior, probably because the contact
time between the ASA and the alkaline stock was not sufficient
for any reaction between the size agent and the bicarbonate
ion to take place (swelling), or because the HCO3¯ ions could
not stop the ASA from reacting with cellulose. 10. The influence of pH and temperature of the paper
Effect of the PCC furnishes at different ASA P addition levels determined
The results obtained with the Cobb60 and contact angle sug- by Cobb60 and contact angle method.
gest that the degree of sizing with 0.2% ASA was dependent on
filler loading. Figures 6, 7, and 8 demonstrate the effect of The Cobb60 results corresponding to the PCC values on
the PCC addition level and the concentration of dissolved cal- the suspension and on the paper, with 25% and 30% of filler
cium ions, as well as the filler loading levels, for ASA P,ASA UP, loading levels, were different, whereas the contact angles
and ASA UP+S,respectively.The graphics suggest that good siz- were not affected by these changes.
ing results were obtained within the level range of filler load- We also examined the effect of three different concentra-
ing used in the fine paper industry, which is 15%-30%. tions of dissolved calcium ions in conjunction with a filler load-
Figures 6-8 also show the role of the filler loading level on ing level of 20%.The concentrations of dissolved calcium ions
the suspension and the paper.These were studied because used were 50 and 100 ppm,and the limit reached in this study
the mechanical retention of the paper machine was 50%.We without alteration in the degree of ASA sizing was 300-500
therefore introduced 60% PCC relative to the fiber in the ppm.The dissolved calcium ion concentrations of 50 and 100
paper furnish to have 30% of the fiber mass in the final paper. ppm,with or without added PCC,did not reduce the sizing ef-
This increase in PCC level influenced the degree of sizing so ficiency of ASA. However, with 20% PCC, the addition of high-
that the quantity of ASA was not effective. er PCC loads did hamper ASA sizing effectiveness.

VOL. 5: NO. 12 TAPPI JOURNAL 21

SIZING

11. The influence of pH and temperature of the paper

furnishes at different ASA UP addition levels deter-
mined by Cobb60 and contact angle method. 12. The influence of pH and temperature of the paper
furnishes at different ASA UP+S addition levels deter-
We can therefore conclude that if the filler loading must be
mined by Cobb60 and contact angle method.
increased, a corresponding increase in ASA loading is recom-
mended.This is in tune with the work of Cates and coworkers
[9], who found that when ASA is added to the paper furnish, it Effect of pH and temperature
can be adsorbed on the surface of the fibers, but it can also be Figures 10,11,and 12 show the effects of pH and tempera-
adsorbed on the surface of the PCC.As a result,the sizing agent ture on paper furnish at different ASA concentrations for the
adsorbed on the filler surfaces cannot contribute to the sheet three ASA emulsions.Three major trends were encountered in
hydrophobicity. Moreover, this hampers filler retention in the this context:
paper sheet [2,10]. • ASA can successfully be used even in acidic environ-
Good filler retention was obtained with each of the three ments (pH = 5) between 40ºC and 60ºC;
ASA emulsions (Fig. 9). • the combination of high temperature (60ºC) with high
pH (11) is detrimental to the ASA sizing; and

22 TAPPI JOURNAL DECEMBER 2006

 SIZING
• with 0.1% of added ASA and a filler is close to 60ºC,the stock pH should be 2. Hodgson, K.T., Appita J. 47(5):
loading of 20%,sizing almost failed. kept between 7 and 8. 402(1994).
This latter observation suggests that The concentration of hydrogen car- 3. Araújo, J.A., Oliveira I., Massoquette A.,
et al., Proceedings of the Associação
the ASA added to the furnish was en- bonate ions did not affect the sizing
Brazileira Técnica de Celulose e Papel
tirely taken up by the PCC particles and quality, independent of the type of ASA (ABTCP) 30th Pulp and Paper Annual
left the fiber surface unmodified. emulsion used. Meeting, ABTCP, São Paulo, Brazil,
The temperature of the circulating The PCC content in the paper furnish 1997, p. 527.
water in the closed water circulation played an important role in the ASA sizing 4. Farley, C.E. and Wasser, R.B., in The
systems used in the paper industry of E. globulus kraft pulps. However, it is Sizing of Paper (Reynold, W.F. Ed.) 2th
edn., TAPPI PRESS, 1989, pp. 51-61.
make is difficult to control. It is there- possible to work without any sizing prob-
fore important to know how an in- lem with the filler contents usually em- 5. Wasser, R.B., J. Pulp Paper Sci., 13(1):
29(1987).
crease in stock temperature influences ployed in the papermaking industry.
6. Savolainen, R.M., Proceedings of the
the ASA sizing efficiency. In our study,
1996 TAPPI Papermakers Conference,
sizing was successful even when the ACKNOWLEDGEMENTS TAPPI PRESS, Atlanta, p. 289.
temperature and the ASA concentration The authors thank Soporcel (Portucel 7. Velho, J., in Mineral fillers for paper
were relatively high, namely 60ºC and Group, Portugal) for the supply of E. Why, What, How (Tecnicelpa Technical
0.3%,but the best results were obtained globulus pulp, and Cristina Lopes, Juli- books Ed.), Tecnicelpa - Portuguese
when the temperature was 40ºC.The eta Sansana, Francisco Franco, João Association of the Pulp and Paper
Technicians, 2003, pp. 185-188.
combination of high temperature and Breda, and João Patrão, for their kind
high pH was detrimental to the ASA siz- help in the use of the equipment to 8. Gess, J.M., Tappi 64(1): 35(1981).
ing efficiency,probably because in these carry out the determination of emul- 9. Cates, R.E., Dumas, D., and Evans, D.,
in The Sizing of Paper (Reynold, W.F.,
extreme conditions, the rate of ASA hy- sion particle size.Thanks also to Paulo
Ed.) 2nd edn., TAPPI PRESS, 1971,
drolysis overcame that of esterification. João (Raisio Chemicals, Portugal) for Chap. 12.
the additives and helpful advice. We 10. Zhmud, B., Seppänen, R., and Tiberg,
CONCLUSION also acknowledge the collaboration and F., Proceedings of the Pira 2001
The main purpose of this study was to assistance of Cristina Gil. TJ Scientific & Technical Advances in the
analyze the influence of different wet- Internal and Surface Sizing of Paper
Submitted: May 22, 2006 and Board, Pira International,
end conditions on ASA sizing using Por-
Revised: September 11, 2006 Leatherhead, UK, paper 6.
tuguese E. globulus kraft pulps. Accepted: September 25, 2006
We found that a high concentration This paper is also published on
of dissolved calcium ions and the asso- LITERATURE CITED
ciation of high temperature with high
www.tappi.org
1. Neimo, L. in Papermaking Science and
and summarized in the December
pH are detrimental to the ASA sizing ef- Technology, Papermaking chemistry,
Helsinki, TAPPI PRESS, 1999, Chapter 7. issue of Paper360º magazine.
ficiency. If the temperature of the stock

INSIGHTS FROM THE AUTHORS energy of the

paper sheets pro-
Our goal with this work was to demonstrate that internal
duced with this in-
sizing with ASA is, in fact, a reliable process, in terms of
ternal sizing ap-
influencing the variables in the wet-end paper machine.
proach, as well as
Moreover, before this work there was a lack of informa-
the evaluation of
tion in the literature concerning the internal sizing with
the quality of the
ASA on fine papers produced with Eucalyptus globulus.
final products.
The stabilization of the ASA emulsion revealed itself
This research
as the most difficult stage, particularly the control and
work was devel- Fernandes Duarte
attainment of the ideal particle size. This problem was
oped in the Sci-
overcome by using appropriated equipment.
ence and Technolo-
This work clearly demonstrated the effectiveness of gy of Paper Department at the University of Beira
the internal sizing with ASA in the paper production Interior, Covilha, Portugal.
using E. globulus bleached kraft pulps. Therefore, this
study represents an important contributionj to the un- Fernandes and Duarte are with the Research Unit of Textile
derstanding of the paper internal sizing processes. and Paper Materials, University of Beira Interior, Covilhã,
The next step will be the assessment of the surface Portugal; email Fernandes at [email protected].

VOL. 5: NO. 12 TAPPI JOURNAL 23