Colloids and Surfaces A: Physicochem. Eng.

Aspects 289 (2006) 219–225

Introduction of aldehyde groups on surfaces of native cellulose

fibers by TEMPO-mediated oxidation
Tsuguyuki Saito, Akira Isogai ∗
Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Received 8 January 2006; received in revised form 18 April 2006; accepted 21 April 2006
Available online 29 April 2006

Abstract
Native cellulose fibers were suspended in water and oxidized to various degrees with sodium hypochlorite and catalytic amounts of 2,2,6,6-
tetramethylpiperidine-1-oxy radical (TEMPO) and sodium bromide at pH 10.5. The oxidation was accomplished within 30 min at room temperature.
The TEMPO-oxidized cellulose fibers were then converted to sheets like paper. Tensile strength of the sheets soaked in water, i.e. wet strength, showed
a maximum value, when 0.3 mmol NaClO per gram cellulose was used in the TEMPO-mediated oxidation. Aldehyde groups up to 0.225 mmol/g
were introduced in native cellulose fibers by the TEMPO-mediated oxidation, and were stably present in there. However, only surface aldehyde
groups in the TEMPO-oxidized cellulose fibers contributed to the wet strength development of the sheets. Carboxylate groups were also formed
not only surfaces but also insides of cellulose fibers by the TEMPO-mediated oxidation, although they had nearly no contribution to wet strength
development of the sheets. These surface aldehyde groups forms hemiacetal linkages with cellulose hydroxyl groups at the inter-fiber bonds, resulting
in the clear wet strength development of the sheets prepared thereof. The TEMPO-mediated oxidation is, therefore, applicable to introduction of
not only carboxylate groups but also aldehyde groups to native cellulose surfaces as an efficient chemical modification under aqueous conditions.
© 2006 Elsevier B.V. All rights reserved.

Keywords: TEMPO; Aldehyde group; Cellulose; Wet strength development; Hemiacetal linkage

1. Introduction TEMPO-oxidized native celluloses were reported [5]. Because

Recently, a new selective and efficient oxidation method
of primary hydroxyl groups of polysaccharides to carboxyl
groups has been developed, where sodium hypochlorite and
catalytic amounts of 2,2,6,6-tetramethylpyperidine-1-oxy rad-
ical (TEMPO) and sodium bromide are applied to aqueous
polysaccharide solutions at pH 10–11 [1,2]. Although cellulose
is insoluble but only suspended in water at the initial stage,
water-soluble ␤-1,4-linked polyglucuronic acid sodium salt, i.e.
cellouronic acid, having a homogeneous chemical structure can
be obtained quantitatively by the TEMPO-mediated oxidation of
regenerated and mercerized celluloses [3,4]. On the other hand,
when native celluloses are used, the initial fibrous morpholo-
gies are mostly maintained even after the TEMPO-mediated
oxidation under harsh conditions. In a previous paper, detailed
analytical results such as carboxylate and aldehyde contents of
∗ Corresponding author. Tel.: +81 3 5841 5269; fax: +81 3 5841 5269.
E-mail address: aisogai@mail.ecc.u-tokyo.ac.jp (A. Isogai).
carboxylate and aldehyde groups are present only on cellulose
I crystal surfaces and in disordered regions [5,6], the TEMPO-
mediated oxidation can be regarded as one of the most efficient
surface modification methods for native cellulose fibers under
aqueous conditions. The mechanism of the TEMPO-mediated
oxidation of cellulose is shown in Fig. 1. The oxidation begins
by the addition of NaClO to aqueous cellulose suspensions in
the presence of catalytic amounts of TEMPO and NaBr at pH
10–11 and room temperature. The C6 primary hydroxyl groups
of cellulose are converted to carboxylate groups via C6 aldehyde
groups, and only inexpensive NaClO and NaOH are consumed
as the oxidation proceeds.
During our studies on TEMPO-mediated oxidation of native
cellulose fibers [5–10], we have found that tensile strength of
cellulose sheets soaked in water, i.e. wet strength, was remark-
ably improved, when TEMPO-oxidized native cellulose fibers
were used for sheet making [7,11,12]. Wet strength is one of
the significant functionalities for cellulosic products such as
wash-and-wear shirt, filter paper, tissue paper, paper towel and
others. Generally, wet strength resins are added to cellulose

0927-7757/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2006.04.038
220 T. Saito, A. Isogai / Colloids and Surfaces A: Physicochem. Eng. Aspects 289 (2006) 219–225
Fig. 1. TEMPO-mediated oxidation of cellulose to form C6-carboxylate groups via C6-aldehyde groups.
slurries to produce wet strength cellulose sheets, where some
water-resistant interactions are formed between cellulose fibers
through the resin molecules during the sheet-making process.
In the case of wet strength development of the TEMPO-
oxidized cellulose sheets, aldehyde groups formed as intermedi-
ate structures by the TEMPO-mediated oxidation may contribute
to the wet strength development of the sheets observed in the
previous papers [7,11]. The contribution of aldehyde groups
to wet strength development of cellulose sheets have already
been proposed for the aldehyde-containing wet strength resins
added to cellulose slurries. Cationic glyoxalated polyacrylamide
resins [13] cationic dialdehyde starch [14] and dextran aldehyde
[15] were aldehyde-containing wet strength resins for cellulose
sheets. These resins are hypothesized to improve wet strength
of cellulose sheets by forming covalent bonds at the inter-
fiber bonds through hemiacetal and/or acetal linkages between
hydroxyl groups of cellulose and the aldehyde groups of the
added resins.
In this paper, the TEMPO-mediated oxidation was applied to
native cellulose fibers, and the mechanism for improving wet
strength of the sheets prepared thereof was studied in terms
of total and surface carboxylate and aldehyde contents in the
TEMPO-oxidized celluloses.
2. Experimental
2.1. Materials
A commercial hardwood bleached kraft pulp beaten, i.e.
mechanically fibrillated, to 529 mL Canadian Standard Freeness
in a PFI mill was used as native cellulose fibers for the TEMPO-
mediated oxidation. Cellulose content of this sample was 90%,
and the rest was mostly xylan. Carboxyl and aldehyde con-
tents of the cellulose were 0.054 and 0.006 mmol/g, respectively.
TEMPO (2,2,6,6-tetramethyl-piperidine-1-oxy radical), sodium
bromide, 9 mass% sodium hypochlorite solution, sodium boro-
hydride, sodium chlorite, and other reagents and solvents were of
laboratory grades (Wako Pure Chemicals Co., Japan). Standard
solutions of 2.5 meq/L poly(diallyldimethylammonium chlo-
ride) (PDADMAC) and potassium poly(vinylsulfate) (KPVS)
were commercial products for polyelectrolyte titration (Wako
Pure Chemicals Co., Japan), and used after dilution to 0.5
and 0.1 meq/L, respectively, with water for determining anionic
charges of cellulose surfaces. The weight average molecular
mass (Mw) of PDADMAC used was 88,700, which was deter-
mined by a batch system using a multi angle laser-light scattering
detector (DAWN EOS, λ 690 nm; Wyatt technologies, USA)
with 0.1 M NaCl as a solvent. Data acquisition and processing
were carried out using the ASTRA software (Wyatt technolo-
gies).
2.2. Preparation of TEMPO-oxidized cellulose fibers
Cellulose (10 g) was suspended in water (750 mL) contain-
ing TEMPO (0.025 g) and sodium bromide (0.25 g) [5,11]. The
9% NaClO solution (0–40.04 g corresponding to 0–4.84 mmol
NaClO per gram of cellulose) was added to the cellulose slurry
under continuous stirring. The pH of the slurry was maintained to
be 10.5 at room temperature by adding 0.5 M NaOH using a pH
stat until no consumption of the NaOH solution was observed.
 T. Saito, A. Isogai / Colloids and Surfaces A: Physicochem. Eng. Aspects 289 (2006) 219–225
It took 5–30 min, depending on the amount of the NaClO solu-
tion added. The TEMPO-oxidized cellulose thus prepared was
washed thoroughly with water on a filter paper set in a Büchner
funnel, and then the wet cellulose of 10% consistency was stored
at 4 ◦ C without drying before use.
Selective reduction and oxidation of aldehyde groups in the
TEMPO-oxidized celluloses were carried out with sodium boro-
hydride at pH 8 and sodium chlorite at pH 4–5, respectively,
as follows. The 10% TEMPO-oxidized cellulose/water mixture
(20 g) was suspended in water (100 mL), and sodium borohy-
dride (1 g) was added to the slurry at pH of about 8, which
was adjusted by adding a dilute ammonium hydroxide solu-
tion. After stirring the slurry at room temperature for 48 h, the
NaBH4 -treated cellulose was washed thoroughly with water by
filtration. On the other hand, a 5 M aqueous acetic acid solution
(20 mL), sodium chlorite (1.81 g) and the 10% TEMPO-oxidized
cellulose/water mixture (20 g) were added to water (82 mL), and
this slurry was stirred at room temperature for 48 h [16]. The
NaClO2 -treated cellulose was washed thoroughly with water by
filtration. These NaBH4 - and NaClO2 -treated celluloses were
stored at 10% consistency in water without drying for the suc-
cessive sheet making. For determination of total and surface
carboxylate contents of the wet cellulose samples, they were
washed with acetone by filtration, dried in air and then vacuum-
dried at 40 ◦ C for 1 day.
2.3. Total and surface carboxylate contents in cellulose
fibers
Total carboxylate content in cellulose fibers was determined
by the electric conductivity titration method [5,11]. To a dried
sample (0.3 g) were added water (55 mL) and 0.01 M NaCl
(5 mL), and this slurry was stirred until sufficiently dispersed
state was obtained. Then 0.1 M HCl was added to the mixture to
set the pH value in the range of 2.5–3.0. A 0.04 M NaOH solu-
tion was added at a rate of 0.1 mL/min up to pH 11 by using a pH
stat. Carboxylate content of cellulose was determined from the
conductivity and pH curves, and expressed as an average value
of three measurements. The TEMPO-oxidized celluloses were
further oxidized with sodium chlorite at pH 4–5 by the afore-
mentioned method, and the carboxylate groups formed by this
NaClO2 oxidation were regarded as those formed from aldehyde
groups originally present in the TEMPO-oxidized celluloses
[16]. Fluctuations of the obtained carboxylate and aldehyde con-
tents were within ±2% for each sample.
Surface carboxylate content in cellulose fibers was deter-
mined by the polyelectrolyte titration method [17,18]. An accu-
rate amount of cellulose (0.050 g) was sufficiently dispersed
in water (20 mL), and the PDADMAC solution of 0.5 meq/L
(20 mL) was added to the cellulose slurry. After stirring for
1 h to reach adsorption equilibrium, the supernatant was sepa-
rated by filtration, and adjusted to 100 mL by adding water. Ten
milliliters of this filtrate was collected and subjected to the back-
titration with 0.1 meq/L KPVS to detect the 0 mV point using
an automatic charge analyzer (PCD-03, BTG Mütek GmbH,
Germany) for determining the amount of PDADMAC remain-
ing in the filtrate. Surface carboxylate content in cellulose was
221
calculated from the amount of PDADMAC adsorbed on the
cellulose fibers, assuming that the polyion complex formation
between carboxylate groups on the cellulose fiber surfaces and
PDADMAC proceeded stoichiometrically [17,18]. Three mea-
surements were made on each sample for determination of total
and surface carboxylate contents, and the average results were
reported.
2.4. Cellulose sheet making
The TEMPO-oxidized celluloses were suspended in tap water
(pH 7.8) under continuous stirring at 500 rpm. Cellulose sheets
with a basis weight of 60 g/m2 were prepared from the cellu-
lose slurry with tap water, according to TAPPI Test Method T
205 om-88 (2001). The wet-pressed sheets were dried at 100 ◦ C
for 2 min using a rotary drum-dryer. The cellulose sheets thus
obtained were conditioned at 23 ◦ C and 50% relative humidity
for more than 1 day. Wet strength of the sheets was measured
in accordance with TAPPI Test Method T 456 om-87 (2001),
and expressed as wet tensile index. Soaking time of the 15 mm
width specimen strips in de-ionized water was set to 30 min for
the wet strength measurement.
3. Results and discussion
3.1. Wet strength of sheets prepared from the
TEMPO-oxidized native celluloses
Intra- and inter-fiber hydrogen bonds are formed in cellu-
lose sheets like paper during pressing and drying processes,
and these bonds lead to dry strength development of the sheets.
Because water molecules break these hydrogen bonds quite eas-
ily, wet strength of the cellulose sheets remarkably dropped by
soaking them in water. On the other hand, the sheets prepared
from cellulose fibers slightly oxidized by the TEMPO-mediated
system had wet strengths higher than that of the original cellu-
lose sheets [11]. Especially, when the cellulose oxidized with
0.3 mmol NaClO (per gram cellulose) in the TEMPO-mediated
system was used, wet tensile strength of the sheets showed a
maximum value (Fig. 1) [11]. It took about 15 min to accomplish
the NaOH consumption in the TEMPO-mediated oxidation of
cellulose fibers at this NaClO addition. This phenomenon indi-
cates that some interactions resistant to water are formed in the
highest quantity at this point between the TEMPO-oxidized cel-
lulose fibers in the sheets. Because wet strength of the sheets
rather decreased by the excessive TEMPO-mediated oxidation,
the intra- and/or inter-fiber interactions contributing to the wet
strength development may be due to some intermediate struc-
tures formed during the course of the TEMPO-mediated oxida-
tion of native cellulose fibers. Judging from the mechanism of
TEMPO-mediated oxidation in Fig. 1, the C6-aldehyde groups
present as intermediates in the native cellulose fibers are the
possible candidates for the wet strength development of the
cellulose sheets in Fig. 2. In one of the previous papers, we
reported that significant amounts of C6 aldehyde groups were
formed during the course of TEMPO-mediated oxidation of
starch [19].
222 T. Saito, A. Isogai / Colloids and Surfaces A: Physicochem. Eng. Aspects 289 (2006) 219–225
Fig. 2. Relationship between the amount of NaClO added in the TEMPO-
mediated oxidation of cellulose and wet tensile strength of sheets prepared
thereof.
The cellulose oxidized by the TEMPO system under the opti-
mum conditions for wet strength development in Fig. 2 (i.e. at
the 0.3 mmol NaClO addition) was then reduced with NaBH4
or further oxidized with NaClO2 to convert aldehyde groups in
the TEMPO-oxidized cellulose to alcohol or carboxyl groups.
Expectedly, wet strength of the sheets decreased from 4.9 to
0.6 Nm/g, i.e. to about one eighth, by the NaBH4 -reduction or
NaClO2 -oxidation of the TEMPO-oxidized cellulose (Fig. 3).
This result clearly supports the hypothesis that aldehyde groups
formed as intermediates in the TEMPO-oxidized cellulose con-
tribute to the wet strength development of the sheets prepared
thereof. Moreover, the wet strengths of 0.6 Nm/g for these cellu-
lose sheets were even lower than that of 1.1 Nm/g for the blank
cellulose sheets. Thus, even though the original cellulose had
aldehyde groups of only 0.006 mmol/g, these aldehyde groups
seemed to more or less contribute to wet strength development
of the cellulose sheets.
Fig. 3. Wet tensile strength of sheets, which were prepared from the original cel-
lulose, the TEMPO-oxidized cellulose prepared under the optimum conditions
in Fig. 2, and that further treated by either reduction with NaBH4 or oxidation
with NaClO2 .
Fig. 4. Carboxylate and aldehyde contents in cellulose fibers oxidized by the
TEMPO-mediated system with 0–0.61 mmol NaClO (per gram of cellulose) at
room temperature.
3.2. Carboxylate and aldehyde contents in the
TEMPO-oxidized native celluloses
Carboxylate and aldehyde contents in the bulk of cellulose
fibers prepared by the TEMPO-mediated oxidation to various
degrees were measured by the conductivity titration method
before and after the selective oxidation of aldehyde groups to
carboxylate ones in the celluloses with NaClO2 (Fig. 4) [16]. The
characteristic point for the TEMPO-mediated oxidation of native
celluloses, like bleached kraft pulp in this case, is that significant
amounts of aldehyde groups are formed and stably present in the
TEMPO-oxidized celluloses [5]. Aldehyde groups remarkably
increased from 0.006 to ca. 0.2 mmol/g by the TEMPO-mediated
oxidation of the cellulose at the 0.3 mmol (per gram cellulose)
NaClO addition, and this aldehyde content was almost twice as
much as the carboxylate content of this TEMPO-oxidized cel-
lulose. It is reasonable that the TEMPO-oxidation of cellulose
with an excessive amount of NaClO led to further oxidation of
aldehyde groups to carboxylate ones, resulting that the amount
of carboxylate groups eventually became higher than that of
aldehyde groups for the TEMPO-oxidized cellulose prepared at
the 0.6 mmol (per gram cellulose) NaClO addition.
It was found in one of the previous papers [6] that carboxy-
late groups are homogeneously present from surface to inside
of cross section of the TEMPO-oxidized native cellulose fibers,
and that carboxylate groups are introduced only on crystal sur-
faces and in disordered regions of native celluloses without any
introduction into the inside of the cellulose I crystallites. Thus,
these aldehyde and carboxylate groups are present on the crystal
surfaces and in disordered regions in relatively high densities,
maintaining not only fibrous form but also microfibril structures
of native celluloses. The aldehyde groups once formed in the
native cellulose fibers are able to form hemiacetals with hydroxyl
groups of cellulose sterically close to each other. This hemiac-
etal formation of aldehyde groups probably participates in the
reason why significant amounts of aldehyde groups are stably
present without converting to carboxylate groups in the TEMPO-
oxidized native celluloses; these hemiacetals once formed must
 T. Saito, A. Isogai / Colloids and Surfaces A: Physicochem. Eng. Aspects 289 (2006) 219–225 223

Fig. 6. Relationship between aldehyde content on the surfaces of the TEMPO-

oxidized cellulose fibers and wet tensile strength of the sheets prepared thereof.
Fig. 5. Carboxylate and aldehyde contents of surfaces of cellulose fibers oxi-
dized by the TEMPO-mediated system with 0–0.61 mmol NaClO (per gram of
cellulose) at room temperature. but also in some inner surfaces must be accounted for cellulose
surfaces in this study. Because the fibrillated cellulose prepared
have some resistance to further attack by the oxidized TEMPO using a PFI mill was used as the starting cellulose fibers, signif-
molecules owing to steric hindrance. However, the pattern of icant amounts of outer and inner surfaces were formed during
aldehyde content in Fig. 4 does not correspond to that of wet the fibrillation process of the cellulose [20], thus resulting in
strength development of the sheets in Fig. 2; all aldehyde groups the relatively high ratios of the surface carboxylate contents. On
formed in the TEMPO-oxidized cellulose fibers do not necessar- the other hand, the ratio of surface aldehyde groups decreased
ily contribute to the development of wet strength of the sheets. from 37 to 2% with increasing the amount of added NaClO
from 0 to 0.6 mmol/g cellulose or increasing the degree of the
3.3. Surface carboxylate and aldehyde contents in the TEMPO-mediated oxidation. This result shows that aldehyde
TEMPO-oxidized native celluloses groups formed on the cellulose fiber surfaces are susceptible to
further oxidation by the TEMPO system, while those formed
Contents of carboxylate and aldehyde groups on the TEMPO- inside the cellulose fibers become relatively resistant to further
oxidized cellulose fiber surfaces were then measured by the poly- oxidation probably by the formation of hemiacetal linkages with
electrolyte titration method, where carboxylate groups accessi- hydroxyl groups of cellulose sterically close to each other.
ble to the adsorption of PDADMAC molecules were regarded
as those present on the cellulose fiber surfaces. As shown 3.4. Mechanism of wet strength development of sheets
in Fig. 5, the surface aldehyde groups increased from 2.0 to prepared from the TEMPO-oxidized native celluloses
19.2 ␮mol/g by the TEMPO-mediated oxidation of the cellulose
at the 0.3 mmol (per gram cellulose) NaClO addition, and then Because aldehyde groups formed in the TEMPO-oxidized
decreased to 4.3 ␮mol/g at the 0.6 mmol (per gram cellulose) celluloses can form intra- and inter-fiber hemiacetal linkages
NaClO addition. On the other hand, surface carboxylate content
in the celluloses increased with increasing the NaClO addition
in the TEMPO-mediated oxidation. The pattern of the surface
aldehyde content having the maximum peak at the 0.3 mmol
(per gram cellulose) NaClO addition was consistent quite well
with that of the wet tensile strength of the sheets (Fig. 6).
Thus, even though the surface aldehyde content of the TEMPO-
oxidized cellulose prepared at the 0.3 mmol NaClO addition
is only 19.2 ␮mol/g, these aldehyde groups significantly con-
tribute to the wet strength development of the cellulose fiber
sheets. In contrast, neither total nor surface carboxylate groups
in the TEMPO-oxidized celluloses have any contribution to wet
strength development of the sheets.
The ratio of surface carboxylate groups to those in the bulk
of TEMPO-oxidized cellulose fibers was roughly constant in
the range of 40–56%, irrespective of the NaClO addition in the
TEMPO-mediated oxidation of cellulose (Fig. 7). These high Fig. 7. Ratio of surface carboxylate or aldehyde content to that of the bulk of
ratios of surface carboxylate contents show that carboxylate cellulose fibers oxidized by the TEMPO-mediated system with 0–0.61 mmol
groups present not only on outer surfaces of the cellulose fibers NaClO (per gram of cellulose) at room temperature.
224 T. Saito, A. Isogai / Colloids and Surfaces A: Physicochem. Eng. Aspects 289 (2006) 219–225
Fig. 8. Possible mechanisms of formation of inter-fiber hemiacetal linkages and improvement of wet-tensile strength of the sheets prepared from the TEMPO-oxidized
cellulose.
with hydroxyl groups of cellulose, wet strength development
of the sheets prepared from the TEMPO-oxidized celluloses is
likely to be due to the formation of these hemiacetal linkages in
the sheets as in the cases of glyoxalated polyacrylamide [13],
dialdehyde starch [14] and dextran aldehyde [15]. The result
in Fig. 6 revealed that the formation of inter-fiber hemiacetal
linkages contributed to wet strength development of the sheets
more directly than that of intra-fiber hemiacetal linkages in the
sheets, which were also possible to form the fiber insides. Hemi-
acetal linkages themselves are unstable and cleavable in water.
However, it must take sufficiently long time to cleave all hemi-
acetal linkages at the inter-fiber bonds even in water because
sufficiently large amounts of hemiacetal linkages are present in
there. Thus, although individual hemiacetal linkage is unstable
to water, the increased amounts of hemiacetal linkages at the
inter-fiber bonds make each inter-fiber bond apparently resis-
tant to water. It is well know that polyion complexes become
insoluble in water because of the increased amounts of ionic
bonds between anionic and cationic polymer molecules like zip-
pers, although individual ionic bonds are possible to dissociate
in water. These mechanisms of wet strength development of cel-
lulose sheets via the formation of inter-fiber hemiacetal linkages
are illustrated in Fig. 8. Thus, the TEMPO-mediated oxidation
of native cellulose fibers is one of the efficient surface modifica-
tion methods, introducing not only carboxylate but also aldehyde
groups into them.
4. Conclusions
Wet strength of cellulose sheets is improved, when the
TEMPO-mediated oxidation is applied to native cellulose fibers
under optimum conditions. Significant amounts of aldehyde
groups are formed in native cellulose fibers by the TEMPO-
mediated oxidation, and are stably present in there. However,
only surface aldehyde groups in the TEMPO-oxidized cellulose
fibers contribute to the wet strength development of the sheets.
Carboxylate groups are also formed not only surfaces but also
insides of cellulose fibers by the TEMPO-mediated oxidation,
although they have nearly no contribution to wet strength devel-
opment of the sheets. Surface aldehyde groups forms hemiacetal
linkages with cellulose hydroxyl groups at the inter-fiber bonds
in the sheets, resulting in the clear wet strength development
of the sheets prepared thereof. The TEMPO-mediated oxidation
of native cellulose fibers, therefore, allows for introduction of
surface aldehyde groups into native cellulose fibers, which form
inter-fiber hemiacetal linkages in sheets.
Acknowledgments
This research has been supported by a Grant-in-Aid for
Scientific Research (Grant number 11660160, 13660157 and
15380116) from the Japan Society for the Promotion of Science
(JSPS).
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