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CCLET-3310; No. of Pages 5

Chinese Chemical Letters xxx (2015) xxx–xxx

Contents lists available at ScienceDirect

Chinese Chemical Letters

journal homepage: www.elsevier.com/locate/cclet

Original article

Adsorption of cationic copolymer nanoparticles onto bamboo fiber

surfaces measured by conductometric titration
Xiu-Ming Liu, Dong-Qin He, Kuan-Jun Fang *
School of Textiles, Tianjin Polytechnic University, Tianjin 300387, China

A R T I C L E I N F O A B S T R A C T

Article history: Monosized nanoparticles of 57.3 nm were prepared by cationic emulsion polymerization using a
Received 9 January 2015 polymerizable emulsifier DMHB. The adsorption of nanoparticles onto bamboo fibers was measured by
Received in revised form 8 April 2015 conductometric titration. The results indicated that the adsorption capacity increased with increasing
Accepted 23 April 2015
contact time until 120 min. The equilibrium data for nanoparticles adsorption onto bamboo fibers were
Available online xxx
well fitted to the Langmuir equation. Moreover, the monolayer adsorption capacity of nanoparticles in
the concentration range (from 0.03 g/L to 0.6 g/L) studied, as calculated from Langmuir isotherm model
Keywords:
at 25 8C, was found to be 38.61 mg/g of fibers. The SEM images showed that the nanoparticles form a
Adsorption
Copolymer
uniform monolayer on bamboo fiber surfaces.
Cationic nanoparticles ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Bamboo fibers Published by Elsevier B.V. All rights reserved.

1. Introduction Spherical polymer nanoparticles with positive surface charges

Cationic latexes have emerged as the subject of vigorous
research for applications in paints, coating industries, papermak-
ing, textile and fiber treatments, functional materials, and so on
[1–7], because cationic copolymer nanoparticles with positive
charge have many attractive characteristics such as preferentially
adding/adsorbing the negative charge on surfaces, eliminating
electrostatic repulsion, and improving properties of materials and
subsequent process [8,9].
As a new regenerated cellulose fiber, bamboo fiber is
hygroscopic and permeable with natural antibacterial and
bacteriostatic properties. Further, it is soft and smooth, as well
as opaque to ultraviolet light. Thus bamboo fibers have wide
applications in different areas. In most cases bamboo fiber surfaces
have negative charges, and cationic polymers nanoparticles are
readily adsorbed onto bamboo fiber surfaces by electrostatic
attraction. Therefore, the adsorption of positively charged colloidal
nanoparticles on bamboo fibers is becoming a promising way to
manufacture functional textiles and to enhance paper strength
[10–13]. Recently, much more attention has been given to the
adsorption of cationic nanoparticles onto cotton fibers [14–16],
however, the adsorption of cationic nanoparticles onto bamboo
fibers has rarely been reported.
* Corresponding author.
E-mail address: kuanjunfang@gmail.com (K.-J. Fang).
are often prepared by emulsion polymerization [17,18]. Cationic
nanoparticles obtained by common emulsifiers are sensitive to
water used in processing [19]. Thus, more stable cationic
nanoparticles were synthesized by using polymerizable emulsi-
fiers [20].
The aim of the present work is to investigate the adsorption
mechanism of cationic nanoparticles onto bamboo fibers by
conductometric titration. We investigate the adsorption rate and
adsorption mechanism of the nanoparticles onto bamboo fibers. In
addition, the morphology of bamboo fiber surfaces deposited by
the nanoparticles is also observed by a field emission scanning
electron microscopy (FE-SEM).
2. Experimental
2.1. Method
Conductometric titration [21–23] was carried out by adding
AgNO3 solution to the nanoparticle dispersion. To obtain high-
resolution data with a constant concentration (AgNO3 = 5.875 
103 mol/L), separate titrations were carried out using a wide
range of nanoparticle (from 0.03 g/L to 0.6 g/L) concentrations. In
addition, all the measurements of the conductometric titration
were carried out at room temperature and atmospheric pressure,
and all the conductivity data were automatically compensated to
25 8C by the conductivity meter. The electrode was immersed in
the dispersion for 1–2 min, and then the conductivity value was

http://dx.doi.org/10.1016/j.cclet.2015.05.006
1001-8417/ß 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: X.-M. Liu, et al., Adsorption of cationic copolymer nanoparticles onto bamboo fiber surfaces measured
by conductometric titration, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.05.006
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Table 1
Recipes used in the emulsion polymerizations.
Reagent Consumption (g)
Emulsifier (DMHB) 0.4
Monomer (St) 19.2
Monomer (BA) 0.8
Initiator (AIBA) 0.105
Deionizer water (H2O) 80
recorded. The same measurement was repeated several times to
check the reliability of the data and the averaged values were given
for the measurement.
2.2. Materials
The materials used in this investigation and their sources are as
follows: Styrene (St) was purchased from Tianjin Guangcheng
Chemical Co., Ltd., China, butyl acrylate (BA) was purchased from
Shanghai Aibi Chemical Co., Ltd., China, and they were purified by
washing with a 10% (w/w) sodium hydroxide aqueous solution and
stored at 18 8C. The cationic polymerizable emulsifier, metha-
cryloxyethyl hexadecyl dimethylammoniumbromide (DMHB, pu-
rity >98.5%), was prepared according to the reference. The cationic
initiator used was 2,20 -azobis[2-methylpropionamidine] dihy-
drochloride (AIBA, purity 98%, Qiongdao Kexin Materials Technol-
ogy Co., Ltd.). Silver nitrate (AgNO3) was purchased from Shanghai
Chemical Reagent Factory. Deionized water was purified by
standard procedures and used in all the experiments. Bamboo
fibers, deionized and scoured were supplied by Huafang Co., Ltd.,
China. Other materials and solvents were used as received.
2.3. Semicontinuous polymerization of cationic copolymer
nanoparticles
P(St-co-DMHB-co-BA)n+Brn was obtained by semicontinuous
emulsion copolymerization of Styrene and DMHB with BA in
different molar ratios. The steps are as follows: The polymeriza-
tions were carried out in a 250 mL round bottomed flask equipped
with a stainless steel stirrer, nitrogen inlet tube, and reflux
condenser. The nitrogen was injected into the flask after the device
was prepared, and then part of DMHB and deionized water (80 g)
were added. After 15 min, parts of St and BA were added at room
temperature for 30 min to make the emulsifier evenly dispersed.
After a part of initiator AIBA was added, the reaction system was
heated to 80 8C. Then residual mixed monomer (St and BA) were
dropped into the reaction system within 1.5 h. After that, residual
DMHB and AIBA were added into the emulsion, and the reaction
Fig. 1. SEM photograph of P(St-co-DMHB-co-BA)n+Brn nanoparticles prepared by semicontinuous emulsion polymerization.
Please cite this article in press as: X.-M. Liu, et al., Adsorption of cationic copolymer nanoparticles onto bamboo fiber surfaces measured
by conductometric titration, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.05.006
system was kept at 80 8C for 3 h and cooled to room temperature. A
dispersion of cationic nanoparticles, P(St-co-DMHB-co-BA)n+Brn,
was obtained at the end of the reaction. The recipes used in the
emulsion polymerization were given in Table 1.
2.4. Adsorption of the nanoparticles
Square pieces of bamboo fabric (2 g) of about 1 cm2 were
washed with deionized water several times. The washed samples
were put into the aqueous suspension of cationic latexes (200 mL)
and kept at 60 8C for 1 h. The adsorption of cationic nanoparticles
onto bamboo fibers was conducted at 25 8C and a moderate
shaking speed in an SHA-V shaker (Changzhou Guohua Electric
Appliance Co., Ltd., China). After that, these samples were washed
thoroughly with deionized water. The conductivity of the
dispersion was measured several times to check the reliability
of the data. Subsequently, the bamboo samples were dried under
vacuum at 50 8C for 30 min for other tests.
2.5. Characterization
2.5.1. Size and distributions of the cationic nanoparticles
The size and distributions of the nanoparticles were measured
by using a Nano-ZS90 instrument (Malvern, UK) at 25 8C. All
samples were diluted with deionized water before test.
2.5.2. Scanning electron microscopy (SEM)
SEM images were obtained using a Hitachi SU-8010 field
emission scanning electron microscope. Prior to the observations,
the samples were coated with Au.
3. Results and discussion
3.1. Properties of the cationic nanoparticles
P(St-co-DMHB-co-BA)n+Brn was prepared by a semicontin-
uous emulsion polymerization, and sizes and distributions of
seeded nanoparticles were measured using the Nano ZS90 at 25 8C.
Scanning electron micrograph (SEM) of the nanoparticles was
shown in Fig. 1. And it is also clear that most of the nanoparticles
have a diameter less than 100 nm (see Fig. 2). The average diameter
of the prepared nanoparticles in water is 57.3 nm, and the PDI is
0.122. The colloid titration analysis indicates that the charge
density and density of the nanoparticles are 0.821  104 C/cm2
and 1.003 g/cm3, respectively. The positive charges on the
nanoparticles surfaces came from the cationic groups of the
cationic initiator and the cationic emulsifier.
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3.2. Relationship between the concentrations of nanoparticles and
bromide ions
Similar to the previously reported phenomena [21], the
concentration of bromide ions measured by conductometric
titration is the concentration of bromide ions at the diffusion
layer of the nanoparticles. It is obvious that the relationship
between the concentration of the P(St-co-DMHB-co-BA)n+Brn
nanoparticles and the bromide ion is a good linear relationship
with R2 = 0.9982 in Fig. 3, which can be written as:
C p ¼ 4:9368C Br  0:083 (1)
Here, Cp is the concentration of particles and C Br is the
concentration of bromide ion.

3.3. Adsorption of the nanoparticles onto bamboo surfaces by

conductivity titration

3.3.1. Adsorption rate

The adsorption rate was systematically studied to further
investigate the adsorption process. Fig. 4 shows that the adsorption
rate enhanced very fast within the first 50 min, this phenomenon

Fig. 2. Particle sizes and distribution of P(St-co-DMHB-co-BA)n+Brn nanoparticles

prepared by semicontinuous polymerization.

Fig. 5. The fitting curve of adsorption isotherms of P(St-co-DMHB-co-BA)n+Brn

nanoparticles onto bamboo fibers. dn = 57.3 nm, T = 298 K, Cp = 0.03–0.6 g/L, pH
6.53, t = 120 min.

Fig. 3. The linear relationship between the concentration of P(St-co-DMHB-co-

BA)n+Brn nanoparticles and the bromide ion. The temperature was 298 K in the
conductivity titration, C AgNO3 ¼ 5:875  103 mol=L, the interval of stirring time is
2 min, dn = 57.3 nm.

Fig. 6. The fitting curve of Adsorption isotherm of P(St-co-DMHB-co-BA)n+Brn

nanoparticles onto bamboo fibers.

Table 2
The parameters of the adsorption isotherm of P(St-co-DMHB-co-BA)n+Brn onto
bamboo fibers.

Particles Langmuir adsorption isotherm

n+ 
Fig. 4. The adsorption rate curve of P(St-co-DMHB-co-BA) Brn nanoparticles onto Q0 KL R2
the surface of bamboo fibers. dn = 57.3 nm, the fiber weight:liquor weight = 1:250,
38.61 3.364 0.9914
T = 298 K, Cp = 0.29 g/L, pH 6.53.

Please cite this article in press as: X.-M. Liu, et al., Adsorption of cationic copolymer nanoparticles onto bamboo fiber surfaces measured
by conductometric titration, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.05.006
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4 X.-M. Liu et al. / Chinese Chemical Letters xxx (2015) xxx–xxx
Fig. 7. SEM images of adsorption of P(St-co-DMHB-co-BA)n+Brn nanoparticles onto bamboo fibers. a0 and b0 are the original fibers. a1 and b1 are the fibers adsorbed P(St-co-
DMHB-co-BA)n+Brn nanoparticles. The fiber weight:liquor weight = 1:250, dn = 57.3 nm, T = 298 K, Cp = 0. 45 g/L, pH 6.84, t = 120 min.
confirmed that the strong electrostatic attractive force between
the positively charged nanoparticles and the negatively charged
bamboo fiber surfaces was the main driving force for adsorption.
Then the amount of particles adsorbed onto the bamboo fiber
increases gradually with increasing contact time until the
maximum amount is reached after 120 min, which means that
the adsorption equilibrium was reached. This can be explained as
following: the quantity of negative charges on bamboo surface is
constant; when partial nanoparticles contact with the bamboo
surfaces, the double electrode layer repulsion exists between the
adsorbed and adsorbing particles, which results in the decrease of
particle adsorption rate.
3.3.2. Adsorption isotherms
The adsorption of particles on negatively charged bamboo fiber
surfaces was governed by electrostatic attractive force. The
adsorption of particles onto bamboo interface mainly takes place
through the mechanisms of ion exchange [24]. To further
understand the adsorption mechanism of the nanoparticles onto
bamboo fibers, the adsorption isotherms were measured at the
Cp = 0.03–0.6 g/L according to Eq. (1). The obtained results were
shown in Fig. 5, which revealed that the adsorbed amount
increased with the nanoparticles concentration at adsorption
equilibrium until the saturation value of adsorption was reached.
The measured equilibrium adsorption data were fitted accord-
ing to Langmuir equation (see Fig. 6) [25]:
1 1 1 1
¼ þ  (2)
qe Q 0 Q 0 K L C e
where Q0 is the saturated adsorption amount in mg/g, KL the
equilibrium adsorption constant, qe the nanoparticles amount
adsorbed on the bamboo surfaces at the equilibrium adsorption in
mg/g, and Ce is the concentration of cationic nanoparticles in the
dispersion at the equilibrium in g/L. According to the equation, the
calculated parameters are shown in Table 2. It can be seen that the
saturated amount of the nanoparticles on bamboo fibers is
38.61 mg/g, the equilibrium constant KL is 3.364. The coefficient
of correlation R2 equals 0.9914, indicating that the adsorption of
the nanoparticles onto bamboo fibers quite well conforms to the
Langmuir model.
3.3.3. Adsorption model
As shown in Fig. 7, the SEM observation reveals that the bamboo
fibers have a smooth surface compared to bamboo fibers (Fig. 7a0
and b0). Thus, after the adsorption, the nanoparticles densely
arranged onto bamboo fiber surfaces at high magnification
(Fig. 7b1) and partial nanoparticles aggregate onto bamboo fibers.
This can be explained as follows: (1) Because bamboo fibers have a
relatively smooth surface, the nanoparticles presented stronger
interaction with themselves than fiber surfaces; (2) the particles
are more inclined to attract each other, which decreases the
Please cite this article in press as: X.-M. Liu, et al., Adsorption of cationic copolymer nanoparticles onto bamboo fiber surfaces measured
by conductometric titration, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.05.006
stability of the copolymer suspension; thus it can be seen that
aggregates of partial nanoparticles can be adsorbed onto bamboo
fiber surfaces. In addition, the nanoparticles have spherical
morphology and form a monolayer on the fiber surface, which
further confirms that the adsorption of the cationic nanoparticles
coincides with the Langmuir model, and chemical adsorption is
predominant in the adsorption processes.
4. Conclusion
In conclusion, we have successfully synthesized P(St-co-DMHB-
co-BA)n+Brn cationic nanoparticles with uniform average size ca.
57.3 nm by semicontinuous emulsion polymerization. The present
study demonstrated the adsorption rate increased sharply within
the first 50 min because of the strong electrostatic attractive force.
The obtained adsorption experimental data are well fitted to the
Langmuir adsorption model. The saturated amount of the
nanoparticles on the bamboo fibers is 38.61 mg/g. In addition,
the morphological investigation by SEM reveals that a uniform
monolayer of nanoparticles is presented on bamboo fiber surfaces,
which further confirms that the adsorption of the nanoparticles
onto bamboo fibers coincides with the Langmuir model.
Acknowledgments
This work is supported by National Natural Science Foundation
of China (No. 1173086), National Key Technology R&D Program
(Nos. 2014A1302 and 2014AEOQO1) and Natural Science Fund of
Tianjin, China (No. 14JCZDJC37200).
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Please cite this article in press as: X.-M. Liu, et al., Adsorption of cationic copolymer nanoparticles onto bamboo fiber surfaces measured
by conductometric titration, Chin. Chem. Lett. (2015), http://dx.doi.org/10.1016/j.cclet.2015.05.006