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COMPOSITES
SCIENCE AND
TECHNOLOGY
Composites Science and Technology 68 (2008) 10881093
www.elsevier.com/locate/compscitech

Novel SiO2/cellulose nanocomposites obtained by in situ synthesis and

via polyelectrolytes assembly
Ricardo J.B. Pinto, Paula A.A.P. Marques, Ana M. Barros-Timmons, Tito Trindade,
Carlos Pascoal Neto *
Chemistry Department, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal
Received 7 September 2006; received in revised form 20 February 2007; accepted 5 March 2007
Available online 16 March 2007

Abstract
SiO2/cellulose nanocomposites were prepared using two distinct methodologies: deposition of morphological well-dened SiO2 nanoparticles at the bres surfaces via polyelectrolytes assembly (layer-by-layer approach, LbL) and the synthesis of SiO2 nanoparticles via
tetraethoxysilane (TEOS) hydrolysis in the presence of cellulose bres. Although both methods were able to produce SiO2/cellulose composites, their nal morphological properties strongly depend on the synthetic strategy employed. Whereas in the LbL approach cellulosic
bres covered with discrete spherical SiO2 nanoparticles have been obtained, for the in situ synthesis of SiO2, nanocomposites consisting
predominantly on bres homogeneously coated with a SiO2 lm have been obtained. Both methodologies induced a signicant decrease
in the water uptake capacity of cellulose bres.
 2007 Published by Elsevier Ltd.
Keywords: A. Nano composites; A. Fibres; A. Nano particles; E. Sol-gel methods

1. Introduction
The general class of nanocomposite inorganic/organic
materials is a fast growing area of research. Signicant
eort is focused on the ability to obtain control of the
nanoscale structures via innovative synthetic approaches.
The properties of nanocomposite materials depend not
only on the properties of their individual components but
also on their morphological and interfacial characteristics.
This rapidly expanding eld is generating many exciting
new materials with novel properties [14]. The properties
of these materials are not only the sum of the individual
contributions of both phases, but the role of the inner interfaces could be predominant [5]. Inorganicorganic hybrid
materials do not present only a creative alternative to
design new materials and compounds for academic

Corresponding author. Tel.: +351 234 370 693; fax: +351 234 370 084.
E-mail address: cneto@dq.ua.pt (C.P. Neto).

0266-3538/$ - see front matter  2007 Published by Elsevier Ltd.

doi:10.1016/j.compscitech.2007.03.001

research, but their improved or unusual features allow

the development of innovative industrial applications [5].
Our work focuses on the preparation of new silica/cellulose composites. These new materials combine inorganic
nanoparticles of silica [68] and the most abundant natural
polymer, cellulose [9,10]. Monodispersed silica particles
with uniform size, shape, and composition have wide application such as in industries related to the production of pigments, pharmaceuticals, ceramics and catalysts [6]. The
need for well-dened silica nanoparticles is constantly
increasing, as high-tech industries (e.g. biotechnology/
pharmaceuticals [11] or photonics [12]) provide a tremendous demand for such materials. On the other hand, cellulose is one of the worlds most abundant polymers; the
unique morphologies of natural bres aorded by hierarchical self-assembly of the polymer chains give superior
properties which are not seen in synthetic bres [13].
Solgel techniques have been widely used for the preparation of organicinorganic hybrid materials. The inorganic phase is mostly obtained from metal alkoxides via

R.J.B. Pinto et al. / Composites Science and Technology 68 (2008) 10881093

hydrolysis and then condensation reactions involving oligomeric species. Tetraethoxysilane (TEOS) is a common
precursor used in the synthesis of silica based materials
using this process. In a rst step, the hydrolysis of TEOS
generates precursor species containing reactive silanol
groups; condensation reactions involving the silanol groups
yield a sol of SiO2 particles dispersed in the solvent, usually
an alcohol. The so called solgel transition, occurs by further condensation reactions of the silanol groups at the surfaces of the SiO2 particles (sol), forming a solid network
containing solvent molecules (gel). Silica surfaces prepared
by this process can be used as protective coatings or to link
a variety of functional molecules, due to the presence of
chemically reactive silanol groups.
The layer-by-layer (LbL) assembly method consists on
the adsorption of alternating layers of oppositely charged
polyelectrolytes on a solid substrate. This technique is a
straightforward method to fabricate multicomposite lms
mainly based on electrostatic interactions between anionic
and cationic polymers. This strategy oers some advantages namely: layer-by-layer construction due to surface
charge reversal in each layer; restriction to single layers
due to repulsion between last layer and excess material;
low steric demand for interaction between oppositely
charged ions deposition on almost any solvent accessible
surface [14].
Recently, we have shown that cellulosic bres can act as
ecient hydrophilic substrates to the nucleation and
growth of inorganic particles in aqueous medium [15,16].
Following our advances in this eld, we present here a
study which compares two distinct methodologies to prepare cellulosic nanocomposites containing SiO2, a prototypical ller in composite science. Thus the following
preparative methods have been investigated here:
(A) In situ synthesis of SiO2 in the presence of cellulose
bres, using a solgel approach.
(B) Deposition of morphological well-dened SiO2 nanoparticles at the bres surface via polyelectrolytes
assembly using the LbL technique.

2. Experimental
2.1. Chemicals
Tetra-ethyl ortosilicate (TEOS) (98%, Aldrich), ammonia (25%, Merck), ethanol (a.r., Riedel-de Haen),
poly(diallyldimethylammonium
chloride)
(PDDA,
20 wt% in water, MW 100,000 200,000) and poly(sodium 4-styrenesulfonate) (PSS, MW 70,000) were purchased from Aldrich and were used as received. Wood
cellulose bres (Eucalyptus globulus), ECF bleached kraft
pulp, composed essentially of cellulose (85%) and glucuronoxlylan (15%) supplied by Portucel (Portugal)
were disintegrated and washed with distilled water before
use.

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2.2. Deposition of silica nanoparticles on cellulosic bres via

polyelectrolytes (LbL)
The so-called Stober method was used for the synthesis
of silica nanoparticles [17]. This method is based on the
hydrolysis of tetra-alkyl silicate in a homogeneous alcoholic medium and using ammonia as a catalyst. Here an
additional study has been carried out to investigate the
ammonium hydroxide concentration required to produce
silica nanoparticles with a specic size average (Table 1).
In a typical synthesis, TEOS (2.25 mL) was added to an
Erlenmeyer ask containing ethanol (42.5 mL), deionised
water (4.5 mL) and ammonium hydroxide (0.75 mL),
under constant stirring. The reaction was allowed to proceed for 24 h, at room temperature, under moderate stirring. The SiO2 particles were then collected by
centrifugation, washed once with ethanol and washed twice
with deionised water and, nally, were placed in an oven to
dry at 50 C, over 24 h.
For the LbL procedures aqueous suspensions of SiO2
nanoparticles were rst submitted to sonication. The following aqueous solutions of polyelectrolytes have been previously prepared: 1% (wt/v) of PDDA in NaCl 0.5 M; 1%
(wt/v) of PSS in NaCl 0.5 M. The LbL technique was
applied to coat the bres by alternate dipping of the bres
in PDDA, PSS and again in the PDDA solutions. After
each immersion step (10 min), the bres were rinsed with
deionised water to remove the excess of polyelectrolyte
and then were dried at room temperature. Finally the surface treated cellulosic bres were immersed in the SiO2 suspension and the bres nanocomposites were washed and
dried as described above.
2.3. In situ synthesis of SiO2 in the presence of cellulosic
bres
Similar experimental conditions as described above were
employed to prepare the SiO2/cellulose nanocomposites. In
a typical synthesis, 0.5 g of cellulosic bres were added to a
mixture of ethanol (42.5 mL), H2O (4.5 mL) and NH3
(0.75 mL), under moderate stirring followed by addition
of TEOS (2.25 mL), the consistency (100 g/mL) of the
mixture being 1%. This mixture was then allowed to kept
under constant stirring, at room temperature, for 24 h.
The resulting nanocomposite bres were collected by lter-

Table 1
Diameter of SiO2 particles prepared in ethanol using [TEOS] =
0.2 mol dm 3 and [H2O] = 5 mol dm 3, for distinct amounts of NH4OH
[NH4OH] (mol dm 3)

D (nm) r (%)

0.2
0.3
0.5
1.0
2.0

127 10
197 7
299 7
381 7
486 4

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R.J.B. Pinto et al. / Composites Science and Technology 68 (2008) 10881093

ing, thoroughly washed with distilled water and then dried

at 50 C.
2.4. Analysis
Scanning electron microscopy (SEM) images were taken
using a FEG-SEM Hitachi S4100 microscope operating at
25 kV. Sample particles were deposited on a glass plate and
coated with carbon for SEM analysis. For each sample, the
average particle size, D, and the standard deviation, r,
were determined by measuring the size of more than 50
particles from the SEM images. Thermogravimetric analysis (TGA) was carried out using a Shimadzu TGA-50, with
a heating rate of 10 C/min. Zeta potential measurements
were performed using a Zeta Sizer Nano Series (Malvern)
instrument. Water retention value (WRV) of the nanocomposites was determined by a standardized method used in
paper technology (SCAN-C60). Typically, the bres were
rst saturated with water, and then centrifuged at
7000 rpm during 10 min. After centrifugation, the samples
were accurately weighted before and after drying at
100 C.

3. Results and discussion

In the synthesis of SiO2 nanoparticles using the Stober
method [17] there is a set of experimental parameters that
inuences the nal particle size and polydispersity. In part,
this justies the tremendous research reported in the literature on silica nanoparticles synthesis and associated growth
mechanisms [1823]. In this context, the eect of parameters such as molar ratio (H2O/TEOS) [7,18], ammonia concentration ([NH4OH]) [7,1922], reaction temperature
[7,18], nature of the alcohol used as solvent [8,22,23], and
reagents feed rate [6,7,18], have been subject investigated.
Thus, as a rst step, our eorts have been directed to the
optimization of synthetic parameters which could allow
us to obtain well-dened SiO2 nanoparticles from distinct
but reproducible batches. We have found that by a judicious control of the NH4OH concentration, present in
the reacting mixture as the catalyst, the morphological
characteristics of the SiO2 nanoparticles could be easily
controlled. Table 1 shows the particle size distribution
parameters for SiO2 samples obtained for distinct
[NH4OH]. Note that the data reports to at least three

Fig. 1. SEM images of SiO2 nanoparticles obtained for distinct NH4OH concentrations: (A) 0.2; (B) 0.3; (C) 0.5; (D) 1 and (E) 2 mol dm 3.

R.J.B. Pinto et al. / Composites Science and Technology 68 (2008) 10881093

batches and that the size dispersion is not superior to 10%.

Representative SEM images are shown in Fig. 1, which
attest the morphological homogeneity of the synthetic
SiO2 nanoparticles. Interestingly, we found that there is a
linear dependence of the particle diameter with the logarithm of [NH4OH] within the concentration range investigated here (Fig. 2). As a consequence, the synthesis of
well-dened SiO2 nanoparticles for a priori selected particle
sizes could be performed just by varying the [NH4OH] and
maintaining all the other experimental parameters constant. This enabled the use of reproducible SiO2 samples
for post-synthetic procedures such as the LbL deposition
on cellulosic bres described below.
The as synthesized SiO2 nanoparticles were deposited
onto the cellulose bres using LbL procedures following
the methodology described previously. Cellulose bres in
aqueous medium are normally negatively charged over a
wide pH range, due to the presence of ionisable moieties
such carboxyl and hydroxyl groups, resulting from chemical processing, or from minor polysaccharides such as glucuronoxylans. In fact, the electrophoretic mobility or zeta
potential of puried cellulose approaches zero for
pH < 2.7 [24]. On the other hand, it is well known that silica surfaces in contact with neutral aqueous solutions are
also negatively charged. The zeta potential of aqueous suspensions of blank cellulose bres and silica particles were
respectively 20 and 29 mV, at pH 6.2. Therefore the
deposition of the SiO2 nanoparticles on the cellulosic bres
was mediated trough a positive polyelectrolyte interlayer
which result from the alternate deposition of the cellulosic
bres in aqueous solutions of PDDA (+), PSS ( ) and
once again in the PDDA(+) solution. The zeta potential
value for the polyelectrolyte treated bres was +12 mV. This
procedure promotes charge and morphological homogeneity of the substrates for subsequent deposition steps.
The LbL technique applied to the composite system
formed by the cellulosic bres and SiO2 nanoparticles,
yields homogeneous SiO2/cellulose nanocomposites. Representative SEM images for two typical SiO2/cellulose

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Fig. 3. SEM images of SiO2/cellulose nanocomposites obtained via

polyelectrolytes adsorption.

nanocomposites obtained after one deposition cycle are

shown in Fig. 3. These nanocomposites contain 10% (w/
w) of SiO2 from two clearly distinct particle size distributions. The smaller silica particles (see Fig. 3B) tend to
agglomerate at the bres surfaces yielding high compact
coatings. The maximum silica load on the bers, obtained
after one deposition cycle, was around 16% (w/w).
Although the amount of silica on the bers could be
increased by subsequent dip coatings, the opposite eect
of displacement of SiO2 from the bers was also observed
when re-immersing the nanocomposites in the positive electrolyte solution. This results from a balance between the
type of interactions occurring between the silica nanocoating and the PDDA polyelectrolyte, rather than a process
driven by mass diusion. In fact, the SiO2 load on the bres
was not altered signicantly when dispersions of the nanocomposites have been submitted to vigorous mechanical
stirring. This means that the SiO2 nanoparticles become
in fact strongly attached to the cellulosic bres as a result
of strong electrostatic interactions between the negatively
charged SiO2 nanoparticles and the positively charged
polyelectrolyte chains previously attached to the bres.
Accordingly, attempts to attach the SiO2 nanoparticles
on the wood cellulosic bres in the absence of polyelectrolytes have not been successful.
3.1. In situ synthesis of SiO2 in the presence of cellulosic
bres

Fig. 2. Eect of NH4OH concentration on the SiO2 particle dimensions.

The controlled hydrolysis of TEOS in the presence of

cellulosic bres yields homogenously silica coated nanocomposites. The SEM images in Fig. 4 show that this pro-

R.J.B. Pinto et al. / Composites Science and Technology 68 (2008) 10881093

cess produces a dense lm of silica on the cellulosic bres.

This compact coating probably results from the condensation of silica oligomers which become attached to the bers
surface during the growth process. However, depending on
the ammonia concentration, discrete SiO2 particles 100
500 nm in diameter have been also observed (Fig. 4A and
B). We suggest that in this case, the SiO2 nanoparticles
result from a distinct event and result mainly from the
adsorption of silica particles homogeneously formed and
dispersed in solution.
Typically, the deposited SiO2 represents about 25% (w/
w) of the nanocomposite weight as determined by TGA.
Similarly to the nanocomposites prepared by LbL, the
present materials have been subject to vigorous washing
and mechanical stirring with no signicant loss of silica;
therefore, the SiO2 lm should be strongly attached to
the bres. We have observed a similar behavior for TiO2/
cellulose nanocomposites resulting from the synthesis of
TiO2 in the presence of cellulose bres [12]. Although the

60
58
56
54
% WRV

1092

52
50
48
46
44
42
40
0

% SiO2

10

15

Fig. 5. Weight percentage of water retention (WRV, %) of SiO2/cellulose

nanocomposites.

presence of electrostatic or chemical interactions between

the polysaccharides (cellulose and glucuronoxylan) of the
bres and the inorganic particles seem plausible, the exact
nature of the interactions between the organic and the inorganic phase remains an open question and will be further
investigated in a near future.
3.2. Water uptake capacity studies
The capacity of water uptake and its consequent impact
on the dimensional stability of cellulose bres constitute a
serious drawback in many applications, namely in bre
reinforced polymer-based composites. Nanocomposites
with distinct SiO2 loads have been prepared in order to
investigate their behavior in relation to their water absorption capacity. Fig. 5 shows the behavior of the water retention in the nanocomposites obtained by the LbL technique.
It is clear that increasing amounts of SiO2 nanoparticles on
the cellulosic nanocomposites decreases the water absorption, thus increasing the dimensional stability of the composites in wet environments. This eect was also noticed
in the case of the nanocomposites obtained by in situ synthesis; for a typical load in SiO2 of 25%, the percentage of
water retention decreased from 60% in blank bres to 26%
in the nanocomposite. A possible, though not denite
explanation, for these results may be related to the role
of SiO2 as a physical barrier at the bres surfaces, preventing water diusion to the inner parts of the highly hydrophilic cellulosic cell walls. In this case, although SiO2 is a
hydrophilic material, the presence of such mechanical rigid
coating, either in the form of lm or discrete nanoparticles,
dicult the cellulosic bres swelling, thus decreasing their
water uptake capacity.
4. Conclusions

Fig. 4. SEM images of SiO2/cellulose nanocomposites obtained by the

hydrolysis of TEOS in the presence of cellulosic bres. (A)
[NH4OH] = 0.06; (B) [NH4OH] = 0.2 and (C) [NH4OH] = 2 mol dm 3.

SiO2/cellulose nanocomposites with distinct morphological properties have been reported. Hence, nanocomposites
containing discrete and morphological well-dened SiO2

R.J.B. Pinto et al. / Composites Science and Technology 68 (2008) 10881093

nanoparticles at the cellulosic bres surfaces have been

obtained using LbL methodologies. On the other hand,
the synthesis in situ of SiO2 in the presence of cellulosic
bres yielded homogeneously coated SiO2/cellulose nanocomposites. The decrease in the bres water uptake capacity observed for both types of nanocomposites, opens up
perspectives to develop novel dimensional stable polymerbased composites.
Acknowledgements
These authors thank the European Commission for the
nancial support of this work (SUSTAINPACK IP500311-2). P.A.A.P. Marques thanks the Portuguese Foundation for Science and Technology (FCT) for the Pos-Doc
Grant SFRH/BPD/20132/2004.
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