Journal of Colloid and Interface Science 289 (2005) 249–261

www.elsevier.com/locate/jcis

Silane adsorption onto cellulose fibers:

Hydrolysis and condensation reactions
Marie-Christine Brochier Salon a , Makki Abdelmouleh b , Sami Boufi b ,
Mohamed Naceur Belgacem a,∗ , Alessandro Gandini c
a LGP2, Ecole Française de Papeterie et des Industries Graphiques (INPG), BP 65, Domaine Universitaire, F-38402 St. Martin d’Hères, France
b LMSE, Faculté des sciences de Sfax, BP 802-3018 Sfax, Tunisia
c Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador São Carlense, 400, CEP 13566-590 São Carlos, SP, Brazil

Received 23 February 2005; accepted 25 March 2005

Available online 23 May 2005

Abstract
The hydrolysis of three alkoxysilane coupling agents, γ -methacryloxypropyltrimethoxysilane (MPS), γ -aminopropyltriethoxysilane
(APS), and γ -diethylenetriaminopropyltrimethoxysilane (TAS), was carried out in an ethanol/water (80/20) solution and followed by 1 H,
13 C, and 29 Si NMR spectroscopy, which showed that its rate increased in the order MPS < APS < TAS. The formation of the silanol groups
was followed by their self-condensation to generate oligomeric structure. APS and MPS only gave soluble products, whereas colloidal parti-
cles precipitated in the medium when TAS was hydrolyzed. Pristine and hydrolyzed MPS were then adsorbed onto a cellulose substrate and
thereafter a thermal treatment at 110–120 ◦ C under reduced pressure was applied to the modified fibers to create permanent bonding of the
coupling agent at their surface.
 2005 Elsevier Inc. All rights reserved.

1. Introduction Usually, the surface treatment is carried out with a silane

Functional trialkoxysilanes, R Si(OR)3 , are widely used
in numerous industrial applications as coupling agents, to
enhance adhesion between polymeric matrices and inorganic
solids [1–5]. The mechanisms of these coupling reactions are
related to the presence of two types of reactive moieties in
their structure, which respond in different ways, according
to the substrates they approach. On one hand, the alkoxy
groups OR enable the silane to be anchored to surfaces
bearing hydroxyl groups [6–8], and on the other hand, the
organic functionality R (amine, methacrylic, vinylic, etc.)
improves their compatibility, or even copolymerizes with
organic matrices, thus enhancing the interfacial adhesion be-
tween the two phases [9,10].
water–alcohol solution in a concentration range of 0.5–2%
by weight. These conditions offer several advantages, in par-
ticular (i) an increase of silane solubilization in the medium,
(ii) better control of the film thickness on the surface, and
(iii) more uniform coverage of the surface. The water in-
duces stepwise hydrolysis of the silane [5,11] to give the cor-
responding silanol derivative R -Si(OH)3 , which promotes
the silane adsorption onto OH-rich substrates through hy-
drogen bonding. The actual chemical condensation is known
to occur after thermal activation, leading to siloxane bridges
[4,12,13], as follows:

* Corresponding author. Fax: +33 (0) 4 76 82 69 33.

.
E-mail address: naceur.belgacem@efpg.inpg.fr (M.N. Belgacem).

0021-9797/$ – see front matter  2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.03.070
250 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261
Subsequently, after solvent evaporation, the residual
silanol groups may undergo a further condensation re-
action with the substrate hydroxyl groups, but also self-
condensation to form a polysiloxane network on the surface
[12–15]. Moreover, in the aqueous medium, the (partially
or totally) hydrolyzed silanes constitute a rather reactive
system, which evolves with time as a result of the conden-
sation of the silanol groups both with each other and with
alkoxy groups, to form dimeric and oligomeric structures
[4,12,16–18], viz.:
, A better knowledge of the structural changes that occur in
.
Further condensation reactions lead to gel-like networks,
which precipitate in the form of colloidal particles. Both
the hydrolysis and the condensation reactions of the silanol
groups are affected by the structure of the organic part of
the silane and by the medium composition (temperature, pH,
concentration, amounts of water and catalyst) [19,20]. The
extent of silane hydrolysis and its degree of oligomerization
are known to exert a great influence on the silane adsorp-
tion and on its configuration at the substrate surface [21–23].
Therefore, these two parameters must be judiciously con-
trolled in order to optimize the surface modification with
silane coupling agents.
Even though the hydrolysis and condensation reactions
of silanes have been investigated using different spectro-
scopic techniques such as FTIR [11,24], Raman [25], and
NMR spectroscopy [16,21,23,26], the multitude of reactions
likely to occur and their dependence on solvent composi-
tion makes it necessary to control the conduct of these re-
actions carefully to favor silane adsorption on the substrate
surface.
In previous studies, we showed that the treatment of cellu-
lose fibers with appropriate silane coupling agents improved
the mechanical properties of the ensuing composite mate-
rials [27–29]. These effects were explained in terms of the
ability of the functional group borne by the silane moiety to
bridge covalently with the polymeric matrix, thus increasing
the fiber/matrix adhesion. However, the actual quantifica-
tion of silanes adsorbed on lignocellulosic substrates and
the mechanisms of their mutual condensation reactions have
been scantily reported [30].
The present investigation deals with a more fundamental
approach, aiming at establishing the kinetics of the hydroly-
sis and the structural changes occurring in a silane solution
after the addition of water. These modifications are then cor-
related with the evolution of the amount of silane adsorbed
onto the cellulose substrate. Indeed, the surface of the cellu-
lose fibers is markedly less reactive than that of the inorganic
oxides onto which the silanes are usually applied [1,31,32].
Furthermore, the cellulose –O–Si–O– linkage may undergo
reversible hydrolysis, which can strip off some of the an-
chored silane from the surface. In order to prevent this draw-
back, it is necessary to ensure a high surface coverage, so
that the silane links to numerous surface sites, and the ad-
sorbed silanol groups are close enough to each other to un-
dergo self-condensation. The ensuing bidimensional silox-
ane network will therefore minimize any desorption of the
coupling agent.
the solution during silane hydrolysis and self-condensation
was deemed necessary for the selection of appropriate con-
ditions favoring the physical adsorption of the silane onto an
organic substrate.
2. Experimental
2.1. Materials
The cellulose fibers used in this work were commercial
microcrystalline fibers (TECHNOCEL-150DM). Their av-
erage length was about 50 µm and their specific surface
area, measured by the BET technique using nitrogen as the
adsorbed gas, was about 2.5 m2 /g. The organofunction-
al trialkoxysilanes γ -methacryloxypropyltrimethoxysilane
(MPS), γ -aminopropyltriethoxysilane (APS), and γ -di-
ethylenetriaminopropyltrimethoxysilane (TAS), were indus-
trial products of high purity used as received from OSI-
WITCO. Their structures and NMR chemical shift assign-
ments are given in Tables 1 and 2, respectively. All other
reagents and solvents were commercial high-purity prod-
ucts, used as received.
2.2. Hydrolysis of silane coupling agents
The hydrolysis and condensation reactions of the three
silanes, carried out in a mixture of ethanol-d6 and deuterated
Table 1
The silane coupling agents used in this work
Silane Formula
APS
TAS
MPS
 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261 251

water CD3 CD2 OD/D2 O: 80/20 (w/w) at a concentration of
10% (w/w), were followed in situ at 25 ◦ C by 1 H, 13 C, and
29 Si NMR.
2.3. NMR kinetic set up
1 H, 13 C,
and 29 Si NMR spectra of the silane solutions
were run on a Varian UNITY 400 spectrometer equipped
with a 5-mm probe and operating at 399.956, 100.572, and
79.455 MHz, respectively. All chemical shifts, relative to
TMS, were measured with a coaxial insert tube contain-
ing the TMS solution as the external reference. The spectral
widths were calibrated to obtain the best resolution for pro-
ton and carbon. For silicon, a 10-mm BB probe was used
to optimize the signal/noise ratio for minimum acquisition
times in relation to the specific reaction rates. The spectral
width was 12 kHz and the relaxation delay 20 s with pro-
ton decoupling only applied during acquisition time, to avoid
negative nOe effects. The T1 measurements were made with
the inversion–recovery method. All compounds and solvents
were weighed directly into clean tubes. The silane was first
added to the ethanol-d6 and the zero reaction time was set
immediately after the addition of D2 O. The kinetic studies
were carried out directly in NMR tubes by following the evo-
lution of the relevant NMR signals.
Solid state 29 Si CP/MAS NMR measurements were car-
ried out with a Bruker Avance 400 operating at 79.490 MHz
with samples in 7-mm rotors of ZrO2 . Magic angle spin-
ning was performed at a 3-kHz spinning rate. The construc-
tor pulse program cp3lev was used with a 25-kHz spec-
tral width, 5-s repetition time, and 2-ms contact time. The
29 Si scale was calibrated by the external standard M Q
8 8
(−109.80 ppm as the highest field signal) [33].
2.4. Adsorption isotherms
The adsorption isotherms were obtained by adding dif-
ferent amounts of the chosen silane, dissolved in a mixture
sions (5% (w/w) with respect to the solvent). The ensuing
suspensions were maintained under stirring for 2 h. Then, af-
ter the cellulose particles had been isolated by centrifugation
at 2500 rpm for 20 min, the quantity of adsorbed coupling
agent was determined using FTIR spectroscopy for MPS and
colorimetry in the case of APS and TAS. The detailed de-
scription of these experimental conditions has been reported
elsewhere [27].
3. Results and discussion
3.1. Hydrolysis followed by NMR
3.1.1. APS hydrolysis
The peak assignments of the 1 H and 13 C NMR spectra
of 10% (w/w) APS solution in ethanol-d6 are given in Ta-
ble 2. The commercial APS was highly pure, since only
traces of nondeuterated free ethanol were detected, probably
arising from minimal hydrolysis of APS when it was mixed
with ethanol-d6 . Immediately after the addition of deuter-
ated water, the APS hydrolysis began, as revealed by the
formation of free ethanol-OD, giving rise to the appearance
of two characteristic peaks at 1.19 and 3.62 ppm. The kinet-
ics of the reaction was followed by measuring the changes
in the intensity of the peaks in 1 H and 13 C NMR spectra,
as shown in Figs. 1 and 2. For 1 H NMR study the evo-
lution of the peaks at 3.9–4.0 and 3.62 ppm, correspond-
ing to –Si–(OCH2 CH3 )3 and CH3 CH2 –OD, respectively,
was set up (see Fig. 1). The plots reported in Fig. 3 show
that the rate of APS hydrolysis was relatively high in the
ethanol/water (80/20) mixture. In fact, 50 and 90% conver-
sions were reached within 40 min and 3 h, respectively.
In addition to the progressive decrease in the intensity of
the peaks at 1.25 and 3.85 ppm, corresponding to the starting
ethoxysilane, and the corresponding increase in those aris-
ing from the liberated ethanol-OD at 1.19 and 3.62 ppm, the
1 H NMR spectra presented in Fig. 1 revealed that all of the

of ethanol and water 80/20 (w/w), to the cellulose suspen- protons of the organic part of the silane underwent a con-

Table 2
NMR chemical shifts of the coupling agents used here, in ethanol-d6 at 25 ◦ C
Name δ 29 Si δ 13 C/δ 1 H
R= αCH2 βCH2 γ CH2 O–CH2 –CH3 O–CH3 R
APS −45.3 ppm 8.8 ppm 27.6 ppm 45.6 ppm 59.4 ppm
19.1 ppm
NH2 – 0.63 ppm 1.6 ppm 2.63 ppm 3.84 ppm 4.995 ppm
1.24 ppm
MPS −42.9 ppm 6.32 ppm 23.3 ppm 67.6 ppm 51.1 ppm (a) 126.0 ppm, (b) 137.2 ppm,
(c) 18.0 ppm, (d) 168.3 ppm
H2 C=C(CH3 )–COO– 0.27 ppm 1.3 ppm 3.7 ppm 3.15 ppm (a) 5.18 and 5.68 ppm,
(c) 1.53 ppm
TAS −42.4 ppm 8.0 ppm 23.9 ppm 53.6 ppm 51.2 ppm (a) 42.2 ppm, (b) 53.1 ppm,
(c) 49.9 ppm, (d) 49.8 ppm
NH2 –(CH2 –CH2 –NH)2 – 0.02 ppm 1.0 ppm 1.96 ppm 2.94 ppm (a) 2.11 ppm, (b) 2.05 ppm,
(c) 2.09 ppm, (d) 2.09 ppm,
NH–NH2 4.19 ppm
252 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261

Fig. 1. 1 H NMR spectra of APS hydrolysis.

Fig. 2. 13 C NMR spectra of APS hydrolysis.

 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261
Fig. 3. Reaction rate of free alcohol release for silane compounds.
tinuous evolution, characterized by the progressive loss of
the peak multiplicity, accompanied by a broadening of these
peak and a slight frequency shift. These changes probably
arose from silanol self-condensation reactions, leading to the
formation of dimeric and oligomeric structures. In order to
investigate the evolution of these structures, a detailed 13 C
NMR analysis was performed. In addition to the decrease in
the starting ethoxy peaks (19 and 59.5 ppm) and the increase
in those coming from free ethanol-OD, at 18 and 57.5 ppm,
already monitored by 1 H NMR, the following changes were
observed, as shown in Fig. 2:
(i) A narrow doublet was detected at 8.78 ppm, accom-
panied by several peaks between 9.5 and 12 ppm. The
sharp structure of these peaks and their quasi-total dis-
appearance after 3 h reaction were attributed to par-
tially hydrolyzed silane. On the other hand, the very
broad featureless signal (between 14 and 11 ppm) prob-
ably corresponded to CH2 (α) relative to the condensed
oligomeric structures. Over a long reaction time (24 h
or more), the CH2 (α) signal shifted toward a more uni-
form peak centered at 12.5 ppm.
(ii) The CH2 (β) resonance split into three peaks close
to each other. The first two, at 26.3 and 26.85 ppm,
appeared at the beginning of the reaction, then in-
creased, and finally disappeared. These peaks were as-
sociated with free and partially hydrolyzed APS. The
third large peak, centered at 27.2 ppm, was attributed to
the oligomeric structures.
(iii) The same observations applied to the CH2 (γ ) res-
onance, namely loss of resolution and enlargement
of peaks, accompanied by a slight shift in frequency
for the oligomeric structures. However, for these car-
253
bons, the signals corresponding to free and partially
hydrolyzed APS were not observed.
(iv) The ethoxysilane groups gave three superimposed sharp
peaks, the most intense corresponding to free APS and
the other two to its partially hydrolyzed structures.
In conclusion, the 1 H and 13 C spectra showed the same
tendencies, except for the transitory partially hydrolyzed
APS, which was clearly detected only in the 13 C NMR spec-
tra.
3.1.2. TAS hydrolysis
Thanks to its particular structure (three amine functions,
one primary and two secondary), TAS is an interesting
silane coupling agent that can interact with OH-rich surfaces
through its hydrolyzed silanol groups, leaving the amino-
containing moieties free to react with the polymeric matrix.
The 1 H and 13 C NMR spectra of pristine TAS (before the
addition of water) revealed that about 20% of the methoxy
groups of TAS had already been hydrolyzed, because of the
well-known high reactivity of this compound toward adven-
titious water during handling and storage. As with APS, the
hydrolysis of TAS was followed by the evolution of the pro-
ton peaks corresponding to both the methyl groups attached
to the silane (–Si–(OCH3 )3 ) and those liberated during the
hydrolysis (CH3 –OD), appearing at 2.95 and 2.7 ppm, re-
spectively. The rate of TAS hydrolysis was considerably
higher than that of APS, since the reaction was completed
in 1 h, as shown in Fig. 3. This reaction was also followed
by 13 C NMR spectroscopy, which displayed the following
features:
(i) The disappearance of the methoxy group of the ini-
tial silane at 51.19 ppm and the concomitant formation
of free methanol, as indicated by the peak growing at
49.79 ppm.
(ii) The emergence of two individual peaks at 8.5 and
9.5 ppm, assigned to monomeric hydrolyzed TAS.
(iii) The presence of a broad peak at 13 ppm, attributed to
the CH2 (α).
(iv) The broadening of the CH2 (β) and CH2 (γ ) peaks, indi-
cating the occurrence of the oligomerization reaction in
parallel to the hydrolysis (see Fig. 4).
The rapid evolution of this system impeded any precise
quantitative analysis using 13 C NMR, as the minimum time
needed for a spectrum acquisition was 8 min. However,
90 min after the water addition, the different monomeric
species had totally disappeared from the solution, and col-
loidal particles, corresponding to insoluble networks, started
to precipitate. Obviously, the presence of three amino func-
tions within the silane structure greatly enhanced the rate of
both the hydrolysis and the silanol condensation reactions.
254 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261
Fig. 4. 13 C NMR spectra of TAS hydrolysis.
3.1.3. MPS hydrolysis
The methacryloxy group of MPS is very interesting be-
cause it can be copolymerized with alkenyl-based matrices,
commonly used in composite materials. The kinetic mea-
surements were made under the same conditions as with
APS and TAS. As with TAS, the MPS hydrolysis generated
free methanol, giving rise to peaks at 2.9 and 49.71 ppm in
the 1 H and 13 C NMR spectra, respectively. The shoulder at
3.1 ppm was assigned to –Si–(OCH3 )3−n (OD)n of the par-
tially hydrolyzed MPS. The rate of hydrolysis of MPS was
particularly low, since after 24 h, the conversion had only
reached 17%, as shown in Fig. 3. This slow reaction can be
related to the hydrophobic character of MPS and to the rela-
tive proportion of water in the medium. Attempts to increase
the amount of water above 30 wt% led to phase separation
of the solution, whereas the addition of a small amount (1%
(w/w) with respect to silane) of triethyl amine (TEA) greatly
accelerated the reaction [35,36], as clearly shown in Fig. 3.
As with the other silanes, the hydrolysis was accompanied
by a condensation reaction among the silanol groups to give
oligomeric structures. The evidence of the presence of such
structures was provided by the broadening of the different
peaks in the 1 H and 13 C NMR spectra. The monomeric hy-
drolyzed MPS were characterized by sharp peaks at 6.47,
23.34 and 67.67 ppm, whereas the oligomeric species gave
broad peaks at 11, 23.5, and 67.4 ppm (Figs. 5 and 6, for 1 H
and 13 C NMR spectra, respectively).
3.1.4. Kinetics of hydrolysis and estimate of the different
products
The fact that the hydrolysis of MPS, APS, and TAS were
performed under the same conditions of temperature, water
concentration, and solvent composition allowed a quanti-
tative comparison of their rates to be made. A first-order
treatment of the data (1) was tested for the removal of the
alkoxy groups and gave straight lines up to conversions ex-
ceeding 95%, as shown in Fig. 7.
d[alkoxy] [alkoxy]
− = Kh [alkoxy][H2 O] ⇒ ln
dt [alkoxy]0
= −Kh [H2 O]t = −Kh t.
The apparent first-order constants Kh , calculated from the
slope of each straight line, were found to be 0.0085, 0.378,
0.76, and 5.04 min−1 for MPS, MPS-TEA, APS, and TAS,
respectively.
With all these reactions, the rate of hydrolysis was deter-
mined by measuring the changes in the peak intensity of the
CH2 of the ethanol released by APS and of the CH3 of the
methanol liberated by MPS and TAS, taking as reference the
corresponding areas of the initial silanes (Fig. 3).
 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261
Fig. 5. 1 H NMR spectra of TEA-catalyzed MPS hydrolysis.
For APS and MPS, we assessed both the extent of hy-
drolysis and the amount of condensation products. Since
MPS is a methoxy derivative, its 1 H NMR spectra display
a singlet and, consequently, it was possible to distinguish
the CH3 protons of the initial compound from those of the
free methanol and those of the partially hydrolyzed silane
(Figs. 8 and 9). In the 13 C NMR spectra, the CH2 (α) gave
well separated peaks. The good overlapping of the curves
obtained from 1 H and 13 C NMR data indicated that under
our conditions, 13 C NMR spectroscopy was a reliable tech-
nique for a quantitative study and the hydrolysis of MPS and
APS was followed accordingly (Figs. 8 and 9). The prod-
ucts of the partial hydrolysis could not be observed in the 1 H
NMR spectra because of the peak width associated with the
CH2 multiplicity (quadruplet), whereas the absence of this
overlapping feature in the 13 C spectra allowed these inter-
mediate products to be quantified through the CH2 (α). The
same behavior was observed with these two silanes, viz.,
(i) the amount of partial hydrolysis products increased up
to a maximum value of 8 and 18% for MPS and APS, re-
spectively, and then (ii) self-condensation started and its rate
increased progressively, while the fraction of hydrolyzed
species decreased accordingly. It is worth noting that no
condensation reaction was observed before the extent of hy-
drolysis reached its maximum value, and that, with MPS,
the presence of TEA greatly enhanced the hydrolysis and
255
the polycondensation rates, but the concentration of partially
hydrolyzed species did not exceed the maximum obtained in
the absence of TEA.
With TAS, the hydrolysis kinetics could be followed only
by 1 H NMR, because the reaction celerity impeded any
quantitative use of 13 C NMR spectra, as mentioned above.
Partially hydrolyzed species were observed, but could not
be quantified.
3.1.5. 29 Si NMR study
29 Si NMR spectroscopy is of great interest to acquire
further information about the structure of the oligomeric
species. The chemical shift of silicon is determined by the
chemical nature of its neighbors, namely, the number of
siloxane bridges attached to a silicon atom, and M, D, T, and
Q structures are the commonly used notation corresponding
to one, two, three, and four Si–O– bridges, respectively.
29 Si NMR also provides a way to follow the hydrolysis
and the condensation reaction of silicon alkoxides. For ex-
ample, a T structure bears only one organic Si–R side group
and the three siloxane bridges could be differentiated be-
tween Si–OSi and Si–OR groups. With the nomenclature of
Mi , Di , Ti , and Qi , taken from Glasser and Wilkes [37–41],
where i refers to the number of –O–Si groups bound to the
silicon atom of interest, Ti corresponds to R–Si(–OSi)i –
OR (3−i) . Four T peaks can be present, namely T0 (−37 to
256 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261

Fig. 6. 13 C NMR spectra of TEA-catalyzed MPS hydrolysis.

Fig. 7. First-order kinetic curves of silane coupling agents hydrolysis.

Fig. 8. MPS hydrolysis kinetics—TEA addition at 24 h, as deduced from
the 1 H and 13 C NMR spectra. Data deduced from 1 H NMR: black forms;
those obtained from the 13 C NMR: gray forms.

−39 ppm), T1 (−46 to −48 ppm), T2 (−53 to −57 ppm),

and T3 (−61 to −66 ppm) [41]. It is also well known that the
transition from Si–OR to the corresponding silanol Si–OH
gives a shift to lower fields (because of the electron-donating
properties of OR) and the extent of the shift increases with
the alkyl group molecular weight [42–44], e.g., 5–6 and
2–3 ppm for ethyl and methyl groups, respectively.
First, 29 Si NMR measurements were made with a 5-mm
probe, but the relaxation times of different species were
too long to give well-resolved spectra during kinetic ob-
servations and only long-lived species could be detected.
The 29 Si NMR spectra of APS in ethanol/water solution
are shown in Fig. 10. Based on the literature data, the sin-
 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261 257

(a)

Fig. 9. APS hydrolysis kinetics, as deduced from the 1 H and 13 C NMR

spectra. Data deduced from 1 H NMR, black forms; those obtained from
13 C NMR, gray forms.

gle peak at −40 ppm observed after 25 min reaction was

assigned to monomeric hydrolyzed silane. Usually, the hy-
drolysis leads to a small downfield shift of about 5–6 ppm.
After 8 h hydrolysis, the spectrum showed two peaks cen-
tered at −55 ppm, assigned to T2 units, followed by a small
peak at −61 ppm and a set of peaks ranging from −60
to −64 ppm, which were assigned to T2 and T3 structures
(b)
[16,34]. After the much longer reaction time of 4 days, the
29 Si NMR spectrum displayed the same peaks, but the in-

tensity of the T3 units at −63 ppm was more uniform and

had increased considerably, whereas the intensity of the T2
units at −55 ppm had decreased correspondingly. This evo-
lution resulted from the condensation reaction between the
silanol groups, which generated structures with higher mole-
cular weight. This result is in agreement with the observation
that the APS solution did not show any precipitation of col-
loidal particles of polysiloxane over a period of several days.
With MPS in the presence of TEA (1% (w/w) with re-
spect to silane), the reaction rates were still too high for the
detection of intermediate short-lived species. Therefore, the
MPS hydrolysis was followed using a ten fold decrease in
TEA, which produced a considerable reduction in the reac-
tion rates, as shown in Figs. 11 and 12. All the observations (c)
related to 1 H and 13 C NMR spectroscopy were qualitatively
Fig. 10. 29 Si NMR spectra of APS hydrolysis after reaction times of (a) 25
unchanged, but, after 48 h, some MPS was still present; i.e., min, (b) 6 h, and (c) 4 days.
the yield of CH3 OD had not reached 100%. These condi-
tions were adopted for a kinetic study followed by 29 Si NMR
spectroscopy, with 3 h acquisition time and 2 h delay be- the end of the run. The T2 units (centered at −59 ppm) were
tween each spectrum (with a 20 s d1 relaxation delay). The not detected at the beginning of the reaction, which is in
spectra obtained are given in Fig. 13. During the first three agreement with the 13 C NMR study, and only appeared at
hours, the major species was still MPS (T0R ), detected at later stages. Then after the first 3 h the broad peaks between
−45.4 ppm. The hydrolyzed moieties (T0H ) and dimeric units −65 and −70 ppm, attributed to the T3 units, appeared and
(T1 ), respectively at −40 and −51 ppm, were also present, increased with time. The observations deduced from 29 Si
but in much smaller amounts. The T1 signals then increased NMR study (Fig. 12) corroborated the 1 H, 13 C NMR results
with reaction time, and then decreased and disappeared at (Fig. 11), namely,
258 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261
Fig. 11. MPS + εTEA kinetic curves, as deduced from the 1 H and 13 C
NMR spectra. Data deduced from 1 H NMR, black forms; those obtained
from 13 C NMR, gray forms.
Fig. 12. MPS + εTEA kinetic curves, as deduced from the 29 Si NMR spec-
tra.
(i) The rate of decrease in initial silane units T0R was con-
firmed.
(ii) The hydrolyzed species T0H , increased up to a maximum
value and then disappeared.
(iii) Intermediate T1 , T2 species, and T3 units were detected.
(iv) The latency delay for the T2 and T3 beginning forma-
tion, as far as the maximum of the hydrolyzed unities
T0H was reached.
(v) The continuous increase of the T3 condensed oligomeric
entities occurred to the detriment of the other intermedi-
ates.
Nevertheless a time shift was noticed between the curves
built up from 13 C and 29 Si NMR studies. In fact, after 48 h
reaction, the initial unhydrolyzed silane was still present in
13 C NMR, while it disappeared after only 36 h in silicone-
Table 3
T1 measurements by inversion recovery method
13 C
Product CH2α CH2β CH2γ CH3methacryl CH3 OSi CH3 ODfree
Initial MPS 2.173 2.082 1.973 5.236 11.700
Condensed 0.230 0.241 0.212 1.600
MPS
29 Si
T0H T0R T1 T2 T3
Initial MPS 20
Condensed 16.4 12.5–12.6
MPS
based NMR spectra. This shift is probably due to the differ-
ent experimental conditions versus relaxation times between
the two nuclei. By some relaxation T1 measurements, on the
pristine silane, the final polycondensated results for 13 C and
29 Si were realized and the results are summarized in Table 3;
they show clearly that if the 13 C experimental conditions
were quantitative for the CH2 (α) signal, the chosen 29 Si ex-
perimental conditions (d1 = 20 s) were fatal to T0 species
detection below some concentration. A relaxation delay of
100 s would be much more appropriate, but in this case the
number of scans would be insufficient to obtain in 3 h acqui-
sition a well-resolved signal for T3 polycondensated units
because of the signals polydispersity.
3.2. Adsorption isotherm of silanes
The adsorption isotherm of nonprehydrolyzed MPS (0 h
of hydrolysis), prehydrolyzed MPS (24 h of hydrolysis) and
nonprehydrolyzed MPS-TEA (0 h of hydrolysis) are pre-
sented in Fig. 14, which shows that the amount of adsorbed
silane increased with increasing initial concentration and
reached a plateau situated at about 0.17 × 10−3 , 0.24 × 10−3 ,
and 0.37 × 10−3 mol of the adsorbed silane per gram of cel-
lulose, respectively. Then, with further increase in the silane
concentration, at C0 above about 0.12 mmol/l, the adsorp-
tion started to rise again. The shape of the isotherm sug-
gested that the silane adsorption proceeded through a mono-
layer formation, followed by multilayer mechanism [45]. At
the plateau region, the silane adsorption increased by 41%
after MPS aging during 24 h, and became more than the
double after the addition of TEA. Based on the previous
study, this enhancement could be explained by the genera-
tion of silanol groups, which promoted specific interactions
through hydrogen bonding with the surface hydroxyl groups
of cellulose. Furthermore, the growth of oligomeric struc-
tures from silanol self-condensation, would also enhance the
adsorption, since each adsorbed oligomer would imply the
presence of several silane molecules. In the case of unhy-
drolyzed MPS (0 h aging), the adsorption was driven by both
dispersive interactions and polar ones, the latter arising be-
tween the C=O groups of the MPS and the surface hydroxyl
groups of cellulose. This hypothesis is supported by the fact
that the C=O vibration in the FTIR spectrum of cellulose
 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261 259

Fig. 13. 29 Si NMR spectra of εTEA-catalyzed hydrolysis of MPS.

Fig. 15. Evolution of FTIR band corresponding to C=O function of MPS.

Fig. 14. Adsorption isotherms of MPS.
treated with MPS (0 h aging) gives two peaks at 1720 and
1710 cm−1 , corresponding to free and OH-bound C=O, re-
spectively (Fig. 15). On the other hand, in the presence of
TEA, the C=O band was dominated by free species, because
the surface OH groups were engaged with Si–OH moieties
through stronger hydrogen bonds.
The adsorption isotherms of APS and TAS were con-
structed before and after 1 h of the silane hydrolysis. As
in the case of MPS the adsorption isotherms displayed a
plateau region followed by a second buildup of the adsorp-
tion above a given concentration (Fig. 16). The plateau val-
ues were at about 0.91 and 0.6 mmol/g for APS and TAS,
260 M.-C. Brochier Salon et al. / Journal of Colloid and Interface Science 289 (2005) 249–261
Fig. 16. Adsorption isotherms of APS and TAS.
respectively. These relatively high values, compared with
those for MPS or MPS-TEA, could be associated, on the
one hand with the faster hydrolysis, which leads to a higher
proportion of silanol groups and oligomeric structure, and
on the other hand, with the presence of the amino func-
tions, which favored the interaction between the coupling
agents and the cellulose substrate, thanks to their ability
to establish of hydrogen bonds. Even though TAS contains
three amino functions, its plateau adsorption level was lower
than that of APS. This apparent anomaly was attributed to
the extremely high reactivity of TAS toward hydrolysis and
condensation reactions, which generated a high proportion
of three-dimensional network (T structure), which was less
readily adsorbed, compared with linear structures. More-
over, these three-dimensional networks tended to precipitate
as colloidal gel-like particles with further condensation, and
thus become unavailable for adsorption.
It is interesting to note that, even though the cellulose sur-
face is less reactive towards silanes than inorganic oxides,
the adsorption efficiency was relatively high once the silane
coupling agents had undergone (partial) hydrolysis. Thus,
the fraction of the adsorbed silane at the beginning of the
plateau, with respect to its initial concentration, was about
14, 40, 67, and 44% for MPS (0 h aging), MPS-TEA, APS,
and TAS, respectively. These results emphasize the poten-
tiality of using trialkoxysilane coupling agent as a relatively
simple method to modify the surface of cellulose substrates.
4. Conclusions
The study of the rates and mechanisms of (i) the hydroly-
sis of three alkoxysilanes, (ii) the self-condensation of their
hydrolyzed products, and (iii) the interaction of these species
with the surface of cellulose fibers opens the way to the ratio-
nal use of silane coupling agents to functionalize the surface
of organic materials. Thus, in some cases, optimal conditions
were established favoring the hydrolysis reaction and limit-
ing the self-condensation of the ensuing silanol groups. This
is particularly interesting, since the grafting efficiency (both
in terms of product configuration at the surface and quantity
of adsorbed molecules) can be modulated, depending on the
envisaged extent of the modification.
Work is in progress to examine the solid state 29 Si NMR
of these systems and their nanomorphology by AFM.
Acknowledgment
The authors thank OSI-WITCO Chemicals for the gift of
the silane coupling agents used in this work.
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