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Surface modification of silica and its compounding with polydimethylsiloxane

matrix: Interaction of modified silica filler with PDMS

Article  in  Iranian Polymer Journal · September 2012

DOI: 10.1007/s13726-012-0062-x

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Iran Polym J
DOI 10.1007/s13726-012-0062-x
ORIGINAL PAPER
Surface modification of silica and its compounding
with polydimethylsiloxane matrix: interaction of modified
silica filler with PDMS
Jiesheng Liu • Shaopeng Wu • Minhu Zou •
Xiongzhen Zheng • Zhengang Cai
Received: 26 October 2011 / Accepted: 12 June 2012
Ó Iran Polymer and Petrochemical Institute 2012
Abstract The present work involved a thorough study on
silane-modified silica filler with special focus on its
chemical interaction with polydimethylsiloxanes (PDMS)
and the structural model of the modified filler. The samples
prepared by addition of modified silica were characterized
by Fourier transform infrared spectroscopy (FTIR), specific
surface test, scanning electron microscopy (SEM) and
fluorescent microscope. FTIR results confirmed the suc-
cessful silica surface modification with silane coupling
agent. The sample containing 80 phr (parts per hundreds of
rubber) modified filler with weak ratio of Si–OH/Si–C
group absorbance areas (A1/A0) showed weak formation of
filler agglomerates while a stronger interfacial interaction
could take place between the modified silica and PDMS.
Specific surface results showed that the dispersion of silica
can be improved when the amount of silane modifier to
silica reached 2.0 wt%. SEM and fluorescent microscope
showed that the filler aggregation was observed in cases of
higher silica loading. As expected, when the silica with
surface treatment was compared with those without surface
modification, the filler particles were found to be fairly
well dispersed in PDMS matrix.
J. Liu (&)
M. Zou
X. Zheng
Z. Cai
School of Civil Engineering and Architecture,
Wuhan Polytechnic University, Wuhan 430023,
People’s Republic of China
e-mail: wsljs628@yahoo.com
J. Liu
S. Wu
Key Laboratory of Silicate Materials Science and Engineering
of Ministry of Education, Wuhan University of Technology,
Wuhan 430070, People’s Republic of China
Keywords Silica
Silane coupling agent

Silicone rubber
PDMS
Introduction
Silicone rubbers (SR) are inorganic polymers with chemi-
cal structures similar to those of inorganic silicic acids and
silicates. Their resistance to moisture, excellent weather-
ability, thermal stability, oxidation resistance and low-
temperature flexibility make this class of materials very
attractive candidate for use in the outdoor applications [1].
In an important number of cases, SR present non-con-
venient mechanical properties and therefore have to be
reinforced by incorporation of silica fillers [2]. However,
the hydroxyl group (–OH) on the silica surface absorbs
moisture and causes the particles to be agglomerated. The
agglomerations cause poor dispersion capacity in the
organic SR matrix. For these reasons, the applications of
silica are largely limited [3]. Various methods are com-
monly used to modify the surface properties of the silica
which are largely introduced in terms of thermal, chemical,
electrochemical, and coupling agent treatments [4–7]. By
modification of the silica surface the interaction between
SR and silica filler has greatly improved [8].
It is important to understand the interaction between the
SR and the modified fillers. In the recent past, a variety of
studies on modified silica/rubber system has been focused
on filler reinforcement of rubber elastomer. However, a
comprehensive study of the interaction between SR and
fillers is still a challenging issue because it could not be
satisfactorily attained.
As one knows that silicone rubbers are made by a vul-
canization (cure) process converting low molecular weight
linear polydimethylsiloxanes (precursor fluid) to a polymer
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network. Polydimethylsiloxane (PDMS) is recognized as
an important organosilicon material, which can produce
more silicic products. The interactions between filler and
PDMS matrix play an important role in the rheology of an
uncured material, which is related to the material behavior
during processing and to the final properties of the cured
SR. Therefore, the study of interaction between uncured
PDMS matrix and silica filler would help our understand-
ing of the interaction of fillers-SR. So far, a detailed
description of interactions that occur between silica filler
and linear PDMS matrix is still lacking.
In this study, we report the incorporation of silica filler
into linear PDMS matrix and, subsequently, the interaction
between the filler particles and PDMS was investigated.
Taking into account the fact that interaction between
silica filler and PDMS is strongly dependent on the surface
modification of filler, the silane was employed to modify
the silica surface. Then, some appropriate studies on sur-
face area, morphological properties of modified filler were
conducted. Also, a complete model was proposed for the
modified filler to describe the modification by silanes. The
samples were characterized by FTIR, specific surface test,
SEM and fluorescent microscope with that reinforced by
the unmodified filler as a comparison. As a result, the
interaction between silica filler and PDMS is well clarified.
Experimental
Materials
Polydimethylsiloxanes (PDMS) with a viscosity of 50,000
Pa.s was purchased from Dow Corning Company. The silica
filler, 20–50 nm particle size, dried at 120 °C for 1 h prior to
use, was supplied by Huanyu Chemical CO., in Hubei
Province of China. Silane coupling agent, A-151[(CH3
CH2O)3–Si–CH=CH2], supplied by Diamond Advanced
Material of Chemical in Hubei Province of China, was used
to modify the silica filler.
Preparation
A known amount (1, 2 and 3 wt%) of A-151 silane cou-
pling agent was dissolved in absolute alcohol, and then
silica was added to form a suspension. The mixture was
stirred at room temperature for 2 h and stayed still for 24 h.
Then the resultant silica was centrifuged and washed with
absolute alcohol to remove the residual silane coupling
agent. Finally, the silica particles were dried in vacuum
oven at 80 °C for 48 h and the modified filler was formed.
The modified filler and PDMS were mixed using a two-
roll mill at 30 °C and rolled for 3 times. Thus, a PDMS/
modified filler compound was obtained. For comparison,
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the compound of PDMS and unmodified filler was prepared
by the same rolling process.
Characterization
FTIR spectra were recorded with a Nicolet 6700 FTIR
spectrometer, using KBr pellets, in the region of
700–4,000 cm-1, with resolution of 4 cm-1. The disper-
sion of silica fillers in the uncured PDMS matrix was
examined by SEM microscope (Jeol, JSM 5800, Japan). To
investigate the micro-scale morphology of the nanocom-
posites, fluorescent microscopy (NikonYS-100) was also
employed. The specific surface calculated with the method
of Brunauer, Emmett and Teller (BET) was determined by
N2 physisorption at liquid N2 temperature on a Miraesi
KICT-SPA 3000 Instrument. The content of silanol groups
on silica surface was determined by acid–base titration of
silica against aqueous sodium hydroxide according to the
literature procedure [9].
Results and discussion
Characterization of silica
In this study, the silica, modified by the silane coupling
agent, was analyzed by FTIR, and the typical spectrum is
shown in Fig. 1. It is apparent that FTIR spectrum of the
unmodified silica displays a number of characteristic bands
near 3,446 cm-1 (broad), 1,096 cm-1 (vs) and 799 cm-1.
These bands are assigned to stretching vibration of
H-bonded silanol group t(Si–OH) along with physisorbed
water t (–OH), t(Si–O–Si) of siloxane backbone, t(Si–OH)
of free silanol group and tetrahedron t(SiO4), respectively.
It can also be seen that the spectrum of modified silica
displays mainly the same characteristic bands of free
unmodified silica with weaker intensity of the free silanol
group at 957 cm-1. Moreover, the spectrum of modified
filler is characterized by the increasing intensity of two
weak bands near 794 and 1,104 cm-1 that are assigned to
asymmetric, symmetric vibrations of Si–O–Si group. It is
worth noting that the disappearance of weak vibration tOH
at 3,400 cm-1 of modified filler is a confirmation of a
successful surface modification process with silane cou-
pling agent.
Quantification of silanol groups and silanol number are
important aspects in evaluation of chemical reactivity of
silica filler particles. The extent of chemical modification
of silica highly depends on the concentration of silanol
groups, which provides the information regarding the dis-
tribution of silanol groups on the silica surface.
The titration test in this study showed that the silanol
group density was calculated to be 3.50 SiOH per nm2 for
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the BET surface area of silica decreases [10]. Meanwhile, it

can be seen from Fig. 2 that the BET surface area of silica
increased slightly with the increases in silane modifier
content. It can be explained that the dispersal state of sil-
ica can be improved when the ratio of silane modifier to
silica reached 2 wt%. More micropores were formed in the
silica when the dispersal state of silica was improved. As a
result, the BET surface area showed slight improvement.
These results are in good agreement with the literature data
[11]. In conclusion, BET results show that the silica filler
was modified by silanes successfully and these results are
consistent with the results of FTIR.

Model of modified silica

The above results of silica filler in FTIR spectra, titration

test for silanol group density and BET test give a good clue
Fig. 1 FTIR Spectrum of silica-modified by the silane coupling agent for the modification of silica. A possible mechanism for the
formation of the silane-modified silica filler could be pro-
untreated silica. For the modified filler, the silanol group posed as follows.
density was about 1.08 SiOH per nm2. This is simply due to The mechanism involves the reaction between the sur-
the fact that silane coupling agent could react with the face hydroxyl groups of silica and the silane coupling
silanol groups. As a result, the silanol groups on the surface agents. The surface modification of silica can be carried on
of silica decrease gradually. These results indicated that the in either dry condition or moist condition, as shown in
filler–filler interaction was weakened by the silanol groups, Schemes 1 and 2.
and the interaction between PDMS and silica filler was
greatly improved.
The BET specific surface test is also employed to
characterize the modification of silica, and the results are
shown in Fig. 2. It can be seen that the unmodified silica
filler has the highest BET surface area (550.75 m2/g).
When the silica particles were modified by silane coupling
agent, the silanes are assumed to bind on the surface of the
silica filler. Due to the fact that the silanes could be
adsorbed on both inner surface of particles and micropore, Scheme 1 Schematic illustration of the reaction on the surface of
silica without water

Scheme 2 Schematic illustration of the reaction on the surface of

Fig. 2 Results of BET surface area silica with water

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large enough to induce more interaction. When the silane

modifier is added to the system, silane modifier reacts with
hydroxyl groups on the silica surface. When modification is
performed under fully dry conditions, the silanol group on
the silica surface can react with the ethoxy groups of
A-151, liberating alcohol, and Si–O–Si groups may be
formed on the surface of silica, as shown in Scheme 1.

Fig. 3 Model of the modified filler The modification of filler with water

The modification of filler with no water When modification is performed under moist conditions,
the presence of a small amount of water has a great effect
First, the size of silica particles was about 20 nm. Thus, the on the modification of the silica. The alkoxy groups of
contact area between silica particles and silane modifier is silane modifier were initially hydrolyzed by the water to

Scheme 3 Reaction between

modified silica and PDMS

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Fig. 4 FTIR Spectra of modified filler with different amounts
Fig. 5 Relationship of absorbance areas ratio-modified filler content
Fig. 6 SEM images of filler
form silanol groups, and the as-formed silanol group can
either react with the silanol groups on the silica surface to
form a stable Si–O–Si bridge, or with neighboring hydro-
lyzed silane molecules to form siloxane by further poly-
merization, as shown in Scheme 2.
As a result, the silica surface becomes hydrophobic due
to the condensation of surface hydroxyl groups and the
formation of siloxane bridges following the above reac-
tions. Based on the FTIR analysis and schematic illustra-
tion of the reaction on silica surface, the model of the
modified filler can be shown as in Fig. 3.
Interaction of filler-PDMS
After mixing the modified filler and PDMS, the chemical
bonds are formed between the modified silica and PDMS
chains. Also, the active groups of modified filler can react
with the methoxy or ethoxy groups of PDMS as shown in
Scheme 3. Then, the possibility for the formation of silica
filler agglomerates in the samples was greatly eliminated.
In order to further study the interaction between the
filler and PDMS, a series of samples were prepared with
different amounts of modified silica (15, 50, 80 and 100
phr), and the surface chemistry of the modified silica was
studied by FTIR. Figure 4 shows the FTIR spectra of four
modified silica samples. It can be seen from Fig. 4 that
FTIR spectrum of different amounts of modified silica
display mainly similar characteristic peak intensities.
However, it is worth noting that the characteristic peak
intensity of –OH (3,300–3,700 cm-1) has become weak
after the compounding process with PDMS and there are
small differences in the peak intensities of –OH in four
samples. The difference in the peak intensity of –OH bands
may indicate that the silane modifier of the surface of silica
filler and PDMS must have interacted with the modified
silica filler.
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Fig. 7 Fluorescent images of
filler/PDMS
Because of the unchangeable properties of Si–C group
in the preparation procedure, the ratio of Si–OH/Si–C
group absorbance areas in the terms of A1/A0 in FTIR
spectrum was employed to verify the optimum amount of
modified filler. As can be seen in Fig. 5, the sample with
80 phr modified filler was found to have the lowest ratio of
A1/A0 compared to those of other samples. It is well known
that the excess of Si–OH groups on the modified filler
results in filler agglomeration and worse dispersion in
PDMS matrix. The sample with 80 phr modified filler with
the weakest A1/A0 ratio reduces the possibility of filler
agglomerates, and presents a stronger interfacial interaction
between the modified silica and PDMS.
From the FTIR analysis, it was safe to conclude that the
functional groups of silane coupling agents were success-
fully introduced, and the sample with 80 phr modified filler
shows a stronger interaction between the modified filler
and PDMS compared to other samples.
The interaction between the silica filler and PDMS is a
complicated process, especially when the filler particles
have their strong tendency to agglomerate [12]. Electron
microscopy is a very useful tool for the investigation of
possible interaction between the filler and PDMS. In this
study, the degree of dispersion of silica in PDMS matrix
was examined by SEM, as shown in Fig. 6a–c. Figure 6a, b
is the images of PDMS matrix added with 15 phr modified
filler and 15 phr unmodified filler. It can be seen from
Fig. 6b that the dispersion of unmodified filler particles is
not homogeneous. The aggregation of filler particles has
occurred and the sizes of aggregated particles range
between 30 and 50 nm. In contrast, the modified filler
particles shown in Fig. 6a seem to be dispersed uniformly in
PDMS matrix without aggregation and their particle size
ranged between 20 and 30 nm. This is simply due to the
ability of silane coupling agent in reducing filler–filler
interaction [13, 14]. In addition, the improvement in PDMS-
filler interaction also results in better filler dispersion [15].
This is further supported by the results obtained from
fluorescent microscopy, as shown in Fig. 7a, b. In the latter
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case as shown in Fig. 7b, large agglomerates are observed
whereas in the former (Fig. 7a), better filler dispersion is
obtained. This phenomenon clearly confirms the findings
already discussed in the previous section of SEM images.
Figure 6c is the image of PDMS matrix added with 150
phr modified filler. Comparing with the sample containing
15 phr modified filler as shown in Fig. 6a, the filler parti-
cles are aggregated enormously. This can be explained by
development of large contact areas among the filler parti-
cles leading to increased formation of filler agglomerates;
and consequently higher silica–silica interaction and hence
decreases in filler-PDMS interactions [16].
Conclusion
A study was performed on silane-modified silica and its
subsequent interactions with PDMS. In order to acquire
good dispersion of fillers and to improve PDMS-filler
interfacial interaction, we carried out silane coupling agent
modification of silica. The FTIR investigation of filler
shows that organic functional group was introduced onto
silica surfaces. All the treated silica fillers were found to
have lower BET surface areas as compared to the
unmodified silica, and due to surface modification, a good
dispersion of silica was achieved. The increase in the
amount of modified filler resulted in the aggregation of
silica filler and the sample with 80 phr modified filler
presents a stronger interfacial interaction of filler-PDMS
compared to those of other samples.
Acknowledgments This work has been supported by the Key
Projects in the National Science & Technology Pillar Program during
the Eleventh Five-Year Plan Period in China (2006BAB04A05).
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