Polymer 52 (2011) 172e179

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Preparation and characterization of thermosensitive organiceinorganic hybrid

microgels with functional Fe3O4 nanoparticles as crosslinker
Tianyou Chen a, Zheng Cao a, Xiaolei Guo a, Jingjing Nie b, Junting Xu a, Zhiqiang Fan a, Binyang Du a, *
a
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science & Engineering, Zhejiang University, Hangzhou 310027, China
b
Department of Chemistry, Zhejiang University, Hangzhou 310027, China

a r t i c l e i n f o a b s t r a c t

Article history: A methodology is described for the preparation of thermosensitive organiceinorganic hybrid microgels
Received 4 September 2010 with functional Fe3O4 nanoparticles as the crosslinker and N-isopropylacrylamide (NIPAm) as the
Received in revised form monomer. Magnetic Fe3O4 nanoparticles were first prepared via a redox reaction in aqueous solution and
30 October 2010
then modified with 3-(trimethoxysilyl)propylmethacrylate (TMSPMA) via the silanization. The bonding
Accepted 7 November 2010
Available online 13 November 2010
of multiple TMSPMA monomers on the surface of Fe3O4 nanoparticles renders them as crosslinker.
Surfactant-free emulsion polymerization (SFEP) of NIPAm was then carried out with the presence of
TMSPMA-modified Fe3O4 nanoparticles at 70
C in aqueous solution, leading to the formation of ther-
Keywords:
Organiceinorganic hybrid microgels
mosensitive PNIPAm-Fe3O4 hybrid microgels crosslinked with Fe3O4 nanoparticles. Transmission elec-
Thermosensitive tron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX),
Superparamagnetic thermogravimetric analysis (TGA), dynamic light scattering (DLS) and physical properties measurement
system (PPMS) were then used to characterize the resultant hybrid microgels. The experimental results
show that the PNIPAm-Fe3O4 hybrid microgels were spherical in shape with a large size distribution and
the Fe3O4 nanoparticles were randomly distributed inside the microgels. The PNIPAm-Fe3O4 hybrid
microgels were thermosensitive, exhibiting a reversible swelling and deswelling behavior as a function of
temperature. The PNIPAm-Fe3O4 hybrid microgels also show superparamagnetic behavior at room
temperature (300 K).
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction properties of organic components and inorganic components, which

Since Pelton and Chibante [1] first reported the preparation and
characterization of thermosensitive poly(N-isopropylacrylamide)
(PNIPAm) microgels via surfactant-free emulsion polymerization
(SFEP) in 1986, microgels have attracted extensive interests due to
their potential applications in many diverse fields, specially such as
drug delivery, biosensor, templates for nanoparticle synthesis and
catalyst [2e6]. It is thus greatly significant to tailor the properties
and functionalities of the microgels. Conventional methods mainly
involve the introduction of the second or third monomer during the
SFEP of N-isopropylacrylamide (NIPAm), which will lead to the
microgels with various functionalities, like response to pH value,
UV irradiation of the environments, etc. [7e10].
In recent decades, a new type of materials, namely organice
inorganic hybrid materials, has emerged [11e16]. These organice
inorganic hybrid materials possess and combine at the same time the
* Corresponding author. Tel.: þ86 571 87953164; fax: þ86 571 87952400.
E-mail address: duby@zju.edu.cn (B. Du).
render them more superior microstructures and properties. Many
researchers have devoted their numerous efforts to the fabrication
and characterization of organiceinorganic hybrid materials
[3,4,6,11e14,17e28]. Concerning the research field of microgels, the
organiceinorganic hybrid microgels have been reported in recent
years [11,24,26,27,29e35]. In a recent review, Karg and Hellweg have
classified the types of hybrid microgels reported in literature [11].
Three typical classes of organiceinorganic hybrid microgels were
discussed. They are: (1) Core-shell microgels with inorganic nano-
particles as cores, of which the gel shells are formed on the surface of
inorganic nanoparticles; (2) Microgels filled with inorganic nano-
particles, of which the inorganic nanoparticles are in-situ synthe-
sized inside the microgels; (3) Microgels covered with nanoparticles,
of which the microgels are first prepared and the inorganic nano-
particles are coated onto the microgels in the following step. Various
inorganic nanoparticles, such as Au, Ag, Fe3O4, SiO2 and TiO2, etc.,
have been incorporated into the microgels, forming the hybrid
systems [17,19,20,22,23,28e35]. Depending on the inorganic nano-
particles used, the resultant hybrid microgels can have various
special properties, such as local surface plasmon, magnetic and

0032-3861/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2010.11.014
 T. Chen et al. / Polymer 52 (2011) 172e179
fluorescence properties, etc. [19,20,28e36] However, most of the
hybrid microgels reported in recent years have microgel-shells or
microgels prepared with the presence of conventional chemical
crosslinker, N,N0 -methylene-bisacrylamide (BIS).
The fourth possible class of organiceinorganic hybrid microgels is
that the hybrid microgels are in-situ formed via covalent crosslinking
with functional inorganic nanoparticles without adding any
conventional chemical crosslinker. In other word, the functional
inorganic nanoparticles act as chemical crosslinkers. Currently,
reports about such fourth class of organiceinorganic hybrid microgels
are still rare. Clay nanoparticles were first successfully used as
crosslinking agent for the preparation of organiceinorganic hybrid
hydrogels [37e40] and microgels [41] in the absence of conventional
chemical crosslinker. However, the crosslinking mechanism of the
clay particles is not well-defined and still unclear [37e41]. It remains
unknown whether there are covalent bonds between the clay parti-
cles and the network chains. For organiceinorganic hybrid solid
nanoparticles, modified clay nanoparticles were successfully encap-
sulated inside latex particles via covalent bonds [42]. In another
report, magneto-responsive polystyrene (PS) gels were fabricated by
using functional Fe nanoparticles as crosslinking agent via the
surface-initiated atomic transfer radical polymerization (SI-ATRP)
without adding any conventional chemical crosslinker [43]. However,
the mechanism of crosslinking and network formation was not well-
established as well and still under debate for such FeePS hybrid gels.
The authors argued that the crosslinking points were formed via the
interparticle termination of propagating radicals on the Fe nano-
particles [43]. Here, we reported the successful preparation of ther-
mosensitive organiceinorganic PNIPAm-Fe3O4 hybrid microgels with
functional Fe3O4 nanoparticles as the crosslinker and NIPAm as the
monomer. The PNIPAm chains were covalently crosslinked with
surface-functional Fe3O4 nanoparticles. The crosslinking mechanism
was well-defined in the present work, which involved the radical
crosslinking polymerization of multiple carbonecarbon double
bonds grafted on the surface of Fe3O4 nanoparticles and the formation
of covalent bonds between Fe3O4 nanoparticles and network chains.
No conventional chemical crosslinker was used. Transmission elec-
tron microscopy (TEM), scanning electron microscopy (SEM), energy
dispersive X-ray analysis (EDX), thermogravimetric analysis (TGA),
dynamic light scattering (DLS), and physical properties measurement
system (PPMS) were then used to characterize the functional Fe3O4
nanoparticles and resultant hybrid microgels. We demonstrated that
the thermosensitive and magnetic PNIPAm-Fe3O4 hybrid microgels
were indeed obtained, which were spherical in shape with a relatively
large size distribution. The Fe3O4 nanoparticles were randomly
distributed inside the hybrid microgels.
2. Experimental
2.1. Chemical and materials
N-isopropylacrylamide (NIPAm: 99%) and 3-(trimethoxysilyl)
propylmethacrylate (TMSPMA: 98%) were purchased from Acros
Organics. Ferrous chloride tetrahydrate (FeCl2$4H2O), anhydrous
ferric chloride (FeCl3), potassium peroxydisulfate (K2S2O8) (Sino-
pharm Chemical Reagent Co. LTD) and ammonia solution (25%,
Hangzhou Changzheng Chemical Reagent Co. LTD) were used
without further treatment. All other reagents were of analytical
grade and used as received. Deionized water was used.
2.2. Preparation and surface modification of Fe3O4 magnetic
nanoparticles
The preparation of Fe3O4 magnetic nanoparticles was adapted
from a literature method [18,44,45]. First, ferric chloride (FeCl3,
173
820.2 mg) was dissolved in 30 ml deionized water under
mechanical stirring and nitrogen atmosphere at 25
C in a three-
neck flask. 10 ml of ferrous chloride tetrahydrate (FeCl2$4H2O,
52.94 mg/ml) aqueous solution was then added into the flask under
stirring. After 10 min, ammonia aqueous solution (w4.5 g, 25%) was
slowly injected into the flask. The reacting solution turned into
black with the injection of ammonia solution. The total amount of
the reacting solution was about 45 ml. The reaction was maintained
for 2 h. When the reaction was complete, the Fe3O4 nanoparticles
were separated and washed with deionized water several times
with the help of a magnet until the deionized water was neutral.
(Fig. S1a in Supplementary Material) The purified Fe3O4 nano-
particles were redispersed into 45 ml deionized water. Afterward,
0.30 ml of 3-(trimethoxysilyl)propylmethacrylate (TMSPMA) was
injected into the Fe3O4 nanoparticles solution under mechanical
stirring at 25
C. The surface silanization of Fe3O4 magnetic nano-
particles was allowed to proceed for 24 h. Surface modified Fe3O4
magnetic nanoparticles were then collected and washed with
deionized water for several times with the help of a magnet.
(Fig. S1b in Supplementary Material).
2.3. Synthesis of PNIPAm-Fe3O4 hybrid microgels via surfactant-free
emulsion polymerization (SFEP)
The thermosensitive organiceinorganic PNIPAm-Fe3O4 hybrid
microgels were synthesized via SFEP. Surface modified Fe3O4
magnetic nanoparticles (2.05 mg/ml) were first well dispersed in
10 ml deionized water by sonication for about 1.5 h, and then
transferred into a three-neck flask. The temperature of the solution
was increased to 70
C under mechanical stirring with a polytetra-
fluoroethene (PTFE) stirrer. Oxygen was eliminated by bubbling
nitrogen through the solution. After 15 min, 20 ml of K2S2O8
aqueous solution (ca.1.09 mg/ml) was added into the flask. After
another 15 min, 10 ml of NIPAm aqueous solution (NIPAm,
30.52 mg/ml) was injected into the reacting solution. The reaction
was continued at 70
C for 12 h. The obtained brown PNIPAm-Fe3O4
hybrid microgels were purified by several centrifugation and
redispersion cycles with the supernatant replaced by deionized
water during each cycle.
2.4. Instrumental and characterization
2.4.1. Fourier transform infrared spectrum (FT-IR)
Fourier Transform Infrared (FT-IR) spectra were recorded by
a Vector 22 Bruker spectrometer in the transmission mode using
potassium bromide (KBr) pellets of the sample. The dried powders
of the pure and TMSPMA-modified Fe3O4 nanoparticles as well as
the PNIPAm-Fe3O4 hybrid microgels were mixed with KBr and
pressed to a plate for the FT-IR measurements, respectively.
2.4.2. Transmission electron microscopy (TEM)
The morphologies of the pure and TMSPMA-modified Fe3O4
nanoparticles as well as the PNIPAm-Fe3O4 hybrid microgels were
observed by transmission electron microscopy (TEM) on a JEOL
JEM-1200 electron microscope operating at an acceleration voltage
of 60 kV. The TEM samples were prepared by dip-coating with
carbon-coated copper grids into the corresponding solutions. The
solvent was gently absorbed away by a filter paper. The grids were
then allowed to dry in air at room temperature before observation.
2.4.3. Scanning electron microscope (SEM) and energy dispersive
X-ray analysis (EDX)
The morphologies of the PNIPAm-Fe3O4 hybrid microgels were
also observed by scanning electron microscope (SEM) on a Hitachi
S4800 electron microscope. A droplet of the microgels solution was
174 T. Chen et al. / Polymer 52 (2011) 172e179
cast onto the aluminum foil at room temperature. After about
15 min, the excess solution was gently absorbed away by a filter
paper and the aluminum foil was then allowed to dry in air at room
temperature. Before SEM observation, the microgel samples were
coated with platinum vapors. Several positions of the samples were
imaged and energy dispersive X-ray analysis (EDX) of the PNIPAm-
Fe3O4 hybrid microgels was also carried out.
2.4.4. Thermogravimetric analyses (TGA)
Thermogravimetric analyses (TGA) of TMSPMA-modified Fe3O4
nanoparticles and PNIPAm-Fe3O4 hybrid microgels were performed
by a NETZSCH STA 409 PC/PG instrument from 30 to 600
C under
a nitrogen atmosphere with a heating rate of 20
C/min.
2.4.5. Dynamic light scattering (DLS)
The hydrodynamic diameter, size distribution, and thermo-
sensitive behavior of the PNIPAm-Fe3O4 hybrid microgels were
investigated by dynamic light scattering (DLS) as a function of
measuring temperature at a scattering angle q of 90
on a 90 Plus
Particle Size Analyzer (Brookhaven Instruments Corporation). The
hybrid microgels were diluted in deionized water to give
a concentration of 0.35 g/L. For each measuring temperature, the
microgel solution was equilibrated for 10 min and measured for
four times with each run of 1 min. The hydrodynamic diameter and
size distribution of the pure and TMSPMA-modified Fe3O4 nano-
particles were also characterized by DLS.
2.4.6. Physical properties measurement system (PPMS)
Magnetic properties of the TMSPMA-modified Fe3O4 nano-
particles and PNIPAm-Fe3O4 hybrid microgels were measured by
using a physical properties measurement system (PPMS-9,
Quantum Design). The magnetization hysteresis loops were
measured at 10 and 300 K, respectively.
3. Results and discussion
The synthesis procedure for the thermosensitve PNIPAm-Fe3O4
hybrid microgels consists of the following three steps as shown
FeCl2· 4H2O + 2 FeCl3 + 8 NH3· H2O
Fe3O4
NIPAm, K2S2O8
70 oC, N2 , Stirring
PNIPAm-Fe3O4 Hybrid Microgels
Scheme 1. The synthetic procedure of thermosensitive PNIPAm-Fe3O4 hybrid microgels with TMSPMA-modified Fe3O4 nanoparticles as the crosslinker.
schematically in Scheme 1: (1) the preparation of magnetic Fe3O4
nanoparticles via redox reaction; (2) the surface modification of
magnetic Fe3O4 nanoparticles by using TMSPMA; (3) the synthesis of
thermosensitive PNIPAm-Fe3O4 hybrid microgels via SFEP by using
TMSPMA-modified Fe3O4 nanoparticles as the crosslinker and NIPAm
as the monomer.
Fig. 1 shows the TEM morphologies of pure Fe3O4 nanoparticles in
aqueous solution and TMSPMA-modified Fe3O4 nanoparticles in
acetone. The pure Fe3O4 nanoparticles and surface modified Fe3O4
nanoparticles were spherical shape with slightly polydispersed size
distribution. The average size of the Fe3O4 nanoparticles was
13  2 nm. The pure Fe3O4 nanoparticles tended to aggregate in
aqueous solution, whereas the TMSPMA-modified Fe3O4 nano-
particles were well dispersed in acetone. There were strong
magnetic interactions among the pure Fe3O4 nanoparticles, which
easily led to the formation of large aggregates. However, after the
surface modification, TMSPMA formed a steric layer on Fe3O4
nanoparticles, which inhibited the formation of aggregates to certain
extent. The DLS results indicated that there were large aggregates of
pure Fe3O4 nanoparticles in aqueous and acetone solutions. (Fig. S2
in Supplementary Material) Due to the existence of large aggre-
gates, the mean apparent sizes of the pure Fe3O4 nanoparticles
measured by DLS were about 1178  27 nm and 1715  21 nm in
aqueous solution and acetone, respectively. With the hydrophilic
hydroxyl groups, the pure Fe3O4 nanoparticles had relatively better
dispersity in aqueous solution. After the modification of TMSPMA,
the dispersity of modified Fe3O4 nanoparticles in both water and
acetone was strongly improved. Although the formation of aggre-
gates can not be completely avoided due to the strong magnetic
interaction, the steric TMSPMA layer indeed inhibited Fe3O4 nano-
particles to form big aggregates to some extent. The hydrodynamic
diameters of TMSPMA-modified Fe3O4 nanoparticles in aqueous
(333  11 nm) and acetone (162  2 nm) solutions were almost ten
times less than the corresponding values of pure Fe3O4 nanoparticles
(Fig. S3 in Supplementary Material). Due to the hydrophobic nature
of TMSPMA, the TMSPMA-modified Fe3O4 nanoparticles exhibited
much improved dispersity in acetone. The DLS results were coinci-
dent with those of TEM (cf. Fig. 1).
8 NH4Cl + 8 H2O + Fe3O4 Fe3O4
Nanoparticles
O
O
O Si
O
O
O
O O
O Si
Si O O
O O
O
O Fe3O4
O O
Si O
O O O
O Si
O
O
TMSPMA-modified Fe3O4 Nanoparticles
 T. Chen et al. / Polymer 52 (2011) 172e179
Fig. 1. (a) TEM image of pure Fe3O4 nanoparticles in aqueous solution and (b) TEM image of TMSPMA-modified Fe3O4 nanoparticles in acetone.
Fourier transform Infrared (FT-IR) spectra of pure Fe3O4 nano-
particles, pure TMSPMA, and TMSPMA-modified Fe3O4 nano-
particles are shown in Fig. 2. In the spectrum of Fe3O4 nanoparticles,
the characteristic absorption band of Fe3O4 appears at 581 cm1,
which also appears in the spectrum of TMSPMA-modified Fe3O4
nanoparticles. An intense and broad band appeared in the region
3200e3600 cm1, corresponding to the OeH stretching vibration.
The surfaces of pure Fe3O4 nanoparticles were readily covered with
hydroxyl groups in aqueous environment. In the spectrum of
TMSPMA-modified Fe3O4 nanoparticles, there are many other
peaks, most of which are the characteristic absorption bands of 3-
(trimethoxysilyl)propylmethacrylate (TMSPMA). For example,
bands at 2955 and 2893 cm1 are attributed to stretching vibrations
of eCH2 group, a strong absorption band at 1719 is attributed to the
stretching vibration of the eCOe groups, band at 1044 cm1 is due
to the stretching vibration of SieO bond. The band at 1636 cm1,
corresponding to the vinyl groups of TMSPMA units on the micro-
spheres, indicates that the carbonecarbon double bonds (C]C)
have been successfully introduced onto the surface of Fe3O4 nano-
particles. The absorption peaks at 818 and 1081 cm1 have dis-
appeared, indicative of decomposition of the methoxysilyl groups
(SieOeCH3). The FT-IR results confirm that TMSPMA was success-
fully grafted onto the Fe3O4 nanoparticles via the silanization
reaction [18,25,46].
Fig. 2. FT-IR spectra of pure Fe3O4 nanoparticles, pure TMSPMA, TMSPMA-modified
Fe3O4 nanoparticles, and PNIPAm-Fe3O4 hybrid microgels.
175
The magnetic properties of Fe3O4 nanoparticles were previously
investigated [18] and here we will focus on the utilization of
TMSPMA-modified Fe3O4 nanoparticles as possible crosslinker for
the fabrication of microgels. The amount of grafted TMSPMA was
determined by TGA to be w15.2 wt%, as shown in Fig. 3. Comparing
with the feeding amount, the TGA result indicates that only part of
TMSPMA successfully grafted onto the surface of Fe3O4 nano-
particles. It was worthy to note that only the grafted TMSPMA could
be preserved after purification with a magnet. If the average size of
the Fe3O4 nanoparticles was taken as w13 nm, the grafted density
of TMSPMA was estimated to be w5 TMSPMAs/nm2 and 2500
TMSPMA molecules on a single Fe3O4 nanoparticle [18]. (See
Supplementary Material) The C]C bonds of the grafted TMSPMA on
Fe3O4 nanoparticles can take part in the free radical polymerization.
The hybrid microgels were hence prepared at 70
C by applying the
surfactant-free emulsion polymerization (SFEP) technique with
TMSPMA-modified Fe3O4 nanoparticles as the crosslinker and
NIPAm as the monomer. The initiator of K2S2O8 was first added into
the aqueous dispersion of TMSPMA-modified Fe3O4 nanoparticles.
After 15 min, the thermosensitive monomer, NIPAm, was then added
into the reaction solution and the radical copolymerization was
allowed to perform at 70
C for 12 h. Thermosensitive PNIPAm
microgels crosslinked with magnetic Fe3O4 nanoparticles were thus
obtained.
Fig. 3. Thermogravimetric analysis (TGA) curves of TMSPMA-modified Fe3O4 nano-
particles (dash line) and PNIPAm-Fe3O4 hybrid microgels (solid line).
176 T. Chen et al. / Polymer 52 (2011) 172e179

Fig. 4. Typical TEM images of the PNIPAm-Fe3O4 hybrid microgels crosslinked with TMSPMA-modified Fe3O4 nanoparticles.

The TEM observation indicates that the PNIPAm-Fe3O4 hybrid
microgels were spherical in shape with large size distribution and
contained many small black spheres, which were Fe3O4 nano-
particles, as shown in Fig. 4. The TEM images suggest that the
TMSPMA-Fe3O4 nanoparticles indeed behaved as crosslinkers. The
covalent bonds of TMSPMA took part in the radical polymerization
of NIPAm. The bonding of multiple TMSPMA monomers on the
surface of Fe3O4 nanoparticles hence led to the crosslinking reac-
tions during the polymerization. In other word, the TMSPMA-
modified Fe3O4 nanoparticles are like chemical crosslinkers with
multiple function groups, leading to the successful formation of
spherical microgels. From the TEM image with higher magnifica-
tion (Fig. 4b), it can be seen that the Fe3O4 nanoparticles were
randomly distributed inside the resultant PNIPAm-Fe3O4 hybrid
microgels and the number of Fe3O4 nanoparticles in each hybrid
microgel was different.
Fig. 5 shows the typical SEM image and the energy dispersive
X-ray analysis (EDX) of the PNIPAm-Fe3O4 hybrid microgels. The SEM
result is consistent with that of TEM. The PNIPAm-Fe3O4 hybrid
microgel particles were rather spherical with a large size dis-
tribution (Fig. 5a). The average diameter of the hybrid microgels
was 226  62 nm. The elemental composition of the PNIPAm-Fe3O4
hybrid microgels was determined by using EDX (Fig. 5b). Elements C,
O, Fe, and Si were found, which confirmed that the microgel particles
indeed contain TMSPMA-modified Fe3O4 nanoparticles. The element
aluminum (Al) was resulted from the aluminum foil substrate and the
element platinum (Pt) was from the coating layer which was used to
increase the surface electronic conductivity of the microgels. Note
that the percentage of each element obtained by EDX can only serve
as qualitative indication of the existence of the element and can not
be used for quantitative calculation due to the experimental uncer-
tainty. For example, the weight percentages of O, Si, and Fe did not fit
to the formulation of the PNIPAm-Fe3O4 hybrid microgels. If the
weight percentage of Fe was chosen as reference, the weight
percentage of O was largely underestimated, while the weight
percentage of Si was overestimated according to w15.2 wt% of
TMSPMA grafted onto Fe3O4 nanoparticles and w25.8 wt% of Fe3O4
nanoparticles inside the hybrid microgels (see below).
The PNIPAm-Fe3O4 hybrid microgels were also characterized by
FT-IR, as shown in Fig. 2. In the spectrum of PNIPAm-Fe3O4 hybrid
microgels, bands at 1655, 1547, and 1458 cm1 were attributed to
the eCOeNHe group of the PNIPAm. Characteristic absorption
bands of Fe3O4 and TMSPMA were also observed. No absorption
bands of vinyl groups was observed for PNIPAm-Fe3O4 hybrid
microgels, indicating all of the carbonecarbon double bonds (C]C)
have taken part in the free radical polymerization. Furthermore, the
TGA results showed that the amount of Fe3O4 nanoparticles inside
the PNIPAm-Fe3O4 hybrid microgels was ca. 25.8 wt%, as shown in
Fig. 3 (solid line).
The TEM, SEM, EDX, TGA, and FT-IR results confirmed that the
PNIPAm-Fe3O4 hybrid microgels was successfully obtained with
TMSPMA-modified Fe3O4 nanoparticles as the crosslinker and

Fig. 5. (a) Scanning electron microscope (SEM) image and (b) energy dispersive X-ray analysis (EDX) of the PNIPAm-Fe3O4 hybrid microgels.
 T. Chen et al. / Polymer 52 (2011) 172e179 177

NIPAm as the monomer. The Fe3O4 nanoparticles and PNIPAm

network chains were connected and crosslinked via the covalent
bonds. As compared with the conventional poly(N-iso-
propylacrylamide) (PNIPAm) microgels prepared by SFEP with
chemical crosslinker N,N0 -methylene-bisacrylamide and P(NIPAm-
co-TMSPMA) microgels [1,9,21], the shortcomings of the present
methodology are that the size of PNIPAm-Fe3O4 hybrid microgels
obtained was relatively polydisperse and the crosslinking density of
each microgel was different. Two possible reasons may lead to the
large size distribution of the PNIPAm-Fe3O4 hybrid microgels. First,
the Fe3O4 nanoparticles were not uniformly modified with TMSPMA,
leading to the heterogeneous crosslinking reaction. Secondly, the
TMSPMA-modified Fe3O4 nanoparticles were hydrophobic in nature
and formed aggregates with various sizes in aqueous solution even
after ultrasonication. These aggregates behaved as crosslinkers,
which then led to the large size variation of resultant PNIPAm-Fe3O4
hybrid microgels. As a consequence, the number of Fe3O4 nano-
particles in each hybrid microgel was different and hence the
crosslinking density of each microgels was different as well. With the
ongoing efforts, these shortcomings could be overcome in the near
future. Nevertheless, the present work offers a new and alternative
way for synthesizing organiceinorganic hybrid microgels, of which
the inorganic nanoparticles have well-defined crosslinking mecha-
nism and are covalently connected with the network chains.
It is well known that PNIPAm chains and PNIPAm microgels
exhibit thermosensitive characters. PNIPAm microgels will swell in
aqueous solution below it’s lower critical solution temperature
(LCST) and deswell upon raising the temperature above it’s LCST. As
expected, the PNIPAm-Fe3O4 hybrid microgels obtained here are
also thermosensitive. Fig. 6 shows the hydrodynamic diameters of
the PNIPAm-Fe3O4 hybrid microgels in aqueous solution as a func-
tion of temperature. The hydrodynamic diameters of the hybrid
microgels decrease from ca. 1100 nm to ca. 329 nm with increasing
the measuring temperature from 15 to 55
C. When the tempera-
ture was cooled from 55
C down to 15
C, the hydrodynamic
diameter of the PNIPAm-Fe3O4 hybrid microgels increase again
along the similar track. There was no apparent hysteresis during the
heating and cooling cycles, suggesting that the thermosensitive Fig. 7. Size distribution of PNIPAm-Fe3O4 hybrid microgels at 15
C (a) and 55
C (b),
behavior of the PNIPAm-Fe3O4 hybrid microgels was reversible. respectively.
Fig. 7 shows that the PNIPAm-Fe3O4 hybrid microgels exhibited
a relative narrow size distribution in aqueous solution at 15
C and
a double-mode size distribution at 55
C, respectively. The PNIPAm- low temperature. Furthermore, DLS was more sensitive to the large
Fe3O4 hybrid microgels were fully swelled in aqueous solution at particles. Therefore, the hybrid microgels exhibited a relative
narrow size distribution at 15
C as measured by DLS. However, the
PNIPAm-Fe3O4 hybrid microgels were shrinking at high tempera-
ture. Due to the different crosslinking density, the collapsed hybrid
microgels at 55
C had various sizes and exhibited a double size
distribution measured by DLS, which were consistent with the size
distribution of dried hybrid microgels obtained by TEM and SEM
(cf. Figs. 4 and 5). It was worthy to note that the double size
distribution started to appear at ca. 35
C.
The volume phase transition temperature of the PNIPAm-Fe3O4
hybrid microgels was determined to be ca. 33
C via the first-
derivative plot of the hydrodynamic diameter of the hybrid
microgels as a function of measuring temperature, (Fig. S4 in
Supplementary Material) which is similar with the P(NIPAm-co-
TMSPMA) microgels (around 30e32
C) [21] and the conventional
PNIPAm microgels (32
C) [1,9,47,48] with chemical crosslinker
N,N0 -methylene-bisacrylamide (BIS) in aqueous solution. The PNI-
PAm-Fe3O4 hybrid microgels show a steep hydrodynamic diameter
change in a narrow temperature range.
The magnetic properties of the TMSPMA-modified Fe3O4
nanoparticles and PNIPAm-Fe3O4 hybrid microgels were measured
Fig. 6. The hydrodynamic diameters of the PNIPAm-Fe3O4 hybrid microgels as a function
at 300 and 10 K, respectively, by using a physical properties
of measuring temperature. measurement system (PPMS-9, Quantum Design). Fig. 8 shows the
178
Fig. 8. (a) The magnetization hysteresis loops of the TMSPMA-modified Fe3O4 nano-
particles at 300 K (solid line) and 10 K (dash line), respectively. (b) The magnetization
hysteresis loops of the PNIPAm-Fe3O4 hybrid microgels at 300 K (solid line) and 10 K
(dash line), respectively. The insets of (a) and (b) show the coercivity and remanence
magnetization of corresponding samples.
magnetization hysteresis loops of the TMSPMA-modified Fe3O4
nanoparticles and PNIPAm-Fe3O4 hybrid microgels at 300 and 10 K,
respectively. At room temperature (300 K), the TMSPMA-modified
Fe3O4 nanoparticles and PNIPAm-Fe3O4 hybrid microgels exhibited
superparamagnetic behavior with negligible coercivity and rema-
nence. The saturation magnetization Ms of the TMSPMA-modified
Fe3O4 nanoparticles and PNIPAm-Fe3O4 hybrid microgels were
about 52.7 and 7.5 emu/g, respectively, at 300 K. At 10 K, obvious
hysteresis loops were observed for both TMSPMA-modified Fe3O4
nanoparticles and PNIPAm-Fe3O4 hybrid microgels, indicating the
typical ferromagnetic behavior. The saturation magnetization Ms of
the TMSPMA-modified Fe3O4 nanoparticles and PNIPAm-Fe3O4
hybrid microgels were about 61.6 emu/g and 8.8 emu/g, respec-
tively, at 10 K. The coercivity of ca. 322 Oe and the remanence of ca.
25 emu/g were observed for TMSPMA-modified Fe3O4 nano-
particles at 10 K. For PNIPAm-Fe3O4 hybrid microgels at 10 K, the
coercivity and remanence were ca. 354 Oe and ca. 4 emu/g,
respectively. Because of the large amount of nonmagnetic PNIPAm
component, the Ms value of PNIPAm-Fe3O4 hybrid microgels
was much lower than that of TMSPMA-modified Fe3O4 nano-
particles. In our previous work [18], a linear relationship between
the amount of organic polymer coating and Ms of poly [N-iso-
propylacrylamide-co-3-(trimethoxysilyl)-propylmethacrylate] [P
T. Chen et al. / Polymer 52 (2011) 172e179
(NIPAm-co-TMSPMA)] capped Fe3O4 nanoparticles was established
(cf. Fig. 7A in Ref. 18).Since the same chemicals (NIPAm and
TMSPMA) were used in the present work, the amounts of organic
components could be estimated form the Ms of PNIPAm-Fe3O4
hybrid microgels. By using Ms of 52.7 emu/g at 300 K, the weight
percent of organic polymer components in the PNIPAm-Fe3O4
hybrid microgels was then calculated to be ca. 76.0 wt %, which was
in good agreement with the TGA result (i.e. 74.2 wt%).
4. Conclusions
The thermosensitive organiceinorganic PNIPAm-Fe3O4 hybrid
microgels were successfully prepared via surfactant-free emulsion
polymerization (SFEP) by using N-isopropylacrylamide (NIPAm) as
the thermosensitive monomer and 3-(trimethoxysilyl)propylme-
thacrylate (TMSPMA)-modified magnetic Fe3O4 nanoparticles as
the crosslinker. The TMSPMA-modified magnetic Fe3O4 nano-
particles were confirmed to behave as crosslinkers, leading to
the formation of PNIPAm-Fe3O4 hybrid microgels. The resultant
PNIPAm-Fe3O4 hybrid microgels were spherical in shape with
a large size distribution and the Fe3O4 nanoparticles were randomly
distributed inside the microgels. The PNIPAm-Fe3O4 hybrid
microgels exhibit reversible thermosensitive swelling and desw-
elling properties with a volume phase transition temperature of
33
C. At room temperature (300 K), the PNIPAm-Fe3O4 hybrid
microgels show superparamagnetic behavior. Such method can be
also adapted for other monomers and inorganic nanoparticles.
Further experiments are ongoing to improve the size distribution of
the resultant hybrid microgels and to control the distribution of the
functional inorganic nanoparticles inside the hybrid microgels as
well as the crosslinking density of the hybrid microgels.
Acknowledgments
The authors thank the National Natural Science Foundation
of China (No. 20604022, 20874087) and 863 project (No.
2009AA04Z125) for financial supports.
Appendix. Supplementary data
Supplementary data related to this article can be found online at
doi:10.1016/j.polymer.2010.11.014.
References
[1] Pelton RH, Chibante P. Colloids Surf 1986;20(3):247e56.
[2] Oh JK, Drumright R, Siegwart DJ, Matyjaszewski K. Prog Polym Sci 2008;33
(4):448e77.
[3] Palioura D, Armes SP, Anastasiadis SH, Vamvakaki M. Langmuir 2007;23
(10):5761e8.
[4] Pich A, Karak A, Lu Y, Ghosh AK, Adler HJP. J Nanosci Nanotechnol 2006;6
(12):3763e9.
[5] Lopez VC, Hadgraft J, Snowden MJ. Int J Pharm 2005;292(1e2):137e47.
[6] Zhang JG, Xu SQ, Kumacheva E. J Am Chem Soc 2004;126(25):7908e14.
[7] Garcia A, Marquez M, Cai T, Rosario R, Hu ZB, Gust D, et al. Langmuir 2007;
23(1):224e9.
[8] Bradley M, Ramos J, Vincent B. Langmuir 2005;21(4):1209e15.
[9] Saunders BR, Vincent B. Adv Colloid Interface Sci 1999;80(1):1e25.
[10] Snowden MJ, Chowdhry BZ, Vincent B, Morris GE. J Chem Soc, Faraday Trans
1996;92(24):5013e6.
[11] Karg M, Hellweg T. J Mater Chem 2009;19(46):8714e27.
[12] Hoffmann F, Cornelius M, Morell J, Froba M. Angew Chem Int Ed 2006;45
(20):3216e51.
[13] Sanchez C, Lebeau B, Chaput F, Boilot JP. Adv Mater 2003;15(23):1969e94.
[14] Sanchez C, Soler-Illia G, Ribot F, Lalot T, Mayer CR, Cabuil V. Chem Mater
2001;13(10):3061e83.
[15] Wen JY, Wilkes GL. Chem Mater 1996;8(8):1667e81.
[16] Judeinstein P, Sanchez C. J Mater Chem 1996;6(4):511e25.
[17] Lu Y, Proch S, Schrinner M, Drechsler M, Kempe R, Ballauff M. J Mater Chem
2009;19(23):3955e61.
 T. Chen et al. / Polymer 52 (2011) 172e179
[18] Du BY, Mei AX, Tao PJ, Zhao B, Cao Z, Nie JJ, et al. J Phys Chem C 2009;113
(23):10090e6.
[19] Wong JE, Gaharwar AK, Muller-Schulte D, Bahadur D, Richtering W. J Colloid
Interface Sci 2008;324(1e2):47e54.
[20] Contreras-Caceres R, Sanchez-Iglesias A, Karg M, Pastoriza-Santos I, Perez-
Juste J, Pacifico J, et al. Adv Mater 2008;20(9):1666e70.
[21] Cao Z, Du BY, Chen TY, Nie JJ, Xu JT, Fan ZQ. Langmuir 2008;24(22):12771e8.
[22] Wang XJ, Hu DD, Yang JX. Chem Mater 2007;19(10):2610e21.
[23] Wang GZ, Zhang Y, Fang Y, Gu ZZ. J Am Ceram Soc 2007;90(7):2067e72.
[24] Pich AZ, Adler HJP. Polym Int 2007;56(3):291e307.
[25] Narain R, Gonzales M, Hoffman AS, Stayton PS, Krishnan KM. Langmuir
2007;23(11):6299e304.
[26] Ballauff M, Lu Y. Polymer 2007;48(7):1815e23.
[27] Das M, Zhang H, Kumacheva E. Annu Rev Mater Res 2006;36:117e42.
[28] Zhang JG, Xu SQ, Kumacheva E. Adv Mater 2005;17(19):2336e40.
[29] Nayak S, Lyon LA. Angew Chem Int Ed 2005;44(47):7686e708.
[30] Agrawal M, Rubio-Retama J, Zafeiropoulos NE, Gaponik N, Gupta S, Cimrova V,
et al. Langmuir 2008;24(17):9820e4.
[31] Gong YJ, Gao MY, Wang DY, Mohwald H. Chem Mater 2005;17(10):2648e53.
[32] Rubio-Retama J, Zafeiropoulos NE, Frick B, Seydel T, Lopez-Cabarcos E. Langmuir
2010;26(10):7101e6.
179
[33] Rubio-Retama J, Zafeiropoulos NE, Serafinelli C, Rojas-Reyna R, Voit B,
Cabarcos EL, et al. Langmuir 2007;23(20):10280e5.
[34] Zhang F, Wang CC. Langmuir 2009;25(14):8255e62.
[35] Lian XM, Jin J, Tian J, Zhao HY. ACS Appl Mater Interfaces 2010;2(8):2261e8.
[36] Pich A, Zhang FB, Shen L, Berger S, Ornatsky O, Baranov V, et al. Small
2008;4:2171e5.
[37] Haraguchi K, Takeshita T. Adv Mater 2002;14:1121.
[38] Haraguchi K, Takeshita T, Fan S. Macromolecules 2002;35:10162e71.
[39] Nie JJ, Du BY, Oppermann WJ. Macromolecules 2005;38:5729e36.
[40] Nie JJ, Du BY, Oppermann WJ. Phys Chem B 2006;110:11167e75.
[41] Zhang QS, Zha LS, Ma JH, Liang BR. Macromol Rapid Commun 2007;28:116e20.
[42] Voorn DJ, Ming W, van Herk AM. Macromolecules 2006;39:4654e6.
[43] Czaun M, Hevesi L, Takafuji M, Ihara H. Chem Commun 2008;18:2124e46.
[44] Ghosh M, Lawes G, Gayen A, Subbanna GN, Reiff WM, Subramanian MA, et al.
Chem Mater 2004;16(1):118e24.
[45] Kang YS, Risbud S, Rabolt JF, Stroeve P. Chem Mater 1996;8(9):2209e11.
[46] De Palma R, Peeters S, Van Bael MJ, Van den Rul H, Bonroy K, Laureyn W, et al.
Chem Mater 2007;19(7):1821e31.
[47] Pinkrah VT, Beezer AE, Chowdhry BZ, Gracia LH, Mitchell JC, Snowden MJ.
Langmuir 2004;20:8531e6.
[48] Kawaguchi H, Fujimoto K, Mizuhara Y. Colloid Polym Sci 1992;270(1):53e7.