NEW APPROACH OF USING EMULSIFIER-FREE EMULSION POLYMERIZATION TO

PREPARE MAGNETIC POLYMERIC NANOPARTICLES

Nguyen Quang Hung, Duong Hong Quyen, Tran Van Thang, Hoang Thi Kieu Nguyen*
School of Chemical Engineering,
Hanoi University of Science and Technology - 1 Dai Co Viet road, Hanoi, Vietnam

* To whom correspondence should be addressed. E-mail:[email protected]

Abstract
A new approach of using emulsifier-free emulsion polymerization to prepare magnetic nanoparticles coated
by poly-methacrylic acid (PMAA) was followed. The results showed the formation of PMAA shells covering
magnetite cores. The shell thickness was customized by varying the synthesis parameters such as mass ratio
of monomer to magnetic particles, temperature and reaction time. The experimental investigations indicate
that the polymerization is dominated by the homogeneous nucleation in solutions and the later growth into
the uniform polymeric layer occurs at the surface of solid particles. The resulting PMMA-coated particles
presented comparatively higher saturation magnetization in the presence of surfactants or emulsifiers.

Key-words: magnetite, magnetic materials, nanoparticles, polymeric encapsulation, core-shell structure,

functionalized surface, emulsion polymerization, poly-methacrylic acid

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1. Introduction
Coating or encapsulating magnetic particles by polymers is considered as an effective solution to stabilize
the magnetic dispersion and to modify these particles suitable with different applications, in particular
clinical and in biotechnology. Various approaches have been performed to prepare such polymer-
encapsulated particles. A commonly used method is that magnetic inorganic particles and polymer particles
are synthesized separately and then mixed together to enable either physical or chemical adsorption of the
polymer onto the magnetic particles.1,2 However, with a system where the polymers and the magnetite
particles are separately dispersed, the improvement in dispersion stability is insufficient and, moreover, the
polymers can dissociate from the magnetic particles in case of a change, for example, an increase in
temperature. An alternative method to this is to suspend magnetic particles in the liquid phase of a
polymerizable formulation and then polymerize the monomers in the presence of the magnetic particles to
form magnetic polymeric particles, including conventional emulsion polymerization, 3,4 mini-emulsion
polymerization,5-7 and dispersion polymerization.8 In these studies, the stabilizers are often preferred to
obtain stable colloids. However, the residual emulsifier in the particle surface has negative effects on the
purification and the properties of the nanoparticles. The magnetization values of the polymer-coated particles
are much lower than that of the bulk.2,6 This result can be attributed not only to the non-magnetic polymeric
coating but also to the surfactant layer covering the magnetic particles. Therefore, emulsifier-free emulsion
polymerization can be considered as a suitable approach to prepare polymer-coated magnetic particles. In
such polymerization systems, ionizable initiators and hydrophilic or ionic co-monomers stabilize polymer
particles instead of surfactants. Nevertheless, in order to enhance the interaction between magnetic
nanoparticles and polymers, some added components such as emulsifiers, co-stabilizers, or cross-linking
agents may also have to be used.9,10 In recent researches, Beyaz et al.11 introduced a new route of emulsifier-
free emulsion polymerization with only four main components: magnetite nanoparticles, methyl
methacrylate, potassium persulfate, and water. Because of the drawbacks associated with coagulation and
polydispersity, however, they could not launch more than 3.1% of the initial ratio of magnetite/monomer.
Therefore, in this study, the preparation of magnetic particles by polymeric encapsulation using emulsifier-
free emulsion polymerization has been developed. A novel process based on homogenous polymerization
mechanism has been presented to synthesize magnetic nanoparticles coated by PMAA with high magnetic
content. To improve the understanding about this method, the effects of monomer concentration,
temperature, and reaction time to the formation of the polymer-coated particles and their magnetic property
has also been investigated.
2. Experimental procedures
2.1 Materials
Ferrous chloride tetrahydrate (FeCl2•4H2O, AR) and ferric chloride hexahydrate (FeCl3•6H2O, AR) were
procured from BDH Chemicals Ltd., England
Ammonium hydroxide [AR, 25% (by mass) NH3 in water] was purchased from Guangdong Xilong Chemical
Co., Ltd., China.
Initiator potassium persulfate (K2S2O8) and monomer methacrylic acid (MAA) of 99% purity were supplied
by Merck.
2.2 Magnetite preparation
The water-based magnetite nanoparticles (MNPs) were prepared by reacting iron (II) and iron (III) ions in an
aqueous ammonia solution as follows:
2FeCl3 + FeCl2 + 8NH3 + 4H2O = Fe3O4  + 8NH4Cl (1)
This preparation method has been described in a previous study.12 Briefly, stock solutions of 2 M FeCl2 in 1
M HCl, 1 M FeCl3 in 2 M HCl, and 0.7 M NH4OH were prepared. Then, 1.0 ml of stock FeCl2 solution and
4.0 ml of stock FeCl3 solution [the 2:1 iron(III)/iron(II) stoichiometric ratio] were combined. A magnetic
stirring bar was placed in the solution flask for vigorous stirring. To this, 50 ml of 0.7 M aqueous NH 3
solution was added at a constant rate of 4.6 ml min−1. The stirring rate of 960 rpm and a temperature of 25 °C
were kept constant throughout the addition of the ammonia solution. The reaction was continued after 30
minutes of ceasing ammonia addition. The precipitate so formed was then decanted and washed several
times with deionized water until the pH value descended to 7.0. A portion of the final product was dried for 4
h at 40 °C for the specification. The remaining portion was used to prepare magnetic polymeric particles.
2.3 Magnetic polymeric particle preparation

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The obtained precipitate after rinsing was dispersed in water at the weight fraction of 2 % by ultrasonication
(Elmasonic S100 at 37 kHz frequency). The dispersion was heated in a thermoregulator until the required
temperature was reached. Then, the appropriate dosage of the initiator K 2S2O8 (5 % of monomer weight) was
added. Next, the MAA solution was dropped into the reaction vessel at a constant rate. The stirring rate was
maintained at 300 rpm and nitrogen gas was continuously added throughout the polymerization reaction.
This process was continued for more than hour after the monomer addition. The obtained polymer-coated
particles were extracted from the solution by a magnetic particle concentrator to remove the free monomers
and polymers. These isolated particles were dried for characterization studies.
In order to control the formation of the magnetic polymeric particles, variations of monomer concentration,
temperature, and polymerization time were investigated. In each series of the experiments, only the
investigated parameter was changed and the other preparation conditions were kept same as the standard
conditions.
2.4 Characterization of particles
The crystalline structure of the magnetic nanoparticles was characterized by X-ray diffraction (XRD). The
measurements were performed on powder samples obtained after evaporation of the liquid carrier by using a
Siemens diffractometer D5000 with Cu Ka radiation at 1.5406 A°.
The formation of magnetite particles with PMAA coatings was studied by Fourier transform infrared
spectroscopy (FTIR; Impact 400, Nicolet) and by transmission electron microscopy (TEM; JEOL EM 1010).
Assuming that each magnetite particle was coated by the polymer, the polymer layer thickness can be
predicted from thermal gravity analysis (TGA) by using a thermo-gravimetric analyzer (TGA 2950, DuPont
Instruments) under nitrogen gas with a heating rate of 5–10 °C min−1 from room temperature to 600 °C. The
weight ratio of the polymer and the magnetite from TGA can be expressed as follows:
N N
 N
N 0 
 2  (ait ) 3   (ai0 ) 3   2  (ai0  t ) 3   (ai  t )
3

 i 1 i 1   
  i 1
   N
2 2 i 1
 1
N N
  1  
1  (ai0 ) 3 1  (ai0 ) 3 1
  (ai0 ) 3 
i 1 i 1 (2) i 1

Where, t is the polymer layer thickness, is the radius of ith uncoated particle, and N is the total number of
particles. The densities of magnetite and PMAA were ρ1 = 5.20 g cm−3 and ρ2 = 1.18 g cm−3, respectively.
From Eq. 2, from the particle size distribution determined by the TEM image of the original magnetite
dispersion, the polymer shell thickness t was calculated with the total number of particles N of 100.
In order to evaluate the efficiency of the polymerization method in this study, the term “polymerization
yield” was used. This parameter is defined by the weight ratio of the polymer formed on the magnetic
particle surface to the initial monomer.

(3)

In Eq. (3), 0 and  are the mass ratios of MAA/Fe3O4 and of PMAA/Fe3O4, respectively.
Vibrating sample magnetometer (VSM; DMS 880) was used for magnetization measurements. These
measurements were taken from −12 to 12 kOe field. From the field versus magnetization curves, the
saturation magnetization values of the samples were determined.
3. Results and discussion
3.1 Formation of PMAA-coated particles
The XRD pattern (Fig. 1) of the nanoparticles synthesized as described in the above section shows the
characteristic peaks (220), (311), (400), (422), (511), and (440) corresponding to the magnetite from JCPDS
card 11-0614. The existence of any impurity other than magnetite was not detected. It can be proposed that
magnetite was the main precipitate in our experiments. The magnetization value of 78 emu g −1 obtained for
these particles (see the last section) that are very close to the bulk Fe 3O4 (approximately 90 emu g−1) also
confirms this conclusion.
The synthesized magnetite particles had an average radius of 6.6 nm, as computed directly from the TEM
images (Fig.2). The FTIR spectra of magnetite particles before and after PMAA coating are presented in Fig.
3.

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Fig.1 X-ray diffractogram of synthesized precipitates

Fig. 2 TEM image of synthesized magnetite

Fig. 3 FTIR spectra of magnetite particles uncoated and coated by PMAA

The absorption band of magnetite at 570 cm−1 can be found at the both spectrum. Meanwhile, the observed
C–H stretching bands immediately below 3000 cm−1 indicate the presence of PMAA on the surface of the
magnetite. The symmetrical C=O stretching band that appears at 1402 cm −1, similar to the observation for the
PMAA-coated maghemite nanoparticles in a previous study2, suggests that the carboxylate may
symmetrically bind to the maghemite nanoparticle surface and that the carboxylate is connected to the
surface through two oxygen atoms. Moreover, the evident C=O stretch at 1656 cm−1 indicates the existence
of free carboxylic acid groups.

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3.2 Effect of mass ratio of monomer to magnetite
In this part, four samples with different weight ratios of MAA/Fe3O4 in the range of 3:1 to 16:1 were
investigated. In each experiment, the total MAA amount was continuously added to the reaction system for 4
h. The polymerization was conducted at 60 ± 2 °C. The parameters of the experiments are reported in Table
1.
Table 1. Polymer layer thicknesses as a function of mass ratio of MAA/Fe3O4

Sample MAA/ PMAA Thickness Polymer-

Fe3O4 /Fe3O4 / nm ization
yield/ %

SM1 3:1 1.4 6.5 47

SM2 8:1 1.8 7.5 23

SM3 11:1 2.9 9.7 26

SM4 16:1 3.5 10.6 22

Fig. 4 shows a typical TEM image of the PMAA-coated Fe3O4 nanoparticles that were synthesized at
different mass ratios of monomer/magnetite. The observation at the TEM image indicates the formation of
polymer-coated magnetite nanoparticles. Most magnetite particles are covered by PMAA and the polymer
shells have a uniform thickness.

Fig. 4 A typical TEM image of PMAA-coated particles prepared at different ratios of MAA/Fe 3O4
(sample SM2)

The polymer layer thickness can be estimated by Eq. (2) from TGA measurements. As seen in Fig. 5, where
thermo-gravimetric charts of PMAA-coated particles of the samples from SM1 to SM4 are presented, the
loss of mass is gradual. An endothermic peak in DTA corresponding to the PMAA degradation can be
observed around 190 °C. The PMAA weight can be estimated by the mass loss from 190 to 450 °C to reveal

5
the complete decomposition of PMAA. The residual mass is considered as the amount of magnetite in
PMAA-coated particles. The thicknesses of polymer layers obtained at the samples are reported in Table 1.
The polymerization yield values are also presented in Table 1.

Fig. 5 Weight loss curves of PMAA coated particles prepared at different ratios of MAA/magnetite
(SM1 top to SM4 bottom)

An increase of the polymer film thickness with an increasing ratio of monomer/magnetite can be found. The
thickness increases approximately 1.6 times as the MAA concentration increases up to 5 times. To explain
this result, it should be noted that, in our work, the MAA addition rate was lower than 0.13% wt.
(approximately 0.015 M) per minute meanwhile, as reported in a previous study. 13 The time for complete
conversion of 0.4 M MAA was about 40 min at similar reaction conditions. This means that the rate of
monomer addition is less than the polymerization rate and that the dynamic concentration of MAA in the
continuous phase is always lower than its aqueous solubility of 9.7% wt.14 Hence, the polymerization may be
considered as a solution polymerization.

At the beginning of the reaction, since the amount of MAA is much smaller than the initiator concentration,
the radical capturing is accelerated to form chain-initiating radicals with sulfate-end groups. These elements
are surface active and absorb on the surface of magnetic particles. The subsequent propagation occurs in

6
incorporation of the added monomers to the particle surface and the structure core-shell is formed.
According to this supposition, the degree of polymerization (DP) as well as the polymer molecular weight
(PMW) determines the polymer layer thickness. The DP is proportional to monomer [M] and initiator
concentration [I] as follows:14

(4)

In the current study, as the ratio of monomer/initiator is a constant, the degree is only dependent on the
square root of monomer concentration. The fact that there is a linear increase of the thickness with the square
root of monomer concentration is presented in Fig. 6. This result implies that the polymer layer thickness is
determined by the PMW and that the propagation process is the growing chain at the surface of magnetite
particles. In addition, the polymer layer thickness depends on the first order of monomer concentration.

Fig. 6 Polymer layer thicknesses as a function of square root of monomer concentration

However, for high water-soluble monomers such as MAA, the growth of the polymer layers coating
magnetite particles (surface polymer) is strongly competed by the polymers that are formed by the
propagation of free-active chains in the medium (bulk polymer). The bulk polymers may become polymer
particles by the precipitation of growing chains upon achievement of a critical chain length 15 or by the
monomer-swollen polymerization of micelles that are created by the chain radicals. On the other hand, the
interaction between the magnetite particles and PMAA as found at the FTIR may be considered as a chain
transfer agent, leading to diminished molecular weight of the surface polymer. 3 Furthermore, the surface and
the growing polymer layer may reduce, to a certain extent, the effective concentration of monomers near the
active ends so that the polymerization rate at the surface reduces. 16 Thus, the preferred formation of free
polymer particles rather than polymer-covering magnetite explains the fact that the polymerization yield is
quite lower than that of the polymerization for pure PMAA under similar reaction conditions. 13 The
polymerization yields (except sample SM1) fluctuate around the value of 25 %, although the monomer
concentration is increased up to 5 times (see Table 1). This result also indicates that the mass ratio of
monomer/magnetite should be equal or lower than 3:1 to obtain the synthesis with high efficiency.
3.3 Effect of polymerization temperature
In this series of experiments, four samples, all with a mass ratio of MAA/Fe 3O4 of 8:1 consequently were
polymerized at 50, 60, 70, and 85 °C. The formation of PMAA covering the magnetite particles was
observed under TEM (Fig. 7). The polymer shell thickness and the polymerization yield were estimated from
TGA measurements, as described in the above section (Fig. 8). The obtained results are reported in Table 2.
As expected, an elevated temperature promotes the transport of monomer to the surface of magnetic
particles. Therefore, the chain growth process is thereby accelerated, leading to an increase in the polymer
shell thickness according to the assumed mechanism mentioned in the previous section.
The obtained results in polymerization yield also confirmed this mechanism. For samples ST1 and ST2, the
low polymerization yields were mainly due to the slow decomposition rate of the initiator. An 80-fold
decrease in the decomposition rate of potassium persulfate was reported by Madan et al. 17 as the temperature
changed from 76 to 45 °C. This reduces the concentration of active radical chains, resulting in decrease of
the overall percent conversion of monomer to polymer. The study of Tanrisever 15 showed that the limiting
monomer conversion for poly-methyl methacrylate (PMMA) synthesis at these temperatures (< 60 °C) is

7
much lower than 100 %. In addition, as mentioned in the previous investigation, the decrease in
polymerization yield may be attributed to the formation of bulk polymer. At temperatures greater than 60 °C,
the effect of temperature on the formation of polymer shells becomes more significant. The enhancement
factor in polymerization yield is about 5, while the temperature is increased by only 25 °C. Even at 85 °C,
the polymerization yield is approximately 100 %. This suggests that the total monomer amount to form the
polymer film covering the magnetic particles and for the formation of small pure polymer particle was not
observed.

Fig. 7 A typical TEM image of PMAA-coated particles prepared at different temperatures (sample
ST4)

Table 2 Polymer layer thicknesses as a function of temperature

Sample Temper- PMAA/ Thick- Polymeriz-
ature/ oC Fe3O4 ness/ nm ation yield/
%

ST1 40 0.94 5.1 12

ST2 50 1.08 5.6 14

ST3 60 1.8 7.5 23

ST4 75 4.64 12.4 58

ST5 85 7.96 15.9 100

The result should be explained by a reduction of the bulk polymer in the aqueous phase because the limiting
monomer conversion of MAA is not changed significantly at over 60 °C (approximately 90–100 %). 15 An
increase of the water solubility of MAA on rising temperature increases the critical chain length for polymer
precipitation, which may retard the formation of polymer particles in the continuous phase. In addition,
increasing temperature increases the fraction of surface-bound initiators () and, thus, the surface polymers
become more competitive with the bulk polymers.16 When η = 100 %, no bulk polymerization are available.
On the other hand, it may be assumed that the acceleration of temperature to decomposition rate of the
initiator that increases the number of free chain radicals to form polymer particles from monomer-swollen
micelles15 was not significant in this investigation.

8
Fig. 8 Weight loss curves of PMAA coated particles prepared at different ratios of MAA/magnetite
(SM1 top to SM4 bottom)

3.4 Effect of polymerization time

To investigate the effect of reaction time, four samples with a mass ratio of MAA/Fe 3O4 of 3:1 were
polymerized at 60 ± 2 °C. The polymerization was conducted for different durations by changing the
addition rate of MAA. The investigated time is shown in Table 3. Note that the reported time excludes the
extra time (an hour) after completing the monomer addition.

Table 3 Polymer layer thicknesses as a function of polymerization time

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Sample Reaction PMAA Thickness Polymer-
time/ h /Fe3O4 /nm ization
yield/ %

SP1 2 - - -

SP2 3 1.55 6.9 52

SP3 4 1.42 6.5 47

SP4 6 1.39 6.4 46

Fig. 9 TEM images of PMAA coated particles prepared at different reaction time: 2 h (above) and
more than 2 h – SP2 (below)

For sample SP1, when the reaction time is 2 h, the formation of PMAA on the surface of magnetic particles
was not observed under TEM (Fig. 9). The TGA measurement for this sample also confirmed this result.
There was no noticeable trace of the polymer on the weight loss curve (Fig. 10). The result is probably
explained that the conversion level of MAA after 2 h is very low. As compared to the study by Polacco, 13 in
which over 80 % of 0.4 M MAA was conversed after 40 min, we may assume that the reaction time of 2 h is
sufficient for the conversion of 0.7 M MAA at this study. However, the gradual addition of monomer (but
not a one-time addition) probably reduces the monomer concentration reacting in the propagation step,
leading to a significant decrease in the polymerization rate and a longer reaction time for high percent
conversion.

10
For the remaining samples, from SP2 to SP4, most particles were coated by the polymer films (Fig. 9). This
implies that a time of 3 h is sufficient to complete the reaction. Extending the reaction time slightly decreases
the thickness of the polymer film and the polymerization yield (Table 3). This result can be attributed to the
decrease of PMW, which is caused by the increase of the monomer addition rate. Nevertheless, the obtained
values prove that the effect of addition rate of monomer is not significant in comparison with the effect of
total monomer concentration in the first series of experiments.

Fig. 10 Weight loss curves of PMAA coated particles prepared at different reaction time (SM1 top to
SM4 bottom)

The experimental results all confirm the polymerization mechanism in which the initiation process takes
place in the solution and the propagation is continued at the surface of magnetic particles. The thickness of
the polymer layer is determined by the resultant PMW.
3.5 Magnetic properties of particles coated with different polymer thicknesses
It is noteworthy that the polymerization method used in this study allows preparing of PMAA-coated
particles with the thin polymer coatings and the polymer-coating thickness can be simply adjusted by
changing the monomer concentration or temperature. Furthermore, the prepared particles demonstrate
magnetic property significantly higher than that in other similar studies. 3,6,10 As the room temperature
magnetization curves illustrated in Fig. 10, the saturation magnetization at 12 kOe of bare Fe 3O4
nanoparticles is 78 emu g−1 and of PMAA-coated magnetite particles with different polymer-coating
thicknesses of 7.5 and 10.6 nm is consequently 62 and 58 emu g−1, respectively.
It can be clearly observed that the higher the polymer layer thickness, the lower the saturation magnetization
is. This result can be attributed to the non-magnetic polymer. Nevertheless, as compared to the magnetic
particles coated with different polymers such as PMAA, PMMA, and PS, the magnetization reduction in this
study is much lower than that in others. For magnetic particles coated by PMMA, Hong et al. 6 found that the
magnetization decreased from 65.6 to 23 emu g−1 by the existence of PMMA and oleic acid (emulsifier). In
addition, the polyethylene glycol methacrylate (PEG-MA)-coated particles of Utkan et al. 10 showed the sharp
reduction in magnetization after polymer coating (from 23 to 2.5 emu g −1). Similar result was also reported
by another previous study.3 The main difference between our and others’ research is in using either very
thick polymer layer (approximately 165 nm)10 or the presence of surfactant layer.3,6

11
Fig. 11 Room temperature magnetization curves of MNPs (a) and MNPs coated with different MAA
thicknesses: (b) 7.5 nm, (c) 10.6 nm

Acknowledgements
We gratefully acknowledge the receipt of a grant from the National Foundation for Science and Technology
Development (NAFOSTED) which enabled us to carry out this work.

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