Materials Letters 60 (2006) 2410 2415

www.elsevier.com/locate/matlet

Study on in situ preparation of nano calcium carbonate/PMMA

composite particles
Wei Wu a , Taobo He a , Jian-feng Chen a,, Xueqin Zhang a , Yuxi Chen b
a

Key Lab for Nanomaterials, Ministry of Education; Research Center of the Ministry of Education for High Gravity Engineering and Technology,
Beijing University of Chemical Technology, Beijing 100029, PR China
b
Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148, USA
Received 14 November 2004; accepted 1 March 2005
Available online 28 February 2006

Abstract
The composite particles of nano calcium carbonate/polymethyl methacrylate (PMMA) were prepared by soapless emulsion polymerization
technique in the aqueous suspension of nano calcium carbonate. The effects of synthesis parameters on monomer conversion were studied, and the
formation mechanism of composite particles was proposed. The results indicated that nano calcium carbonate that existed in the suspension can
boost the monomer conversion. Appropriate stirring rate can enhance the probabilities for polymer to coat on the surface of nano calcium
carbonate. PMMA is chemically grafted and physically wrapped on the surface of nano calcium carbonate to form nano calcium carbonate/PMMA
composite particles.
2006 Published by Elsevier B.V.
Keywords: Nano calcium carbonate; Composite particles; Soapless emulsion polymerization; PMMA; Mechanism

1. Introduction
The materials formed by embedding of inorganic particles
into polymeric matrices represent a new class of polymeric
materials that combine the properties of the inorganic particles
(in terms of mechanical strength, modulus, and thermal
stability) with the processability and the flexibility of organic
polymer matrix. Of course, such materials can be obtained by
simply mixing the organic and inorganic components. However,
in order to achieve the best dispersion of the inorganic particle
in polymer matrix and interfacial adhesion between the polymer
and inorganic particle, the techniques for synthesizing composite particles made of inorganic particles coated by polymers
have been developed [1,2], including mini-emulsion [3,4],
suspension [5], dispersion [6], and emulsion polymerization
[7,8]. The soapless emulsion polymerization with organic
monomers in the aqueous suspensions of inorganic particles
has been considered as a promising and preponderant approach
to prepare nano composite particles, because the organic
Corresponding author. Tel.: +86 10 64446466; fax: +86 10 64434784.
E-mail address: chenjf@mail.buct.edu.cn (J. Chen).
0167-577X/$ - see front matter 2006 Published by Elsevier B.V.
doi:10.1016/j.matlet.2005.03.077

components on the surface of inorganic particles can be

synthesized in accordance with the applying systems. The
inorganic particles can be well dispersed into polymer matrix.
Moreover, due to lack of surfactants, the application fields of
composite particles are enlarged compared with the products
from emulsion polymerization. The prepared composite
particles have great potential applications in Painting, Plastics,
and Rubber, etc.
The inorganic particles were mainly nano silicon dioxide,
nano titanium dioxide, nano aluminum oxide, etc., all of which
have high surface activities and more active radicals [911].
Nano calcium carbonate that has lower surface activity and
fewer active radical was used to prepare inorganicorganic
nano composite particles by the technology only after its surface
had been commendably modified by surfactants [1216].
In the paper, it was innovatively validated that nano calcium
carbonate without surface modification can also be well coated
by polymers to form composite particles. The effects of
synthesis parameters on monomer conversion were studied.
The formation mechanisms of composite particles were
proposed. The applications in epoxy varnish were investigated
preliminarily.

W. Wu et al. / Materials Letters 60 (2006) 24102415

2. Experimental
2.1. Main raw material and reagents
Nano calcium carbonate in the form of filter cake was provided by Nanotech Science and Technology Ltd and produced
by high gravity technology with a mean size of 40 nm, cubic
shape and crystalline structure of calcite. Chemicals are
generally reagent grade from commercial sources without
further purification. Analytical-grade methyl methacrylate
made by Beijing Yili Fine Chemicals Ltd was used as monomer.
Analytical-grade ammonia persulphate (APS) made by Beijing
Chemical Plant was used as initiating agent. Analytically grade
toluene made by Beijing Yili Fine Chemicals Ltd was used as
extraction solvent of polymer. Sodium salt of poly (acrylic) acid
purchased from market was used as dispersing agent.

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elements on the surface of nano calcium carbonate and

composite particles after extraction.
The characteristics of paint film, which were in terms of
adhesive force, impaction, toughness, hardness, were tested
according to the China National Standards and their units were
also in accordance with the standards.
3. Results and discussions
3.1. The effects of synthesis parameters on the preparation of nano
composite particles
The basic technology of preparation of composite particles is
soapless emulsion polymerization of methyl methacrylate in nano
calcium carbonate aqueous suspension. The conversion is defined as
the percentage of the mass of created polymer comparing with the total
mass of monomer; its calculating formula is that
M1 M2 M3
 100%
M

2.2. The process

2.2.1. The preparation of aqueous suspension of nano calcium

carbonate
The mixtures comprising of filter cakes of nano calcium
carbonate and appropriate amounts of deionized water as well as
a small quantity of dispersing agent were stirred with
experimental high-speed disperser at 3000 rpm for 1 h to get
8% aqueous suspension. The pH values of suspension were
adjusted to 78 with diluted hydrochloric acid.

where C denotes the monomer conversion; M1 denotes the dried mass

of composite particles; M2 denotes the mass of added calcium
carbonate; M3 denotes the mass of added initiating agent; M denotes
the mass of added monomer.
The preparations of composite particles are greatly relevant to the
monomer conversion. The monomer conversion in the system is
affected by temperature, stirring rate, the dosage of initiating agent,
calcium carbonate concentration.

2.2.2. The preparations of nano composite particles

The as-prepared aqueous suspension of nano calcium
carbonate was fed into a three-necked flask equipped with a
condenser and then stirred at 600 rpm under the circumstance of
N2 gas. When the temperature of the aqueous suspension
reached 7080 C that was maintained by cycling water from
aqueous thermostat baths, the initiating agent aqueous solution
was added. The 30 ml monomer was added in dropwise within
30 min. After being farther stirred for another 3 h, the
suspension was filtrated and dried at 7080 C in vacuum.
Part of the dried product was extracted by toluene for 12 h with
Solvet extracting apparatus and used for the characterizations.

3.1.1. The effects of temperatures

Fig. 1 is the relationships between the systematic temperatures and
monomer conversions. The radical polymeric reaction needs energy
that is provided by heating in the system. As the temperature rises, the
decomposing rate of initiating agent is speeded and the collision
probability among monomers, polymers and particles is increased.
Accordingly, the conversion is quickly boosted. When the temperature
is over 80 C, it has no obvious effects on the decomposition of
initiating agent, so the conversion is basically invariable.
3.1.2. The effects of stirring rate
The mass transfer is one of the important influence factors in the
non-homogeneous phase reaction system, which is reflected in the
changes of stirring rate.

2.3. Characterizations
H-800 Transmission Electron Microscopy (TEM) was used
to characterize the particle size and morphologies. PCT-1A
differential thermal analyzer made by Beijing Optical Instrument Factory was employed to conduct Thermo-Gravimetric
(TG) analysis of nano calcium carbonate and composite
particles to determine the content of organic substances in
composite particles and bonding states between nano calcium
carbonate and polymer. Nicolet 60SXB Fourier Transform
Infrared (FT-IR) Spectrometer was used to characterize the
surface components of the nano calcium carbonate, the
composite particles and the composite particles after extraction.
PHI5300 X-ray Photoelectron Spectrometer (XPS) made by
American PERKIN-ELMER Physics Electronics Company was
used to characterize the changes of chemical environment of

Fig. 1. Effects of temperature for monomer conversion.

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W. Wu et al. / Materials Letters 60 (2006) 24102415

Fig. 2. Relationships between conversion and stirring rate.

Fig. 2 is the relationships between stirring rate and conversion. The

conversion decreases as the stirring rate rises and becomes stable as the
stirring rates go higher than 450 rpm. It was found that incompact floc
and amounts of froths were created in the products at lower stirring rate.
However, homogeneous suspension with less froth is created at higher
stirring rate. The polymerization happens either on the surface of nano
calcium carbonate or in the micelles of polymethyl methacrylate in
water phase. When the stirring rate is lower, the mass transfer rate
reduces. Consequently, the Tronumsdorff gel effect is obvious [12,13]
and causes high conversion and drastic polymerization reaction in
water mainly other than on the surface of nano calcium carbonate. At
the higher stirring rate, the Tronumsdorff gel effect is indistinctive,
homogeneous suspension is created. Moreover, the polymerization
reaction mainly happens on the surface of nano calcium carbonate
although the conversion is lower. The stirring rate should be kept in
higher level in order to weaken the effects of mass transfer. The results
are different from that of Seul et al. [15], in which the conversions rise
at the low mixing rates and become stable at the high mixing rates, the
differences are relevant to the surface properties of calcium carbonate
that result in different reaction mechanisms. In Ref. [15], the surface of
calcium carbonate used is hydrophobic, on which the monomers are
easy to polymerize, even at a low mixing rate.

Fig. 3. Relationships between conversion and dosage of APS.

Fig. 4. Time-conversion curves for different CaCO3 concentration.

3.1.3. The effects of the dosages of the initiating agent

The decomposing equation of ammonia persulphate (APS) is that
[14]:

S2 O2
8 2SO4

This reaction coincides with the regulation of first order reaction.

The equation of reaction rate is as follow:



dS2 O2
8 
k S2 O2
8
dt

where t is reaction time with the unit of hour; [S2O2

8 ] is the
concentration of ammonia persulphate with the unit of mol/L; k is
reaction rate constant.
During the preparation of composite particles, ammonia persulphate
decomposes by heating to create free radicals that initiate

Fig. 5. TEM of nano CaCO3 particles.

W. Wu et al. / Materials Letters 60 (2006) 24102415

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Fig. 8. Relationships between extraction time and mass of composite particles.

Fig. 6. TEM of nano CaCO3/PMMA composite particles.

polymerization of methyl methacrylate. The high concentration of

persulphate radicals can speed the polymerization reaction to raise
conversion. It can be known from Fig. 3 that when the dosages of
ammonia persulphate are lower than 0.4% of monomer mass, the
conversion rise as the dosage of APS increase; when the dosages are
higher than 0.4% of monomer mass, the conversion is hardly
changed. The existence of an optimal value is owed to the monomer
dosage and concentration of calcium carbonate being fixed in the
system and the reaction time being constant for different dosage of
APS.

apparently in the presence of nano calcium carbonate. It was reported

that the stable emulsions could be formed when there were particles on
the interfaces between water and oil [17]. Based on the experimental
phenomenon and results, it is deduced that nano calcium carbonate can
be located on the interfaces of monometer-water to stabilize the formed
micelles that provide more polymerization sites than that without nano
calcium carbonate.
3.2. Characterizations of composite particles
Figs. 5 and 6 are TEM micrographs of nano calcium carbonate
before and after modification. The particle size becoming large after
modification indicates that there are polymers coated on the surface of
nano calcium carbonate.
Fig. 7 is thermogravimetric analysis curves of composite particles
and nano calcium carbonate. The lost weight above 270 C for
composite particles is about 43% of the total weight, which is due to the
decomposition of polymer in the composite particles.

3.1.4. The effects of calcium carbonate concentrations

Fig. 4 is the relationships between monomer conversion and
reaction time in the suspensions of different concentrations of nano
calcium carbonate. The rate of polymerization reaction increases

3.3. The bonding mechanisms between nano calcium carbonate and

PMMA

Fig. 7. Thermogravimetric analysis curves for pure CaCO3 and CaCO3/PMMA

composite particles.

Fig. 9. FT-IR curves of samples. 1: Pure CaCO3; 2: composite particles after

calcination; 3: composite particles after extraction; 4: composite particles.

In order to study the bonding status between nano calcium

carbonate and polymer in composite particles, the relationships

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W. Wu et al. / Materials Letters 60 (2006) 24102415

Table 1
The results of XPS analysis for pure nano-CaCO3 and composite particles after
extraction
Sample

Element

Bonding
energy (eV)

Pure CaCO3

C1S
O1S
Ca2P 3/2
Ca2P 1/2
C1S
O1S
Ca2P 3/2
Ca2P 1/2

289.6
531.3
347.0
350.4
289.0
531.5
346.9
350.4

Composite particles
after extraction

Chemical
shift (eV)

Atom relative
content
19.94
61.68
18.39

0.6
0.2
0.1
0.1

33.96
56.94
9.10

excellent anti-chemicals and excellent electrical isolation. However,

the solidifying velocity of epoxy varnish has strong effects on its
applications. Generally, the quicker its solidifying velocity varnish
especially at lower temperature, the wider its application fields and
the better its application properties. In the paper, the composite
particles of CaCO3/PMMA were used to improve performances of
epoxy varnish. Table 2 shows the performances of epoxy varnish
after adding composite particles of 3.7% of epoxy varnish mass. The
solidifying velocity at 20 C is quickened after composite particles
were added.

4. Discussions of formation mechanism of nano composite

particles

between the extraction time and the mass of composite particles were
investigated and the results are shown in Fig. 8. The mass of composite
particles is stable after extraction for 24 h. The lost mass is 38.7% of the
total mass, which is less than the lost weight obtained by thermogravimetric analysis, i.e., 43%. 7.54% of the total mass bonds hardly
with nano calcium carbonate.
Fig. 9 shows typical FITR spectrums of nano calcium carbonate,
composite particles, composite particles after calcination and composite particles after extraction. Characteristic peaks for PMMA in the
spectrums of the composite particles and the composite particles after
extraction suggest that the polymer chains are covalently bonded to the
surface of nano calcium carbonate. For example, the peaks at bands of
30002900 cm 1, 1388 cm 1 and 1452 cm 1 are assigned to the
stretching vibrations and bending vibrations of CH3 of PMMA,
respectively. The peak at 1735 cm 1 is assigned to the characteristic
vibration adsorption of carbonyl.
Table 1 shows the XPS characterization results of nano calcium
carbonate and composite particles after extraction. The ratio of
relative atom numbers of Ca, O, C on the surface of nano calcium
carbonate is 1:3.35:1.08, which is close to that of CaCO3. However,
the ratio of relative atom numbers of Ca, O, C on the surface of
composite particles after extraction is 1:6.26:3.73, showing that
there exists PMMA on the surface of composite particles after
extraction and great changes have taken place on the surface of
calcium carbonate after modification. The relatively great change of
chemical shift of C1s suggests that the PMMA are grafted on the
surface of calcium carbonate after reacting with C atoms of
carbonate radicals.
3.4. The preliminary investigations of applications of nano composite
particles in epoxy varnish
The epoxy varnish with high quality has found extensive
applications because of its excellent adhesion to polar substances,

Based on the previous investigation, a formation mechanism

of composite particles is proposed:

S2 O2
8 SO4

5
At the beginning, there are few radicals in the system. The
probabilities of termination reactions among increasing radicals
chains is low. The collision probabilities of increasing radicals
chains with nano calcium carbonate particles are high. Although
CaCO3 is a electrovalent bonded compound, the CO32 is
covalence radicals which contain CfO double bonds. The
increasing polymer chains react with the CfO double bonds to
create more stable radicals and then graft on the surface of nano
calcium carbonate. The remained monomers and radicals'
chains are adsorbed easily on the surface of nano calcium
carbonate, where polymer has been grafted on and further

Table 2
Comparisons of the properties of epoxy resin varnishes (20 C)

Pure epoxy varnish

Adding 3.7% Nano
calcium carbonate
Adding 3.7% composite
particles
Test methods (China
national standards)

Adhesive force
(grade)

Impact resistance
(J)

Toughness
(mm)

Hardness
(after 1.5 days)

Hardness
(after 7 days)

1
12

4.9
4.9

1
1

0.34
0.33

0.53
0.45

4.9

0.42

0.55

GB/T1720-1993

GB/T1732-1993

GB/T1731-1993

GB/T1720-1993

W. Wu et al. / Materials Letters 60 (2006) 24102415

2415

Fig. 10. The formation process of composite particles.

polymerize and wrap on the surface of nano calcium carbonate.

Finally, composite particles are formed. The whole process is
shown in Fig. 10.

2001BA310A01), the Talent Training Program of the Beijing

City (no. 9558103500), and the Fok Ying Tung Foundation (no.
81063).

5. Conclusions

References

In this paper, the effects of synthesis parameters on monomer

conversions were studied. The formation mechanism of
composite particles was proposed. The conclusions obtained
in the paper are as follows:

[1] C.F. Lee, W.Y. Chiu, Polym. Int. 30 (1993) 475.

[2] W. Wu, J.F. Chen, L. Shao, S.C. Lu, J. Univ. Sci. Technol. Beijing 9 (2002)
426.
[3] F. Tiarks, K. Landfester, M. Antonietti, Langmuir 17 (2001) 5775.
[4] B. Erdem, E.D. Sudol, V.L. Dimonie, J. Polym. Sci., A, Polym. Chem. 38
(2000) 4419.
[5] E. Duguet, M. Abboud, F. Morvan, Macromol. Symp. 151 (2000) 365.
[6] J. Stejskal, P. Kratochvil, S.P. Armes, Macromolecules 29 (1996) 6814.
[7] Y. Haga, T. Watanabe, R. Yosomiya, Angew. Makromol. Chem. 189
(1991) 23.
[8] W.-D. Hergeth, U.-J. Steinau, H.-J. Bittrich, Polymer 30 (1989) 254.
[9] W.-D. Hergeth, P. Starre, K. Schmutzler, Polymer 29 (1988) 1323.
[10] K. Furasawa, Y. Kimura, T. Tagawa, J. Colloid Interface Sci. 109 (1986)
69.
[11] C.H.M. Caris, P.M. Louisa, A.M. Herk, Br. Polym. J. 21 (1989) 133.
[12] J.F. Chen, W. Wu, T.B. He, Chem. React. Eng. Technol. 19 (2003) 135
(in chinese).
[13] M. Cioffi, A.C. Hoffmann, L.P.B.M. Janssen, Chem. Eng. Sci. 56 (2001)
911915.
[14] T.Y. Cao, Q.P. Liu, J.S. Hu, Mechanisms, Properties and Applications of
Polymer Emulsion Preparation, Chemical Industry Press, Beijing, 1997
(Chinese version).
[15] S.D. Seul, S.R. Lee, Y.H. Kim, J. Polym. Sci., A, Polym. Chem. 42 (2004)
40634073.
[16] J.M. Shi, Y.Z. Bao, Z.M. Huang, Z.X. Weng, J. Zhejiang Univ. SCI 3
(2004) 709713.
[17] L. Chen, J. Lin, M. Lin, H.S. Huang, Acta Polym. Sinica 3 (1993) 338
(in Chinese).

(1) Appropriate amounts of nano calcium carbonate can

promote soapless emulsion polymerization of methyl
methacrylate. Increasing stirring rate can enhance the
probabilities for polymer to coat on the surface of nano
calcium carbonate. When the temperature is lower than 80
C and the dosages of initiating agent is lower than 0.4%
of monomer mass, increasing temperature and dosage of
initiating agent can raise monomer conversion.
(2) There are chemical bonds to create between carbon atoms
of nano calcium carbonate and polymethyl methacrylate.
Polymers are chemically grafted and physically wrapped
on the surface of nano calcium carbonate to form nano
calcium carbonate/PMMA composite particles.
Acknowledgments
Prof. J.F. Chen would like to thank the support by the
National Natural Science Foundation of China (no. 20236020,
20325621), the National R&D Program of China (no.