Colloids and Surfaces A: Physicochem. Eng.

Aspects 366 (2010) 95–103

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Facile surface modification of nanoprecipitated calcium carbonate by

adsorption of sodium stearate in aqueous solution
Hoang Vinh Tran a , Lam Dai Tran b,∗ , Hoang Dinh Vu a , Hoang Thai c
a
Faculty of Chemical Technology, Hanoi University of Technology, 1, Dai Co Viet Road, Hanoi, Viet Nam
b
Institute of Materials Science, Vietnamese Academy of Science and Technology, 18, Hoang Quoc Viet Road, Hanoi, Viet Nam
c
Institute of Tropical Technology, Vietnamese Academy of Science and Technology, 18, Hoang Quoc Viet Road, Hanoi, Viet Nam

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

Article history: A simple and solvent free two-step process for nanosized and surface-modified precipitated calcium
Received 22 April 2010 carbonate (ns-PCC) synthesis has been proposed. Synthesized ns-PCC was thoroughly characterized by
Received in revised form 18 May 2010 infra-red (IR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and Langmuir adsorp-
Accepted 18 May 2010
tion study. Dynamic laser scattering (DLS) results on particle size showed a good correlation with those
Available online 25 May 2010
obtained by the proposed empirical model. Two aspects of nucleation and surface modification and the
relationship of particle size on impact experimental parameters were also discussed.
Keywords:
© 2010 Elsevier B.V. All rights reserved.
Nanosized precipitated calcium carbonate
(n-PCC)
Nanosized and surface-modified
precipitated calcium carbonate (ns-PCC)
Aqueous adsorption
Carbonation

1. Introduction carbonation of slaked lime is limited possibility of controlling the

The industrial importance of precipitated calcium carbonate
(PCC) as a filler in composite materials such as plastics, textiles,
rubbers, paints, pigments, and paper is well known. PCC nanopar-
ticles (<100 nm) have shown many unique properties compared to
regular PCC particles (1–3 ␮m) [1–16]. It has been demonstrated
that fatty acid-treated PCC of particle size less than 100 nm is par-
ticularly useful for filling sealants. Wang et al. [17] synthesized
nanosized PCC (15–40 nm) using high gravity multiphase reac-
tive precipitation method with a rotating packed-bed reactor to
generate acceleration higher than that of earth gravity. However,
this technology required expensive synthetic equipment and large
amount of energy. Tsuzuki et al. [18] synthesized calcium carbon-
ate nanoparticles using a mechanochemical reaction followed by
heat treatment, which ensured completion of the reaction. Mechan-
ical milling caused irregularities in particle shape and distribution,
limited the morphology of the particle to calcite, and again, had
a high energy consumption. Up to date, the most widely used
method of PCC production at industrial scale is the so-called car-
bonation route, comprising a batch process of CO2 bubbling through
an aqueous Ca(OH)2 suspension. The main disadvantage of batch
∗ Corresponding author. Tel.: +84 4 37564129; fax: +84 4 38360705.
E-mail addresses: tdlam@vast.ac.vn, lamtd-fct@mail.hut.edu.vn (L.D. Tran).
supersaturation of the system which in its turn greatly determines
the particle size. Bench scale investigations have shown that an
additional control of the morphology and size of precipitated parti-
cles is possible by running carbonation as a semicontinuous process
[19,20]. It was also shown that calcite crystals, having different
morphologies could be produced by varying a range of process
parameters like temperature, concentration of total dissolved cal-
cium, CO2 flow rate, mass concentration of Ca(OH)2 and addition
rate of Ca(OH)2 .
The incompatibility of PCC hydrophilic surface with the
hydrophobic polymers is a particular problem, related to the dis-
persion of the filler particles in the polymer matrix, especially when
PCC of high specific surface area with tendency to agglomerate were
used. Therefore, the surface of calcite is often modified by a vari-
ety of surfactants, among which fatty acids, or one of their salts,
are most commonly used [21]. As a result, a hydrophobic alkyl
chains is chemisorbed to the mineral surface, thus affecting the
surface forces between the filler and the polymer matrix. Keum
et al. prepared hydrophobic composite particles of CaCO3 directly
by crystallization via solution route with a sodium trisilanolate
[22], rather then modifying the resultant PCC products. Hydropho-
bic PCC was also obtained by the batch carbonation process [23].
Many studies have shown that the presence of additives during the
precipitation could greatly affect crystal nucleation and/or crystal
growth of CaCO3 .

0927-7757/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2010.05.029
96 H.V. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 366 (2010) 95–103

tion and surfactants, added during the carbonation process greatly

Nomenclature determined the particle size distribution of PCC. In this study, a col-
umn reactor of 110 mm inner diameter and 200 mm height is made
Notation
of stainless steel, equipped with fluid heat exchanger to control the
d50 mean particles size of PCC (d50 ) (␮m)
reaction temperature. The mixed gas (25–35%, v/v, CO2 + 75–65%,
[NaTPP] concentration of additive per 100 g PCC (wt.%)
v/v, N2 ) was introduced up-stream from the bottom of the reactor,
 density of lime slurry (kg m−3 )
with controlled flow rate (3–4.5 l/min) and constant stirring speed
n stirring rate (s−1 )
(800–1200 rpm). Final carbonation point was stopped at pH 7–7.5.
S supersaturation of solution
Supersaturation value (S) was defined from the following equa-
T reaction temperature (◦ C)
tion:
{Ca2+ }{CO2−
3 }
S= (1)
In this paper, nanosized surface-modified (ns-PCC) particles {Ca2+ }eq {CO2−
3 }eq
were synthesized by adjusted carbonation method which con- where {Ca2+ }eq and {CO3 2− }eq are the activities of the cal-
sists of inhibited crystallization and surface modification by cium and carbonate ions respectively, in a saturated solution.
fatty salt adsorption (sodium stearate). As mentioned above, {Ca2+ }eq × {CO3 2− }eq = Kcalcit (=10−8.48 at 25 ◦ C, calcite solubil-
the choice of the carbonation method as well as those inhibit- ity product). Activity coefficients were calculated according to
ing and modifying agents like sodium tripolyphosphate (NaTPP) Debye–Huckel equation [24]. Total calcium concentration TCa , free
and sodium stearate (NaS) respectively were rationalized on [Ca2+ ] and other species from the mass balance equation were
economic–industrial aspect of the process. Furthermore, while cur- determined with ethylenediaminetetraacetic acid (EDTA) titration
rently used methods normally obtain dried n-PCC first, and then method [24,25].
disperse them again into mixture of surface modifiers with organic
solvents, our method proposed two-step process consisting of 2.2. Surface modification experiment of n-PCC by NaS adsorption
preparing n-PCC and surface modifying n-PCC in situ in Ca(OH)2
slurry. In addition, this method is eco-friendly because toxic organic Nanosized precipitated calcium carbonate (n-PCC) was synthe-
solvents like hexane, benzene or chloroform are avoided. sized as described in details in an earlier study [26]. Briefly, a certain
volume of sodium tripolyphosphate (NaTPP) solution with con-
2. Experimental procedure centration of 10 g/l was added into calcium hydroxide Ca(OH)2
slurry (20 ml NaTPP for 1 l Ca(OH)2 ). Density of Ca(OH)2 was var-
2.1. Experimental factors of carbonation process ied in the range of 1–4.76 g/ml. The carbonation batch experiments
between Ca(OH)2 slurry and mixed gas (CO2 + N2 ) in the reactor
Main experimental parameters (Table 1) of carbonation process were operated at different temperatures from room temperature
such as stirring rate, concentration of Ca(OH)2 slurry, temperature, up to 70 ◦ C. At the end of carbonation stage (pH ∼ 7.0–7.5), a certain
concentration of CO2 gas in the mixture gases, pH, supersatura- volume of NaS (d = 1.164 g/l) was added into the reactor containing
200 ml of 13.2 g PCC. NaS content varied in the range of 0–5% (w/w).
Table 1 The whole system was kept at the stirring speed of 200 rpm for
Summary of experimental factors and their variable range. 10–15 min to ensure all PCC particles were surface-modified. NaS
volume and its mass content in different samples were recorded
Experimental Units Value range
factors in Table 2. ns-PCC powders were collected by filtering and dried at
100 ◦ C for 4 h before further characterizations.
Particle size of ␮m 0.5–125
Ca(OH)2
Slurry wt.% 1–4.76 2.3. Characterization
concentration of
Ca(OH)2 XRD patterns were obtained at room temperature on D8
Volume of lime l 0.8–1.0
Advance, Bruker ASX, using Cu K␣ radiation ( = 1.5406 Å) in the
milk
Blowing rate of l/min 3–4.5 range of 2 = 10–60◦ , a scanning rate of 0.02 s−1 . FTIR spectra were
mixture gas recorded with Nicolet 6700 FT-IR Spectrometer, using KBr pellets,
Volume v/v (%) 25–35 in the region of 400–4000 cm−1 , with resolution of 4 cm−1 . SEM
concentration of and TEM images were analyzed by Field Emission Hitachi S-4500
CO2 gas
Rotation speed of Rounds per 800–1200
Scanning Electron Microscope (FE-SEM) and transmission electron
stirrer minute microscope (TEM, JEOL, voltage: 100 kV, magnification 200,000×)
(RPM) respectively. The agglomerate size was estimated by dynamic laser
◦
Reaction C 18–70 scattering (DLS) Zetasizer 2000 (Malvern, UK). Thermal analyses
temperature
(thermogravimetry (TG), differential scanning calorimetry (DSC))

Table 2
Surface modification experiment of n-PCC by adsorption of sodium stearate (NaS) as a surface modifier.

Samples N0 N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11

mnPCC (g) 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2 13.2
VNaS (ml) 0 56.7 113.4 170.1 226.8 283.5 340.2 396.9 451.2 510.3 538.7 567
Vtotal (ml)a 200 256.7 313.4 370.1 426.8 483.5 540.2 596.9 651.2 710.3 738.7 767
% NaS (mg/g) 0 5 10 15 20 25 30 35 40 45 47.5 50
% NaS (wt.%)b 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 4.75 5

Surface modification experiment of n-PCC by adsorption of NaS as a surface modifier.

a
Vtotal = VNaS + 200 ml.
b
%NaS (wt.%) = %NaS (mg/g)/10.
 H.V. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 366 (2010) 95–103 97

Fig. 1. Different ion concentrations in carbonate solution versus pH. Fig. 3. Evolution of PCC formation rate during carbonation with different percent-
ages of inhibiting agent (NaTPP).

of particles were carried out on Shimadzu TGA 50H with heating

an approach and the multiple correlation analysis of the obtained
rate 10 ◦ C/min in N2 atmosphere.
results can significantly help to optimize the large scale PCC pro-
duction process.
3. Results and discussion
Along the batch carbonation process, monitoring of the electri-
cal conductivity (k) and/or pH is normally used as a tool to detect
3.1. Empirical model and main experimental parameters
the end point of the reaction [27]. In this study, this end point
was supposed from pH and supersaturation observations and mea-
Basically, the industrial process of PCC production involves
surements. Effectively, from equilibrium and conjugated acid–base
the following steps: (a) calcinations of limestones (natural CaCO3
constants percentage of each type of ions in carbonate solution
rocks) to produce quicklime (CaO) and CO2 ; (b) slaking process,
in which the quicklime is transformed to slaked lime slurry by
controlled addition of H2 O; and finally (c) the carbonation reac-
tion, in which the by-product CO2 mixed with the surrounding
air is bubbled through the Ca(OH)2 suspension. Production of PCC
in the Ca(OH)2 (s)–CO2 (g)–H2 O system, a multiphase precipitation
system, in which solid, liquid and gaseous reactants and products
are involved, is highly complex and difficult to model, owing to
a number of physical–chemical processes taking place simultane-
ously [27]. In this case, the role of phase interfaces (solid–liquid,
gas–liquid, gas–solid) is of particular importance, because mass
transfer, as well as heterogeneous nucleation or epitaxial growth,
can occur. Therefore, we applied an empirical approach using
experimental design techniques to determine the effects of process
parameters (like conductivity, temperature, CO2 flow rate, stirring
rate and mass concentration of Ca(OH)2 suspension) on either the
specific surface area of PCC or the extent of CO2 conversion. Such

Fig. 2. Evolution of supersaturation during carbonation with different percentages Fig. 4. Experimental DLS analyzed particle size distribution of ns-PCC (a) and model-
of inhibiting agent (NaTPP). calculated particle size distribution at different temperatures (b).
98 H.V. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 366 (2010) 95–103

Fig. 6. IR spectra of NaS, n-PCC and ns-PCC.

Fig. 5. Langmuir isotherm of NaS adsorption on n-PCC.

Ca(OH)2  Ca2+ + 2OH− (3)

versus pH could be calculated and presented in Fig. 1: Ca2+ + CO3 2−  CaCO3 (4)

CO2 + 2OH−  CO3 2− + H2 O (2) CO3 2− + CO2 + H2 O  2HCO3 − (5)

Table 3
Langmuir isotherm parameters for the adsorption of NaS on n-PCC.

Samples mPCC (g) VNaS used (ml) MNaS calc. (mg) %NaS (wt.%) (calc.) %NaS (wt.%) (exp.)a MNaS exp. (mg) Vtotal (ml) Ce (mg/l) qe (mg/g) Ce /qe (g l−1 )

N1 13.2 56.7 66.0 0.50 0.49 64.68 256.7 5.14 4.90 1.048
N2 13.2 113.4 132.0 1.00 0.97 128.04 313.4 12.63 9.70 1.302
N3 13.2 170.1 198.0 1.50 1.45 191.94 370.1 16.37 15.00 1.091
N4 13.2 226.8 264.0 2.00 1.92 253.03 426.8 25.68 20.00 1.284
N5 13.2 283.5 330.0 2.50 2.38 314.16 483.5 32.75 23.80 1.376
N6 13.2 340.2 396.0 3.00 3.00 369.75 540.2 48.58 30.01 1.619
N7 13.2 396.9 462.0 3.50 3.50 424.65 596.9 62.56 35.01 1.787
N8 13.2 451.2 525.2 3.98 3.60 475.20 651.2 76.78 36.00 2.133
N9 13.2 510.3 594.0 4.50 3.98 525.36 710.3 96.62 39.80 2.427
N10 13.2 538.7 627.1 4.75 4.15 547.80 738.7 107.28 41.50 2.585
N11 13.2 567.0 660.0 5.00 4.20 554.40 767.0 137.66 42.00 3.278
a
Experimental TG data.

Fig. 7. TEM images of n-PCC.

 H.V. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 366 (2010) 95–103 99

Fig. 8. (a) TEM images of ns-PCC. (b) Core–shell structure of ns-PCC.

From the dependence of ion concentration on pH predominant (ii) 7.5 < pH < 8.5: [HCO3 − ] reaches a maximum value (at pH = 8.35:
ions at a certain pH could be learnt, namely: (i) pH > 9: Eqs. [HCO3 − ] ≈98%, CO2 is competitively consumed in both equations
(2)–(4) are predominant with high conversion efficiency of CO2 (at (4) and dissolved PCC equation (5), therefore conversion efficiency
pH = 10.32: [CO3 2− ] = [HCO3 − ] = 50%, at pH = 12.6 [CO3 2− ] ≈99%); of CO2 decreases in that pH range); (iii) 7 < pH < 7.5: CO2 is mostly
100 H.V. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 366 (2010) 95–103
Fig. 9. XRD patterns of n-PCC (a) and ns-PCC (b).
used for Eq. (5), conversion efficiency of CO2 is very low, the car-
bonation process should be stopped.
On the other hand, from Eq. (1) supersaturation variation could
be monitored and plotted: two peaks, corresponding to the nucle-
ation and crystal growth processes respectively were observed
(Fig. 2). The presence of inhibiting agent of NaTPP has a significant
effect on the particle formation: it increased the number of nucle-
ation seeds while decreased active growth ones. Otherwise, the
particle should be less agglomerated using this additive. This result
was confirmed by calcite formation rate curve (Fig. 3), calculated
from equation:
−d[Ca2+ ]
r=
dt
The relationship between particle size and key experimental
factors such as temperature, concentration, supersaturation, stir-
ring rate, density of lime slurry in heterogeneous process of
Ca(OH)2 (solid–liquid)–CO2 /N2 (gases) could be elaborated empir-
ically and expressed as follows [28]:
[NaTPP]3.8 S 9.2712 T 0.6763
d50 = 6.08 × 1019 .
n4.079 8.5
To check its validity, mean agglomerated size of PCC was mea-
sured experimentally by DLS technique. The experimental results
correlated well with those obtained from simulated model (Fig. 4).
It means that the model is adequate and may be used for study-
ing the main impact experimental parameters on PCC particle size.
Furthermore, by comparing the magnitude of the coefficients, it
is evident that supersaturation S has the strongest effect. The posi-
tive coefficients of [NaTPP], S or T contribute to the increase of mean
particle size d50 , whereas the negative coefficient of n (stirring rate)
and  (density of lime slurry) has a reverse trend on d50 .
3.2. Surface modification
Adsorption of ionic surfactants on charged particulate solids has
been the subject of considerable research owing to its fundamen-
tal and practical importance. Langmuir adsorption isotherm was
usually employed for analyzing adsorbate–adsorbent interaction
according to the following equation:
Ce 1 Ce
= +
qe qm KL qm
where Ce is the equilibrium concentration of adsorbed ions (mg/l),
qe is the amount of adsorbed ions per gram adsorbent (mg/g), qm is
the maximum adsorption (mg/g), and KL is the Langmuir adsorption
equilibrium constant (l/mg). Langmuir isotherm parameters for the
adsorption of NaS on n-PCC were calculated and given in Table 3 and
Fig. 10. TG/DSC curves of n-PCC (lines (a) and (c)) and ns-PCC (lines (b) and (d)).
Fig. 5. From this figure qmax is determined to be ca. 61.61 mg/g and
specific surface area S is calculated according to: S = (ıqmax /M)NA
(m2 /g) = 595.92 × qmax = 36.12 m2 /g. Using d = (6/S) (nm) where
 is the density of PCC (2.71 g/cm3 ); S is the specific surface area
of PCC (m2 /g) and d can be calculated to be ca. 60.3 nm. Due to
the aggregated nature of nanoparticles precise determination of
primary particle size will inevitably be accompanied with a cer-
tain error. This explains why different methods should be used to
(6) evaluate the particle size. In that case, it was inferred from Lang-
muir adsorption isotherm that the average particle size of ns-PCC
is in the range of 75–80 nm, which agrees well with TEM-observed
(70–80 nm) and XRD Sherrer-calculated particle size determination
for ns-PCC (see Sections 3.3 and 3.3.3). This consistency also vali-
dated the monolayer stearate coverage, a very important criterion
to be fulfilled for Langmuir adsorption calculation (see Sections 3.3
and 3.3.5).
(7)
3.3. ns-PCC characterization
3.3.1. IR spectra
To confirm the existence of the surface modifying layer, IR
spectra of n-PCC, NaS, ns-PCC (with different ratio of NaS) were
recorded and presented in Fig. 6. IR spectrum of n-PCC showed
three strong peaks at 1454.9, 873.3 and 706 cm−1 corresponding
to 2 , 3 and 4 vibrations of CO3 2− , respectively. Broad and weak
vibration at 3500 cm−1 is assigned to OH stretching [26,29]. IR spec-
trum of NaS showed strong peaks at 3500, 2920.2 and 2843.5 cm−1
corresponding to OH , C–H and C–C vibrations respectively. Union-
ized carboxylic acid (–COOH), usually showing a typical peak at
1710 cm−1 , downshifted to 1557 cm−1 when ionization of –COOH
to –COO− occurs, accompanied by the presence of antisymmetric
(as) and symmetric (s) stretching. IR spectrum of ns-PCC summa-
rized all vibrations of both n-PCC and SS, with a slight difference in
peak position, and intensity. Also, it was observed that the inten-
sity of C–H and C–C increases with NaS content, indicating the
(8) relationship between these peak intensities with degree of surface
modification of PCC. The latter, in its turn, may lead to peak upshift-
ing and width enlarging of 2 vibration. In summary, although there
is no direct evidence on interaction between COO− groups and Ca2+
cations by IR data alone, on the basis of above observations it is
safe to conclude that PCC was successfully surface-modified to form
core–shell type structure.
 H.V. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 366 (2010) 95–103 101

Fig. 11. (a) Hydrophobicity of ns-PCC with different NaS content. (b) Dependence of contact angle of ns-PCC on NaS content.
102 H.V. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 366 (2010) 95–103
3.3.2. TEM analysis
The TEM micrograph of n-PCC shows that the particles have a
cubic form, rough surface with many aggregates of primary par-
ticle (Fig. 7). In contrast, ns-PCC particles seem to be much less
agglomerated (Fig. 8a). Interestingly, a thin layer of NaS (4.5–5 nm),
coated on the surface of core n-PCC (40–60 nm) was also observed
(Fig. 8b).
3.3.3. XRD analysis
The crystal phase of obtained ns-PCC can be indexed as trigonal
structure (space group R-3c) (ICSD Card no. 81-2027). Main charac-
teristic planes of (0 1 2), (1 0 4), (1 1 0), (1 1 3), (2 0 2), (0 1 8), (1 1 6)
and (1 2 2), corresponding to 2 value of 23.2◦ , 29.5◦ , 36◦ , 39.3◦ , 43◦ ,
47.5◦ , 48.4◦ and 57.3◦ respectively were unambiguously assigned to
calcite structure. Any characteristic peaks for vaterite and aragonite
polymorphs (usually appeared at 2 = 25.0◦ and 2 = 45.9◦ ) were
detected, indicating calcite structure was mainly produced [26].
The pattern of ns-PCC does not exhibit any characteristic diffrac-
tion peak for NaS, and the intensity of the strongest diffraction
peak (at 2 = 29.5◦ ) is weaker than that of n-PCC (Fig. 9), indicat-
ing that the coating of NaS on n-PCC surface succeeded. Particle
size can be quantitatively evaluated from the XRD broadening with
Debye–Scherrer equation: d = (k/ˇ cos ), where d is the thickness
of the crystal, k is the Debye–Scherrer constant (0.89),  is the
X-ray wavelength (0.15406 nm) and ˇ is the line broadening (in
Radian) obtained from the full width at half maximum,  is the
Bragg angle. According to the Debye–Scherrer equation, particle
sizes of n-PCC and ns-PCC were estimated as 60 nm and 65 nm,
respectively.
3.3.4. Thermal analyses
TG/DSC curves showed that n-PCC powders remain stable in
the whole range of temperature from 25 to 700 ◦ C, only thermal
treatment beyond 700 ◦ C leads to their decomposition (Fig. 10).
From this figure, it was observed that a weight loss of 3.81% occurs
significantly in the temperature range of 328–380 ◦ C, owing to
the decomposition of stearate ion. TG data weight loss (3.81%),
compared with theoretical calculation derived from solution prepa-
ration (4%) indicated that adsorption efficiency of NaS on PCC was
around 95.3%.
3.3.5. Hydrophobicity of ns-PCC
Apart from the importance of specific surface area and mor-
phology of PCC, when it is produced for particular purposes, the
hydrophobicity of surfaces could be of major significance when
PCC is used as filler in polymer composites. Therefore, the extent of
hydrophobicity of PCC samples, governed at different experimen-
tal conditions, was estimated (Fig. 11a). The relation between NaS
content and wetting angle was shown in Fig. 11b. Since NaS made
ns-PCC hydrophobic, it is evident that wetting angle increases with
NaS content: it increases significantly with 0.5–3% of NaS, whereas
it changed unnoticeably with more than 3% of NaS. The suitable
volume of NaS therefore was chosen as 2.5–3%. It should be empha-
sized that under given experimental conditions when the surface
modification occurs, the first layer (monolayer) of stearate ions
is chemically adsorbed onto n-PCC surface, leaving a hydropho-
bic alkyl chain at the outermost surfaces. Then, the building up
of stearate ions should continue extending to bi, tri or multi-
layer coverage with randomly oriented of alkyl chains and left
hydrophilic Na+ head at the outermost surface of PCC, thus making
them hydrophilic. After filtration and drying, the outermost layers
were removed, only the monolayer, firmly adjacent to the n-PCC
(thanks to Ca2+ –COO− interaction) remained making ns-PCC finally
hydrophobic and floated on the water surface.
4. Conclusions
Surface-modified ns-PCC was synthesized by a carbonation pro-
cess with controlled nucleation and surface modification through
NaS adsorption in Ca(OH)2 slurry. Being a simplified and sol-
vent free procedure, this method has been proved to be a
cost-effective and eco-friendly compared to other currently used
ones. Thorough characterizations by IR, XRD, TEM and adsorption
studies have pointed out core–shell typed, surface-modified and
highly hydrophobic properties of the obtained ns-PCC, which are
important characteristics controlling good dispersity and thermal
stability of ns-PCC filled composites.
Acknowledgements
Financial support from DOST project (2009-2010, code 01C-
01/08-2009-2) is acknowledged. The authors are also grateful
for partial financial support provided by Korea-Vietnamese joint
research MOST project (2010–2011, code 59/2615/2010/HÐ-NÐT).
References
[1] S. Sahebian, S.M. Zebarjad, J.V. Khaki, S.A. Sajjadi, The effect of nano-sized cal-
cium carbonate on thermodynamic parameters of HDPE, Journal of Materials
Processing Technology 209 (2009) 1310–1317.
[2] H. Wang, L. Tang, X. Wu, W. Dai, Y. Qiu, Fabrication and anti-frosting perfor-
mance of super hydrophobic coating based on modified nano-sized calcium
carbonate and ordinary polyacrylate, Applied Surface Science 253 (2007)
8818–8824.
[3] F.L. Jin, S.J. Park, Thermo-mechanical behaviors of butadiene rubber reinforced
with nano-sized calcium carbonate, Materials Science and Engineering A 478
(2008) 406–408.
[4] C. Karagiozov, D. Momchilova, Synthesis of nano-sized particles from metal
carbonates by the method of reversed micelles, Chemical Engineering and Pro-
cessing 44 (2005) 115–119.
[5] T. Guo, L. Wang, A. Zhang, T. Cai, Effects of nano calcium carbonate modified by
a lanthanum compound on the properties of polypropylene, Journal of Applied
Polymer Science 97 (2005) 1154–1160.
[6] Y.W. Leong, M.B. Abu Bakar, Z.A.M. Ishak, A. Ariffin, Effects of filler treatments
on the mechanical, flow, thermal, and morphological properties of talc and
calcium carbonate filled polypropylene hybrid composites, Journal of Applied
Polymer Science 98 (2005) 413–426.
[7] C. Wang, Y. Sheng, X. Zhao, Y. Pan, H. Bala, Z. Wang, Synthesis of hydrophobic
CaCO3 nanoparticles, Materials Letters 60 (2006) 854–857.
[8] M. Shui, Polymer surface modification and characterization of particulate cal-
cium carbonate fillers, Applied Surface Science 220 (2003) 359–366.
[9] Y.F. Yang, G.S. Gai, S.M. Fan, Surface nano-structured particles and characteri-
zation, International Journal of Mineral Processing 78 (2006) 78–84.
[10] M. Kontopoulou, J.S. Parent, The dynamics of montmorillonite clay dis-
persion and morphology development in immiscible ethylene–propylene
rubber/polypropylene blends, Polymer 48 (2007) 4520–4528.
[11] N. Chen, C. Wan, Y. Zhang, Y. Zhang, Effect of nano-CaCO3 on mechanical prop-
erties of PVC and PVC/Blendex blend, Polymer Testing 23 (2004) 169–174.
[12] A.P. Kozminski, R.J. Hill, T.G.M. van de Ven, Flocculation of starch-coated solid-
ified emulsion droplets and calcium carbonate particles, Journal of Colloid and
Interface Science 309 (2007) 99–105.
[13] C. Wang, Y. Xu, Y. Liu, J. Li, Synthesis and characterization of lamellar aragonite
with hydrophobic property, Materials Science and Engineering C 29 (2009)
843–846.
[14] L. Chen, Y. Mai, B. Cotterell, Impact fracture energy of mineral-filled polypropy-
lene, Polymer Engineering and Science 29 (2004) 505–512.
[15] V. Kovacevic, S. Lucic, M. Leskovac, Morphology and failure in nanocomposites.
Part I: Structural and mechanical properties, Journal of Adhesion Science and
Technology 16 (2002) 1343–1365.
[16] Q. Sunqing, D. Junxiu, C. Guoxu, Wear and friction behaviour of CaCO3 nanopar-
ticles used as additives in lubricating oils, Lubrication Science 12 (2006)
205–212.
[17] M. Wang, H.K. Zou, L. Shao, J.F. Chen, Controlling factors and mechanism of
preparing needle-like CaCO3 under high-gravity environment, Powder Tech-
nology 142 (2004) 166–174.
[18] T. Tsuzuki, K. Pethick, P.G. McCormick, Synthesis of CaCO3 nanoparticles
by mechanochemical processing, Journal of Nanoparticle Research 2 (2000)
375–380.
[19] M. Ukrainczyk, J. Kontrec, V.B. Ivančić, L. Brečević, D. Kral, Experimental design
approach to calcium carbonate precipitation in a semicontinuous process, Pow-
der Technology 171 (3) (2007) 192–199.
[20] M. Ukrainczyk, J. Kontrec, D. Kral, Precipitation of different calcite crystal mor-
phologies in the presence of sodium stearate, Journal of Colloid and Interface
Science 329 (1) (2009) 89–96.
 H.V. Tran et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 366 (2010) 95–103
[21] M.A. Osman, U.W. Suter, Surface treatment of calcite with fatty acids: structure
and properties of the organic monolayer, Chemistry of Materials 14 (2002)
4408–4415.
[22] D.K. Keum, K.M. Kim, K. Naka, Y. Chujo, Preparation of hydrophobic CaCO3
composite particles by mineralization with sodium trisilanolate in a methanol
solution, Journal of Materials Chemistry 12 (2002) 2449–2452.
[23] C. Wang, Y. Sheng, H. Bala, X. Zhao, X. Ma, Z. Wang, A novel aqueous-phase
route to synthesize hydrophobic CaCO3 particles in situ, Materials Science and
Engineering C 27 (2007) 42–45.
[24] R. Lina, J.Y. Zhanga, P. Zhang, Nucleation and growth kinetics in synthesizing
nanometer calcite, Journal of Crystal Growth 245 (2002) 309–320.
[25] R. Didier, J.B. Baillière, Chimie Générale, 1979, Paris.
103
[26] D.L. Tran, V.H. Tran, T.Q. Duong, J.S. Kim, Effect of nanosized and
surface-modified precipitated calcium carbonate on properties of
CaCO3 /polypropylene nanocomposites, Materials Science and Engineering A
501 (2009) 87–93.
[27] J.G. Carmona, J.G. Morales, R.R. Clemente, Morphological control of pre-
cipitated calcite obtained by adjusting the electrical conductivity in the
Ca(OH)2 –H2 O–CO2 system, Journal of Crystal Growth 249 (2003) 561–571.
[28] V.H. Tran, Empirical model describing experimental impact factors on pre-
cipitated calcium carbonate particle size from heterogeneous system, Master
Thesis, Hanoi University of Technology, December, 2006.
[29] K. Nakamoto, Infrared Spectra of Inorganic and Coordination Compounds,
Wiley–Interscience, New York, 1970.