Advanced Powder Technology 25 (2014) 591–598

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Advanced Powder Technology

journal homepage: www.elsevier.com/locate/apt

Original Research Paper

Preparation of amorphous calcium carbonate nanoparticles from impure

dolomitic marble with the aid of poly(acrylic acid) as a stabilizer
M.M.M.G.P.G. Mantilaka a,b, R.M.G. Rajapakse a, D.G.G.P. Karunaratne c, H.M.T.G.A. Pitawala d,⇑
a
Department of Chemistry, Faculty of Science, University of Peradeniya, Peradeniya, Sri Lanka
b
Postgraduate Institute of Science, University of Peradeniya, Peradeniya, Sri Lanka
c
Department of Chemical and Process Engineering, Faculty of Engineering, University of Peradeniya, Peradeniya, Sri Lanka
d
Department of Geology, Faculty of Science, University of Peradeniya, Peradeniya 20400, Sri Lanka

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

Article history: Nanomaterials of Precipitated Calcium Carbonate (PCC) such as Amorphous Calcium Carbonate (ACC)
Received 29 May 2013 nanoparticles are highly demanded industrial products. These products are prepared in industrial scale,
Received in revised form 7 August 2013 using pure CaCO3 natural resources such as pure carbonate rocks, cockle shells, corals, and pearls. Such
Accepted 18 September 2013
natural resources could be consumed rapidly due to their excessive use in PCC industries. Therefore,
Available online 3 October 2013
the development of novel procedures to prepare nanoparticles of PCC using impure minerals is desirable.
Herein, we report a simple, novel and economical method to synthesize poly(acrylic acid) (PAA) stabi-
Keywords:
lized ACC nanoparticles using extensively distributed impure dolomitic marbles in place of natural pure
Amorphous calcium carbonate
Impure dolomitic marble
CaCO3 raw materials. The yields of final ACC products are enhanced using a bubbling column which can
Calcium sucrate produce small bubbles to improve bubbling efficiency. The average particle sizes of final calcium carbon-
Poly(acrylic acid) ate products are in the range 21–53 nm. The best conditions to produce ACC, among the conditions used
Nanoparticles in the proposed method, are temperature of 40 °C, pH of 4.5 and PAA concentration of 10 2 M. One or
more crystalline phase(s) of PCC is associated with ACC in each product and its nature depends on the
conditions used in the synthesis of these products. The unstable vaterite form of PCC is formed when
the PAA concentration is less than 0.5 M and at lower temperatures such as room temperature. The sta-
bility of the vaterite phase decreases when the temperature and the PAA concentration are increased. The
synthesized ACC nanoparticles are in required purity and quality to be suitable for industrial applications.
Ó 2013 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction ability to function as a precursor phase to synthesize a particular

Biomimetic synthesis of Precipitated Calcium Carbonate (PCC)
with various phases, sizes and morphologies by using organic sub-
strates has become an interesting topic in recent years [1–5]. PCC is
a value-added product and is highly demanded in industries such
as paper, textile, rubber, plastic, paint, cosmetic, sealant, tooth
paste and food stuff [6–8]. Conventionally, powders of micrometer
sized coarse particles of PCC are used in these industries. As far as
the filling ability and the dramatic increase in the surface area-to-
volume ratio are concerned, nanoparticles are much superior to
conventional powders and many industries now opt for PCC nano-
particles [9,10]. PCC occurs in three crystalline forms (calcite, ara-
gonite and vaterite) as well as in the metastable amorphous form
[2]. Out of these structural forms, Amorphous Calcium Carbonate
(ACC) nanoparticles have become an attractive product due to its
⇑ Corresponding author. Tel.: +94 81 2394211.
E-mail address: apitawala@pdn.ac.lk (H.M.T.G.A. Pitawala).
crystalline form [11–14], its use as an inexpensive absorbent of
toxic metals [15] and its role as a monodispersed filler for many
polymers [16]. The thermodynamic stability of ACC is, however,
low and is readily converted to the crystalline forms. Therefore,
additives such as poly(acrylic acid) (PAA) and Mg2+ ions have to
be used to stabilize ACC nanoparticles [13,15,17–19].
Production of PCC using natural resources is only done by pure
carbonate resources such as carbonate rocks with high percentage
of CaCO3, cockle shells, corals, and pearls [20–23]. However, these
valuable resources can be exhausted due to the widespread pro-
duction of PCCs to meet with its high demand. Marble is the largest
ore body for carbonate minerals in the world which contains dolo-
mite and calcite as major rock forming minerals [24]. However, the
use of marbles to synthesize PCC has been limited as a result of
high variability of Ca and Mg percentages and due to the presence
of impurities [25–27]. Therefore, the development of methods to
synthesize PCC products from marbles is a timely needed require-
ment for fulfillment of current demand and to save the naturally

0921-8831/$ - see front matter Ó 2013 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
http://dx.doi.org/10.1016/j.apt.2013.09.008
592 M.M.M.G.P.G. Mantilaka et al. / Advanced Powder Technology 25 (2014) 591–598
occurring pure carbonate resources. To the best of our knowledge,
marble has not yet been used to synthesize nanoparticles of ACC or
nanocomposites of ACC and polymers.
There are two basic synthetic routs to synthesize PCC: (1) Solu-
tion route in which, carbonate salt and calcium salt in aqueous
form are mixed together in equal molar ratio and (2) Carbonation
route wherein, CO2 is bubbled through a slurry of Ca(OH)2 or solu-
tions of Ca2+ salts [25,28–31]. Most of researchers have synthesized
ACC nanoparticles through solution routes [15,32,33]. However,
the economical, conventional and industrial method that is often
applied to synthesize PCC products from minerals is carbonation
route [20,34]. ACC can be synthesized by bubbling CO2 through a
slurry of hydrated calcined dolomite which contains dissolved
Ca(OH)2, Ca(OH)2(s), MgO(s) and Mg(OH)2(s) and a very little
amount of dissolved Mg(OH)2. The Mg2+ ions present in this mix-
ture can penetrate to calcium carbonate structure and prevent
the crystal growth thus facilitating the formation of ACC phase in
the resulting PCC product [19]. However, the associated Mg2+ com-
ponents will reduce the quality and purity of final ACC product
which are crucial factors on value estimation. Therefore, it is re-
quired to remove Mg2+ component of dolomite before synthesis.
Moreover, carbonation route is associated with a drawback of
low reactivity of CO2 with Ca2+ solution due to poor intermolecular
interactions of the reactants as a result of low interfacial area
[35,36]. This drawback can be overcome through the size reduction
of CO2 bubbles which strongly influences to enhance the reaction
rate [35,37] and the yield of final PCC product.
Herein, we focus, for the first time, on synthesis of PAA stabi-
lized ACC nanoparticles using dolomite via carbonation route by
mimicking the biomineralization process. The CO2 bubbling effi-
ciency of the carbonation route has been improved by designing
a bubbling column which produces small bubbles of CO2. Influ-
ences of pH of PAA solution and temperature of the reaction mix-
ture on complexation of PAA and calcium sucrate as well as on the
final PCC products are studied. Effect of PAA concentration on final
PCC products is also reported. The proposed method is potentially
important in the production of ACC in industrial scale by utilizing
dolomite as calcium source in place of high quality calcium carbon-
ate resources.
2. Experimental
2.1. Materials
Acrylic acid (P99%) and sodium persulfate (P99%) were pur-
chased from Sigma–Aldrich. Dolomite samples were collected from
a working marble quarry at Digana area located in the central part
of Sri Lanka [25].
2.2. Preparation of soluble calcium sucrate from dolomite
This procedure has been documented elsewhere [25]. In brief,
the dolomite samples were crushed, ground and filtered through
300 mesh sieve. The powder thus obtained was heated to
1000 °C for 3 h in a Muffle furnace to produce calcined dolomite
(CaO
MgO). An aliquot of 5.00 g of calcined dolomite was dispersed
in 100.0 mL of 0.50 M sucrose solution and stirred for 1 h. The sus-
pension thus obtained was filtered under suction to obtain soluble
calcium sucrate and thereby to remove insoluble Mg2+ components
and silicate impurities.
2.3. Preparation of PAA/PCC composite
A stock solution of PAA was prepared (0.5 M of repeat unit) by
the radical polymerization of acrylic acid (AA) using 1.00 g of
Na2S2O8 initiator and dissolving the polymer formed in 1 M NaO-
H(aq). In the preparation of PAA stabilized PCC, 100.0 mL of previ-
ously prepared calcium sucrate solution was added dropwise to
100.0 mL of the above PAA solution while stirring. CO2 was bub-
bled through the resulted reaction mixture at a flow rate of 1 L/
min. The column designed for bubbling CO2 through calcium su-
crate is schematically illustrated in Fig. 1. It is a cylindrical design
with 10 sieve plates fixed inside the cylinder together with down
comers for the liquid to flow to the plate below the down comer
(see Fig. 1). Carbon dioxide gas is bubbled counter currently and
the pressure of CO2 gas is maintained in such a way to prevent
the leakage of the solution through the holes of sieve plates but
to allow CO2 gas to flow upwards through the holes in the plates.
The operating principle of the column is equivalent to that of a
bubble cap tray columns used in industry. The products obtained
after bubbling CO2 were collected into a flask and washed with
50.0 mL aliquots of hot water for three times to remove impurities
and dried in a vacuum oven for 12 h at 45 °C and 600 mm Hg
pressure.
2.4. Characterization techniques used
The phases of PCC products were analyzed from the Fourier
Transform Infrared (FT-IR) spectroscopy. The FTIR spectra of the
products were recorded on a Shimadzu IRPrestige 21 instrument
with the KBr pellet method. Each sample was well ground and
thoroughly mixed to homogenize them. The homogenized samples
were mixed with dry KBr in 1:40 mass ratio and pellets were
pressed at 5 Tons. The spectra of the sample pellets were recorded
by using pure KBr pellet as the blank. The X-ray diffraction (XRD
studies were performed to study the crystalline phases of synthe-
sized PCC products. The XRD spectra were recorded with a Siemens
D5000 X-ray Powder Diffractometer with Cu Ka radiation of wave-
length k = 0.1540562 nm. The samples were carefully ground to a
fine powder and thoroughly mixed to homogenize them and their
powder XRD spectra were recorded. The resulted XRD patterns
were analyzed using XPowder 12 software with the aid of ICDD
PDF 2 database. Morphologies of the products were observed with
the help of Hitachi SU6600 Scanning Electron Microscope (SEM).
Fig. 1. Schematic illustration of carbonation column.
 M.M.M.G.P.G. Mantilaka et al. / Advanced Powder Technology 25 (2014) 591–598 593

Thermo Gravimetric Analysis (TGA) was performed to investigate at 1455 cm 1 and 1420 cm 1 [32]. These FTIR bands are character-
the weight percentages of PAA, CaCO3 and water in PCC products istic of those of ACC [13,15,32]. FTIR bands centered at 710, 873
using a Scinco STA S-1500 instrument at a heating rate of 10 °C/ and 2515 cm 1 reveal the presence of calcite form of PCC. Descrip-
min in air flow. Mg2+ contents in the final products were analyzed tions of these bands and the bond vibrations responsible for these
with a Varian AA240FS Atomic Absorption Spectrophotometer bands are tabulated in Table 1. The FTIR peak intensity ratio of the
(AAS). This was performed by digesting final PCC products in 1 M bands at 873 cm 1 and 710 cm 1 (I873/I710) can be used to deter-
HCl(aq) solution. Each sample was analyzed in triplicate to check mine the dominant phase among the calcite and ACC [3]. If the ra-
the accuracy of the results. The readings obtained for three trials tio is over 3, the dominant phase is ACC [3]. The intensity ratio of
were very close to each other showing the high precision of the re- PCC products prepared at pH values of 4.5, 6.5, 9.0 and 12.0 are
sults. Therefore, the average of the three readings was taken in 5.7, 4.6, 4.0 and 3.7 respectively. Therefore, according to these re-
each case. The AAS results together with the sample preparation sults, it can be concluded that the dominant phase of all the PCC
conditions are given in Supplementary Table A.1. products is ACC. The content of ACC reduces with increasing pH
of the precursor solutions. The XRD patterns of the PCC samples
prepared at different pH values of the precursor solutions are given
3. Results and discussion
in Fig. 3. All these samples have XRD peaks located at 2h values of
29.4°, 36.0°, 39.4°, 43.1°, 47.4° and 48.5°, which can be assigned to
3.1. Synthesis of PAA/PCC composite
be due to those of calcite crystalline form of PCC (JCPDS Card No.
05-0586). Since no peaks other than those given above are present,
We have already documented that the weight percentages of
it can be concluded that the only crystalline form of PCC present in
CaCO3, MgCO3 and impurities of Digana dolomite to be 49.9%,
our samples prepared using high concentrations of PAA, for e.g.
35.8% and 14.3%, respectively from AAS measurements [25]. When
0.5 M is calcite. The XRD does not show the presence of ACC as
this dolomite sample is calcined at 1000 °C for 3 h, CaCO3 and
ACC is not a crystalline product. The calcite form is present in vary-
MgCO3 are converted to CaO and MgO respectively, while the
ing amounts in these PCC samples as the characteristic XRD peak
impurities remain as silicate particles. The powder thus obtained
intensities are different in different samples. Thus the integrated
is dispersed in 0.5 M sucrose solution. The CaO present in the mix-
results of FT-IR and XRD, therefore, reveal that our PCC samples
ture is then converted to water-soluble calcium sucrate. The MgO
are composed of ACC as the major component with varying
component of calcined dolomite is converted to less water-soluble
amounts of the crystalline calcite in different samples. The results
Mg(OH)2 (solubility product of Mg(OH)2, Ksp = 7.1  10 12 mol3 -
also show that the progressive increase of the pH of the precursor
dm 9 at 25 °C) and is precipitated together with water-insoluble
solution gives increased amount of the crystalline calcite form in
silicate impurities [25]. The water-soluble Ca2+ component can
the final PCC product. It is important to note here that the pH of
then be separated from the rest of the less water-soluble magne-
the precursor solution cannot be lowered below 4.5 since PCC is
sium hydroxide and water-insoluble silica impurities simply by
soluble in sufficiently acidic solutions [41]. Therefore, the optimum
the filtration. This procedure for separating Ca2+ from other com-
pH value of the precursor solution that helps to produce more of
ponents present in dolomite has already been published elsewhere
the ACC form is 4.5. The total yields of the PCC products, however,
[25,38]. When an aqueous PAA solution is mixed with the calcium
show the opposite trend; the higher the pH of the precursor solu-
sucrate solution, colloidal particles of PAA-Ca2+ was obtained due
tion the higher is the PCC yield because PCC is soluble when the pH
to the complexation of Ca2+ ions with carboxylate groups of PAA
of the preparation medium is lowered (Table 2) [41]. Table 2 also
[23] which was observed as turbidity. Once CO2 was bubbled
gives the Mg2+ substituted in the lattice of PCC products. As can
through the mixture of PAA-calcium sucrate using the bubbling
be clearly seen from this Table, the Mg2+ content is very much
column, the turbidity of the mixture was increased as a result of
low in all the PCC products which were produced under different
the formation of PCC nanoparticles as confirmed by X-ray diffrac-
conditions. The maximum Mg2+ content in PCC is only 0.18%.
tion studies and FTIR studies of the dried powder (vide infra Sec-
Therefore, these PCC products are of sufficient purity to be used
tions 3.2, 3.3 and 3.4). The bubbling column designed and
in industrial applications.
developed in this work, can generate a large number of small bub-
bles of CO2 which are well distributed throughout the reaction
mixture. Since the total surface area of a large number of small
bubbles is greater than that of a few large bubbles, this design of
the bubbling column enhances the interfacial area for the encoun-
ter of reactants, which is extremely important in heterogeneous
reactions of this nature, thus helping to speed up the reaction
[35,36]. Another advantage of the column is the enhancement of
the contact time of CO2 bubbles and Ca2+ reactants due to the step-
wise flow of Ca2+ solution in the column through several sieves.
The bubbling process in the designed column is schematically rep-
resented in Fig. 1.

3.2. Effect of the pH value of the PAA solution on PCC products

obtained

The complex formation of Ca2+ with PAA, the phases of final PCC
products obtained and their yield can be influenced by the pH va-
lue of the PAA solution [28,29,39]. Therefore, the PCC products
were synthesized using 0.5 M PAA solutions at different pH values
of 4.5, 6.5, 9.0 and 12.0 at 25 °C. The FTIR spectra of PCC products,
as illustrated in Fig. 2, have bands centered at 1070 cm 1 and Fig. 2. FTIR spectrum of PCC samples prepared from of PAA solutions having pH
1450 cm 1 and the latter has been split into two bands centered values of (a) 12.0, (b) 9.0, (c) 6.5 M and (d) 4.5.
594 M.M.M.G.P.G. Mantilaka et al. / Advanced Powder Technology 25 (2014) 591–598

Table 1
Dominant FTIR bands for PCC products [3,13,16,25,32].
1
IR band (cm ) Responsible bond for IR band
710 Out-of-plane bending vibration (m2) in carbonate ion of calcite [3,25,32]
744 Symmetric stretching vibration (m4) in carbonate ion of vaterite [32]
873 Symmetric stretching vibration (m4) in carbonate ion of calcite [3,25]
1070 Symmetric stretching vibration (m1) of carbonate ion of ACC [13,16,32]
Split 1450 Asymmetric stretching vibration (m3) of carbonate ion of ACC [16]
2515 C–O bond of carbonate ion of calcite [25]
3440 Stretching vibration of O–H bond of water [32]

studies further confirm the formation of vaterite together with cal-

Fig. 3. XRD patterns of PCC samples prepared from of PAA solutions having pH
values of (a) 12.0, (b) 9.0, (c) 6.5 and (d) 4.5.
3.3. Influence of the PAA concentration on PCC products
PAA content is another significant factor affecting on ACC stabil-
ization [32]. The precursor solutions containing PAA concentra-
tions of 10 4 M, 10 3 M, 10 2 M and 10 1 M were used for the
preparation of PCC to study the effect of PAA concentration on
ACC stabilization. The pH of the precursor solutions were kept at
12 and the syntheses were carried out at constant temperature
of 25 °C. The FT-IR (Fig. 4) studies reveal the presence of ACC as
major constituent in all the products which is confirmed by the
bands of 1070, 1450 cm 1 and intensity ratio of bands at 873 and
710 cm 1 (I873/I710) as explained above. The values of FTIR intensity
ratios are indicated in Table 2. FT-IR bands centered at 873 cm 1
and 710 cm 1 reveal the association of calcite with ACC in all the
PCC products [19,42]. Also, IR absorption band at 744 cm 1 reveals
the presence of vaterite form of CaCO3 in all the products [43]. XRD
cite at the studied concentrations of PAA below 0.5 M (25 °C and
pH = 12.0) (Fig. 5). The corresponding vaterite peaks of XRD pat-
terns are found at 2h values of 24.8°, 27.0°, 32.7°, 43.8° and 55.7°
(JCPDS card No. 74-1867). The XRD peaks of calcite are found at
2h values of 29.4°, 36.0° and 39.4° (JCPDS card No. 05-0586). The
XRD peak intensities were used to evaluate ratio of calcite and
vaterite in each PCC product [40] (the ratios are based on compar-
ison in calcite and vaterite without considering the amorphous
phase) which is described next. The ratio of vaterite to calcite at
PAA concentrations of 10 1 M, 10 2 M, 10 3 M and 10 4 M are
6:4, 7:3, 4:6 and 4:6 respectively. Based on XRD peak intensity
analysis, the best PAA concentration for the stabilization of vaterite
is 10 2 M. It is interesting to note that both increase and decrease
of the PAA concentration in the precursor solution from 10 2 M de-
creases the stability of the vaterite phase. It is, therefore, possible
that at this optimum PAA concentration, the spherical vaterite par-
ticles are fully covered with polymer molecules and caged within
the polymer structure. The vaterite phase is totally absent when
the PAA concentration used is 0.5 M. The reason for this may be ex-
plained by the coordination environment of the preparation med-
ium which is discussed in Section 3.5 in detail. The yields (Table 2)
of the PCCs have been increased with increasing the PAA concen-
tration in the precursor solution. A possible explanation is as fol-
lows. Since the nonpolar CO2 molecules are more soluble in an
organic polymer like PAA than in water, the extent of reaction be-
tween Ca2+ and CO2 would be higher when PAA is present in large
excess thus giving higher PCC yields when the PAA concentration is
increased.
3.4. Effect of temperature of the precursor solution on PCC products
Temperature is a crucial controlling factor of morphology, sta-
bility, nucleation and phase of CaCO3 products [30]. We have,
therefore, synthesized PCC at different reaction temperatures
keeping the PAA concentration at 0.5 M and pH at 12. The PCC
products synthesized at 40 °C, 60 °C and 80 °C invariably contain

Table 2
The preparative conditions of PCC products, their yields and some properties analyzed by the FT-IR and ASS data. The yields of PCC products were calculated by dividing CaCO3
content in the product by CaCO3 content in the dolomite used.

Sample pH of PAA concentration Preparation temperature FTIR intensity ratio (I874/ Polymorphism Mg2+ content Yield
number PAA (M) (°C) I712) (%) (%)
1
1 4.5 5  10 25 5.7 Amorphous + calcite 0.16 42
1
2 6.5 5  10 25 4.6 Amorphous + calcite 0.13 60
1
3 9.0 5  10 25 4.0 Amorphous + calcite 0.11 61
1
4 12.0 5  10 25 3.7 Amorphous + calcite 0.10 73
1
5 12.0 5  10 40 13.2 Amorphous + vaterite + calcite 0.11 78
1
6 12.0 5  10 60 3.2 Amorphous + vaterite + calcite 0.13 79
1
7 12.0 5  10 80 3.2 Amorphous + vaterite + calcite 0.16 77
1
8 12.0 5  10 100 3.0 Amorphous + calcite 0.18 80
1
9 12.0 1  10 25 4.3 Amorphous + vaterite + calcite 0.15 57
2
10 12.0 1  10 25 5.9 Amorphous + vaterite + calcite 0.13 57
3
11 12.0 1  10 25 4.2 Amorphous + vaterite + calcite 0.10 54
4
12 12.0 1  10 25 3.2 Amorphous + vaterite + calcite 0.11 49
13 12.0 0 25 3.2 Amorphous + vaterite + calcite 0.14 41
 M.M.M.G.P.G. Mantilaka et al. / Advanced Powder Technology 25 (2014) 591–598 595

Therefore, the separation of calcium and magnesium components

from dolomite has accomplished as required.
SEM images (Fig. 8) shows the spherical morphology of final
ACC products. These particles are in nanoscale with the average
particle size ranging from 21 to 53 nm as estimated using SEM.
The ACC particles have been aggregated during preparation. The
particles in sample 5 (Table 2) have been more aggregated than
that of the other samples. TGA weight losses of PCC products
(Fig. 9) range from 23% to 26% at 450–513 °C which are attributed
to the combustion of PAA contents. PCC products show weight
losses of 23–40% at 716–800 °C which are attributed to the decom-
position of CaCO3 to CaO [1,45]. TGA plots of all PCC products re-
veal the presence of water in the weight percentage range of 4–
19%. The presence of water in PCC products is further confirmed
by broad band of FT-IR centered at 3440 cm 1.

3.5. Discussion

ACC is a hydrous form of CaCO3 where Ca2+ ions and CO23 ions
4
Fig. 4. FTIR spectra of PCC prepared with PAA concentrations of (a) 0 M, (b) 10 M,
(c) 10 3 M, (d) 10 2 M and (e) 10 1 M.
are coordinated with water molecules [7,16,32,46]. The stability of
ACC depends on its hydrous nature [46]. Based on the Ostwald’s
phase rule, the least stable ACC is nucleated first and then it trans-
vaterite as shown in XRD peaks at 2h values of 24.8°, 27.0°, 32.7°,
forms to the most stable calcite through intermediate vaterite dur-
43.8° and 55.7° (JCPDS card No. 74-1867) which is depicted in
ing the synthesis of PCC [31]. The transformation of ACC to vaterite
Fig. 6. Calcite is found in all the PCC products, which is confirmed
takes place by rapid dehydration of ACC to reorganize the poorly
by the XRD peaks at 2h values of 29.4°, 36.0° and 39.4° (JCPDS card
ordered structure of ACC [47]. In some experimental conditions,
No. 05-0586). Based on XRD peak intensities, the minimum con-
moderately stable aragonite is formed by vaterite and the arago-
tent of crystalline phases with highest amount of ACC is found in
nite transforms to calcite if the aragonite phase is not stabilized
the PCC obtained at 40 °C. As explained in Section 3.3 above, ratios
[4]. Kinetic studies of PCC formation given in the literature reveal
of calcite to vaterite in each PCC product were estimated based on
that the transformation of vaterite to calcite occurs through disso-
comparison of XRD peak intensities of calcite and vaterite without
lution of vaterite (Ksp = 1.2  10 8 mol2 dm 6 at 25 °C) followed by
considering amorphous phase. The ratios of calcite to vaterite ob-
recrystallization to achieve calcite structure [29,31,47]. The disso-
tained at temperatures of 40 °C, 60 °C, 80 °C and 100 °C are 2:8,
lution of vaterite is mainly controlled by the diffusion rate of Ca2+
6:4, 8:2 and 1:0 respectively. Therefore, the best temperature to
and CO23 ions in the solution [29]. The formation of calcite from
stabilize vaterite is 40 °C [44]. Also, the stability of vaterite de-
vaterite is favored by slow diffusion rates and low concentrations
creases when the temperature is increased. Vaterite is completely
of Ca2+ and CO23 ions [29]. However, high contents of CO2, which
absent in PCC synthesized at 100 °C. FTIR (see Fig. 7) intensity ra-
later form CO23 ions, favor the formation of vaterite since the inter-
tios depicted in Table 2 shows that, at this optimum temperature
facial energy difference of polymorphs is predominant at high con-
of 40 °C, the ACC is present in its highest percentage. Table 2 de-
tents of CO2 according to the Ostwald’s step rule [31]. In our study,
picts the ASS readings obtained Although the AAS results reveal
the bubbling efficiency and flow rate are enhanced by designing a
that the solubility of Mg2+ is increased when the temperature is in-
bubbling column to improve the production yield. Therefore, a
creased, the Mg2+ contents present in all the PCC products synthe-
small fraction of initially formed and stabilized ACC would have
sized in this work are very low (less than 0.2%, see Table 2).
been transformed to vaterite in most of the samples. Furthermore,
aragonite has not mineralized in any of the provided preparation
conditions since the aragonite forms in low flow rates and low

Fig. 5. XRD patterns of PCC prepared with PAA concentrations of (a) 0 M, (b)
10 4 M, (c) 10 3 M, (d) 10 2 M and (e) 10 1 M. Fig. 6. XRD patterns of PCC prepared at (a) 40 °C, (b) 60 °C, (c) 80 °C and (d) 100 °C.
596 M.M.M.G.P.G. Mantilaka et al. / Advanced Powder Technology 25 (2014) 591–598
Fig. 7. FTIR spectra of PCC prepared at (a) 40 °C, (b) 60 °C, (c) 80 °C and (d) 100 °C.
bubbling efficiencies [48]. Therefore, a fraction of ACC has been
transformed quickly into vaterite [47] and then some of which
has been transformed into stable calcite through dissolution and
recrystallization mechanism [29]. As we have shown above (Sec-
tion 3.4), the reaction temperature affects the formation of vaterite.
The best temperature to stabilize vaterite is 40 °C and the amount
of vaterite has been decreased by increasing temperature. This may
be due to the increase of dissolution of vaterite with the increasing
temperature. At 100 °C, the vaterite must have been dissolved
completely and recrystallized to calcite. Moreover, vaterite has
not found in PCC samples prepared at the highest concentration
of PAA (0.5 M) used, which may be explained by the coordination
environment of the preparation medium. PAA forms strong coordi-
nation complexes with Ca2+ ions in the preparation medium of
ACC. The coordination complexes of the precursor of ACC is
PAA–Ca2+–H2O in which PAA can be coordinated to Ca2+ ions via
unidentate, bidentate and bridging structures [32]. Formation of
the coordination complex can be observed as turbidity because
of the sticking of shielded polyanions of PAA by Ca2+ ions [49].
Fig. 8. SEM image of PCC (a) sample 1, (b) sample 5, (c) sample 10, and (d) sample 13 indicated in Table 1.
Fig. 9. TGA plots of PCC products of sample numbers 1–13 indicated in Table 1.
Disordering of the complex structure induces the stability of ACC
[32]. Therefore, the ordered structures of PAA–Ca2+–H2O com-
plexes may result in the stabilization of calcite without forming
vaterite [32]. At 0.5 M PAA the amount of carboxylate ions of
PAA is equal to Ca2+ amount. This may result in formation of more
ordered structure of PAA–Ca2+–H2O complex than that in other low
concentrations of PAA. Therefore, only calcite is found in PCC sam-
ples prepared using 0.5 M PAA solutions. The phase transformation
of ACC often happens even in careful preparation of ACC in solution
routes with effective and expensive additives [16]. Exposure of ACC
product to humidity is another well known reason for the transfor-
mation of ACC to crystalline forms [16,50]. Formation of vaterite
particles in the final ACC product may not cause any drawback
for applications of ACC since vaterite has similar properties of
 M.M.M.G.P.G. Mantilaka et al. / Advanced Powder Technology 25 (2014) 591–598
ACC such as high solubility, hydrophilicity and spherical morphol-
ogy [31].
CO2 gas is evolved while heating dolomite at 1000 °C to produce
calcined dolomite which can be confirmed from the TGA. The
evolved CO2 can be collected and reused for the production of
PCC [26]. This concept is very important in industrial design of a
continuous process [26]. Sucrose can be recovered during carbon-
ation of calcium sucrate [38]. The recovered sucrose product can
also be reused in the production step of calcium sucrate. Therefore,
the proposed entire process is economical due to the possibilities
for reusing these two end products.
4. Conclusions
PAA stabilized ACC nanoparticles are synthesized, for the first
time, using dolomite via a carbonation route. The yields of PCC
can be improved by enhancing the bubbling efficiency and produc-
tion of small bubbles. The maximum yields of PCC can be obtained
in basic pH values. Best studied conditions to synthesize ACC in the
proposed method are temperature of 40 °C, pH of PAA of 4.5 and
the PAA concentration of 10 2 M. Increase of PAA concentration
tends to decrease the stability of vaterite. The high flow rate and
the bubbling efficiency favor the formation of vaterite. The yields
of the PCCs are increased with increasing PAA concentrations due
to the complexation of PAA and Ca2+ ions. Extensively distributed
impure dolomitic marbles is the best option to replace expensive
and consumable pure natural CaCO3 resources to synthesize ACC
nanoparticles with sufficient quality to meet with industrial
requirements. Value addition to impure dolomitic marbles can be
achieved through synthesis of PAA stabilized ACC nanoparticles.
Therefore, the proposed method is a best method to synthesize
ACC nanoparticles from impure dolomitic carbonate rocks.
Acknowledgements
The authors gratefully acknowledge the financial assistance by
the National Research Council (Grant No. 11-178), Sri Lanka. The
authors also thank Ms. N.I. Attanayake and Mr. M.L. Paranawithar-
ana (Technical officers at Department of Chemistry, University of
Peradeniya) for their technical assistance.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apt.2013.09.008.
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