Korean J. Chem. Eng.

, 22(6), 852-856 (2005)

Synthesis of Single Phase Aragonite Precipitated Calcium Carbonate

in Ca(OH) -Na CO -NaOH Reaction System
2 2 3

Ji-Whan Ahn , Jeong-Hwan Kim, Hyun-Seo Park, Jung-Ah Kim, Choon Han* and Hwan Kim**
†

Minerals & Materials Processing Division, Korea Institute of Geoscience & Mineral Resources, Daejeon 305-350, Korea
*Department of Chemical Engineering, Kwangwoon University, Nowon, Seoul 139-701, Korea
**School of Materials Science and Engineering, Seoul National University, Seoul 151-742, Korea
(Received 26 September 2005 • accepted 4 November 2005)

Abstract −The formation behavior of precipitated calcium carbonate polymorphs was investigated in three different
supersaturation levels. Because the most easily adjustable and influential variable determining supersaturation is the
ion concentration of the major reactants - Ca2+ and CO32− - the supersaturation can be adjusted by changing the ion con-
centration of these two ions. At high supersaturation, free energy is necessary for a decrease in nucleation, promoting
the formation of a sphere-shaped vaterite, while aragonite and calcite were seen to co-exist at medium supersatura-
tion. At low supersaturation, aragonite was mainly formed by mixing with some calcite. Hence, we considered that
lower supersaturation was necessary to obtain a single phase aragonite. Furthermore, we found that the solubility of
Ca(OH)2 was decreased with the addition of NaOH by a common ion effect. Thus, it is possible to perform an experi-
ment at a lower Ca2+ concentration. The aragonite was synthesized by adding the Na2CO3 solution to the Ca(OH)2 slurry
containing several concentrations of NaOH solution at 75 oC and under the addition rate of Na2CO3 at 3 ml/min. The
formation yield of calcite decreased when the NaOH concentration was increased. In conclusion, in the case of the
reaction of the 2.5 M NaOH solution over 210 minutes, single-phase aragonite with an aspect ratio of 20 was obtained.
Key words: Precipitated Calcium Carbonate, Aragonite, Solution Process, Supersaturation, NaOH

INTRODUCTION industries; however, its synthesis mechanism has not been clearly
understood. In most cases, there was a problem in realizing the same
Precipitated calcium carbonate (PCC) is fine particles that are result even under the same experimental conditions since the stud-
synthesized either by carbonation and/or solution process after cal- ies focused on experimental variables. Konno et al. reported that
cination and hydration reaction of limestone [Arai and Yasue, 1990; the precipitation of aragonite increased as the Ca(OH) suspension
2

Tanaka, 1990]. Generally, commercially available PCC is synthe- was increased, occurring predominantly in the presence of NaOH
sized by a carbonation process in which hydrated lime is reacted [Konno et al., 2003]. Kitamura et al. reported that highly alkaline
with pure CO or CO containing gas. However, it is difficult to con-
2 2
solutions are advantageous for the nucleation of aragonite, and that
trol precisely the phase, shape, and aspect ratio of the crystal. An at a pH larger than about 13.5 the nucleation of aragonite begins
alternative synthetic method for PCC is a solution process by which [Kitamura et al., 2002]. Hu and Deng demonstrated that magne-
Na CO is reacted with hydrated lime. PCC is obtained as the main
2 3
sium ions increase the aragonite fraction but slightly decrease the
product and recyclable NaOH is produced as a by-product of the aspect ratio, and that a high synthesis temperature is favorable to
solution process. In this solution process the phase and morphol- both the aragonite fraction and its aspect ratio [Hu and Deng, 2004].
ogy can be controlled more easily by controlling supersaturation Kawano et al. reported a method of producing sediment selectively
than in the carbonation process [Kim et al., 2004]. Calcium car- by maintaining the components in a solution higher than the solubil-
bonate is used in various industrial fields as an additive in medical ity of the products [Kawano et al., 2002]. Since these studies were
supplies, foods, paper, plastics, printing ink, etc [Wang et al., 1999]. performed within a narrow boundary of supersaturation, they are
In particular, aragonite has a slightly greater average index of refrac- insufficient for an understanding of the comprehensive trends of
tion than calcite, and possesses a needle-like characteristic shape. the three polymorphs of calcium carbonate.
Hence, aragonite is expected to have higher performance properties Therefore, the purpose of this study was to synthesize single phase
as a filler in the paper and plastics industries when compared with aragonite PCC by a solution process using Ca(OH) slurry and Na
2 2

calcite [Dalas et al., 1988; Konno et al., 2002]. Furthermore, arago- CO solution as the main reactants. First, the formation mechanism of
3

nite has a needle-like shape with a very large aspect ratio [Sohnel the PCC polymorphs was investigated from the kinetic point of view;
and Mullin, 1982], so it can be used in various high-tech industrial then, based on the formation mechanism of the PCC polymorphs and
fields as a new inorganic material with high functionality and high the role of NaOH in the bulk solution, the optimum synthetic con-
added value. Recently, many studies have been conducted on the dition of single-phase aragonite PCC was intensively investigated.
synthesis of aragonite precipitated calcium carbonate used in many
EXPERIMENTAL
To whom correspondence should be addressed.
†

E-mail: [email protected] The reactor used a cylinder made of Pyrex glass with a diameter
852
 Synthesis of Single Phase Aragonite Precipitated Calcium Carbonate in Ca(OH)2-Na2CO3-NaOH Reaction System 853
of 10 cm and a volume of 1.0 L, with a 4 cm long impeller attached. 0.5 M Na CO solution. To maintain a high CO − ion concentra-
2 3
2

The temperature in the reactor was maintained constantly with a tion, the 1.5 M Na CO solution was simultaneously added to the
2 3

water bath (Jeio Tech, WB02). In order to adjust the concentration Ca(OH) ; for a lower concentration, it was injected gradually at the
2

of the CO − ions, 0.5M Na CO solution (150 ml) was added at a

2

3 2 3
rate of 3 ml/min. The synthesized samples were washed with eth-
rate of 3 ml/min to the Ca(OH) slurry (50 ml) at the same time for
2
anol two to three times to remove any residual ion components, then
a lower concentration. All of the experiments were conducted at filtered and dried in an oven at 80 C. The dry precipitates were char-
o

75 C under a constant agitation speed of 400 rpm. The Ca(OH)

o

2
acterized by XRD (MacScience Co. M18XHF-SRA) using CuKα 1

solutions were divided into three parts following the concentration radiation, and the shapes of the particles were observed by SEM.
of Ca : a high-concentration the Ca solution was prepared by add-
2+ 2+
A schematic diagram and a flow chart for this experiment are shown
ing HNO to 1.5 M Ca(OH) slurry and dissolving it completely;
3 2
in Fig. 1.
the medium-concentration Ca solution consisted of 1.5 M slurry
2+

only, and the low-concentration Ca solution was prepared by add-

2+
RESULTS AND DISCUSSION
ing NaOH to Ca(OH) slurry. In order to adjust the concentration
2

of the CO − ions, changes were made to the method of adding the

2

3
In general, supersaturation is directly related to formation behav-

Fig. 1. Schematic diagram and a flow chart for this experiment : (1) Reactor (2) Water bath (3) pH electrode (4) pH meter (5) Thermometer
(6) Stirrer (7) Na2CO3 solution (8) Valve.

Fig. 2. XRD patterns and SEM photographs of precipitated calcium carbonate synthesized in the three reaction systems; Reaction systems
for the supersaturation levels (a) High, (b) Medium, (c) Low.
Korean J. Chem. Eng.(Vol. 22, No. 6)
854 J.-W. Ahn et al.
ior of PCC polymorphs, and supersaturation in precipitation reac-
tion depends on the ion concentration of the reactants present in
the solution. The range of supersaturation was adjusted to three dif-
ferent levels: high, medium and low. Formation properties of PCC
synthesized in the three reaction systems are shown Fig. 2. At high
supersaturation, both Ca and CO − had a high concentration (Fig.
2+ 2

2a), the nucleation rate increased, and the size of the critical nuclei
then became smaller. This result occurs because vaterite has the small-
est particle size among PCC polymorphs and it has spherical shapes
which free energy necessary for critical nucleation is the smallest.
Fig. 2b shows the result for medium supersaturation. In this reac-
tion, calcite was mainly formed and some aragonite was mixed with
it. In particular, the existence of Ca(OH) peaks should be noted. Fig. 4. Critical free energy for nucleation having size of L1 for the
2

This suggests that the dissolution rate of Ca(OH) is slower than polymorphs of precipitated calcium carbonate.
2

the formation rate of calcium carbonate, and that the dissolution

reaction of Ca(OH) is the rate-limiting step of the overall reaction. (a : activity of a calcium ion, a : activity of carbonate, Ksp : solubility
2+ 2−
Ca CO 3

Fig. 2c shows the results of the reaction at low supersaturation; the product of calcium carbonate)
supersaturation of this reaction was lowered by adding Na CO so- 2 3

lution to 1.5 M Ca(OH) slurry without HNO at 3 ml/min. In this

2 3
Ion activity is expressed as the product of the activity coefficient
case, aragonite was mainly formed, mixed with some calcite. and ion concentration in the solution. Fig. 4 shows the plotting of
Consequently, we confirmed that aragonite was mainly formed the critical energy necessary for nucleation by using these values.
in low supersaturation. From these results, the formation mecha- The free energy necessary for the formation of a spherical, cubic,
nism of PCC polymorphs was investigated from a kinetic point of and needle-like nucleus with the size of the characterization dimen-
view. The critical free energy necessary for stabile nucleation can sion L is G , G , and G respectively. Thus, we can see that the free
1 s c n

be expressed by the following Eq. (1) [Langerak et al., 1999]. energy needed for the formation of calcium carbonate polymorphs
increases for vaterite, calcite, and aragonite.
βν γ -
∆G = --------------------
2 3

(1) Based on these results and the relevant theoretical background,

(kT lnS) it was considered that lower supersaturation was necessary to obtain
cr
2

(β : shape factor, ν : molecular volume, γ : surface tension, k : Boltz- a single-phase aragonite. As can be seen from Eq. (2),
mann’s constant, T : temperature, S : supersaturation) Ion concentration in this solution should be low because super-
saturation greatly depends on the ion concentration of the reactants
In this equation, nucleation energy depends on the shape factor present in the solution. In the first place, NaOH was added to the
and supersaturation at a fixed temperature. To begin with, regard- solution to adjust the Ca ion concentration. If NaOH is added to
2+

ing the three polymorphs of calcium carbonate - vaterite, calcite, Ca(OH) slurry, the solubility of Ca(OH) is significantly decreased
and aragonite - their representative shapes are spherical, cubic and
2 2

by a common ion effect; thus, it is possible to perform an experi-

needle-like, and their shape factors are 16.75, 32.00 and 109.76, ment at a lower Ca concentration. We added 2.5 to 6.0 M NaOH
2+

respectively (Fig. 3) [Nyvlt, 1985]. to the Ca(OH) slurry to confirm whether single-phase is created in
Next, assuming that the temperature remains constant, a vari-
2

some Ca ion concentration (Fig. 5). In this reaction, the formation

2+

able to consider is supersaturation, which can be expressed by Eq. yield of aragonite was increased with the increasing of NaOH up
(2) [Kitamura et al., 2002], to 4.5 M, and it shows a tendency to decrease in concentrations above
4.5 M NaOH; whereas calcite decreased with increases in the NaOH
S = ⎛⎝a-----------------
a -⎞
2+ 2− 1/2
Ca CO3

(2) concentration and disappeared altogether at 6.0 M. Un-reacted Ca

K ⎠ sp

(OH) showed a tendency to increase with an increase in the NaOH

2

concentration. The reason why a quantity of Ca (OH) remaining 2

un-reacted increases as the addition of NaOH is increased may be

attributed to the fact that the quantity of Ca(OH) that can be dis- 2

solved for 30 minutes falls owing to a decrease in solubility.

Formation behavior of PCC polymorphs can be controlled by
controlling the calcium and carbonate ions, and that aragonite is
synthesized at low supersaturation. The addition rate of Na CO 2 3

had to be fixed at 3 ml/min to decrease the of CO − ions concentra- 2

tion (Fig. 6). In the same way, in this reaction, the un-reacted Ca
(OH) was increased with the increase in NaOH. The reason why
2

is that the quantity of Ca ion by solubility decrease in Ca(OH) is

2+

decreased with the increasing in NaOH concentration. So, the for-

mation yield of calcite decreased continually, disappearing altogether
Fig. 3. Shape factors for various geometries. at 2.5 M. With the increase of NaOH, the aspect ratio of aragonite
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 Synthesis of Single Phase Aragonite Precipitated Calcium Carbonate in Ca(OH)2-Na2CO3-NaOH Reaction System 855

Fig. 5. Ratio of concentration and SEM images of samples obtained by simultaneous reaction in various concentrations of NaOH for
30 minutes.

Fig. 6. Ratio of concentration and SEM images of samples obtained in several concentrations of NaOH.

decreased with the increase in thickness. Therefore, based on these of Ca(OH) is the rate-limiting step of the overall reaction because
2

results, we confirmed the changes of formation yield of the sam- Ca(OH) remained despite the termination of the reaction. This result
2

ples obtained in 2.5 M NaOH solution as a function of the reaction indicates that the dissolution rate of Ca(OH) is slower than the for-
2

time (Fig. 7). mation rate of calcium carbonate. We can show that un-reacted Ca
In this reaction, calcite did not appear and the aragonite nuclei (OH) remained despite the termination of the reaction over 50 min,
2

were formed about 10 minutes after the start of the reaction. Sub- and that the contents of the unreacted Ca(OH) disappeared in a re-
2

sequently, single-phase aragonite with an aspect ratio of 20 was ob- action time of 210 minutes. Therefore, it has been concluded that
tained with a concentration of 2.5 M NaOH and the addition rate the dissolution rate of Ca(OH) is the rate limiting step of the overall
2

of Na CO at 3 ml/min over 210 minutes. In addition, there is a ten-

2 3
reaction. In conclusion, it was confirmed that the PCC polymorphs
dency for the particle size and aspect ratio to increase with the reac- and the formation yield were controlled by the supersaturation fol-
tion time. However, it was considered that the dissolution reaction lowing the concentration of calcium and carbonate ions.
Korean J. Chem. Eng.(Vol. 22, No. 6)
856 J.-W. Ahn et al.

Fig. 7. Formation yield and SEM images of samples obtained in 2.5 M NaOH solution as a function of reaction time.

CONCLUSION cium Carbonate on Polymeric Substrates,” J. Crystal Growth, 89,

287 (1988).
In this study, from results obtained by adjusting experimental Hu, Z. and Deng, Y., “Synthesis of Needle-like Aragonite from Calcium
variables based on the kinetics, the formation mechanism of pre- Chloride and Sparingly Soluble Magnesium Carbonate,” Powder
cipitated calcium carbonate was investigated. Ranges of the super- Technology, 140, 10 (2004).
saturation for formation of the three polymorphs were classified by Kawano, J., Shimobayashi, N., Kitamura, M., Shinoda, K. and Aikawa,
considering the mechanism. At high supersaturation, vaterite was N., “Formation Process of Calcium Carbonate from Highly Super-
mainly synthesized even though some calcite was mixed. It was saturated Solution,” J. Crystal Growth, 237-239, 419 (2002).
realized that vaterite was mainly synthesized in the lowest region Kim, J. H., Ahn, J. W., Park, H. S. and Park, C. H., “Synthesis Peculiar-
of nucleation energy that is the highest nucleation rate among three ity of the Precipitated Calcium Carbonate Polymorphs Following
polymorphs. Secondly, at medium supersaturation, calcite was formed Variation of Supersaturation in Ca(OH)2 and Na2CO3 Reaction Sys-
primarily. This result is because that supersaturation in this reaction tem,” Geosystem Engineering, 7(4), 95 (2004).
system was lowered together with a lowered nucleation rate, and Kitamura, M. and Konno, K., “Controlling Factors and Mechanism of
the free energy for stable nucleation finally passed over the range Reactive Crystallization of Calcium Carbonate Polymorphs from
of free energy for nucleation of the vaterite. Lastly, at low supersat- Calcium Hydroxide Suspensions,” J. Crystal Growth, 236, 323
uration, aragonite predominated. At this point, the addition of NaOH (2002).
to adjust supersaturation lowers the solubility of Ca(OH) , a main
2
Konno, H., Nanri, Y. and Kitamura, M., “Crystallization of Aragonite
reactant by common ion effect. The addition of NaOH reduced Ca 2+
in the Causticizing Reaction,” Powder Technology, 123, 33 (2002).
ion concentration in the solution. As the reaction continued, the for- Konno, H., Nanri, Y. and Kitamura, M., “Effect of NaOH on Aragonite
mation yield of aragonite was increased, whereas that of calcite de- Precipitation in Batch and Continuous Crystallization in Causticiz-
creased continually and disappeared at 2.5 M. It is considered that ing Reaction,” Powder technology, 129, 15 (2003).
lower supersaturation at the early stage of reaction and sufficient Langerak, P. A. E., Beekmans, M. H. M., Janneke, J. B. and Hamelers,
aging time would be necessary to obtain single phase aragonite. In V. W. H., “Influence of Phosphate and Iron on the Extent of Calcium
conclusion, single phase aragonite was obtained in the 2.5 M NaOH Carbonate Precipitation During Anaerobic Digestion,” J. Chem. Tech.
solution for 210 minutes. Also, the rate limiting step in the calcium and Biotech., 74, 1030 (1999).
carbonate synthesis reaction by the solution method is the dissolu- Nyvlt, J., The Kinetics of Industrial Crystallization, Elsevier, Amster-
tion reaction of Ca(OH) ; hence it is to be expected that single-phase
2
dam (1985).
aragonite was produced by adjusting the Ca concentration at low
2+
Sohnel, O. and Mullin, J. W., “Precipitation of Calcium Carbonate,” J.
concentration of CO −. 2

3
Crystal Growth, 60, 239 (1982).
Tanaka, H., “Application of Carbonate as a Pigment for Coated Paper,”
REFERENCES Gypsum & Lime, 227, 229 (1990).
Wang, L., Sondi, I. and Matijevic, E., “Preparation of Uniform Need-
Arai, Y. and Yasue, T., “Controls of Crystal Shape and Modification in like Aragonite Particles by Homogeneous Precipitation,” J. Colloid
Preparation of Calcium Carbonate,” Gypsum & Lime, 228, 41 (1990). & Interface Science, 218, 545 (1999).
Dalas, E., Kallitsis, J. and Koutsoukos, P. G., “The Crystallization of Cal-
November, 2005