DOI: 10.

1021/cg9012813

Synthesis of All Crystalline Phases of Anhydrous Calcium Carbonate 2010, Vol. 10

2129–2135
Arpita Sarkar and Samiran Mahapatra*
Unilever R&D Bangalore, 64 Main Road, Whitefield, Bangalore 560066, India

Received October 15, 2009; Revised Manuscript Received March 5, 2010

ABSTRACT: Usually, the metastable vaterite phase transforms to the thermodynamically most stable calcite phase. We report
here the phase transformation of vaterite to aragonite, which is seldom observed in the synthetic processes of calcium carbonate.
The vaterite, upon equilibration with distilled water at room temperature, gradually transforms to aragonite. This transforma-
tion process is further accelerated when the vaterite sample is refluxed in distilled water. Under a different set of conditions, when
equilibrated in the mother liquor, the same vaterite sample transforms to calcite without going through aragonite as an
intermediate phase. The formation of all three crystalline polymorphs of calcium carbonate is achieved without the use of any
additive. These polymorph transformations have been monitored using powder X-ray diffraction and FTIR spectroscopy. The
morphological changes of the calcium carbonate samples isolated during the course of phase transformation processes are
captured using scanning electron microscopy. The transformation either to aragonite or to calcite has been explained based on
the dissolution-recrystallization mechanism.

Introduction recrystallization processes, viz., the dissolution of an unstable

polymorph and the growth of a stable polymorph.17 Very few
Polymorphism has tremendous technological importance
reports deal with the transition of one metastable phase
due to the dependence of material properties such as dissolu-
(vaterite) to yet another metastable phase (aragonite).14b,18
tion kinetics, hardness, and density or optical properties on
In this paper we report an unusual transformation of vaterite
the solid-state structure. Polymorphism in crystalline calcium
to aragonite in the absence of any additives. The aragonite
carbonate has been the focus area of research for many years.
samples thus obtained are very stable in their solid states and
In particular, one of the long-standing challenges is the ability
do not transform into calcite. To the best of our knowledge,
to predict and control the occurrence of polymorphism during
this is the first report of such polymorph transformation
the crystallization of calcium carbonate.1 Calcium carbonate
without the use of any additive. We also report conditions
occurs as three anhydrous crystalline polymorphs (trigonal
under which the same vaterite sample transforms to calcite
calcite, orthorhombic aragonite, and hexagonal vaterite), in
and propose a possible mechanism for the same.
two hydrated crystal forms (calcium carbonate hexahydrate
ikaite and calcium carbonate monohydrate), and also as Experimental Section
amorphous material.2-5 While calcite is the most thermo-
dynamically stable form of calcium carbonate under ambient CaCl2 3 2H2O (AR grade) and K2CO3 (anhydrous, AR grade) were
conditions, the other two anhydrous crystalline forms are meta- obtained from Merck (India) and were used as received. Aqueous
solutions of the reactants were made using distilled water. Distilled
stable in nature, with vaterite being particularly unstable.6 water used in all reactions had the following characteristics: pH 7.1,
In biomineralization, polymorph selection is a key issue electrical conductance 2
10-6 S cm-1, total dissolved salt 0.9 mg/L,
because the different polymorphs offer the possibility of diffe- and turbidity <0.1 NTU.
rent materials properties. Excellent examples of polymorph The synthesis of various calcium carbonate samples was con-
control are found in organisms such as mollusks, which can ducted in a three-necked glass round bottomed flask with a diameter
selectively deposit a specific polymorph of CaCO3 (aragonite of 16 cm and an internal working volume of 2 L. Mixing was
performed with the help of an overhead stirrer attached to a speed
or calcite) under the control of biopolymers.7 Aragonite, for
regulator. The overhead stirrer was fitted with a glass rod impeller
example, which is difficult to synthesize under ambient con- having a Teflon blade (6 cm length, 2 cm breadth) attached to it. The
ditions but can offer beneficial mechanical properties, can be impeller was inserted through the central neck of the three-necked
nucleated in the presence of soluble proteins extracted from an round bottomed flask. The impeller speed for all reactions was
aragonite nacre layer.8 maintained at 200 rpm. Reactants were added through the side necks
Control of polymorphism is a complex interplay between of the three-necked round bottomed flask, and the rate of addition
thermodynamic and kinetic factors. Traditional strategies for was controlled at 25 mL/min with the help of a peristaltic pump
(manufacturer: Trishul Eequipments, Bhandup, Mumbai).
selection of polymorphs often involve changing parameters, Preparation of Sample S-1 (100% Vaterite). Aqueous CaCl2 3
such as initial supersaturation, mixing and stirring conditions, 2H2O (73.5 g dissolved in 250 mL of distilled water, 2 M) was added
temperature, pH, solvents, and the presence of organic or at a feed rate of 25 mL/min to an aqueous solution of K2CO3 (69.1 g
inorganic additives.9-14 The primary objective is to achieve dissolved in 250 mL of distilled water, 2 M) whose temperature was
polymorph selectivity by driving the reaction from thermo- maintained at 30 ( 1 °C. There was an initial reduction in the
dynamic to kinetic control or vice versa.15 impeller speed because of the resistance offered by the thick
gelatinous mass formed during the initial stages of the reaction.
The phase transition of metastable phases such as vaterite Subsequently, the gel nature of the precipitated mass decreased
and aragonite to the stable phase calcite has been exten- and the slurry was more amenable to stirring. After the addition of
sively reported and studied.6b,16 The transformation of vater- CaCl2 solution was completed, the mixture was immediately filtered
ite or aragonite into calcite has been explained by two-step through a Whatman 40 filter paper. The precipitate was washed

r 2010 American Chemical Society Published on Web 04/02/2010 [Link]/crystal

2130 Crystal Growth & Design, Vol. 10, No. 5, 2010 Sarkar and Mahapatra

Table 1. List of Vaterite and Aragonite Samples Prepared under Table 2. List of Vaterite and Calcite Samples Prepared
Different Conditions under Different Conditions
aragonite vaterite calcite vaterite
sample reaction conditions (%) (%) sample reaction conditions (%) (%)
S-1 CaCl2 (2 M) added to K2CO3 (2 M) 0 100 S-1 CaCl2 (2 M) added to K2CO3 (2 M) 0 100
at 30 ( 1 °C at 30 ( 1 °C
S-2 S-1 refluxed in distilled water for 30 min 19 81 S-11 S-1 refluxed in the mother liquor for 30 min 7 93
S-3 S-1 refluxed in distilled water for 60 min 71 29 S-12 S-1 refluxed in the mother liquor for 60 min 37 63
S-4 S-1 refluxed in distilled water for 75 min 100 0 S-13 S-1 refluxed in the mother liquor for 120 min 68 32
S-5 S-1 refluxed in distilled water for 120 min 100 0 S-14 S-1 refluxed in the mother liquor for 180 min 100 0
S-6 S-1 refluxed in distilled water for 300 min 100 0 S-15 S-1 dispersed in the mother liquor and 100 0
S-7 S-1 refluxed in distilled water for 2 days 100 0 equilibrated at 25 °C for 30 days
S-8 S-1 dispersed in distilled water and 100 0
equilibrated at 25 °C for 30 days
(λ =1.5406 Å) radiation. The 0.02° steps and the 2θ range from 20°
to 60° were selected to analyze the crystal structure. The percentage
with distilled water for at least six times (total volume of about 1 L) of each polymorph of calcium carbonate was calculated from their
to ensure the complete removal of mother liquor, followed by characteristic XRD peak intensities by using the following formula,
rinsing with a minimum volume of acetone to facilitate the drying as described in the literature.19
process. The washing and rinsing steps were carefully carried out in
the Buckner funnel. The precipitate was then dried at room tem- 3:157ðIA 221 Þ
perature for about 24 h in a vacuum desiccator containing anhy- XA ¼
IC 104
þ 3:157ðIA 221 Þ þ 7:691ðIV 110 Þ
drous CaO. The dried mass was ground to a powder using a table-
top mixer. This material was obtained as a dense free-flowing white XV ¼ 1 - XA - XC
powder. Yield: 48 g (96%).
Preparation of Aragonite Samples (S-2 to S-10) from the Vaterite 7:691ðIV 110 Þ
Precursor. Method A;Vaterite to Aragonite Transformation under XV ¼ XC ¼ 1 - XV
IC 104 þ 7:691ðIV 110 Þ
Refluxing Conditions. About 10 g of the vaterite sample S-1 was
dispersed in 500 mL of distilled water in a round-bottom flask fitted In the above formulas, XA, XC, and XV are the molar fractions of
with a condenser. The suspension was refluxed at 100 °C for aragonite, calcite, and vaterite in a mixture, respectively. The
different time durations and cooled to room temperature, and the intensities of the peaks of the 221 plane of aragonite, the 104 plane
solid mass was filtered through a Whatman 40 filter paper. The solid of calcite, and the 110 plane of vaterite are represented as IA221,
thus obtained was washed with distilled water followed by rinsing IC104, and IV110, respectively.
with a minimum volume of acetone to hasten the drying process. The Fourier transformed infrared (FTIR) measurements were
The solid was then dried at room temperature for 24 h in a vac- performed on a Bomem FTIR spectrophotometer (model MB 102)
uum desiccator containing anhydrous CaO. The samples were with a resolution of 2 cm-1. Pressed pellets of the samples diluted
found to be either a mixture of vaterite/aragonite or 100% aragonite with potassium bromide (2 mg in 200 mg) were used.
depending on the duration of reflux (Table 1). Scanning electron micrographs (SEM) of the powder samples
Method B;Vaterite to Aragonite Transformation at Room Tem- were taken on a Hitachi S-4700 scanning electron microscope fitted
perature. About 10 g of the vaterite sample S-1 prepared as above with a field emission source and with an accelerating voltage of
was dispersed in 500 mL of distilled water in a conical flask fitted 20 kV. Samples were uniformly spread on double sided carbon wafer
with a glass stopper. This suspension was equilibrated at room tapes and gold-coated prior to microscopy experiments.
temperature (25-30 °C) and under atmospheric pressure for about
a month. The equilibrated solid was then filtered through a What-
man 40 filter paper. The solid cake was washed with distilled water
Results and Discussion
and rinsed with a minimum volume of acetone to facilitate the Synthesis and Polymorph Transformation. The pure vater-
drying process. The solid was then dried at room temperature for
ite sample (S-1) was synthesized by employing the solution
about 24 h in a vacuum desiccator containing anhydrous CaO.
Preparation of Calcite Samples (S-11 to S-15) from the Vaterite route of synthesis (eq 1) by reacting equimolar concentra-
Precursor. Vaterite samples were prepared as described above by tions of aqueous CaCl2 and K2CO3 solutions at near room
adding an aqueous solution of CaCl2 (2 M) to an aqueous solution temperature.
of K2CO3 (2 M) at 30 ( 1 °C. After the vaterite precipitation was CaCl2 þ K2 CO3 f CaCO3 þ 2KCl ð1Þ
completed, the precipitated solid (about 48 g as obtained for the
preparation of S-1) was refluxed at 100 °C along with the mother The sequence of addition of reactants was found to be
liquor. After the mixture was heated under reflux for different critical in polymorph selectivity in this case. When CaCl2 was
durations of time, it was cooled to room temperature and the solid
was filtered through a Whatman 40 filter paper. The solid thus added to K2CO3, vaterite was the main product; on the other
obtained was washed with distilled water followed by rinsing with a hand, calcite was the main product when the reverse se-
minimum volume of acetone to hasten the drying process. The solid quence of addition was followed. During the course of the
was then dried at room temperature for 24 h in a vacuum desiccator reaction, an increase in viscosity suggests the formation of
containing CaO. The samples were found to be either a mixture of amorphous calcium carbonate (ACC) as transient intermedi-
vaterite/calcite or 100% calcite depending on the refluxing time ate, which transforms to the crystalline vaterite.
(Table 2).
Mother Liquor Characteristics. After the vaterite precipitate was
The vaterite sample thus prepared remained stable in the
filtered through a Whatman 40 filter paper, the entire filtrate (∼500 mL) solid state for a prolonged period (several months) without
was collected and characterized by various wet chemical methods. getting converted to other polymorphs of calcium carbonate.
Metal ion contents were confirmed by inductively coupled plasma However, when this vaterite sample was suspended in dis-
electron spectroscopy (ICPES) (Perkin-Elmer Optima 2000 DV tilled water and refluxed for just over an hour, it transformed
model). The major components of the mother liquor were found to 100% aragonite (Table 1). A similar vaterite to aragonite
to be as follows: potassium ion, 48000 ppm; calcium ion, 4.5 ppm;
transformation was observed even at room temperature
magnesium ion, 0.1 ppm; carbonate ion, 1600 ppm; pH 10.5; elec-
trical conductance 0.2 S cm-1. when the vaterite sample was equilibrated in distilled water
Crystal Characterization. The powder X-ray diffraction patterns for about one month. Aragonite samples thus isolated remai-
were recorded on a Siemens D-5000 diffractometer using Cu KR ned stable both in their dry solid powder form and under wet
Article Crystal Growth & Design, Vol. 10, No. 5, 2010 2131

Figure 1. Powder X-ray diffractograms of (a) the vaterite sample S-1, and when it was refluxed in distilled water for (b) 30 min (S-2), (c) 60 min
(S-3), (d) 75 min (S-4), and (e) 300 min (S-6).

conditions (aqueous suspension) and did not transform to active for aragonite because of the nondegeneracy of the ν3
calcite even after refluxing for several days. and ν4 bands due to the reduction in symmetry.
Interestingly, when the vaterite sample (S-1) was refluxed In our infrared measurements, the vaterite sample (S-1)
in the presence of the “mother liquor” (i.e., filtrate from displayed three characteristic peaks at 744, 876, and 1088 cm-1.
which it was isolated), it transformed to 100% calcite in Aragonite samples displayed four characteristic peaks at
about 3 h (Table 2). This transformation process did not go 700, 712, 852, and 1083 cm-1. Characteristic carbonate
through aragonite as an intermediate, as evident from pow- infrared vibrations for S-1 and its phase transformed arago-
der X-ray patterns, FTIR spectra, and SEM images of the nite samples (S-2, S-3, S-4) are shown in Figure 2. The
intermediate samples. vibration at 744 cm-1 is often used to quantify vaterite from
Characterization. Aragonite can be distinguished from a mixture of vaterite/aragonite. Figure 2B displays the
calcite and vaterite on the basis of its characteristic powder decrease in the 744 cm-1 peak intensity and the gradual
X-ray diffraction (XRD) pattern and vibrational (FTIR) appearance of 700 and 712 cm-1 peaks. As can be seen from
spectra.20,21 Figure 1 represents the powder X-ray diffraction the figure, vaterite completely transforms to aragonite after
patterns of S-1 and its phase transformed aragonite contain- refluxing in distilled water for 75 min. This result is in com-
ing products when refluxed in distilled water for different plete agreement with the powder X-ray diffraction patterns.
durations of time. X-ray diffraction patterns unambiguously Scanning electron microscope (SEM) images of pure vate-
establish S-1 to be 100% vaterite, S-4 and S-6 to be 100% rite, intergrowth of vaterite/aragonite, and pure aragonite
aragonite, and S-2 and S-3 to be mixtures of vaterite/ samples (S-1 to S-4) are represented in Figure 3. The diffe-
aragonite. Once the transformation to aragonite is com- rences in the topography become evident from their SEM
pleted in about 75 min under reflux conditions, prolonged micrographs. While S-1 displays typical agglomerated spheres
refluxing in distilled water does not alter the polymorph of vaterite, S-2 and S-3 display a mixture of spheres and
composition, and pure aragonite is isolated in each of these needles, and S-4 displays particles with only needle morpho-
cases (Table 1). Aragonite prepared at room temperature logy. Gradual transformation of vaterite to aragonite is reflec-
after equilibration in distilled water (S-8) also displays the ted in the deagglomeration of spheres to individual crystal-
characteristics X-ray diffraction patterns. No calcite char- lites and the formation of needles.
acteristic peaks are observed for any of the above samples. Polymorph transformation to calcite in the presence of
FTIR spectra of CaCO3 polymorphs display characteristic mother liquor was systematically monitored by powder
absorption bands corresponding to the C-O bond vibra- X-ray diffraction. Figure 4 represents the powder X-ray
tions, namely, symmetric stretching (ν1), out-of-plane bend- diffractograms of the original vaterite sample and its phase
ing (ν2), a doubly degenerate asymmetric stretching (ν3), and transformed calcite samples as a function of time. The gra-
a doubly degenerate in-plane bending (ν4). While three of dual phase transition from vaterite to calcite is evident from
these bands are observed for calcite and four are observed for Figure 4. The intermediate samples are completely devoid
vaterite in their infrared spectra, all six bands are infrared of aragonite, suggesting that vaterite directly transforms to
2132 Crystal Growth & Design, Vol. 10, No. 5, 2010 Sarkar and Mahapatra

Figure 2. (A) Segmented FTIR spectra (650-1200 cm-1) of (a) the vaterite sample S-1, and when it was refluxed in distilled water for (b) 30 min
(S-2), (c) 60 min (S-3), and (d) 75 min (S-4). (B) Gradual decrease of the 744 cm-1 peak of vaterite with concomitant increase of the 700 and
712 cm-1 peaks of aragonite.

Figure 3. Scanning electron micrographs of (a) agglomerated spheres of vaterite (S-1), and its phase transformed needle-shaped aragonite
products (b) S-2, (c) S-3, and (d) S-4. Intergrowth of sphere and needle morphologies due to vaterite and aragonite, respectively, is clearly visible
for samples S-2 and S-3.

calcite. This inference is further strengthened by the FTIR spheres break down to primary crystallites and get trans-
spectral analysis (Figure 5). For calcite and vaterite, the out formed to calcite, exhibiting caps and macrosteps.
of plane bending vibrations, leading to the most intense Insights into the Polymorph Control and Phase Transfor-
peak, are at very similar positions, 874 and 876 cm-1 respec- mation. In spite of the vast amount of research invested in the
tively, and thus are not used to quantify calcite from a mix- field of polymorph control by using additives during pre-
ture of calcite/vaterite. However, the gradual transformation cipitation reactions, and in the domain of biomineralization,
was monitored from the disappearance of the 744 cm-1 peak control of polymorphism is still considered as an empirical
of vaterite and the appearance of the 712 cm-1 peak for cal- process. The stabilities of the intermediate products and
cite. The complete transformation to calcite was further estab- their transformation to the next stable species according to
lished from the absence of the peak at 1088 cm-1. The SEM Ostwald’s step rule22 depend on the solubility of the miner-
images of the intermediate vaterite/calcite samples and the als. Usually, the least dense phase is formed first and trans-
fully transformed calcite are shown in Figure 6. Agglomerated forms to the next dense phase, until the densest phase, which
Article Crystal Growth & Design, Vol. 10, No. 5, 2010 2133

Figure 4. Powder X-ray diffractograms of (a) vaterite sample S-1, and when it was refluxed in the “mother liquor” for (b) 30 min (S-11),
(c) 60 min (S-12), (d) 120 min (S-13), and (e) 180 min (S-14).

Figure 5. Segmented FTIR spectra (650-1200 cm-1) of (a) the vaterite sample S-1, and when it was refluxed in the “mother liquor” for
(b) 30 min (S-11), (c) 60 min (S-12), (d) 120 min (S-13), and (e) 180 min (S-14).

is normally the most stable phase, is formed. This kinetic trans- transition23 and (ii) the solution-mediated transformation or
formation sequence follows in order of increasing thermo- dissolution-recrystallization.17 While, in the first case, the
dynamic stability. internal rearrangements of the crystal lattice occur, in the
There are two possible pathways of transformation of the second, the transformation takes place through the dissolu-
unstable polymorph into the stable forms: (i) the solid-state tion of the unstable phase and the nucleation and growth of
2134 Crystal Growth & Design, Vol. 10, No. 5, 2010 Sarkar and Mahapatra

Figure 6. Scanning electron micrographs of intermediate samples during vaterite-to-calcite transformation: (a) S11, (b) S-12, (c) S-13, and
(d) fully transformed calcite, S-14.

the more stable polymorph. Because the energies for the Scheme 1. Polymorph Transformations in Calcium Carbonatea
solid-state transformations of the metastable polymorphs
into calcite are high, the solution-mediated transformation is
the primary mechanism for polymorph transformation in
calcium carbonate.
The present study demonstrates that it is possible to trans-
form vaterite to aragonite without using any additive and
only by carefully controlling the reaction conditions. Though
we do not fully understand the mechanistic insights of the
preferential transformation to aragonite over the most stable a
Vaterite transforms to aragonite in distilled water in about 1.5 h
polymorph calcite, we believe that this transformation fol- under reflux or in about 30 days under equilibration at 25 °C. Vaterite
lows the dissolution-recrystallization pathway. The solubi- transforms to calcite in mother liquor in about 3 h under reflux or in
lity products for vaterite, aragonite, and calcite at 25 °C are about 30 days under equilibration at 25 °C. Aragonite does not convert
1.22
10-8, 4.61
10-9, and 3.31
10-9 M2, respectively.2a to calcite under any of these conditions.
From the solubility point of view, the dissolution of vaterite
particles leading to the formation of aragonite is a thermo- was found to be very low, similar to the other system. Also,
dynamically feasible process, but this transformation is not the aragonite when refluxed at 100 °C in the mother liquor
observed commonly. In a recent publication, Kitamura et al. for an extended period (4-12 h) did not undergo any further
described the precipitation diagrams of different poly- transformation. This ruled out the possibility of a major role
morphs of calcium carbonate to explain the formation of of potassium ion and chloride ion in promoting the vaterite
different polymorphs in nature.24 Solubility curves (ln AP to aragonite transformation. We carried out another experi-
versus temperature) for vaterite, aragonite, and calcite are ment in which K2CO3 was replaced by Na2CO3 during the
almost parallel to each other. Thus, in addition to solubility synthesis of vaterite. Similar phase transformation behavior
explanation, kinetic parameters can also be the alternative was observed when such vaterite was refluxed in distilled
mechanism for phase transformation. This is also corrobo- water. However, the kinetics of conversion to aragonite was
rated by the fact that the phase transformation process is slower and a trace level of calcite was detected along with
faster at elevated temperature. aragonite.
The characterization of filtrates in both cases did not Polymorph transformations go through the following
unravel the mechanistic implications of the preference of sequence of processes in calcium carbonate. Initially formed
the aragonite phase over calcite. In the case of the vaterite-to- amorphous phase transforms to crystalline vaterite phase,
calcite transformation system, the mother liquor was found which then transforms to either aragonite or calcite depend-
to contain the entire amount of added potassium and chlo- ing on the reaction conditions (Scheme 1). During the initial
ride ions and a very low amount of calcium ions (similar to stages of reaction, formation of a thick gelatinous mass is a
the solubility of aragonite in water at 25 °C), and the pH of strong indication of the presence of an amorphous calcium
the mother liquor remained almost constant (∼10.5) during carbonate phase. Typically the stable rhombohedral calcite
the process. In the case of the vaterite-to-aragonite transfor- is the final product and the other metastable polymorph,
mation system, an increase in pH from 7.1 (distilled water) to aragonite, is not observed in this sequence. In the present
10.5 was observed, and the soluble calcium ion concentration study, however, we have been able to isolate and stabilize
Article Crystal Growth & Design, Vol. 10, No. 5, 2010 2135

aragonite in its pure form. The kinetics of these polymorph (6) (a) Colfen, H. Curr. Opin. Colloid Interface Sci. 2003, 8, 23. (b) Addadi,
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