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Journal of Crystal Growth 279 (2005) 439–446


www.elsevier.com/locate/jcrysgro

On the crystallization of calcium carbonate modulated by


anionic surfactants
Hao Weia, Qiang Shenb,1, Ying Zhaoa, Yong Zhoua, Dujin Wanga,c,, Duanfu Xua
a
State Key Laboratory of Polymer Physics and Chemistry, Joint Laboratory of Polymer Science and Materials, Institute of Chemistry,
Chinese Academy of Sciences, Zhongguancum, Beijing 100080, China
b
Key Laboratory for Colloid and Interface Chemistry of Education Ministry, Shandong University, Ji’nan 250100, China
c
Key Laboratory of Engineering Plastics, Joint Laboratory of Polymer Science and Materials, Institute of Chemistry,
Chinese Academy of Sciences, Beijing 100080, China
Received 7 November 2004; accepted 25 February 2005
Available online 7 April 2005
Communicated by M. Schieber

Abstract

Crystallization experiments of calcium carbonate (CaCO3) in the presence of different anionic surfactants are carried
out by rapidly mixing CaCl2 with Na2CO3 in aqueous solutions. The selected anionic surfactants are sodium
dodecylsulfate (SDS), sodium dodecylsulfonate (DDS), and sodium dodecylbenzenesulfonate (SDBS), respectively. The
concentration and the head group of the anionic surfactants intensively influence the crystalline phase and morphology
of the precipitated crystals. When the concentration is as low as 0.05 mM, the crystal particles obtained in the presence
of all the investigated anionic surfactants are rhombohedral calcite crystals. As the surfactant concentration is increased
to 0.5 mM, vaterite crystals are produced in SDBS system, while for SDS and DDS systems, there is no obvious change
both for the crystalline phase and morphology of CaCO3. As the surfactant concentration is further increased to as high
as 5 mM, vaterite particles are produced in SDBS system, and hollow-spherical calcite crystals obtained in the presence
of SDS, whereas rhombohedral calcite crystals in DDS system. Possible formation mechanism of different CaCO3
polymorphs from different anionic surfactants solutions is proposed based on the experimental results.
r 2005 Elsevier B.V. All rights reserved.

PACS: 81.10.Dn; 81.10.h; 82.70.y; 83.80.Pc

Keywords: A1. Anionic surfactants; A3. Controlled crystallization; B1. Calcium carbonate

Corresponding author. Tel.: +86 10 82618533;


1. Introduction
fax: +86 10 82612857.
E-mail addresses: qshen@sdu.edu.cn (Q. Shen),
Biological materials have unique structures and
djwang@iccas.ac.cn (D. Wang). morphologies, which acquire much better perfor-
1
Also for correspondence. mance than the relatively crude minerals. More

0022-0248/$ - see front matter r 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2005.02.064
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440 H. Wei et al. / Journal of Crystal Growth 279 (2005) 439–446

than 60 kinds of inorganic minerals have been As widely and efficiently used processing ad-
found in various organisms. For example, the ditives in industrial end products, anionic surfac-
calcium carbonate (CaCO3)/protein hybrids in tants aroused the particular interest in the
mollusk shells have superior mechanical proper- crystallization process of inorganic species. In
ties, which arouse scientists great interest in recent years, people have made great progress on
understanding the natural biomineralization pro- the investigation of the effect of anionic surfac-
cess [1]. As we know that CaCO3 is one of the most tants on crystallization process and controlled-
commonly mentioned biominerals and has poly- polymorph of inorganic materials [6,7]. It is a
morphs of calcite, aragonite, and to the lesser common sense that anionic surfactants can influ-
extent of amorphous state, vaterite or monohy- ence one or several crystallization steps (nuclea-
drate in calcareous structures of organisms [2]. The tion, crystal growth, aggregation) and, as a
size and aggregation state of these polymorphic consequence, can control the formation of crystal
species are quite different for various natural phase, which are not usually formed under natural
biominerals, possibly owing to the controlling environments. However, difficulties in understand-
effect of organic matrix over the morphology, ing the role of anionic surfactants on the crystal-
composition and spatial organization of CaCO3 lization behavior of inorganic species arise not
crystals. only because of theoretical problems in the
A number of studies have been carried out to thermodynamic treatment of solid–liquid systems
elucidate the effect of various organic molecules on but also because of the ability of surfactants to
the crystallization of CaCO3 [3,4]. Recently, it is form a variety of supramolecular structures
reported that the mechanism of the interaction of (micelles, vesicles, etc.) in solutions [8]. It is
CaCO3 with organic molecules depends on the therefore the aim of this paper to compare the
size, ionic charge, and structure of the additives influence of three surfactants with same hydro-
[5]. Small molecules with high charge density are phobic alkyl chains but different head groups on
preferentially believed to interact electrostatically the crystallization habit of CaCO3, and especially
with charged lateral faces and high-energy tips of to study the effect of surfactant concentration on
the growing crystals, while rigid polymers require a the variation of crystalline phases of CaCO3. The
structural fit with the ionic structure of a particular schematic structures of the anionic surfactants
crystal face for efficient interaction. used are shown in Fig. 1.

H2 H2 H2 H2 H2 H2
C C C C C C OSO3Na
H3C C C C C C
H2 H2 H2 H2 H2
(a)

H2 H2 H2 H2 H2 H2
C C C C C C SO3Na
H3C C C C C C
H2 H2 H2 H2 H2
(b)

H2 H2 H2 H2 H2 H2
C C C C C C SO3Na
H3C C C C C C
(b) H2 H2 H2 H2 H2

Fig. 1. Schematic structures of the three surfactants used for CaCO3 crystallization. (a) SDS, (b) SDBS and (c) DDS.
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H. Wei et al. / Journal of Crystal Growth 279 (2005) 439–446 441

2. Experimental procedure synthesized CaCO3 crystals is operated at the


accelerating voltage of 200 kV on a JEOL 2010
2.1. Reagents transmission electron microscope. The X-ray
diffraction (XRD) measurements are conducted
All the chemicals, including calcium chloride using a Rigaku D/max-2400 powder X-ray dif-
(CaCl2, 499%), sodium carbonate (Na2CO3, fractometer with Cu Ka radiation (40 kV,
99.95%), sodium dodecylsulfate (SDS) (499%), 120 mA), and 0.021 step and 2 theta range of
sodium dodecylbenzenesulfonate (SDBS) (499%), 201–601 are selected to analyze the crystal structure
and sodium dodecylsulfonate (DDS) (499%) are and crystal orientation. Micro-IR spectral mea-
of the analytical grade and used without further surements are performed on a Nicolet Magna-750
purification. Doubly deionized water is used to IR spectrometer, with scanning times of 100, and
prepare aqueous solutions of CaCl2 and Na2CO3 resolution of 4 cm1. The surfactant content in the
just before crystallization experiment. In all the prepared CaCO3 crystals is tested by thermogravi-
reaction systems, surfactant solutions are only metric analysis (TGA) using a Netzsch Sta409
added into Na2CO3 solution before mixing with TGA analyzer, purged with nitrogen gas.
CaCl2 solution.

2.2. Crystallization procedure and subsequent 3. Results


treatment of CaCO3 crystals
According to current models of crystal growth,
CaCO3 crystals are precipitated by the method the nucleation mechanism depends on the
of quickly pouring aqueous solution of CaCl2 supersaturation of the solution [9]. Söhnel and
(0.1 M, 100 mL) into a 300 mL beaker containing Mullin suggested that in CaCO3 crystallization
aqueous solution of Na2CO3 (0.1 M, 100 mL), experiments, at low supersaturations nucleation is
which is stirred at a constant rate of 200 rpm by a predominantly heterogeneous, whereas at high
teflon-coated magnetic stirring bar. The mixing supersaturations homogeneous nucleation became
solution is then continuously stirred at the same predominant [10]. As we reported before [11], in
frequency to minimize the heterogeneous nuclea- fast-reaction crystallization experiments, the nuclei
tion at the glass wall, and this process lasted 10 h of amorphous CaCO3, the most instable solid-
to allow further crystal growth by Ostwald state phase, are initially obtained, and then
ripening. In the process of precipitation and aggregate and transform to calcite or vaterite or
incubation, the reaction systems are all kept at the mixture of both, depending on the reactants
26 1C70.2 1C in a thermostatic bath and at a concentration and the additive varieties [12,13]. As
constant pH value of ca. 7.0. After the crystal- same as the control system, only the calcite is
lization experiment, the obtained CaCO3 crystals obtained in all three anion surfactant system at the
are filtered through cellulose nitrated/acetate low concentration 0.05 mM, which is proved by
membrane filters (0.2 mm), and subsequently rinsed XRD and IR analysis.
three times with doubly deionized water, then However, the different kinds of anion surfac-
dried in vacuous desiccator at room temperature tants and higher concentration led to the various
for at least 24 h. morphology and crystalline of CaCO3. Despite
that XRD (not shown in this paper) data suggest
2.3. Characterization of CaCO3 crystals pure calcite are obtained both in DDS and SDS
system at 0.5 and 5 mM, the SEM images shown in
All samples are Au-coated prior to be examined Fig. 2 indicated the obviously different morphol-
by a Hitachi S-4300 scanning electron microscope ogy. For the DDS (Fig. 2a and b), it is very clear
(SEM), fitted with a field emission source and there is not obvious change in morphology except
operated at an accelerating voltage of 15 kV. the narrower size distribution. An interesting
Selected area electron diffraction (SAED) of the phenomenon is that more smooth crystal face is
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442 H. Wei et al. / Journal of Crystal Growth 279 (2005) 439–446

Fig. 2. SEM micrographs of CaCO3 crystals prepared from anion surfactant solutions: (a) DDS, 0.5 mM, (b) DDS, 5 mM, (c) SDS,
0.5 mM and (d) SDS, 5 mM.

obtained at the higher concentration than at low tion is 0.5 mM, the crystal edge gradually becomes
concentration. illegibly and the average crystal size decreases
Compared with the crystals prepared from DDS (Fig. 3a). As the concentration of SDBS rises up
system, both the crystal shape and the crystal size to 1 mM (Fig. 3b), a few amount of spherical
changed greatly with the variation of SDS particles with size range of 2–6 mm emerged, but
concentrations. When SDS concentration is rhombohedral calcite is the predominant compo-
0.5 mM, mixture-shaped particles with averaged nent. When the SDBS concentration increased to
size of 3–4 mm are obtained (Fig. 2c), which 3mM, more spherical particles are produced,
contain regularly rhombohedral crystal and irre- meanwhile, the fraction of rhombohedral particle
gular spheres with rough surface. Higher magni- decreased and more spherical particles are formed
fication image (Fig. 2c, inserted) reveals that the (Fig. 3c). When the SDBS concentration is as high
irregular spheres are composed of many little as 5 mM, rhombohedral particles vanished, and
rhombus slabs with length of 100–300 nm. Surpris- only spherical particles are observed (Fig. 3d).
ing results are obtained for SDS ¼ 5 mM system Fig. 4 showed the typical XRD curves and
(Fig. 2d). The rhombohedral crystals disappeared FT-IT spectra of precipitated CaCO3 in the
and monodispersed hollow-spherical particles with presence of SDBS with different concentration.
average size of 3–4 mm are obtained. Magnified Because there is no signal for amorphous CaCO3
picture shows that the hollow sphere with an and aragonite crystal, Rao’s equation is used here
opening hole is composed of very small crystallites. to express the relative fraction (fv) of vaterite in the
It should be pointed out that higher SDS crystalline phase [14]:
concentration led to the formation of smaller
I 110v þ I 112v þ I 114v
crystal. fv ¼ . (1)
I 110v þ I 112v þ I 114v þ I 104c
Different from the CaCO3/DDS and CaCO3/
SDS systems, the change of SDBS concentration The subscripts v and c indicate vaterite and
results in both the morphological and crystalline calcite, respectively. The relative content of vater-
changes of CaCO3 crystals. As SDBS concentra- ite (fv) and the crystallite size of both calcite and
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H. Wei et al. / Journal of Crystal Growth 279 (2005) 439–446 443

Fig. 3. SEM micrographs of CaCO3 crystals prepared from SDBS solutions of different concentration: (a) 0.5 mM, (b) 1 mM, (c)
3 mM and (d) 5 mM.

Fig. 4. XRD (left) and FT-IR (right) results of CaCO3 crystals obtained from SDBS solutions of different concentration: (a) 0.05 mM,
(b) 0.5 mM, (c) 1 mM, (d) 3 mM and (e) 5 mM.

vaterite obtained from different concentration of increases to 0.5 mM, a weak diffraction peak of
SDBS are listed in Table 1. It is easily concluded vaterite is observed, and the crystallite size of 104
that the percentage of vaterite increases linearly lattice face is decreased to 63 nm. FT-IR spectra
with the increase of SDBS concentration. also proved the existence of vaterite (745 cm1). As
At the lowest concentration (0.05 mM) of the concentration is continuously increased, both
SDBS, the corresponding XRD and FT-IR the percent of vaterite and the size of crystallite
(712 cm1) results indicate that only calcite is rise, leading the decrease of the relative content of
formed, and the crystallite size of typical lattice calcite. As the SDBS concentration reaches 5 mM,
face 104 is 65 nm. When the SDBS concentration both XRD and FT-IR results indicate that calcite
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444 H. Wei et al. / Journal of Crystal Growth 279 (2005) 439–446

Table 1 value (0.5 mM) below CMC, aggregates formed


The CMC values of three anionic surfactants
by surfactant interact with CaCO3 more inten-
Surfactant CMC/mM, in 0.1 M NaCl sively, thus inducing the formation of spherical
particles. As the surfactant concentration (5 mM)
SDS 1.5 (25 1C) [15] is larger than CMC value, micelles are formed and
SDBS 2.5 (30 1C) [16]
their surface is covered by the little nuclei though
DDS 2.5 (25 1C) [17]
the electrostatic interaction of CaCO3 and the
polar head groups of surfactant, consequently
inducing the formation of narrowly size-distribu-
could not be detected, and only vaterite crystals ted CaCO3 particles. However, the reason is still
are obtained with the crystallite size of about unclear for why hollow spheres are obtained in
20 nm. SDS system, while solid spheres in SDBS system.
At present stage we can only speculate that
‘‘bubble effect’’ of SDS in solutions maybe leads
4. Discussion the formation of hollow spheres of CaCO3. As for
SDBS and DDS, the ‘‘bubble effect’’ is not as
From the results showed above, it can be evident as SDS, so no hollow spheres are obtained.
concluded that both surfactant concentration and TGA results show that CaCO3 crystals precipi-
varieties can modulate the crystal shape, size, size tated from 5mM SDBS contains 10 wt% SDBS,
distribution as well as the crystalline phases of the while only 2 wt% SDS are included in the CaCO3
precipitated CaCO3. hollow spheres produced from 5 mM SDS (Fig. 5).
One fact is that organic additives control the The TGA results indicate that because the com-
crystallization of CaCO3 by the adsorption of plexation interaction of benzenesulphonate with
organic molecules on the nuclei and then inducing calcium ion is much stronger than that of sulphate,
the transformation of amorphous CaCO3 to SDBS molecules are easier to be included into the
calcite or vaterite [18]. The electrostatic interac- crystal lattice of CaCO3.
tions appear to govern the strength of the The crystalline phase variation of CaCO3
adsorption of organic molecules, and the stereo- obtained in the presence of different surfactants
chemical and geometric relationships of additives may be attributed to the difference of the polar
also play an important role for the expression of head groups. In the anionic surfactant/Na2CO3/
specific crystalline faces [19]. Since the growth of CaCl2 solution, the positively charged crystalline
CaCO3 crystals is controlled by surface processes
[20], their growth morphology is quite susceptible
to the aggregation state of the used surfactants, 100
(a)
which is mainly determined by the concentration
[21]. The CMC values of SDS, SDBS and DDS in
96
Weight loss / %

the presence of NaCl are listed in Table 1. At low


concentration (0.05 mM), surfactant monomers
are dispersed in bulk solution and each crystal 92
face can only adsorb several surfactant molecules,
because the concentration of CaCO3 ‘‘molecules’’
88 (b)
on the surface of specific crystal face is much larger
than that of surfactant. So the effect of the anion
surfactants on the crystal growth is neglectable. As 84
a result, well-defined rhombohedral crystals of 0 100 200 300 400 500 600
CaCO3 are obtained at low surfactant concentra- Temperature / degree
tion in all the three surfactant systems. As the Fig. 5. Thermogravimetric runs of the CaCO3 precipitation
surfactant concentration increases to a higher obtained in the presence of 5 mM SDS (a) and 5 mM SDBS (b).
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H. Wei et al. / Journal of Crystal Growth 279 (2005) 439–446 445

plane of amorphous CaCO3 nuclei are electro- formed. With the crystal growth, the DDS
statically bound onto the negative exterior of aggregates will leave the surface of CaCO3 crystal
micelles [22], which in turn control the transition plane, because of the shearing effect in the fast
of the amorphous phase to crystalline phase, stirring solution. As a result, only typical rhom-
calcite or vaterite. In order to visualizedly inves- bohedral crystals of calcite are obtained with
tigate the control effect of anionic surfactant on narrower size distribution in the system of DDS/
the crystal phase transition of CaCO3, electron CaCO3, while aggregate of smaller CaCO3 crystals
diffraction studies of CaCO3 crystal are carried are prepared from SDS system, due to the more
out (Fig. 6). Fig. 6a unambiguously shows a hydrophilic properties of –OSO 3 group.
perfect hexagonal pattern of vaterite, while Fig. 6b A comparison study of the head group structure
corresponds to a typical trigonal (rhombohedral) of DDS and SDBS shows that SDBS is more
structure of calcite. The SAED pattern of CaCO3 polarized [25], because its benzene ring accommo-
crystal obtained from DDS solution is similar to dates the polarity on the surface of the micelles,
that from SDS solution, and is not given in this making it easy for the CaCO3 nuclei to be
paper. The SAED results are in good agreement adsorbed on the SDBS micelle/bulk phase inter-
with the conclusions extracted from XRD data. face and consequently to grow into vaterite.
According to the viewpoint of Mann and co- Another possibility for the formation of vaterite
workers [23], the formation of calcite from both in SDBS system is that the existence of benzene
SDS and DDS solutions may be attributed to ring in SDBS increases the distances between two
the tridentate motif of oxygen atoms in HSO 3 neighboring head groups, which probably con-
terminated monolayers, favoring the nucleation of tribute to vaterite formation.
the (0 0 1) plane of calcite in which carbonate In order to examine the rationality of the above
anions are parallel to the plane. The different assumption, crystallization kinetics experiment is
morphology produced from SDS and DDS solu- performed in the presence of 5 mM SDS or SDBS.
tion can be attributed to the hydrophilicity The XRD and IR results (not shown in this paper)
dissimilarity of their head groups [24]. As we reveal that only calcite is produced in the system of
know, –OSO 3 group is more hydrophilic than SDS during all the crystallization process, while
–SO 3 , for –SO 
3 is easily hydrated, subsequently vaterite in the presence of SDBS. In general, kinetic
weakening the electrostatic interaction between the control is based predominantly on the modification
head groups and the CaCO3 nuclei. So, the of the activation-energy barriers of nucleation,
micelles formed by DDS only play the role of crystal growth, and phase transformation. In such
nucleation point on which the calcite nuclei are case, crystallization often proceeds by a sequential

Fig. 6. Selected area electron diffraction patterns of CaCO3 crystals obtained in the presence of 5 mM SDBS (a) and 5 mM SDS (b).
The image plane is perpendicular to the [0 0 1] zone axis.
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446 H. Wei et al. / Journal of Crystal Growth 279 (2005) 439–446

process involving structural and compositional References


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