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