FULL PAPER

DOI: 10.1002/asia.201300745

Tuning the Stability of CaCO3 Crystals with Magnesium Ions for the
Formation of Aragonite Thin Films on Organic Polymer Templates

Fangjie Zhu,[a] Tatsuya Nishimura,*[a] Takeshi Sakamoto,[a] Hidekazu Tomono,[b]

Hiroki Nada,*[b] Yasushi Okumura,[c] Hirotsugu Kikuchi,[c] and Takashi Kato*[a]

Abstract: Thin-film growth of aragon-
ite CaCO3 on annealed poly(vinyl alco-
hol) (PVA) matrices is induced by
adding Mg2 + into a supersaturated so-
lution of CaCO3. Both the growth rate
and surface morphology of the aragon-
ite thin films depend upon the concen-
tration of Mg2 + in the mineralization
solution. In the absence of PVA matri-
ces, no thin films are formed, despite
the presence of Mg2 + . Molecular dy-
namics simulation of the CaCO3 pre-
Keywords: biomineralization
calcium carbonate · magnesium ·
molecular dynamics · organic–inor-
ganic hybrid composites · thin films
cursor suggests that the transition of
amorphous calcium carbonate to crys-
tals is suppressed in the presence of
Mg2 + . The role for ionic additives in
the crystallization of CaCO3 on organic
·
templates obtained in this study may
provide useful information for the de-
velopment of functional hybrid materi-
als.

Introduction materials, morphological control is essential. CaCO3-based

Biogenic hard tissues are called biominerals because of their
high content of inorganic components: calcium carbonate
for invertebrates and calcium phosphate for vertebrates, in
general.[1] Biominerals have an organic–inorganic hybrid
nature and hierarchical structures.[2] A promising way to
obtain environmentally benign and functional materials is to
mimic the self-organization processes of biomineralization
and the elaborate structures of biominerals.[3]
Inspired by the observation that insoluble matrices and
soluble additives are involved in biomineralization,[4] our ap-
proach is to employ both soluble additives and insoluble
matrices to prepare organic–inorganic hybrids.[5] By using
this approach, we have developed thin-film CaCO3/organic
hybrids.[6–8] For the development of CaCO3-based hybrid
[a] F. Zhu, Dr. T. Nishimura, Dr. T. Sakamoto, Prof. Dr. T. Kato
Department of Chemistry and Biotechnology
School of Engineering
The University of Tokyo
Bunkyo-ku, Tokyo 113-8656 (Japan)
Fax: (+ 81) 3-5841-8661
E-mail: tatsuya@chembio.t.u-tokyo.ac.jp
kato@chiral.t.u-tokyo.ac.jp
[b] Dr. H. Tomono, Dr. H. Nada
National Institute of Advanced Industrial Science
and Technology (AIST)
Onogawa, Tsukuba 305-8569 (Japan)
Fax: (+ 81) 29-861-8722
E-mail: hiroki.nada@aist.go.jp
[c] Prof. Dr. Y. Okumura, Prof. Dr. H. Kikuchi
Institute for Materials Chemistry and Engineering
Kyushu University, Kasuga, Fukuoka 816-8580 (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201300745.
thin films with flat surfaces,[6a, d] periodically patterned surfa-
ces,[6b] and thin films consisting of oriented crystals[6c] have
been prepared by tuning the soluble and insoluble macro-
molecular templates.
Polymorph control, that is, selective induction of calcite,
aragonite, vaterite, and amorphous phases is also important
for the development of hybrid materials based on CaCO3.
Aragonite is thermodynamically less stable than calcite;[9]
however, it is widely used by living organisms as the build-
ing blocks for their skeletons, for example, in the nacreous
layer of bivalve shells. Thus, the induction of aragonite has
attracted attention.[10] We previously succeeded in the prepa-
ration of aragonite thin films by exploiting the cooperative
effects of magnesium ions and acidic macromolecules[7] and
by using annealed crystalline poly(vinyl alcohol) (PVA) ma-
trices as lattice-sized templates.[8] For Mg2 + , its roles for
CaCO3 thin-film crystallization on an organic polymer tem-
plate have not yet been well examined. It should be noted
that, in all of these cases, the addition of soluble acidic poly-
mers was necessary for the preparation of CaCO3 thin
films.[7, 8]
We have been interested in the role of magnesium ions in
aragonite crystallization. Some previous studies showed that
the main effects of Mg2 + on CaCO3 crystallization were the
facilitation of aragonite formation[11] and the stabilization of
amorphous calcium carbonate (ACC).[12, 13] Compared with
the Ca2 + ion in the aragonite lattice, the Ca2 + ion in calcite
is more readily substituted by Mg2 + .[14] This substitution in-
creases the solubility of calcite.[15] As a consequence, the
presence of a high Mg2 + concentration favors the formation
of aragonite, despite its lower stability.[11] ACC, which is the
precursor form of crystalline CaCO3, is thermodynamically
unstable and crystallizes rapidly in the presence of water.[16]

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The presence of Mg2 + as an additive was found to greatly
stabilize ACC and disturb its crystallization.[12, 13] For exam-
ple, in the cuticle (CaCO3/organic hybrid) of the terrestrial
crustacean, the amorphous region was found to contain
more Mg2 + than the crystalline region.[12c] Mg2 + is intimately
involved in both natural biomineralization and the artificial
synthesis of CaCO3. In nature, Mg2 + is abundant in seawa-
ter,[17] and takes part in the formation of the CaCO3 skele-
tons of marine organisms.[12a, b, 18] For example, in the teeth of
sea urchins, the distribution of Mg2 + in calcite is con-
trolled.[18] In synthetic systems, Mg2 + is extensively used as
an additive in CaCO3 crystallization for the purposes of de-
creasing the CaCO3 crystallization rate,[19] stabilizing the
amorphous precursor,[13] obtaining polymorph selectivity,[7, 20]
facilitating the development of spherulites,[13b, 21] and control-
ling the morphology of calcite.[13a, 22] In the present study, we
have examined the roles of Mg2 + in CaCO3 crystallization
on polymer templates. We have taken this approach be-
cause, in biomineralization, a macromolecular template is
essential and because Mg2 + exists in seawater. We expect
that studying the effects of ions in the presence of macromo-
lecular templates on the crystallization of minerals will be
useful for the development of new synthetic organic–inor-
ganic hybrid materials.[23]
Herein, we report on the effects of the addition of Mg2 +
on CaCO3 crystallization from supersaturated solutions of
CaCO3 containing Mg2 + on PVA matrices. Simulation stud-
ies for ACC structures in the presence of Mg2 + are also de-
scribed.
Results and Discussion
2+
Effects of Mg on the Formation of CaCO3 Thin Films
Thin films of CaCO3 were deposited on annealed PVA ma-
trices from supersaturated solutions of CaCO3 containing
Figure 2. a) Polarizing optical micrograph, b) SEM image (top view), c) SEM image (cross-section), d) IR spectrum, and e) Raman spectrum of the
CaCO3 thin films grown on PVA matrices (annealed for 10 min) in the presence of Mg2 + (5 mm).
Chem. Asian J. 2013, 8, 3002 – 3009
Tatsuya Nishimura, Takashi Kato et al.
Figure 1. Schematic illustration of approaches to the induction of thin-
film CaCO3. Approach I: Use of Mg2 + as an additive (the present study);
Approach II: Use of acidic polymer additives (our previous studies).
Mg2 + (Figure 1, Approach I). The thin films induced by
Mg2 + exhibit crossed-extinction patterns indicative of spher-
ulitic structures, when observed under crossed polarizers
(Figure 2 a). It is of interest that the ionic additive alone
(without additional polymer additives) gave thin films of
CaCO3 on the PVA matrices. In our previous normal
method to obtain CaCO3 thin films,[6–8] the cooperative
effect of organic acidic polymers, such as poly(acrylic acid)
(PAA), played an essential role (Figure 1, Approach II).
The top-view SEM images (Figure 2 b, for example) of these
thin films revealed radially aligned dendritic morphologies.
The cross-sectional SEM image (Figure 2 c) indicates that
these films are about 1 mm thick, and that each dendrite of
the spherulitic thin films consists of nanocrystals with diam-
eters in the order of tens of nanometers. The polymorph of
the thin films is aragonite, as confirmed by the IR bands of
CO32 at ṽ = 1491 (v3, asymmetric stretching mode), 859 (v2,
out-of-plane bending mode), 715 (v4, in-plane bending
mode), and 701 cm 1 (v4), together with the Raman bands of
CO32 at ṽ = 1085 (v1, symmetric stretching mode), 705 (v4),
and 206 cm 1 (librational lattice mode; Figure 2 d and e).
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 www.chemasianj.org Tatsuya Nishimura, Takashi Kato et al.

The measured magnesium content of these thin films is

(0.38  0.01) mol % MgCO3. The XRD patterns of the
CaCO3 thin films (Figure 3) also suggest that the polymorph
for the thin-film crystals is aragonite. In these thin-film

Figure 3. Out-of-plane and in-plane XRD patterns of the CaCO3 thin

films formed on PVA matrices (annealed for 10 min) in the presence of
Mg2 + (5 mm). The standard powder diffraction data of aragonite (extract-
ed from Powder Diffraction File Card No. 41-1475) are shown below.

XRD patterns, the relative intensity between the peaks is

Figure 5. a) IR spectra and b) micro-Raman spectra of CaCO3 thin films
different from the standard diffraction pattern of aragonite
grown on PVA matrices (annealed for 10 min) in the presence of Mg2 +
powder; for example, the 130 reflection is intensified in the ([Mg2 + ] = 0, 20, and 50 mm).
out-of-plane measurement. The change in relative intensity
indicates a preferred orientation during the growth of the
thin films. However, it is not clear whether the preferred
orientation is homogeneous through the thickness of the that the products in the absence of Mg2 + are principally cal-
thin films. cite. These results suggest that Mg2 + plays an essential role
No thin films form in solutions without Mg2 + (Figure 4 a in the thin-film growth of aragonite on PVA matrices. The
and d); only granular CaCO3 crystals are obtained. In con- average diameter of the spherulitic thin films decreased as
trast, Mg2 + concentrations higher than 20 mm in the supersa- the Mg2 + concentration of the mineralization solution in-
turated solution of CaCO3 also induce the formation of creased from 5 to 50 mm (Figures 2 a and 4 b and c). Surface
thin-film CaCO3 (Figure 4 b, c, e, and f) in the aragonite features of the resultant CaCO3 thin films also changed with
polymorph (Figure 5). The IR bands at ṽ = 1432 (v3), 878 Mg2 + concentration (Figures 2 b and 4 e and f). Compared
(v2), and 715 cm 1 (v4), and the Raman bands at ṽ = 1086 with the dendritic morphology of the CaCO3 thin films
(v1) and 282 cm 1 (librational lattice mode; Figure 5) imply formed with 5 mm Mg2 + (Figure 2 b), at 20 mm Mg2 + , the
surface of the deposited thin
films is composed of finer den-
drites (Figure 4 e), which are
segmented perpendicularly to
their growth directions. For the
solution containing 50 mm
Mg2 + , no dendritic structures
are observed. Instead, a con-
centric pattern is formed on
the surface of the thin films
(Figure 4 f). Some previous re-
ports showed that bulk ACC
deposited prior to the forma-
tion of CaCO3 thin films.[13b, 24]
However, in this study, we did
not observe the deposition of
bulk ACC on the PVA matri-
ces during crystallization of the
Figure 4. a)–c) Polarizing optical micrographs and d)–f) SEM images of the CaCO3 crystals grown on PVA ma- CaCO3 thin films, even at the
trices (annealed for 10 min) in the presence of 0 (a, d), 20 (b, e), and 50 mm Mg2 + (c, f). highest concentration of Mg2 +

Chem. Asian J. 2013, 8, 3002 – 3009 3004  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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(50 mm). The CaCO3 thin films induced by Mg2 + possibly
grow through the deposition of ACC particles from solution.
A time-resolved dynamic light scattering (DLS) study was
performed to follow the development of the CaCO3 parti-
cles after mixing solutions of CaCl2 and (NH4)2CO3 in the
presence of Mg2 + . These results indicate that the presence
of Mg2 + retards the growth of the CaCO3 particles in solu-
tion (Figure 6). In the absence of Mg2 + , after 35 min, the di-
ameter of the particles in the solution reached a macroscopic
size (> 1 mm) and became too large for precise measure-
ment. In contrast, the particles are about 500–600 nm in di-
ameter at 45 min in the presence of Mg2 + . In other words,
the diameter of the particles increases more rapidly in the
absence of Mg2 + .
Figure 6. Average diameter of the particles at specific time intervals after
mixing solutions of (NH4)2CO3 and CaCl2 (containing MgCl2). The mixed
solution contained (NH4)2CO3 (20 mm), CaCl2 (10 mm), and MgCl2 (0–
20 mm). The error bars indicate the standard deviation of the Gaussian
fits of the particle size distribution.
Because Mg2 + is a single atom, the steric stabilization or
depletion stabilization mechanism[25] proposed for polymer
additives is unlikely to apply to the stabilization of small
CaCO3 particles by Mg2 + . Considering that Mg2 + is
“harder” than Ca2 + , and that Mg2 + is more strongly hydrat-
ed,[26] Mg2 + ions located on the surface of the CaCO3 parti-
cles may suppress the aggregation of particles through
strengthening the hydration layers around them.
Other metal ions (Na + , Li + , Sr2 + , and Zn2 + ) were used as
additives to examine their effects on CaCO3 crystallization.
These ions were selected because they were reported either
to interact with CaCO3[22a, 27] or to be associated with the
biomineralization of CaCO3.[28] In the presence of Na + , Li + ,
or Sr2 + , few thin films are obtained and rhombohedral cal-
cites are the main products (Figure S1 a–c in the Supporting
Information). Inhibition of CaCO3 crystal growth by Zn2 + is
significant; no CaCO3 crystals form in the solution contain-
ing Zn2 + (5 mm; Figure S1 d in the Supporting Information).
Lower concentrations of Zn2 + , down to 0.25 mm, were also
examined, but only granular crystals were observed (data
not shown). These findings indicate that Mg2 + is more effec-
tive than other metal ions at inducing the thin-film state of
CaCO3 crystals.
Chem. Asian J. 2013, 8, 3002 – 3009
Tatsuya Nishimura, Takashi Kato et al.
Effects of PVA Matrices on the Formation of CaCO3 Thin
Films
PVA matrices, annealed for different times, were used to
control the thin-film growth of CaCO3. First, we examined
the effects of annealing time on the PVA matrices. The
thickness of the annealed PVA matrices before and after
swelling was measured by SEM (Figure 7). The swelling
Figure 7. Cross-sectional SEM images of swollen PVA matrices annealed
for a) 3, b) 10, and c) 30 min; scale bar = 1 mm. d) Thicknesses of the
PVA matrices before and after swelling, as measured from the SEM
images.
ratio of the PVA matrices decreases as the annealing time
increases (Figure 7 d). After swelling, the thickness of the
PVA matrices showed a 3-fold increase when annealed for
3 min (Figure 7 a), and a 1.5-fold increase when annealed for
10 min (Figure 7 b), whereas swelling was negligible when
the PVA matrices were annealed for more than 30 min (Fig-
ure 7 c). Structural changes to the matrices were character-
ized by IR spectroscopy (Figure S2 in the Supporting Infor-
mation). A new band at ṽ = 1142 cm 1 emerged after anneal-
ing. This band corresponds to the symmetric C C stretching
mode and has been reported to correlate with the crystallin-
ity of PVA.[29] The crystalline regions induced by annealing
may help increase the cross-linking of PVA, and thus, de-
crease the swelling ratio.
These PVA matrices were subsequently used for crystal
growth of CaCO3 in the presence of Mg2 + (5 mm). Birefrin-
gent aragonite thin films formed on the PVA matrix an-
nealed for 10 min, as shown in Figure 2 a. Conversely, when
PVA matrices annealed for 3 min were used (Figure 8 a),
both birefringent thin films (type 1) and partially or com-
pletely non-birefringent thin films (type 2, areas surrounded
by dashed lines in Figure 8 a) appeared. The SEM image
showed that the surface of the type 2 thin films was smooth-
er than that of type 1 thin films. The IR spectrum (Fig-
ure S3 a in the Supporting Information) of the thin films sug-
gested that both vaterite and aragonite were present be-
cause, as well as the aragonite v4 bands at ṽ = 715 and
701 cm 1, the v4 band of vaterite at ṽ = 749 cm 1 was ob-
served. Micro-Raman characterization (Figure S3 b in the
Supporting Information) indicated that the two polymorphs
were associated with different types of thin films. The type 1
thin films were characterized as aragonite from the Raman
bands at ṽ = 1085 (v1), 705 (v4), and 206 cm 1 (librational lat-
tice mode); the type 2 thin films showed a split v1 band be-
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Figure 8. Polarizing optical micrographs (left) and SEM images (right) of
CaCO3 thin films grown in the presence of Mg2 + (5 mm) on PVA matri-
ces annealed for a) 3 and b) 30 min. In the polarizing optical micrograph
of a), the numbers indicate the two different types of thin films; all thin
films of type 2 in the image are surrounded by dashed lines.
tween ṽ = 1090 and 1076 cm 1, which was indicative of vater-
ite. The PVA matrices annealed for 30 min gave only bire-
fringent thin films (Figure 8 b). The surface of these films
showed a dendritic morphology, for which each dendrite
was slightly segmented perpendicular to its growth direction.
IR characterization revealed that these thin films were ara-
gonite (Figure S3 a in the Supporting Information).
Mg2 + has been reported to induce aragonite formation.[11]
However, the results given herein suggest that vaterite is
also induced by the combined effects of Mg2 + and PVA ma-
trices on CaCO3 crystallization. We previously reported that
aragonite was formed in the crystallization of CaCO3 when
PVA was employed as the matrix.[8] We assume that the
crystalline regions of PVA matrices promote the nucleation
of aragonite. PVA matrices annealed for 3 min favor the for-
mation of vaterite; this may be because these PVA matrices
are less ordered than matrices that have been annealed for
longer times.
Other polymer matrices, chitin and chitosan, were used
for CaCO3 crystallization through the same crystallization
method. These matrices gave sporadically formed granular
crystals when Mg2 + was added to the crystallization solu-
tion.
Simulation Study on the Roles of Mg2 +
In recent studies of crystallization either with[13b, 30] or with-
out[31] additives, it was suggested that, under the supersatura-
tions typical of most experimental crystallization systems,
amorphous precursors emerged before the nucleation of
crystal phases. As the crystallization conditions employed in
the present study resemble the conditions in previous stud-
ies,[13b, 30a, c] which showed the formation of transient ACC
Chem. Asian J. 2013, 8, 3002 – 3009
Tatsuya Nishimura, Takashi Kato et al.
precursors, we assume that, in the present study, such pre-
cursors also form during the crystallization of CaCO3. Mo-
lecular dynamics (MD) simulations were employed to study
the effects of Mg2 + on ACC (Figure 9). The simulation
Figure 9. a) Illustration of the CaCO3 system used in this study. Gray,
blue, and red spheres represent Ca2 + ions and the C and O atoms of
CO32 ions, respectively. The dimensions of the system, which were ob-
tained as the time average over 0.5 ns in the NPT-ensemble simulation,
were 31.55, 31.20, and 31.04  for fMg = 0, 0.33, and 0.67, respectively.
b) The definition of q formed by the three nearest neighbor O atoms of
the CO32 ions. c) P(q) for ACC at each fMg (upper) and P(q) for calcite,
aragonite, and vaterite (lower). P(q) = 1/2sin q for the random distribu-
tion are also shown. P(q) for each of the CaCO3 crystals was obtained
from a MD simulation of each crystal at 300 K and 1 atm. The structure
of vaterite predicted from the quantum chemical calculations by Wang
and Becker was used for the simulation of vaterite.[32]
study was performed for anhydrous bulk ACC, assuming
that its structure approximates that of the real ACC precur-
sors in solution. Changes in the local structure of the bulk
ACC caused by the addition of Mg2 + were quantitatively
analyzed. Strictly speaking, the real ACC precursors in solu-
tion are hydrated. However, features of the structure of an-
hydrous ACC do not significantly change by hydration.[33]
Therefore, we assumed that the effect of Mg2 + on the struc-
ture of ACC is essentially the same for both anhydrous and
hydrated ACC.
To analyze the local structure of ACC in detail, we intro-
duced the distribution function, P(q), of the angle q into the
present study. The angle q is formed by the three nearest
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neighbor O atoms of the CO32 ions (Figure 9 b). A selected
pair of O atoms was defined as a nearest neighbor pair if
the distance between the pair was less than 3.8 . Figure 9 c
shows P(q) for ACC at each fMg. For comparison, P(q) for
calcite, aragonite, and vaterite are also shown. Many distinct
peaks appear in P(q) for the CaCO3 crystals, indicating
a strongly ordered local structure. P(q) for ACC also shows
small peaks at around q = 35, 60, and 958, indicating
a weakly ordered local structure. However, as fMg increases,
the heights of the peaks around q = 35 and 958 decrease, in-
dicating the disappearance of the weakly ordered local
structure. As a result, P(q) approaches a random distribu-
tion. Furthermore, we observed that P(q) for other q angles,
created by other atomic species, also approached a random
distribution as fMg increased. Therefore, it is concluded that
Mg2 + suppresses the formation of the ordered local struc-
ture of ACC.
We assume that the ACC obtained in this simulation cor-
responds to a part of the ACC precursors and that the for-
mation of the ordered local structures in ACC precursors ki-
netically favors the nucleation of CaCO3 crystals. Then, the
disappearance of the ordered local structure of ACC upon
the addition of Mg2 + gives us a reason for the suppression
of the nucleation of CaCO3 crystals from the ACC precur-
sors in the presence of Mg2 + , as reported previously.[12, 13]
The DLS results in the present study revealed that Mg2 +
delays the size increase of the CaCO3 particles. The results
obtained by the present simulation study also supported the
assumption that Mg2 + suppressed the crystallization of
ACC. Therefore, in the presence of Mg2 + , higher stability
can be expected for the ACC precursor particles in solution.
Conversely, PVA matrices may promote the crystallization
of CaCO3 by providing an organic template, which has been
reported to stabilize the dynamic crystalline domains and
promote the nucleation of CaCO3.[31b] The observed thin-
film state of CaCO3 could be a result of the cooperative ef-
fects of Mg2 + and the PVA matrices; in other words, be pro-
duced by the combination of the suppression of crystalliza-
tion by Mg2 + , and the promotion of heterogeneous crystalli-
zation by the PVA matrices.
Conclusion
Aragonite thin-film composites have been obtained by using
the combination of Mg2 + as an additive and PVA as
a matrix. The morphologies of the thin films depend on the
concentration of Mg2 + in the supersaturated solution of
CaCO3. The annealing time of the PVA matrices also affects
their morphologies. In our previous studies (Figure 1, Ap-
proach II), the biomimetic synthesis of CaCO3 thin films
employed the cooperative effects of polymer additives and
insoluble matrices.[5] In contrast, in the present study, we
found that Mg2 + induced thin-film formation of CaCO3 in
the presence of insoluble polymer matrices (Figure 1, Ap-
proach I), without requiring soluble polymer additives. A
simulation study on the roles of Mg2 + on CaCO3 crystalliza-
Chem. Asian J. 2013, 8, 3002 – 3009
Tatsuya Nishimura, Takashi Kato et al.
tion suggested that the order of the local structure of ACC
was suppressed in the presence of Mg2 + . In biomineraliza-
tion, the incorporation of Mg2 + into CaCO3 was reported to
be controlled by living organisms.[34] Further study of the
roles of Mg2 + in CaCO3 crystallization is of interest to de-
velop biomineralization-inspired hybrid materials.
Experimental Section
Materials
PVA (87–89 % hydrolyzed, Mw 1.5  105 to 1.9  105) was obtained from
Sigma–Aldrich Japan (Tokyo, Japan). Zinc chloride was purchased from
Kanto (Tokyo, Japan). Chitin, chitosan, and all other inorganic salts were
purchased from Wako (Tokyo, Japan). All reagents were of the highest
grade and used without further purification.
Preparation of Polymer Matrices
PVA matrices were prepared by spin coating of solutions of PVA
(4 wt %, 400 mL) in dimethylsulfoxide onto glass substrates. The matrices
were then air-dried and annealed at 180 8C. To study the swelling behav-
ior of the PVA matrices, they were soaked in deionized water for 2 h and
then freeze dried for SEM observation. Chitosan and chitin matrices
were obtained as previously reported.[6c, d]
Crystallization of CaCO3
Purified water obtained from an Auto Pure WT100 purification system
(Yamato, Tokyo, Japan) was employed for crystallization. The procedure
for crystal growth of CaCO3 followed the previous method with minor
modifications.[12a] Mg2 + or other metal ions were added to an aqueous so-
lution of CaCl2 ([Ca2 + ] = 10 mm) containing (NH4)2CO3 (1 mm). The solu-
tion was subsequently transferred into vessels containing the polymer
matrices. The vessels were placed in a closed desiccator, together with
a vial containing (NH4)2CO3 (75, 200, or 300 mg for solutions with [Mg2 +
] = 5, 20, or 50 mm, respectively). An FMU-131I incubator (Fukushima,
Tokyo, Japan) was used to maintain a constant temperature for crystalli-
zation (25 8C). Crystallization was performed for 22 h. The samples were
then taken out of the solution and air-dried for characterization. A solu-
tion obtained by the mixing of a solution containing (NH4)2CO3 (40 mm)
and a solution containing CaCl2 (20 mm) and MgCl2 (0–40 mm) was mea-
sured by DLS to examine the early stages of crystallization.
Characterization
The crystal morphology was characterized by SEM. A Hitachi S-4700
field-emission SEM instrument (Hitachi, Tokyo, Japan) was used to
obtain the SEM images. Samples were platinum-coated by using a Hitachi
E-1030 ion sputter (Hitachi, Tokyo, Japan). Polarizing optical micro-
graphs were obtained with an Olympus BX51 polarizing optical micro-
scope (Olympus, Tokyo, Japan). A Jasco FT/IR-660 Plus spectrometer
(Jasco, Tokyo, Japan) was employed to collect FTIR spectra as KBr pel-
lets. XRD measurements were performed by using a Rigaku SmartLab
X-ray diffractometer (Rigaku, Tokyo, Japan) with CuKa radiation. Raman
characterization over the spectral range of ṽ = 150–1200 cm 1 was per-
formed by using a Jasco NRS-1000 micro-Raman system (Jasco, Tokyo,
Japan) at an excitation wavelength of 514 nm. The Mg contents of the ob-
tained thin films were measured by a Thermo Scientific iCAP 6300 Duo
ICP spectrometer (Thermo Scientific, MA, USA). The time-resolved
measurements of particle size in the supersaturated solution of CaCO3
were performed at 25 8C by using a DLS-7000 spectrometer (Otsuka
Electronics, Osaka, Japan). The light source was a He–Ne laser (wave-
length of 632.8 nm).
MD Simulations
The simulations were performed for amorphous mixtures of Ca2 + , CO32 ,
and Mg2 + . The system for ACC was a cube containing 432 cations (Ca2 +
and Mg2 + ) and 432 CO32 . Three-dimensional periodic boundary condi-
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tions were imposed on the system. The fractions of Mg2 + , fMg =
NMg/ACHTUNGRE(NCa+NMg), were 0, 0.33, and 0.67, in which NCa and NMg were the
numbers of Ca2 + and Mg2 + , respectively.
For the simulation of ACC, the CaCO3 potential model proposed by
Pavese and co-workers[35] was used to estimate the interactions of CaCO3
in ACC. In this model, CO32 was treated as a polarizable flexible ion.
The interactions for Mg2 + were estimated by using the Mg2 + potential
model proposed by de Leeuw and Parker,[36] which was developed to be
compatible with the Pavese CaCO3 model. The Pavese CaCO3 model re-
produced the structures of calcite, aragonite, and vaterite.[37] The combi-
nation of the Pavese CaCO3 model and the Mg2 + model proposed by de
Leeuw and Parker reproduced the structure of magnesite.[37] Therefore,
these potential models were considered suitable for the simulation of
ACC in the presence of Mg2 + .
The initial ACC structure for fMg = 0 was obtained by using the following
method. Initially, all Ca2 + and CO32 ions were randomly arranged in the
system. An MD simulation of the NVT ensemble was performed for
a period of 1 ns with a time step of 1 fs at T = 10 000 K to accelerate the
formation of an amorphous state in the system. During this simulation,
the volume of the system was fixed, so that the density of the system was
30 % lower than that of calcite at 300 K and 1 atm. Subsequently, an MD
simulation of the NPT ensemble was performed at 300 K and 1 atm for
a period of 1 ns with a time step of 2 fs. The final structure obtained
from this simulation was used as the initial ACC structure for fMg = 0.
The computation of the Pavese CaCO3 model is time consuming. There-
fore, simulations for the creation of the initial ACC structure for fMg = 0,
which were mentioned above, were performed by using the Raiteri
CaCO3 model,[38] in which CO32 was treated as a non-polarizable rigid
body instead. The Raiteri CaCO3 model does not apply to simulations of
ACC including Mg2 + . Therefore, the initial ACC structures for fMg = 0.33
and 0.67, respectively, were created by randomly replacing 144 and 288
Ca2 + in the initial ACC structure for fMg = 0 with Mg2 + .
By using the initial ACC structure created, the Pavese CaCO3 model,
and the Mg2 + model proposed by de Leeuw and Parker, simulation of
the NPT ensemble was performed to analyze the local structure of ACC
for each fMg at 300 K and 1 atm with a time step of 0.2 fs. The system
reached an equilibrium state within 0.5 ns. Therefore, the simulation data
for the subsequent 0.5 ns period was used to analyze the local structure
of ACC.
The computation was performed with the Verlet leapfrog algorithm.[39]
Temperature and pressure were controlled by the Nos–Hoover thermo-
stat with a relaxation time of 0.1 ps[40] and the barostat proposed by Mel-
chionna and co-workers with a relaxation time of 2 ps,[41] respectively.
The Coulomb potential energy and force were calculated by using the
smooth particle mesh Ewald method.[42] DL_POLY version 2.20 was used
for the present MD simulation.[43]
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific Research (no.
22107003) on the Innovative Areas: “Fusion Materials: Creative Devel-
opment of Materials and Exploration of Their Function through Molecu-
lar Control” (Area no. 2206) from the Ministry of Education, Culture,
Sports, Science and Technology in Japan. We are grateful to Shusen Mei
and Dr. Hiroki Higuchi for their help with the DLS measurements.
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Received: June 2, 2013
Revised: July 16, 2013
Published online: September 4, 2013
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