PAPER www.rsc.

org/materials | Journal of Materials Chemistry

Crystallization of calcium carbonate on polyethylene c-radiation-grafted

with acrylic acid{
Fengying Zhang,ab Zhengchi Hou,*a Kanglong Sheng,a Bo Denga and Leidong Xiea
Received 12th December 2005, Accepted 24th January 2006
First published as an Advance Article on the web 10th February 2006
DOI: 10.1039/b517550j

The use of high-density polyethylene (HDPE) films grafted with acrylic acid by c-ray irradiation
as a template to control the nucleation and growth of calcium carbonate crystals was attempted.
The morphology evolution of crystals formed from supersaturated calcium bicarbonate
solution on the grafted HDPE films was observed by scanning electron microscopy, and
the interaction between the formed crystals and the grafted HDPE films was revealed by
Fourier transform infrared spectroscopy. Results of the characterizations proved that
carboxylic acid functional groups on the grafted HDPE films significantly facilitated the
heterogeneous nucleation of calcium carbonate crystals, and the distribution of the crystals
was in congruity with that of the grafted carboxylic acid groups, as discovered by the atomic
force microscopic images. It can be concluded that radiation-induced grafting, a method for
functional modification of polymer surfaces, is also an effective means for studying
biomineralization.

1. Introduction polymers, ionizing radiation enables one to perform grafting

Organisms produce biominerals with unique shapes and pro-
perties. A typical example is a mollusc shell, which possesses
high strength and toughness, due to its layered structure of
calcium carbonate (CaCO3) in the form of calcite, aragonite,
or both, with a small amount of organic molecules.1,2 In the
biomineralization of a living creature, the inorganic crystal
growth is regulated by organic template molecules. This has
given rise to great interest in the artificial reproductions of
these attributes. Among them, biomimetically coating organic
polymers with inorganic crystals in a supersaturated aqueous
solution has been explored extensively, owing to its potential
for biomedical and industrial applications.3–6 CaCO3, the
most important building material in living biomineralizing
systems, has been utilized as a model crystal for the bio-
mineralization studies.7
It is generally accepted that polymers with polar functional
groups are favorable to heterogeneous nucleation of CaCO3
crystals in a supersaturated aqueous solution.7,8 Various kinds
of polymers, natural or synthetic, were adopted as templates
to control nucleation and growth of CaCO3 crystals.9–16 And
studies showed that chitosan, chitin, cellulose,17–20 Langmuir
monolayers,21–26 self-assembled monolayers27–30 and poly-
amide31 were of significance to the crystallization.
In this paper, we propose a new method to control CaCO3
crystal formation on a polymer substrate, which has been
grafted with selected polar groups by ionizing radiation. Due
to its ability to form reactive radicals in practically all known
a
Shanghai Institute of Applied Physics, Chinese Academy of Sciences,
Shanghai 201800, China. E-mail: houzhengchi@sinap.ac.cn
b
Graduate School of the Chinese Academy of Sciences, Beijing 100049,
China
{ Electronic supplementary information (ESI) available: ATR-IR
spectra of grafted PE substrates. See DOI: 10.1039/b517550j
on various polymers as well as on industrial products made of
polymers under a wide range of conditions (lower tempera-
tures, viscous media etc.).32,33 Radiation-induced grafting
possesses quite a few characteristics that make it superior in
constructing functionalized polymers. As we know, radiation-
induced grafting can occur even in the solid state without
structural deformation, which helps modify the chemical and
physical properties of various shaped solid substances. In
addition, by confining radiation to some region where the
radiation energy is absorbed, modification of the desired part
of a solid substance can be achieved. The size and form of the
modified area can be precisely controlled by shielding
radiation to the unwanted area. Moreover, it is possible to
control the region three-dimensionally by changing the field of
exposure and the depth of penetration that depends on the
energy of the ionizing radiation. Besides, radiation grafting can
be induced without additives, which is conducive to maintain-
ing the purity of materials. As a versatile means, radiation-
induced grafting is able to introduce various functional groups
into different polymer materials by using selected monomers,
which facilitates the study of how chemical structures control
the heterogeneous nucleation and growth of inorganic crystals.
A deeper understanding of the mechanism will lead to a higher
degree of control over synthetic materials, which might
therefore result in superior material properties.
In the present study, HDPE films were grafted with acrylic
acid by 60Co c-ray irradiation. CaCO3 crystal formation on the
grafted HDPE films in a supersaturated calcium bicarbonate
[Ca(HCO3)2] solution was examined using atomic force
microscopy (AFM), scanning electron microscopy (SEM),
X-ray diffraction (XRD) and Fourier transform infrared
spectroscopy (FTIR). The mechanisms of the formation of
CaCO3 crystals on the grafted HDPE films as a template
were discussed.

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2. Experimental
2.1 Preparation
Grafting of acrylic acid onto HDPE films by c-ray
irradiation. HDPE films of about 45 mm thick were prepared
in a thermo-extruding process. Acrylic acid (AAc) was
purchased from Shanghai Chemical Reagents Corp. The
AAc contains 0.05 wt% hydroquinone, but was used without
further purification, since hydroquinone has a negligible effect
on the grafting process.34 An HDPE film of 15 cm 6 4 cm was
washed with acetone, ethanol and distilled water successively
before it was put into a glass ampoule containing 85 ml of
5.0 wt% AAc aqueous solution as shown in Fig. 1. The used
grafted HDPE film is reasonably large to ensure that all the cut
slices used in subsequent experiments are obtained from the
same experimental conditions and thus the experimental
results are comparable. The glass ampoule was deaerated with
bubbling N2 gas for 5 minutes before it was irradiated by 60Co
c-rays at room temperature to 15 kGy at a dose rate of
0.269 Gy s21. The grafted film was washed thoroughly with
distilled water to extract residual monomer and homo-
polymer, and vacuum-dried at 60 uC until no further weight
loss could be observed. The degree of grafting was determined
by the weight increase of the grafted films:
Degree of grafting (%) = (W2W0)/W0 6 100% where W0
and W represent the weight of the initial film and grafted film,
respectively.
Nucleation and growth of CaCO3 crystals on grafted HDPE
films. The supersaturated Ca(HCO3)2 solution was prepared as
follows.35 An aqueous suspension of CaCO3 was first placed in
a beaker with a magnetic stirrer. While stirring, carbon dioxide
(CO2) gas was bubbled into the system at room temperature
for 6 hours. The suspension was then filtered and the filtrate
was bubbled with CO2 gas for another hour to dissolve all
remaining crystals. The pH value of the obtained super-
saturated solution was about 6.0.
The sliced grafted HDPE films (1 cm 6 1 cm), and the
control films (ungrafted HDPE films), were suspended in the
supersaturated Ca(HCO3)2 solution to see whether CaCO3
crystals would form on the film surfaces. We noted that one
surface of the grafted films was marked (because both surfaces
were grafted) and set face-down in the supersaturated solution
so that the possibility of deposition of precipitates from
homogeneous nucleation of CaCO3 crystals was non-existent
Fig. 1 Ampoule with PE film submerged in AAc solution.
1216 | J. Mater. Chem., 2006, 16, 1215–1221
on this surface. If crystals were found on the marked grafted
HDPE surface, they would be crystals grown on the surface.
At regular intervals of the experiment (every day), the soaked
films were taken out, purged ultrasonically in water to
remove any residue, and vacuum-dried at 60 uC for their
characterizations.
2.2 Characterization
A pH meter (Orilon 868, Orilon Corp.) was used to measure
the pH value of the solution. The surface chemical structures
of the HDPE films before and after c-radiation grafting were
characterized by Fourier transform infrared attenuated total
reflection spectroscopy (ATR-IR: Avater 360, Nicolet Corp.).
The chemical structure of the composite films was detected by
FT-IR in transmitted mode. Distributions of the polar
functional groups on the grafted films were studied by AFM
(Nanoscope III a, Veeco Instruments Inc.) under ambient
conditions in contact mode. Morphology of the CaCO3
crystals formed was analyzed by SEM (LEO 1530VP, LEO
Corp), with the sample surface having been sputtered with a
layer of gold. In addition, the films were examined by XRD
(B/max 2550A, Rigaku Corp.) to study the phase of the CaCO3
crystals. Cu-Ka rays were used in the XRD characterization
and the 2h angles were measured at a scan rate of 2u min21.
3. Results and discussion
3.1 Characterization of grafting
Similar to biomineralization, heterogeneous nucleation of
CaCO3 crystals is crucial for their successful growth on
grafted HDPE films, because only heterogeneous nucleation
may produce strong bonds at the interface between the
polymer substrates and mineral crystals.17 Thus the challenge
in biomimetic growth of CaCO3 crystals is how to design a
system to promote heterogeneous nucleation of CaCO3
crystals. It has been proven that the existence of carboxyl
groups on polymer surfaces can regulate the crystallization of
CaCO3.31–36 In this study, AAc was chosen to be grafted onto
HDPE films. The enhanced concentration of carboxyl groups
on the grafted HDPE surfaces would increase the HDPE
surface energy, which could be the driving force for hetero-
geneous nucleation of CaCO3 crystals.37
Radiation-induced grafting of AAc onto polyethylene (PE)
films has been extensively studied.38–40 The graft reaction can
be schematically shown in Scheme 1.
Scheme 1 Radiation-induced grafting of acrylic acid onto poly-
ethylene films.
This journal is ß The Royal Society of Chemistry 2006
 It is believed that graft copolymerization induced by c-rays
under the conditions of this article (with dose less than 20 kGy)
would not affect the bulk properties of the PE substrate.41
Fig. 2 shows the ATR-IR spectra of the HDPE films before
and after grafting. The IR spectrum of the grafted HDPE
film presenting a new peak at 1716 cm21 due to the carbonyl
stretching absorption of the carboxyl group and a broad
band at y3300 cm21 due to the hydroxyl stretching absorp-
tion indicates that AAc has been grafted onto the HDPE
films. The degree of grafting is 9%, determined by gravimetric
analysis.
The morphological or topological changes of the HDPE
films produced by radiation-induced graft polymerization have
not been directly investigated to any appreciable extent. This
may be partially due to experimental difficulties inherent to the
use of scanning or transmission electron microscopic techni-
ques for these purposes.42 By using AFM in contact mode, the
distribution of the grafted polar polyacrylic acid (PAA) chains
on the non-polar surface of the HDPE film can be studied
since the tip is subject to a larger friction force at the polar Fig. 3 Images of the HDPE films’ surface before and after grafting:
groups than at the non-polar groups.43,44 Fig. 3 shows the (a) control sample; (b) HDPE film grafted with acrylic acid; left:
AFM images of the HDPE surfaces before and after grafting. topography image; right: friction image.
By comparing the friction images with the corresponding
topography images, it can be found that the frictional radiation-induced grafting on the heterogeneous nucleation
differences are not caused by topography. Thus the features and growth of CaCO3 crystals.
shown in the friction images should originate from the local
chemical contrast. 3.2. Characterization of crystal formation on HDPE film
Compared to the surface of the control sample, there is an surfaces
obvious increase in fibrous features on the grafted surface. It
suggests an uneven distribution of graft chains on the HDPE The crystallization of CaCO3 was controlled thermodynami-
film surface, which is in agreement with the previous research cally by the following equilibrium.
result that a degree of grafting less than 10% causes an uneven
distribution of graft chains on PE film surfaces.38 Usually,
PAA is distributed on the PE surface as granular formations
According to the nucleation and growth theory,45 to form a
when the degree of grafting is low, and when the degree of
new nucleator, the activation energy (DGN) must be overcome.
grafting is close to 10%, the growing PAA grains join together,
DGN can be expressed as: DGN = 16pDG1)3/3(DGB)2 and DGB =
and a compact coating with few defects is formed, where
kTln S, where DG1 is the energy that is needed to form a new
defects are due to the unreacted HDPE on the film surface.
interface as a new phase has grown from the unstable
The uneven distribution is favorable to clarifying the effects of
subphase, which in the current article refers to the super-
saturated Ca(HCO3)2 solution. DGB is the energy released in
the formation of bonds in the bulk of the aggregation and is
a function of the supersaturation of the solution S, the
Boltzmann constant k, and the temperature T. Thus, the
decrease of DG1 or the increase of the supersaturation S can
decrease the activation energy for the nucleation of CaCO3
crystals. Usually, an increase of the supersaturation for the
bulk solution by loss of water and/or CO2 causes homo-
geneous nucleation of CaCO3 crystals. Once a foreign body or
surface (grafted HDPE) is introduced to the supersaturated
solution, heterogeneous nucleation will take place more readily
than homogeneous nucleation since an increase in the amount
of surface carboxyl groups will result in enhancing the polymer
surface energy, i.e. the nucleation of CaCO3 crystals occurs in
the chemical microenvironments near the PAA chains grafted
on the HDPE films. In these microenvironments, there
emerges an organic–inorganic interface region, where more
Fig. 2 FT-IR spectra of the HDPE films: (a) control sample; (b) Ca2+ and CO322 ions are enriched. Therefore, the super-
grafted with AAc. saturation of CaCO3 in this region is obviously higher than

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that in the bulk solution, which in turn leads to a facile
nucleation of CaCO3 crystals due to a decrease of the
activation energy DGN. Generally, heterogeneous nucleation
can take place at a comparatively lower degree of super-
saturation than is required for homogeneous nucleation17 and
results in a selective growth of CaCO3 crystals on polymer
surfaces. Heterogeneous nucleation can occur alone or
together with homogeneous nucleation depending on the
experimental conditions such as the bulk supersaturation. If
the induction period of homogeneous nucleation is reduced
to a very short time, the influence from heterogeneous
nucleation may be weakened. Therefore, a suitable bulk
supersaturation should be chosen to avoid CaCO3 precipitates
on the surface of ungrafted HDPE films and highlight the
role of the template.
In the control experiment, CaCO3 crystals were not found
on the original HDPE surface. Fig. 4 shows the SEM images of
the surface of HDPE films grafted with AAc which were
soaked in the supersaturated Ca(HCO3)2 solution for different
intervals. Fibrous CaCO3 deposits loomed up after 2 days on
the grafted surfaces. This feature was more apparent after
5 days. It can be found that the fibrous precipitates grow in a
serpentine fashion and are fairly uniform in thickness, with a
diameter of about 20 nm. The fact that crystals appeared only
on some locations on the films implied that the nucleation of
CaCO3 crystals is initiated by PAA chains grafted on the
HDPE films and the serpentine fashion results from the
distribution of the functional groups on the HDPE surfaces.
From the point of molecular recognition, the distribution and
size of different groups have affected the magnitude and
shapes of the CaCO3 crystals formed.31 With the lapse of time,
the stacked aggregates composed of bundles and patches of
CaCO3 crystals appeared and spread across the whole surfaces
gradually. The overgrowth is speedier than the fibrous
precipitates. Obviously, the precursory fibrous precipitates
Fig. 4 Micrographs of the surface of grafted HDPE films soaked in supersaturated calcium bicarbonate solution for different periods of time.
1218 | J. Mater. Chem., 2006, 16, 1215–1221
influence the following growth (overgrowth) of CaCO3
crystals, because when particles of specific shapes are formed,
the activation energy for crystallization is further decreased,
and the growth of CaCO3 crystals becomes easier.21
The crystallization process observed on the grafted HDPE
films differed significantly from our previous experiments with
chitosan films46 under the same conditions except for the
presence of a low molecular weight PAA (Mw = 2000) in the
supersaturated Ca(HCO3)2 solution in the latter case, where a
much denser calcite coating was formed on the chitosan film,
and the time required for the nucleation of CaCO3 crystals
was longer (more than 10 days). From the contrast, it can be
deduced that the carboxylic functional groups on the grafted
HDPE films in this study are not as compact as the functional
groups on chitosan films and the carboxyl groups are more
effective for the nucleation of CaCO3 crystals than the
hydroxyl groups and/or the amino groups on chitosan films.
Furthermore, the faster overgrowth of CaCO3 crystals under
the conditions described in this article should be ascribed to the
absence of soluble polymers which can inhibit the crystal-
lization process.47
In order to illustrate further the information on the chemical
interaction of the formed CaCO3 crystals and the grafted
HDPE films, FT-IR spectroscopy measurements were taken
(Fig. 5 and Fig. 6) of the grafted HDPE films before and after
soaking in the supersaturated Ca(HCO3)2 solution respec-
tively. It can be seen in Fig. 5 that the intensities of the
absorption bands at y872 cm21, which are attributed to the
stretching mode of the (CO3)22 ions, increase with soaking
time. The above results mean that the CaCO3 crystals were
formed on the surface of grafted films and the amount of
CaCO3 crystals increased with the soaking time. Furthermore,
it can be found that the carbonyl stretching absorption shifts
from y1716 cm21 to y1708 cm21 and the red-shift amount is
about y8 cm21. In addition, the intensities of the absorption
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Fig. 5 FT-IR spectra of grafted HDPE films soaked in super-
saturated calcium bicarbonate solution for different periods of time.
Fig. 6 FT-IR spectra of grafted HDPE films soaked in super-
saturated calcium bicarbonate solution for 0 and 9 days.
bands around 1550–1600 cm21, which can be assigned to
–COO–Ca, increase with the soaking time. For a grafted
HDPE film with a higher grafting degree, about 50%, the
absorption bands around 1550–1600 cm21 become more
obvious and increase with the incubation time (see ESI{).
These two phenomena may be explained by the complexa-
tion between Ca2+ ions and carboxylic acid groups on the
grafted HDPE films,48 as it is widely believed49–53 that –COO2
groups existing along the PAA backbone have a substantial
tendency for complexation of Ca2+ ions. It can be concluded
that carboxylic acid groups existing on the grafted HDPE
films may be involved in the CaCO3 crystallization process at a
molecular level.
The polymorph of the crystals was determined by XRD,
since in nature, CaCO3 exists in three polymorphs: calcite,
vaterite and aragonite.9 The XRD patterns (see Fig. 7) of these
crystals showed sharp peaks at 2h = 29.5u, 39.6u and 48.2u,54
which accords with the features of calcite. Obviously, forma-
tion of the calcite owes to the existence of carboxylic acid
This journal is ß The Royal Society of Chemistry 2006
Fig. 7 XRD patterns of grafted HDPE films soaked in super-
saturated calcium bicarbonate solution for different periods of time.
groups (–COOH) on the grafted HDPE films’ surfaces. The
intensities increased with the incubation time, which is in
agreement with the above mentioned FT-IR results (Fig. 5). It
is worth noting that the first available XRD (2 days) result
indicates that the polymorph of the formed crystals is calcite.
In other words, we did not find evidence of the existence of
amorphous CaCO3 (ACC). As far as we know, there are two
pathways for the formation of critical nuclei, i.e. one-step
formation of crystalline nuclei and multi-step formation of
nuclei.21 For the multi-step crystallization of CaCO3 crystals,
the formation of calcite crystals takes place through the
transformation of a transient amorphous CaCO3 phase.
Although the presence of ACC was not recognized in our
products, it is believed that amorphous CaCO3 should exist as
a precursor because the activation energy required for the
multi-step process may be lower than that for the one-step
process.21 The strategic forming of crystalline aragonite or
calcite via a transient amorphous CaCO3 phase is widespread
in nature.55–58 The difficulty in detecting ACC comes from
the fact that amorphous CaCO3 is a metastable phase
that rapidly transforms into crystalline polymorphs—calcite,
vaterite, or aragonite—when formed in vitro from highly
saturated solutions14 and the fact that it often coexists with
crystalline forms.59
3.3. Mechanism
The above results indicate that the use of the grafted HDPE
film as a template remarkably lowers the activation energy
required for heterogeneous nucleation of the CaCO3 crystals
from a supersaturated Ca(HCO3)2 solution, whereby the
heterogeneous nucleation is critically dependent on carboxylic
acid functional groups existing on the grafted HDPE surfaces.
Based on the above discussions, a possible mechanism for
the crystallization of CaCO3 on HDPE films c-radiation-
grafted with AAc could be explained as follows. Since the
dissociation constant of AAc is 4.5, the carboxylic acid
groups on the grafted HDPE film surfaces are mainly in the
form of carboxylate (–COO2) ions when the pH of the
solution is about 6.0.60 Therefore, the presence of negatively
charged groups on the grafted HDPE films will increase the
J. Mater. Chem., 2006, 16, 1215–1221 | 1219
electrostatic interaction between the grafted films and calcium
ions (Ca2+). Hence, more and more cations are attracted onto
the substrate surfaces. The Ca2+ ions are anchored along
the PAA chains existing on the grafted HDPE films both
through electrostatic attraction and through chelation between
the carboxylic acid functional groups and the Ca2+ ions.
Subsequently, the anions (CO3)22 are attracted to the region
where the concentration of Ca2+ is high. Consequently, the
high local supersaturation of Ca(HCO3)2 solution (higher than
the bulk supersaturation) leads to the heterogeneous nuclea-
tion of CaCO3 crystals. The nucleation occurs preferentially on
high-density COOH-terminated regions, and does not occur
on the CH3-terminated areas which are not covered with PAA
chains. Therefore, the space for mineral deposition is confined
by the distribution of the functional groups. The polymorph
and orientation of the formed CaCO3 crystals might be
controlled by the match between the conformation of the
carboxylic acid groups and the crystal lattice of calcite.36 As is
well known, the crystallization process involves two major
phases: nucleation and growth.45 The growth of the crystal
following nucleation is much easier because once the nucleus is
formed, the activation energy required for further growth of
the crystal becomes lower.21 The morphology of the over-
grown CaCO3 crystals in this study is mainly induced by the
precursory precipitates of CaCO3 instead of the grafted
surfaces.
4. Conclusion
We have used radiation-induced grafting as a new methodo-
logy to probe the possibility of preparing specially designed
surfaces for the growth of inorganic crystals (e.g. CaCO3
in this work) and shown that using the grafted HDPE films
as a template remarkably reduced the activation energy
required for heterogeneous nucleation of CaCO3 crystals
from a supersaturated Ca(HCO3)2 solution. The hetero-
geneous nucleation depends critically on carboxylic acid
functional groups on the grafted HDPE surfaces. We believe
that radiation-induced grafting shows promising potential
for studies on organic–inorganic composites with high
performance.
Acknowledgements
We thank Dr Jinlong Gong, Dr Jun Hu and Dr Yi Zhang for
their guidance on SEM and AFM experiments. Thanks to
Prof. Side Yao, Dr Yin Ye and Dr Hengdong Wang for their
constructive suggestions. This study was financially supported
by the ‘‘Discipline Forefront Project’’ of SINAP, CAS.
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