Materials Science and Engineering A 477 (2008) 217–225

Amorphous calcium carbonate in form of spherical nanosized

particles and its application as fillers for polymers
K. Gorna a , M. Hund b , M. Vučak c , F. Gröhn a , G. Wegner a,∗
a Max Planck Institute for Polymer Research, 55128 Mainz, Germany
b KTC Consulting GmbH, 67434 Neustadt, Germany
c Schaefer Kalk GmbH & Co. KG, 65582 Diez, Germany

Received 28 March 2007; received in revised form 7 May 2007; accepted 9 May 2007

Abstract
The synthesis of amorphous calcium carbonate (ACC) via a liquid precursor to give spherical particles with monodisperse distribution of diameters
in the range of 0.4–1.2 ␮m has been optimized to the level to obtain multigram yields per batch. The synthesis was achieved by precipitation of
ACC from a strongly alkaline solution of calcium chloride (CaCl2 ) at ambient temperature using the hydrolysis of water soluble dimethyl carbonate
(DMC) as the internal source of CO2 .
As ACC produced by this novel method contains a small fraction of bound water a drying process, namely annealing at 200 ◦ C for 6 h was
developed. The water free powder was blended with conventional polyolefins (linear low density polyethylene (LLDPE), high density polyethylene
(HDPE), polypropylene (PP), polystyrene (PS)) in a melt extrusion process. Blending with poly(lactic acid) (PLA) as a model of a biomedically
relevant polymer was also achieved.
While a homogenous dispersion of the dried amorphous calcium carbonate (DACC) particles in the polymer composites was easily achieved,
the interaction between the polymer continuous phase and particle surface seems to be rather weak.
Consequently, the physical properties of the blends having volume fractions from 10 to 40% of the filler behave as expected for non-interacting
materials, e.g. the melt viscosity increases as predicted from Einstein’s law, the glass transition and melting temperature of the polymer matrices
remain largely unaffected. The Young’s modulus did increase while tensile strength and elongation at break decrease.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Amorphous calcium carbonate; Precipitation; Stabilization; Fillers; Compounding

1. Introduction inorganics. The properties of the resulting composite material

Calcium carbonate is extensively used as an additive or
modifier in paper, paints, plastics, inks, adhesives and pharma-
ceuticals, to mention but a few. New discoveries and refined
processes in the plastic, paper and pharmaceutical industries
call for high-end type of products consisting of particles, whose
crystalline phase, morphology, size and distribution of sizes are
strictly controlled and can be modulated according to specific
requirements.
Calcium carbonate is traditionally used in plastics as bulking
agent to substitute the expensive polymers. All properties of the
pure polymer are subject to change as a result of filling, and
in fact a new material is created by blending a polymer with
∗ Corresponding author. Fax: +49 6131379100.
E-mail address: wegner@mpip-mainz.mpg.de (G. Wegner).
are determined by the properties of the components, namely type
of polymer and filler, filler particle size, shape and modulus, the
concentration of filler in the polymer matrix and the kind of
interaction between the filler particles as well as filler particles
and polymer host [1–4]. Calcium carbonate particles of an aspect
ratio close to unity are expected to modify the viscosity of the
polymer melt. Their good thermal conductivity contributes to
the homogeneity of the melt and good dispersion in the polymer
matrix [5].
Synthetic, so-called precipitated calcium carbonate (PCC)
is commonly produced by a recarbonizing process in which
natural calcium carbonate is decomposed to calcium oxide
(lime) and carbon dioxide. Calcium oxide with water forms cal-
cium hydroxide that reacts with carbon dioxide and as a result
pure, synthetic calcium carbonate precipitates. Unfortunately,
PCC synthesized by this traditional method usually comprises
a mixture of various crystalline polymorphs with anisotropic,

0921-5093/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2007.05.045
218 K. Gorna et al. / Materials Science and Engineering A 477 (2008) 217–225
elongated particles having high aspect ratio. Particles are usu-
ally highly agglomerated and there is inadequate control over
the distribution of their sizes.
Recently, a new method to obtain amorphous calcium car-
bonate (ACC) in form of isotropic, spherical particles has been
reported [6,7]. This process makes use of the base-catalyzed
hydrolysis of dimethyl carbonate as a source of CO2 . The latter
is homogenously produced in the solution and formation of a
gas–liquid interface is avoided. This interface clearly serves as a
nucleation site for crystalline PCC and must be avoided under all
circumstances when one wants to produce ACC reproducibly.
Consequently, ACC is precipitated in a very reproducible way
as monodisperse spherical particles of sub-micrometer diam-
eter. Additionally, it has been shown that ACC is formed in
consequence of a liquid–liquid phase separation between a low
concentrated and high concentrated calcium carbonate hydrate
phase by which droplets are formed spontaneously in course of
the binodal decomposition of the supersaturated solution. The
droplets dehydrate rapidly and form colloidal particles of glassy,
hydrated ACC which is stable for a long time in the dry state.
Although preparation of the synthetic ACC from water under
various reactive conditions has been already reported [8–15],
only the method via hydrolysis of alkyl carbonate results in pure
amorphous material without any crystalline contaminations.
It is worth mentioning that ACC has received consider-
able attention in very recent years since it is believed that this
metastable material plays an important role in biological miner-
alization. As has been shown by evaluation of sea urchin larvae,
ACC is a precursor to calcite in the formation of spicules [16,17]
and it serves as a kind of storage material from which later crys-
talline calcium carbonate is formed during the moulting period
in Crustaceans [18]. One of the reasons why organisms use ACC
as the precursor in formation of calcite or aragonite is that the
disordered structure of ACC can be easily cast into any shape
and that it has higher solubility as compared to the crystalline
polymorphs [19–21] which makes it attractive as an intermediate
source of the final crystalline material.
The process of ACC synthesis via hydrolysis of alkyl car-
bonate has been well characterized and optimized with respect
to the morphology of the material but only in a diluted sys-
tem [6,7]. The use of higher concentrations of the necessary
components in this process will determine the degree of supersat-
uration at which ACC will precipitate, and this, in consequence,
will affect the properties of the final material. A higher concen-
tration of the components can also favor precipitation of other
modifications of calcium carbonate according to their solubility
product [14,22–24]. Therefore, the following questions need to
be addressed: How much can the concentration of the compo-
nents be increased in order to maximize throughput and obtain
ACC without any deterioration of its properties and to what
extent do the conditions of high concentration affect the final
material’s properties?
Once ACC can be obtained in sufficiently large amount and
quality its potential as a filler and modifier of polymers can be
investigated.
In the following study, we wish to describe how the reaction
conditions for synthesis of ACC can be optimized to repro-
ducibly enhance the yield of spherical particles of defined size
and size distribution. Since these particles contain bound water,
a stabilizing process is reported which is able to remove water
without disturbing size and shape of the particles. Finally, first
experiments characterizing these particles as additives for poly-
mers and properties of the resulting polymer/particle blends will
be reported.
2. Experimental
2.1. Synthesis of ACC
Calcium chloride dihydrate (Fluka) (CaCl2 ), dimethyl car-
bonate (Fluka) (DMC) and sodium hydroxide (Fluka) (NaOH)
were used for precipitation of ACC as described [6,7]. Shortly,
in this process CaCl2 and DMC are dissolved in MQ water
at 20 ◦ C. Solution of NaOH is prepared in a separate glass
vessel also in MQ water at 20 ◦ C. After quickly mixing both
solutions hydrolytic decomposition of DMC takes place with
release of CO2 and ACC starts to precipitate. The precipitate
is isolated from the mother liquid by centrifugation, washed in
acetone and subsequently dried in vacuum at room tempera-
ture.
The precipitation of ACC was performed at increasing con-
centration of components ranging from 10 to 100 mM. In this
work, equimolar concentrations of CaCl2 and DMC were used
in all experiments. The following code will be used to identify
materials obtained under different conditions: samples marked
as 20–30, or 30–50 refer to the materials that have been syn-
thesized using 20 mM of CaCl2 (DMC) and 30 mM of NaOH,
or 30 mM of CaCl2 (DMC) and 50 mM of NaOH, respec-
tively.
2.2. Compounding with polymers
Linear low density polyethylene (LLDPE), high density
polyethylene (HDPE), polypropylene (PP), polystyrene (PS),
and poly(lactic acid) (PLA) were used to prepare compos-
ites with ACC synthesized using 20 mM of CaCl2 (DMC)
and 30 mM of NaOH (ACC 20–30), for comparison, blends
were also made with commercially available crystalline PCC
(SCHAEFER PRECARB® 400 (Precarb 400) supplied by
Schaefer Kalk GmbH & Co. KG). Before mixing the ACC
20–30 was dried in an air-vented oven at 200 ◦ C for 6 h to
remove structural water. Dried amorphous calcium carbonate
(DACC 20–30) or Precarb 400 powders were first mechani-
cally mixed with polymer powders or pellets to achieve 10, 20
or 40 vol.% of CaCO3 in the composites. A twin-screw micro-
extruder was used for compounding the fillers with the polymers.
Pre-mixed calcium carbonate and polymer in a total amount of
5 g were fed into the extruder hopper and the composite mate-
rial was squeezed through the extruder and was collected in
the shape of bar. The operation temperature of the extruder
was 230 ◦ C for the LLDPE, HDPE, PP, and 200 ◦ C for the PS
and PLA. The extruding was performed at a screw speed of
100 rpm under nitrogen to avoid the degradation of the mate-
rial.
 K. Gorna et al. / Materials Science and Engineering A 477 (2008) 217–225
2.3. Characterization of calcium carbonate
The morphology and size of the calcium carbonate parti-
cles were characterized using a low voltage scanning electron
microscope (Leo Gemini 1530) operated at 3 kV.
IR-spectra were recorded using a Nicolet 730 FTIR spec-
trometer. Spectra of the samples dispersed in KBr powder were
recorded in the diffusive mode (DRIF). The crystal form of cal-
cium carbonate was evaluated by means of X-ray diffraction (Cu
K␣ radiation).
DSC measurements were carried out under nitrogen on a
Mettler-Toledo DSC 30S. Thermogravimetry was done under
nitrogen on a Mettler-Toledo ThermoSTAR TGA. The specific
surface area of the particles was determined by the BET method
(Micromeritics Gemini 2360 Analyser) using nitrogen adsorp-
tion. The samples were prepared for adsorption analysis by
degassing (FlowPrep 060 Degasser) at 130 ◦ C for at least 3 h.
The oil absorption was measured using diisononyl phthalate
(DINP) by the rubout test similar to EN ISO 787-5. In this test,
DINP is mixed with a sample and rubbed with a spatula on a
smooth surface until a stiff putty-like paste is formed which does
not break or separate. The oil absorption in g/100 g sample was
calculated by
DINP absorbed, g
Oil absorption = 100
sample weight, g
This value represents the quantity of oil required per unit
weight of sample particles to completely saturate the calcium
carbonate sorptive capacity.
2.4. Characterization of polymer composites
The dispersion of the particles in the polymer matrices was
visualized using a low voltage scanning electron microscope
(Leo Gemini 1530) operated at 3 kV or using a high voltage scan-
ning electron microscope (Zeiss DSM 962) operated at 15 kV.
The extruded samples were fractured in liquid nitrogen and in
the case of using the high voltage SEM, the sample surface was
sputtered with a gold–palladium layer.
Mettler-Toledo DSC 30S differential scanning calorimeter
calibrated with indium was used for the evaluation of the thermal
characteristics of the polymers and the composite materials. The
measurements were carried out under dry, oxygen free nitrogen
flowing at a rate of 40 ml/min to protect the materials from degra-
dation. The weight of samples was in the range of 15–20 mg. The
samples were first heated from 25 to 230 ◦ C, and then cooled
to 25 ◦ C and finally heated a second time from 25 to 230 ◦ C
at a rate of 10 ◦ C/min. The content of calcium carbonate in the
polymers was assessed from thermogravimetric analysis using
Mettler Toledo ThermoSTAR TGA-SDTA 851. The measure-
ments were carried out in nitrogen at temperatures in the range
of 25–800 ◦ C at a heating rate of 10 ◦ C/min.
The mechanical properties of selected composites filled
with 10 vol.% of calcium carbonate were evaluated by tensile
tests carried out on a Instron 4200 equipped with a 0.1 or
1 kN load cell operating at a cross-head speed of 10 mm/min.
For this measurement the samples in the shape of dog-bone
219
(2 mm × 15 mm × (0.16 ± 0.02) mm) were cut out from the film
prepared by melting the extruded bars in a hydraulic press at a
temperature of 180 ◦ C and under pressure of 40 kN. At least four
samples for each material were tested at room temperature.
3. Results and discussion
3.1. Precipitation of ACC from concentrated solution
ACC was synthesized according the method [6] in which car-
bon dioxide is supplied to the solution of a calcium salt (CaCl2 )
as a result of alkaline hydrolysis of dimethyl carbonate (DMC).
This method works in dilute conditions and allows to produce
ACC as very regular spheres of narrow distribution of diame-
ters. The diameter of particles oscillated around 700 nm when the
reaction was run in diluted solution at 20 ◦ C and the precipitate
was isolated after 20 min of reaction time.
The morphology of the calcium carbonate particles obtained
from solutions containing CaCl2 and DMC in a concentration
ranging from 20 to 60 mM but constant concentration of NaOH
(20 mM) are presented in Fig. 1. The average size of the parti-
cles decreased from 790 to 430 nm for the systems 20–20 and
60–20, respectively. The distribution of sizes became broader as
the concentration of CaCl2 was increased. The particles main-
tain their spherical shape when produced from up to 60 mM of
calcium chloride and DMC, further increase of CaCl2 concentra-
tion leads, however, to a material with rather ill defined particle
shape and, in addition, a small amount of big spherical particles
with diameter of up to 3–4 ␮m are observed. FTIR analysis of
the samples as prepared showed in all cases some features char-
acteristic for ACC (data not presented). The presence of a broad
carbonate out-of plane bending vibrational band at 863 cm−1
(v2), a symmetric stretch absorption at 1075 cm−1 (v1), broad
but not split peak at 1440 cm−1 , and a broad absorption peak
at around 3350 and 1640 cm−1 due to water molecules is seen
[9,10,12,18]. For materials obtained at higher concentration of
the reactants poorly developed absorption peaks characteristic
for calcite could be observed (712 cm−1 ). XRD measurements
confirmed that the material synthesized at a concentration of
60 mM of CaCl2 (DMC) showed XRD pattern characteristic for
calcite and vaterite (Fig. 2). However, the XRD shows that the
crystalline polymorphs are not the dominating component but a
large part of the material remains still amorphous. This explains
that the peaks detected in the FTIR spectrum are neither typi-
cally “amorphous” nor “crystalline” indicating the presence of
poorly developed crystalline material.
The induction time for precipitation characterized by the
appearance of turbidity became shorter with increasing concen-
tration of calcium chloride and DMC. A higher amount of dialkyl
carbonate not only allowed to reach the sufficient amount of CO2
for the nucleation faster but also led to a high consumption of
base at the beginning of the process which caused a sudden
drop in pH. In consequence, the growth of the particles was sup-
pressed as a result of gradual reduction of CO2 concentration.
Irrespective of the higher concentration of components the yield
of product decreased (Fig. 3) and the particle diameter became
smaller. The reduction in the amount of base used in the pro-
220 K. Gorna et al. / Materials Science and Engineering A 477 (2008) 217–225
Fig. 1. SEM micrographs of ACC synthesized at increasing concentration of CaCl2 (DMC) from 20 to 60 mM, and constant concentration of NaOH (20 mM).
cess slowed down the hydrolysis process of DMC and created
a different (decreasing) supersaturation level. Elfil and Roques
demonstrated in their work [23,24] that homogenous nucleation
occurs once the solubility product for amorphous calcium car-
bonate is surpassed. At such condition amorphous or calcium
carbonate hydrates are initially formed, but as they are thermo-
dynamically not stable, they transform to a mixture of crystalline
calcium carbonate polymorphs. Which polymorph is eventually
formed depends on the conditions of precipitation like temper-
ature and the range of supersaturation achieved in the system
[14,22,25]. In fact, this was observed in the present study as
well. As the base concentration used in the reaction was too
low, the supersaturation level rapidly changed in the course of
precipitation and as a result, initially formed ACC started to
transform into vaterite and calcite. A small fraction of spherical
particles of vaterite with diameter in the range of 3–4 ␮m was
observed in the material obtained from systems deficient of base
(60–20).
In consequence of the results so far described the concen-
tration of base was increased, even though a rough calculation
showed that the increase of base concentration can favor the
undesired precipitation of calcium hydroxide in the system. The
product yield at various concentrations of components is pre-
Fig. 2. XRD pattern of calcium carbonate synthesized at 40 and 60 mM of CaCl2
(DMC) and 20 mM of NaOH; expected Brags reflections for calcite—solid lines,
and vaterite—dashed lines.
sented in Fig. 3. It shows that in order to obtain more yield per
batch it is essential to use higher concentrations of base as the
higher pH enhances hydrolysis of the alkyl carbonate and this
leads to production of sufficient amount of CO2 in the system.
From the SEM micrographs presented in Fig. 4 it can be seen that
the particle shape is strongly affected by the concentration of the
components from which precipitation occurs. The higher is the
solution concentration the smaller are the particles, which result.
However, the smaller particles are more agglomerated (Fig. 4,
100–100). FTIR and XRD measurement reveal the amorphous
nature of all the materials synthesized from solutions in which
the initial concentration of NaOH was at least 30 mM.
The concentration of the components determines not only the
particle diameter but also the thermal characteristics of the mate-
rial. Depending on the initial concentration of components ACC
showed one or two distinct thermal transitions in the DSC curves
(Fig. 5). The first broad endothermic transition is assigned to the
release of water from ACC [6,7,13,16,18]. This transition was
usually composed of two, more or less distinguishable peaks.
A broad peak with maximum at around 100–120 ◦ C was more
pronounced for the calcium carbonate precipitated at lower pH.
The second narrow peak occurred in the range of 150–175 ◦ C.
The position and shape of this second peak depended again on
Fig. 3. Yield of ACC at various concentrations of CaCl2 (DMC) and NaOH.
Material obtained under conditions indicated by the arrow was selected for
further studies in blending with polymers.
 K. Gorna et al. / Materials Science and Engineering A 477 (2008) 217–225
Fig. 4. SEM micrographs of ACC synthesized at various concentration of CaCl2 (DMC) and NaOH.
the pH at which ACC had been precipitated. For higher pH the
peak was located at a slightly higher temperature and became
broader.
The small exothermic transition in the DSC curves seen
around 290 ◦ C seems to be related to the complete water release
associated with the transition of ACC into calcite [6]. For the
material precipitated at higher concentration of CaCl2 and DMC
but lower concentration of base this transition, however, was
not always detected (Fig. 5, system 20–20). There was also a
decrease in the enthalpy of endothermal process related to the
water release form the calcium carbonate precipitated at higher
concentration but lower pH. Release of water observed by DSC
corresponds to the weight loss observed by TGA. The amount of
water detected by TGA measurement was in the range of 8–10%
of total weight for materials synthesized using at least 30 mM of
base. Calcium carbonate obtained from the system deficient of
base contained much less water and its relative amount decreased
to 2% as the concentration of CaCl2 increased. It should be
stressed, however, that materials obtained under such conditions
showed evidence to be partially crystalline.
Similar relations between thermal characteristics and pH
of the starting solution have been observed by others authors
[14,15,26]. From the structure of the endothermal transition one
Fig. 5. DSC of ACC synthesized from solutions of 20 mM CaCl2 (DMC) at
various concentrations of NaOH ranging from 20 to 50 mM.
221
may conclude that the water included in the material may have
different environments. In other words, the water may be incor-
porated as bound water, may be coordinated to calcium ions in
ACC and eventually may be occluded in ill-defined positions in
the ACC structure [14,15,26].
Among different ACC particles precipitated from various
concentrations of components for the further study we selected
material synthesized using 20 mM of CaCl2 , DMC and 30 mM of
NaOH with yield of about 30% (ACC 20–30). These conditions
allow to produce ACC in form of non-agglomerated particles
with average sizes ranging from 0.9 to 1.2 ␮m depending on the
volume of the reactor used. Material was not contaminated by
the crystalline forms of calcium carbonate and showed a long
time stability over 3 months of storage, even though, it is known
that ACC is not a stable material, and with time, when exposed
to humidity, spontaneously undergoes crystalline transforma-
tion. This process, however, can be induced thermally and the
crystallization occurs, following some authors, by a solid-state
transformation [16,26]. ACC 20–30 has been treated at tempera-
tures ranging from 80 to 200 ◦ C in order to remove the structural
water and to evaluate the progress of crystallization. Drying the
material for 72 h at 80 ◦ C in air activated the crystallization of
the material and XDR showed weak reflections of calcite. Still
about 2% of water was present at the end of annealing as deter-
mined by TGA. The effect of temperature and time of heating
on the amount of water remaining in the calcium carbonate is
shown in Fig. 6. The higher the temperature and longer the time
of heating the higher is the amount of water that was released.
The loss of water was accompanied by transformation of the
material into calcite (Fig. 7). The crystallization process during
heating occurred only sluggishly even at higher temperature as
can be seen from the XRD pattern. Even after 6 h at 200 ◦ C,
still part of the material remained amorphous. It is important
that the morphology of the particles did not change upon dry-
ing. Only the surface of the spheres became somewhat rougher
as shown by SEM micrographs (Fig. 8(a)). A change of surface
roughness of ACC particles resulting from the loss of water has
been reported previously [16,26]. Some of the spherical particles
exhibited a restructured surface and the presence of small parti-
cles inside the bulk material with diameter of around 30–40 nm
that could be assigned to calcite. The crystal size evaluated from
222 K. Gorna et al. / Materials Science and Engineering A 477 (2008) 217–225

Fig. 6. The effect of temperature and time of heating on the amount of remaining
water in the particles of calcium carbonate 20–30. The fraction of remaining
water was determined by TGA.

Debye–Scherrer XRD patterns pointed to presence of crystals

with diameter in the range of 25–35 nm.

3.2. Effect of calcium carbonate on the properties of

composites

The ACC 20–30 (e.g. Fig. 3) was used for compounding with
a series of archetypical polymers, namely LLDPE, HDPE, PP,
PS, and PLA. The ACC 20–30 as synthesized was first stabi-
lized at 200 ◦ C for 6 h, meaning that the ACC lost the structural
water and was partially crystallized to give calcite, without loss
of its spherical morphology. The characteristics of this calcium
carbonate after drying (DACC 20–30) and a commercial mate-
rial (Precarb 400) used in this study as a reference are shown
in Fig. 8, and Table 1. The two materials differ significantly
in the shape of particles. DACC 20–30 particles have a regu-
lar spherical shape while the Precarb 400 consists partially of
needles of rather high aspect ratio. Specific surface area and
DIPN absorption (see Section 2) are slightly lower for DACC
20–30 compared to Precarb 400 but the surface accessibility is
comparable.
Fig. 8. SEM images of (a) DACC 20–30 after drying at 200 ◦ C for 6 h, (b)
Precarb 400.
The composites were prepared with a theoretical content of
fillers of 10, 20 or 40 vol.%. The calcium carbonate powder was
mixed with the polymers in a small twin extruder. The material
after feeding was processed a few times trough the extruder in
closed cycle to ensure god mixing of both phases—polymer and
inorganic filler. The quality of the dispersion of the filler in the
polymer matrix was evaluated from visual inspection of cross-
sections of the composites by SEM. Examples are shown in
Fig. 9. Both types of fillers were used without any modification
of their surfaces which could potentially improve the dispersion.
Nevertheless, reasonable good distribution of calcium carbonate
particles was achieved in all cases. A more detailed analysis of

Table 1
Characteristics of the calcium carbonate fillers used for compounding with
polymers
Parameters Inorganic fillers

DACC 20–30a Precarb 400b

Polymorph Calcite/amorphous Calcite/aragonite

Particle size Spheres: 1.15 ␮m Spindles/needles:
1.16 ␮m × 0.20 ␮m
Specific surface (BET) 12.2 m2 /g 8.4 m2 /g
DINP absorption 51 g/100 g 68 g/100 g
a
Fig. 7. The XRD of calcium carbonate 20–30 dried at 200 ◦ C for 6 h; expected Preparation as described in the work, sample 20–30, see also Figs. 3 and 8a.
b Supplied by Schaefer Kalk GmbH & Co. KG.
Brags reflections of calcite—solid lines, and vaterite—dashed lines.
 K. Gorna et al. / Materials Science and Engineering A 477 (2008) 217–225
Fig. 9. SEM micrographs of (a) PP filled with 40 vol.% of DACC 20–30; (b) PP filled with 40 vol.% of Precarb 400; (c) PLA filled with 20 vol.% of DACC 20–30;
(d) PLA filled with 20 vol.% of Precarb.
the SEM micrographs, showed, however, that a better disper-
sion can be obtained for the spherical particles of DACC 20–30.
Large aggregates were not observed indicating that the shear
forces during the extrusion process were sufficiently large. In
the case of Precarb 400 small aggregates of particles could be
observed occasionally which were not broken up to yield indi-
vidual primary particles during compounding. The elongated
particles of this material tend to become aligned parallel to the
direction of extrusion, although some needles can be observed
lying normal to the preferred direction indicating that the shear
forces were too low to align them perfectly. Moreover, compar-
ison of the surface finishing of the extruded samples shows a
higher roughness for samples filled with Precarb 400 as a con-
sequence of the poor alignment of particles along the direction
of extruding.
Examination of fracture surfaces reveals the presence of voids
between the calcium carbonate particles and the polymer matrix
as a result of not optimized compatibility of the inorganic and
organic components. Some of the particles are disattached from
the polymer upon fracture. Slightly better adhesion of the poly-
mer to the inorganic filler can be discerned when one inspects
SEM micrograph from cross-section of PLA-based composites.
One may speculate that the presence of lactic acid which could
be released upon thermal degradation of PLA during extrusion
in the composite acts as a binding agent of the polymer to the
calcium carbonate surface.
Although, the stabilization process of ACC caused its partial
crystallization and appearance of small, most likely calcite crys-
223
tals inside of the spheres, the particle of DACC 20–30 withstood
the shear forces upon extrusion and did not break up.
The real content of inorganic filler in the compounded mate-
rials was estimated from TGA analysis and the results are
summarized in Table 2. The experimentally determined frac-
tion of calcium carbonate was in most cases consistent with the
data of the initial mixture. This indicates that calcium carbonate
does not decompose during processing.
The composite materials obtained in this study were also
characterized by DSC. LLDPE, HDPE and PP showed single
melting endotherms and, upon cooling, crystallization peaks
(Table 2). There is very little if at all effect of fillers on the ther-
mal characteristics of the semicrystalline polyolefins indicating
that the interaction between filler surface and polymer matrix is
negligibly small. This is quite different for the case of PLA as
matrix. The presence of both types of fillers decreases the glass
transition and melting temperature in PLA proportional to the
content of filler.
Altogether, these data are not surprising as it is well known
that calcium carbonate has a very weak nucleation effect in
polymers [4,27].
The influence of the fillers on the tensile properties of com-
posites is presented in Table 3. In general, the presence of both
types of filler increased the Young’s modulus, decreased ten-
sile strength and elongation at break, what is typically observed
for the fillers with rather limited capacity of reinforcement
[1–3]. The elongation at break decreased for all filled polymers,
although, the decrease was lower for polymers filled with DACC
224 K. Gorna et al. / Materials Science and Engineering A 477 (2008) 217–225

Table 2
TGA and DSC data for the polymers and composites

Material Wt.% of fillera Wt.% of fillerb Hm (J/g) Tm (◦ C) Tc (◦ C) Tg

HDPE – – 167.0 136.8 109.8 –

HDPE10%DACC 20–30 23.1 25.0 164.7 139.0 106.7 –
HDPE 10% Precarb 400 23.1 23.7 160.0 140.0 105.2 –
LLDPE – – 90.0 127.2 104.0 –
LLDPE 10% DACC 20–30 23.1 21.1 112.9 129.6 104.8 –
LLDPE 10% Precarb 400 23.1 20.8 104.8 129.3 105.8 –
PP – – 66.7 169.0 111.3 –
PP 10% DACC 20–30 23.1 19.3 71.3 167.4 116.1 –
PP 40% DACC 20–30 64.3 55.2 70.5 163.1 126.4 –
PP 10% Precarb 400 23.1 14.5 71.1 165.4 116.6 –
PP 40% Precarb 400 64.3 56.4 69.5 163.7 120.9 –
PLA – – 31.5 159.8 – 68.2
PLA 10% DACC 20–30 19.5 22.6 23.9 158.2 – 60.8
PLA 20% DACC 20–30 40.0 32.9 22.5 161.2 – 59.9
PLA 10% Precarb 400 19.5 4.3 26.3 159.4 – 61.9
PLA 20% Precarb 400 40.0 41.3 32.5 162.0 – 59.3
a Fraction of filler used in the mixture before compounding.
b Real fraction of filler after compounding estimated from TGA.

Table 3
Mechanical properties of selected polymers after extrusion and composites filled with 10 vol.% of DACC 20–30 or Precarb 400
Tensile strength (MPa) Tensile modulus (MPa) Elongation at fracture (%)

LLDPE 22 ± 0.8 161 ± 4 686 ± 24

LLDPE + DACC 20–30 20 ± 2.5 169 ± 26 689 ± 60
LLDPE + Precarb 400 13 ± 3.7 168 ± 40 390 ± 182
HDPE 38 ± 4 631 ± 27 531 ± 51
HDPE + DACC 20–30 23 ± 6.4 823 ± 46 415 ± 186
HDPE + Precarb 400 27 ± 3.7 844 ± 157 511 ± 47
PP 47 ± 2.6 798 ± 91 933 ± 29
PP + DACC 20–30 32 ± 5 990 ± 40 651 ± 129
PP + Precarb 400 28 ± 2.2 1029 ± 95 58 ± 14

20–30. The spindle and needle-like particles of Precarb 400 seem
to cause failure at very low elongation most probably due to the
shape of the particles or as a result of inhomogeneous dispersion
of the particles in the polymer matrix. Aggregated particles act
as crack initiation sites under dynamic loading condition [4].
4. Conclusions
ACC in form of spherical particles of diameter between 0.4
and 1.2 ␮m can be obtained by reacting calcium chloride in
aqueous solution with carbon dioxide at a pH > 11 under the
condition by which CO2 is homogenously supplied by hydroly-
sis of a water soluble dialkyl carbonate. Dimethyl carbonate was
used as the source of CO2 in the present case. The droplets of
initially strongly hydrated and fluid ACC are formed in conse-
quence of a liquid–liquid phase segregation. Once formed they
loose water and undergo a transition to glassy but still hydrated
ACC. The nucleation of the particles of ACC can be controlled to
give comparatively narrow size distributions. Among other fac-
tors, temperature of formation process and pH, the letter being
connected to the scale of the hydrolysis of the dialkyl carbonate
and supersaturation with regard to CO2 dissolved in the reac-
tion medium play a major role. The ACC is metastable at room
temperature and needs to be dried by a short heat treatment to
remove water around 200 ◦ C. Partial crystallization to give cal-
cite may occur under these conditions; however, the form of
spheres which are mostly non-aggregated remains unaffected.
The reaction conditions for formation of this material have
been optimized with respect to yield and scale as to obtain multi-
gram quantities in a single batch at overall yield near 30% with
regard to the starting material calcium chloride.
ACC as prepared by this novel process may have interest as
a high-end filler material for polymers. Thus, compounding of
dried ACC with the archetypical polyolefins HDPE, LLDPE,
PP, PS was tried to demonstrate its principal capabilities and
potential. Moreover, compounding of PLA as a representation
of a polymer for biomedical applications with dried ACC was
studied as well.
The particles of dried ACC maintain their identity during
mixing and extrusion of a polymer host melt. They remain
mostly individual and do not form irreversibly aggregates. In
other words, the interaction between the ACC particles and the
polymers is rather weak and the shear forces exerted onto the par-
ticle/polymer melt mixture suffice to establish quickly a rather
homogenous dispersion. However, the particles as prepared in
the above described precipitation process followed by a drying
step do not have a specific interaction with the polymer matrix.
Thus, reinforcing phenomena are barely seen with exception of
 K. Gorna et al. / Materials Science and Engineering A 477 (2008) 217–225 225

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