J Mater Sci (2018) 53:4022–4033

Ceramics
CERAMICS

Physical and nanomechanical properties

of the synthetic anhydrous crystalline CaCO3
polymorphs: vaterite, aragonite and calcite
Radek Ševčı́k1,* , Petr Šašek1, and Alberto Viani1

1
Institute of Theoretical and Applied Mechanics of the Czech Academy of Sciences, Centre of Excellence Telč, Batelovskà 485-486,
588 56 Telč, Czech Republic

Received: 20 July 2017 ABSTRACT

Accepted: 30 November 2017
Published online:
8 December 2017
© Springer Science+Business
Media, LLC, part of Springer
Nature 2017
The synthetic anhydrous crystalline CaCO3 polymorphs—vaterite, aragonite
and calcite—were tested using dilatometry and nanoindentation. Microstruc-
tural changes in the samples before and after measurements were observed
under scanning electron microscope and their phase composition quantified
with X-ray powder diffraction with the Rietveld method. The thermal expansion
coefficients of vaterite and the hardness and elastic modulus of synthetic
aragonite are reported for the first time. The physical and nanomechanical
properties were measured under similar conditions for each CaCO3 polymorph.
Aragonite, calcite and vaterite showed volumetric thermal expansion coefficient
at 303 K of 49.2(8), 48.6(2) and 44.1(3) 10−6 K−1, respectively. The elastic modulus
increased from 5(4), 16(7) to 31(8) GPa for aragonite, calcite and vaterite,
respectively. Average hardness was found lower than values from the literature,
ranging from 0.3 to 1.3 GPa. The results are considered of interest for the design
of CaCO3-based materials for applications.

biomineralization processes, its use in several

Introduction
Calcium carbonate (CaCO3) is one of the most
abundant compounds on the Earth crust. It is largely
present in limestone rocks, marine reefs and shells,
exhibiting three anhydrous crystalline polymorphs
(calcite, aragonite and vaterite), two hydrated crystal
forms (CaCO3·6H2O (ikaite) and CaCO3·H2O), and an
amorphous phase [1, 2]. CaCO3 raises scientific
interest mostly because of its importance in the
industrial sectors [3, 4] and, recently, because of
geologic sequestration of carbon dioxide [5]. Lime
(CaO), produced by burning limestone rocks, largely
composed of CaCO3, is a key material for the build-
ing industry, where it is used as binder in mortars.
Setting occurs due to the carbonation of lime. Car-
bonation is an exothermic process which comprises:
(i) diffusion of the atmospheric CO2 gas into the pore
structure of the mortar, and (ii) chemical reaction
between the dissolved CO2 and Ca(OH)2 [6, 7]. The

Address correspondence to E-mail: sevcik@itam.cas.cz

https://doi.org/10.1007/s10853-017-1884-x

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J Mater Sci (2018) 53:4022–4033
result is the transformation of Ca(OH)2 into CaCO3,
producing the hardening of the mortars. Recently,
suspensions of Ca(OH)2 sub-micrometric particles in
alcohols (nanolimes) have been proposed for the
conservation of the culture heritage objects in order
to improve the treatment with lime [8–12]. The car-
bonation process following the treatment with
nanolime results in the formation of vaterite, arago-
nite and/or calcite [13–16]. Vaterite was detected also
in several historical mortars [17–19] and after the
biodeposition treatment of construction materials
[7, 20, 21]. The three anhydrous CaCO3 polymorphs
display different crystal habit, mean crystal size and
anisotropy of physical properties. The measurement
of their physical and mechanical properties is thus
essential for the critical evaluation of the effectiveness
of conservative actions of cultural heritage objects.
Nanoindentation is a well-established technique for
the determination of the mechanical properties [22].
Examples of its application to calcium carbonate
materials include biogenic, as well as some synthetic
samples [23–28]. As for the determination of physical
properties, the literature reports only few examples
of the measurement of thermal expansion [29–32],
hardness and elastic modulus [28, 33–35]. However,
most of these reports focused on biogenic samples
that are not directly comparable with the synthetic
ones because of their different properties due to the
fact that they are highly organized structures. In this
work, we report the investigation of thermal expan-
sion coefficients, elastic modulus and hardness, of
calcite, vaterite and aragonite. The synthesis has been
conducted without use of additives, which are
known to alter the morphology of the CaCO3 crystals,
therefore, influencing the measured properties.
Materials and methods
Synthesis of CaCO3 polymorphs
The synthesis of vaterite was conducted using pro-
cedures described elsewhere [28] from two super-
saturated solutions of CaCl2·2H2O (p.a.) and K2CO3
(p.a.) without use of additives. The reagents were
purchased from Lach-Ner (Czech Republic) and used
as received. Aqueous solutions (c = 2 mol l−1,
V = 50 ml) of these reactants were prepared using
deionization water (Barhstead Smart2pure, Thermo
Scientific) of the following characteristics:
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4023
λ = 0.055 µS cm−1; R = 18.2 MΩ 9 cm; pH = 8.2. The
synthesis of aragonite was performed from the
vaterite precursor refluxed for the 150 min [36, 37].
The synthesis of calcite was previously described
elsewhere [28]. The composition of the synthetic
products was assessed with X-ray powder diffraction
quantitative phase analysis using the Rietveld
method.
Dilatometric analysis
Samples were measured with the horizontal
dilatometer Linseis L75 in air and at ambient pres-
sure, in the temperature interval 293–573 K,
employing the heating rate 2 K min−1. The sample
was placed in a corundum container designed for the
measurement of powders. The sample weight of
40 mg of CaCO3 was used for all the measurements,
and the powder CaCO3 was carefully compacted in
the measuring container by hand.
Volumetric coefficient of thermal expansion αv was
calculated according to the expression:
1 dV
aV ¼  ð1Þ
V0 dT
where V0 is the volume of the sample at 293 K and
dV is the volume change in the temperature interval
dT. The average αV was calculated from the 10 mea-
suring cycles for each anhydrous CaCO3 polymorphs.
Nanoindentation analysis
Nanoindenter TI 750 L Ubi (Hysitron) was used for
testing of the prepared specimens. A three-sided
pyramidal diamond Berkovich indenter and the Oli-
ver–Pharr method [22, 38] were used to measure the
elastic modulus and hardness. Indentation experi-
ments were performed on a grid 20 9 20 (400
indentations) for each sample with spacing between
indents of 10 μm. Maximum load (Pmax) was 0.5 mN,
load increased linearly for 5 s to reach Pmax, held at
Pmax for 2 s and then unloaded linearly for 5 s.
Sample of vaterite, calcite and aragonite was pre-
pared in the form of pellets to assure flat surfaces.
Pellets were made from 0.250 mg of samples and
pressed for 30 s with force of 40 kN and then pressed
for the same time with force 80 kN by means of an
hydraulic press for each sample. Force and depth of
penetration were recorded. Initial unloading stiffness
is expressed as follows:
4024
pffiffiffiffi pffiffiffi
dP 2E A 1 p dP
S¼ ¼ pffiffiffi ) E ¼ pffiffiffiffi ð2Þ
dh p 2 A dh
   
1 1  t2 1  t2i
¼ þ ð3Þ
E E Ei
where A is the projected contact area at load values
peak, E* is the reduced elastic modulus and E and ν
are Young´s modulus and Poisson’ ratio for the
sample and Ei and νi are the same parameters for the
indenter tip [22, 39]. For the Berkovich indenter used
in the experiments, the elastic modulus Ei is 1140 GPa
and Poisson’ ratio νi was 0.07. Each calcium carbon-
ate polymorph sample was scanned by in situ scan-
ning probe microscopy imaging to select a
suitable place for experimental testing possessing
minimum roughness. Average roughness of all
samples was below 50 nm. All measurements were
performed in load controlled mode.
X-ray powder diffraction analysis
The phase composition of the synthetized CaCO3
polymorphs before and after dilatometric and
nanoindentation tests was investigated with X-ray
powder diffraction (XRPD) employing a Bragg–
Brentano D8 Advance diffractometer (Bruker)
equipped with a LynxEye 1-D silicon strip detector,
using CuKα radiation and Ni filter. Patterns were
recorded at 40 kV and 40 mA at ambient temperature
in the angular range 15–90° 2θ with a virtual step scan
of 0.01° and counting time 0.4 s per step. The samples
were allowed to spin at 15 rpm to increase the par-
ticle statistics. Quantitative phase analysis (QPA) was
performed with the Rietveld method [40] using the
Topas 4.2 software from Bruker AXS.
Scanning electron microscopy analysis
The surface of the samples was examined with a
high-resolution scanning electron microscope (SEM)
Quanta 450 FEG (FEI) using a secondary electron
detector. Analyses were performed at accelerating
voltage between 5 and 20 kV. The samples used for
dilatometry were dispersed as powders on carbon
tape. All the samples were gold coated with a 5-nm-
thick layer.
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J Mater Sci (2018) 53:4022–4033
Results and discussion
The XRPD patterns collected from the synthesized
samples with the attribution of the main Bragg peaks
are reported in Fig. 1. QPA with the Rietveld method
takes into account the whole diffraction pattern and
not only a discrete number of diffraction lines. As
already shown [28], in order to fit the powder
diffraction pattern of vaterite, including the broad
peaks at 38.5° and 85° 2θ (neglected in many publi-
cations), two structural models were included in the
Rietveld refinement. They are: the hexagonal struc-
ture proposed by Mayer (space group P63/mmc) [41]
and the triclinic structure of Demichelis et al. (space
group C1) [42]. The results of the QPA, together with
the agreement factor Rwp of the refinements as
defined in [43] are shown in Table 1. Results indi-
cated that pure calcite and vaterite were obtained.
Aragonite was prepared with the presence of a small
amount of calcite (4.7(2) wt%).
The morphologies of the CaCO3 polymorphs were
observed under SEM, and a selection of micrographs
is reported in Fig. 2. In case of calcite and vaterite,
only one CaCO3 polymorph was detected in the
samples, confirming the results from XRPD. Calcite
crystals displayed the typical euhedral to subhedral
habit (Fig. 2a). The size ranged between 1.0 and
3.5 µm. Some minor amount of smaller crystals,
around 0.5 µm, was also detected. In Fig. 2b, spherical
vaterite particles, forming larger aggregates up to
10 μm, are depicted. Single vaterite spherules were
clearly recognized and their sizes varied in the range
from 0.6 to 3.2 µm. All the spherules were built up by
nanometric vaterite particles (40–300 nm) [28].
Aragonite is shown in Fig. 2c. The typical aragonite
acicular crystals together with a minor amount of
euhedral calcite (2.5–8.0 µm) were observed. Arago-
nite was present as isolated needle-like crystals, but
mainly as larger clusters radiating from a common
center. In both cases, maximum length of aragonite
rods ranged between 17 and 60 µm. The morphology
of synthetic CaCO3 polymorphs is known to depend
on the conditions of synthesis and introduction of
additives, e.g, several different morphologies are
known for aragonite, such as needle-, hedgehog-,
cauliflower-, spindle-, flake- or hubbard squash-like
[36, 44]. The SEM investigation clearly showed the
remarkable difference in crystal habit of synthetized
anhydrous CaCO3 polymorphs, which is expected to
J Mater Sci (2018) 53:4022–4033 4025

calcite include the microstructural variations affecting the

A A vaterite
A bulk thermal expansion, because of the formation of
aragonite
A A A A A
C A microcracks [48]. Crystal habit and symmetry may
A A A CA C
lead to anisotropy of thermal expansion, e.g., calcite
Normalized Intensity

V V crystal is trigonal and therefore shows two coeffi-

V
V cients of thermal expansion (CTE), one includes the
V
V
VV V V V optical axis c (positive value α) and the other at right
V
angle thereto (negative α). In this work, the volu-
C metric thermal expansion coefficients (αV) have been
measured for powdered CaCO3 samples, assuming
C C C C C C random crystal orientation. The αV values obtained
C CC
from the investigated samples and relevant data from
20 25 30 35 40 45 50 55 60 the literature are summarized in Table 2. Different
2θ [°] methods, such as temperature resolved XRPD (TR-
XRPD), laser dilatometry, single crystal XRD, have
Figure 1 Selected region of measured XRPD spectra of the been employed for the measurement of αV of calcite
synthesized calcium carbonate polymorphs. Main Bragg peaks of and aragonite, both synthetic and natural, whereas
polymorphs are indicated (V vaterite, C calcite, A aragonite). no literature data are known to the authors for
vaterite. The measured temperature dependencies of
Table 1 Phase fractions (in wt%) of calcium carbonate poly-
αV are illustrated in Fig. 3.
morphs (Cal calcite, Vat H hexagonal model of vaterite; Vat T
The αV values were increasing with increasing
triclinic model of vaterite, Vat Tot total amount of vaterite, Ara
aragonite) in the samples before (a) and after (b) dilatometry temperature until 363 K. Then, a slight decrease is
measurements detected until a local minimum at 393 K. Afterward,
αV values were again increasing up to 573 K. We
Sample c (wt%) interpret the increase in αV up to 363 K as partly
Vat H Vat T Vat Tot Ara Cal Rwp contributed by the formation of the nano/microc-
racks in crystals of CaCO3 polymorphs, owing to the
Calcite complicated tensile and compressive stress fields
a – – – – 100.0 10.6
insisting within the crystals at the boundaries
b – – – 100.0 6.9
between crystallites of different orientation [48] and
Vaterite
a 52.0 (6) 48.0 (6) 100 (2) – – 12.1 also partly contributed by the formation of microc-
b 48.9 (6) 51.1 (6) 100 (2) – – 10.3 racks at the grain boundaries, due to the release of
Aragonite stress accumulated during the compaction of the
a – – – 95.3 (4) 4.7 (2) 13.1 powder. The slight αV decrease could be ascribed to
b – – – 94.5 (1) 5.5 (1) 11.9 the partially re-healing of such nano/microcracks. A
The standard deviation obtained from Rietveld refinements is similar behavior was observed in case of anisotropic
reported in brackets. Rwp is the agreement factor of the refinement ceramics [49]. Aragonite showed the same αV as cal-
cite up to 353 K (Table 2, Fig. 3), whereas the lowest
αV values were determined for vaterite in this region.
have an impact on their physical and nanomechanical After 353 K, the αV of aragonite is lower than for the
properties. other CaCO3 polymorphs.
Compared to the literature data, αV for calcite was
Dilatometric analysis found two times higher than the value reported in
[30], and three times higher than the value detected
As well known, physical properties of crystalline by Wu et al. [31]. These discrepancies can be ascribed
solids reflect their crystal symmetry [45]. The to the experimental conditions adopted, that is,
dimensional changes occurring in crystalline materi- application of high pressure on the limestone speci-
als as a function of temperature are due to the men composed of calcite [31], as well as the different
intrinsic or extrinsic effects. The intrinsic effects affect origins of the calcite samples [30, 31]. No literature
the lattice parameters [46, 47]. The extrinsic effects data, to the best of our knowledge, are available for

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4026
Figure 2 SEM images of the synthetized calcium carbonate
polymorphs (a calcite, b vaterite, c aragonite).
vaterite. In case of aragonite, the detected αV value
was found to be in good agreement with the work of
Lucas et al. [29]. In the both cases, synthetic aragonite
was used for the measurements. In this case, the
different procedure of synthesis, affecting the mor-
phology of aragonite crystals might account for the
observed differences. The needle-like aragonite
showed an average length of 5–10 µm and an average
width of 1–2 µm, thus, smaller than those produced
by our method. A direct comparison with single
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J Mater Sci (2018) 53:4022–4033
crystal data of natural aragonite presented by Ye et al.
[32], is, of course, not possible. Analogously, for the
biogenic samples, because of the presence of
biomacromolecules that are causing the rise in inter-
nal pressure because their tendency to evaporate
from the sample with increasing temperature [50].
The XRPD results obtained after the dilatometric
tests are summarized in the Table 1. The sample
containing the most thermodynamically
stable CaCO3 polymorph (at least under Earth sur-
face conditions), calcite, did not show changes in
phase composition. Although no partial conversion
of the metastable vaterite into calcite was detected, a
slight increase in the contribution of the triclinic
structural model was observed, probably due to the
changes in the nano/microstructure of the vaterite
particles after the thermal cycles. The partial trans-
formation of metastable aragonite to calcite, although
limited to 1 wt%, agrees with the conversion
observed in biogenic samples at temperatures below
250 °C [50]. The SEM micrographs of the samples
after dilatometric tests are shown in Fig. 4. The
morphological changes are clearly visible. Such
variations are ascribed to the effect of thermal treat-
ment. The SEM observations of CaCO3 samples
before the dilatometric test, after the compaction into
the alumina sample holders, did not reveal morpho-
logical alterations (Fig. S1). Figure 4a shows some of
the calcite crystals disintegrated after the ten cycles of
thermal treatment. Some of them lost their typical
euhedral to subhedral crystal habit. In Fig. 4b, three
non-healed separate microcracks (highlighted by red
rectangles) on the calcite crystal surface are visible.
Their length varied from 0.55 to 0.93 µm with the
width in the range 15–55 nm. The vaterite morphol-
ogy was found to be mainly comparable before and
after the thermal treatments (compare Figs. 2b, 4c).
Nonetheless, some of the polycrystalline vaterite
bodies, as well as the spherules, were found to be
highly disordered with their nanostructure (even at
low magnifications, Fig. 4d) composed of particles
with size in range 90–150 nm, well distinguishable.
No cracks were detected in the vaterite sample, thus,
it seems that, instead of cracking, the thermal treat-
ment was affecting mainly the nanostructure of this
polymorph, causing, to a limited extent, the phase
transformation. Small aragonite crystals, likely below
the detection limit of XRPD, were detected (Fig. 4e).
Aragonite crystals with the diameter around 100 nm
and lengths in the range 0.6–7.5 µm, were found in
J Mater Sci (2018) 53:4022–4033 4027

Table 2 Volumetric thermal

expansion coefficients (αV) of T (K) αV 9 10−6 (K−1) Technique Refs.
anhydrous calcium carbonate Cal Vat Ara
polymorphs (Cal calcite, Vat
vaterite, Ara aragonite) in the 298 39.6 (4) 35.5 (3) 40.4 (4) Dilatometer This work
investigated samples 298a – – 48.1 TR-XRPD [29]
298b 20.0 – 64.0 Laser dilatometer [30]
298c 13.1 – – XRD, high press [31]
\ 300d – – 58 (2) XRD [32]
 300d – – 69 (1)
303 48.6 (2) 44.1 (3) 49.2 (8) Dilatometer This work
373 91.9 (3) 90 (1) 87 (2) Dilatometer This work
473 99.1 (2) 97.1 (9) 93.2 (9) Dilatometer This work
573 107.1 (4) 103 (1) 103.3 (9) Dilatometer This work
Standard deviations are in brackets
a
Synthetic sample; bunknown origin, cpiece of Solnhofen limestone measured at pressures up to
10 kbar; dnatural single crystal with unknown origin

morphological changes could be ascribed to the

internal pressure developed inside the crystals dur-
ing the thermal treatment.

Nanoindentation analysis

As mentioned in the experimental part (“Nanoin-

Figure 3 The dependence of the volumetric thermal expansion
coefficients (αV) in the temperature range 293–573 K.
contact with the vaterite bodies, in agreement with
the detected transition vaterite-aragonite at higher
temperature [51]. The dilatometric tests mostly
influenced the morphology of the aragonite crystals,
especially the big aragonite clusters (Figs. 4f–h, S2).
The formations of cracks were detected at the higher
magnification and they were formed partially or
along the whole crystal faces (as depicted in Fig. 4g).
These cracks ranged from 1.1 to 2.5 µm in length with
diameter 33–105 nm. SEM observation revealed also
the shredding of the aragonite particles into smaller
fibers with diameter ranging from 90 to 270 nm with
length up to 14 µm (Fig. 4h); moreover, several
aragonite crystals were found to be split in two or
more fragments (Fig. S2). The observation of such
dentation analysis” section), the tested samples were
shaped as pressed pellets of CaCO3 powders. This
sample preparation had two advantages: it was not
necessary to ground and polish the samples and there
was no contamination with epoxy resins or other
chemicals. The presence of epoxy resin was reported
to interfere with the measurement, complicating the
analysis and subsequent evaluation of nanoindenta-
tion results [52]. One possible downside of the
approach adopted in this work is the dependence of
the measured properties from the degree of com-
paction of the powder (apparent density, porosity).
This aspect has not been considered here and is
matter for future investigations. The QPA of crushed
pellets revealed no changes in the mineralogical
compositions. The used Berkovich tip and the sur-
faces of the prepared samples are visualized on the
SEM images (see Fig. 5). As it is visible on the images
obtained at higher magnification (see Fig. 5), some
microholes between CaCO3 crystals and/or the
micro-sized cracks in the CaCO3 crystals, likely due
to the pressure exerted during sample preparation,
were detected. For this reason, as written in the
experimental part, 400 indentations points were
perform for the each sample and the surfaces were

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4028
Figure 4 SEM images of the synthesized calcium carbonate
polymorphs after the dilatometric measurements (a calcite, b crack
in calcite crystal highlighted by the red rectangles, c vaterite,
scanned by in situ scanning probe microscopy to
select the optimal area for the indentation grid.
However, still limited irregular responses, as illus-
trated on the example of P–h nanoindation curves in
Fig. S3, were recorded and such curves were exclu-
ded for the subsequent calculations. The typical load–
displacement curves (P–h curves) for synthetized
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J Mater Sci (2018) 53:4022–4033
d disordered vaterite, e vaterite with newly formed aragonite
crystals, f aragonite, g crystal detail of the cracks appearing in
aragonite crystals, h detail of the shredding of aragonite crystal).
anhydrous CaCO3 polymorphs are graphically com-
pared in Fig. 6.
Nanoindentation results are graphically summa-
rized in Fig. 7 as dependence of elastic modulus (Er)
on contact depth (Hmax), as well as distribution
curves, for all three CaCO3 polymorphs. As is clearly
visible from Fig. 7, each tested sample can be dis-
tinguished by the Er value calculated at maximum
J Mater Sci (2018) 53:4022–4033
Figure 5 SEM images of the used Berkovich tip and one of the
indents on the vaterite sample (inset) (a) and prepared samples of
synthesized calcium carbonate polymorphs (b calcite, c vaterite,
Figure 6 The comparison of the typical load–displacement (P–h
curve) curves for the synthetized calcite, vaterite and aragonite.
load 0.5 mN. The highest Young’s modulus values
were obtained for vaterite. Modulus value for calcite
and aragonite were similar up to 130 nm depths.
Below 130 nm, the aragonite Er values continuously
decreased until the final depth at 1300 nm was
reached. Er values of vaterite, calcite and aragonite
were found to be in the ranges of 16 to 61 GPa, 6 to 41
GPa and 2 to 34 GPa, respectively. The calculated
mean modulus values are lower for aragonite and
higher for vaterite. The estimated standard
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4029
d aragonite) for the nanomechanical testing using nanoindentation
instrument.
deviations of the mean values are high due to the
significant differences of the measured values with
increasing indentation depth.
Hardness of calcite, vaterite and aragonite was
found to range between 3.4 to 0.1 GPa, 4.2 to 0.3 GPa
and 4.2 to 0.01 GPa, respectively. These values were
calculated using the full contact depths regions, as
illustrated in Fig. 7. Mean calculated values are
reported in Table 3. No relevant difference can be
considered between calcite (1.3 ± 0.5 GPa) and
vaterite (0.9 ± 0.5 GPa). Aragonite’s mean hardness is
the lowest between the measured CaCO3 poly-
morphs, 0.3 ± 0.4 GPa. Hardness of calcite and
vaterite is lower than average reported values, but
also the hardness values of calcite and vaterite from
the literature are similar (see Table 3).
As reported in Table 3, only a limited number of
works reports results of nanomechanical tests on
synthetically prepared CaCO3. Only in the work of
Calvaresi et al. [27], calcite, synthetized via gas dif-
fusion method, without use of additives, was tested.
The reported values are higher in comparison with
ours probably because the calcite single crystal was
tested at 200 nm indentation depths that could have
affected the values of modulus and hardness. As
mentioned above, the detected hardness of the
4030 J Mater Sci (2018) 53:4022–4033

Figure 7 Reduced modulus as calcite

calcite
function of the contact depth 60 vaterite
vaterite 250
and distribution curves of aragonite aragonite
reduced modulus of discussed
50
calcium carbonate
200
polymorphs.
40

Er [GPa]
150

A.U.
30

100
20

10 50

0 0
0 300 600 900 1200 0 10 20 30 40 50 60 70
Hmax [nm] Er [GPa]

Table 3 Overview of mechanical properties of the discussed calcium carbonate polymorphs determined using nanoindentation instrument
and values from the literature, as indicated

Er (GPa) H (GPa) Drift correction (nm s−1) Disp at max load (nm) Load at max load (µN)

Calcite 16 (7) 1.3 (5) − 0.162 177 (60) 499.7 (2)

Calcitea 56 (3) 4.0 (3) – – –
Calciteb 55 (20) 3 (1)
Calcitec 80 (4) 2.4 (1) – – –
Calcited 43 (20) 1.1 (9) – – –
Calcitee 60–120 3–6 – 50 –
Calcitef 20–80 0–3 – 50 –
Vaterite 31 (8) 0.9 (6) 0.023 117 (28) 499.7 (2)
Vateriteg 36 (10) 2.3 (2) 0.255 155 960
Vateriteh 57 3.2 (2) – – –
Aragonite 5 (4) 0.3 (4) 0.026 292 (81) 499.7 (2)
Aragonitei 67 4.9 (3) – – –
Standard deviation of the calculated constants in brackets
a
Synthetic, values calculated at an indentation depth of 200 nm [27]; bnatural [34]; ccomposite—20 mM OPO3HPhOH-terminated hb-PG
[34]; dcomposite—2.5 mM OPO3HPhOH-terminated hb-PG [34]; b–dloading rate 7.5 mN with max. depth 500 nm; esemi-nacre of
Novocrania anomala [35]; ffibers of Terebratulina retusa [35]; gmicrobiological with minor amount of calcite [51]; hfresh water carp
astericus [23]; ifresh water carp lapilus [23]

anhydrous crystalline CaCO3 polymorphs were
found to be in the range 0.01–4.2 GPa. These values
are more similar to those measured on brachiopods
calcite fibers [35].
Moreover, the crucial factor influencing the
mechanical properties is the crystal morphology,
which, in turn, can be modified with the use of
additives during synthesis. Malinova et al. [34]
reported the effect of the oligomer (OPO3HPhOH-
terminated hb-PG) concentrations on the mechanical
properties of the calcite composite. The higher oli-
gomer concentrations led to the slightly increase in
modulus and increase in the hardness by 20% in
comparison with the neat calcite. Some of the highly
CaCO3 organized structures (e.g., shells) formed by
biomineralization processes show the highest hard-
ness values (see Table 3). Indeed, the aragonite from
carp lapillus has got significantly higher Er in

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J Mater Sci (2018) 53:4022–4033
comparison with the synthetic one, 67 GPa instead of
5 GPa. Interestingly, in our synthetic samples Er was
found to be lower for calcite in comparison with
vaterite. Dhami et al. [52] reported opposite results in
the samples of microbial carbonates composed of
calcite and vaterite in different ratios. The values of Er
and H were decreasing with the increasing amount of
vaterite in the specimens. The present work sum-
marizes, for the first time, the Er and H values of the
synthetic anhydrous CaCO3 polymorphs measured
under identical conditions.
We believe that the present investigation may
provide some useful data to help in designing
products for applications, e.g., in the conservation of
cultural heritage objects, as mentioned in the intro-
duction. It is well known that different polymorphs
form according to the conditions of product appli-
cation, climate conditions, type of consolidant agent,
substrate. Therefore, in order to match the mechani-
cal properties of the original material (in agreement
with the rules of good conservation practice), the
predominant polymorph can be selected on the basis
of its mechanical properties.
Conclusion
This work was focused on the physical and
nanomechanical characterization of the synthetic
anhydrous CaCO3. The thermal expansion coeffi-
cients of these materials were characterized using the
bulk dilatometric testing. The volumetric thermal
coefficients of each CaCO3 polymorphs were calcu-
lated in the range of temperatures from 293 to 573 K.
It was found that αV values were lowest for vaterite
up to 353 K. At higher temperatures, the lowest αV
was detected for aragonite. The phase composition of
the synthetically prepared CaCO3 was measured
using XRPD before and after dilatometric testing. To
the best of our knowledge, thermal expansion of
vaterite is reported for the first time. In case of
aragonite, limited transformation to calcite was
detected after ten thermal cycles, which resulted in
the increment of  1 wt% of calcite. The second
metastable CaCO3 polymorph, vaterite, did not show
any conversion into calcite. The SEM observations
confirmed XRPD results. The hardness and elasticity
modulus of CaCO3 polymorphs were determined
using nanoindentation. H and Er values for aragonite
were obtained for the first time. All three polymorphs
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
4031
were measured under the identical conditions, and
significant differences were found. Er values
decreased from 31(8), to 16(7), and 5(4) GPa for
vaterite, calcite and aragonite, respectively. The
obtained results may help in designing and engi-
neering materials containing CaCO3, for example for
producing more durable lime-based material used in
the preservation of cultural heritage objects.
Acknowledgements
The authors gratefully acknowledge support from the
Czech Grant Agency GA ČR Grant 17-05030S and the
Project No. LO1219 under the Ministry of Education,
Youth and Sports National sustainability program I
of Czech Republic. We thank Jaroslav Buzek for
dilatometry measurements and Mgr. Petra Mácová
for the pellets preparation.
Electronic supplementary material: The online
version of this article (https://doi.org/10.1007/
s10853-017-1884-x) contains supplementary material,
which is available to authorized users.
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