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Ab initio study of thermodynamic, structural, and elastic propertiesof Mg-substituted crystalline calcite
Pavlína Elstnerová
a,b
, Martin Friák
a,
, Helge Otto Fabritius
a
, Liverios Lymperakis
a
, Tilmann Hickel
a
,Michal Petrov
a
, Svetoslav Nikolov
c
, Dierk Raabe
a
, Andreas Ziegler
d
, Sabine Hild
e
, Jörg Neugebauer
a
a
Department of Computational Materials Design, Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Strasse 1, Düsseldorf 40237, Germany
b
Department of Chemistry, Faculty of Science, Masaryk University, Kotlár ˇ ská 2, Brno 611 37, Czech Republic 
c
Institute of Mechanics, Bulgarian Academy of Sciences, Acad. G. Bonchev Str. Bl. 4, 1113 Sofia, Bulgaria
d
Central Facility for Electron Microscopy, University of Ulm, Albert-Einstein-Allee 11, Ulm 89069, Germany
e
Department of Polymer Science, Johannes Kepler University Linz, Altenbergerstrasse 69, Linz 4040, Austria
a r t i c l e i n f o
 Article history:
Received 21 April 2010Received in revised form 9 July 2010Accepted 14 July 2010Available online 2 August 2010
Keywords:
Ab initioCalciteStiffeningMg-substitutionElasticity
a b s t r a c t
Arthropoda, which represent nearly 80% of all known animal species, are protected by an exoskeletonformed by their cuticle. The cuticle represents a hierarchically structured multifunctional biocompositebased on chitin and proteins. Some groups, such as Crustacea, reinforce the load-bearing parts of theircuticlewithcalcite.AsthecalcitesometimescontainsMgitwasspeculatedthatMgmayhaveastiffeningimpact on the mechanical properties of the cuticle (Becker et al., Dalton Trans. (2005) 1814). Motivatedby these facts, we present a theoretical parameter-free quantum-mechanical study of the phase stabilityand structural and elastic properties of Mg-substituted calcite crystals. The Mg-substitutions were cho-sen as examples of states that occur in complex chemical environments typical for biological systems inwhich calcite crystals contain impurities, the role of which is still the topic of debate. Density functionaltheory calculations of bulk (Ca,Mg)CO
3
 were performed employing 30-atom supercells within the gener-alized gradient approximation as implemented in the Vienna Ab-initio Simulation Package. Based on thecalculated thermodynamic results, low concentrations of Mg atoms are predicted to be stable in calcitecrystals in agreement with experimental findings. Examining the structural characteristics, Mg additionsnearly linearly reduce the volume of substituted crystals. The predicted elastic bulk modulus resultsrevealthattheMgsubstitutionnearlylinearlystiffensthecalcitecrystals.Duetothequitelargesize-mis-match of Mg and Ca atoms, Mg substitution results in local distortions such as off-planar tilting of theCO
2
3
 group.
 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
In the course of evolution nature has developed numerousmaterials with outstanding functional and structural properties.These structures mostly consist of an organic matrix of structuralbiopolymers which is modified and reinforced with various pro-teins and biominerals [1–9]. Such materials possess excellent stiff-ness, toughness, and strength related to their low density, whilethe mechanical characteristics of their underlying constituentsare rather modest [8,10]. This remarkable performance is a conse-quence of their hierarchical structure, the specific design at eachlevel of organization and the inherent strong heterogeneity [10].Therefore, to understand macroscopic mechanical properties of thesematerials,oneshouldtakeintoaccounttheirstructure–prop-erty relations at all length scales down to the molecular level.Hence, multiscale modeling that can systematically describe andinvestigate material properties from the atomistic scale up to themacroscopic level has become the most widely used method fortackling the structure–property relations of biological nanocom-posites and has been applied to bone, nacre, mother of pearl,arthropod cuticle, and other materials (e.g. [7,11–16]).Recently Nikolov et al. [17,16] developed a bottom-up multi-scale approach to model hierarchically structured nanocompos-ites. This approach combines quantum mechanical
 ab initio
calculations with hierarchical homogenization continuum meth-ods and has been successfully applied to study the elastic proper-ties of the chitin-based mineralized cuticle of an arthropod, thelobster
 Homarus americanus
. In this hierarchical constitutive mod-el
 ab initio
 calculations are used to describe the ground-statestructure and elastic properties of chitin which are relevant onthe nanometer-scale where experimental data are missing. How-ever, the properties of these materials do not depend only onthe specific microstructure at all levels of hierarchy but also onthe chemical composition of both the organic and inorganic com-ponents. Among the over 60 different biogenic minerals known at
1742-7061/$ - see front matter
 
 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.doi:10.1016/j.actbio.2010.07.015
Corresponding author. Tel.: +49 211 67 92 461.
E-mail address:
Contents lists available at ScienceDirect
Acta Biomaterialia
 
present [1–4,6], Ca carbonate is the most widespread biomineralused by invertebrates. It serves as the skeletal element in theshells of marine protists and corals, as material for the shells of molluscs and echinoderms, and in the exoskeletons of crustaceans[18]. In these organisms, it occurs either in its amorphous form(ACC) or as crystalline calcite, which is frequently associated withsignificant amounts of Mg. In crustaceans, the presence of Mg cal-cite has been shown for a number of species [19,20], and an Mgcontentashighas11%wasreportedinbiogeniccalcitesamplesta-ken from the spines and the body skeleton of the sea urchin
 Para-centrotus lividus
 [21]. It was speculated [22] that the Mg content may affect the mechanical properties of the cuticle since Mg cal-cite is harder than calcite without Mg, suggesting that it is formedfor mechanical reasons. Fig. 1a shows an electron micrograph of amicrotome polished cross-section from the dorsal carapace of alarge decapod crustacean, the edible crab
 Cancer pagurus
 and itselemental composition measured by energy dispersive X-ray spec-trometry (EDX), showing the presence of Ca, O, C, P, Ca and Mg.Qualitative EDX mappings show the heterogeneous distributionof Ca (Fig. 1b), Mg (Fig. 1c) and P (Fig. 1d) in the two mechanically relevant main layers, the exocuticle and endocuticle. Similar inho-mogeneous distributions of organic and inorganic componentswithin crustacean cuticles have been reported earlier [23,24],and were correlated to the functions of particular skeletalelements. Ca carbonate plays a generally important role in thestructure and mechanic properties of these materials. However,there is still an ongoing debate about the specific role of Mg. Inaddition to enhancing the mechanical properties of calcite, it hasalso been proposed that Mg
2
þ
 ions can block the formation of cal-cite in the presence of biopolymers and therefore favour precipita-tion of amorphous CaCO
3
 [25]. Studying the thermodynamic,structural, and elastic properties of Mg-substituted crystalline cal-cite on the molecular level can help to gain a deeper understand-ing of the role Mg plays in biological materials.Previoustheoretical calculations, basedonvalenceforcefieldaswell as
 ab initio
 methods, on the system of Ca and Mg carbonateshave focused on the thermodynamics, structural, vibrational andelastic properties for the stoichiometric end-members of thepseudobinaryalloysystemCa
n
Mg
m
ð
CO
3
Þ
n
þ
m
 [26–35]).Theenerget-ics and atomic geometry of Mg-substitutions in calcite have beenaddressed by using Hartree–Fock linear-combination-of-atomic-orbitals (HF-LCAO) calculations [36]. However, a detailed studyon the atomic geometry, the energetics, and the elastic propertiesof the pseudobinary alloy system Ca
n
Mg
m
ð
CO
3
Þ
n
þ
m
 for the wholerange of compositions is lacking. Therefore, in the present studywe focus on the mineral matrix inhomogeneities and address theelastic properties of calcite
 ð
CaCO
3
Þ
, magnesite
 ð
MgCO
3
Þ
 and thepseudobinary alloy system Ca
n
Mg
m
ð
CO
3
Þ
n
þ
m
.
Fig. 1.
 Elemental distribution in cuticle fromthe dorsal carapace of the crab
 Cancer pagurus
. (a) Electronmicrograph of a microtome-polished cross-section showingthe twostructurally different main layers exocuticle (exo) and endocuticle (endo) and the elemental composition measured by qualitative energy dispersive X-ray spectrometry(EDX). (b–d) Qualitative EDX mapping showing the heterogeneous distribution of Ca (b), Mg (c) and P (d) throughout the thickness of the cuticle.
P. Elstnerová et al./Acta Biomaterialia 6 (2010) 4506–4512
 4507
 
1. Methodology 
CaCO
3
 is a common carbon-bearing mineral found on theEarth’s surface and mantle [37]. CaCO
3
 and MgCO
3
 crystallize un-der ambient conditions in the hexagonal/rhombohedral
3c phaselayered structure in which CO
2
3
 planes alternate with cation (Ca
2
þ
or Mg
2
þ
) ones (see Fig. 2). The rhombohedral unit cell of these car-bonates contains two formula units and thus 10 atoms. The re-duced coordinates of the cation atoms are (0,0,0) and
 12
;
 12
;
 12
, of the C atoms
 14
;
 14
;
 14
 and
 34
;
 34
;
 34
, and of the O atoms
 u
;
 12
u
;
 14
,
14
;
u
;
 12
u
,
 12
u
;
 14
;
u
,
 u
;
 12
;
þ
u
;
 34
,
 34
;
u
;
 12
þ
u
, and
 12
þ
u
;
 34
;
u
,in units of the primitive vectors
 ð
a
;
0
;
Þ
,
 
12
a
;
 ffiffi 
3
2
 a
;
, and
12
a
;
 ffiffi 
3
2
 a
;
, where
 u
 is the internal lattice parameter and
 a
and
 
 are the lattice constants. The hexagonal elementary cell isthree times bigger and it contains 6 formula units and 30 atoms.Since most of the previous studies [26–30,32–35] published thestructural parameters (e.g. the equilibrium volume) with respectto the 30-atom elementary cell (rather then to the formula unit)we keep this nomenclature throughout this work. Since a singlesupercell contains 6 formula units of calcite, 6 different ratios of Ca and Mg atoms could be studied.Our calculations are based on density functional theory (DFT)[38,39] using the generalized gradient approximation (GGA) [40]and the projected augmented wave approach (PAW) as imple-mented in the Vienna Ab-initio Simulation Package (VASP) code[41–43]. The GGA was chosen due to its satisfactory performancein the studied class of materials (e.g. [44–47]). The plane-wavecut-off energy was 390Ry and a 4
8
6 Monkhorst–Pack meshwas used to sample the Brillouin zone of the 30-atom supercells(see Fig. 3). Convergence with respect to cutoff energy and
 k
-pointsampling has been explicitly checked.
2. Results for calcite and magnesite
The equilibrium structural and elastic characteristics are sum-marizedinTable1for calciteandinTable2formagnesitetogether with previously calculated values and experimental data. As seenin Tables 1 and 2, our results are in close agreement with theexperimental data. The equilibrium volumes are slightly overesti-mated for both carbonates and the bulk moduli are slightly under-estimated as compared to experimental data but the qualitativetrends are well reproduced. The calculated larger equilibrium vol-ume is attributed to the use of GGA for the exchange and correla-tion potential, which is well known to slightly overestimate thelattice constant and slightly underestimate the bulk modulus(e.g. [44–46]).As far as the interatomic distances are concerned, it is interest-ing to note that the distances within the CO
2
3
 groups are nearlyindependent of the composition of the actual carbonate. The C–Odistance differs only by 0.23% in CaCO
3
 and MgCO
3
, being a bitsmaller in the latter. This is in agreement with both previous the-oretical studies and experimental findings as listed in Tables 1 and2. In contrast, the Ca–O or Mg–O interatomic distances are pre-dicted to differ substantially (10.82%) in the two studied com-pounds in agreement with previous theoretical and experimentalfindings. This canbe explained interms of the larger atomic radiusof a Ca atom with respect to a Mg atom. This is clearly depicted inTable 3: the volume per atom in the face-centered cubic (fcc) Caground state is almost two times larger than the correspondingvolume in the experimentally observed ambient-condition groundstate hexagonal close-packed (hcp) Mg. Furthermore, the experi-mental nearest neighbor distance, 3.95Å in fcc Ca [52], is larger than the corresponding distance, 3.20Å, in hcp Mg [53].In order to examine how pressure affects the structure, we plotinFig.4thedependenceoftheinteratomicbondsasfunctionoftheapplied hydrostatic strain. In agreement with a previous theoreti-cal study by Catti et al. [27], three different trends for the inter- atomic distance can be seen. The interlayer Ca–O and Mg–Odistances(seeFig. 2) showthestrongest responseuponvolumetricchanges. The response of the interplanar Ca–Ca and Mg–Mglengthsarelesssensitiveandthesmallestchangesareinthelengthof C–O bonds within the CO
2
3
 groups. These differences in thebehavioroftheC–Obondswithrespecttotheotherbondsindicatethe different character (covalent vs. ionic) and strength of inter-atomic bonding in the studied compounds. A similar behaviorhasbeenobservedfortransition-metal(TM) disilicidesinresponseto tensile loading [57,58]) where Si–Si and TM–Si bonds with dif-
Fig. 2.
 Layered crystalline structure of CaCO
3
. The Ca atoms are visualized as light-blue sphere, O atoms as light-green spheres, and C as gray spheres.4508
 P. Elstnerová et al./Acta Biomaterialia 6 (2010) 4506–4512

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