Abstract
The synthetic anhydrous crystalline CaCO3 polymorphs—vaterite, aragonite and calcite—were tested using dilatometry and nanoindentation. Microstructural 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.
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References
Dobrev J, Markovic P (2012) Calcite: formation, properties, and applications. Nova Science Publishers, New York
Rodriguez-Blanco JD, Shaw S, Benning LG (2011) The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite. Nanoscale 3:265–271. https://doi.org/10.1039/C0NR00589D
Dhami NK, Reddy MS, Mukherjee A (2013) Biomineralization of calcium carbonates and their engineered applications: a review. Front Microbiol 4:1–13. https://doi.org/10.3389/fmicb.2013.00314
Yao H-B, Ge J, Mao L-B et al (2014) 25th anniversary article: artificial carbonate nanocrystals and layered structural nanocomposites inspired by Nacre: synthesis, fabrication and applications. Adv Mater 26:163–188. https://doi.org/10.1002/adma.201303470
Radha AV, Navrotsky A (2013) Thermodynamics of carbonates. Rev Mineral Geochem 77:73–121. https://doi.org/10.2138/rmg.2013.77.3
Balen KV, Gemert DV (1994) Modelling lime mortar carbonation. Mater Struct 27:393–398. https://doi.org/10.1007/BF02473442
Cowper AD, Building Research Station, Building Research Establishment (1998) Lime and lime mortars. Donhead, Shaftesbury
Daniele V, Taglieri G (2011) Ca(OH)2 nanoparticle characterization: microscopic investigation of their application on natural stones. Mater Char 72:55–66. https://doi.org/10.2495/MC110051
Daniele V, Taglieri G, Quaresima R (2008) The nanolimes in cultural heritage conservation: characterisation and analysis of the carbonatation process. J Cult Herit 9:294–301. https://doi.org/10.1016/j.culher.2007.10.007
Drdácký M, Slížková Z, Ziegenbalg G (2009) Α nano approach to consolidation of degraded historic lime mortars. J Nano Res 8:13–22. https://doi.org/10.4028/www.scientific.net/JNanoR.8.13
Licchelli M, Malagodi M, Weththimuni M, Zanchi C (2013) Nanoparticles for conservation of bio-calcarenite stone. Appl Phys A 114:673–683. https://doi.org/10.1007/s00339-013-7973-z
Natali I, Saladino ML, Andriulo F et al (2014) Consolidation and protection by nanolime: recent advances for the conservation of the graffiti, Carceri dello Steri Palermo and of the 18th century lunettes, SS. Giuda e Simone Cloister, Corniola (Empoli). J Cult Herit 15:151–158. https://doi.org/10.1016/j.culher.2013.03.002
Gomez-Villalba LS, López-Arce P, Alvarez de Buergo M, Fort R (2011) Structural stability of a colloidal solution of Ca(OH)2 nanocrystals exposed to high relative humidity conditions. Appl Phys A 104:1249–1254. https://doi.org/10.1007/s00339-011-6457-2
Gomez-Villalba LS, López-Arce P, Fort R (2012) Nucleation of CaCO3 polymorphs from a colloidal alcoholic solution of Ca(OH) nanocrystals exposed to low humidity conditions. Appl Phys A 106:213–217. https://doi.org/10.1007/s00339-011-6550-6
López-Arce P, Gómez-Villalba LS, Martínez-Ramírez S et al (2011) Influence of relative humidity on the carbonation of calcium hydroxide nanoparticles and the formation of calcium carbonate polymorphs. Powder Technol 205:263–269. https://doi.org/10.1016/j.powtec.2010.09.026
Rodriguez-Navarro C, Elert K, Ševčík R (2016) Amorphous and crystalline calcium carbonate phases during carbonation of nanolimes: implications in heritage conservation. CrystEngComm 35:6594–6607. https://doi.org/10.1039/C6CE01202G
Fiori C, Vandini M, Prati S, Chiavari G (2009) Vaterite in the mortars of a mosaic in the Saint Peter basilica, Vatican (Rome). J Cult Herit 10:248–257. https://doi.org/10.1016/j.culher.2008.07.011
Marey Mahmoud HH, Ali MF, Pavlidou E et al (2011) Characterization of plasters from ptolemaic baths: new excavations near the Karnak temple complex, Upper Egypt. Archaeometry 53:693–706. https://doi.org/10.1111/j.1475-4754.2010.00572.x
Signorelli S (1996) The presence of vaterite in bonding mortars of marble inlays from Florence Cathedral. Mineral Mag 60:663–665. https://doi.org/10.1180/minmag.1996.060.401.13
Rodriguez-Navarro C, Jimenez-Lopez C, Rodriguez-Navarro A et al (2007) Bacterially mediated mineralization of vaterite. Geochim Cosmochim Acta 71:1197–1213. https://doi.org/10.1016/j.gca.2006.11.031
De Muynck W, De Belie N, Verstraete W (2010) Microbial carbonate precipitation in construction materials: a review. Ecol Eng 36:118–136. https://doi.org/10.1016/j.ecoleng.2009.02.006
Fischer-Cripps AC (2011) Nanoindentation. Springer, New York
Ren D, Meyers MA, Zhou B, Feng Q (2013) Comparative study of carp otolith hardness: lapillus and asteriscus. Mater Sci Eng C 33:1876–1881. https://doi.org/10.1016/j.msec.2012.10.015
Müller WEG, Neufurth M, Schlossmacher U et al (2013) The sponge silicatein-interacting protein silintaphin-2 blocks calcite formation of calcareous sponge spicules at the vaterite stage. RSC Adv 4:2577–2585. https://doi.org/10.1039/C3RA45193C
Presser V, Gerlach K, Vohrer A et al (2010) Determination of the elastic modulus of highly porous samples by nanoindentation: a case study on sea urchin spines. J Mater Sci 45:2408–2418. https://doi.org/10.1007/s10853-010-4208-y
Bruet BJF, Qi HJ, Boyce MC et al (2005) Nanoscale morphology and indentation of individual nacre tablets from the gastropod mollusc Trochus niloticus. J Mater Res 20:2400–2419. https://doi.org/10.1557/jmr.2005.0273
Calvaresi M, Falini G, Pasquini L et al (2013) Morphological and mechanical characterization of composite calcite/SWCNT–COOH single crystals. Nanoscale 5:6944–6949. https://doi.org/10.1039/C3NR01568H
Ševčík R, Pérez-Estébanez M, Viani A et al (2015) Characterization of vaterite synthesized at various temperatures and stirring velocities without use of additives. Powder Technol 284:265–271. https://doi.org/10.1016/j.powtec.2015.06.064
Lucas A, Mouallem-Bahout M, Carel C et al (1999) Thermal expansion of synthetic aragonite condensed review of elastic properties. J Solid State Chem 146:73–78. https://doi.org/10.1006/jssc.1999.8310
Salje E, Viswanathan K (1976) The phase diagram calcite-aragonite as derived from the crystallographic properties. Contrib Mineral Petrol 55:55–67. https://doi.org/10.1007/BF00372754
Wu T-C, Shen AH, Weathers MS et al (1995) Anisotropic thermal expansion of calcite at high pressures; an in situ X-ray diffraction study in a hydrothermal diamond-anvil cell. Am Mineral 80:941–946. https://doi.org/10.2138/am-1995-9-1010
Ye Y, Smyth JR, Boni P (2012) Crystal structure and thermal expansion of aragonite-group carbonates by single-crystal X-ray diffraction. Am Mineral 97:707–712. https://doi.org/10.2138/am.2012.3923
Gebauer D, Oliynyk V, Salajkova M et al (2011) A transparent hybrid of nanocrystalline cellulose and amorphous calcium carbonate nanoparticles. Nanoscale 3:3563–3566. https://doi.org/10.1039/c1nr10681c
Malinova K, Gunesch M, Pancera SM et al (2012) Production of CaCO3/hyperbranched polyglycidol hybrid films using spray-coating technique. J Colloid Interface Sci 374:61–69. https://doi.org/10.1016/j.jcis.2012.02.011
Pérez-Huerta A, Cusack M, Zhu W et al (2007) Material properties of brachiopod shell ultrastructure by nanoindentation. J R Soc Interface 4:33–39. https://doi.org/10.1098/rsif.2006.0150
Ševčík R, Mácová P, Pérez-Estébanez M (2015) Crystallization of aragonite from vaterite precursor during various refluxing times. Adv Mater Res 1119:466–470. https://doi.org/10.4028/www.scientific.net/AMR.1119.466
Sarkar A, Mahapatra S (2010) Synthesis of all crystalline phases of anhydrous calcium carbonate. Cryst Growth Des 10:2129–2135. https://doi.org/10.1021/cg9012813
Oliver WC, Pharr GM (1992) An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J Mater Res 7:1564–1583. https://doi.org/10.1557/JMR.1992.1564
Han J, Pan G, Sun W et al (2012) Application of nanoindentation to investigate chemomechanical properties change of cement paste in the carbonation reaction. Sci China Technol Sci 55:616–622. https://doi.org/10.1007/s11431-011-4571-1
Rietveld HM (1969) A profile refinement method for nuclear and magnetic structures. J Appl Crystallogr 2:65–71. https://doi.org/10.1107/S0021889869006558
Meyer HJ (1959) Über vaterit und seine struktur. Angew Chem 71:678–679
Demichelis R, Raiteri P, Gale JD, Dovesi R (2013) The multiple structures of vaterite. Cryst Growth Des 13:2247–2251. https://doi.org/10.1021/cg4002972
Young RA (2002) The Rietveld method, Repr. Oxford University Press, Oxford
Meldrum FC, Cölfen H (2008) Controlling mineral morphologies and structures in biological and synthetic systems. Chem Rev 108:4332–4432. https://doi.org/10.1021/cr8002856
Putnis A (1992) An introduction to mineral sciences. Cambridge University Press, Cambridge
Grima NJ, Zammit V, Gatt R (2006) Negative thermal expansion. Xjenza J Malta Chamb Sci 11:17–29
Barrera GD, Bruno JAO, Barron THK, Allan NL (2005) Negative thermal expansion. J Phys Condens Matter 17:R217–R252. https://doi.org/10.1088/0953-8984/17/4/R03
Prisco LP, Romao CP, Rizzo F et al (2013) The effect of microstructure on thermal expansion coefficients in powder-processed Al2Mo3O12. J Mater Sci 48:2986–2996. https://doi.org/10.1007/s10853-012-7076-9
Srikanth V, Subbarao EC, Rao GV (1992) Thermal expansion anisotropy, microcracking and acoustic emission of Nb2O5 ceramics. Ceram Int 18:251–261. https://doi.org/10.1016/0272-8842(92)90103-K
Wardecki D, Przeniosło R, Brunelli M (2008) Internal pressure in annealed biogenic aragonite. CrystEngComm 10:1450–1453. https://doi.org/10.1039/B805508D
Tai CY, Chen F-B (1998) Polymorphism of CaCO3 precipitated in a constant-composition environment. AIChE J 44:1790–1798. https://doi.org/10.1002/aic.690440810
Dhami NK, Mukherjee A, Reddy MS (2016) Micrographical, minerological and nano-mechanical characterisation of microbial carbonates from urease and carbonic anhydrase producing bacteria. Ecol Eng 94:443–454. https://doi.org/10.1016/j.ecoleng.2016.06.013
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.
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Ševčík, R., Šašek, P. & Viani, A. Physical and nanomechanical properties of the synthetic anhydrous crystalline CaCO3 polymorphs: vaterite, aragonite and calcite. J Mater Sci 53, 4022–4033 (2018). https://doi.org/10.1007/s10853-017-1884-x
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DOI: https://doi.org/10.1007/s10853-017-1884-x