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Snapshots of calcium carbonate formation – a step by step analysis

  • Michael Dietzsch , Iryna Andrusenko , Robert Branscheid , Franziska Emmerling , Ute Kolb and Wolfgang Tremel EMAIL logo
Published/Copyright: February 3, 2017
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 232 Issue 1-3

Abstract

Recent advances in our understanding of CaCO3 nucleation from solution have provoked new and challenging questions. We have studied CaCO3 formation using precipitation by carbonate ester hydrolysis which ensures precipitation from a strictly homogeneous solution state and allows “titrating” carbonate to a solution with a given Ca2+ concentration on a timescale suited for kinetic studies. Nucleation and crystallization were traced by combining dynamic light scattering (DLS) and transmission electron microscopy (TEM). DLS served as in situ technique to identify the nucleation time, to monitor particle size evolution, to discriminate different precipitation mechanisms and to validate reproducibility. TEM snapshots taken during different stages of the precipitation process identified different phases and morphologies. At a high level of supersaturation homogeneous nucleation in solution led to the formation of amorphous CaCO3 particles (Ø≈30 nm), which transformed via vaterite to calcite. Nucleation occurred uniformly in solution which appears to be unique for the CaCO3 system. In the presence of Na-polymethacrylate (Na-PMA), heterogeneous nucleation was suppressed and Ca-polymer aggregates were formed in the prenucleation stage. Beyond a critical threshold supersaturation CaCO3 particles formed in solution outside of these aggregates. The nucleation process resembled that without additive, indicating that Na-PMA exerts only a minor effect on the CaCO3 nucleation. In the postnucleation stage, the polymer led to the formation of extended liquid-like networks, which served as a precursor phase for solid ACC particles that formed alongside the network.

Keywords: biomineralization; calcium carbonate; nucleation; polymer additives

Acknowledgments

This study was funded by the Deutsche Forschungsgemeinschaft (DFG) within the priority program 1415. M. Dietzsch is recipient of a Carl-Zeiss Fellowship and a collegiate of the MAINZ Graduate School of the State of Rhineland-Palatinate. We are indebted to M. Schmidt for giving access to the light scattering instruments. We are grateful to Prof. Dr. M. Schmidt and Dr. K. Fischer for helpful discussions. The facilities of the Electron Microscopy Center in Mainz (EZMZ) were supported by the State Excellence Cluster COMATT and SFB 625.

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Supplemental Material:

The online version of this article (DOI: 10.1515/zkri-2016-1973) offers supplementary material, available to authorized users.

Received: 2016-6-4
Accepted: 2016-12-5
Published Online: 2017-2-3
Published in Print: 2017-2-1

©2017 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Editorial
  4. Synthesis and characterization of metastable transition metal oxides and oxide nitrides
  5. Control of organic polymorph formation: crystallization pathways in acoustically levitated droplets
  6. Thermal annealing of natural, radiation-damaged pyrochlore
  7. The formation of CdS quantum dots and Au nanoparticles
  8. Crystalline chalcogenido metalates – synthetic approaches for materials synthesis and transformation
  9. Fundamental theoretical and practical investigations of the polymorph formation of small amphiphilic molecules, their co-crystals and salts
  10. A density-functional theory approach to the existence and stability of molybdenum and tungsten sesquioxide polymorphs
  11. The ZIF system zinc(II) 4,5-dichoroimidazolate: theoretical and experimental investigations of the polymorphism and crystallization mechanisms
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  14. Scaled-up solvothermal synthesis of nanosized metastable indium oxyhydroxide (InOOH) and corundum-type rhombohedral indium oxide (rh-In2O3)
  15. Development and application of novel NMR methodologies for the in situ characterization of crystallization processes of metastable crystalline materials
  16. Phase formation and stability in TiOx and ZrOx thin films: Extremely sub-stoichiometric functional oxides for electrical and TCO applications
  17. Investigations on the growth of bismuth oxido clusters and the nucleation to give metastable bismuth oxide modifications
  18. Divalent metal phosphonates – new aspects for syntheses, in situ characterization and structure solution
  19. Type-I silicon clathrates containing lithium
  20. Experimental and theoretical investigation of the chromium–vanadium–antimony system
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https://doi.org/10.1515/zkri-2016-1973
Keywords for this article
biomineralization; calcium carbonate; nucleation; polymer additives

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Editorial
  4. Synthesis and characterization of metastable transition metal oxides and oxide nitrides
  5. Control of organic polymorph formation: crystallization pathways in acoustically levitated droplets
  6. Thermal annealing of natural, radiation-damaged pyrochlore
  7. The formation of CdS quantum dots and Au nanoparticles
  8. Crystalline chalcogenido metalates – synthetic approaches for materials synthesis and transformation
  9. Fundamental theoretical and practical investigations of the polymorph formation of small amphiphilic molecules, their co-crystals and salts
  10. A density-functional theory approach to the existence and stability of molybdenum and tungsten sesquioxide polymorphs
  11. The ZIF system zinc(II) 4,5-dichoroimidazolate: theoretical and experimental investigations of the polymorphism and crystallization mechanisms
  12. Element allotropes and polyanion compounds of pnicogenes and chalcogenes: stability, mechanisms of formation, controlled synthesis and characterization
  13. Structure and ion dynamics of mechanosynthesized oxides and fluorides
  14. Scaled-up solvothermal synthesis of nanosized metastable indium oxyhydroxide (InOOH) and corundum-type rhombohedral indium oxide (rh-In2O3)
  15. Development and application of novel NMR methodologies for the in situ characterization of crystallization processes of metastable crystalline materials
  16. Phase formation and stability in TiOx and ZrOx thin films: Extremely sub-stoichiometric functional oxides for electrical and TCO applications
  17. Investigations on the growth of bismuth oxido clusters and the nucleation to give metastable bismuth oxide modifications
  18. Divalent metal phosphonates – new aspects for syntheses, in situ characterization and structure solution
  19. Type-I silicon clathrates containing lithium
  20. Experimental and theoretical investigation of the chromium–vanadium–antimony system
  21. Synthesis and crystal structure of three new bismuth(III) arylsulfonatocarboxylates
  22. Snapshots of calcium carbonate formation – a step by step analysis
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