Skip to main content
Log in

High-yield synthesis of vaterite CaCO3 microspheres in ethanol/water: structural characterization and formation mechanisms

  • Original Paper
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Calcium carbonate (CaCO3) is widely used as an important model system for investigating inorganic precipitation reaction or crystallization. However, recent results show that the yield of vaterite CaCO3 microspheres is poor in ethanol/water in the presence of polyelectrolyte poly(sodium 4-styrenesulfate) (PSS), which is up to 16 mM. We now report on an approach to synthesize pure vaterite CaCO3 microspheres through improving the concentration of polymer PSS and the yield is greatly high up to 80 mM. The exploration provides the possibility for large-scale synthesis of CaCO3 materials with controllable morphology and crystallographic structure in aqueous solution at room temperature. The possible formation mechanism toward the occurrence of vaterite CaCO3 microspheres has also been illustrated in virtue of a series of time-resolved experimental results. It is revealed that the vaterite microspheres evolve gradually from the initial amorphous precursor, to poorly crystallized nanoparticles, to sphere-like aggregates, and then to vaterite microspheres embedded with the calcite rhombohedra, finally to the vaterite microspheres with smooth surface. This research may provide a new viewpoint into the forming process of vaterite CaCO3 microspheres.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Cölfen H, Qi L (2001) A Systematic examination of the morphogenesis of calcium carbonate in the presence of a double-hydrophilic block copolymer. Chem Eur J 7:106–116

    Article  Google Scholar 

  2. Preisig D, Haid D, Varum FJ et al (2014) Drug loading into porous calcium carbonate microparticles by solvent evaporation. Eur J Pharm Biopharm 87:548–558

    Article  Google Scholar 

  3. Tang H, Yu JG, Ng DHL (2007) PSSS-controlled synthesis of CaCO3 superstructures. Cryst Res Technol 42:856–861

    Article  Google Scholar 

  4. Mann S, Ozin GA (1996) Synthesis of inorganic materials with complex form. Nature 382:313–318

    Article  Google Scholar 

  5. Yang H, Coombs N, Ozin GA (1997) Morphogenesis of shapes and surface patterns in mesoporous silica. Nature 386:692–695

    Article  Google Scholar 

  6. Tang H, Yu JG, Zhao XF, Ng DHL (2008) Influence of PSSS on the morphology and polymorph of calcium carbonate in the ethanol–water mixed system. J Alloy Compd 463:343–349

    Article  Google Scholar 

  7. Suda S, Ichikawa S, Wada N, Umegaki T (2000) Morphology of calcium carbonate coating on amorphous silicate powder. J Mater Sci 35:3023–3028. doi:10.1023/A:1004791129661

    Article  Google Scholar 

  8. Zhao LN, Wang JK, Wang ZC (2013) Influnence of sodium polyacrylate on crystallization and aggregation of butterfly-like calcium carbonate. Chem Res Chin Univ 29:969–973

    Article  Google Scholar 

  9. Zhao YY, Du W, Sun LM, Yu L, Jiao JJ, Wang R (2013) Facile synthesis of calcium carbonate with an absolutely pure crystal form using 1-butyl-3-methylimidazolium dodecyl sulfate as the modifier. Colloid Polym Sci 291:2191–2202

    Article  Google Scholar 

  10. Guo YM, Wang FF, Zhang J et al (2013) Biomimetic synthesis of calcium carbonate with different morphologies under the direction of different amino acids. Res Chem Intermed 39:2407–2415

    Article  Google Scholar 

  11. Flaten EM, Seiersten M, Andreassen JP (2009) Polymorphism and morphology of calcium carbonate precipitated in mixed solvents of ethylene glycol and water. J Cryst Growth 311:3533–3538

    Article  Google Scholar 

  12. Wang CY (2008) Control the polymorphism and morphology of calcium carbonate precipitation from a calcium acetate and urea solution. Mater Lett 62:2377–2380

    Article  Google Scholar 

  13. Bao SP, Chen XY, Li Z, Yang BJ, Wu YC (2011) Effects of solvent and additive on controllable mineralization of MCO3 (M = Ca, Ba, Sr) crystals and their applications as red phosphors doped with Eu3+ ions. Cryst Eng Comm 13:2511–2520

    Article  Google Scholar 

  14. Xu AW, Ma YR, Cölfen H (2007) Biomimetic mineralization. J Mater Chem 17:415–449

    Article  Google Scholar 

  15. Mihai M, Mountrichas G, Pispas S et al (2013) Calcium carbonate microparticle templates using a PHOS-b-PMAA double hydrophilic copolymer. J Appl Crystallogr 46:1455–1466

    Article  Google Scholar 

  16. Lei M, Tang WH, Cao LZ, Li PG, Yu JG (2006) Effects of poly (sodium 4-styrene-sulfonate) on morphology of calcium carbonate particles. J Cryst Growth 294:358–366

    Article  Google Scholar 

  17. Yu JG, Tang H, Cheng B (2005) Influence of PSSS additive and temperature on morphology and phase structures of calcium oxalate. J Colloid Interf Sci 288:407–411

    Article  Google Scholar 

  18. Meldrum F, Cölfen H (2008) Controlling mineral morphologies and structures in biological and synthetic systems. Chem Rev 108:4332–4432

    Article  Google Scholar 

  19. Wang SS, Picker A, Cölfen H, Xu AW (2013) Heterostructured calcium carbonate microspheres with calcite equatorial loops and vaterite spherical cores. Angew Chem Int Ed 52:6317–6321

    Article  Google Scholar 

  20. Chen HI, Chang HY (2004) Homogeneous precipitation of cerium dioxide nanoparticles in alcohol/water mixed solvents. Colloid Surf A 242:61–69

    Article  Google Scholar 

  21. Dickinson SR, McGrath KM (2003) Switching between kinetic and thermodynamic control: calcium carbonate growth in the presence of a simple alcohol. J Mater Chem 13:928–933

    Article  Google Scholar 

  22. Zhang L, Yue LH, Wang F, Wang Q (2008) Divisive effect of alcohol-water mixed solvents on growth morphology of calcium carbonate crystals. J Phys Chem B 112:10668–10674

    Article  Google Scholar 

  23. Yao Y, Dong WY, Zhu SM, Yu XH, Yan DY (2009) Novel morphology of calcium carbonate controlled by poly(l-lysine). Langmuir 25:13238–13243

    Article  Google Scholar 

  24. Smeets PJ, Cho KR, Kempen RG, Sommerdijk NA, De Yoreo JJ (2005) Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy. Nat Mater 14:394–399

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Baojun Yang.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (PDF 373 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, Z., Yang, B., Tang, H. et al. High-yield synthesis of vaterite CaCO3 microspheres in ethanol/water: structural characterization and formation mechanisms. J Mater Sci 50, 5540–5548 (2015). https://doi.org/10.1007/s10853-015-9101-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-015-9101-2

Keywords

Navigation