A series of inverse-microemulsion quasi-ternary system phase diagrams of CTAB + n-butanol + n-hexane + brine (MgCl₂/CaCl₂) is systematically drawn by adjusting the ratio of MgCl₂ and CaCl₂. On this basis, a microemulsion has been prepared with five different molar ratios of magnesium ions to calcium ions, and a calcium carbonate and magnesium carbonate coprecipitation product is obtained by reaction with an equimolar amount of sodium carbonate. The samples were characterised by scanning electron microscopy (SEM), a Fourier transform infrared (FTIR) spectrometer and X-ray diffraction (XRD). The SEM photographs indicated that when the content of Ca²⁺ was higher, some large fusiform aggregates of coprecipitation particles were formed in solution, but with the content of Mg²⁺ increased gradually, they eventually formed small and uniform sphere particles. The measurement results of XRD and FTIR indicated that the crystal structures of calcium carbonate in coprecipitation changed gradually from vaterite into aragonite and finally turned into being amorphous with the increasing of the proportion of magnesium ions.

References

1. 1)
  - 8. Chen, D.H., Chen, Y.Y.: ‘Synthesis of strontium ferrite ultrafine particles using microemulsion processing’, J. Colloid. Interface. Sci., 2001, 23, pp. 41–46 (doi: 10.1006/jcis.2000.7389).
2. 2)
  - 28. Kang, S.H., Hirasawa, I., Kim, W.S., Choi, C.K.: ‘Morphological control of calcium carbonate crystallized in reverse micelle system with anionic surfactants SDS and AOT’, J. Colloid Interface Sci., 2005, 288, pp. 496–502 (doi: 10.1016/j.jcis.2005.03.015).
3. 3)
  - 21. Folk, R.L.: ‘The natural of history of crystalline calcium carbonate; effect of magnesium content and salinity’, J. Sedimentol. Pet., 1974, 44, pp. 40–53.
4. 4)
  - 30. Mandell, G.K., Rock, P.A.: ‘Lattice energies of calcite structure metal carbonates II. Results for CaCO3, CdCO3, FeCO3, MgCO3 and MnCO3’, J. Phys. Chem. Solid, 1998, 59, pp. 703–712 (doi: 10.1016/S0022-3697(97)90225-0).
5. 5)
  - 19. Balogh, L., Tomalia, D.A.: ‘Poly(amidoamine) dendrimer-templated nanocomposites. 1. Synthesis of zerovalent copper nanoclusters’, J. Am. Chem. Soc., 1998, 120, pp. 7355–7356 (doi: 10.1021/ja980861w).
6. 6)
  - 24. Zhang, Z.N., Xie, Y.D., Xun, X.R., Pan, H.H., Tang, R.K.: ‘Transformation of amorphous calcium carbonate into aragonite’, J. Cryst. Growth, 2012, 343, pp. 62–67 (doi: 10.1016/j.jcrysgro.2012.01.025).
7. 7)
  - 16. Xu, A.W., Yu, Q., Dong, W.F., Antonietti, M., Colfen, H.: ‘Stable amorphous microparticles with hollow spherical superstructures stabilized by phytic acid’, Adv. Mater., 2005, 17, pp. 2217–2221 (doi: 10.1002/adma.200500747).
8. 8)
  - 27. Wang, N., Wang, X.Q., Yang, L.J., Chen, H.S.: ‘The morphology and size control of nano calcium carbonate crystallised in reverse micelle system with cationic surfactant CTAB’, Micro Nano Lett., 2013, 8, pp. 94–98 (doi: 10.1049/mnl.2012.0831).
9. 9)
  - 6. Curri, M.L., Gostiano, A., Mavelli, F.: ‘Reverse micellar systems: self organized assembly as effective route for the synthesis of colloidal semiconductor nanocrystals’, Mater. Sci. Eng. C., 2002, 22, pp. 423–426 (doi: 10.1016/S0928-4931(02)00196-0).
10. 10)
  - 29. Glasser, L., Jenkins, H.D.B.: ‘Lattice energies and unit cell volumes of complex ionic solids’, J. Am. Chem. Soc., 2000, 122, pp. 632–638 (doi: 10.1021/ja992375u).
11. 11)
  - 1. Lowenstam, H.A.: ‘Spicular morphology and mineralogy in some Pyuridae (Ascidiacea)’, Bull. Mar. Sci., 1989, 45, pp. 243–252.
12. 12)
  - 31. Yang, S.H., Wu, G.H.: ‘Model of ionic hydrate and calculation of hydration energy’, J. Inorg. Chem., 1988, 4, pp. 124–129.
13. 13)
  - 4. Schulman, J.H., Stoekenius, W., Prince, L.M.: ‘Mechanism of formation and structure of microemulsions by electron microscopy’, J. Phys. Chem., 1959, 63, pp. 1677–1680 (doi: 10.1021/j150580a027).
14. 14)
  - 9. Pillai, V., Kumar, P.: ‘Structure and magnetic properties of nanoparticles of barium ferrite synthesized using microemulsion processing’, Colloids Surf. A, 1993, 80, pp. 69–75 (doi: 10.1016/0927-7757(93)80225-4).
15. 15)
  - 20. Groot, K.D., Duyvis, E.M.: ‘Crystal form of precipitated calcium carbonate as influenced by adsorbed magnesium ions’, Nature, 1966, 212, pp. 183–184 (doi: 10.1038/212183a0).
16. 16)
  - 3. Addadi, L., Raz, S., Weiner, S.: ‘Taking advantage of disorder: amorphous calcium carbonate and its role in biomineralization’, Adv. Mater., 2003, 15, pp. 959–970 (doi: 10.1002/adma.200300381).
17. 17)
  - 17. Naka, K.: ‘Effect of dendrimers on the crystallization of calcium carbonate in aqueous solution’, Top. Curr. Chem., 2003, 228, pp. 141–158 (doi: 10.1007/b11009).
18. 18)
  - 11. Bischoff, W.D., Mackenzie, F.T., Bishop, F.C.: ‘Stabilities of synthetic magnesian calcites in aqueous solution: comparison with biogenic materials’, Geochim. Cosmochim. Acta, 1987, 51, pp. 1413–1423 (doi: 10.1016/0016-7037(87)90325-5).
19. 19)
  - 10. Chave, K.E.: ‘Aspects of the biogeochemistry of magnesium 2. Calcareous marine organisms’, J. Geol., 1954, 62, pp. 587–599 (doi: 10.1086/626208).
20. 20)
  - 12. Chave, K.E.: ‘Aspects of the biogeochemistry of magnesium 1. Calcareous marine organisms’, J. Geol., 1954, 62, pp. 266–283 (doi: 10.1086/626162).
21. 21)
  - 25. Tlili, M.M., Amor, M.B., Gabrielli, C., Joiret, S., Maurin, G., Rousseau, P.: ‘Characterization of CaCO3 hydrates by micro-Raman spectroscopy’, J. Raman Spectrosc., 2002, 33, pp. 10–16 (doi: 10.1002/jrs.806).
22. 22)
  - 2. Zenger, D.H.: ‘Sedimentary carbonate minerals’ (Springer, Berlin,Germany, 1973).
23. 23)
  - 13. Yong, J.H., Aizenberg, J.: ‘Effect of magnesium ions on oriented growth of calcite on carboxylic acid functionalized self-assembled monolayer’, J. Am. Chem. Soc., 2003, 125, pp. 4032–4033 (doi: 10.1021/ja034094z).
24. 24)
  - 14. Loste, E., Wilson, R.M., Seshadri, R., Meldrum, F.C.: ‘The role of magnesium in stabilising amorphous calcium carbonate and controlling calcite morphologies’, J. Cryst. Growth, 2003, 254, pp. 206–218 (doi: 10.1016/S0022-0248(03)01153-9).
25. 25)
  - 7. Lu, C.H., Saha, S.K.: ‘Synthesis of ultrafine strontium bismuth tantalate powder by colloid-emulsion technique’, Mater. Lett., 2000, 42, pp. 150–154 (doi: 10.1016/S0167-577X(99)00174-3).
26. 26)
  - 23. Xu, X.R., Han, J.T., Cho, K.: ‘Formation of amorphous calcium carbonate thin films and their role in biomineralization’, Chem. Mater., 2004, 16, pp. 1740–1746 (doi: 10.1021/cm035183d).
27. 27)
  - 18. Zhao, M.Q., Sun, L., Crooks, R.M.: ‘Preparation of Cu nanoclusters within dendrimer templates’, J. Am. Chem. Soc., 1998, 120, pp. 4877–4878 (doi: 10.1021/ja980438n).
28. 28)
  - 15. Shen, F.H., Feng, Q.L., Wang, C.M.: ‘The modulation of collagen on crystal morphology of calcium carbonate’, J. Cryst. Growth, 2002, 242, pp. 239–244 (doi: 10.1016/S0022-0248(02)01376-3).
29. 29)
  - 5. Wang, C.C., Dong, H.C., Huang, T.C.: ‘Synthesis of palladium nanoparticies in water-in-oil microemulsion’, Colloids Surf. A., 2001, 189, pp. 145–154 (doi: 10.1016/S0927-7757(01)00576-3).
30. 30)
  - 22. Lahann, R.W.: ‘A chemical model for calcite crystal growth and morphology control’, J. Sedimentol. Pet., 1978, 48, pp. 337–347.
31. 31)
  - 26. Neumann, M., Epple, M.: ‘Monohydrocalcite and its relationship to hydrated amorphous calcium carbonate in biominerals’, J. Inorg. Chem., 2007, 14, pp. 1953–1957 (doi: 10.1002/ejic.200601033).

Study of the influence between magnesium ions and calcium ions on the morphology and size of coprecipitation in microemulsion

References

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