Yıl 2021, Cilt 8 , Sayı 1, Sayfalar 117 - 124 2021-02-28

Polymorphic Phase Change of Calcium Carbonate with Glutamic Acid as an Additive

Sevgi POLAT [1] , Tuba ÖZALP [2] , Perviz SAYAN [3]

The calcium carbonate (CaCO3) crystals were successfully synthesized in the presence of glutamic acid used as an additive at 30 °C and at a pH of 8.5. The synthesized product was characterized in detailed by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectrometry and scanning electron microscopy (SEM) to identify the structure and habit of the crystals. Moreover, the size and surface charge of the crystals were measured by particle size and zeta potential analyzer. XRD and FTIR results showed that both calcite and vaterite in forms of apparently CaCO3 crystals were obtained in the presence of 50 ppm additive concentration at t=30 min. When increasing the glutamic acid concentration in the suspension, the formed CaCO3 were only in the vaterite form. The SEM analysis results pointed out that the addition of the glutamic acid significantly changed the shape of the CaCO3. At t=30 min the resulting product sample was found to contain two types of polymorphs; larger cubic shaped calcite crystals and smaller spherical-like vaterite crystals. Further addition of high concentrations of the additive enhanced the adsorption of the glutamic acid, resulting in the smaller spherical-like ellipsoidal vaterite crystals. Investigation of the zeta potential analysis indicated that higher additive concentration (100 ppm) resulted in a positive surface charge of the crystals, whereas lower concentration (50 ppm) gave negative electrical charge. Moreover, filtration analysis pointed out that adding glutamic acid additive resulted in a less specific cake resistance value (5.01 × 1011 m/kg) than that in pure media, which was 1.03 × 1012 m/kg.
Calcium carbonate, polymorphism, crystal morphology, additive
  • Zhao Z, Zhang L, Dai H, Du Y, Meng X, Zhang R, et al. Surfactant-assisted solvo- or hydrothermal fabrication and characterization of high-surface-area porous calcium carbonate with multiple morphologies. Microporous Mesoporous Mater. 2011;138:191-199.
  • Butler MF, Frith WJ, Rawlins C, Weaver AC, Heppenstall-Butler M. Hollow calcium carbonate microsphere formation in the presence of biopolymers and additives. Cryst Growth Des. 2009;9:534-545.
  • Koga N, Kasahara D, Kimura T. Aragonite crystal growth and solid-state aragonite-calcite transformation: A physico-geometrical relationship via thermal dehydration of included water. Cryst Growth Des. 2013;13:2238-2246.
  • Zhang J, Zhou X, Dong C, Sun Y, Yu J. Investigation of amorphous calcium carbonate’s formation under high concentration of magnesium: The prenucleation cluster pathway. J Cryst Growth. 2018;494:8-16.
  • Trushina DB, Bukreeva T V., Kovalchuk M V., Antipina MN. CaCO3 vaterite microparticles for biomedical and personal care applications. Mater Sci Eng C. 2014;45:644-658.
  • Saulat H, Cao M, Khan MM, Khan M, Khan MM, Rehman A. Preparation and applications of calcium carbonate whisker with a special focus on construction materials. Constr. Build. Mater. 2020;236:117613.
  • Aghajanian S, Koiranen T. Dynamic modeling and semibatch reactive crystallization of calcium carbonate through CO2 capture in highly alkaline water. J CO2 Util. 2020;38:366-374.
  • Ševčík R, Pérez-Estébanez M, Viani A, Šašek P, Mácová P. Characterization of vaterite synthesized at various temperatures and stirring velocities without use of additives. Powder Technol. 2015; 284:265-271.
  • Jung GY, Shin E, Park JH, Choi BY, Lee SW, Kwak SK. Thermodynamic Control of Amorphous Precursor Phases for Calcium Carbonate via Additive Ions. Chem Mater. 2019; 31:7547-7557.
  • Miyashita M, Yamada E, Kawano M. Influence of low-molecular-weight dicarboxylic acids on the formation of calcium carbonate minerals in solutions with Mg2+ ions. J Mineral Petrol Sci. 2018; 113:207-217.
  • Wang T, Cölfen H, Antonietti M. Nonclassical crystallization: Mesocrystals and morphology change of CaCO3 crystals in the presence of a polyelectrolyte additive. J Am Chem Soc. 2005; 127:3246-3247.
  • Kirboga S, Oner M, Akyol E. The effect of ultrasonication on calcium carbonate crystallization in the presence of biopolymer. J Cryst Growth. 2014; 401:266-270.
  • Yang L, Zhang X, Liao Z, Guo Y, Hu Z, Cao Y. Interfacial molecular recognition between polysaccharides and calcium carbonate during crystallization. J Inorg Biochem. 2003; 97:377-383.
  • Yao Y, Dong W, Zhu S, Yu X, Yan D. Novel morphology of calcium carbonate controlled by poly(L-lysine). Langmuir. 2009; 25:13238-13243.
  • Zheng T, Zhang X, Yi H. Spherical vaterite microspheres of calcium carbonate synthesized with poly (acrylic acid) and sodium dodecyl benzene sulfonate. J Cryst Growth. 2019; 528:125275.
  • Wei Y, Xu H, Xu S, Su H, Sun R, Huang D, et al. Synthesis and characterization of calcium carbonate on three kinds of microbial cells templates. J Cryst Growth. 2020;547:125755.
  • Abeywardena MR, Elkaduwe RKWHMK, Karunarathne DGGP, Pitawala HMTGA, Rajapakse RMG, Manipura A, et al. Surfactant assisted synthesis of precipitated calcium carbonate nanoparticles using dolomite: Effect of pH on morphology and particle size. Adv Powder Technol. 2020;31:269-278.
  • Zheng T, Yi H, Zhang S, Wang C. Preparation and formation mechanism of calcium carbonate hollow microspheres. J Cryst Growth. 2020; 549:125870.
  • Fujiwara M, Shiokawa K, Kubota T, Morigaki K. Preparation of calcium carbonate microparticles containing organic fluorescent molecules from vaterite. Adv Powder Technol. 2014; 25:1147-1154.
Birincil Dil en
Konular Kimya, Ortak Disiplinler
Bölüm Makaleler

Orcid: 0000-0002-0934-2125
Yazar: Sevgi POLAT (Sorumlu Yazar)
Kurum: Marmara University
Ülke: Turkey

Orcid: 0000-0002-5216-490X
Yazar: Tuba ÖZALP
Kurum: Marmara University
Ülke: Turkey

Orcid: 0000-0003-4407-6464
Yazar: Perviz SAYAN
Ülke: Turkey

Destekleyen Kurum Marmara University Scientific Research Projects Commission
Proje Numarası FYL-2020-10025

Başvuru Tarihi : 16 Ekim 2020
Kabul Tarihi : 2 Aralık 2020
Yayımlanma Tarihi : 28 Şubat 2021

Vancouver Polat S , Özalp T , Sayan P . Polymorphic Phase Change of Calcium Carbonate with Glutamic Acid as an Additive. Journal of the Turkish Chemical Society Section A: Chemistry. 2021; 8(1): 117-124.