Controlled Preparation of High Aspect Ratio Calcium Carbonate Whiskers from Dolomite Refined Solution

doi:10.16553/j.cnki.issn1000-985x.2024.0293

Abstract

Abstract: Aragonite calcium carbonate whiskers with a high aspect ratio were prepared by carbonization method using high concentration dolomite refined solution as the raw material. The calcium carbonate whisker samples were characterized by XRD， SEM， TEM， etc. The effects of carbonization temperature， stirring rate， CO₂ aeration rate， and aging time on the dispersion degree and aspect ratio of calcium carbonate whiskers were investigated. The results show that the optimum process conditions for the preparing calcium carbonate whiskers are as follows： carbonization temperature 80 ℃， CO₂ aeration rate 25 mL/min， stirring rate 200 r/min， and aging time 1 h. Under these conditions， calcium carbonate with a yield of 95%， whisker aspect ratio of 30~35， whisker content of 99.7%， whiteness of 99.9%， and uniform distribution can be obtained. The growth mechanism of calcium carbonate was analyzed. The results show that Mg²⁺ can inhibit the growth of calcite calcium carbonate and promote the growth of aragonite calcium carbonate during the carbonization process， and calcium carbonate whiskers have a preferential growth along （120） crystal plane.

Key words: dolomite; calcium carbonate whisker; carbonization method; high aspect ratio; crystal growth

CLC Number:

O784

YU Feng, ZHENG Qiang, QI Tingyu, ZHANG Yubai, MA Yali, JIA Songyan, LI Xue. Controlled Preparation of High Aspect Ratio Calcium Carbonate Whiskers from Dolomite Refined Solution[J]. Journal of Synthetic Crystals, 2025, 54(5): 898-908.

Figures/Tables 19

Table 1 XRF composition analysis of dolomite

Component	CaO	MgO	SiO₂	SO₃	Fe₂O₃	ZnO	MnO	SrO
Mass fraction/%	62.17	33.62	3.40	0.52	0.21	0.03	0.03	0.02

Table 2 Composition of dolomite refined solution

Refined solution composition	Ca²⁺	Mg²⁺	NH₄⁺	NH₃	NO₃^-
Concentration/（mol·L^-1）	0.70	0.05	1.60	1.95	3.40

Fig.1 Experimental flowchart

Fig.2 SEM images of calcium carbonate samples prepared at different temperatures

Fig.3 XRD patterns of calcium carbonate samples at different carbonization temperatures

Fig.4 Effect of temperature on conversion rate of Ca2+

Fig.5 SEM images of calcium carbonate samples at different stirring rates

Fig.6 XRD patterns of calcium carbonate samples carbonate at different stirring rates

Fig.7 SEM images of calcium carbonate samples at different ventilation rates

Fig.8 XRD patterns of calcium carbonate samples at different CO2 aeration rates

Fig.9 Whisker content of calcium carbonate samples prepared at different CO2 aeration rates

Fig.10 SEM images of calcium carbonate samples for different aging time

Fig.11 XRD patterns of calcium carbonate samples for different aging time

Table 3 Conversion rate of Ca2+， size and purity of calcium carbonate whiskers for different aging time

Parameter	0 h	1 h	2 h	3 h
Conversion rate of Ca²⁺/%	93.15	95.22	95.41	94.19
Whisker length/μm	10~30	25~35	20~35	20~35
Whisker diameter/μm	1.5~2.5	0.5~1.0	0.5~1.0	0.5~1.0
Whisker aspect ratio	4~12	25~35	20~35	20~35
Purity/%	98.65	99.43	99.44	99.43

Table 4 Composition of refined solution

Group	Ion concentration/（mol·L^-1）
Group	Ca²⁺	Mg²⁺	NH₄⁺	NH₃	NO₃^-
A	0.70	0.05	1.60	1.95	3.40
B	0.70	0	1.60	1.45	3.40

Fig.12 SEM images of calcium carbonate samples prepared from refined solutions A and B

Fig.13 XRD patterns of calcium carbonate samples with different carbonization time for two sets of refined solutions

Fig.14 TEM （a），（b）， HRTEM （c）和SAED （d） images of calcium carbonate samples prepared from dolomite refined solution

Table 5 SAED object matching calculation

Crystal plane spacing	d value of measurement/nm	d value of the PDF card/nm
（120）	0.314	0.310
（121）	0.275	0.273
（001）	0.546	0.574
（ $\bar{1}$ $\bar{2}$ 1）	0.269	0.273
Angle of crystal plane	Angle of measurement/（°）	Angle calculated from PDF card/（°）
（120）/（121）	28.20	28.41
（121）/（001）	61.11	61.59
（001）/（ $\bar{1}$ $\bar{2}$ 1）	59.14	61.59

Table 5 SAED object matching calculation

Crystal plane spacing	d value of measurement/nm	d value of the PDF card/nm
（120）	0.314	0.310
（121）	0.275	0.273
（001）	0.546	0.574
（ $\bar{1}$ $\bar{2}$ 1）	0.269	0.273
Angle of crystal plane	Angle of measurement/（°）	Angle calculated from PDF card/（°）
（120）/（121）	28.20	28.41
（121）/（001）	61.11	61.59
（001）/（ $\bar{1}$ $\bar{2}$ 1）	59.14	61.59

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