醇钙法和醇-水二元溶剂法制备亚稳态球霰石相CaCO3

doi:10.15541/jim20180472

无机材料学报 ›› 2019, Vol. 34 ›› Issue (7): 755-760.DOI: 10.15541/jim20180472

醇钙法和醇-水二元溶剂法制备亚稳态球霰石相CaCO₃

陈传杰¹,魏李庚¹,吴月¹,胡成沛¹,胡元聪¹,蒋久信^1,^2,³()

^1. 绿色轻工材料湖北省重点实验室湖北工业大学
^2. 绿色轻质材料与加工湖北工业大学协同创新中心
^3. 材料与化学工程学院, 武汉 430068

收稿日期:2018-10-10 修回日期:2018-12-03 出版日期:2019-07-20 网络出版日期:2019-06-26
作者简介:陈传杰(1994?), 男, 硕士研究生. E-mail:chenchuanjie0808@hotmail.com
基金资助:
国家自然科学基金(51402097);绿色轻质材料与加工湖北工业大学协同创新中心开放基金(201806B06);湖北省大学生创新创业训练计划项目(201810500098)

Synthesis of Metastable Vaterite Phase of CaCO₃ via Ethanol-calcium Method and Ethanol-water Binary Solvent Method

CHEN Chuan-Jie¹,WEI Li-Geng¹,WU Yue¹,HU Cheng-Pei¹,HU Yuan-Cong¹,JIANG Jiu-Xin^1,^2,³()

^1. Hubei Provincial Key Laboratory of Green Materials for Light Industry, Hubei University of Technology, Wuhan 430068, China
^2. Collaborative Innovation Center of Green Light-weight Materials and Processing, Hubei University of Technology, Wuhan 430068, China
^3. School of Material and Chemistry Engineering, Hubei University of Technology, Wuhan 430068, China

Received:2018-10-10 Revised:2018-12-03 Published:2019-07-20 Online:2019-06-26
Supported by:
National Natural Science Foundation of China(51402097);Open Foundation of Collaborative Innovation Center of Green Light-weight Materials and Processing, Hubei Provincial Key Laboratory of Green Materials for Light Industry(201806B06);Training Program of Innovation and Entrepreneurship for Undergraduates(201810500098)

摘要/Abstract

摘要：

提出了醇钙法概念, 并采用该方法制备了亚稳态球霰石相CaCO₃, 即利用CaCl₂溶解于乙醇形成的络合物与Na₂CO₃水溶液之间的反应制备球霰石相CaCO₃。主要研究了陈化时间和反应温度对产物晶相组成和颗粒形貌的影响, 并与相同条件下传统醇-水二元溶剂法制备CaCO₃进行了对比。X射线衍射(XRD)表征结果表明, 两种制备方法得到的产物中球霰石相的含量均随反应时间的延长和反应温度的升高而降低, 但是醇钙法得到的球霰石的含量远大于醇-水二元溶剂法, 且醇钙法得到的球霰石的稳定性也远优于醇-水二元溶剂法。SEM观察结果表明, 两种制备方法得到的产物中的球霰石和方解石颗粒均为其典型形貌, 即球状和菱方状。

关键词: 球霰石, CaCO₃, 醇钙法, 陈化时间, 反应温度

Abstract:

Ethanol-calcium method was proposed, and the metastable vaterite phase of CaCO₃ was synthesized by this method, i.e. the complex compound between CaCl₂ and ethanol reacted with Na₂CO₃ aqueous solution. Effects of aging time and reaction temperature on the polymorphs and morphologies of CaCO₃ were investigated, and the comparative study on the synthesis of CaCO₃ via ethanol-water binary solvent (EWBS) method at the same conditions was carried out. XRD results indicate that the fraction of vaterite in the product decreases with the aging time prolonging and reaction temperature increasing in both systems. However, the fraction of vaterite in the product prepared by ethanol-calcium method is much higher than that in the product prepared by EWBS method, and the stability of vaterite prepared by ethanol-calcium method is also much better. SEM observation shows that the morphologies of vaterite and calcite are their typical sphere and rhombohedra, respectively.

Key words: vaterite, calcium carbonate, ethanol-calcium, aging time, reaction temperature

中图分类号:

TQ174

陈传杰, 魏李庚, 吴月, 胡成沛, 胡元聪, 蒋久信. 醇钙法和醇-水二元溶剂法制备亚稳态球霰石相CaCO₃[J]. 无机材料学报, 2019, 34(7): 755-760.

CHEN Chuan-Jie, WEI Li-Geng, WU Yue, HU Cheng-Pei, HU Yuan-Cong, JIANG Jiu-Xin. Synthesis of Metastable Vaterite Phase of CaCO₃ via Ethanol-calcium Method and Ethanol-water Binary Solvent Method[J]. Journal of Inorganic Materials, 2019, 34(7): 755-760.

图/表 6

图1 醇钙法(a)~(e)和醇-水二元溶剂法(f)~(j)经不同陈化时间得到产物的XRD图谱

Fig. 1 XRD patterns of CaCO3 prepared from ethanol-calcium method (a-e) and EWBS method (f-j) after aging for different time (a, f) 0 min; (b, g) 20 min; (c, h) 90 min; (d, i) 22 h; (e, j) 42 h

表1 不同条件下得到的产物的物相组成

Table 1 Phase compositions of CaCO3 prepared at different conditions

Aging time/min	Temperature/℃	*Polymorphs/%		**Polymorphs/%
Aging time/min	Temperature/℃	Vaterite	Calcite	Vaterite	Calcite
0	20	90.4	9.6	46.5	53.5
20	20	84.4	15.6	12.3	87.7
90	20	83.5	15.9	10.5	89.5
1320	20	82.5	17.5	0	100
2520	20	81.4	18.6	0	100
60/10^#	0	85.8	14.2	57.1	42.9
60/10^#	20	84.1	15.9	44.3	55.7
60/10^#	40	73.3	26.7	22.6	77.4
60/10^#	60	70.2	29.8	0	100
60/10^#	80	64.8	35.2	0	100

图2 醇钙法(a)~(d)和醇-水二元溶剂法(e)~(h)经不同陈化时间得到产物的SEM照片

Fig. 2 SEM images of CaCO3 prepared from ethanol-calcium method (a-d) and EWBS method (e-h) after aging for different times (a, e) 0 min; (b, f) 20 min; (c, g) 90 min; (d, h) 42 h

图3 醇钙法(a)~(e)和醇-水二元溶剂法(f)~(j)经不同反应温度得到的产物的XRD图谱

Fig. 3 XRD patterns of CaCO3 prepared from ethanol-calcium method (a-e) and EWBS method (f-j) at different reaction temperatures (a, f) 0 min; (b, g) 20 ℃; (c, h) 40 ℃; (d, i) 60 ℃; (e, j) 80 ℃

图4 醇钙法(a)~(e)和醇-水二元溶剂法(f)~(j)经不同反应温度下得到产物的SEM照片

Fig. 4 SEM images of CaCO3 prepared from ethanol-calcium method (a-e) and EWBS method (f-j) at different reaction temperatures (a, f) 0 min; (b, g) 20 ℃; (c, h) 40 ℃; (d, i) 60 ℃; (e, j) 80 ℃

图5 醇钙法反应过程示意图

Fig. 5 The reaction process of ethanol-calcium method (a) Homogeneous anhydrous ethanol; (b) Formation of CaCl2·6C2H5OH complex and complex solution; (c) Decomplexation of CaCl2·6C2H5OH complex after the addition of Na2CO3 aqueous solution; (d) Ionization of CaCl2 in ethanol-aqueous solution and combination of Ca2+ and CO32-; (e) Formation of ACC; (f) Transformation of ACC to vaterite and calcite; (g) Growth of vaterite and calcite and phase transformation of vaterite to calcite at different aging time (g1) and different temperatures (g2)

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醇钙法和醇-水二元溶剂法制备亚稳态球霰石相CaCO₃

Synthesis of Metastable Vaterite Phase of CaCO₃ via Ethanol-calcium Method and Ethanol-water Binary Solvent Method

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