亚稳态球霰石相碳酸钙的调控制备进展

doi:10.15541/jim20160484

无机材料学报 ›› 2017, Vol. 32 ›› Issue (7): 681-690.DOI: 10.15541/jim20160484 CSTR: 32189.14.10.15541/jim20160484

亚稳态球霰石相碳酸钙的调控制备进展

蒋久信^1,2, 吴月¹, 何瑶¹, 高松¹, 张晨¹, 沈彤³, 刘嘉宁^3,4

(1. 绿色轻质材料与加工湖北工业大学协同创新中心武汉 430068; 2. 湖北工业大学材料与化学工程学院武汉430068; 3. 南京信息工程大学物理与光电工程学院, 南京210044; 4. TU. Braunschweig, Institut für Pharmazeutische Technologie, Mendelssohnstr. 1, D-38106, Braunschweig, Germany)

收稿日期:2016-08-29 修回日期:2016-10-29 出版日期:2017-07-20 网络出版日期:2017-06-23
作者简介:蒋久信(1974—), 男, 博士, 副教授. E-mail: jiuxinjiang@hotmail.com
基金资助:
国家自然科学基金(11174075);湖北省教育厅科学技术研究计划重点项目(D20151405);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(201611A02);校人才启动基金(S8113127001)

Progress in Tuning of Metastable Vaterite Calcium Carbonate

JIANG Jiu-Xin^1,2, WU Yue¹, HE Yao¹, GAO Song¹, ZHANG Chen¹, SHEN Tong³, LIU Jia-Ning^3,4

(1. Collaborative Innovation Center of Green Light-Weight Materials and Processing, Hubei University of Technology, Wuhan 430068, China; 2. School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068, China; 3. School of Physics and Optoelectronic Engineering, Nanjing University of Information Science and Technology, Nanjing 210044; 4. Institut fur Pharmazeutische Technologie, Technische Universit?t Braunschweig, Mendelssohnstr. 1, D-38106 Braunschweig, Germany)

Received:2016-08-29 Revised:2016-10-29 Published:2017-07-20 Online:2017-06-23
About author:JIANG Jiu-Xin. E-mail: jiuxinjiang@hotmail.com
Supported by:
National Natural Science Foundation of China (11174075);Science and Technology Research Program of Educational Commission, Hubei Province of China (D20151405);Open Foundation of Collaborative Innovation Center of Green Light-weight Materials and Processing, Hubei Provincial Key Laboratory of Green Materials for Light Industry (201611A02);Initial Funding of Nanjing University of Information Science & Technology (S8113127001)

摘要/Abstract

摘要：

球霰石以其独特的机械、物理和化学性能, 在日用品与生物医学等领域表现出广阔的应用前景。然而在三种无水碳酸钙晶体中, 球霰石的热力学性能最不稳定, 在后续的反应和处理过程中常常转变为更稳定的文石或方解石, 因此如何抑制球霰石向稳定晶型转变一直都是碳酸钙领域研究的热点。本文在概述了球霰石晶体结构、性质、应用及其转化途径的基础上, 以碳酸钙的三种基本制备体系为线索, 综述了碳化法、复分解法、微乳液法和溶剂热法等传统方法以及自组装单分子膜法、仿生合成法和热分解法等一些新型调控制备球霰石相方法的研究进展, 还就利用添加剂促进球霰石形成与稳定的相关机制加以剖析。文章旨在为球霰石相碳酸钙的有效制备提供理论和实践的参考。

关键词: 球霰石, 碳酸钙, 亚稳相, 调控, 综述

Abstract:

Vaterite has broad application prospects in the field of daily necessities and biomedical science because of its unique mechanical, physical and chemical properties. However, vaterite is the thermodynamically least stable phase in the three anhydrous crystalline phases of calcium carbonate, and such thermal metastability often transforms it into more stable aragonite or calcite phases, so how to inhibit the phase transformation of vaterite is always a hot topic in the study of calcium carbonate. In this paper, structure, properties, application, and phase transformation from vaterite to aragonite and/or calcite are briefly introduced. Particularly, based on the three basic routes of synthesis of calcium carbonate, some traditional methods, such as carbonization, double decomposition, microemulsion, solvothermal method, and some latest progress, e.g. self-assembly of monolayer, biomimetic synthesis and thermal decomposition methods of tuning and preparation on vaterite are then summarized. Moreover, some analysis on the mechanism of formation and stabilization of vaterite by some additives are given. The aim of this review is to provide a more systematic theoretical and practical guidance to fabrication vaterite phase of calcium carbonate.

Key words: vaterite, calcium carbonate, metastable, tuning, review

中图分类号:

TQ174

蒋久信, 吴月, 何瑶, 高松, 张晨, 沈彤, 刘嘉宁. 亚稳态球霰石相碳酸钙的调控制备进展[J]. 无机材料学报, 2017, 32(7): 681-690.

JIANG Jiu-Xin, WU Yue, HE Yao, GAO Song, ZHANG Chen, SHEN Tong, LIU Jia-Ning. Progress in Tuning of Metastable Vaterite Calcium Carbonate[J]. Journal of Inorganic Materials, 2017, 32(7): 681-690.

图/表 11

图1 (a)球霰石中碳酸根和钙原子位置的垂直投影[10]; (b)球霰石的晶胞结构[11]

Fig. 1 (a) Vertical projection of vaterite showing orientation of carbonate group relative to calcium atoms[10]; (b) Structure of the vaterite unit cell[11]

图2 CaCO3从非晶相转变为球霰石球晶和典型方解石的形成示意图[25]

Fig. 2 Schematic depiction of the CaCO3 transformation from amorphous phase to vaterite spherulites and typical calcite[25]

图3 无水对氨基苯磺酸与L-赖氨酸不同混合比CaCO3晶体的SEM照片[29]

Fig. 3 SEM images of CaCO3 particles in different concentration ratios between p-aminobenzene sulfonic acid anhydrous and l-Lys solutions [29] (a) 0.1 g/L:0.1 g/L; (b) 0.1 g/L:0.3 g/L; (c) 0.1 g/L:0.5 g/L; (d) 0.5 g/L:0.1 g/L; (e) High magnification of selective area of (d)

图4 添加PEG10000-SDS的SEM和TEM照片[35]

Fig. 4 SEM images of CaCO3 hollow spheres obtained in the presence of PEG10000-SDS[35](a) Low magnification image, (b) high and (c) middle magnification SEM images; and (d) TEM image of CaCO3 hollow spheres obtained in the presence of PEG2000-SDS

图5 不同浓度表面活性剂下制备的CaCO3晶体的SEM照片[38]

Fig. 5 SEM images of CaCO3 prepared at different surfactant concentrations [38](a) 0.1 mol/L; (b) Magnification of (a); (c) 0.07 mol/L; (d) 0.04 mol/L

图6 蒸发水包油饱和微乳液制备海绵状球霰石的扫描电镜照片[41]

Fig. 6 SEM images showing sponge-like vaterite spheroids prepared by evaporation[41] from water-in-oil supersaturated microemulsions with compositions of (a) octane︰SDS︰CaHCO3 =71︰4︰25(wt%); (b) octane︰dodecanol︰SDS︰CaHCO3 = 70.8︰0.7︰3.5︰25(wt%); (c) schematic diagram showing the mechanism for the formation of vaterite microsponges in water-in-oil microemulsions

图7 CaCO3的SEM照片, 其中(a~c)和(d~f)分别为加入10 mL、20 mL的丝素蛋白, 且所加镁离子浓度(mmol/L)分别为(a) 10; (b) 20; (c) 50; (d) 10; (e) 20; (f) 50[42]

Fig. 7 SEM images of CaCO3 where (a-c) and (d-f) with 10 mL and 20 mL of silk fibroin, respectively, affter being added Mg2+ at the concentration of (a) 10; (b) 20; (c) 50; (d) 10; (e) 20; (f) 50 mmol/L[42]

图8 不同水溶液中制备的CaCO3的SEM照片[51]

Fig. 8 SEM images of the CaCO3 prepared in different aqueous solutions [51](a) L-valine; (b) L-arginine; (c) L-serine

图9 不同分解温度下碳酸钙的XRD图谱[58]

Fig. 9 XRD patterns of CaCO3 decomposed under different temperatures[58](a) 70 ℃; (b) 80 ℃; (c) 90 ℃

图10 不同分解温度下CaCO3的SEM照片[58]

Fig. 10 SEM images of CaCO3 decomposed under different temperatures[58](a) 70℃; (b) 80℃; (c) 90℃

图11 (a)和(b)方解石和球霰石的原子结构, (c)球霰石结构中(0001)晶面Ca2+的排列以及在搅拌影响下的移动方向, (d)移动后Ca2+的排列及移动过程[ 59]

Fig. 11 Atomic structure of (a) calcite and (b) vaterite, (c) Ca2+ ions stacking in vaterite and the motion direction in the (0001) faces under agitation, and (d) Ca2+ ions stacking in the (0001) faces after motion[59]

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亚稳态球霰石相碳酸钙的调控制备进展

Progress in Tuning of Metastable Vaterite Calcium Carbonate

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