沉淀反应制备碳酸钙粒子及其形貌和结构控制

doi:10.3724/SP.J.1077.2013.13163

摘要/Abstract

摘要： 调节CaCl₂与Na₂CO₃简单沉淀反应的实验条件制备了微米及纳米级CaCO₃粒子, 探讨了晶型控制剂种类及用量、反应物浓度、分散方式等多种因素对CaCO₃粒子形貌及其分散性等性能的影响。使用光学显微镜、扫描电镜、动态光散射激光粒度仪、X射线衍射等对产物进行了表征。结果表明, 无晶型控制剂时, 所得产物主要为大小均一方解石晶型CaCO₃, 尺寸为4~5 μm。相对于机械搅拌, 超声波分散制备粒子的形貌更规整, 尺寸更均一。在超声波分散条件下, 分别采用三聚磷酸钠(STP)、羧甲基纤维素钠(CMC)和聚苯乙烯磺酸钠(PSS)为晶型控制剂, 并改变其用量通过沉淀反应制备了CaCO₃粒子, 对所得产物的结构及其形貌进行了表征。结果表明, 晶型控制剂及其用量对CaCO₃粒子的结构及其形貌有重要影响。使用STP为晶型控制剂时, 除了用量极低的条件下(≤0.10wt%)形成主要为球霰石结构的产物外, 一般都形成无定型CaCO₃; 使用CMC时, 一般都形成方解石结构产物; 与CMC相反, 使用PSS为晶型控制剂时, 得到的主要是球霰石结构产物, 掺杂少量方解石结构产物。对晶型控制剂在沉淀反应中的作用机理进行了讨论。

关键词: 碳酸钙粒子, 晶型控制剂, 分散方式, 粒子大小, 形貌

Abstract: Nano- to micron-meter CaCO₃ particles with different shape and crystal structures were prepared by adjusting the experimental conditions, including use of crystal growth inhibitors, concentrations of CaCl₂ and Na₂CO₃, and dispersing methods. CaCO₃ particles were characterized using electronic microscope, dynamic light scattering and X-ray diffraction. The results indicated that the nature and concentration of the crystal growth inhibitors had important effects on the morphology and crystal structure of the product. Without inhibitor, the product was of cubic blocks of about 4-5 μm, and cubic crystals were more uniform with ultrasonic dispersion than with mechanical stirring. However, crystal morphology and structures were easily altered by usage of crystal growth inhibitors. Using sodium triphosphate as the inhibitor, amorphous spherulites were usually formed, except at very low amount of the inhibitor where vaterite crystals were detected. With carboxymethylcellulose sodium (CMC) as the inhibitor, relatively uniform ellipsoidal particles, mostly calcite with small portion of vaterite spherulites of size about 3 μm, were observed, and the size of the spherulites changed with CaCl₂ concentration. While using sodium polystyrene sulfonate (PSS) as the inhibitor, uniform crystal spherulites were easily obtained by adjusting concentration of the inhibitors and the reactants. Opposite to the case where CMC was used, the crystalline structure was mostly vaterite with calcite in small portion. Formation mechanism of CaCO₃ particles in the presence of the inhibitors was discussed.

Key words: calcium carbonate particle, crystal growth inhibitor, dispersion method, particle size, morphology

中图分类号:

O643

杨亚囡, 朱晓丽, 孔祥正. 沉淀反应制备碳酸钙粒子及其形貌和结构控制[J]. 无机材料学报, 2013, 28(12): 1313-1320.

YANG Ya-Nan, ZHU Xiao-Li, KONG Xiang-Zheng. Controls of Crystal Morphology, Size and Structure in Spontaneous Precipitation of Calcium Carbonate[J]. Journal of Inorganic Materials, 2013, 28(12): 1313-1320.

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