微纳分级结构碳酸钙中空微球的可控制备

doi:10.15541/jim20150660

摘要/Abstract

摘要：

以CaCl₂和Na₂CO₃为反应原料, 以聚乙烯吡咯烷酮(PVP)和十二烷基磺酸钠(SDSN)为模板剂, 在50℃采用化学沉淀反应, 干燥、煅烧后成功制备了具有微纳分级结构的CaCO₃中空微球。采用扫描电子显微镜、透射电子显微镜和X射线衍射等检测手段对所制备的样品形貌、结构进行了表征, 结果显示：所制备的微纳分级结构CaCO₃中空微球直径为4~6 μm, 壳壁由直径约60 nm的CaCO₃颗粒组成, 壳层厚度约为200 nm, CaCO₃中空微球晶相组成为方解石和球霰石的共混体。同时, 在反应温度为50℃、PVP添加量为0.4 g, SDSN浓度为0.1 mol/L的条件下, 所制备的微纳分级结构CaCO₃中空微球分散性好, 且形貌比较完整。

关键词: 微纳分级结构, 碳酸钙中空微球, 作用机理, 模板法

Abstract:

With polyvinyl pyrrolidone (PVP) and sodium dodecyl sulfonate (SDSN) as the template, calcium carbonate hollow microspheres with micro-nano hierarchical structure were successfully synthesized using sodium carbonate and calcium chloride as starting materials through a precipitation reaction method at reaction temperature of 50℃. The products were characterized by scanning electronic microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and other detection methods. The results show that the hollow calcium carbonate microspheres with micro-nano hierarchical structure are about 4-6 μm in diameter. The shell thickness of calcium carbonate hollow microspheres is about 200 nm, which consists of calcium carbonate particles with size about 60 nm. The phase of calcium carbonate hollow microspheres is composed of calcite and vaterite. Excellent dispersibility and spherical morphology of calcium carbonate hollow microspheres can be achieved with addition of 0.1 mol/L SDSN and 0.4 g PVP consequently.

Key words: micro-nano hierarchical structure, calcium carbonate hollow microspheres, mechanism, template

中图分类号:

R318

邹俭鹏, 杨洪志, 肖平, 潘一峰. 微纳分级结构碳酸钙中空微球的可控制备[J]. 无机材料学报, 2016, 31(7): 711-718.

ZOU Jian-Peng, YANG Hong-Zhi, XIAO Ping, PAN Yi-Feng. Controllable Fabrication of Calcium Carbonate Hollow Microspheres with Micro-nano Hierarchical Structure[J]. Journal of Inorganic Materials, 2016, 31(7): 711-718.

图/表 11

图1 反应流程图

Fig. 1 The flow chart of reaction

图2 微纳分级结构CaCO3中空微球的SEM照片

Fig. 2 SEM micrographs of calcium carbonate hollow microspheres with micro-nano hierarchical structure

图3 微纳分级结构CaCO3中空微球的TEM照片

Fig. 3 TEM micrographs of calcium carbonate hollow microspheres with micro-nano hierarchical structure a: Morphology of calcium carbonate hollow microspheres; b: Morphology of nano-calcium carbonate on the micro-spherical shell wall; c: Electron diffraction pattern of calcium carbonate hollow microspheres; d: Crystal calibration in HRTEM)

图4 微纳分级结构CaCO3中空微球XRD图谱

Fig. 4 XRD patterns of calcium carbonate hollow microspheres with micro-nano hierarchical structure

图5 不同添加剂下, 微纳分级结构CaCO3中空微球的XRD图谱

Fig. 5 XRD patterns of calcium carbonate hollow microspheres with micro-nano hierarchical structure at different additives

图6 微纳分级结构CaCO3中空微球的IR图谱

Fig. 6 IR spectrum of calcium carbonate hollow microspheres with micro-nano hierarchical structure

图7 不同反应温度对微纳分级结构CaCO3中空微球的影响

Fig. 7 Influence of the reaction temperature on calcium carbonate hollow microspheres with micro-nano hierarchical structure (a) 20℃; (b) 40℃; (c) 60℃; (d) 80℃

图8 不同浓度SDSN对微纳分级结构CaCO3中空微球的影响

Fig. 8 Influence of the concentration of SDSN on calcium carbonate hollow microspheres with micro-nano hierarchical structure (a) 0.08 mol/L; (b) 0.1 mol/L; (c) 0.12 mol/L; (d) 0.14 mol/L

图9 不同PVP添加量对微纳分级结构CaCO3中空微球的影响

Fig. 9 Influence of the additive of PVP on calcium carbonate hollow microspheres with micro-nano hierarchical structure (a) 0.32 g; (b) 0.4 g; (c) 0.8 g; (d) 1.2 g

表1 相关化合物的标准热力学数据

Table 1 Standard thermodynamic data of related compounds

图10 SDSN与PVP调控生成CaCO3中孔微球机理图

Fig. 10 The mechanism diagram of being modulated by SDSN and PVP for preparation of calcium carbonate hollow microspheres with micro-nano hierarchical structure

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