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

参考文献 30

[1]	LOU X W D, ARCHER L A, YANG Z. Hollow micro/ nanostructure: synthesis and applications.Advanced Materials, 2008, 20(21): 3987-4019.
[2]	QI L, COLFEN H, ANTONIETTI M.Crystal design of barium sulfate using double-hydrophilic block copolymers.Angewandte Chemie International Edition, 2000, 39(3): 604-607.
[3]	KRYSZTAFKIEWICZ A, JESIONOWSKI T, BINKOWSKI S.Precipitated silicas modified with 3-aminopropyltriethoxy silane.Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2000, 173(1/2/3): 73-84.
[4]	NAKA K, CHUJO Y.Control of crystal nucleation and growth of calcium carbonate by synthetic substrates.Chemistry of Materials, 2001, 13(10): 3245-3259.
[5]	KATO T. SUGAWARA A, HOSODA N.Calcium carbonate- organic hybrid materials.Advanced Materials, 2002, 14(12): 869-877.
[6]	DONG L H, CHU Y, LIU Y, et al.Surfactant-assisted fabrication PbS nanorods, nanobelts, nanovelvet-flowers and dendritic nanostructures at lower temperature in aqueous solution.Colloid and Interface Science, 2006, 301(2): 503-510.
[7]	LI S Z, ZHANG H, WU J B, et al.Shape-control fabrication and characterization of the sirplane-like FeO(OH) and Fe2O3 nanostructures.Crystal Growth&Design, 2006, 6(2): 351-353.
[8]	GONG J Y, YU S H, QIAN H S, et al.Acetic acid-assisted solution process for growth of complex copper sulfide micrombes constructed by hexagonal nanoflakes.Chem. Mater., 2006, 18(8): 2012-2015.
[9]	ZHENG D S, SUN S X, FAN W L, et al.One-step preparation of single-crystalline β-MnO2 nanotubes.Phys. Chem. B, 2005, 109(34): 16439-16443 .
[10]	ZHANG M, WANG Z H, MO M S, et al.A simple approach to synthesize KNiF3 hollow spheres by solvothermal method.Materials Chemistry and Physics, 2005, 89(2/3): 373-378.
[11]	SHEN Q, WEI H, ZHAO Y, et al.Morphological control of calcium carbonate crystals by polyvinylpyrrolidone and sodium dodecylbenzene sulfonate.Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2004, 251(1/2/3): 87-91.
[12]	WEN Y., XIANG L, JIN Y.Tribological investigation of PTFE composite filled with lead and rare earths-modified glass fiber.Materials Letters, 2003, 57(16/17): 2553-2557.
[13]	QI LM, LI J, MA J M.Biomimetic morphogenesis of calcium carbonate in mixed solutions of surfactants and double-hydrophilic block copolymers.Advanced Materials, 2002, 14(4): 300-303.
[14]	PENG C Y, ZHAO Q H, GAO C Y.Sustained delivery of doxorubicin by porous CaCO3 and chitosan/alginate multilayers- coated CaCO3 microparticles.Colloids and Surface A: Physicochemical and Engineering Aspects, 2010, 353(2/3): 132-139.
[15]	WON Y H, JANG H S, CHUNG D W, et al.Multifunctional calcium carbonate microparticles: synthesis and biological applications.Journal of Materials Chemistry, 2010, 20(36): 7728-7733.
[16]	HAN GUO-HUA, LI MEI-QIN, ZHU CHENG-YUN.Research progress of drug-loaded hollow microspheres.Journal of Shenyang Pharmaceutical University, 2011, 28(7): 575-580.
[17]	ZHAO I N, WANG J K.Biomimetic synthesis of hollow microspheres of calcium carbonate crystals in the presence of polymer and surfactant.Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2012, 393(5): 139-143.
[18]	YUE I H, ZHENG Y F, JIN D I.Spherical porous framework of calcium carbonate prepared in the presence of precursor PS-PAA as template.Microporous and Mesoporous Materials, 2008, 113(1/2/3): 538-541.
[19]	LI LIANG, ZHU YING-JIE, CAO SHAO-WEN, et al.Preparation and drug release properties of nanostructured CaCO3 porous hollow microspheres.Journal of Inorganic Materials, 2009, 24(1): 166-170.
[20]	WANG XIN, CHEN RI-XIN, YANG HUI.Study on wet surface modification of nanometer calcium carbonate.Non-metallic Mines, 2005, 28(6): 8-10.
[21]	NIE QIU-LIN, ZHEN YI-FEN, YUE LIN-HAI, et al.Template induced synthesis of spherical CaCO3 by polyvinylpyrrolidone.Chinese Journal Of Inorganic Chemistry, 2003, 19(4): 445-448.
[22]	TANG YANG-JUN, LI YOU-MING, SONG JING, et al.Structural characterization and thermal decomposition behavior of microsized and nanosized CaCO3.Acta Physico-Chimica Sinica, 2007, 23(5): 717-722.
[23]	WANG Y, MOO YX, CHEN C, et al.Fast precipitation of uniform CaCO3 nanospheres and their transformation to hollow hydroxyapatite nanospheres.J. Colloid Interface Science, 2010, 352(2): 393-400.
[24]	ZENG LENG, HE QUAN-GUO, WU ZHAO-HUI.Preparation, surface modification and application of nano-calcium carbonate.Fine Chemical Intermediates, 2009, 39(4): 1-6.
[25]	ZHAO LINA, KONG ZHI-GUO, WANG JI-KU.Preparation and mechanism of CaCO3 hollow microspheres.CIESC Journal, 2012, 63(6): 1976-1980.
[26]	YU J G, GUO H, DAVIS S A, et al. Fabrication of hollow inorganic microspheres by chemically induced self-transformation.Advanced Functional Materials, 2006, 16(15): 2035-2041.
[27]	HE GUO-XU, ZHANG LI, LI GUANG.Influence of inorganic salt on critical micelle concentration of sodium dodecyl sulfonate solution determined by conductivity method.Chemical Research, 2011, 22(2): 68-71.
[28]	YANG XIAO-DENG, SHEN QIANG, XU GUI-YING.Crystallization of calcium carbonate using water-soluble macromolecules.Acta Physico-Chimica Sinica, 2010, 26(8): 2087-2095.
[29]	ZHAO DONG-NAN, ZUO YI-SHI, MEI QIN, et al.Formation process and thermodynamic properties of calcite.Chinese Journal of Chemistry, 2007, 25(5): 592-595.
[30]	YANU HUI, LI HUAN.The preparation of porous superfine calcium carbonate microspheres.Journal of Shanxi University of Science&Technology, 2013, 31(5): 111-115.

编辑推荐 0

Metrics

阅读次数

全文

1699

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	11	0	0	1688

来源	本网站	其他网站

次数	1204	495
比例	71%	29%

摘要

1215

最新录用	在线预览	正式出版

0	0	1215

来源	本网站	其他网站

次数	447	768
比例	37%	63%