CaCO_3微球的制备及表征
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摘要
采用搅拌共沉淀法,用表面活性剂CMC调控合成微米级CaCO_3微球。利用SEM、粒径分布、N2吸附/脱附测试、微球表面ζ电势、TGA对所得CaCO_3微球进行表征。探讨了CMC浓度、搅拌速率、搅拌时间对微球形貌的影响,优化制备工艺条件,搅拌速率2600 r×min~(-1)(15 min),20℃静置60 min得CaCO_3(n)微球粒径为1.5～2.5μm,平均孔径为30 nm,比表面积为7.03 m~2×g~(-1),孔体积为0.09 cm~3×g~(-1),表面电荷为+12.6 mV;在CMC质量浓度为0.5 g×L-1,搅拌速率2600 r×min~(-1)(15min),沉积温度20℃,沉积时间8h,得CaCO_3(CMC)微球中CMC量约为w=3.9%,粒径为3～5μm,平均孔径为3.84 nm,比表面积为44.0 m2×g~(-1),孔体积为0.07 cm3×g~(-1),表面电荷为-33.6 mV。结果表明,CMC的加入对CaCO_3微球的形貌、微结构和表面电荷起到调控作用。
CaCO_3 micropaticles were synthesized by addition of carboxymethylcellulose(CMC) via stirring co-precipitation. The microparticles were characterized by SEM, size distribution measurement, N2 adsorption/desorption, zeta potential and TGA. Effects of CMC concentration, stirring speed, and stirring time on morphology were discussed and the conditions were optimized. Microparticles with size 1.5～2.5 mm, average pore diameter 30 nm, specific surface area 7.03 m~2×g~(-1), pore volume 0.09 cm3×g~(-1) and surface charge +12.6 m V was prepared at the stirring speed of 2600 r×min~(-1) for 15 min and standing for 60 min at 20 ℃ without CMC. When the CMC mass concentration was 0.5 g×L~(-1) and prepared under stirring speed of 2600 r×min~(-1) for 15 min and deposition temperature of 20 ℃ for 8 h, CaCO_3(CMC) microparticles containing w=3.9 % CMC are obtained with particle size, average pore size, specific surface area, pore volume and surface charge of 3～5 mm, 3.84 nm, 44.0 m2×g~(-1), of 0.07 cm3×g~(-1) and-33.6 m V, respectively. These results indicate that the morphology, microstructure and surface charge of CaCO_3 microparticles are affected by CMC.
CaCO_3 micropaticles were synthesized by addition of carboxymethylcellulose(CMC) via stirring co-precipitation. The microparticles were characterized by SEM, size distribution measurement, N2 adsorption/desorption, zeta potential and TGA. Effects of CMC concentration, stirring speed, and stirring time on morphology were discussed and the conditions were optimized. Microparticles with size 1.5～2.5 mm, average pore diameter 30 nm, specific surface area 7.03 m~2×g~(-1), pore volume 0.09 cm3×g~(-1) and surface charge +12.6 m V was prepared at the stirring speed of 2600 r×min~(-1) for 15 min and standing for 60 min at 20 ℃ without CMC. When the CMC mass concentration was 0.5 g×L~(-1) and prepared under stirring speed of 2600 r×min~(-1) for 15 min and deposition temperature of 20 ℃ for 8 h, CaCO_3(CMC) microparticles containing w=3.9 % CMC are obtained with particle size, average pore size, specific surface area, pore volume and surface charge of 3～5 mm, 3.84 nm, 44.0 m2×g~(-1), of 0.07 cm3×g~(-1) and-33.6 m V, respectively. These results indicate that the morphology, microstructure and surface charge of CaCO_3 microparticles are affected by CMC.
引文
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[5]LI Z B,YUAN D,JIN G R,et al.Facile Layer-by-Layer self-assembly toward enantiomeric Poly(lactide)stereocomplex coated magnetite nanocarrier for highly tunable drug deliveries[J].ACS Applied Materials&Interfaces,2016,8(3):1842-1853.
[6]TONG W J,ZHU Y,WANG Z P,et al.Micelles-encapsulated microcapsules for sequential loading of hydrophobic and water-soluble drugs[J].Macromolecular Rapid Communications,2010,31(11):1015-1019.
[7]DI C,JING J,THOMAS B,et al.Hydrophobic shell loading of biopolyelectrolyte capsules[J].Advanced Materials,2011,23(24):H200-H204.
[8]VOLODKIN D V,PETROV A,PREVOT M,et al.Matrix polyelectrolyte microcapsules:new system for macromolecule encapsulation[J].Langmuir,2004,20(8):3398-3406.
[9]ZHAO L N,KONG Z G,WANG J K.Preparation and mechanism of CaCO3 hollow microspheres[J].CIESC Journal,2012,63(6):1976-1980.
[10]WANG C Y,SHENG Y,ZHAO X,et al.Synthesis of Hydrophobie CaCO3 Nanoparticles[J].Materials Letters,2006,60(6):854-857.
[11]LUO R C,VENKATRAMAN S S,NEU B.Layer-by-layer polyelectrolyte-polyester hybrid microcapsules for encapsulation and delivery of hydrophobic drugs[J].Biomacrolecules,2013,14(7):2262-2271.
[12]张晓蕾,邱勇波.球霰石碳酸钙的制备及其稳定性研究[J].无机盐工业.2018,50(2):46-49.ZHANG X L,QIU Y B.Study on synthesis and stability of vaterite calcium carbonate[J].Inorganic Chemicals Industry.2018,50(2):46-49.
[13]谭件云,姚善泾.羧甲基纤维素钠作用下CaCO3微球的制备及表征[J].浙江大学学报(工学版).2012,46(2):226-231.TAN J Y,YAO S J.Preparation and charaterisation of spherical calcium carbonate particles in the presence of carboxylmethyl cellulose sodium[J].Journal of Zhejiang University(Engineering Science).2012,46(2):226-231.
[14]BUNKER S,STALLER C,WILLENBACHER N.Miniemulsion polymerization of acrylated methyl oleate for pressure sensitive[J].International Journal of Adhesives,2003,23(2):29-38.