O/W/O多重乳液法制备毫米级氧化铝空心球（英文）
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摘要
采用O/W/O多重乳液法,以液体石蜡为内核,氧化铝溶胶为外壳层组成的复合液滴作为前驱体,制备毫米级氧化铝空心球,研究了装置几何结构对前驱体的形成和固化过程对空心球结构的影响。结果表明,内部油相通过直流通道直接注射到水相液滴内部时,形成的复合液滴具有均一核壳结构,壁厚和直径在30~80mm和800~2200mm可控。液滴置于水平方向旋转固化,保持转速在20~60 r/min,所得凝胶球可以保持完整的球形度和核壳结构。1200℃高温煅烧制备出的氧化铝空心微球维持高的球形度和空心结构,表面粗糙度大约22 nm,壁厚达到几十微米,直径达到毫米级,主要晶型为稳定的a-Al_2O_3。
To prepare millimeter-scale alumina hollow spheres by oil_1-in-water-in-oil_2 emulsions, the influence factors of formation of precursor and curing process were studied. Composite droplets with paraffin liquid as inner core and alumina sol as outer shell were used as precursor. Results showed that the com-droplets had homogeneous and complete core-shell structure when emulsion generator was designed that inner oil could be injected into water phase with the size of millimeters scale. Thickness and diameter of droplets were adjusted by both controlling the injection speed of oil and water phase in the range of 30–80 μm and 800–2200 μm. In the curing process, the semisolid spheres kept hollow structure and spherical when the speed of rotation between 20 r/min to 60 r/min and the flask being put in horizontal. Finally, the prepared hollow ceramic spheres with wall thickness in micrometer-scale and diameter in millimeter-scale formed complete hollow structure and high sphericity after calcining at 1200 ℃ for 4 h. The surface of sphere was relatively smooth with roughness of about 22 nm. The main crystal of the prepared ceramic hollow spheres was alpha alumina.
To prepare millimeter-scale alumina hollow spheres by oil_1-in-water-in-oil_2 emulsions, the influence factors of formation of precursor and curing process were studied. Composite droplets with paraffin liquid as inner core and alumina sol as outer shell were used as precursor. Results showed that the com-droplets had homogeneous and complete core-shell structure when emulsion generator was designed that inner oil could be injected into water phase with the size of millimeters scale. Thickness and diameter of droplets were adjusted by both controlling the injection speed of oil and water phase in the range of 30–80 μm and 800–2200 μm. In the curing process, the semisolid spheres kept hollow structure and spherical when the speed of rotation between 20 r/min to 60 r/min and the flask being put in horizontal. Finally, the prepared hollow ceramic spheres with wall thickness in micrometer-scale and diameter in millimeter-scale formed complete hollow structure and high sphericity after calcining at 1200 ℃ for 4 h. The surface of sphere was relatively smooth with roughness of about 22 nm. The main crystal of the prepared ceramic hollow spheres was alpha alumina.
引文
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[2]ZENG YAN,WANG FU,LIAO QI-LONG,et al.Synthesis and characterization of translucent Mg O-doped Al2O3 hollow spheres in millimeter-scale.Journal of Alloys and Compounds,2014,608:185-190.
[3]CHEN JIN-MEI,XU LEI,LI YA-NING,et al.Preparation of nickel-based alloy closed-pore hollow spheres.Rare Metal Materials and Engineering,2014,43:1308-1311.
[4]LIU RUN-JING,LI YAN-JV,ZHAO HUA,et al.Synthesis and characterization of Al2O3 hollow spheres.Materials Letters,2008,62:2593-2595.
[5]KANG SHI-ZHAO,YIN DIE-ER,LI XIANG-QING,et al.One-pot template-free preparation of mesoporous Ti O2 hollow spheres and their photocatalytic activity.Materials Research Bulletin,2012,47:3065-3069.
[6]ZHAO WEI-WEI,LIU YANG,LI HU-LIN,et al.Preparation and characterization of hollow Co3O4 spheres.Materials Letters,2008,62:772-774.
[7]TANG ZHE,LIU YUN-QI,LI GUANG-CI,et al.Ionic liquid assisted hydrothermal fabrication of hierarchically organizedγ-Al OOH hollow sphere.Materials Research Bulletin,2012,47:3177-3184.
[8]WENJEA J TSENG,CHAO PO-SUNG.Synthesis and photocatalysis of Ti O2 hollow spheres by a facile template-implantation route.Ceramics International,2013,39:3779-3787.
[9]LI ZHENG-ZHENG,ZHANG YONG,CHEN ZHI-ZHAN,et al.Synthesis of multi-shelled Mn-doped Zn O hollow spheres.Journal of Inorganic Materials,2009,6(24):1263-1266.
[10]HUANG YANG-FENG,XIAO HAN-NING,CHEN SHU-GUANG,et al.Preparation and characterization of Cu S hollow spheres.Ceramics International,2013,35:905-907.
[11]WANG CHAO,LE YAO,CHENG BEI.Fabrication of porous ZrO 2 hollow sphere and its adsorption performance to Congo red in water.Ceramics International,2014,40:10847-10856.
[12]YODTHONG BAIMARK,YAOWALAK SRISUWAN.Hollow chitosan microspheres prepared by an oil1-in-water-in-oil2 double emulsion method.Powder Technology,2013,249:436-442.
[13]WANG HAI-YANG,WANG FU,LIAO QI-LONG,et al.Synthesis of millimeter-scale Al2O3 ceramic hollow spheres by an improved emulsion microencapsulation method.Ceramics International,2015,41:4959-4965.
[14]LIU HONG-JIANG,NI YONG-HONG,WANG FEI,et al.Fabrication of submicron Cu2O hollow spheres in an O/W/Omultiple emulsions.Colloids and Surfaces A:Physicochem.Eng.Aspects,2004,235:79-82.
[15]GERALD MUSCHIOLIK.Multiple emulsions for food use.Current Opinion in Colloid&Interface Science,2007,12:213-220.
[16]ISAO KOBAYASHI,MITSYTOSHI NAKAJIMA,SUKEKUNIMUKATAKA.Preparation characteristics of oil-in-water emulsions using differently charged surfactants in straight-through microchannel emulsification.Colloids and Surfaces A:Physicochem.Eng.Aspects,2003,229:33-41.
[17]LAETITIA OLIVIERI,MONIQUE SEILLER,LEV BROMBERG,et al.Optimization of a thermally reversible W/O/W multiple emulsion for shear-induced drug release.Journal of Controlled Release,2003,88:401-412.
[18]XU J H,LI S W,WANG Y J,et al.Controllable preparation of monodisperse O/W and W/O emulsions in the same microfluidic device.Langmuir,2006,22:7943-7946.
[19]MARILYN RAYNER,GUN TR?G?RDH,CHRISTIANTR?G?RDH,et al.Using the surface evolver to model droplet formation processes in membrane emulsification.Journal of Colloid and Interface Science,2004,279:175-185.
[20]MARIJANA M DRAGOSAVAC,RICHARD G HOLDICH,GORAN T VLADISAVLJEVI?,et al.Stirred cell membrane emulsification for multiple emulsions containing unrefined pumpkin seed oil with uniform droplet size.Journal of Membrane Science,2012,392-393:122-129.
[21]GALDER CRISTOBAL,JEAN-PHILIPPE BENOIT,MATHIEUJOANICOT,et al.Microfluidic bypass for efficient passive regulation of droplet traffic at a junction.Appllied Physics Letter,2006,89:034104.
[22]FU TAO-TAO,MA YOU-GUANG,DENIA FUNFSCHILLING,et al.Dynamics of bubble breakup in a microfluidic T-junction divergence.Chemical Engineering Science,2011,66:4184-4195.
[23]ISAO KOBAYASHI,YOICHI MURAYAMA,TAKASHIKUROIWA,et al.Production of monodisperse water-in-oil emulsions consisting of highly uniform droplets using asymmetric straight-through microchannel arrays.Microfluid Nanofluid,2009,7:107-119.
[24]KEI NAKAGAWA,SATOSHI IWAMOTO,MITSUTOSHINAKAJIMA,et al.Microchannel emulsification using gelatin and surfactant-free coacervate microencapsulation.Journal of Colloid and Interface Science,2004,278:198-205.
[25]CRAMER CARSTEN,FISCHER PETER,WINDHAB ERICH J.Drop formation in a co-flowing ambient fluid.Chemical Engineering Science,2004,59:3045-3058.
[26]FU TAO-TAO,MA YOU-GUANG,DENIS FUNFSCHILLING,et al.Squeezing-to-dripping transition for bubble formation in a microfluidic T-junction.Chemical Engineering Science,2010,65:3739-3748.
[27]AMIT GUPTA,HARPEET S MATHAROO,DEVAVRET MAKKAR,et al.Droplet formation via squeezing mechanism in a microfluidic flow-focusing device.Computers&Fluids,2014,100:218-226.
[28]SCHMIDTS T,DOBLER D,SCHLUPP P,et al.Development of multiple W/O/W emulsions as dermal carrier system for oligonucleotides:Effect of additives on emulsion stability.International Journal of Pharmaceutics,2010,398:107-113.
[29]WU PING,LUO ZHAO-FENG,LIU ZHI-FENG,et al.Drag-induced breakup mechanism for droplet generation in dripping within flow focusing microfluidics.Chinese Journal of Chemical Engineering,2015,23:7-14.