双重乳液的微流控制备进展

doi:10.16085/j.issn.1000-6613.2016.s2.004

摘要/Abstract

摘要： 双重乳液是一种离散相液滴中还包裹着更小的液滴的高度结构化流体，单分散的在食品、化工、医疗等领域有着广泛的应用。微流控技术作为一门研究微尺度流体的新兴技术，已经成为制备优质双重乳液的首选。本文对被动式微流控技术进行了系统地综述，介绍了协流式、交叉流式、流动聚焦式微通道的结构及其乳化机理，展望了该项技术在微液滴制备方面的发展前景。在学科交叉应用的背景下，通过对微流控装置的改进与升级，可以克服常见微流控方法出现的双乳液生产效率低，不具备超薄壁结构等问题。此外，本文还讨论了微流控技术背景下双重乳液流型演化研究的进展，提出可以通过单乳液的研究基础，联系和发展双重乳液流型演化的完备理论体系。

关键词: 双重乳液, 稳定性, 微通道, 微流控, 流型演化

Abstract: Double emulsion is a highly structured fluid in which smaller drops are encapsulated by bigger drop,and it is widely applied in food,chemical engineering industries and medical treatment.Since droplets can be manipulated at microscale level,microfluidic has become first choice for the preparation of high-quality double emulsion.This paper summarizes the passive microfluidics and introduces the structure and emulsification mechanism in co-flowing,cross-flowing,flow-focusing microchannels.The outlook about the development of technologies in preparation of micro droplets is discussed.Through improving microfluidic devices,the common problems with microfluidic methods such as low double emulsion production efficiency and impossibility of building super thin wall construction can be overcome in interdisciplinarity applications.Moreover,the progresses on the study in the evolution of flow-patterns during double emulsion formation in microfluidic are discussed.Integrated theoretical system can be established from the investigation of the flow-pattern of single emulsion.

Key words: double emulsions, stability, microchannels, microfluidic, flow-pattern evolution

中图分类号:

王锴, 李浩, 高峥, 唐炜洁, 张程宾, 吴梁玉, 刘向东. 双重乳液的微流控制备进展[J]. 化工进展, 2016, 35(S2): 24-31.

WANG Kai, LI Hao, GAO Zheng, TANG Weijie, ZHANG Chengbin, WU Liangyu, LIU Xiangdong. Progress in microfluidic method for double emulsion preparation[J]. Chemical Industry and Engineering Progree, 2016, 35(S2): 24-31.

参考文献

[1] 刘文丽,焦纬洲,刘有智,等.W/O/W型多重乳液的稳定性和应用研究进展[J].日用化学工业,2012,42(5):366-370.
[2] IQBAL M,ZAFAR N,FESSI H,et al.Double emulsion solvent evaporation techniques used for drug encapsulation[J].International Journal of Pharmaceutics,2015,496:173-190.
[3] SEIFRIZ W J.Studies in emulsions[J].Phys.Chem.,1925,29:738-749.
[4] LAETITIA O,MONIQUE S,LEV B,et al.Optimization of a thermally reversible W/O/W multiple emulsion for shear-induced drug release[J].Journal of Controlled Release,2003,88:401-412.
[5] WANG W,ZHANG M J,CHU L Y.Microfluidic approach for encapsulation via double emulsions[J].Current Opinion in Pharmacology,2014,18:35-41.
[6] MATSUMOTO S,KITA Y,YONESAWA D.An attempt at preparing water-in-oil-in-water multiple-phase emulsions[J].Colloid Interface Science,1976,57(2):353-361.
[7] DICKINSON E.Double emulsions stabilized by food biopolymers[J].Food Biophysics,2011,6:1-11.
[8] 毛丽娟,刘夫国,简俊丽,等.乳状液及其在功能食品中的应用研究进展[J].中国食品添加剂,2014(9):147-153.
[9] FLORENCE A T.New drug delivery systems[J].Chemical Industry,1993,20(24):1000-1004.
[10] GIRI T K,CHOUDHARY C.Prospects of pharmaceuticals and biopharmaceuticals loaded microparticles prepared by double emulsion technique for controlled delivery[J].Saudi Pharmaceutical Journal,2013,21:125-141.
[11] NORDLY P,ROSE F,CHRISTENSEN D,et al. Immunity by formulation design:induction of high CD8+T-cell responses by poly(I:C)incorporated into the CAF01 adjuvant via a double emulsion method[J].Journal of Controlled Release 2011,150:307-317.
[12] RAJIAN J R,FABⅡLLI M L,FOELKES J B,et al.Drug delivery monitoring by photoacoustic tomography with an ICG encapsulated double emulsion[J].Optics Express,2011,19(15):14335-14347.
[13] TADROS T F.Future development in cosmetic formulations[J].International Journal of Cosmetic Science,1992,14(3):93-111.
[14] 赵娟,戴彩丽,汪庐山,等.聚合物一多重乳液交联剂深部调剖体系研究[J].油田化学,2009,26(3):304-307.
[15] PAL R.Rheology of double emulsions[J].Journal of Colloid and Interface Science,2007,307(2):509-515.
[16] 程靖,汪寿建,孙国恩.乳状液膜的研究进展[J].广州化工,2009,37(4):20-25.
[17] 于清波,李宪华.利用双重乳液法制备蜂窝状聚砜空心微球[J].化工新型材料,2012,40(4):69-71.
[18] 简科,王军,王浩,等.核聚变用靶丸材料研究进展[J].功能材料,2014(18):18001-18005.
[19] 程靖,文利雄,陈建峰.水/油/水双重乳液内、外水相间作用能分析[J].高校化学工程学报,2006,20(3):338-344.
[20] ESPINOSA-PAREDES G,VÁZQUEZ-RODRÍGUEZ A,VÁZQUEZ-RODRÍGUEZ A.Heat transfer processes in double-emulsion systems[J].Petroleum Science and Technology,2012,30(9):864-874.
[21] RUAN G,FENG S S,LI Q T.Effects of material hydro-phobicity on physical properties of polymeric microspheres formed by double emulsion process[J].Journal of Controlled Release,2002,84:151-160.
[22] 刘红晶,贺高红,林畅,等.W/O/W多重乳液中水传递的控制[J].物理化学学报,2007,23(6):935-939.
[23] SCHMIDTS T,DOBLER D,GULDAN A C,et al. Multiple W/O/W emulsions-Using the required HLB for emulsifier evaluation[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2010,372(1):48-54.
[24] MUN S,CHOI Y,KIM Y R.Lipase digestibility of the oil phase in a water-in-oil-in-water emulsion[J].Food Science and Biotechnology,2015,24(2):513-520.
[25] PRYBISKI C.W/O/W multiple Emulsion-Manufacturing and Formulation Consideration[J].C&T,1991,106(11):97-100.
[26] 王传好,曹光群,孙谦.W/O/W型多重乳状液的制备及应用概述[J].日用化学工业,1991(8):133-142.
[27] VAN DER G S,SCHROEN C G P H,BOOM R M. Preparation of double emulsions by membrane emulsification-a review[J].Journal of Membrane Science,2005,251:7-15.
[28] NAKASHIMA T,SHIMIZU M,KUKIZAKI M. Membrane emulsification by microporous glass[J].Key Engineering Materials,1991,61/62:513-516.
[29] KAWAKATSU T,TRÄGÅRDH G,TRÄGÅRDH C. Production of W/O/W emulsions and S/O/W pectin microcapsules by microchannel emulsification[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2001,189:257-264.
[30] SEO M,NIE Z,KUMACHEYA E.Continuous microfluidic reactors for polymer particles[J].Langmuir,2005,21(25):11614-11622.
[31] WEITZ D A,UTADA A S,CHU L Y,et al.Dripping,jetting,drops,and wetting:The magic of microfluidics. Mrs Bulletin[J],2007,32(9):702-708.
[32] SHAH R K,SHUM H C,ROWAT A C,et al.Designer emulsions using microfluidics[J].Materials Today,2008,11(4):18-27.
[33] LEAL-CALDERO F,HOMER S,GOH A,et al.W/O/W emulsions with high internal droplet volume fraction[J]. Food Hydrocolloids,2012,27(1):30-41.
[34] 李艳,何宗泽,陈欢乐,等.一种双重抗菌乳液凝胶的制备方法:104938615 A[P].2015-09-30.
[35] 邓伟健,卢颂昇.一种双重美白乳液及其制备方法:105168080 A[P].2015-12-23.
[36] 邓楠楠,汪伟,巨晓洁,等.微流控技术操控微尺度液滴及其聚并的研究进展[J].中国科学(化学),2015,45(1):7-15.
[37] 吴梁玉.协流式微通道内乳化过程的流变行为特性研究[D].南京:东南大学,2013.
[38] 徐丹.聚焦流微通道内液液两相流及液滴夹断的研究[D].天津:天津大学,2013.
[39] DATTA S S,ABBASPOURRAD A,AMSTAD E.25th anniversary article:double emulsion templated solid microcapsules:mechanics and controlled release[J]. Advanced Materials,2014,26,2205-2218.
[40] OKUSHIMA S,NISISAKO T,TORRI T,et al. Controlled production of monodisperse double emulsions by two-step droplet breakup in microfluidic devices[J]. Langmuir,2004,20(23):9905-9908.
[41] 王勇.基于毛细管的三维微流控装置实验应用[D].合肥:中国科学技术大学,2015.
[42] NIE Z H,XU S Q,SEO M,et al.Polymer particles with various shapes and morphologies produced in continuous microfluidic reactors[J].Journal of the American Chemical Society,2005,127(22):8058-8063.
[43] SEO M,PAQUET C,NIE Z,et al.Microfluidic consecutive flow-focusing droplet generators[J].Soft Matter,2007,3(8):986-992.
[44] 汪伟,谢锐,巨晓洁,等.微流控法制备新型微颗粒功能材料研究新进展[J].化工学报,2014,65(7):2555-2562.
[45] LAO K L,WANG J H,LEE G B.A microfluidic platform for formation of double-emulsion droplets[J].Microfluidics & Nanofluidics,2009,7(5):709-719.
[46] KIM S H,KIM B.Controlled formation of double-emulsion drops in sudden expansion channels[J].Journal of Colloid and Interface Science,2014,415(2):26-31.
[47] LEE S S,Abbaspourrad A,Kim S H.Nonspherical double emulsions with multiple distinct cores enveloped by ultrathin shells[J].Acs Applied Materials & Interfaces,2014,6(2):1294-1300.
[48] 陈永平,吴梁玉,张程宾,等.一种双重微乳液快速制备装置:104069757 A[P].2014-10-01.
[49] SUGIURA S,NAKAJIMA M,ITOU H,et al.Synthesis of polymeric microspheres with narrow size distributions employing microchannel emulsification[J].Macromol.Rapid Commun.,2001,22:773-778.
[50] 张晓乐,侯丽雅,章维一.规整双重乳液的微流体数字化制备原理实验[J].华中科技大学学报(自然科学版),2007,35(s1):57-60.
[51] 邓楠楠,褚良银,汪伟,等.一种单分散多组分多重乳液的制备方法:103240043 A[P].2013-08-14.
[52] TOOSE E M,GEURTS B J,KUERTEN J G M.A 2D boundary element method for simulating the deformation of axisymmetric compound non-Newtonian drops[J]. International Journal for Numerical Methods in Fluids,1999,30(6):653-674.
[53] 杨丽,周围,王学浩,等.基于流动聚焦结构的微液滴形成机理[J].微纳电子技术,2015,52(9):576-580.
[54] 吴平.液滴微流控的实验应用和理论研究[D].合肥:中国科学技术大学,2014.
[55] 刘金侠.微通道中复乳液流变学的研究[D].天津:天津大学,2013.
[56] WANG J T,LIU J X,HAN J J,et al.Rheology investigation of the globule of multiple emulsions with complex internal structures through a boundary element method[J],Chemical Engineering Science,2013,96(96):87-97.
[57] 吴梁玉,陈永平,施明恒,等.流动聚焦微通道中双重乳液乳化行为研究[J].工程热物理学报,2014,35(6):1167-1169.
[58] UTADA A S,et al.Monodisperse double emulsions generated from a microcapillary device[J].Science,2005,308(5721):537-541.
[59] NABAVI S A,GU S,Vladisavljević G T,et al.Dynamics of double emulsion break-up in three phase glass capillary microfluidic devices[J].Journal of Colloid & Interface Science,2015,12:279-287
[60] ZHOU C F,YUE P T,FENG J J.Deformation of a compound drop through a contraction in a pressure-driven pipe flow[J].International Journal of Multiphase Flow,2008,34:102-109.
[61] PARK J M,ANDERSON P D.A ternary model for double-emulsion formation in a capillary microfluidic device[J].Lab on a Chip,2012,12(15):2672-2677.
[62] CHEN Y P,LIU X D,ZHANG C B,et al.Enhancing and suppressing effects of an inner droplet on deformation of a double emulsion droplet under shear[J].Lab on a Chip,2015,15(5):1255-1261.
[63] CHEN H S,LI J,SHUM H C,et al.Breakup of double emulsions in constrictions[J].Soft Matter,2011,7(6):2345-2347.
[64] LI J,CHEN H S,STONE H A.Breakup of double emulsion droplets in a tapered nozzle[J].Langmuir the Acs Journal of Surfaces & Colloids,2011,27(8):4324-4327.
[65] 李小端,微通道内复乳液流变及取向性研究[D].天津:天津大学,2014.