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Pickering emulsions and their use in production of polymer nanostructured materials

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In this article both types of Pickering emulsions – oil/water and water/oil – and their applications in the synthesis of different polymers have been considered. Pickering emulsions are dispersions stabilized by solid particles adsorbed at oil-water interface instead of conventional emulsifier. The influence of various solid particles, their amount and interaction on emulsions formation, stability and morphology with various suspended solid particles have been considered. Phase inversion phenomena and factors (such as wettability of solid particles) affecting them have been described. The interest to Pickering emulsions for the last decade is highly fueled by eco-friendly and cost-effective manufacture of hybrid polymer particles and nanocomposites with supracolloidal structures. The Pickering emulsion polymerization or suspension polymerization allows preparing in situ reinforced nanostructural polymer composites, unusual latexes and microcapsules with unique properties.

About the Authors

B. V. Pokidko
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation

D. A. Botin
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation

M. Yu. Pletnev
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


1. Ramsden W. Separation of solids in the surface-layers of solutions and suspensions // Proc. Royal Soc. London. 1903. V. 72. Р. 156–164.

2. Pickering S.U. Emulsions // J. Chem. Soc. 1907. V. 91. Р. 2001–2021.

3. Velev O.D., Furusava K., Nagayama K. Assembly of latex particles by using emulsion droplets. 1. Microconstructed Hollow spheres // Langmuir. 1996. V. 12. Р. 2374–2384.

4. Noble P.F., Cayre O.J., Alagrova R.G., Velev O.D., Paunov V.N. Fabrication of «hairy» colloidosomes with shells of polymeric microrods // J. Am. Chem. Soc. 2004. V.126. Р. 8092–8093.

5. Kaiser A., Liu T., Richtering W., Schmidt A.M. Magnetic capsules and Pickering emulsions stabilized by core-shell particles // Langmuir. 2009. V. 25. № 13. P. 7335–7341.

6. Miesch C., Kosif I., Lee E., Kim J.-К., Russell T.P., Hayward R.C., Emrick T. Nanoparticle-stabilized double emulsions and compressed droplets // Angew. Chem. Int. Ed. 2012. V. 51. № 1. P. 145–149.

7. He J., Zhang Q., Gupta S., Emrick T., Russell T.P., Thiyagarajan P. Drying droplets: A window into the behavior of nanorods at interfaces // Small. 2007. V.3. Р. 1214–1217.

8. Бабак В.Г. Высококонцентрированные эмульсии. Физико-химические принципы получения и устойчивость // Успехи химии. 2008. Т. 77. №. 8. С. 729–756.

9. Polymer Nanocomposites by Emulsion and Suspension Polymerization / Ed. V. Mittal. – London: RSC Nanosci. & Nanotechnol., 2011. 317 р.

10. Cauvine S., Colver P.J., Bon S.A.F. Pickering stabilized miniemulsion polymerization: Preparation of clay armored latexes // Macromolecules. 2005. V. 38. Р. 7887–7889.

11. Kim Y.J., Liu Y.D., Choi H.J., Park S.J., Facile fabrication of Pickering emulsion polymerized polystyrene/laponite composite nanoparticles and their electrorheology // J. Colloid Interface Sci. 2012 doi: 10.1016/j.jcis.2012.12.040.

12. Yang J., Hasell T., Wanget W.X., Li J, Brown PD, Poliakoff M. Preparation of hybrid polymer nanocomposite microparticles by a nanoparticle stabilized dispersion polymerization // J. Mater. Chem. 2008. V. 18. Р. 998–1002.

13. Gao Q., Wang C., Liu H., Wang C., Liu, X. Tong, Z. Suspension polymerization based on inverse Pickering emulsion droplets for thermo-sensitive hybrid microcapsules with tunable supracolloidal structures // Polymer. 2009. V. 50. Р. 2587–2594.

14. Dai L.L. Advanced core-shell composite nanoparticles through Pickering emulsion polymerization. In: The Delivery of Nanoparticles / Ed. A.A. Hashim. – InTech, 2012. Chap. 12.

15. Giermanska-Kahn J., Shmitt V., Binks B.P., Leal-Calderon F. A new method to prepare monodisperse Pickering emulsions // Langmuir. 2003. V. 18. Р. 2515–2518.

16. He Y.J. A novel emulsion route to sub-micrometer polyaniline/nano-ZnO composite fibers // Appl. Surface Sci. 2005. V. 249. Р. 1–6.

17. Yang F., Nui Q., Lan Q., Sun D.J. Effect of dispersion pH on the formation and stability of Pickering emulsions stabilized by layered double hydroxides // J. Colloid Interface Sci. 2007. V. 306. Р. 285–295.

18. Lagaly G., Reese M., Abend S. Smectites as colloidal stabilizers of emulsions. I. Preparation and properties of emulsions with smectites and nonionic surfactants // Appl. Clay Sci. 1999. V. 14. Р. 83–103.

19. Chen J., Vogel R., Werner S., Heinrich G. Clausse D. Dutschk V. Influence of the particle type on the rheological behavior of Pickering emulsions // Colloids & Surfaces A: Physicochem. Eng. Aspects. 2011. Р. 238–245.

20. Sacanna S., Kegel W.K., Philipse A.P. Thermodynamically stable Pickering emulsions // Phys. Rev. Lett. 2007. V. 98. Р. 158–301.

21. Fujii S., Murakami R. Smart particles as foam and liquid marble stabilizers // KONA Powder & Particle J. 2008. № 26. Р. 153–166.

22. Aveyard R., Binks B.P., Clint J.H. Emulsion stabilized solely by colloidal particles // Adv. Colloid Interface Sci. 2003. V. 100-102. Р. 503–546.

23. Binks B.P., Whitby C.P. Silica particle-stabilized emulsions of silicone oil and water: Aspects of emulsification // Langmuir. 2004. V. 20. Р. 1130–1137.

24. Whitby C.P., Fornasiero D., Ralston J. Effect of adding anionic surfactant on the stability of Pickering emulsions // J. Colloid Interface Sci. 2009. V. 329. Р. 173–181.

25. Rao S.R. Surface Chemistry of Froth Flotation. V. 2. – NY: Plenum Publishers, 2004. 758 р.

26. Tsamantakis C., Masliyah J., Yeung A., Gentzis T. The behavior of micro-bitumen drops in aqueous clay environments // J. Colloid Interface Sci. 2005. V. 288. Р. 129–139.

27. Rousseau D. Fat crystals and emulsion stability // Food Res. Intl. 2000. V. 33. Р. 3–14.

28. Frelichowska J., Bolzinger M.-A., Chevalier Y. Effect of solid particles content on properties of O/W Pickering emulsions // J. Colloid Interface Sci. 2010. V. 351. Р. 348–356.

29. Shulman J.H., Leja J. Control of contact angles at the oil-water-solid interfaces. Emulsions stabilized by solid particles (BaSO4) // Trans. Faraday Soc. 1954. V. 50. Р. 598–605.

30. Hassander H., Johansson B., Tornell B. The mechanism of emulsion stabilization by small silica (Ludox) particles // Colloids Surf. 1989. V. 40. Р. 93–105.

31. Subramaniam A.B., Mejean C., Abkarian M., Stone H.A. Microstructure, morphology, and lifetime of armored bubbles exposed to surfactants // Langmuir. 2006. V. 22. Р. 5986–5990.

32. Cui Y., Therelfall M., van Duijneveldt J.S. Optimizing organoclay stabilized Pickering emulsions // J. Colloid Interface Sci. 2011. V. 356. Р. 665–671.

33. Ashby N.P., Binks B.P. Pickering emulsions stabilized by laponite clay particles // Phys. Chem. Chem. Phys. 2000. V. 2. Р. 5640–5646.

34. Arditty S., Schmitt V., Lequeux F. Leal-Calderon. Interfacial properties in solid-stabilized emulsions // Eur. Phys. J. E. 2005. V. 44. Р. 381–393.

35. Yan Y., Masliyah J.H. Solids-stabilized oil-in-water emulsion: Scavenging of emulsion droplets by fresh oil addition // Colloids Surf. A. 1993. V. 75. Р. 123–132.

36. Whitby C.P., Fischer F.E., Fornasiero D., Ralston J. Shear-induced coalescence of oil-in-water Pickering emulsions // J. Colloid Interface Sci. 2011. V. 361. Р. 170–177.

37. Marinova K.G., Alargova R.G., Denkov N.D., Velev O.D., Petsev D.N., Ivanov I.B., Borwankar R.P. Charging of oil-water interfaces due to spontaneous adsorption of hydroxyl ions // Langmuir. 1996. V. 12. Р. 2045–2051.

38. Wang X., Alvarado V. Effect of salinity and pH on Pickering emulsion stability // Rep. at SPE Annual Technical Conference and Exhibition, 21–24 Sept. 2008. Denver, Colorado, USA. Р. 17–19.

39. Abend S., Bonnke N., Gutschner U., Lagaly G. Stabilization of emulsions by heterocoagulation of clay minerals and layered double hydroxides // Colloid Polym. Sci. 1998. V. 276. Р. 730–737.

40. Li C., Liu Q., Mei Z. Pickering emulsions stabilized by paraffin wax and laponite clay // J. Colloid Interface Sci. 2009. V. 336. Р. 314–321.

41. Wang S., He Y., Zou Y. Study of Pickering emulsion stabilization by mixed particles of silica and calcite // Particuology. 2010. V. 8. Р. 390–393.

42. Lin Y., Skaff H., Emrick T., Dinsmore A.D., Russell T.P. Nanoparticle assembly and transport at liquid-liquid interfaces // Science. 2003. V. 299. Р. 226–229.

43. Binks B.P., Rodrigure J.A. Types of phase inversion of silica particle stabilized emulsions containing triglyceride oil // Langmuir. 2003. V. 19. Р. 4905–4912.

44. Binks B.P., Lumsdon S.O. Effects of oil type and aqueous phase composition on oil-water mixtures containing particles of intermediate hydrophobicity // Phys. Chem. Chem. Phys. 2000. V. 2. Р. 2959–2967.

45. Nonomura Y., Kobayashi N. Phase inversion of the pickering emulsions stabilized by plate-shaped clay particles // J. Colloid Interface Sci. 2009. V.330. Р. 463–466.

46. Torres L.G., Iturbe R., Snowden M.J., Chowdhry B. Z., Leharne S. A. Preparation of o/w emulsions stabilized by solid particles and their characterization by oscillatory rheology // Colloids Surf. A: Physicochem. Eng. Aspects. 2007. V. 302. Р. 439–448.

47. Stancik E.J., Kouhkan M., Fuller G.G. Coalescence of particle-laden fluid interfaces // Langmuir. 2004. V. 20. Р. 90–94.

48. Ross-Murphy S.B. Rheology of biopolymer solutions and gels / In: New Physico-Chemical Techniques for the Characterization of Complex Food Systems / Ed. E. Dickinson. – London: Blackie, 1995. Р. 139–156.

49. Hohenstein W.P. The method of polymerization in suspension // Polymer Bull. 1945. V. 1. Р. 13–16.

50. Voorn D.J., Ming W., van Herk A.M. Polymer-clay nanocompiste latex particles by inverse Pickering emulsion polymerization stabilized with hydrophobic montmorillonite plates // Macromolecules. 2006. V. 39. Р. 2137–2143.

51. Ianchis R., Donescu D., Petcu C. Surfactant-free emulsion polymerization of styrene in the presence of silylated montmorillonite // Appl. Clay Sci. 2009. V. 45. Р. 164–170.

52. Khatana S., Dhibar A.K., Ray S. Sinha, Khatua B.B. Use of pristine clay platelets as a suspension stabilizer for the synthesis of poly(methyl methacrylate)/clay nanocomposite // Macromol. Chem. Phys. 2009. V. 210. Р. 1104–1113.

53. Bon S.A.F., Colver P.J. Pickering emulsion polymerization using laponite clay as a stabilizer // Langmuir. 2007. V. 23. Р. 8316–8322.

54. Guillot S., Bergaya F., de Azevedo C., Warmont F., Tranchant J.F. Internally structured Pickering emulsions stabilized by clay mineral particles // J. Colloid Interface Sci. 2009. V. 333. Р. 563–569.

55. Sedlakova Z., Plestil J., Baldrian J., Slouf M., Holub P. Nanostructured hybrid materials prepared via in-situ emulsion polymerization // Polym. Bull. 2009. V. 63. Р. 365–384.

56. Chen T., Colver P.J., Bon S.A.F. Organic–inorganic hybrid hollow spheres prepared from TiO2-stabilized Pickering emulsion polymerization // Advanced Materials. 2007. V. 19. № 17. Р. 2286–2289.

57. Zhang W.H., Fan X.D., Tian W., Fan W.W. Polystyrene/nano-SiO2 composite microspheres fabricated by Pickering emulsion polymerization: Preparation, mechanisms and thermal properties // eXPRESS Polymer Lett. 2012. V. 6. № 7. Р. 532–542.


For citations:

Pokidko B.V., Botin D.A., Pletnev M.Yu. Pickering emulsions and their use in production of polymer nanostructured materials. Fine Chemical Technologies. 2013;8(1):3-14. (In Russ.)

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