Skip to main content
SpringerLink
Log in

Fluidization of Highly Concentrated Colloidal Dispersions by Tailoring of Attractive Interactions

  • Chapter
  • First Online:
Colloid Process Engineering

  • 1648 Accesses

Abstract

Mode coupling theory (MCT) predicts fluid states of colloidal dispersions at particle volume fractions ϕ well above the hard sphere (HS) colloidal glass transition due to weak attractive interactions among particles. This opens a versatile, new route to manufacture highly concentrated, freely flowing dispersions with narrow particle size distribution. Our investigations are based on two model systems: polystyrene (PS)-microgel particles suspended in an isorefractive organic solvent and an aqueous polymer dispersion based on a well-stabilized, commercial polymer latex. Both systems exhibit hard sphere type flow behavior with a divergence of zero-shear viscosity at ϕ = 0.58. Suspensions were fluidized via addition of non-adsorbing polymers to the continuous phase, thus introducing weak depletion attraction among particles. The index-matched microgel system was used to study phase behavior as a function of particle and polymer concentration as well as polymer to particle size ratio and particle rigidity. A tight correlation between structural relaxation times from dynamic light scattering (DSL) experiments and rheological data was found. Fluid states were observed at particle loadings close to ϕ = 0.7 and a minimum viscosity has been achieved at polymer concentrations below the overlap concentration c*. Low viscosity values at particle loadings beyond ϕ = 0.58 could so far only be obtained for dispersions with bi- or multimodal particle size distribution. Flow curves obtained here for monomodal dispersions fluidized due to weak attractive interactions are similar to those of commercial dispersions with broad particle size distribution, demonstrating the competitive strength of the new concept. Sharply monodisperse aqueous polymer dispersions were used to demonstrate that beyond the predictions of MCT, also densely packed, crystalline suspensions can be fluidized upon adding small amounts of non-adsorbing polymer. A microfluidic flow channel attached to an inverted fluorescence microscope was used to study the true flow profiles of suspensions doped with size-matched fluorescent tracer particles. Reducing the range of weak depletion attraction by reducing the size of free, non-adsorbing polymer extended the fluidized region to even higher particle loadings of about ϕ = 0.72—in qualitative agreement with MCT predictions. However, an increase of the microgel crosslink density from 1:50 to 1:10 reduced the fluidized region significantly to about the effect observed with hard sphere-like PMMA dispersions. Particle softness and osmotic deswelling are discussed as possible origins of the exceptionally effective depletion fluidization in case of 1:50 crosslinked microgels. To enable similar studies combining DLS and rheology on model systems which are closer to aqueous, technical dispersions, perfluoroacrylate particles sterically stabilized with polyethylene-glycol (PEG) chains have been synthesized and characterized. A first study indicates that such dispersions can be refractive index matched in aqueous media and undergo a glass transition, thereby exposing dynamics in DLS which are quite analogous to that seen in so far studied model systems. The potential of fluidizing such dispersions at high particle loading by addition of free PEG or other depletants will be systematically explored in future work.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 79.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Hardcover Book
USD 109.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Notes

  1. 1.

    A crosslinking of 1:50 implies one crosslink per 50 monomer units.

  2. 2.

    It should be noted that the polymer to size ratio δ and the size ratio N of the reference system have in Refs. [25–27] been reported as δ = 0.054 and N = 2.75 on the basis of a size determination of S and L particles via DLS. A lateron refinement on the basis of a HS mapping of the fluid-crystal coexistence region yielded values of δ = 0.078 and N = 2.5 instead [56].

References

  1. Hiemenz PC, Rajagopalan R (1997) Principles of colloid and surface chemistry, 3rd edn. Dekker, New York

    Google Scholar 

  2. Irvine DJ, Stachowiak A, Jain S (2003) Engineering biomaterials for control of immune cell functions. Mat Sci Forum 426:3213–3218

    Google Scholar 

  3. Vlasov YA, Yao N, Norris DJ (1999) Synthesis of photonic crystals for optical wavelengths from semiconductor quantum dots. Adv Mat 11:165–169

    Google Scholar 

  4. Gratson GM, Mingjie X, Lewis JA (2004) Microperiodic structures: direct writing of threedimensional webs. Nature 428:386–389

    Google Scholar 

  5. Lewis JA (2000) Colloidal processing of ceramics. J Am Cer Soc 83:2341–2359

    Google Scholar 

  6. Terray A, Oakey J, Marr DWM (2002) Microfluidic control using colloidal devices. Science 296:1841–1844

    Google Scholar 

  7. Farris RJ (1968) Prediction of the viscosity of multimodal suspensions from unimodal viscosity data. Trans Soc Rheol 12:281–301

    Google Scholar 

  8. Wouterson ATJM, de Kruif CG (1991) The rheology of adhesive hard sphere dispersions. J Chem Phys 94:5739–5749

    Google Scholar 

  9. Dames B, Willenbacher N (2001) An empirical model predicting the viscosity of highly concentrated, bimodal dispersions with colloidal interactions. Rheol Acta 40:434–440

    Google Scholar 

  10. Willenbacher N, Börger L, Urban D (2003) Tailoring PSA-dispersion rheology for high-speed coating. Adhes Sealants 10(9):26–35

    Google Scholar 

  11. Pusey PN, van Megen W (1986) Phase behaviour of concentrated suspensions of nearly hard colloidal spheres. Nature 320:340–342

    Google Scholar 

  12. Liu AJ, Nagel SR (1998) Nonlinear dynamics: jamming is not just cool any more. Nature 6706:21–22

    Google Scholar 

  13. Meeker SP, Poon WCK, Pusey PN (1997) Concentration dependence of the low-shear viscosity of suspensions of hard-sphere colloids. Phys Rev E 55:5718

    Google Scholar 

  14. Götze W (1991) Aspects of structural glass transitions. In: Hansen J-P, Levesque D, Zinn-Justin J (Eds) Liquids, freezing and glass transition. North-Holland, Amsterdam, pp 287–504

    Google Scholar 

  15. Barrat JL, Götze W, Latz A (1989) The liquid-glass transition of the hard-sphere system. J Phys Condens Matter 1:7163–7170

    Google Scholar 

  16. Nägele G, Bergenholtz J (1998) Linear viscoelasticity of colloidal mixtures. J Chem Phys 108(23):9893–9904

    Google Scholar 

  17. Fuchs M, Cates ME (2002) Theory of nonlinear rheology and yielding of dense colloidal suspensions. Phys Rev E 89:248304-2

    Google Scholar 

  18. Fuchs M, Cates ME (2003) Schematic models for dynamic yielding of sheared colloidal glasses. Faraday Discuss 123:267

    Google Scholar 

  19. Fuchs M, Ballauff M (2005) Flow curves of dense colloidal dispersions: Schematic model analysis of the shear-dependent viscosity near the colloidal glass transition. J Chem Phys 122:094707

    Google Scholar 

  20. Siebenbürger M, Fuchs M, Winter H, Ballauff M (2009) Viscoelasticity and shear flow of concentrated, noncrystallizing colloidal suspensions: Comparison with mode-coupling theory. J Rheology 53:707

    Google Scholar 

  21. Bergenholtz J, Fuchs M (1999) Non-ergodicity transitions in colloidal suspensions with attractive interactions. Phys Rev E 59:5706–5715

    Google Scholar 

  22. Dawson K, Foffi G, Fuchs M, Götze W, Sciortino F, Sperl M, Tartaglia P, Voigtmann Th, Zaccarelli E (2001) Higher-order glass-transition singularities in colloidal systems with attractive interactions. Phys Rev E 63:011401

    Google Scholar 

  23. Pham KN, Puertas AM, Bergenholtz J, Egelhaaf SU, Moussaïd A, Pusey PN, Schofield AB, Cates ME, Fuchs M, Poon WCK (2002) Multiple glassy states in simple model system. Science 296:104–106

    Google Scholar 

  24. Pham KN, Egelhaaf SU, Pusey PN, Poon WCK (2004) Glasses in hard spheres with shortrange attraction.Phys Rev E 69:011503

    Google Scholar 

  25. Eckert T, Bartsch E (2002) Re-entrant glass transition in a colloid-polymer mixture with depletion attractions. Phys Rev Lett 89:125701

    Google Scholar 

  26. Eckert T, Bartsch E (2003) The effect of free polymer on the interactions and the glass transition dynamics of microgel colloids. Faraday Discuss 123:51

    Google Scholar 

  27. Eckert T, Bartsch E (2004) Glass transition dynamics of hard sphere like microgel colloids with short-ranged attractions. J Phys Condens Matter 16:S4937

    Google Scholar 

  28. Shah SA, Chen YL, Schweizer KS, Zukoski CF (2003) Phase behavior and concentration fluctuations in suspensions of hard spheres and nearly ideal polymers. J Chem Phys 118:3350

    Google Scholar 

  29. Shah SA, Chen YL, Schweizer KS, Zukoski CF (2003) Viscoelasticity and rheology of depletion flocculated gels and fluids. J Chem Phys 119:8747

    Google Scholar 

  30. Gopalakrishnan V, Zukoski CF (2004) Effect of attractions on shear thickening in dense suspensions. J Rheol 48(6):1321–1344

    Google Scholar 

  31. Krishnamurthy LN, Wagner NJ (2005) The influence of weak attractive forces on the microstructure and rheology of colloidal dispersions. J Rheol 49(3):475–499

    Google Scholar 

  32. Pham KN, Petekidis G, Vlassopoulos D, Egelhaaf SU, Poon WCK, Pusey PN (2008) Yielding behavior of repulsion-and attraction-dominated colloidal glasses. J Rheol 52(2):649–676

    Google Scholar 

  33. Degiorgio V, Piazza R, Bellini T et al (1994) Static and dynamic light scattering study of fluorinated polymer colloids with a crystalline internal structure. Adv Coll Interf Sci 48:61–69

    Google Scholar 

  34. Härtl W, Zhangheider X (1997) The synthesis of a new class of polymer colloids with a low index of refraction. J Coll Interf Sci 185:398–401

    Google Scholar 

  35. Koenderink GH, Philipse AP (2000) Rotational and translational self-diffusion in colloidal sphere suspensions and the applicability of generalized Stokes-Einstein relations. Langmuir 16:5631–5638

    Google Scholar 

  36. Koenderink GH, Sacanna S, Pathmamanoharan C, Raca M, Philipse AP (2001) Preparation and properties of optically transparent aqueous dispersions of monodisperse fluorinated colloids. Langmuir 17:6086–6093

    Google Scholar 

  37. Hunter GL, Weeks ER (2012) The physics of the colloidal glass transition. Rep Prog Phys 75:066501

    Google Scholar 

  38. Russel WB, Wagner NJ, Mewis J (2013) Divergence in the low shear viscosity for Brownian hard-sphere dispersions: at random close packing or the glass transition? J Rheol 57:1555–1567

    Google Scholar 

  39. Segre PN, Meeker SP, Pusey PN, Poon WCK (1995) Viscosity and structural relaxation in suspensions of hard-sphere colloids. Phys Rev Lett:958–961

    Google Scholar 

  40. Royall CP, Poon WCK, Weeks ER (2012) In search of colloidal hard spheres. Soft Matter 9:17–27

    Google Scholar 

  41. Poon WCK, Weeks ER, Royall CP (2012) On measuring colloidal volume fractions. Soft Matter 8:21–30

    Article  Google Scholar 

  42. Willenbacher N, Vesaratchanon JS, Thorwarth O, Bartsch E (2011) An alternative route to highly concentrated, freely flowing colloidal dispersions. Soft Matter 7:5777–5788

    Article  Google Scholar 

  43. Paulin SE, Ackerson BJ (1996) Equilibrium and shear induced nonequilibrium phase behavior of PMMA microgel spheres. J Colloid Interf Sci 178:251–262

    Article  Google Scholar 

  44. Senff H, Richtering W (1999) Temperature sensitive microgel suspensions: colloidal phase behavior and rheology of soft spheres. J Chem Phys 111:1705–1711

    Article  Google Scholar 

  45. Koumakis N, Pamvouxoglou A, Poulosa AS, Petekidis G (2012) Direct comparison of the rheology of model hard and soft particle glasses. Soft Matter 8:4271–4284

    Article  Google Scholar 

  46. Lange E, Caballero JB, Puertas AM, Fuchs M (2009) Comparison of structure and transport properties of concentrated hard and soft sphere fluids. J Chem Phys 130:174903

    Article  Google Scholar 

  47. Götze W, Voigtmann T (2003) Effect of composition changes on the structural relaxation of a binary mixture.Phys Rev E 67:021502

    Article  Google Scholar 

  48. Vesaratchanon JS, Takamura K, Willenbacher N (2010) Surface characterization of functionalized latexes with different surface functionalities using rheometry and dynamic light scattering. J Colloid Interf Sci 345:214–221

    Article  Google Scholar 

  49. Kawaguchi S et al (1997) Aqueous solution properties of oligo- and poly (ethylene oxide) by static light scattering and intrinsic viskosity. Polymer 38:2885–2891

    Article  Google Scholar 

  50. Asakura S, Oosawa F (1958) Interaction between particles suspended in solutions of macromolecules. J Polym Sci XXXIII:183–192

    Google Scholar 

  51. Willenbacher N, Börger L, Urban D, Varela de la Rosa L (2003) Tailoring PSA-dispersion rheology for high-speed coating, ASI, Adhes Sealants 10(9):26–35

    Google Scholar 

  52. Weis C, Natalia I, Willenbacher N (2014) Effect of weak attractive interactions on flow behavior of highly concentrated crystalline suspensions. J Rheol 58:1583–1579 http://dx.doi.org/10.1122/1.4882955

  53. Ilett SM et al (1995) Phase behavior of a model colloid-polymer mixture. Phys Rev E 51:1344–1352

    Article  Google Scholar 

  54. Palberg T, Stipp A, Bartsch E (2009) Unusual crystallization Kinetics in a hard sphere colloid-polymer mixture. Phys Rev Lett 102:038302-1–038302-4

    Google Scholar 

  55. Beyer R et al (2012) Polymer induced changes of the crystallization scenario in suspensions of hard sphere like microgel particles. J Chem Phys 136:234906-1–234906-8

    Google Scholar 

  56. Eckert T (2004) Ph.D. thesis, Mainz

    Google Scholar 

  57. Burger S, Bartsch E (2014) Influence of the polymer size on depletion attraction—induced gel and glass transitions of microgel colloids. Coll Surf A 442:6–15

    Article  Google Scholar 

  58. Kozina A, Sagawe D, Díaz-Leyva P, Bartsch E, Palberg T (2012) Polymer—enforced crystallization of a eutectic binary hard sphere mixture. Soft Matter 8:627–630

    Article  Google Scholar 

  59. Kozina A (2009) Ph.D. thesis, Freiburg

    Google Scholar 

  60. Sciortino F, Tartaglia P (2005) Glassy colloidal systems. Adv Phys 54:471–524

    Article  Google Scholar 

  61. Götze W (1999) Recent tests of the mode—coupling theory for glassy dynamics. J Phys Condens Matter 11:A1–A45

    Article  Google Scholar 

  62. Wiemann M (2013) Ph.D. thesis, Freiburg

    Google Scholar 

  63. Wiemann M, Willenbacher N, Bartsch E (2012) Effect of cross-link density on re-entrant melting of microgel colloids. Coll Surf A 413:78–83

    Article  Google Scholar 

  64. Saunders BR, Vincent B (1997) Osmotic de-swelling of polystyrene microgel particles. Colloid Polym Sci 275:9–17

    Article  Google Scholar 

  65. Bastide J, Candau S, Leibler L (1981) Osmotic deswelling of gels by polymer solutions. Macromolecules 14:719–726

    Article  Google Scholar 

  66. Hermes M, Dijkstra M (2010) Jamming of polydisperse hard spheres: the effect of kinetic arrest. Europhys Lett 89:38005-1–38005-6

    Google Scholar 

  67. Fleer GJ, Skvortsov AM, Tuinier R (2007) A simple relation for the concentration dependence of osmotic pressure and depletion thickness in polymer solutions. Macromol Theory Simul 16:531–540

    Article  Google Scholar 

  68. Schneider R (2011) Ph.D. thesis, Freiburg

    Google Scholar 

  69. Wiemann M, Schneider R, Bartsch E (2012) Synthesis of PEG-stabilized fluoro-Acrylate particles and study of their glass transition in aqueous dispersion. Z Phys Chem 226:761–778

    Article  Google Scholar 

  70. Burger D, Gisin J, Bartsch E (2014) Synthesis of sterically stabilized perfluorinated aqueous latices. Colloids Surf A 442:123–131

    Article  Google Scholar 

  71. Brindley A, Davis SS, Davies MC, Watts JF (1995) Polystyrene colloids with surface-grafted polyethylene oxide as model systems for site-specific drug delivery: I. preparation and surface chemical characterization using SIMS and XPS. J Colloid Interface Sci 171:150–161

    Article  Google Scholar 

  72. Tadros TF (1996) Correlation of viscoelastic properties of stable and flocculated suspensions with their interparticle interactions. Adv Colloid Interf Sci 68:97–200

    Article  Google Scholar 

  73. Zackrisson M, Stradner A, Schurtenberger P, Bergenholtz J (2006) Structure, dynamics, and rheology of concentrated dispersions of poly(ethylene glycol)-grafted colloids. Phys Rev E 73:11408-1–11408-8

    Google Scholar 

  74. Werner M, M.Sc. thesis, work in progress

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institut für Physikalische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79104, Freiburg, Germany

    E. Bartsch, D. Burger, S. Burger, J. Gisin, R. Schneider, O. Thorwarth & M. Wiemann

  2. Institut für Makromolekulare Chemie, Albert-Ludwigs-Universität Freiburg, Stefan-Meier-Str. 31, 79104, Freiburg, Germany

    E. Bartsch, D. Burger, S. Burger, J. Gisin, R. Schneider, O. Thorwarth & M. Wiemann

  3. Bereich Angewandte Mechanik, KIT, Institut für Mechanische Verfahrenstechnik und Mechanik, Gotthard-Franz-Straße 3, 76131, Karlsruhe, Germany

    J. Vesaratchanon, C. Weis & N. Willenbacher

Authors
  1. E. Bartsch
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. D. Burger
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. S. Burger
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. J. Gisin
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. R. Schneider
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. O. Thorwarth
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. J. Vesaratchanon
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. C. Weis
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. M. Wiemann
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. N. Willenbacher
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to E. Bartsch or N. Willenbacher .

Editor information

Editors and Affiliations

  1. Institute of Thermal Process Engineering, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany

    Matthias Kind

  2. Institute of Particle Technology, Friedrich-Alexander-Universität Erlangen, Erlangen, Germany

    Wolfgang Peukert

  3. Physical Chemistry II, TU Dortmund, Dortmund, Germany

    Heinz Rehage

  4. Institute of Process Engineering in Life Section I: Food Process Engineering, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany

    Heike P. Schuchmann

Rights and permissions

Reprints and permissions

Copyright information

© 2015 Springer International Publishing Switzerland

About this chapter

Cite this chapter

Bartsch, E. et al. (2015). Fluidization of Highly Concentrated Colloidal Dispersions by Tailoring of Attractive Interactions. In: Kind, M., Peukert, W., Rehage, H., Schuchmann, H. (eds) Colloid Process Engineering. Springer, Cham. https://doi.org/10.1007/978-3-319-15129-8_11

Download citation

  • DOI: https://doi.org/10.1007/978-3-319-15129-8_11

  • Published:

  • Publisher Name: Springer, Cham

  • Print ISBN: 978-3-319-15128-1

  • Online ISBN: 978-3-319-15129-8

  • eBook Packages: EngineeringEngineering (R0)

Publish with us

Policies and ethics

Search

Navigation