Dynamic shear rheology of colloidal suspensions of surface-modified silica nanoparticles in PEG

  • Swarna
  • Sudip Kumar Pattanayek
  • Anup Kumar Ghosh
Research Paper


The present work illustrates the effect of surface modification of silica nanoparticles (500 nm) with 3-(glycidoxypropyl)trimethoxy silane which was carried out at different reaction times. The suspensions prepared from modified and unmodified silica nanoparticles were evaluated for their shear rate-dependent viscosity and strain-frequency-dependent modulus. The linear viscoelastic moduli, viz., storage modulus and loss modulus, were compared with those of nonlinear moduli. The shear-thickened suspensions displayed strain thinning at low-frequency smaller strains and a strong strain overshoot at higher strains, characteristics of a continuous shear thickening fluids. The shear-thinned suspension, conversely, exhibited a strong elastic dominance at smaller strains, but at higher strains, its strain softened observed in the steady shear viscosity plot indicating characteristics of yielding material. Considering higher order harmonic components, the decomposed elastic and viscous stress revealed a pronounced elastic response up to 10% strain and a high viscous damping at larger strains. The current work is one of a kind in demonstrating the effect of silica surface functionalization on the linear and nonlinear viscoelasticity of suspensions showing a unique rheological fingerprint. The suspensions can thus be predicted through rheological studies for their applicability in energy absorbing and damping materials with respect to their mechanical properties.


Microstructural changes in the suspenions corresponding to their flow behaviour.


Colloidal suspensions Silica modification Nonlinear rheology Shear thickening Strain thinning Nanoparticles 


Funding information

The authors are grateful to Defense Research and Development Organization, Govt. of India, for their financial support.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. Barnes HA (1989) Shear-thickening (“dilatancy”) in suspensions of nonaggregating solid particles dispersed in Newtonian liquids. J Rheol (N Y N Y) 33(2):329–366. CrossRefGoogle Scholar
  2. Bender J, Wagner NJ (1996) Reversible shear thickening in monodisperse and bidisperse colloidal dispersions. J Rheol (N Y N Y) 40(5):899–916. CrossRefGoogle Scholar
  3. Boersma WH, Laven J, Stein HN (1990) Shear thickening(dilatancy) in concentrated dispersions. AICHE J 36(3):321–332. CrossRefGoogle Scholar
  4. Brady JF, Bossis G (1985) The rheology of concentrated suspensions of spheres in simple shear flow by numerical simulation. J Fluid Mech 155:105–129. CrossRefGoogle Scholar
  5. Brown E, Forman NA, Orellana CS, Zhang H, Maynor BW, Betts DE, DeSimone JM, Jaeger HM (2010) Generality of shear thickening in dense suspensions. Nat Mater 9(3):220–224. CrossRefGoogle Scholar
  6. Citerne GP, Carreau PJ, Moan M (2001) Rheological properties of peanut butter. Rheol Acta 40(1):86–96. CrossRefGoogle Scholar
  7. Dong J, Trulsson M (2017) Discontinuous shear thickening of dense suspensions under confining pressure. Soft Condens Matter. arXiv:1701.06934v1Google Scholar
  8. Egres RG, Wagner NJ (2005) The rheology and microstructure of acicular precipitated calcium carbonate colloidal suspensions through the shear thickening transition. J Rheol (N Y N Y) 49(3):719–746. CrossRefGoogle Scholar
  9. Ewoldt RH, Hosoi AE, McKinley GH (2008) New measures for characterizing nonlinear viscoelasticity in large amplitude oscillatory shear. J Rheol (N Y N Y) 52(6):1427–1458. CrossRefGoogle Scholar
  10. Fall A, Huang N, Bertrand F, Ovarlez G, Bonn D (2008) Shear thickening of cornstarch suspensions as a reentrant jamming transition. Phys Rev Lett 100(1):1–4. CrossRefGoogle Scholar
  11. Fernandez-Nieves A, Puertas AM (2016) Fluids, colloids, and soft materials: an introduction to soft matter physics. Wiley, Hoboken, p 432Google Scholar
  12. Fischer C, Braun SA, Bourban P-E, Michaud V, Plummer CJG, Månson JAE (2006) Dynamic properties of sandwich structures with integrated shear-thickening fluids. Smart Mater Struct 15(5):1467–1475. CrossRefGoogle Scholar
  13. Fletcher WP, Gent AN (1954) Nonlinearity in the dynamic properties of vulcanized rubber compounds. Rubber Chem Technol 27(1):209–222. CrossRefGoogle Scholar
  14. Galindo-Rosales FJ, Rubio-Hernández FJ, Velázquez-Navarro JF (2009) Shear-thickening behavior of Aerosil® R816 nanoparticles suspensions in polar organic liquids. Rheol Acta 48(6):699–708. CrossRefGoogle Scholar
  15. Glagovich N (2015) IR absorptions for respresentatuve functional groups. 162/Chem162 Labs/Interpreting IR Spectra/IR Absorptions for Functional Groups.htm. Accessed 23 Dec 2017
  16. Gopalakrishnan V, Zukoski CF (2004) Effect of attractions on shear thickening in dense suspensions. J Rheol (N Y N Y) 48(6):1321–1344. CrossRefGoogle Scholar
  17. Gürgen S, Li W, Kuşhan MC (2016) The rheology of shear thickening fluids with various ceramic particle additives. Mater Des 104:312–319. CrossRefGoogle Scholar
  18. He Q, Gong X, Xuan S, Jiang W, Chen Q (2015) Shear thickening of suspensions of porous silica nanoparticles. J Mater Sci 50(18):6041–6049. CrossRefGoogle Scholar
  19. Hoffman RL (1972) Discontinuous and dilatant viscosity behavior in concentrated suspensions. I. Observation of a flow instability. J Rheol (N Y N Y) 16(1):155–173. Google Scholar
  20. Hyun K, Kim SH, Ahn KH, Lee SJ (2002) Large amplitude oscillatory shear as a way to classify the complex fluids. J Nonnewton Fluid Mech 107(1-3):51–65. CrossRefGoogle Scholar
  21. Innocenzi P, Figus C, Kidchob T, Valentini M, Alonso B, Takahashi M (2009) Sol-gel reactions of 3-glycidoxypropyltrimethoxysilane in a highly basic aqueous solution. Dalt Trans 9146(42):9146–9152. CrossRefGoogle Scholar
  22. Kalman DP, Rosen BA, Wagner NJ, et al (2008) Effects of particle hardness on shear thickening colloidal suspension rheology. In: AIP Conference Proceedings. AIP, pp 1408–1410Google Scholar
  23. Khandavalli S, Rothstein JP (2015) Large amplitude oscillatory shear rheology of three different shear-thickening particle dispersions. Rheol Acta 54(7):601–618. CrossRefGoogle Scholar
  24. Lee Y, Wagner N (2003) Dynamic properties of shear thickening colloidal suspensions. Rheol Acta 42(3):199–208. Google Scholar
  25. MacDonald IF, Marsh BD, Ashare E (1969) Rheological behavior for large amplitude oscillatory motion. Chem Eng Sci 24(10):1615–1625. CrossRefGoogle Scholar
  26. Majumdar S, Krishnaswamy R, Sood AK (2011) Discontinuous shear thickening in confined dilute carbon nanotube suspensions. Proc Natl Acad Sci 108(22):8996–9001. CrossRefGoogle Scholar
  27. Maranzano BJ, Wagner NJ (2001) The effects of particle size on reversible shear thickening of concentrated colloidal dispersions. J Chem Phys 114(23):10514–10527. CrossRefGoogle Scholar
  28. Metzner AB, Whitlock M (1958) Flow behavior of concentrated (dilatant) suspensions. Trans Soc Rheol 2(1):239–254. CrossRefGoogle Scholar
  29. Mewis J, Biebaut G (2001) Shear thickening in steady and superposition flows effect of particle interaction forces. J Rheol (N Y N Y) 45(3):799–813. CrossRefGoogle Scholar
  30. Payne AR (1962) The dynamic properties of carbon black loaded natural rubber vulcanizates. Part II J Appl Polym Sci 6(21):368–372. CrossRefGoogle Scholar
  31. Prasada Rao TSR, Dhar GM, Catalysis Society of India. National Symposium (13th : 1997 : Dehra Dūn I (1998) Recent advances in basic and applied aspects of industrial catalysis: proceedings of 13th National Symposium and Silver Jubilee Symposium of Catalysis of India, Dehradun, India, April 2–4, 1997. ElsevierGoogle Scholar
  32. Raghavan S, Khan S (1997) Shear-thickening response of Fumed silica suspensions under steady and oscillatory shear. J Colloid Interface Sci 185(1):57–67. CrossRefGoogle Scholar
  33. Raghavan SR (1995) Shear-induced microstructural changes in flocculated suspensions of fumed silica. J Rheol (N Y N Y) 39(6):1311–1325. CrossRefGoogle Scholar
  34. Raghavan SR, Riley MW, Fedkiw PS, Khan SA (1998) Composite polymer electrolytes based on poly(ethylene glycol) and hydrophobic fumed silica: dynamic rheology and microstructure. Chem Mater 10(1):244–251. CrossRefGoogle Scholar
  35. Raghavan SR, Walls HJ, Khan SA (2000) Rheology of silica dispersions in organic liquids: new evidence for solvation forces dictated by hydrogen bonding. Langmuir 16(21):7920–7930. CrossRefGoogle Scholar
  36. Rahimi A, Gharazi S, Ershad-Langroudi A, Ghasemi D (2006) Synthesis and characterization of hydrophilic nanocomposite coating on glass substrate. J Appl Polym Sci 102(6):5322–5329. CrossRefGoogle Scholar
  37. Rangari V, Hassan T, Mahfuz H, Jeelani S (2006) Synthesis of shear thickening fluid using sonochemical method. NSTI-Nanotech 2:637–640Google Scholar
  38. Eslami-Farsani R, Hamed Khosravi SF (2015) Using 3-glycidoxypropyltrimethoxysilane functionalized SiO2 nanoparticles to improve flexural properties of glass fibers/epoxy grid stiffened composite panels. Int J Chem Mol Nucl Mater Metall Eng 9:1455–1458Google Scholar
  39. Rostamzadeh P, Mirabedini SM, Esfandeh M (2014) APS-silane modification of silica nanoparticles: effect of treatment’s variables on the grafting content and colloidal stability of the nanoparticles. J Coatings Technol Res 11(4):651–660. CrossRefGoogle Scholar
  40. Sarkar S, Shatoff E, Ramola K, et al (2017) Shear-induced organization of forces in dense suspensions: signatures of discontinuous shear thickening. cond-mat.soft. doi: arXiv:1701.04186v1Google Scholar
  41. Sha X, Yu K, Cao H, Qian K (2013) Shear thickening behavior of nanoparticle suspensions with carbon nanofillers. J Nanopart Res 15(7).
  42. Sharma I, Pattanayek SK, Aggarwal V, Ghosh S (2017) Morphology of self assembled monolayers using liquid phase reaction on silica and their effect on the morphology of adsorbed insulin. Appl Surf Sci 405:503–513. CrossRefGoogle Scholar
  43. Socrates G (2007) Infrared and raman characteristic group frequencies: tables and charts. John Wiley & SonsGoogle Scholar
  44. Stuart B (1996) Infrared spectroscopy: fundamentals and applications, 2004th edn. John Wiley & Sons LtdGoogle Scholar
  45. Sun W, Yang Y, Wang T, Liu X, Wang C, Tong Z (2011) Large amplitude oscillatory shear rheology for nonlinear viscoelasticity in hectorite suspensions containing poly(ethylene glycol). Polymer (Guildf) 52(6):1402–1409. CrossRefGoogle Scholar
  46. Swarna, Pattanayek SK, Ghosh AK (2017) Role of hydrogen bond interactions in water–polyol medium in the thickening behavior of cornstarch suspensions. Colloid Polym Sci 295(7):1117–1129. CrossRefGoogle Scholar
  47. Votano J, Parham M, Hall L (2004) IR TABLE. Chem … 1–4Google Scholar
  48. Wagner NJ, Brady JF (2009) Shear thickening in colloidal dispersions. Phys Today 62(10):27–32. CrossRefGoogle Scholar
  49. Xu Y, Gong X, Peng C et al (2010) Shear thickening fluids based on additives with different concentrations and molecular chain lengths. Chinese J Chem Phys 23(3):342–346. CrossRefGoogle Scholar
  50. Yang H, Ruan J, Zou J et al (2009) Rheological responses of fumed silica suspensions under steady and oscillatory shear. Sci China, Ser E Technol Sci 52(4):910–915. CrossRefGoogle Scholar
  51. Yang W, Wu Y, Pei X, Zhou F, Xue Q (2017) Contribution of surface chemistry to the shear thickening of silica nanoparticle suspensions. Langmuir 33(4):1037–1042. CrossRefGoogle Scholar
  52. Zhang XZ, Li WH, Gong XL (2008) The rheology of shear thickening fluid (STF) and the dynamic performance of an STF-filled damper. Smart Mater Struct 17(3):35027. CrossRefGoogle Scholar
  53. Zheng S-B, Xuan S-H, Jiang W-Q, Gong X-L (2015) High performance shear thickening fluid based on calcinated colloidal silica microspheres. Smart Mater Struct 24(8):85033. CrossRefGoogle Scholar
  54. Zou H, Wu S, Shen J (2008) Polymer/silica nanocomposites : preparation, characterization, properties, and applications. Chem Rev 108(9):3893–3957. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  • Swarna
    • 1
  • Sudip Kumar Pattanayek
    • 2
  • Anup Kumar Ghosh
    • 1
  1. 1.Centre for Polymer Science and EngineeringIndian Institute of Technology DelhiHauz KhasIndia
  2. 2.Department of Chemical EngineeringIndian Institute of Technology DelhiHauz KhasIndia

Personalised recommendations