Iranian Polymer Journal

, Volume 22, Issue 8, pp 613–622 | Cite as

Nanoconfined segmental dynamics in miscible polymer blend nanocomposites: the influence of the geometry of nanoparticles

Original Paper

Abstract

The influence of nanoconfinement on segmental relaxation behavior of poly(methyl methacrylate) and poly(styrene-ran-acrylonitrile) miscible blend and its nanocomposites with spherical and layered nanoparticles have been investigated. Dynamic mechanical analysis was employed to examine the effect of geometry of nanoparticles on the temperature dependence and relaxation function breadth of segmental dynamics (α-relaxation) in the glass transition region. The maxima of the loss modulus curves were used to fit to the Vogel–Fulcher–Tamman equation to describe the temperature dependence of the characteristic relaxation times. Furthermore, the Tg-normalized semi-logarithmic Arrhenius plots (fragility plots) were exploited to indicate the changes in cooperative segmental motions across the glass transition. The master curves for relaxation modulus were also constructed for each sample as a function of time using the time–temperature superposition principle. The investigated nanocomposites showed a narrower segmental dispersion in the glass transition region compared to the neat systems. The relaxation modulus master curves were fitted by the Kohlrausch–Williams–Watts (KWW) function. It was observed that the distribution parameter of segmental relaxation time increased with addition of nanoparticles which was correlated with a decrease in fragility index. In addition, the increase of the KWW distribution parameter (βKWW) for spherical silica nanocomposites was less than that for nanocomposites prepared with layered silicates (organoclay).

Keywords

Glass transition Nanoconfinement Nanocomposites Segmental dynamics Polymer blends 

References

  1. 1.
    Yurekli K, Alamgir K, Amis EJ, Krishnamoorti R (2003) Influence of layered silicates on the phase-separated morphology of PS–PVME blends. Macromolecules 36:7256–7267CrossRefGoogle Scholar
  2. 2.
    Yousefi AA (2011) Influence of polymer blending on crystalline structure of polyvinylidene fluoride. Iran Polym J 20:109–121Google Scholar
  3. 3.
    Yousefi AA (2011) Hybrid polyvinylidene fluoride/nanoclay/MWCNT nanocomposites: PVDF crystalline transformation. Iran Polym J 20:725–733Google Scholar
  4. 4.
    Lee MH, Dan CH, Kim JH, Cha J, Kim S, Hwang Y, Lee CH (2006) Effect of clay on the morphology and properties of PMMA/poly(styrene-co-acrylonitrile)/clay nanocomposites prepared by melt mixing. Polymer 47:4359–4369CrossRefGoogle Scholar
  5. 5.
    Park JH, Jana SC (2003) The relationship between nano- and micro-structures and mechanical properties in PMMA–epoxy–nanoclay composites. Polymer 44:2091–2100CrossRefGoogle Scholar
  6. 6.
    Wang S, Hu Y, Wang Z, Yong T, Chen Z, Fan W (2003) Synthesis and characterization of polycarbonate/ABS/montmorillonite nanocomposites. Polym Degrad Stab 80:157–161CrossRefGoogle Scholar
  7. 7.
    Moussaif N, Groeninckx G (2003) Nanocomposites based on layered silicate and miscible PVDF/PMMA blends: melt preparation, nanophase morphology and rheological behaviour. Polymer 44:7899–7906CrossRefGoogle Scholar
  8. 8.
    Colmenero J, Arbe A (2007) Segmental dynamics in miscible polymer blends: recent results and open questions. Soft Matter 3:1474–1485CrossRefGoogle Scholar
  9. 9.
    Starr FW, Douglas JF (2011) Modifying fragility and collective motion in polymer melts with nanoparticles. Phys Rev Lett 106:115702–115706CrossRefGoogle Scholar
  10. 10.
    Casalini R, Snow AW, Roland CM (2013) Temperature dependence of the Johari–Goldstein relaxation in poly(methyl methacrylate) and poly(thiomethyl methacrylate). Macromolecules 46:330–334CrossRefGoogle Scholar
  11. 11.
    Zhang C, Guo Y, Shepard KB, Priestley RD (2013) Fragility of an isochorically confined polymer glass. J Phys Chem Lett 4:431–436CrossRefGoogle Scholar
  12. 12.
    Angell CA (1995) Formation of glasses from liquids and biopolymers. Science 267:1924–1935CrossRefGoogle Scholar
  13. 13.
    Wu J, Huang G, Qu L, Zheng J (2009) Correlations between dynamic fragility and dynamic mechanical properties of several amorphous polymers. J Non-Cryst Solids 355:1755–1759CrossRefGoogle Scholar
  14. 14.
    Syamaladevi RM, Barbosa-Cánovas GV, Schmidt SJ, Sablani SS (2012) Influence of molecular weight on enthalpy relaxation and fragility of amorphous carbohydrates. Carbohydr Polym 88:223–231CrossRefGoogle Scholar
  15. 15.
    Ngai KL, Casalini R, Roland CM (2005) Volume and temperature dependences of the global and segmental dynamics in polymers: functional forms and implications for the glass transition. Macromolecules 38:4363–4370CrossRefGoogle Scholar
  16. 16.
    Cole KS, Cole RH (1941) Dispersion and absorption in dielectrics I. alternating current characteristics. J Chem Phys 9:341–352CrossRefGoogle Scholar
  17. 17.
    Davidson DW, Cole RH (1950) Dielectric relaxation in glycerine. J Chem Phys 18:1417–1418CrossRefGoogle Scholar
  18. 18.
    Havriliak S, Negami S (1966) A complex plane analysis of α-dispersions in some polymer systems. J Polym Sci Polym Symp 14:99–117Google Scholar
  19. 19.
    Williams G, Watts DC (1970) Non-symmetrical dielectric relaxation behavior arising from a simple empirical decay function. J Trans Faraday Soc 66:80–85CrossRefGoogle Scholar
  20. 20.
    Williams G, Watts DC, Dev SB, North AM (1971) Further considerations of nonsymmetrical dielectric relaxation behaviour arising from a simple empirical decay function. J Trans Faraday Soc 67:1323–1335CrossRefGoogle Scholar
  21. 21.
    Kohlrausch R (1854) Theorie des elektrischen rückstandes in der leidener flasche. Ann Phys 167:56–82CrossRefGoogle Scholar
  22. 22.
    Qazvini NT, Mohammadi N (2007) Segmental dynamics of reactively prepared polystyrene blends: unsaturated polyester resin versus high impact polystyrene. J Appl Polym Sci 106:498–504CrossRefGoogle Scholar
  23. 23.
    Alves NM, Ribelles JLG, Tejedor JAG, Mano JF (2004) Viscoelastic behavior of poly(methyl methacrylate) networks with different cross-linking degrees. Macromolecules 37:3735–3744CrossRefGoogle Scholar
  24. 24.
    Pazmiño Betancourt BA, Douglas JF, Starr FW (2013) Fragility and cooperative motion in a glass-forming polymer–nanoparticle composite. Soft Matter 9:241–254CrossRefGoogle Scholar
  25. 25.
    Pfennig JLG, Keskkula H, Barlow JW, Paul DR (1985) Experimental simulation of the effect of intramolecular repulsion on the heat of mixing for polymer blends. Macromolecules 18:1937–1940CrossRefGoogle Scholar
  26. 26.
    Kambour RP, Bendler JT, Bopp RC (1983) Phase behavior of polystyrene, poly(2,6-dimethyl-1,4-phenylene oxide), and their brominated derivatives. Macromolecules 16:753–757CrossRefGoogle Scholar
  27. 27.
    Feng HQ, Ye CH, Feng ZL (1996) The miscibility of homopolymer/random copolymer blends. IV. poly(vinylidene chloride-co-acrylonitrile)/poly(methyl methacrylate) blends. Polymer 28:678–681CrossRefGoogle Scholar
  28. 28.
    Fowler ME, Barlow JW, Paul DR (1987) Effect of copolymer composition on the miscibility of blends of styrene–acrylonitrile copolymers with poly (methyl methacrylate). Polymer 28:1177–1184CrossRefGoogle Scholar
  29. 29.
    Du M, Gong J, Zheng Q (2004) Dynamic rheological behavior and morphology near phase-separated region for a LCST-type of binary polymer blends. Polymer 45:6725–6730CrossRefGoogle Scholar
  30. 30.
    Berzosa AE, Ribelles JLG, Kripotou S, Pissis P (2004) Relaxation spectrum of polymer networks formed from butyl acrylate and methyl methacrylate monomeric units. Macromolecules 37:6472–6479CrossRefGoogle Scholar
  31. 31.
    Vogel H (1921) The law of the relation between the viscosity of liquids and the temperature. Physik Z 22:645–646Google Scholar
  32. 32.
    Fulcher GA (1925) Analysis of recent measurements of the viscosity of glasses. J Am Ceram Soc 8:339–355CrossRefGoogle Scholar
  33. 33.
    Tamman G, Hesse WZ (1926) The dependence of viscosity upon the temperature of supercooled liquids. Z Anorg Allg Chem 156:245–257CrossRefGoogle Scholar
  34. 34.
    Angell CA (1997) Why C 1 = 16–17 in the WLF equation is physical—and the fragility of polymers. Polymer 38:6261–6266CrossRefGoogle Scholar
  35. 35.
    Ruocco G, Sciortino F, Zamponi F, DeMichele C, Scopigno T (2004) Landscapes and fragilities. J Chem Phys 120:10666–10681CrossRefGoogle Scholar
  36. 36.
    Roland CM, Ngai KL (1991) Segmental relaxation and molecular structure in polybutadienes and polyisoprene. Macromolecules 24:5315–5319CrossRefGoogle Scholar
  37. 37.
    Angell CA (1991) Relaxation in liquids, polymers and plastic crystals—strong/fragile patterns and problems. J Non-Cryst Solids 131–133:13–31CrossRefGoogle Scholar
  38. 38.
    Erwin BM, Colby RH (2002) Temperature dependence of relaxation times and the length scale of cooperative motion for glass-forming liquids. J Non-Cryst Solids 307:225–231CrossRefGoogle Scholar
  39. 39.
    Solunov CA (1999) Cooperative molecular dynamics and strong/fragile behavior of polymers. Eur Polym J 35:1543–1556CrossRefGoogle Scholar
  40. 40.
    Böhmer R, Ngai KL, Angell CA, Plazek DJ (1993) Nonexponential relaxations in strong and fragile glass formers. J Chem Phys 99:4201–4210CrossRefGoogle Scholar
  41. 41.
    Williams ML, Landel RF, Ferry JD (1955) The temperature dependence of relaxation mechanisms in amorphous polymers and other glass-forming liquids. J Am Chem Soc 77:3701–3707CrossRefGoogle Scholar
  42. 42.
    Ferry JD (1980) Viscoelastic properties of polymers, 3rd edn. Wiley, New YorkGoogle Scholar
  43. 43.
    Matsuoka S (1992) Relaxation phenomena in polymers. Hanser, MunichGoogle Scholar
  44. 44.
    Ngai KL, Plazek D (1986) A quantitative explanation of the difference in the temperature dependences of the viscoelastic softening and terminal dispersions of linear amorphous polymers. J Polym Sci Polym Phys 24:619–632CrossRefGoogle Scholar
  45. 45.
    Ngai KL, Rendell RW, Rajagopal AK, Teitler S (1986) Three coupled relations for relaxations in complex systems. Ann NY Acad Sci 484:150–184CrossRefGoogle Scholar
  46. 46.
    Vyazovkin S, Dranca I (2004) A DSC study of α- and β-relaxations in a PS–clay system. J Phys Chem B 108:11981–11987CrossRefGoogle Scholar
  47. 47.
    Tran TA, Saïd S, Grohens Y (2005) Nanoscale characteristic length at the glass transition in confined syndiotactic poly(methyl methacrylate). Macromolecules 38:3867–3871CrossRefGoogle Scholar
  48. 48.
    Ngai KL (2007) Predicting the changes of relaxation dynamics with various modifications of the chemical and physical structures of glass-formers. J Non-Cryst Solids 353:4237–4245CrossRefGoogle Scholar
  49. 49.
    Si M, Araki T, Ade H, Kilcoyne ALD, Fisher R, Sokolov JC, Rafailovich MH (2006) Compatibilizing bulk polymer blends by using organoclays. Macromolecules 39:4793–4801CrossRefGoogle Scholar
  50. 50.
    Fang Z, Harrats C, Moussaif N, Groeninckx G (2007) Location of a nanoclay at the interface in an immiscible poly(ε-caprolactone)/poly(ethylene oxide) blend and its effect on the compatibility of the components. J Appl Polym Sci 106:3125–3135CrossRefGoogle Scholar
  51. 51.
    Andreozzi L, Faetti M, Giordano M, Zulli F (2005) Molecular-weight dependence of enthalpy relaxation of PMMA. Macromolecules 38:6056–6067CrossRefGoogle Scholar
  52. 52.
    Kalakkunnath S, Kalika DS, Lin H, Freeman BD (2005) Segmental relaxation characteristics of cross-linked poly(ethylene oxide) copolymer networks. Macromolecules 38:9679–9687CrossRefGoogle Scholar
  53. 53.
    Ngai KL, Tsang KY (1999) Similarity of relaxation in supercooled liquids and interacting arrays of oscillators. Phys Rev E 60:4511–4517CrossRefGoogle Scholar

Copyright information

© Iran Polymer and Petrochemical Institute 2013

Authors and Affiliations

  1. 1.Department of Polymer EngineeringAmirkabir University of Technology, Mahshahr BranchMahshahrIran
  2. 2.Polymer Division, School of Chemistry, University College of ScienceUniversity of TehranTehranIran
  3. 3.Biomaterials Research Center (BRC)University of TehranTehranIran

Personalised recommendations