Rheologica Acta

, Volume 57, Issue 11, pp 745–756 | Cite as

Characterization of physical aging by time-resolved rheometry: fundamentals and application to bituminous binders

  • Olli-Ville LaukkanenEmail author
  • H. Henning Winter
  • Jukka Seppälä
Original Contribution


Physical aging is a ubiquitous phenomenon in glassy materials and it is reflected, for example, in the time evolution of rheological properties under isothermal conditions. In this paper, time-resolved rheometry (TRR) is used to characterize this time-dependent rheological behavior. The fundamentals of TRR are briefly reviewed, and its advantages over the traditional Struik’s physical aging test protocol are discussed. In the experimental section, the TRR technique is applied to study physical aging in bituminous binders. Small-diameter parallel plate (SDPP) rheometry is employed to perform cyclic frequency sweep (CFS) experiments over extended periods of time (from one to 8.6 days). The results verify that the mutation of rheological properties is relatively slow during physical aging (mutation number Nmu << 1), thus allowing rheological measurements on a quasi-stable sample. The effects of temperature, crystallinity, and styrene-butadiene-styrene (SBS) polymer modification on the physical aging of bitumen are evaluated. The time-aging time superposition is found to be valid both for unmodified and for polymer-modified bitumen. Vertical shifts are necessary, in addition to horizontal time-aging time shifts, to generate smooth master curves for highly SBS-modified bitumen.


Physical aging Sample mutation Time-resolved rheometry Time-aging time superposition Bitumen 



This study received financial support from Osk. Huttunen Foundation and Nynas AB.


  1. Alcoutlabi M, Martinez-Vega JJ (1999) Effect of physical ageing on the relaxation time spectrum of amorphous polymers: the fractional calculus approach. J Mater Sci 34:2361–2369. CrossRefGoogle Scholar
  2. Anderson D, Marasteanu M (1999) Physical hardening of asphalt binders relative to their glass transition temperatures. Transp Res Rec J Transp Res Board 1661:27–34. CrossRefGoogle Scholar
  3. Anderson DA, Christensen DW, Bahia HU, et al (1994) Binder characterization and evaluation. Volume 3: Physical characterization. Strategic Highway Research ProgramGoogle Scholar
  4. Araki O, Horie M, Masuda T (2001a) Physical aging of polycarbonate investigated by dynamic viscoelasticity. J Polym Sci Part B Polym Phys 39:337–341.<337::AID-POLB1006>3.0.CO;2-N CrossRefGoogle Scholar
  5. Araki O, Masuda T (2001) Role of a small amount of comonomer on the physical aging of poly(methyl methacrylate) copolymer investigated by dynamic viscoelasticity. Polymer (Guildf) 43:857–861. CrossRefGoogle Scholar
  6. Araki O, Shimamoto T, Yamamoto T, Masuda T (2001b) Physical aging of polystyrene investigated by dynamic viscoelasticity. Polymer (Guildf) 42:4433–4437. CrossRefGoogle Scholar
  7. Bahia H, Tabatabaee H, Velasquez R (2012) Importance of bitumen physical hardening for thermal stress buildup and relaxation in asphalt. In: 5th Eurasphalt & Eurobitume Congress. pp 13–15Google Scholar
  8. Baumgaertel M, Winter HH (1989) Determination of discrete relaxation and retardation time spectra from dynamic mechanical data. Rheol Acta 28:511–519. CrossRefGoogle Scholar
  9. Beiner M, Garwe F, Schröter K, Donth E (1994a) Dynamic shear modulus in the splitting region of poly(alkyl methacrylates). Colloid Polym Sci 272:1439–1446. CrossRefGoogle Scholar
  10. Beiner M, Garwe F, Schröter K, Donth E (1994b) Ageing effects on dynamic shear moduli at the onset of the dynamic glass transition in two poly(alkyl methacrylate)s. Polymer (Guildf) 35:4127–4132. CrossRefGoogle Scholar
  11. Booij HC, Thoone GPJM (1982) Generalization of Kramers-Kronig transforms and some approximations of relations between viscoelastic quantities. Rheol Acta 21:15–24. CrossRefGoogle Scholar
  12. Bradshaw RD, Brinson LC (1997) Physical aging in polymers and polymer composites: an analysis and method for time-aging time superposition. Polym Eng Sci 37:31–44. CrossRefGoogle Scholar
  13. Brennan AB, Feller F III (1995) Physical aging behavior of a poly (arylene etherimide). J Rheol (N Y N Y) 39:453–470. CrossRefGoogle Scholar
  14. Brinson LC, Gates TS (1995) Effects of physical aging on long term creep of polymers and polymer matrix composites. Int J Solids Struct 32:827–846. CrossRefGoogle Scholar
  15. Cavaille JY, Etienne S, Perez J, Monnerie L, Johari GP (1986) Dynamic shear measurements of physical ageing and the memory effect in a polymer glass. Polymer (Guildf) 27:686–692. CrossRefGoogle Scholar
  16. Chambon F, Winter HH (1985) Stopping of crosslinking reaction in a PDMS polymer at the gel point. Polym Bull 13:499–503. CrossRefGoogle Scholar
  17. Chambon F, Winter HH (1987) Linear viscoelasticity at the gel point of a crosslinking PDMS with imbalanced stoichiometry. J Rheol (N Y N Y) 31:683–697. CrossRefGoogle Scholar
  18. Chen K, Schweizer KS (2007) Molecular theory of physical aging in polymer glasses. Phys Rev Lett 98.
  19. Claudy P, Letoffe JM, Rondelez F, et al (1992) A new interpretation of time-dependent physical hardening in asphalt based on DSC and optical thermoanalysis. In: ACS Symposium on Chemistry and Characterization of Asphalts, Washington, DCGoogle Scholar
  20. Cugini AV, Lesser AJ (2015) Aspects of physical aging, mechanical rejuvenation, and thermal annealing in a new copolyester. Polym Eng Sci 55:1941–1950. CrossRefGoogle Scholar
  21. De Rosa ME, Mours M, Winter HH (1997) The gel point as reference state: a simple kinetic model for crosslinking polybutadiene via hydrosilation. Polym Gels Networks 5:69–94. CrossRefGoogle Scholar
  22. Delin MR, Rychwalski W, Kubát J et al (1996) Physical aging time scales and rates for poly(vinyl acetate) stimulated mechanically in the Tg-region. Polym Eng Sci 36:2955–2967. CrossRefGoogle Scholar
  23. Drozdov a D, Dorfmann a (2003) Physical aging and the viscoelastic response of glassy polymers: comparison of observations in mechanical and dilatometric tests. Math Comput Model 37:665–681. CrossRefGoogle Scholar
  24. Drozdov AD (2001) The effect of temperature on physical aging of glassy polymers. J Appl Polym Sci 81:3309–3320. CrossRefGoogle Scholar
  25. Evans M, Marchildon R, Hesp S (2011) Effects of physical hardening on stress relaxation in asphalt cements. Transp Res Rec J Transp Res Board 2207:34–42. CrossRefGoogle Scholar
  26. Filippone G, Carroccio SC, Curcuruto G, Passaglia E, Gambarotti C, Dintcheva NT (2015a) Time-resolved rheology as a tool to monitor the progress of polymer degradation in the melt state - part II: thermal and thermo-oxidative degradation of polyamide 11/organo-clay nanocomposites. Polym (United Kingdom) 73:102–110. CrossRefGoogle Scholar
  27. Filippone G, Carroccio SC, Mendichi R et al (2015b) Time-resolved rheology as a tool to monitor the progress of polymer degradation in the melt state–part I: thermal and thermo-oxidative degradation of polyamide 11. Polymer (Guildf) 72:134–141. CrossRefGoogle Scholar
  28. Freeston JL, Gillespie Gh, Paliukaite M, Taylor R (2015) Physical hardening in asphalt. In: Proceedings of the Sixtieth Annual Conference of the Canadian Technical Asphalt Association (CTAA): Winnipeg, ManitobaGoogle Scholar
  29. Ghiringhelli E, Roux D, Bleses D, Galliard H, Caton F (2012) Optimal Fourier rheometry: application to the gelation of an alginate. Rheol Acta 51:413–420. CrossRefGoogle Scholar
  30. Guerdoux L, Duckett RA, Froelich D (1984) Physical ageing of polycarbonate and PMMA by dynamic mechanical measurements. Polymer (Guildf) 25:1392–1396. CrossRefGoogle Scholar
  31. Haidar B, Smith TL (1990) Physical ageing of stretched specimens of a polycarbonate film and its temperature dependence. Polymer (Guildf) 31:1904–1908. CrossRefGoogle Scholar
  32. Hesp SAM, Genin SN, Scafe D et al (2009a) Five year performance review of a Northern Ontario Pavement Trial: Validation of Ontario’s Double-Edge-Notched Tension (DENT) and extended Bending Beam Rheometer (BBR) test methods. Can Tech Asph Assoc Proc Annu Conf 54:99–126Google Scholar
  33. Hesp SAM, Iliuta S, Shirokoff JW (2007) Reversible aging in asphalt binders. Energy and Fuels 21:1112–1121. CrossRefGoogle Scholar
  34. Hesp SAM, Soleimani A, Subramani S, Phillips T, Smith D, Marks P, Tam KK (2009b) Asphalt pavement cracking: analysis of extraordinary life cycle variability in eastern and northeastern Ontario. Int J Pavement Eng 10:209–227. CrossRefGoogle Scholar
  35. Hodge IM (1995) Physical aging in polymer glasses. Science (80- ) 267:1945–1947. CrossRefGoogle Scholar
  36. Holly EE, Venkataraman SK, Chambon F, Henning Winter H (1988) Fourier transform mechanical spectroscopy of viscoelastic materials with transient structure. J Nonnewton Fluid Mech 27:17–26. CrossRefGoogle Scholar
  37. Hutcheson SA, McKenna GB (2008) The measurement of mechanical properties of glycerol, m -toluidine, and sucrose benzoate under consideration of corrected rheometer compliance: an in-depth study and review. J Chem Phys 129:074502. CrossRefGoogle Scholar
  38. Hutchinson JM (1995) Physical aging of polymers. Prog Polym Sci 20:703–760. CrossRefGoogle Scholar
  39. Iliuta S, Andriescu A, Hesp SAM, Tam KK (2004a) Improved approach to low temperature and fatigue fracture performance grading of asphalt cements. In: Proceedings of the Forty-Ninth Annual Conference of the Canadian Technical Asphalt Association (CTAA)-Montreal, QuebecGoogle Scholar
  40. Iliuta S, Hesp S, Marasteanu M, Masliwec T, Tam K (2004b) Field validation study of low-temperature performance grading tests for asphalt binders. Transp Res Rec 1875:14–21. CrossRefGoogle Scholar
  41. Jelčić Ž, Ocelić Bulatović V, Jurkaš Marković K, Rek V (2017) Multi-fractal morphology of un-aged and aged SBS polymer-modified bitumen. Plast Rubber Compos 46:77–98. CrossRefGoogle Scholar
  42. Jelimir J, Bulatović VO, Rek V, Marković KJ (2016) Relationship between fractal, viscoelastic, and aging properties of linear and radial styrene-butadiene-styrene polymer-modified bitumen. J Elastomers Plast 48:14–46. CrossRefGoogle Scholar
  43. Joshi YM (2014) Long time response of aging glassy polymers. Rheol Acta 53:477–488. CrossRefGoogle Scholar
  44. Kaushal M, Joshi YM (2014) Validation of effective time translational invariance and linear viscoelasticity of polymer undergoing cross-linking reaction. Macromolecules 47:8041–8047. CrossRefGoogle Scholar
  45. Kovacs AJ (1964) Transition vitreuse dans les polymères amorphes. Etude phénoménologique. Fortschritte der Hochpolym 3:394–507. CrossRefGoogle Scholar
  46. Kovacs AJ, Stratton RA, Ferry JD (1963) Dynamic mechanical properties of polyvinyl acetate in shear in the glass transition temperature range. J Phys Chem 67:152–161. CrossRefGoogle Scholar
  47. Kramers HA (1927) La diffusion de la lumière par les atomes. In: Atti cong intern fisici, Transactions of Volta Centenary Congress. p 545Google Scholar
  48. Kronig R de L (1926) On the theory of dispersion of x-rays. Josa 12:547–557Google Scholar
  49. Kruse M, Wagner MH (2016) Time-resolved rheometry of poly(ethylene terephthalate) during thermal and thermo-oxidative degradation. Rheol Acta 55:789–800. CrossRefGoogle Scholar
  50. Laukkanen O-V (2017) Small-diameter parallel plate rheometry: a simple technique for measuring rheological properties of glass-forming liquids in shear. Rheol Acta 56:661–671. CrossRefGoogle Scholar
  51. Laukkanen O-V, Soenen H, Winter HH, Seppälä J (2018a) Low-temperature rheological and morphological characterization of SBS modified bitumen. Constr Build Mater 179:348–359. CrossRefGoogle Scholar
  52. Laukkanen O-V, Winter HH, Soenen H, Seppälä J (2018b) Systematic broadening of the viscoelastic and calorimetric glass transitions in complex glass-forming liquids. J Non-Cryst Solids 483:10–17. CrossRefGoogle Scholar
  53. Laukkanen O-V, Winter HH, Soenen H, Seppälä J (2018c) An empirical constitutive model for complex glass-forming liquids using bitumen as a model material. Rheol Acta 57:57–70. CrossRefGoogle Scholar
  54. Lu X, Isacsson U (2000) Laboratory study on the low temperature physical hardening of conventional and polymer modified bitumens. Constr Build Mater 14:79–88. CrossRefGoogle Scholar
  55. Mandare P, Winter HH (2007) Shear-induced long-range alignment of BCC-ordered block copolymers. Rheol Acta 46:1161–1170. CrossRefGoogle Scholar
  56. Masson JF, Polomark GM (2001) Bitumen microstructure by modulated differential scanning calorimetry. Thermochim Acta 374:105–114. CrossRefGoogle Scholar
  57. Masson JF, Polomark GM, Collins P (2002) Time-dependent microstructure of bitumen and its fractions by modulated differential scanning calorimetry. Energy and Fuels 16:470–476. CrossRefGoogle Scholar
  58. McKenna GB (2013) Physical aging in glasses and composites. In: Long-Term Durability of Polymeric Matrix Composites. pp 237–309Google Scholar
  59. Mours M, Winter HH (1994) Time-resolved rheometry. Rheol Acta 33:385–397. CrossRefGoogle Scholar
  60. Mours M, Winter HH (1998) Relaxation patterns of endlinking polydimethylsiloxane near the gel point. Polym Bull 40:267–274. CrossRefGoogle Scholar
  61. Mours M, Winter HH (1996) Relaxation patterns of nearly critical gels. Macromolecules 29:7221–7229. CrossRefGoogle Scholar
  62. O’Connell PA, McKenna GB (1999) Arrhenius-type temperature dependence of the segmental relaxation below Tg. J Chem Phys 110:11054–11060. CrossRefGoogle Scholar
  63. Paul Togunde O, Hesp SAM (2012) Physical hardening in asphalt mixtures. Int J Pavement Res Technol 5:46–53. CrossRefGoogle Scholar
  64. Pixa R, Goett C, Froelich D (1985) Influence of deformation on the physical ageing of polycarbonate - 1. Mechanical properties near ambient temperature. Polym Bull 14:53–60. CrossRefGoogle Scholar
  65. Planche J, Claudy P, Létoffé J, Martin D (1998) Using thermal analysis methods to better understand asphalt rheology. Thermochim Acta 324:223–227. CrossRefGoogle Scholar
  66. Pogodina NV, Winter HH (1998) Polypropylene crystallization as a physical gelation process. Macromolecules 31:8164–8172. CrossRefGoogle Scholar
  67. Polios IS, Soliman M, Lee C, Gido SP, Schmidt-Rohr K, Winter HH (1997) Late stages of phase separation in a binary polymer blend studied by rheology, optical and electron microscopy, and solid state NMR. Macromolecules 30:4470–4480. CrossRefGoogle Scholar
  68. Ricco T, Smith TL (1990) Rate of physical aging of polycarbonate at a constant tensile strain. J Polym Sci Part B Polym Phys 28:513–520. CrossRefGoogle Scholar
  69. Salehiyan R, Malwela T, Ray SS (2017) Thermo-oxidative degradation study of melt-processed polyethylene and its blend with polyamide using time-resolved rheometry. Polym Degrad Stab 139:130–137. CrossRefGoogle Scholar
  70. Schröter K, Hutcheson SA, Shi X, Mandanici A, McKenna GB (2006) Dynamic shear modulus of glycerol: corrections due to instrument compliance. J Chem Phys 125:214507. CrossRefGoogle Scholar
  71. Simon SL (2001) Aging, physical. In: Encyclopedia of Polymer Science and Technology. Wiley Online LibraryGoogle Scholar
  72. Soenen H, Ekblad J, Lu X, Redelius P (2004) Isothermal hardening in bitumen and in asphalt mix. In: Eurasphalt & Eurobitume Congress Vienna. pp 1364–1375Google Scholar
  73. Struik LCE (1966) Volume relaxation in polymers. Rheol Acta 5:303–311. CrossRefGoogle Scholar
  74. Struik LCE (1977) Physical aging in amorphous polymers and other materials. Ph.D. thesis, Delft University of TechnologyGoogle Scholar
  75. Tabatabaee HA, Velasquez R, Bahia HU (2012) Predicting low temperature physical hardening in asphalt binders. Constr Build Mater 34:162–169. CrossRefGoogle Scholar
  76. Tian F, Luo Y, Yin S, Wang H, Cao C (2015) Dynamic viscoelastic properties of polyvinyl chloride with physical aging. Korea-Australia Rheol J 27:259–266. CrossRefGoogle Scholar
  77. Venditti RA, Gillham JK (1992a) Physical aging deep in the glassy state of a fully cured polyimide. J Appl Polym Sci 45:1501–1516. CrossRefGoogle Scholar
  78. Venditti RA, Gillham JK (1992b) Isothermal physical aging of poly(methyl methacrylate): localization of perturbations in thermomechanical properties. J Appl Polym Sci 45:501–506. CrossRefGoogle Scholar
  79. Wang SF, Ogale AA (1989) Effects of physical aging on dynamic mechanical and transient properties of polyetheretherketone. Polym Eng Sci 29:1273–1278. CrossRefGoogle Scholar
  80. Winter HH (2016) Gel point. In: Encyclopedia of Polymer Science and Technology. pp 1–15Google Scholar
  81. Winter HH (1997) Analysis of dynamic mechanical data: inversion into a relaxation time spectrum and consistency check. J Nonnewton Fluid Mech 68:225–239. CrossRefGoogle Scholar
  82. Winter HH, Chambon F (1986) Analysis of linear viscoelasticity of a crosslinking polymer at the gel point. J Rheol (N Y N Y) 30:367–382. CrossRefGoogle Scholar
  83. Winter HH, Morganelli P, Chambon F (1988) Stoichiometry effects on rheology of model polyurethanes at the gel point. Macromolecules 21:532–535. CrossRefGoogle Scholar
  84. Winter HH, Mours M, Baumgaertel M, Soskey PR (1998) Computer-aided methods in rheometry. In: Rheological measurement. Springer, pp 47–98Google Scholar
  85. Yee P, Aida B, Hesp SAM, Marks P, Tam K (2006) Analysis of premature low-temperature cracking in three Ontario, Canada, pavements. Transp Res Rec J Transp Res Board Transp Res Board Natl Acad 1962:44–51. CrossRefGoogle Scholar
  86. Zhang Q, Huang X, Wang X, Jia X, Xi K (2014) Rheological study of the gelation of cross-linking polyhedral oligomeric silsesquioxanes (POSS)/PU composites. Polym (United Kingdom) 55:1282–1291. CrossRefGoogle Scholar
  87. Zhao MO, Hesp SAM (2006) Performance grading of the Lamont, Alberta C-SHRP pavement trial binders. Int J Pavement Eng 7:199–211. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Olli-Ville Laukkanen
    • 1
    • 2
    • 3
    Email author
  • H. Henning Winter
    • 1
    • 2
  • Jukka Seppälä
    • 3
  1. 1.Department of Polymer Science and EngineeringUniversity of MassachusettsAmherstUSA
  2. 2.Department of Chemical EngineeringUniversity of MassachusettsAmherstUSA
  3. 3.Department of Chemical and Metallurgical Engineering, School of Chemical EngineeringAalto UniversityAaltoFinland

Personalised recommendations