Abstract
The evolution of linear viscoelasticity during the vulcanization of polyethylene is studied through the gel point. The material in the vicinity of the gel point is described by two scaling laws: one characterizes the viscoelasticity at the critical point and a second characterizes the evolution of viscoelasticity near the gel point. Time Resolved Mechanical Spectroscopy is used to observe both scaling phenomena. The material at the gel point displays power law relaxation over five decades of time with a power-law relaxation exponent equal to 0.32. This study conforms with previous findings that this exponent is composition-dependent. The longest relaxation time diverges in the vicinity of the gel point as λmax ∼ |p c - p| −1/κ, and we find κ = 0.2. This result conforms with previous reports that this exponent may be independent of composition. The Arrhenius flow activation energy for this material undergoes three-fold changes during crosslinking up to the gel point. A single-adjustable-parameter stretched-exponential-power law relaxation function is an inadequate representation of crosslinked materials over any significant range of extent of the reaction up to the gel point.
Similar content being viewed by others
References
Stauffer D (1985) Introduction to Percolation Theory. Taylor and Francis, London
Stauffer D, Coniglio A, Adam M (1982) Adv Polym Sci 44:103
Chambon F, Winter HH (1985) Polym Bull 13:499
Winter HH, Chambon F (1986) J Rheol 30:367
Chambon F, Winter HH (1987) J Rheol 31:683
Scanlan JC, Winter HH (1991) Macromolecules 24:47
Martin JE, Adolf D, Wilcoxon JP (1988) Phys Rev Lett 61:2620
Durand D, Delsanti M, Adam M, Luck JM (1987) Europhys Lett 3:97
Scanlan JC, Winter HH (1991) Makromolekulare Chemie (in press)
Adolf D, Martin JE, Wilcoxon JP (1990) Macromolecules 23:527
Rubinstein M, Colby RH, Gillmor JR (1989) Polym Prepr (Am Chem Soc, Div Poly Sci) 30:81
Muthukumar M (1985) J Chem Phys 83:3161
Hess W, Vilgis TA, Winter HH (1988) Macromolecules 21:2536
Lazar M, Rado R, Rychly J (1990) Adv Polym Sci 95:149
Grest GS, Kremer K (1990) Macromolecules 23:4994
Sanlan JC, Winter HH (1991) to be submitted
Ferry JD (1980) Viscoelastic Properties of Polymers. Wiley, New York
Hodgson DF, Amis EJ (1990) Macromolecules 23:2512
Allain C (1990) Macromolecules 23:982
Winter HH (1987) Prog Coll Polym Sci 75:104
Schosseler F, Benoit H, Gallot Z, Strazielle CL, Leibler L (1989) Macromolecules 22:400
Patton EV, Wesson JA, Rubenstein M, Wilson JC, Oppenheimer LE (1989) Macromolecules 22:1946
Tschoegl NW (1989) The Phenomenological Theory of Linear Viscoelastic Behavior. Springer, Berlin
Scanlan JC, Janzen J: under review
Raju VR, Rachapudy H, Graessley WW (1979) J Polym Sci Polym Phys 17:1183
Raju VR, Smith GG, Marin G, Knox JR, Graessley WW (1979) J Polym Sci Polym Phys 17:1183
Ngai KL, Plazek DJ (1985) J Polym Sci Polym Phys Ed 23:2159
Shirayama K, Matsuda T, Kita SI (1971) Makromolekulare Chemie 147:155
Hughes JK (1983) Soc Plast Eng Tech Conf, May 3–5
Whitte WM, Randall JC, Leigh CH (1983) Chem Eng Comm 24:139
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Scanlan, J.C., Hicks, M.J. The evolution of linear viscoelasticity during the vulcanization of polyethylene. Rheola Acta 30, 412–418 (1991). https://doi.org/10.1007/BF00396527
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00396527