Abstract
For an ageing process involving the consumption of a small molecule (typically O2 or H2O) by reaction with the polymer, there are critical conditions of reaction rate and/or thickness above which the process becomes kinetically controlled by the diffusion of the small molecule in the polymer. Suitable lifetime prediction models must then involve the thickness distribution of reaction products. This latter can be predicted from Fick's law, modified by a term relative to the rate of consumption of the diffusing species by the chemical reaction. Some problems related to the use of this approach are examined here. It appears that, in the most frequent case, the thickness of the degraded layer is of the order of magnitude of D/k, where D is the diffusion coefficient and k the pseudo-first-order rate constant for reactant consumption. Some examples of application related to photochemical, radiochemical and thermochemical ageing are examined. It can, for instance, be shown that in photochemical or radiochemical ageing, the thickness of the oxidized layer (TOL) is proportional to the reciprocal of l β, where l is the radiation intensity and Β an exponent depending essentially on the radical chain mechanism. It is generally expected that in the case of thermal ageing, the TOL is a decreasing function of the temperature. Some consequences of diffusion control on accelerated and natural ageing methods are briefly examined. The consequences of the ageing-induced “skin-core” structure due to the diffusion control are examined. The main features of the observed polymer embrittlement can be explained in terms of fracture mechanics.
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R. C. Golike and S. W. Lazoski, J. Phys. Chem. 64 (1960) 895.
G. C. Furneaux, K. J. Leddury and A. Davis, Polym. Degrad. Stab. 3 (1986) 431.
A. V. Cunliffe and A. Davis, ibid 4 (1982) 17.
T. Seguchi, S. Hashimuto, K. Akakawa, N. Hayakawa, W. Kawakami and J. Kuryama, Rdiat. Phys. Chem. 17 (1981) 191.
S. P. Fairgreve and J. R. McCallum, Polym. Degrad. Stab. 11 (1985) 251.
J. R. Puig, “Les techniques de l/Ingéniew-Génie nucléaire” (Paris) B 3770 (1982) 1.
M. V. Belusova and V. D. Skirda Acta Polym. 10 (1985) 36.
G. Papet, L. Audouin-Jirackova and J. Verdu, Radiat. Phys. Chem. 33 (1989) 329.
S. G. Kiryushkin and Y. A. Shlyapnikov, Polym. Degrad. Stab. 23 (2) 185.
K. T. Gillen and R. L. Clough, in “Handbook of Polymer Science and Technology”, Vol. 2, edited by N. P. Cheremisinoff (Dekker, New York, 1989) p. 170.
G. S. Park and J. Crank, “Diffusion in Polymers” (Academic, New York, 1981) pp. 4–20.
L. Audouin and J. Verdu, ACS Symp. Ser. 475 (1991) 473.
M. Lehuy, thesis, ENSAM, Paris (1990).
Idem, Polym. Degrad. Stab. in press.
J. Petruj and J. Marchal, ibid 16 (1980) 27.
A. Huvet, J. Philippe and J. Verdu, Euro. Polym. J. 14 (1978) 709.
K. T. Gillen and R. L. Clough, J. Polym. Sci., Polym. Chem. Edn. 19 (1985) 2041.
H. Wilski, Radiat. Phys. Chem. 29 (1) (1987) 1.
de J. C. M. Bruijn, thesis, Delft University Press, 1992.
T. G. Ryan, P. D. Calvert and N. C. Billingham, “Stabilization and Degradation of Polymers”, ACS Chemistry Series Vol. 169 p. 261.
X. Jouan and L. Gardette, Polym. Commun. 28 (1987) 239.
V. Langlois, M. Meyer, L. Audouin and J. Verdu, Polym. Degrad. Stab. 40 (1993) 399.
J. L. Gardon, J. Coll. Interf. Sci 59 (1977) 582.
Idem, Progr. Org. Coatings 5 (1977) 1.
H. H. Kausch, in “Interrelations between Processing, Structure and Properties of Polymeric materials”, edited by J. C. Seferis and P. S. Theocaris (Elsevier, Amsterdam, 1984) p. 363.
J. Pabiot and J. Verdu, Polym. Eng. Sci. 21 (1) (1981) 32.
R. J. Gardner and J. R. Martin, J. Appl. Polym. Sci. 24 (1979) 1269.
B. Mortaigne, thesis, ENSAM, Paris (1989).
J. Verdu, B. Mortaigne and P. A. Hoarau, in Proceedings of 11th International Conference on Advances in the Stabilization and Controlled Degradation of Polymers, Luzern, 24–26 May 1989.
C. B. Bucknall and D. G. Street, J. Appl. Polym. Sci. 12 (1968) 1311.
G. M. Ruhnke and L. F. Biritz, Plast. Polym. 6 (1972) 118.
E. Priebe and J. Stabenow, Kunststoffe 64 (1974) 497.
D. J. Carlsson and D. Wiles, J. Macromol. Sci. C 14 (1) (1976) 65.
M. D. Wolkowicz and S. K. Gaggar, Polym. Eng. Sci. 21 (1981) 571.
P. So and L. J. Broutman, ibid. 22 (1982) 888.
L. Rolland, K. Thomson, S. Mostovoy and L. J. Broutman, in Proceedings of International Conference on Deformation, Yield and Fracture of Polymers, Cambridge, 1982.
L. Rolland and L. J. Broutman, in Proceedings of ANTEC 83, May 1983 (1983) p. 451.
N. Rosenzweig and L. J. Broutman, ibid. p. 455.
L. Rolland and L. J. Broutman, in Proceedings of ANTEC 85 (1985) p. 634.
P. So and L. J. Broutman, ibid. p. 639.
L. J. Broutman and L. Rolland, in Proceedings of ANTEC 86, April 1986 (1986) p. 600.
G. E. Schoolenberg, thesis, Technical University of Delft (1988).
Idem, J. Mater. Sci. 23 (1988) 1580.
D. W. Van Krevelen and P. J. Hoftyzer in “Properties of Polymers” (Elsevier Scientific, New York 1976) p. 410.
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Audouin, L., Langlois, V., Verdu, J. et al. Role of oxygen diffusion in polymer ageing: kinetic and mechanical aspects. Journal of Materials Science 29, 569–583 (1994). https://doi.org/10.1007/BF00445968
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DOI: https://doi.org/10.1007/BF00445968