A Study on Vulcanization Reaction of Modified Rubber Blends Using Dynamic Differential Scanning Calorimetry

Dynamic DSC를 이용한 개질 고무 블랜드의 가황 반응에 관한 연구

  • Lee, Seung-Hyun (Department of Chemical Engineering, Keimyung University) ;
  • Ahn, Won-Sool (Department of Chemical Engineering, Keimyung University)
  • 이승현 (계명대학교 공과대학 화학공학과) ;
  • 안원술 (계명대학교 공과대학 화학공학과)
  • Published : 2003.12.31


Even though many studies have been reported about rubber vulcanization, it is still remained difficult to find a quantitative relationship between the final states of vulcanized rubber and initial formulation or processing conditions. Dynamic differential scanning calorimetry (DSC) method is known as a comparatively easy method to research for the rubber vulcanization in both experimental and analysis. In the present research, a study on the vulcanization reaction of NR/CB composites modified by isoprene(IR) and chloroprene(CR) rubbers is carried out using dynamic DSC method. Thermograms with several different heating rates were obtained and analyzed using the Kissinger method. Analysis showed that the vulcanization reaction was progressed through the first order reaction mechanism. In addition, the reaction temperature was severely influenced by the kinds or rubber modifiers, in this case, more influenced by CR than by IR. Those effects were clearly verified in the values of activation energy. Kinds of carbon blacks, however, could hardly influence on the reaction mechanism.


  1. P. K. Das, R. N. Datt, and D. K. Basu, 'Cure Modification Effected by Cycloalkylthioamines in The Vulcanazation of NR Accelerated by Thiocarbamyl Sulfenamides and Dibenzothiazyl Disulfide', Rubber Chem. Technol., 61, 760 (1988)
  2. E. Morita and E. J. Young, 'A study of Sulfena-mide Acceleration', Rubber Chem. Technol., 36, 844 (1963)
  3. D. Pal, B. D. Adhikari, K. Baus, and A. K. Chaudhuri, 'Study of Cure Synergism of The Thio-carbamylsulfenamide Dibenzothioazyl Disulfide Acce-lerator System in The Vulcanization of Natural Rubber', Rubber Chem. Technol., 56, 827 (1983)
  4. M. Morton, 'Rubber technology', Van Nostrand Reinhold, New York, 1973
  5. G. A1liger and I. J. Sjothum, 'Vulcanization of Elastomer', Van Nostrand Reinhold, New York, 1963
  6. F. P. Baldwin and G. Ver Strate, 'Polyolefin Elastomers Based on Ethylene and Propylene', Rubber Chem. Technol., 45, 709 (1972)
  7. M. R. Krejsa and 1. L. Koenig, 'A Review of Sulfur Crosslinking Fundamentals for Accelerated and Unaccelerated Vulcanization', Rubber Chem. Technol., 66, 376 (1993)
  8. B. Hom, 'Rubber Technology and Manufacture', The Plastics and Rubber Institute, New York, 1982
  9. S. C. EinHorn, Rubber World, 148, 40 (1963)
  10. V. J. Duchacek, 'Effect of temperature on the course of thiuram-accelerated sulfur vulcanization', Appl. Polym. Sci., 19, 1617 (1975) https://doi.org/10.1002/app.1975.070190613
  11. D. S. Champbell, 'Structural Characterization of Vul-canizates. XI. Network-Bound Accelerator Residues', Rubber chem. Technol., 44, 771 (1971)
  12. S. S. Labana, 'Encyclopedia of Polymer Science and Engineering', John Wiley & Sons, New York, 1986
  13. R. N. Rees, 'Encyclopedia of Polymer Science and Engineering', John Wiley & Sons, New York, 1986
  14. P. W. Allen, D. Barnard, and B. Saville, Chem. Brit., 6, 382 (1970)
  15. N. J. Morrison and M. Porter, 'Temperature Effects on The Stability of Intermediates and Crosslinks in Sulfur Vulcanization', Rubber Chem. Technol., 57, 63 (1984)
  16. A. Y. Coran and F. R. Eirich, 'Science and Techno-logy of Rubber', Academic Press, New York, 1978
  17. P. J. Flory and 1. Rehner, J. CheM. Phys., 11, 512 (1943)
  18. M. J. Mooeny, Appl. Phys., 11, 582 (1940)
  19. G. Gee and S. H. Morrel, Rubber Chem. Technol., 25, 254 (1952).
  20. M. L. Bhaumik, D. Banerjee, and A. K. Sircar, J. Appl. Polyrn. Sci., 9, 1367 (1975)
  21. J. F. Rabek, 'Experimental Method in Polymer Chemistry', John Wiley & Sons, New York, 1980
  22. T. Hatekyama and F. X. Quinn, 'Thermal Analysis Fundamentals and Applications to Polymer Science', John Wiley & Sons, New York, 1994
  23. T. Hatekyama and Z. Liu, 'Handbook of Thermal Analysis', John Wiley & Sons, New York, 1998
  24. H. E. Kissinger, Analytical Chemistry, 29, 1702 (1957)
  25. S. H. Goh, J Elastomersand Plastics, 9, 186 (1977) https://doi.org/10.1177/009524437700900205
  26. A. Turi, 'Thermal Characterization of Polymeric Materials', Academic Press, New York, 1983