Experimental Validation of the Horikx Theory to be Used in the Rubber Devulcanization Analysis

  • Saïd Seghar
  • Lucia Asaro
  • Nourredine Aït HocineEmail author
Brief Communication


The waste rubber and end-of-life tires management has become a serious environmental problem. It is well known that the best way to carry out the disposal of these wastes is through recycling by devulcanization. Therefore, in the last decades, many methods have been developed to perform this treatment. Nevertheless, the degree and quality of the achieved devulcanization is still difficult to evaluate. The Horikx theory is an approach often used for this purpose. Hence, in this work, the validity of this theory was experimentally checked. The theoretical curve that represents crosslink scission was experimentally built for sulfur-cured natural rubber, sulfur-cured natural rubber reinforced with carbon black, sulfur-cured ethylene propylene diene monomer rubber and peroxide-cured ethylene propylene diene monomer rubber. Several samples with vulcanization (or devulcanization) degree ranging from 0 to 100% were processed, and the corresponding soluble fractions and crosslink densities were measured by the swelling test. The experimental results were in good agreement with the theoretical predictions, independently of the studied material, fact that confirms the validity of the Horikx approach. This finding will contribute to improve the waste rubber devulcanization, and therefore to progress in the environmental protection.


Rubber Recycling Devulcanization Horikx theory Waste management 



Funding was provided by Conseil Régional du Centre-Val de Loire (Grant No. 2014-00091856).

Compliance with Ethical Standards

Conflict of interest

The authors declare that they have not conflict of interest.


  1. 1.
    Moulin L, Da Silva S, Bounaceur A et al (2017) Assessment of recovered carbon black obtained by waste tires steam water thermolysis: an industrial application. Waste Biomass Valoriz 8:2757–2770. CrossRefGoogle Scholar
  2. 2.
    Dunuwila P, Rodrigo VHL, Goto N (2018) Sustainability of natural rubber processing can be improved: a case study with crepe rubber manufacturing in Sri Lanka. Resour Conservat Recycl 133:417–427. CrossRefGoogle Scholar
  3. 3.
    Myhre M, MacKillop DA (2002) Rubber recycling. Rubber Chem Technol 75:429–474. CrossRefGoogle Scholar
  4. 4.
    Ghorai S, Bhunia S, Roy M, De D (2016) Mechanochemical devulcanization of natural rubber vulcanizate by dual function disulfide chemicals. Polym Degrad Stab 129:34–46. CrossRefGoogle Scholar
  5. 5.
    Asaro L, Gratton M, Seghar S, Aït Hocine N (2018) Recycling of rubber wastes by devulcanization. Resour Conserv Recycl 133:250–262. CrossRefGoogle Scholar
  6. 6.
    Seghar S, Aït Hocine N, Mittal V et al (2015) Devulcanization of styrene butadiene rubber by microwave energy: effect of the presence of ionic liquid. Express Polym Lett 9:1076–1086. CrossRefGoogle Scholar
  7. 7.
    Aoudia K, Azem S, Aït Hocine N et al (2017) Recycling of waste tire rubber: microwave devulcanization and incorporation in a thermoset resin. Waste Manag 60:471–481. CrossRefGoogle Scholar
  8. 8.
    de Sousa FDB, Scuracchio CH, Hu GH, Hoppe S (2017) Devulcanization of waste tire rubber by microwaves. Polym Degrad Stab 138:169–181. CrossRefGoogle Scholar
  9. 9.
    Mangili I, Collina E, Anzano M et al (2014) Characterization and supercritical CO2 devulcanization of cryo-ground tire rubber: influence of devulcanization process on reclaimed material. Polym Degrad Stab 102:15–24. CrossRefGoogle Scholar
  10. 10.
    Sabzekar M, Chenar MP, Mortazavi SM et al (2015) Influence of process variables on chemical devulcanization of sulfur-cured natural rubber. Polym Degrad Stab 118:88–95. CrossRefGoogle Scholar
  11. 11.
    Anu Mary J, Benny G, Madhusoodanan KN, Rosamma A (2016) The current status of sulphur vulcanization and devulcanization chemistry: devulcanization. Rubber Sci 29:62–100Google Scholar
  12. 12.
    Isayev AI, Liang T, Lewis TM (2014) Effect of particle size on ultrasonic devulcanization of tire rubber in twin-screw extruder. Rubber Chem Technol 87:86–102. CrossRefGoogle Scholar
  13. 13.
    Mangili I, Lasagni M, Anzano M et al (2015) Mechanical and rheological properties of natural rubber compounds containing devulcanized ground tire rubber from several methods. Polym Degrad Stab 121:369–377. CrossRefGoogle Scholar
  14. 14.
    Mangili I, Lasagni M, Huang K, Isayev AI (2015) Modeling and optimization of ultrasonic devulcanization using the response surface methodology based on central composite face-centered design. Chemom Intell Lab Syst 144:1–10. CrossRefGoogle Scholar
  15. 15.
    Karger-Kocsis J, Mészáros L, Bárány T (2013) Ground tyre rubber (GTR) in thermoplastics, thermosets, and rubbers. J Mater Sci 48:1–38. CrossRefGoogle Scholar
  16. 16.
    Shi J, Zou H, Ding L et al (2014) Continuous production of liquid reclaimed rubber from ground tire rubber and its application as reactive polymeric plasticizer. Polym Degrad Stab 99:166–175. CrossRefGoogle Scholar
  17. 17.
    Meysami M, Tzoganakis C, Mutyala P et al (2017) Devulcanization of scrap tire rubber with supercritical CO2: a study of the effects of process parameters on the properties of devulcanized rubber. Int Polym Process 32:183–193. CrossRefGoogle Scholar
  18. 18.
    Khavarnia M, Movahed SO (2016) Butyl rubber reclamation by combined microwave radiation and chemical reagents. J Appl Polym Sci 43363:1–11. Google Scholar
  19. 19.
    Liu Z, Li X, Xu X et al (2015) Devulcanizaiton of waste tread rubber in supercritical carbon dioxide: operating parameters and product characterization. Polym Degrad Stab 119:198–207. CrossRefGoogle Scholar
  20. 20.
    Edwards DW, Danon B, van der Gryp P, Görgens JF (2016) Quantifying and comparing the selectivity for crosslink scission in mechanical and mechanochemical devulcanization processes. J Appl Polym Sci 133:1–10. CrossRefGoogle Scholar
  21. 21.
    Molanorouzi M, Mohaved SO (2016) Reclaiming waste tire rubber by an irradiation technique. Polym Degrad Stab 128:115–125. CrossRefGoogle Scholar
  22. 22.
    Horikx M (1956) Chain scissions in a polymer network. J Polym Sci B 19:445–454. CrossRefGoogle Scholar
  23. 23.
    Verbruggen MAL, van der Does L, Dierkes WK, Noordermeer JWM (2016) Experimental validation of the Charlesby and Horikx models applied to de-vulcanization of sulfur and peroxide vulcanizates of Nr and Epdm. Rubber Chem Technol 89:671–688. CrossRefGoogle Scholar
  24. 24.
    Seghar SA, Asaro L, Rolland-Monnet M, Aït Hocine N (2019) Thermo-mechanical devulcanization and recycling of rubber industry waste. Resour Conserv Recycl 144:180–186. CrossRefGoogle Scholar
  25. 25.
    Saiwari S, van Hoek JW, Dierkes WK et al (2016) Upscaling of a batch de-vulcanization process for ground car tire rubber to a continuous process in a twin screw extruder. Materials (Basel). Google Scholar
  26. 26.
    Charlesby A (1953) Solubility and molecular size distribution of crosslinked polystyrene. J Polym Sci 11:513–520. CrossRefGoogle Scholar
  27. 27.
    Flory PJ (1944) Network structure and the elastic properties of vulcanized rubber. Chem Rev 35:51–75. CrossRefGoogle Scholar
  28. 28.
    Formela K, Cysewska M (2016) thermomechanical reclaiming of ground tire rubber via extrusion at low temperature : efficiency and limits. J Vinyl Addit Technol. Google Scholar
  29. 29.
    Kraus G (1963) Swelling of Filler-reinforced vulcanizates. J Appl Polym Sci 7:861–871. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Saïd Seghar
    • 1
  • Lucia Asaro
    • 2
  • Nourredine Aït Hocine
    • 3
    Email author
  1. 1.PHENIX TECHNOLOGIESSanchevilleFrance
  2. 2.Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET)Mar del PlataArgentina
  3. 3.INSA CVL, Univ. Tours, Univ. Orléans, LaMéBlois CedexFrance

Personalised recommendations