Investigation of modified bitumen binders via Fourier-transform infrared spectroscopy

Objectives. This study evaluates the effect of the modification process on the group composition of bitumen and bitumen binders containing rubber powder and hybrid modifier that is based on styrene–butadiene thermoplastic elastomer and rubber crumb. The aim of the study was to determine the presence or absence of functional groups that reflect the direction of physicochemical processes during the preparation of a hybrid modifier in rotary dispersers and during the modification of bitumen binders.

Methods. Rubber powder and hybrid modifier were obtained by high-temperature shear grinding using a rotary disperser. Bitumen and modified bitumen binders were investigated via Fouriertransform infrared spectroscopy. Using the method of spectral subtraction, it was determined that during the process of manufacturing modified bitumen binders, structural changes occur in both bitumen and modifiers. During this study, the extraction of modifiers (rubber powder and hybrid modifier) in toluene was performed.

Results. The quantitative analysis of changes in the group composition of modifiers before and after the modification procedure was carried out. The active polymer and structural indices were determined. The general trend of the change in the active polymer and structural indices was noted for the initial spectra of the rubber powder and hybrid modifier, and their spectra were obtained after the procedure of subtraction from the spectra of bitumen binders.

Conclusions. The interdiffusion of aromatic compounds between the bitumen component and modifier particles was confirmed. On the basis of the results of the extraction of modifiers in toluene, and by taking into account the infrared spectroscopy data, it was determined that during the production of hybrid modifier during the simultaneous grinding of rubber crumb and styrene– butadiene thermoplastic elastomer, there was a chemical interaction between them. 

1. Partl M.N., Bahia H.U., Canestrari F., Roche Ch., Benedetto H.D., Piber H., Sybilski D. (eds.) Advances in Inter- laboratory Testing and Evaluation of Bituminous Materials: State-of-the-Art Report of the RILEM Technical Committee 206-ATB. Springer; 2013. V. 9. 453 p.

2. Leseur D., Gerard J.-F, Claudy P., Letoffe J.-M., Planche J.-P., Martin D. A structure-related model to describe asphalt linear viscoelasticity. J. Rheol. 1996;40:813-856. https://doi.org/10.1122/1.550764

3. Gokhman, L.M. Bitumy, polimerno-bitumnye vyazhushchie, asfalʼtobeton, polimerasfalʼtobeton: uchebnometodicheskoe posobie (Bitumen, polymer-bitumen binders, asphalt concrete, polymerasphaltobeton: teaching aid). Moscow: EKON-INFORM; 2008. 117 p. (in Russ.).

4. Soenen H., Lu X., Redelius P. The morphology of SBS modified bitumen in binders and in asphalt mix. In: Advanced Testing and Characterization of Bituminous Materials, London: Taylor & Francis Group; 2009. P. 151160. ISBN 978-0-415-55854-9

5. Behnood A., Gharehveran M.M. Morphology, rheology, and physical properties of polymer-modified asphalt binders. Eur. Polym. J. 2019;112:766-791. https://doi.org/10.1016/j.eurpolymj.2018.10.049

6. Nikolskii V.G., Dudareva T.V., Krasotkina I.A., Zvereva U.G., Bekeshev V.G., Rochev, V.Ya., Kaplan A.M., Chekunaev N.I., Vnukova L.V., Styrikovich N.M., Gordeeva I.V. Development and properties of new nanomodifiers for road coating. Khimicheskaya Fizika. 2014;33(7):87-93 (in Russ.). https://doi.org/10.7868/s0207401x14070073

7. Schaur A., Unterberger S., Lackner R. Impact of molecular structure of SBS on thermomechanical properties of polymer modified bitumen. Eur. Polym. J. 2017;96:256-265. https://doi.org/10.1016/j.eurpolymj.2017.09.017

8. Loderer C., Partl M.N., Poulikakos L.D. Effect of crumb rubber production technology on performance of modified bitumen. Constr. Build. Mater. 2018;191:11591171. https://doi.org/10.1016/j.conbuildmat.2018.10.046

9. Biro S., Fazekas B. Asphalt rubber versus other modified bitumens. Road Mater. Pavement. 2012. Available from: http://www.ra-foundation.org/wp-content/uploads/2013/02/020-PAP_017.pdf

10. Greene J., Chun S., Nash T., Choubane B. Evaluation and Implementation of PG 76-22 Asphalt Rubber Binder in Florida. Transport. Res. Rec. 2015;2524(1);3-10. https://doi.org/10.3141/2524-01

11. Iliopolov S.K., Martirosova I.V., Shcheglov G.A., Chubenko E.N., Cherskov R.M., Haddad L.N. Rubber-polymer bitumen modifier. Patent RF No. 2266934. Bul. No. 36. 27.12.2005 (in Russ.).

12. Frolov I. N., Yusupova T. N., Ganeeva Yu. M., Barskaya E. E., Romanov G. V. Physical and chemical features of modification of commodity bitumen by mixed olefin thermoplastics. Neftegazovoe delo. 2008(2). Available from: http://ogbus.ru/authors/Frolov/Frolov_1.pdf (in Russ.).

13. Senise S., Carrera V., Navarro F.J., Partal P. Thermomechanical and microstructural evaluation of hybrid rubberised bitumen containing a thermoplastic polymer. Construct. Build. Mater. 2017;157:873-884. https://doi.org/10.1016/j.conbuildmat.2017.09.126

14. Gordeeva I.V., Nikolskii V.G., Naumova Yu.A. Hybrid modifier on the basis of crushed vulcanizate obtained by the method of high-temperature shear grinding. Collection of papers of the XX Anniversary Scientific-Practical Conference “Rubber Industry: Raw Stocks, Materials, Technologies” Moscow: NIISHP; 2015:217-220 (in Russ.).

15. Zvereva U.G. Rubber-bitumen composites on the basis of bitumen and active rubber powder (APDDR): preparation, structure, rheological properties, application. Diss. of Cand. of Chem. Sci.: 02.00.06. Moscow: 2016. 149 p. (in Russ.).

16. Berlin A.A., Dudareva T.V., Krasotkina I.A., Nikolskii V.G. Disposal of waste tire rubber and active powder of discretely devulcanized rubber. All materials. Encyclopedic reference book. 2018;2:27-35 (in Russ.).

17. Zhu C., Zhanga H., Xua G., Wub C. Investigation of the aging behaviors of multi-dimensional nanomaterials modified different bitumens by Fourier transform infrared spectroscopy. Construct. Build. Mater. 2018;167:536-542. https://doi.org/10.1016/j.conbuildmat.2018.02.056

18. Weigel S., Stephan D. The prediction of bitumen properties based on FTIR and multivariate analysis methods. Fuel. 2017;208(15):655-661. https://doi.org/10.1016/j.fuel.2017.07.048

19. Yao H., Dai Q., You Zh. Fourier Transform Infrared Spectroscopy characterization of aging-related properties of original and nano-modified asphalt binders. Construct. Build. Mater. 2015;101:1078-1087. https://doi.org/10.1016/j.conbuildmat.2015.10.085

20. Nivitha M.R., Prasad E., Krishnan J.M. Transitions in unmodified and modified bitumen using FTIR spectroscopy. Mater. Struct. 2019;52(7):1-11. https://doi.org/10.1617/s11527-018-1308-7

21. Makarov D.B., Agung E.M., Ayupov D.A., Murafa A.V., Faskhutdinov K.A., Khozin V.G., Yakhin R.G. Study of bitumen-polymer binders, modified by mixed thermoplastic elastomer by the method of IR-spectroscopy. Izvestiya KGASU = News of the KSUAE. 2015;4(34):280-286. (in Russ.).

22. Bellamy L.J. The Infra-red Spectra of Complex Molecules. Dordrecht: Springer; 1975. https://doi.org/10.1007/978-94-011-6017-9

23. Nakamoto K. Infrared Spectra of Inorganic and Coordination Compounds. New York: John Wiley & Sons, Inc.; 1963.

24. Tang N., Huang W., Xiao F. Chemical and rheological investigation of high-cured crumb rubber-modified asphalt. Construct. Build. Mater. 2016;123:847-854. https://doi.org/10.1016/j.conbuildmat.2016.07.131

25. Zhang F., Hu C. The research for structural characteristics and modification mechanism of crumb rubber compound modified asphalts. Construct. Build. Mater. 2015;76(1):330-342. https://doi.org/10.1016/j.conbuildmat.2014.12.013