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Frontiers of Structural and Civil Engineering

Front. Struct. Civ. Eng.    2020, Vol. 14 Issue (2) : 435-445
Evaluation of the compatibility between rubber and asphalt based on molecular dynamics simulation
Fucheng GUO1, Jiupeng ZHANG1(), Jianzhong PEI1, Weisi MA1, Zhuang HU1, Yongsheng GUAN2
1. Key Laboratory for Special Area Highway Engineering of Ministry of Education, Chang’an University, Xi’an 710064, China
2. Jiangsu Sinoroad Engineering Research Institute Co., Ltd., Nanjing 211806, China
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Using of rubber asphalt can both promote the recycling of waste tires and improve the performance of asphalt pavement. However, the segregation of rubber asphalt caused by the poor storage stability always appears during its application. Storage stability of asphalt and rubber is related to the compatibility and also influenced by rubber content. In this study, molecular models of different rubbers and chemical fractions of asphalt were built to perform the molecular dynamics simulation. The solubility parameter and binding energy between rubber and asphalt were obtained to evaluate the compatibility between rubber and asphalt as well as the influence of rubber content on compatibility. Results show that all three kinds of rubber are commendably compatible with asphalt, where the compatibility between asphalt and cis-polybutadiene rubber (BR) is the best, followed by styrene-butadiene rubber (SBR), and natural rubber (NR) is the worst. The optimum rubber contents for BR asphalt, SBR asphalt, and NR asphalt were determined as 15%, 15%, and 20%, respectively. In addition, the upper limits of rubber contents were found as between 25% and 30%, between 20% and 25%, and between 25% and 30%, respectively.

Keywords rubber asphalt      compatibility      rubber content      molecular dynamics simulation     
Corresponding Author(s): Jiupeng ZHANG   
Just Accepted Date: 19 January 2020   Online First Date: 31 March 2020    Issue Date: 08 May 2020
 Cite this article:   
Fucheng GUO,Jiupeng ZHANG,Jianzhong PEI, et al. Evaluation of the compatibility between rubber and asphalt based on molecular dynamics simulation[J]. Front. Struct. Civ. Eng., 2020, 14(2): 435-445.
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Fucheng GUO
Jiupeng ZHANG
Jianzhong PEI
Weisi MA
Zhuang HU
Yongsheng GUAN
Fig.1  Three-component molecular structure of asphalt. (a) Asphaltene molecule; (b) naphthene aromatic molecule; (c) Saturate molecule.
component of asphalt molecular number mass fraction (%)
asphaltene 5 20.7
naphthene aromatic 27 19.7
saturate 41 59.6
Tab.1  Molecular number and mass fraction of each component of asphalt
Fig.2  Molecular structure of asphalt binder (puce: asphaltene, light brown: naphthene aromatic, yellow: saturate).
Fig.3  Repeating units of (a) NR and (b) BR.
Fig.4  Structures of (a) NR and (b) BR molecular chains.
temperature of polymerization structure (%)
trans-1,4-butadien cis-1,4-butadiene 1,2-butadiene others
5°C 76 7 16 1
Tab.2  Content of butadiene with different structure for emulsion polymerized SBR
Fig.5  Structure of repeating units of SBR monomer. (a) Repeating units of styrene; (b) repeating units of cis-1,4-butadiene; (c) repeating units of trans-1,4-butadien; (d) repeating units of 1,2-butadiene.
Fig.6  Structure of SBR molecular chain.
Fig.7  Molecular structures of asphalt and rubber for solubility parameter analysis. (a) Molecular structure of asphalt; (b) molecular structure of NB; (c) molecular structure of BR; (d) molecular structure of SBR.
parameters asphalt NR BR SBR
d ((J·cm3)1/2) 15.394 14.835 15.491 14.963
|Dd| 0 0.559 0.097 0.431
Tab.3  Solubility parameters between rubber and asphalt as well as their differences (453K)
parameters asphalt NR BR SBR
d ((J·cm3)1/2) 18.236 16.574 18.024 17.210
|Dd| 0 1.66 0.212 1.026
Tab.4  Solubility parameters between rubber and asphalt as well as their differences (298K)
Fig.8  Rubber and rubber asphalt structures for binding energy analysis (puce: asphaltene, light brown: naphthene aromatic, yellow: saturate, gray: rubber). (a) NR molecular structure; (b) NR asphalt molecular structure; (c) BR molecular structure; (d) BR asphalt molecular structure; (e) SBR molecular structure; (f) SBR asphalt molecular structure.
content of NR (%) energy (kcal/mol)
energy of NR asphalt energy of asphalt energy of NR binding energy of NR asphalt
5 15765.144 15436.174 360.269 31.299
10 16061.878 710.96 85.256
15 16320.939 1031.728 146.963
20 16766.87 1533.101 202.405
25 17151.773 1776.144 60.545
30 17549.522 2076.794 -36.554
Tab.5  Binding energy of NR asphalt
content of BR (%) energy (kcal/mol)
energy of BR asphalt energy of asphalt energy of BR binding energy of BR asphalt
5 15796.302 15436.174 402.136 42.008
10 16121.357 801.222 116.039
15 16418.489 1171.078 188.763
20 16987.73 1597.566 46.01
25 17457.859 1955.259 18.997
30 17894.937 2348.979 -41.995
Tab.6  Binding energy of BR asphalt
content of SBR (%) energy (kcal/mol)
energy of SBR asphalt energy of asphalt energy of SBR binding energy of SBR asphalt
5 15816.019 15436.174 415.921 36.076
10 16148.476 808.674 96.372
15 16496.918 1228.696 167.952
20 17060.339 1636.67 12.505
25 17496.404 2048.445 -11.785
30 17879.589 2376.724 -66.691
Tab.7  Binding energy of SBR asphalt
Fig.9  Variation of binding energy between rubber and asphalt for three kinds of rubber asphalt with rubber content.
1 Y Huang, R N Bird, O Heidrich. A review of the use of recycled solid waste materials in asphalt pavements. Resources, Conservation and Recycling, 2007, 52(1): 58–73
2 D Lo Presti. Recycled tyre rubber modified bitumens for road asphalt mixtures: A literature review. Construction & Building Materials, 2013, 49: 863–881
3 X Shu, B S Huang. Recycling of waste tire rubber in asphalt and Portland cement concrete: An overview. Construction & Building Materials, 2014, 67: 217–224
4 X Ding, T Ma, W Zhang, D Zhang. Experimental study of stable crumb rubber asphalt and asphalt mixture. Construction & Building Materials, 2017, 157: 975–981
5 T Ma, H Wang, L He, Y Zhao, X Huang, J Chen. Property characterization of asphalt binders and mixtures modified by different crumb rubbers. Journal of Materials in Civil Engineering, 2017, 29(7): 04017036
6 D C Esch. Construction and Benefits of Rubber-modified Asphalt Pavements.Report to Transportation Research Board. 1982
7 G B Way. OGFC meets CRM where the rubber meets the rubber 12 years of durable success. Asphalt Rubber, 2000, 2000: 15–31
8 B Huang, L Mohammad, P Graves, C Abadie. Louisiana experience with crumb rubber-modified hot-mix asphalt pavement. Transportation Research Record: Journal of the Transportation Research Board, 2002, 1789(1): 1–13
9 M Heitzman. Design and construction of asphalt paving materials with crumb rubber modifier. Transportation Research Record: Journal of the Transportation Research Board, 1992: 1–8
10 M Liang, X Xin, W Fan, H Sun, Y Yao, B Xing. Viscous properties, storage stability and their relationships with microstructure of tire scrap rubber modified asphalt. Construction & Building Materials, 2015, 74: 124–131
11 B Brûlé . Polymer-modified asphalt cements used in the road construction industry: Basic principles. Transportation Research Record: Journal of the Transportation Research Board, 1996, 1535(1): 48–53
12 M Y Liao, X Li. The stability of crumb rubber modified asphalt and the factors of the effect on stability. Journal of Petrochemical Universities, 2004, 17(4): 38–41
13 J Li, Y Zhu, H Wang, S Wang, Y Zhang, Y Zhang. High temperature storage stability of asphalt modified with crumb rubber. China Synthetic Rubber Industry, 2009, 32(4): 259–263
14 J Pei, Z Fan, P Wang, J Zhang, B Xue, R Li. Micromechanics prediction of effective modulus for asphalt mastic considering inter-particle interaction. Construction & Building Materials, 2015, 101: 209–216
15 A Ghavibazoo, M Abdelrahman, M Ragab. Effect of CRM dissolution on storage stability of CRM modified asphalt. In: The 92nd TRB Annual Meeting. Washington, D.C.: Transportation Research Record, 2013
16 L F M Leite, B G Soares. Interaction of asphalt with ground tire rubber. Petroleum Science and Technology, 1999, 17(9–10): 1071–1088
17 I Gawel, R Stepkowski, F Czechowski. Molecular interactions between rubber and asphalt. Industrial & Engineering Chemistry Research, 2006, 45(9): 3044–3049
18 B Arash, H S Park, T Rabczuk. Coarse-grained model of the j-integral of carbon nanotube reinforced polymer composites. Carbon, 2016, 96(5): 1084–1092
19 A A Mousavi, B Arash, X Zhuang, T Rabczuk. A coarse-grained model for the elastic properties of cross linked short carbon nanotube/polymer composites. Composites. Part B, Engineering, 2016, 95: 404–411
20 T Takanohashi, M Iino, K Nakamura. Evaluation of association of solvent-soluble molecules of bituminous coal by computer simulation. Energy & Fuels, 1994, 8(2): 395–398
21 L Zhang, M L Greenfield. Effects of polymer modification on properties and microstructure of model asphalt systems. Energy & Fuels, 2008, 22(5): 3363–3375
22 H Yao, Q Dai, Z You. Molecular dynamics simulation of physicochemical properties of the asphalt model. Fuel, 2016, 164: 83–93
23 R Li, H Du, J Pei, Q. Guo Mechanical property and analysis of asphalt components based on molecular dynamics simulation. Journal of Chemistry, 2017, 2017: 1531632
24 Z Chen, J Pei, R Li, F Xiao. Performance characteristics of asphalt materials based on molecular dynamics simulation—A review. Construction & Building Materials, 2018, 189: 695–710
25 Y Hou, L Wang, D Wang, X Qu, J Wu. Using a molecular dynamics simulation to investigate asphalt nano-cracking under external loading conditions. Applied Sciences (Basel, Switzerland), 2017, 7(8): 770
26 X Yao, B Liu, X Wang. Molecular dynamics simulation on compatibility of hydroxyl-terminated polybutadiene-organic solvents. Science Technology and Engineering, 2014, 14(29): 110–113 (in Chinese)
27 W Xu, W Hao, D Ma, L Liang. Dynamic mechanical property of styrene-butadiene rubber/natural rubber composite. Chinese Journal of Applied Chemistry, 2001, 18(1): 44–47
28 Q Liu, H Yue, H Jiang, C Chen. Molecular dynamics and dissipative particle dynamics simulation of TPI/NR blends. Materials Review, 2012, 26(6): 141–145
29 T Kuznicki, J H Masliyah, S Bhattacharjee. Aggregation and partitioning of model asphaltenes at toluene-water interfaces: Molecular dynamics simulations. Energy & Fuels, 2009, 23(10): 5027–5035
30 R Li, H Du, Z Fan, J Pei. Molecular dynamics simulation to investigate the interaction of asphaltene and oxide in aggregate. Advances in Materials Science and Engineering, 2016, 2016: 1–10
31 J Zhang, X Li, G Liu, J Pei. Effects of material characteristics on asphalt and filler interaction ability. International Journal of Pavement Engineering, 2017, 20(8): 928–937
32 J Zhang, Z Fan, D Hu, Z Hu, J Pei, W Kong. Evaluation of asphalt-aggregate interaction based on the rheological properties. International Journal of Pavement Engineering, 2018, 19(7): 586–592
33 Y Ding, B Tang, Y Zhang, J Wei. Molecular dynamics simulation to investigate the influence of SBS on molecular agglomeration behavior of asphalt. Journal of Materials in Civil Engineering, 2013, 27(8): C4014004
34 F Khabaz, R Khare. Glass transition and molecular mobility in styrene-butadiene rubber modified asphalt. Journal of Physical Chemistry B, 2015, 119(44): 14261–14269
35 K Liu, L Deng, J Zheng, K Jiang. Compatibility evaluation of waste tire rubber powder modified asphalt binder. New Building Materials, 2017, 44(5): 13–16
36 S Maccarrone, G Holleran, G. Gnanaseelan Properties of polymer modified binders and relationship to mix and pavement performance. In: Asphalt Paving Technology: Association of Asphalt Paving Technologists-Proceedings of the Technical Sessions. Portland: Association of Asphalt Paving Technologists (AAPT), 1995
37 H Fu, L Xie, D Dou, L Li, M Yu, S Yao. Storage stability and compatibility of asphalt binder modified by SBS graft copolymer. Construction & Building Materials, 2007, 21(7): 1528–1533
38 B Zhang, M Xi, D Zhang, H Zhang, B Zhang. The effect of styrene-butadiene-rubber/montmorillonite modification on the characteristics and properties of asphalt. Construction & Building Materials, 2009, 23(10): 3112–3117
39 L Xiang, J Cheng, G Que. Microstructure and performance of crumb rubber modified asphalt. Construction & Building Materials, 2009, 23(12): 3586–3590
40 H Liu, Z Chen, W Wang, H Wang, P Hao. Investigation of the rheological modification mechanism of crumb rubber modified asphalt (CRMA) containing TOR additive. Construction & Building Materials, 2014, 67: 225–233
41 I A Wiehe, K S Liang. Asphaltenes, resins, and other petroleum macromolecules. Fluid Phase Equilibria, 1996, 117(1–2): 201–210
42 J Zhang, H Tan, J Pei, T Qu, W Liu. Evaluating crack resistance of asphalt mixture based on essential fracture energy and fracture toughness. International Journal of Geomechanics, 2018, 19(4): 1–8
43 J Murgich, Y Rodríguez, Aray. Molecular recognition and molecular mechanics of micelles of some model asphaltenes and resins. Energy & Fuels, 1996, 10(1): 68–76
44 H Shi, T Xu, R Jiang. Combustion mechanism of four components separated from asphalt binder. Fuel, 2017, 192: 18–26
45 H Shi, T Xu, P Zhou, R Jiang. Combustion properties of saturates, aromatics, resins, and asphaltenes in asphalt binder. Construction & Building Materials, 2017, 136: 515–523
46 L Artok, Y Su, Y Hirose, M Hosokawa, S Murata, M Nomura. Structure and reactivity of petroleum-derived asphaltene. Energy & Fuels, 1999, 13(2): 287–296
47 D A Storm, J C Edwards, S J Decanio, E Y Sheu. Molecular representations of Ratawi and Alaska north slope asphaltenes based on liquid-and solid-state NMR. Energy & Fuels, 1994, 8(3): 561–566
48 L Zhang, M L Greenfield. Analyzing properties of model asphalts using molecular simulation. Energy & Fuels, 2007, 21(3): 1712–1716
49 Y Ding, B Huang, X Shu, Y Zhang, M E Woods. Use of molecular dynamics to investigate diffusion between virgin and aged asphalt binders. Fuel, 2016, 174: 267–273
50 D A Storm, S J Decanio, M M Detar, V P Nero. Upper bound on number average molecular weight of asphaltenes. Fuel, 1990, 69(6): 735–738
51 D Sun, T Lin, X Zhu, Y Tian, F Liu. Indices for self-healing performance assessments based on molecular dynamics simulation of asphalt binders. Computational Materials Science, 2016, 114: 86–93
52 Y Zhang, M Sun. Rubber variety and performance manual. Beijing: Chemical Industry Press, 2012
53 T Wang, X Huang, Y Zhang. Application of Hansen solubility parameters to predict compatibility of SBS-modified bitumen. Journal of Materials in Civil Engineering, 2010, 22(8): 773–778
54 Y Fu, Y Liu, Y Lan . Molecular dynamics simulation insight into two-component solubility parameters of graphene and thermodynamic compatibility of graphene and styrene butadiene rubber. Acta Physico-Chimica Sinica, 2009, 25(7): 1267–1272 (in Chinese)
55 J H Hildebrand, R L Scott. The Solubility of Non-Electrolytes. New York: Reinhold, 1950
56 J A Mason, L H Sperling. Polymer Blends and Composites. New York: New York Plenum Press, 1976
57 H Abou-Rachid, L S Lussier, S Ringuette, X Lafleur-Lambert, M Jaidann, J Brisson. On the correlation between miscibility and solubility properties of energetic plasticizers/polymer blends: Modeling and simulation studies. Propellants Explosives Pyrotechnics, 2008, 33(4): 301–310
58 F Chen, J Wang, L Chen, M Duan, Z Wei, B Ren. Molecular dynamics simulation of mechanical properties and binding energies of ε-CL-20 /F2311 PBXs. Journal of Atomic and Molecular Physics, 2015, 3: 360–365
59 Q Sha, H Yue, J Zhao, Z Wei, H. JiangMolecular dynamics simulation on glass transition temperature of NR/CIIR/TPI polymer blend. China Adhesives, 2013, 9: 14–18
60 H Jiang, H Yue, Q Liu. Molecular dynamics simulation of mechanical properties and surface interaction for NR/BR blends. China Plastics, 2012, 26(5): 64–68
61 H Sun. COMPASS: An ab initio force-field optimized for condensed-phase applications overview with details on alkane and benzene compounds. Journal of Physical Chemistry B, 1998, 102(38): 7338–7364
62 P Wang, Z Dong, Y Tan, Z Liu. Investigating the interactions of the saturate, aromatic, resin, and asphaltene four fractions in asphalt binders by molecular simulations. Energy & Fuels, 2015, 29(1): 112–121
63 P C. Painter Characterization of Asphalt and Asphalt Recyclability. Washington, D.C.: National Research Council, 1993
64 W Kang, H Yue, Q Sha, J Zhao. Molecular dynamics simulation of compatibility and mechanical properties for NR/CIIR/TPI blends. Adhesion, 2014, 4: 68–72
65 W Liu, J Zhang. Experimental study on storage stability of crumb rubber modified asphalt. Petroleum Asphalt, 2014, 28(1): 31–35
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