Multi-scale study of rejuvenation mechanism and evaluation method for aged bitumen recycling

The increasing popularity of sustainable asphalt pavement stems from its advantageous attributes, such as cost-saving, environmental protection, and reductions in energy and material consumption. Although there is a desire to maximize the reuse of reclaimed asphalt (RA) waste materials in road construction, this is hindered by the poor performance of aged bitumen. In response, rejuvenation technology has been developed to restore the cohesive and adhesive properties of aged binders. To effectively select appropriate rejuvenators for aged bitumen derived from diverse RA sources and showing varying chemo-mechanical properties, it is crucial to establish an evaluation method that can assess and differentiate the rejuvenation efficiency of different rejuvenator-aged bitumen blends. Furthermore, it is essential to gain a fundamental understanding of the underlying mechanisms responsible for the variations.
This dissertation aims to develop a comprehensive and multi-scale approach for assessing the rejuvenation efficiency and mechanisms of various rejuvenator-aged bitumen blends. The combination of molecular dynamics (MD) simulations prediction and experimental validation is throughout the whole thesis to evaluate the compatibility potential and diffusive capacity of rejuvenators within aged bitumen, as well as their rejuvenation effectiveness in the chemo-thermodynamic-rheological performance. Additionally, the intermolecular interactions occurring between the rejuvenator and aged bitumen molecules are visualized and quantified by MD simulations.
The accurate construction of molecular models for aged bitumen is crucial for investigating the fundamental effects of aging on bitumen behavior at the molecular scale. To accomplish this, the long-term aging influence on the chemical characteristics of bitumen was assessed through Saturate, Aromatic, Resin, and Asphaltene (SARA) fractionation, Fourier Transform Infrared Spectroscopy (FTIR) test and element analysis method. The chemical information obtained served as a foundation for determining the molecular structures of bitumen models. Various thermodynamic parameters of both virgin and aged bitumen were predicted to fundamentally evaluate the aging effect on bitumen properties. Lastly, functional group and SARA-based long-term aging reaction kinetics models were proposed to anticipate the chemical characteristics of aged bitumen with different aging degrees, thereby establishing the corresponding molecular models without the need for additional experimental procedures.
Simultaneously, novel average and multi-component molecular models for various rejuvenators (bio-oil BO, engine-oil EO, naphthenic-oil NO, aromatic-oil AO) were established. The average models were based on the average chemical characteristics, such as functional group distribution, element component, and average molecular weight. On the other hand, multi-component models were derived from molecular component distribution in rejuvenators through Gas Chromatography-Mass spectrometry (GC-MS) analysis. Both models were validated by comparing MD outputs with experimental results. It was found that the average models provided more accurate predictions regarding the glass transition temperatures, especially for the aromatic-oil. Additionally, a range of thermodynamic parameters for the rejuvenators were predicted and compared. Finally, the average structures of rejuvenators were adopted to construct subsequent molecular models of rejuvenated binders.
The consideration of compatibility between the rejuvenator and aged bitumen is crucial due to the potential phase separation. In this thesis, different thermodynamic parameters, such as solubility parameter difference Δδ, Flory-Huggins parameter\chi, and mixing free energy ΔGm were predicted and calculated using MD simulations for various rejuvenated bitumen systems. The predicted compatibility ranking for four rejuvenators was AO > BO > NO > EO, aligned with the experimentally measured thermal stability results. Moreover, separation index (SI) parameters based on rheological and chemical indices were available to assess the thermal stability of rejuvenated bitumen.
Furthermore, a comprehensive investigation was implemented to explore the effects of rejuvenator type, temperature, and aging degree of bitumen on the diffusion behavior of rejuvenators in aged binders at multiple scales. The molecular dynamics (MD) simulation method was employed to detect the molecular-level diffusion characteristics of rejuvenators and predict their diffusion coefficient (D) parameters. At the atomic scale, it was observed that there was a mutual but partial interfacial diffusion feature between rejuvenators and aged bitumen molecules. Meanwhile, the concentration distribution of rejuvenator molecules in aged bitumen was well described by Fick's Second Law. The calculated D values for the four rejuvenators ranged from 10-11 to 10-10 m2/s, and the diffusive capacities followed the order of BO > EO > NO > AO. To verify the MD simulation outputs, diffusion tests and dynamic shear rheometer (DSR) characterizations were conducted. The experimental results regarding the magnitude and order of the D values were in good agreement with the MD simulation findings. Lastly, it was observed that an increased aging degree of bitumen had a negative impact on the molecular diffusivity of BO, EO, and NO rejuvenators, whereas the D value of AO molecules enlarged as the aging level deepened.
A series of measurements were conducted to estimate the combined effects of rejuvenator type/dosage and aging degree of bitumen on the rheological properties of rejuvenated bitumen. Importantly, several critical indicators were identified that effectively assess and differentiate the rejuvenation efficiency of different rejuvenators on aged bitumen performance. In terms of high-temperature performance, parameters rutting failure temperature (RFT) and zero-shear viscosity (ZSV) from the linear viscoelastic (LVE) and flow tests were found to be useful. Additionally, parameters R3.2, Jnr0.1 or Jnr3.2, and Jnrslope were recommended for estimating the elastic performance, creep potential, and stress sensitivity of rejuvenated bitumen. Among these, the RFT parameter played a crucial role in evaluating and distinguishing the rejuvenation effectiveness of various rejuvenators on the high-temperature performance of aged bitumen. For the low-temperature relaxation property, parameters τ50s, t25%, and A were proposed as critical indicators. Regarding fatigue life improvement, BO demonstrated the highest rejuvenation effectiveness, followed by EO, NO, and AO rejuvenators. The fatigue failure temperature (FFT) parameter was identified as an effective indicator for fatigue performance evaluation in LVE tests. In linear amplitude sweep (LAS) tests, the fatigue life (Nf5), peak strain (ɛsr), and elastic modulus (E) parameters were optimized as effective fatigue indicators. Nonetheless, crack width (C) results were consistent with conclusions drawn from LVE and LAS tests. Particularly, the crack width C500 parameter showed strong correlations with other critical fatigue indicators, and its prediction could be achieved using correlation equations without the need for time-consuming TS tests.
At the atomic-level evaluation, several key thermodynamic properties of variable rejuvenated bitumen models were outputted by molecular dynamics (MD) simulation. The rejuvenation effectiveness of different rejuvenators on the thermodynamic indices of aged bitumen was estimated and compared. Importantly, the potential connections between these essential nanoscale parameters and critical macroscale indicators in terms of high-and-low temperature performance and fatigue behaviors of rejuvenated binders were explored. It was revealed that the addition of rejuvenators inherently catalysed a restoration of density and cohesive energy density (CED) values toward those of virgin bitumen. A suite of indicators, including UVEP, UWEK, EN, UVET, UNED, and ECT, are introduced as critical energetic parameters, each reflecting rejuvenator efficacy on atomic-level energetic features, except for specific cases involving aromatic-oil rejuvenated binders. Meanwhile, it is recommended to predict the relaxation properties of different rejuvenated bitumen by the fractional free volume parameter from MD simulation. The surface free energy (γ) emerges as a dependable index for assessing the rejuvenation efficacy of the cohesive cracking potential of aged bitumen.
In summary, a multiscale evaluation framework of rejuvenated bitumen was proposed and developed in this dissertation, together with a full understanding of the difference in rejuvenation efficiency and mechanism between various rejuvenators on chemo-thermodynamic-rheological performance restoration of aged bitumen. The outcomes of this thesis would be beneficial to promoting the formation of classification standards of rejuvenator additives, development of advanced multifunctional rejuvenators, and improvement of all-round evaluation method on rejuvenated binder.