This study employs strain-controlled oscillatory deformations in Molecular Dynamics (MD) simulations to evaluate the dynamic properties of all-atom molecular systems, specifically targeting the SARA fractions of bitumen. Twelve molecular systems representing these fractions were modeled using the PCFF force field. The simulations effectively captured their viscoelastic properties across multiple frequency domains, including Elastic, Glassy, Rubbery, and Viscous responses. Reported storage and loss moduli range from thousands to tens of megapascals, with viscosities from tens to near-zero Pascal-seconds across various frequencies and temperatures, aligning well with experimental observations. Saturates and Aromatics were identified as the softest and most thermally susceptible fractions, while Resins and Asphaltenes were the stiffest and least susceptible. The study reveals that the relaxation time of all-atom molecular systems is significantly shorter than in experimental setups, necessitating careful comparison of stress-related phenomena across equivalent relaxation times. Although this allows for the exploration of response profiles in computationally tractable simulations, the nature of all-atom force fields and simulation algorithms introduces spatiotemporal scale discrepancies that must be addressed in future simulations involving the study of stress-related phenomena using MD.

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Developed by Delft University of Technology, the tri-component polyurethane modified cold binder (PMCB) displays impressive durability and strength in asphalt mixtures, showing promise as a reliable binder for cold in-place recycling. However, when applying PMCB for rapid, in-situ recycling, the presence of moisture in reclaimed asphalt pavement (RAP) poses a significant challenge. To address this, an innovative approach involving treatment of the wet RAP with Calcium dioxide (CaO) prior to the integration of PMCB was tested. Evaluation methods used included the Indirect Tensile Test (ITT), followed by the calculation of the Indirect Tensile Strength Ratio (ITSR) to assess moisture susceptibility. Furthermore, Cantabro tests were performed to determine the material loss under abrasion and weathering conditions. These assessments underscored the feasibility of this approach. The treatment of wet RAP with CaO has proven a viable strategy for rapid in-situ recycling with PMCB, contributing to sustainable pavement construction. In addition, the research identified that a 5.5% concentration of the PMCB binder maximizes structural integrity and performance in the considered RAP.

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In order to explore the feasibility and efficacy of reed-fiber-modified bitumen (RFMB), three lengths and three dosages of reed fibers were selected to modify bitumen and bituminous mortar, while the physicochemical properties of RFMB and RFMB mortar were analyzed. In this work, FTIR spectroscopy was employed to characterize the chemical impact of fiber on bitumen. The viscidity and rheology of RFMB and the tensile strength of RFMB mortar were evaluated using a Brookfield viscometer, dynamic shear rheometer, and monotonic tensile test. The results showed that adding fibers primarily affects the physical structure rather than the chemical composition of bitumen, confirmed by FTIR spectroscopy. RFMB viscosity increased with higher fiber dosage and fiber length. Rheological evaluations showed an enhanced complex shear modulus for RFMB, suggesting improved performance at higher temperatures but increased stiffness at lower temperatures, with the latter indicating reduced flexibility. RFMB also demonstrated superior fatigue and rutting resistance, albeit with compromised stress sensitivity. Tensile tests on RFMB mortar highlighted significant improvements, especially with longer fibers, while shorter 0.4 mm fibers showed modest reinforcement effects, possibly due to uneven distribution during sample preparation.@en

Elastomer/plastic compound-modified bitumen was created by adding reactive elastomeric terpolymer (RET) to plastic-modified bitumen, made of either high-density polyethylene (HDPE) or recycled polyethylene (RPE). The rheological properties of the modified bitumen were analyzed. The results indicated that RET elastomer improved high-temperature modulus, temperature insensitivity, anti-rutting properties, elastic recovery, and shear-resistance of both HDPE and RPE-modified bitumen. A high dosage of RET had a negative impact on the cracking resistance of plastic-modified bitumen, thus it is recommended to use 1wt% for optimal results. The increased elasticity in the bitumen was attributed to the creation of a polymer network by RET.

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An asphalt joint is formed when a fresh mix is laid and compacted next to an existing layer, brings about temperature difference during compaction, and therefore requires extra care in quality control and expose to higher cracking risks. Self-healing asphalt aims to stimulate the healing capacity of asphalt mixture and prolong its service life. The main objective of this study is to develop and optimize a calcium alginate capsules healing system for an asphalt joint mix. Capsules following two different self-healing concepts were prepared, namely conventional alginate capsules and conductive alginate capsules. Microscopy, Computed Tomography (CT) and Thermogravimetry analysis (TGA) were used to investigate the performance of alginate capsules. The results show that both types of capsules have a porous structure and a stable performance under high temperature, and therefore potentially survive from the asphalt mixing and production process. These capsules will be implemented and evaluated in full asphalt mix in future research.

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This study implements molecular dynamics (MD) simulations to explore the atomic-level energy properties of rejuvenated bitumen, considering the influence of different recycling agent (RA) types, dosages and aging levels of bitumen. Moreover, the potential correlations between energy indices and high-temperature performance of rejuvenated bitumen are explored. Our findings show that recycling agents can effectively reinstate the cohesive energy density (CED) values of aged bitumen, correlating well with their high-temperature rheological properties. The results reveal that the energy parameters of potential energy (UVEP), kinetic energy (UWEK), non-bond energy (EN), total energy (UVET), diagonal energy (UNED), and cross-terms energy (ECT) can reflect the restoration level of recycling agents (RAs) on atomic-level energy characteristics of aged bitumen. Compared to rutting failure temperature (RFT), elastic recovery (R3.2), and creep compliance (Jnr3.2), the zero-shear viscosity (ZSV) greatly correlates with CED. Meanwhile, the UWEK index from MD simulations demonstrates a strong correlation with high-temperature rheological indicators of rejuvenated bitumen. With the rise in UWEK, there is a linear decrease in the RFT, Log(ZSV), and R3.2 values of rejuvenated bitumen. Conversely, the Log(Jnr3.2) exhibits a linear increasing trend. However, the correlation patterns between rheological indicators and either EN or ECT are contingent on the aging degree of bitumen. Based on the correlation coefficient, the UWEK stands out as the primary choice among all energy indices for predicting high-temperature rheological performance of rejuvenated bitumen.@en

This paper presents a United Atom (UA) force field for simulating hydrocarbon molecules in bituminous materials, integrating explicit hydrogens into beads with their parent atom. This method simplifies all-atom molecular models, significantly accelerating Molecular Dynamics (MD) simulations of bitumen by 10 to 100 times. Key advantages include halving the particle count, eliminating complex hydrogen interactions, and decreasing the degrees of freedom of the molecules. Developed by mapping forces from an all-atom model to the centers of mass of UA model beads, the force field ensures accurate replication of energies, forces, and molecular conformations, mirroring properties like pressure and density. It features 17 bead types and 287 interaction types, encompassing various hydrocarbon molecules. The UA force field's stability, surpassing all-atom models, is a notable achievement. This stability, stemming from smoother potential energy surfaces, leads to consistent property measurements and improved stress tensor accuracy. It enables the extension of MD simulations to larger spatiotemporal scales, crucial for understanding complex phenomena such as phase separation in bituminous materials. This foundational work sets the stage for future developments, including refining parameters and introducing new bead types, to enhance the modeling capabilities of the force field, thereby advancing the application and understanding of bituminous materials.

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This study explores the use of chemical descriptors derived from force field atom types to predict Fickian diffusion coefficients of rejuvenators in bitumen, utilizing machine learning models trained on data from 240 non-equilibrium molecular dynamics simulations. The simulations cover three bitumen types (NO, TO, FO), five aging degrees, and four temperatures (60 °C, 120 °C, 160 °C, 200 °C), capturing diffusion coefficients ranging from 0.0068e-10 m2/s in highly aged bitumens at 60 °C to 4.35e-10 m2/s in fresher samples at 200 °C. The MLM, built with 18 chemical descriptors for bitumen and rejuvenator sides, achieves an R2 of 0.97, accurately predicting diffusion across varied conditions. This approach abstracts away from the need for repeated MD simulations, enabling diffusion predictions even for systems outside the original dataset. The manuscript presents three case studies to illustrate how the model can be used for the iterative design of rejuvenators by optimizing molecular structures based on critical chemical features, such as rejuvenator oxygen content, bitumen sulfur content, and molecular weights. It also demonstrates how the model offers a practical framework for understanding the diffusion and performance of rejuvenators by linking time-dependent factors—such as concentration, depth, and rejuvenation time—with the bulk properties of bitumen-rejuvenator systems, facilitating industrial applications.@en

Atomistic simulations are crucial for understanding material properties at the molecular level but are limited by high computational costs, especially for large, complex systems like bituminous materials. Our team developed a Force-matched United Atom (UA) Coarse Graining (CG) force field to enhance computational efficiency while retaining atomic detail. However, converting all-atom models to CG models is complex, requiring detailed atom-to-bead mapping and compatibility with molecular dynamics (MD) engines like LAMMPS. To address this, we introduce AA2UA, an open-source software that simplifies the conversion of PDB files into LAMMPS-readable structure topology files, facilitating broader use of the developed UA force field.@en

The low-temperature relaxation and fatigue cracking performance are two essential aspects in estimating the rejuvenation efficiency of recycling agents (RAs). This study aims to fundamentally investigate the effects of recycling agent type/dosage and aging degree of bitumen on thermodynamic and rheological properties of rejuvenated bitumen at low and intermediate temperatures. Molecular dynamics (MD) simulations are utilized to predict thermodynamic indices of rejuvenated bitumen, further linked to critical low-temperature and fatigue indicators from experiments. The results reveal that all RAs show a regeneration effect on fractional free volume (FFV), self-diffusion coefficient (DS), glass transition temperature (Tg), and surface free energy (γ). Bio-oil and engine-oil exhibit higher rejuvenation efficiency on these thermodynamic properties than naphthenic-oil and aromatic-oil. The aging degree of bitumen and temperature show significant effects on rejuvenation efficiency. It is recommended to use the FFV parameter to predict the relaxation properties of rejuvenated bitumen. However, these thermodynamic indicators inadequately differentiate between rejuvenators and softeners. Based on crossover parameter results, most recycling agents (bio-oil, engine oil, and naphthenic oil) in this study display softening characteristics. Only aromatic oil effectively rejuvenates the crossover modulus (Gc) of aged binder. Notably, engine oil demonstrates the least rejuvenation in crossover parameters for the recovery of aged bitumen. Further, γ demonstrates a strong association with both Glover-Rowe (G-R) and fatigue crack width C500 indices across all cases involving rejuvenated bitumen. This work will build a multi-scale evaluation framework on the rejuvenation effectiveness of recycling agents on low-temperature and fatigue performance of aged bitumen.@en

This study enhances the molecular analysis of bitumen by transitioning from traditional chemical descriptors, such as SARA (Saturates, Aromatics, Resins, and Asphaltenes) fractions and elemental compositions, to specific force field atom types in Molecular Dynamics (MD) models. This shift improves the precision in predicting material properties critical for bituminous material characterization. Machine Learning Models (MLMs) were developed to use these atom types as input features, inherently reflecting fundamental chemical characteristics. Trained on data from over 1,770 LAMMPS simulations of diverse bitumen types and conditions, these MLMs enable the prediction of properties like density, heat capacity, solubility parameters, and thermal expansion coefficients without the need for additional MD simulations. The models utilize 30 chemical descriptors corresponding to specific atom types in the PCFF force field, which collectively account for over 95% of the influence on these properties. By accurately predicting fundamental, thermodynamic, and kinetic properties, the use of MLMs and force field atom types allows researchers to efficiently tweak the chemical nature of organic molecules and mixtures to achieve desired properties. With near-instantaneous prediction times, these MLMs offer valuable insights for advancing bitumen research in the construction and petroleum industries, reducing the need for more intensive simulation techniques.@en

Bitumen fatigue resistance is critical to determine the overall fatigue performance and service life of asphalt pavements. However, the mechanisms responsible for fatigue damage of bitumen have previously not been well understood. Molecular dynamics (MD) simulation has recently emerged as a powerful computer-aided numerical technique to model the microscopic failure behaviours in materials. This study aims to use the MD method to investigate the molecular origin of bitumen fatigue damage. The molecular models of the virgin and aged PEN70/100 bitumen were firstly constructed based on their saturate, aromatic, resin and asphaltene (SARA) four fractions. An MD equilibrium was run on the developed bitumen models with the assigned interatomic potentials. Following an MD-based tensile simulation, a strain-controlled fatigue simulation was performed to study the nanostructure and damage behaviours of the virgin and aged bitumen under fatigue loading by calculating the stress-strain response, potential energy, molecular structure and nanovoid volumes. Furthermore, a rheometer measurement was also conducted to characterise the fatigue damage of the bitumen directly by a crack length at the macroscale. Results indicate that the bitumen molecules become unfolded and tend to align along the loading direction when fatigue loading was applied. The change in the molecular configuration helped the molecular chains move closer together and thus contributed to the reduction of the intermolecular interactions including the van der Waals and Coulombic energies. With the increasing load cycles, nanovoids were formed and grew in the bitumen through molecular rearrangement and movement, leading to microscopic fatigue damage of the bitumen. It was found that the aged bitumen produced more severe fatigue damage than the virgin bitumen, which was indicated by the MD-based nanovoid volume at the molecular scale and the DSR-based crack length at the macroscale. The findings from MD simulation provide a fundamental understanding of the molecular origin of fatigue damage, that cannot be experimentally detected for bitumen materials.@en

The advent of computational techniques, particularly atomistic simulations, has lessened the dependency on physical experiments in various scientific fields. Yet, the preparation complexity for simulations using platforms like LAMMPS and GROMACS persists. We introduce SMI2PDB, a Python tool that automates molecular systems assembly from SMILES to PDB format, easing molecular dynamics simulation setups. SMI2PDB manages molecule configuration and quantification effortlessly, establishes stable conformers, applies random rotations, and positions them in a simulation box with a Sobol sequence to reduce overlaps. This script facilitates the rapid preparation of complex organic mixtures for use in simulations, enhancing the exploration of novel materials.@en

Pdb2dat, developed in Python, is an open-source, self-contained utility that facilitates the conversion of PDB files into LAMMPS data files, catering to the need of initializing atomistic simulation from initial atomic configurations. It extracts molecular details from PDB files, uses Rdkit and Xyz2mol for bonding analysis and 3D conformer generation, and uses Pysimm for assigning force field types and charges. Designed to be lightweight and fully Pythonic, pdb2dat is suitable for use in privilege-limited high-throughput environments. The output details system topologies for use in MD simulations, significantly simplifying the preparatory steps needed by researchers to explore materials phenomena through LAMMPS.@en

Two types of elastomer/plastic compound-modified bitumen were developed by means of incorporating the reactive elastomeric terpolymer (RET) into the plastic (high-density polyethylene HDPE or recycled polyethylene RPE) modified bitumen and adding the wax residue (WR) into the bitumen/elastomer (crumb rubber CR or styrene–butadiene–styrene SBS) blends. The rheological properties, morphology microstructure and storage stability of these novel elastomer/plastic compound-modified binders were characterised. The results revealed that RET elastomer positively improved the high-temperature modulus, temperature insensitivity, rut resistant, elastic recovery and shear-resistance of HDPE- and RPE-modified bitumen. However, excessive RET dosage adversely influenced the cracking resistance of plastic-modified bitumen, and its optimum dosage was recommended as 1 wt%. Moreover, RET elastomer significantly strengthened the storage stability of HDPE and RPE-modified binders. The elasticity improvement effect of RET was attributed to the generated polymer network. On the other hand, adding WR limitedly deteriorated the rutting resistance and weakened the elastic recovery performance of elastomer (CR and SBS) modified bitumen. To ensure the low-temperature performance, the optimum level of WR was 2 wt%. Furthermore, the addition of WR promoted the compatibility and dispersion of CR and SBS modifiers in bitumen.@en

This study aims to systematically investigate the influence of rejuvenator type/dosage and the aging degree of bitumen on the rutting resistance, flow behavior, and elastic/creep potential of rejuvenated bitumen at high temperatures. The rutting parameter (G*/sinδ), rutting failure temperature (RFT) from Linear viscoelastic test (LVE), zero-shear viscosity (ZSV) from flow test,
recovery percentage (R0.1, R3.2), creep compliance (Jnr0.1, Jnr3.2), and stress sensitivity parameters (Rdiff, Jnrslope) from multiple stress creep and recovery (MSCR) tests of rejuvenated bitumen are characterized. The results reveal that bio-oil rejuvenator weakens the high-temperature performance of aged bitumen maximally, followed by engine-oil and naphthenic-oil, while aromatic-oil
rejuvenated bitumen exhibits the best rutting, flow, and creep resistance. The RFT index can most effectively evaluate and differentiate the rejuvenation efficiency of various rejuvenators on the high-temperature performance, which correlates well with ZSV, R3.2, Jnr0.1, Jnr3.2, Rdiff, and Jnrslope indices. Therefore, the RFT index is recommended as the critical indicator for evaluating.
the high-temperature performance of rejuvenated binders. The flow and MSCR characteristics of rejuvenated bitumen can be predicted based on RFT values. The determination of critical indicators is beneficial to compare the rejuvenation effectiveness of variable rejuvenators on the high-temperature performance of aged bitumen. @en

Polycyclic Aromatic Hydrocarbons (PAHs) in asphalt materials is a type of serious environmental hazard, and the main pollution resource in road engineering. Aiming at the requirement of PAHs rapid detection method in asphalt pavement construction for low environmental hazard, this research concentrated in experiments about PAHs content, fluorescence characteristics, solvent environment impact mechanism and correlation between fluorescence intensity and concentration in different asphalt materials, based on the fluorescence effect of PAHs from condensed ring structure. It is found that coal tar asphalt has a typical aggregation-caused quenching phenomenon and higher fluorescence quantum efficiency. Taking the three solvent environment parameters polarity, viscosity and pH value as the research objects, the optimal solvent environment for the fluorescence phenomenon of PAHs in asphalt materials was explored and established as dimethyl sulfoxide: tetrahydrofuran: deionized water: glycerol = 1 : 1 : 1 : 2. Under the optimal solvent environment, fluorescence intensity and concentration of the three asphalt materials all showed obvious linear relationship. Under the same concentration condition, fluorescence intensity of asphalt material showed positive correlation with the PAHs content. This study proves that the asphalt material has the linear relationship between fluorescence intensity and PAHs concentration, which will provide theoretical basis for the detection of PAHs content in asphalt materials, and support the development of low environmental hazard in construction technology for road engineering.

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Epoxy asphalt attracted the attention of road authorities in many countries as a solution for du-rable open-graded porous asphalt (OGPA) surface layers with enhanced longevity. Nevertheless, the recycla-bility of aged epoxy asphalt materials has not been thoroughly studied yet. This research presents an experi-mental program conducted in the laboratory to assess the potential recyclability of epoxy-modified open-graded porous asphalt (EMOGPA) mixes. Results indicate that the aging increased the tensile strength of studied mixes, with the strength and strength development rate of aging EMOGPA mixes to be almost identi-cal to standard OGPA mixes. The EMOGPA mixes have shown higher resistance against water damage than the OGPA mixes supporting the claim that the stone-mastic adhesion is improved with the use of epoxy bind-er. It was also proven that the aged material containing the epoxy binder could be re-melted to produce new pavement materials. The new EMOGPA mixes with the recycled epoxy material exhibited similar durability characteristics with the recycled standard OGPA mixes.@en

This study aims to multiscale investigate the effects of rejuvenator type, temperature, and aging degree of bitumen on the diffusion behaviors of rejuvenators (bio-oil BO, engine-oil EO, naphthenic-oil NO, and aromatic-oil AO) in aged binders. The molecular dynamics (MD) simulation method is performed to detect the molecular-level diffusion characteristics of rejuvenators and predict their diffusion coefficient (D) parameters. At an atomic scale, the mutual but partial interfacial diffusion feature between rejuvenators and aged bitumen molecules is observed. Moreover, Fick’s Second Law well fits the concentration distribution of rejuvenator molecules in aged bitumen. The magnitude for D values of four rejuvenators varies from 10-11 to 10-10 m2/s, and the diffusive capacity order is BO > EO > NO > AO. Meanwhile, diffusion tests and dynamic shear rheometer (DSR) characterizations are employed to validate the MD simulation outputs. The experimental results in magnitude and order of D values agree well with MD simulation outputs. Lastly, the increased aging degree of bitumen exhibits a negative impact on the molecular diffusivity of BO, EO, and NO rejuvenators, while the D value of AO molecules enlarges as the aging level deepens. The underlying mechanism may be composed of the free volume fraction in aged bitumen and the intermolecular force between rejuvenator and aged bitumen molecules, which differs remarkably for various rejuvenators.@en