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Understanding the fundamental mechanisms of oxidative ageing in bitumen is considered of paramount importance in order to take steps towards durable binders able to tackle distresses related to this phenomenon which deteriorates the asphalt performance. This paper focuses on the identification of the intermediate and final oxygenated products after short- and long-term laboratory ageing simulated with rolling thin-film oven testing (RTFOT) and pressurised ageing vessel (PAV) respectively. Three binders were investigated in this study, two originated from the same wax-free crude source, while the third was obtained from a different source, containing natural wax, and followed a different manufacturing process. Fourier-Transform Infrared (FTIR) spectroscopy demonstrated a clear increase of the sulfoxide and carbonyl functional groups upon ageing for all the binders independently of origin, manufacturing or performance. Electron Paramagnetic Resonance (EPR) spectroscopy showed an increase of the organic carbon-centred radicals after short-term ageing (RTFOT), whereas after PAV these radicals remained constant in the two wax-free binders originating from the same crude source, and even decreased for the third, waxy binder. Proton Nuclear Magnetic Resonance (1H NMR) spectroscopy reported differences in the relative distribution of protons between the binders in the unaged state, and similar minor changes after both ageing steps regardless of the binder's crude source and distillation. The results of Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) revealed that SOx- and (OH)x-containing compounds are produced after the sequentially occurring short- and long-term ageing in both wax-free bitumens, whereas an almost constant behaviour of aliphatics after PAV ageing can be seen for the same bitumens. Finally, the strengths and weaknesses of each of these experimental techniques were reviewed and compared versus the obtained results and possible ageing mechanisms.

Bitumen, the heavy residue of crude oil, can display a rich microscale morphology, including so-called Bee structures. The use of Atomic Force Microscopy (AFM) measurements in literature strongly indicates that the appearance of Bee structures is related to the presence of paraffin wax crystals. Most studies have investigated standard bitumen surfaces when cooling bitumen in an air atmosphere. Only a few investigations have analysed surfaces formed in other media or have analysed fractured surfaces which relate to the bulk morphology. Although considerable research has focussed on identifying Bee structures, less attention has been paid to the Bee structure morphology of different bitumen types and the relations to other binder parameters. The comparison between the micro morphology of the air-oil interface compared to the bulk phase volume has been studied even less. In this experimental study, five bitumen samples were selected based on differences in their natural wax content. Both the air-cooled surface interface and fractured surfaces were characterised using AFM in tapping mode. All the air-cooled surfaces revealed Bee structures, except the wax-free bitumen, which did not display the presence of any Bee structure. None of the fracture surfaces revealed Bee structures. Reheating a fractured surface of a wax-containing bitumen transformed the morphology into Bee structures. The experiments demonstrate that Bee structures are present in different binders but display very different shapes and sizes. Flowever: image analysis indicates that the unit cell inside these structures is rather constant and independent of the binder type. This work confirms a relationship between natural wax and Bee structures and it also shows that Bee structures, as such, are a surface phenomenon which is not present in the bulk phase volume of samples. (C) 2018 Elsevier Ltd. All rights reserved.

Oxidative ageing in bituminous materials is considered one of the most important factors for distress types in road applications. This paper aims to offer insights into the validity of commonly held beliefs regarding the oxidation phases of ageing in bitumen, the fast- and the slow-rate phase, and explore the main oxidation products formed upon ageing. In order to evaluate possible differences between bitumen types, the penetration grade as well as the bitumen production process was varied. Thus, the ageing of three different binders was first studied by Fourier-Transform Infrared (FTIR) and Electron Paramagnetic Resonance (EPR) spectroscopy. The formation of oxygen-containing molecular structures on the bitumen surface during ageing was studied with Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). The results of FTIR reveal a gradual increase of sulfoxides upon ageing, while the EPR results show an increase of organic carbon-centred radicals. In parallel, TOF-SIMS results provide evidence for an increase of oxygenated compounds, such as SOx--, HOx-- and NOx--containing compounds. It appears also that paramagnetic metal species, such as vanadyl-porphyrins, are insusceptible during ageing. Overall, the findings of this study are in agreement with a mechanism comprising two rate-determining phases and support the formation of different oxygenated products. It is believed that the experimental approach used in this work may contribute further to an improved understanding of the ageing mechanisms in bitumen.

Nowadays, Reclaimed Asphalt (RA) is widely used in pavement applications as part of new asphalt mixtures. To design high-quality asphalt mixes, the RA material and especially the RA binder must be systematically characterised with the purpose to explore its ageing state, especially when RA is added in high rates (above 20%). In this research, chemical (SARA and FTIR ageing indexes) and rheological properties (master curve parameters, Glower-Rowe parameter and ΔΤc) of a large selection of RA binders (19 samples) were determined to reveal their ageing level. The results of this experimental validation were further analysed statistically to discover clusters of similar chemorheological properties, reflecting in this way their ageing state. The exploratory techniques PCA and HCA were able to detect five clusters of RA binders with different ageing states. The five clusters clearly distinguish the RA binders in groups with statistically different properties, assessed using one-way ANOVA. The method proposed here is a potential tool to “fingerprint” RA binders with similar ageing states, particularly for decision-making strategies, to optimise the use and treatment of RA.

Polymer modification is widely used to improve the engineering properties of bitumen, the most commonly used polymer modifier being styrene-butadiene-styrene (SBS) block copolymer. Although extensive studies have been performed on polymer modified bitumen (PMB), no reliable data is currently available on the effect of polymer modification on the dynamic rheological properties at low temperatures. In this study, we focus on the rheology of SBS modified bitumen near and below the glass transition temperature (Tg) using the 4-mm DSR technique. In addition, fluorescence microscopy and temperature-modulated differential scanning calorimetry are used to study the phase behavior and interactions in the SBS-bitumen blends. At high SBS concentrations, thermorheological complexity is observed in the investigated temperature range, attributable to the formation of a continuous SBS-rich network structure. In the case of compatible SBS-bitumen blends, a linear correlation is established between the flexural creep stiffness measured by bending beam rheometry (BBR) and the complex shear modulus measured by 4-mm DSR. Deviations from this linear trend are shown to result from the macro-phase separation induced by the poor compatibility of SBS and bitumen.