Crystallinity of Bitumen via WAXD and DSC and Its Effect on the Surface Microstructure

It is well documented that most bituminous binders contain crystallisable material. This crystallisable fraction, often referred to as paraffinic or natural wax, is associated with the bitumen's origin and has an influence on its rheological performance. In the literature, Differential Scanning Calorimetry (DSC) is the primary technique used to determine the melting and crystallisation behaviour of this waxy fraction. However, in bitumen, thermal transitions in DSC are typically very broad and can be combined with recrystallisation effects upon reheating. This work explores the potential crystallisation and melting process of a waxy and a wax-free bitumen via three different approaches: DSC, Wide-Angle X-ray Diffraction (WAXD) and Confocal Laser Scanning Microscopy (CLSM). The findings reveal that the DSC transitions of the waxy bitumen are in good agreement with the corresponding occurrence of WAXD signals and to some extent with the formation and disappearance of the surface microstructures which were followed at two cooling and heating rates. WAXD results additionally demonstrate that the crystalline material in bitumen is organised in an orthorhombic unit cell, typical for straight chain aliphatic structures. On the other hand, DSC and WAXD support the lack of crystallinity for the wax-free bitumen which could explain its featureless CLSM surface. Overall, the originality of this work resides in the disclosure of connections between crystallographic properties, thermal transitions and the surface micromorphology of bitumen.