Hybrid modification is a relatively new concept of incorporating two or more polymeric modifiers of different nature to a bitumen, in order to take advantage of their complementary features. Aiming to this, in this paper, the so-called Hybrid Systems (HSs) were prepared by the addition of an ethylene-based copolymer (reactive or non-reactive) to a model rubberised binder (Crumb Tyre Rubber Modified Bitumen). The resulting binders (referred to as reactive and non-reactivate HSs, depending on copolymer used) were evaluated by means of thermorheological analysis, technological characterisation, fluorescence microscopy and modulated differential scanning calorimetry. From the experimental results, it may be deduced a positive synergistic effect of non-dissolved Crumb Tyre Rubber (CTR) particles and a second polymeric phase that not only improves the in-service performance but also the high-temperature storage stability. This enhancement is attributed to the development of a multiphasic system composed of non-dissolved CTR particles, a polymer-rich phase and an asphaltene-rich phase. In the case of non-reactive HSs, droplets of swollen ethylene copolymer form a well-defined dispersed phase. By contrast, reactive HSs display a different morphology, almost invisible by optical microscopy, related to the development of a chemical network that yields, by far, the highest degree of modification.
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