Asphalt Binder Modification with Hazelnut and Walnut Shells as Valued Antioxidant Sources: Effects on Rheological and Main Physicochemical Post-Oxidation Indicators

Abstract

Oxidative aging drives asphalt pavement degradation, causing critical structural failures. This study evaluated hazelnut (HS) and walnut shell (WS) powders (0–3% w/w; 10–12 μm) as sustainable antioxidants, from valued residues, to mitigate thermo-oxidative aging in CA-24 binders. After evaluating the antioxidant potential (ORAC; Oxygen radical absorbance capacity, and TPC; Total phenolic content), modified binders underwent RTFO (Rolling thin film oven) and PAV (Pressure aging vessel) aging, evaluated by Fraass fragility, Relative Aging Index (RAI), dynamic shear rheometry (G*/sin δ), and Multiple Stress Creep Recovery (MSCR). WS exhibited significantly higher antioxidant capacity (6000 μmol TE g DW−1) and TPC than HS. The 3% treatments demonstrated optimal antioxidant efficacy, reducing long-term RAI by 14% and improving low-temperature flexibility by 3.8 °C (Fraass point −12.3 °C). However, MSCR revealed initial plasticizing effects decreasing elastic recovery (70%) and increasing non-recoverable compliance (Jnr) compromising unaged rutting resistance. Principal component analysis confirmed progressive diversification of aging-induced properties, evidencing complex multivariate trajectories. Ultimately, while nutshell derived phenolic modifiers provide effective concentration-dependent antioxidant protection, practical application requires optimization through targeted phenolic extraction, particle engineering, or elastomeric co-modification. Balancing aging resistance with high temperature stability remains essential for advancing these sustainable biomodification strategies in road infrastructure.