Microscopic Endurance of Rubber Compounds Investigated by In Situ Ultra Small‐Angle X‐Ray Scattering

ABSTRACT The strength and durability of silica‐reinforced rubber compounds depend on how effectively the filler network distributes stress and maintains structural integrity under deformation. This work employs a novel ultra small‐angle X‐ray scattering method to investigate how increased silica surface area influences cavitation and filler network deformation within the rubber matrix. Our analysis reveals an optimal filler concentration at which the macroscopic properties of ultra‐high surface area (UHSA) silica reach maximum and links this behavior to microscopic observations of cavity growth and silica cluster deformation. Compared to the previously studied Ultrasil‐VN3 silica, UHSA silica achieves this optimum at lower volume fractions, indicating improved filler efficiency. Although UHSA silica's smaller primary particle size has been shown to lead to higher local stresses and cavitation, its clusters are shown to be less rigid, more deformable, allowing sufficient reinforcement even at lower filler loadings. This deformability offsets strain‐induced cavitation, despite the increased local stresses at higher concentrations, making UHSA silica a strong alternative. Reduced amounts of UHSA silica can match the reinforcement and crack resistance of Ultrasil‐VN3, offering practical benefits for industrial use. These findings also highlight the role of particle size in determining cluster rigidity, with smaller particles enhancing flexibility and deformation potential.