Assembly of Zinc‐Single‐Site‐Containing Silica Nanoparticles to Supraparticle Powders with Destructibility to Serve as Filler and Vulcanization Activator in Rubbers

• Published in: Particle & particle systems characterization Vol. 41; no. 5
• Main Authors: Wenderoth, Sarah, Milana, Paola, Zimmermann, Thomas, Deues, Moritz, Oppmann, Maximilian, Prieschl, Johannes, Mostoni, Silvia, Scotti, Roberto, Wintzheimer, Susanne, Mandel, Karl
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01-05-2024
• Subjects: Complexation; Curing; Disintegration; Drying; Dynamic mechanical properties; Ethanol; Fillers; Leaching; Mechanical properties; morphology control; Nanoparticles; Rubber; rubber nanocomposite; silica nanoparticles; Silicon dioxide; spray‐dried supraparticles; surface modification; Tires; Vulcanization; Zinc oxide; Zinc oxides; zinc‐activated vulcanization
• ISSN: 0934-0866; 1521-4117
• DOI: 10.1002/ppsc.202300161

The vulcanization process is widely used in industry for tire manufacturing. Therefore, zinc oxide is commonly utilized as an activator material, but unreacted zinc oxide remains in the final products and can be released into the environment with a significant impact. To reduce the amount of required zinc and to prevent leaching from tire material, zinc single site‐containing silica fillers are interesting candidates. In these materials, zinc sites are anchored on the surface of silica nanoparticles through their complexation with functionalized aminosilanes. Based on these, a novel powder sample is prepared via spray‐drying. The obtained supraparticles allow for a homogeneous distribution of the filler nanoparticles in the rubber matrix via their disintegration during the incorporation process. All synthesis steps are carried out in ethanol and water, respectively, at very mild temperatures to account for sustainability demands. As core of this study, the role of zinc ions and their amino‐complexation in nanoparticle dispersion stability and in supraparticle formation during spray‐drying is elucidated. Additionally, the superior performance of supraparticles as activator in rubber vulcanization is demonstrated. These show a higher curing efficiency, leading to lower curing time (−70%), higher torque values (+15%), and improved dynamic mechanical properties compared to the conventional ZnO activator.
In this study, the role of the zinc ions and their amino‐complexation in nanoparticle dispersion stability as well as in the obtained supraparticle morphology upon spray‐drying‐assisted assembly is elucidated. Additionally, the superior performance of such zinc single site‐containing silica supraparticles that are synthesized in an environmentally friendly, scalable manner, is demonstrated as activators in rubber vulcanization.