RESUMEN
The tire industry needs to become more sustainable to reduce pollution and fight climate change. Replacing fossil ingredients in a tire-tread compound with bio-based alternatives is an approach to create a more sustainable product. For instance, the plasticizer can be replaced, which is a petroleum-based ingredient used in relatively high amounts in the rubber. This approach was followed in the current study. Three plant-based plasticizers were selected as potential substitutes for treated distillate aromatic extract (TDAE) in a simplified tire-tread compound formulation, namely, sunflower oil, coconut oil, and cardanol. Additionally, squalane was used as a TDAE replacement to further investigate the possible interactions between plasticizers and other compound ingredients. Squalane (C30H62) is a fully saturated substance, containing six methyl groups but no additional chemical functional groups. Therefore, it was expected that squalane would result in limited interactions within the studied system. All alternatives to TDAE showed an increased cure rate and decreased scorch time, except squalane. This indicates that the three bio-based plasticizers might interact with the vulcanization system. For example, they could function as an additional coactivator of the curing system and/or shield the silica surface. A severe decrease in maximum torque and an increase in elongation at break were obtained for cardanol and sunflower oil. Both plasticizers also resulted in lower crosslink densities compared to the other compounds. A model study with the bio-plasticizers and sulfur verified that the unsaturation in the cardanol and sunflower oil reacted with the crosslinking agent. This leads to less sulfur available for the curing reaction, explaining the low maximum torque. The tan δ curves showed that all replacements resulted in a decrease in the glass transition temperature of the compound. Although all oil alternatives displayed promising results, none of them are suitable as a direct substitute for TDAE in a tire-tread compound due to its ability to interact additionally with other rubber ingredients and contribute in this form to the reinforcement of the compound.
RESUMEN
Composites revolutionize material performance, fostering innovation and efficiency in diverse sectors. Elastomer-based polymeric composites are crucial for applications requiring superior mechanical strength and durability. Widely applied in automotives, aerospace, construction, and consumer goods, they excel under extreme conditions. Composites based on recycled rubber, fortified with reinforcing fillers, represent a sustainable material innovation by repurposing discarded rubber. The integration of reinforcing agents enhances the strength and resilience of this composite, and the recycled polymeric matrix offers an eco-friendly alternative to virgin elastomers, reducing their environmental impact. Devulcanized rubber, with inherently lower mechanical properties than virgin rubber, requires enhancement of its quality for reuse in a circular economy: considerable amounts of recycled tire rubber can only be applied in new tires if the property profile comes close to the one of the virgin rubber. To achieve this, model passenger car tire and whole tire rubber granulates were transformed into elastomeric composites through optimized devulcanization and blending with additional fillers like carbon black and silica-silane. These fillers were chosen as they are commonly used in tire compounding, but they lose their reactivity during their service life and the devulcanization process. Incorporation of 20% (w/w) additional filler enhanced the strength of the devulcanizate composites by up to 15%. Additionally, increased silane concentration significantly further improved the tensile strength, Payne effect, and dispersion by enhancing the polymer-filler interaction through improved silanization. Higher silane concentrations reduced elongation at break and increased crosslink density, as it leads to a stable filler-polymer network. The optimal concentration of a silica-silane filler system for a devulcanizate was found to be 20% silica with 3% silane, showing the best property profile.
RESUMEN
Pre-treated silica with a plasma-deposited (PD) layer of polymerized precursors was tested concerning its compatibility with Natural Rubber (NR) and its influence on the processing of silica-silane compounds. The modification was performed in a tailor-made plasma reactor. The degree of deposition of the plasma-coated samples was analyzed by ThermoGravimetric Analysis (TGA). In addition, Diffuse Reflectance Infrared Fourier Transform spectroscopy (DRIFTs), X-ray Photoelectron Spectroscopy (XPS), and Transmission Electron Microscopy (TEM) were performed to identify the morphology of the deposited plasma polymer layer on the silica surface. PD silica samples were incorporated into a NR/silica model compound. NR compounds containing untreated silica and in-situ silane-modified silica were taken as references. The silane coupling agent used for the reference compounds was bis-(3-triethoxysilyl-propyl)disulfide (TESPD), and reference compounds with untreated silica having the full amount and 50% of silane were prepared. In addition, 50% of the silane was added to the PD silica-filled compounds in order to verify the hypothesis that additional silane coupling agents can react with silanol groups stemming from the breakdown of the silica clusters during mixing. The acetylene PD silica with 50% reduced silane-filled compounds presented comparable properties to the in-situ silane-modified reference compound containing 100% TESPD. This facilitates processing as lower amounts of volatile organic compounds, such as ethanol, are generated compared to the conventional silica-silane filler systems.
RESUMEN
The disposal of tires at the end of their lifespan results in societal and environmental issues. To tackle this, recycling and reuse are effective solutions. Among various recycling methods, devulcanization is considered to be a very sustainable option, as it involves the controlled breakdown of crosslinks while maintaining the polymer backbones. The objective of this study is to develop a sustainable devulcanization process for passenger car tire rubber using silanes. In this study, a thermo-mechanical-chemical devulcanization process was conducted to screen six potential devulcanization aids (DAs). Silanes were chosen as they are widely used in tire rubber as coupling agents for silica. The efficiency of the devulcanization was studied by the degree of network breakdown, miscibility of the devulcanized material, and mechanical properties of the de- and revulcanized material. Compared to the parent compound, a 55-60% network breakdown was achieved for the devulcanizate along with 50-55% of tensile strength recovery. In addition to superior devulcanization efficiency, this DA offers a sustainable alternative to the conventional ones, such as di-phenyl-di-sulphide, due to its compliance with safety regulations. The devulcanizate can be utilized in high-performance applications, such as tires and seals, while 100% devulcanizate can be employed in low-strength technical rubber products.