Degradation during Mixing of Silica-Reinforced Natural Rubber Compounds.

The optimal mixing conditions for silica-filled NR compounds dictate the need to proceed at a high temperature, i.e., 150 °C, to achieve a sufficient degree of silanization. On the other hand, natural rubber is prone to degradation due to mechanical shear and thermal effects during mixing, particularly at long exposure times. The present work investigates NR rubber degradation during mixing in relation to prolonged silanization times. The Mooney viscosity and stress relaxation rates, bound rubber content, storage modulus (G'), and delta δ were investigated to indicate the changes in the elastic/viscous responses of NR molecules related to rubber degradation, molecular chain modifications, and premature crosslinking/interaction. In Gum NR (unfilled), an increase in the viscous response with increasing mixing times indicates a major chain scission that causes a decreased molecular weight and risen chain mobility. For silica-filled NR, an initial decrease in the Mooney viscosity with increasing silanization time is attributed to the chain scission first, but thereafter the effect of the degradation is counterbalanced by a sufficient silanization/coupling reaction which leads to leveling off of the viscous response. Finally, the higher viscous response due to degradation leads to the deterioration of the mechanical properties and rolling resistance performance of tire treads made from such silica-filled NR, particularly when the silanization time exceeds 495 s.

Dynamic Response and Molecular Chain Modifications Associated with Degradation during Mixing of Silica-Reinforced Natural Rubber Compounds.

Mixing silica-reinforced rubber for tire tread compounds involves high shear forces and temperatures to obtain a sufficient degree of silanization. Natural Rubber (NR) is sensitive to mastication and chemical reactions, and thus, silica-NR mixing encounters both mechanical and thermal degradation. The present work investigates the degradation phenomena during the mixing of silica-reinforced NR compounds in-depth. The Mooney stress relaxation rates, the dynamic properties with frequency sweep, a novel characterization of branch formation on NR using Δδ values acc. Booij and van Gurp-Palmen plots, together, indicate two major competitive reactions taking place: chain scission or degradation and preliminary cross-linking or branch formation. For masticated pure NR and gum compounds, the viscous responses increase, and the changes in all parameters indicate the dominance of chain scission with increasing dump temperature. It causes molecular weight decrease, broader molecular weight distribution, and branched structures. Different behavior is observed for silica-filled NR compounds in which both physical and chemical cross-links are promoted by silanization and coupling reactions. At high dump temperatures above 150 °C, the results indicate a significant increase in branching due to preliminary cross-linking. These molecular chain modifications that cause network heterogeneity deteriorate the mechanical properties of resulting vulcanizates.

The Effect of Silanization Temperature and Time on the Marching Modulus of Silica-Filled Tire Tread Compounds.

Marching modulus phenomena are often observed in silica-reinforced solution styrene-butadiene rubber/butadiene rubber (S-SBR/BR) tire tread compounds. When such a situation happens, it is difficult to determine the optimum curing time, and as a consequence the physical properties of the rubber vulcanizates may vary. Previous studies have demonstrated that the curing behavior of silica compounds is related to the degree of silanization. For the present work, the effect of silanization temperature and time on the marching modulus of silica-filled rubber was evaluated. The correlations between these mixing parameters and their effect on the factors that have a strong relation with marching modulus intensity (MMI) were investigated: the amount of bound rubber, the filler flocculation rate (FFR), and the filler-polymer coupling rate (CR). The MMI was monitored by measuring the vulcanization rheograms using a rubber process analyzer (RPA) at small (approximately 7%) and large (approximately 42%) strain in order to discriminate the effects of filler-filler and filler-polymer interactions on the marching modulus of silica-filled rubber compounds. The results were interpreted via the correlation between these factors and their effect on the MMI. A higher temperature and a longer silanization time led to a better degree of silanization, in order of decreasing influence.

Implications of the Use of Silica as Active Filler in Passenger Car Tire Compounds on Their Recycling Options.

Tires are an important vehicle component, as car handling, safety and fuel economy depend for a major part on the tire composition and construction. As a consequence, tires are improved continuously. The most prominent improvement in the recent past was the use of a silica-silane filler system in passenger car tread compounds, instead of traditionally used carbon black. For recycling and re-use of end-of-life car tire rubber one of the most promising recycling methods is devulcanization: re-plasticizing the vulcanized rubber by selectively breaking the sulfur bridges between the polymer molecules. In the present paper, the influence of silica, which is present in the passenger car tires granulate, on both devulcanization and subsequent revulcanization, is investigated. In a step-wise approach it is shown that the presence of silica influences both devulcanization and revulcanization. The best tensile strength of the revulcanizate, using a carbon-black-based revulcanization formulation, was 5 MPa. This could be improved to 6.5 MPa by using 2.8 phr of 1,3-DiPhenylGuanidine (DPG) in the revulcanization formulation. After addition of a silanization step during revulcanization by adding 3.2 phr bis[3-(TriEthoxySilyl)Propyl] Tetrasulfide (TESPT), a silane, to the formulation, the tensile strength of the revulcanizate was further improved to 8 MPa. With these results it is shown that the silica in the granulate can be used to improve the revulcanization properties. To check the benefits of using pure tire tread material for the devulcanization and subsequent revulcanization, of both a carbon black and a silica-based virgin tread compound, it is shown that a tensile strength of the revulcanizate of 13 MPa can be reached. This shows the potential of devulcanized rubber when the various tire components are separated before whole car tire material is granulated as the beginning of the recycling.

Upscaling of a Batch De-Vulcanization Process for Ground Car Tire Rubber to a Continuous Process in a Twin Screw Extruder.

As a means to decrease the amount of waste tires and to re-use tire rubber for new tires, devulcanization of ground passenger car tires is a promising process. Being an established process for NR and EPDM, earlier work has shown that for ground passenger car tire rubber with a relatively high amount of SBR, a devulcanization process can be formulated, as well. This was proven for a laboratory-scale batch process in an internal mixer, using diphenyl disulfide as the devulcanization aid and powder-sized material. In this paper, the devulcanization process for passenger car tire rubber is upscaled from 15 g per batch and transformed into a continuous process in a co-rotating twin screw extruder with a capacity of 2 kg/h. As SBR is rather sensitive to devulcanization process conditions, such as thermal and mechanical energy input, the screw design was based on a low shear concept. A granulate with particle sizes from 1-3.5 mm was chosen for purity, as well as economic reasons. The devulcanization process conditions were fine-tuned in terms of: devulcanization conditions (time/temperature profile, concentration of devulcanization aid), extruder parameters (screw configuration, screw speed, fill factor) and ancillary equipment (pre-treatment, extrudate handling). The influence of these parameters on the devulcanization efficiency and the quality of the final product will be discussed. The ratio of random to crosslink scission as determined by a Horikx plot was taken for the evaluation of the process and material. A best practice for continuous devulcanization will be given.

Liquid chromatography/coordination ion spray-mass spectrometry for the analysis of rubber vulcanization products.

Liquid chromatography/coordination ion spray-mass spectrometry has been used for the identification of reaction products in a model rubber vulcanization process. After LC separation using reversed-phase conditions, AgBF(4) in acetonitrile was added, and strong signals were observed for silica-rubber coupling agents and products of the reaction between these and alkenes. The method performs best for substances containing sulfur chains with chain lengths between two and eight sulfur atoms, but sulfur-free compounds containing triethoxysilyl groups were detected as well. For the latter, the postcolumn addition of NaBF(4) proved to be a suitable alternative. Besides the coupling agents, various reaction products, including sulfur-chain bridged alkenes were identified.