Maurício Azevedo

Injection moulding of liquid silicone rubber (LSR) requires reliable computer-aided engineering simulations to support process optimisation, which in turn depend on accurate material data. In this study, thermo-physical and kinetic properties of a highly filled injection moulding (IM) grade of LSR were systematically characterised using complementary experimental approaches and their impact on simulation fidelity was critically assessed. Specific heat capacity was measured using both modulated DSC and the standard sapphire method, revealing temperature dependence but no intrinsic change during curing, with sapphire-based data incorporating enthalpic effects more realistically for process prediction. Thermal conductivity was found to be nearly constant across the processing temperature range. Curing kinetics were investigated by calorimetry and rheology, with the former supporting an autocatalytic mechanism and the latter suggesting an $n^{th}$-order model, reflecting differences in detection sensitivity and onset characterization. When implemented into injection moulding simulations, viscosity primarily affected injection pressures, while differences in specific heat capacity and curing kinetics strongly influenced predicted curing profiles and cycle times. These results emphasize that dataset choice, particularly for curing-related parameters, is critical to achieving predictive accuracy in LSR injection moulding simulations.

Selecting the optimal settings for the production of rubber goods can be a very time-consuming and resource-intensive process. A promising method for optimizing rubber processing in a short period of time is the use of simulation routines. However, process simulations have only recently enabled meaningful predictions of not only the part’s state of cure but also its mechanical characteristics. As a first approach, second-order polynomials were considered suitable for describing the properties of compression-molded parts. However, more precision is required for injection molding due to the narrower distribution of mechanical characteristics of parts produced at different vulcanization temperatures. This became evident when the approximation of mechanical data with second order models partly revealed significant failures of part behavior prediction. To tackle this issue, a combined approach for approximation is proposed in this contribution by means of logistic growth function in addition to second order polynomials. To feed the model, an experimental plan was designed for producing injection-molded parts from an SBR compound at various temperatures and to different degrees of cure. The parts obtained were then characterized mechanically, and the results were opposed to varying degrees of cure and extents of reaction to calculate the model coefficients. Once available, a simulation-based calculation of the mechanical part quality is possible. The comparison of test results from the simulation and the real process has shown a reliable prediction, as simulation results were found within the natural deviation of the real measurements.

Application of elastomers in general demands the conversion of their soluble networks into crosslinked structures. This abrupt change causes several modifications, both in the atomic/molecular level and at the macro‐scale. In this study, solid silicone rubber (high molecular weight poly(dimethylsiloxane)), was crosslinked with dicumylperoxide (DCP), a widely used crosslinking agent by the rubber industry. The changes caused by different DCP concentrations were investigated, aiming to bring attention to the molecular transformations, usually neglected when processing‐oriented studies are conducted. DCP concentration showed a limited contribution to the network's molecular dynamics, which was found to be mainly dominated by entanglements. The dominance of entanglements over other molecular constraints, like crosslink points, justifies the threshold and counter‐intuitive behavior of tensile and hardness properties. However, differences were found in the crystallization ability after crosslinking, when the more crosslink points were introduced, the lower the crystallinity was and the less stable the PDMS crystallites were. In addition to providing a deeper understanding of an industrially applied rubber system n terms of the effective concentration of DCP, and the reasoning behind such concentration, the findings of this study add to the state‐of‐the‐art comprehension of elastomeric networks, and how they behave on a molecular level.

Silica-filled styrene butadiene rubber (SBR)/butadiene rubber (BR) compounds plasticized with mineral oils are mainly used to produce green tire treads. Previous works have demonstrated that the partial replacement of naphthenic oil (ONAF) by bio-based oils can provide processing and performance improvements for rubber compounds, along with environmental benefits. In this study, two modified soybean oils (esterified, OEST or esterified and epoxidized, OEPX) were investigated with the aim of evaluating the complete replacement of ONAF and determining whether the chemical properties of the oils affect the performance of silica-filled E-SBR/BR compounds, using the compound with ONAF as a reference. The physical properties, curing characteristics, morphology, and dynamic mechanical behavior were evaluated. The use of the modified soybean oils decreased the optimal cure time while increasing the crosslink density and the abrasive wear resistance. Further, the compounds with both modified soybean oils showed a good balance of mechanical properties. The modified soybean oils decreased the glass transition temperature of the rubber compounds, thus acting as true plasticizers. At 0°C, the tan δ value of E-SBR/BR/OEPX increased relative to that of E-SBR/BR/ONAF, whereas at 60°C, the values of the compounds with both modified soybean oils showed slight increases. The tan δ values reveal that compared with E-SBR/BR/ONAF, E-SBR/BR/OEPX has better wet grip and a similar rolling resistance, whereas E-SBR/BR/OEST has a higher rolling resistance. Thus, both modified soybean oils can fully replace ONAF and appear to be extremely attractive plasticizers for use in silica-filled E-SBR/BR compounds employed as green tire treads for passenger cars.