Time-Temperature Superposition Principle in Shearing Tests Compared to Tension Conditions for Polymers Close to Glass Transition.

The well-known principle of time-temperature superposition (TTS) is of prime interest for polymers close to their glass transition. First demonstrated in the range of linear viscoelasticity, it has been more recently extended to large deformations in tension. However, shear tests were not yet addressed. The present study depicted TTS in shearing conditions and compared it to results in tensile conditions both for low and high strains for a polymethylmethacrylate (PMMA) of different molar masses. The main objectives were to enlighten the relevance of the principle of time-temperature superposition for shearing at high strain and to discuss the way shift factors should be determined. It was suggested that shift factors could be dependent on compressibility, which should be taken into account when addressing various types of complex mechanical loadings.

Multipurpose Processing Additives for Silica/Rubber Composites: Synthesis, Characterization, and Application.

Processing additives are a special group of chemicals included in rubber formulations to facilitate the flowability of the resultant compounds. Their addition generally affects the cured properties of the subsequent rubber composites, and fine-tuning of the compound formulation is therefore required. In this work, an attempt has been made to address this issue through the preparation of new bio-based processing additives capable of promoting the mixing of the rubber compound while at the same time enhancing mechanical properties following curing. A significant decrease in the mixing energy at the first stage of mixing (~10%) has been observed by substituting only a small percentage of the conventional petroleum-derived process oil with aminated epoxidized soybean oil. Concomitantly, it is found that this aminated epoxidized soybean oil promotes rubber curing and increases the tensile strength of the final composite by ~20% compared to the control.

Influence of Silica Specific Surface Area on the Viscoelastic and Fatigue Behaviors of Silica-Filled SBR Composites.

This work aimed at studying the effect of a silica specific surface area (SSA), as determined by the nitrogen adsorption method, on the viscoelastic and fatigue behaviors of silica-filled styrene-butadiene rubber (SBR) composites. In particular, silica fillers with an SSA of 125 m2/g, 165 m2/g, and 200 m2/g were selected. Micro-computed X-ray tomography (µCT) was utilized to analyze the 3D morphology of the fillers within an SBR matrix prior to mechanical testing. It was found with this technique that the volume density of the agglomerates drastically decreased with decreasing silica SSA, indicating an increase in the silica dispersion state. The viscoelastic behavior was evaluated by dynamic mechanical analysis (DMA) and hysteresis loss experiments. The fatigue behavior was studied by cyclic tensile loading until rupture enabled the generation of Wöhler curves. Digital image correlation (DIC) was used to evaluate the volume strain upon deformation, whereas µCT was used to evaluate the volume fraction of the fatigue-induced cracks. Last, scanning electron microscopy (SEM) was used to characterize, in detail, crack mechanisms. The main results indicate that fatigue life increased with decreasing silica SSA, which was also accompanied by a decrease in hysteresis loss and storage modulus. SEM investigations showed that filler-matrix debonding and filler fracture were the mechanisms at the origin of crack initiation. Both the volume fraction of the cracks obtained by µCT and the volume strain acquired from the DIC increased with increasing SSA of silica. The results are discussed based on the prominent role of the filler network on the viscoelastic and fatigue damage behaviors of SBR composites.

Plasticization of Polylactide with Myrcene and Limonene as Bio-Based Plasticizers: Conventional vs. Reactive Extrusion.

Polylactide (PLA) was blended by conventional and reactive extrusion with limonene (LM) or myrcene (My) as bio-based plasticizers. As-processed blends were carefully analyzed by a multiscale and multidisciplinary approach to tentatively determine their chemical structure, microstructure, thermal properties, tensile and impact behaviors, and hydrothermal stability. The main results indicated that LM and My were efficient plasticizers for PLA, since compared to neat PLA, the glass transition temperature was reduced, the ultimate tensile strain was increased, and the impact strength was increased, independently of the type of extrusion. The addition of a free radical initiator during the extrusion of PLA/LM was beneficial for the mechanical properties. Indeed, the probable formation of local branched/crosslinked regions in the PLA matrix enhanced the matrix crystallinity, the tensile yield stress, and the tensile ultimate stress compared to the non-reactive blend PLA/LM, while the other properties were retained. For PLA/My blends, reactive extrusion was detrimental for the mechanical properties since My polymerization was accelerated resulting in a drop of the tensile ultimate strain and impact strength, and an increase of the glass transition temperature. Indeed, large inclusions of polymerized My were formed, decreasing the available content of My for the plasticization and enhancing cavitation from inclusion-matrix debonding.