We have investigated the influence of hard spherical hydrophilic nanoparticles (fumed silica) on the phase behavior of PS/PVME (polystyrene/polyvinyl methyl ether) blend as a compatibilizer. The size of nanoparticles is comparable to the radius of gyration of the polymers and the particles preferentially segregate into one of the polymeric components. Phase separation was assessed using rheological analysis (RMS), differential scanning calorimetry (DSC), and optical microscopy (OM). In order to investigate the kinetics of phase separation in the presence of nanoparticles, time sweep experiments were employed via rheological analysis and OM. A certain composition of PS/PVME was highly concerned to shed light on the dynamic of phase separation, in the presence of nanoparticles, in the unstable region of phase diagram. The phase diagram shifted up nearly 10°C in the presence of nanoparticles. Blends compatibilized by spherical nanoparticles could provide an interesting and economic alternative to the conventional methods of compatibilization by block copolymers.

Attempts were made to follow and correlate morphological development with the crosslinking density, or state of cure (SOC), and the surface tension (␥) of the rubber phase in dynamically cured thermoplastic elastomers (TPEs) based on ethylene propylene diene rubber and polypropylene (PP) with 60/40 (w/w) ratios. Samples were taken from a hot running mixer without interruption and quickly quenched in liquid nitrogen both before and after the onset of vulcanization at various SOCs to carry out this process. The quick cooling of the samples prevented the coalescence and agglomeration of the dispersed rubber particles. A two-phase morphology with the rubber particles dispersed throughout the PP matrix was observed for the uncured but frozen samples, whereas unfrozen blend samples showed a particulate cocontinuous morphology in the uncured state. An increase in the mixing torque with the SOC was observed after the addition of a curing system. This was understood to be caused by the increase in the rubber crosslinking density and also by the enhancement of the interfacial adhesion between the cured rubber phase and the PP matrix, leading to the better wetting of the two phases. Above a certain crosslinking density (SOC), ␥ of the rubber particles decreased through elastic shrinkage. This phenomenon, together with the breakdown of the agglomerate structure formed by the cured rubber particles, led to a decrease in the mixing torque after a maximum was passed and, finally, to a defined morphology. Based on the obtained results, a four-stage model is proposed to describe the microstructural development in dynamically vulcanized TPEs. Dynamic mechanical thermal analysis and differential scanning calorimetry results are also used to support the model.

Relationship between the rheological properties and morphology of dynamically vulcanized thermoplastic elastomers (TPVs) based on Ethylene Propylene Diene Monomer (EPDM) and Polypropylene (PP) blends containing 20, 40 and 60% of EPDM were studied. The samples were prepared in a laboratory internal mixer at a rotor speed of 60 rpm. We performed morphological studies on the cryogenically fractured samples using scanning electron microscopy (SEM). The rheological behavior and melt viscoelastic properties of the samples were studied by rheometric mechanical spectrometry (RMS) at a temperature of 220°C. The TPV samples showed a significant viscosity upturn and a strong storage modulus that tended to plateau at low shear rates, with the highest extent for the sample containing 60% of EPDM. These results were attributed to a network structure resulting from agglomerates formed between the cured rubber particles, as evidenced by the morphological features of the samples. The multiple elastic response, expressed in terms of relaxation time distribution, H(λ), exhibited by the molten TPV sample containing 60% of EPDM suggests that apart from the contribution of flow‐induced molecular orientation of the PP matrix, there may also exist some elastic response induced by agglomerates formed between the cured rubber particles. The results predicted from the linear viscoelastic model proposed in the present work were found to be in good agreement with the experimental results. POLYM. ENG. SCI. 45:84–94, 2005. © 2004 Society of Plastics Engineers.

Formation of agglomerate structure by the rubber particles through flocculation or networking mechanism during dynamic crosslinking of thermoplastic elastomers based on EPDM rubber and polypropylene has been evidenced. Scanning electron microscopy (SEM) examination performed on the crosslinked blend samples which had been etched by hot xylene suggested that agglomeration occurs mainly through a joint shell mechanism. Reduction of the mixing torque after passing the peak maximum at the dynamic crosslinking stage was concluded to be due to the shear induced breaking down of agglomerates leading to a more defined morphology. Samples removed after the maximum mixing torque showed higher dynamic loss tangent (tan δ) above the PP glass transition. This is attributed to the broadening of the retardation time spectra for the PP matrix in the blend system. Higher mixing torque, higher tensile strength, as well as better extensibility were found for the blend samples based on PP with low MFI value as a result of higher density of aggregates and more extent of their interfacial adhesion with the PP matrix. More defined morphology and higher rate of network breakdown was observed at high mixing shear rate. Mixing torque increased significantly with increasing the rubber content of the blend system from 40% to 60% (W : W) as a consequence of higher interaction of rubber aggregates with the PP matrix. Based on the obtained results, the structure of the rubber aggregates and associated networks as well as extent of interaction between the two phases play an important role in controlling the final morphology, processing behavior and therefore mechanical properties of the dynamically cured blend system.

Rheological behavior of polypropylene (PP)/organoclay nanocomposites varying in compatibilizer (PP-g-MA) and organoclay concentration was investigated. The samples were prepared by melt intercalation method in an internal mixer. The wide angle X-ray diffraction patterns and results of rheological measurements showed that the compatibilizer had strong influence in increasing the interlayer spacing. The observed low frequency liquid-like to solid-like transition and apparent yield stress in simple shear flows, along with convergence of transient shear stress to nonzero values in stress relaxation after the cessation of flow experiments, were found to be consistent with formation of a physical network in quiescent conditions which could be easily ruptured with applying low shear rates. The values of stress overshoot strain in flow reversal experiments were independent of shear rate, organoclay, and compatibilizer content. From the results of frequency sweep experiments in different nonlinear strain amplitudes it was shown that extended Cox-Merz analogy was valid in nonlinear dynamic deformations while the shear viscosity showed positive deviation from this analogy with higher deviations at lower shear rates. Results of storage modulus recovery and flow reversal experiments at different shear rates suggested that network structure is reformed with a much slower rate compared to the rotational relaxation of organoclay platelets. FIG. 13. The results of flow reversal experiments after various resting periods for PN7.5-3 samples at _ c ¼ 1ð1=sÞ. FIG. 14. Effect of shear rate on microstructure reformation rate in flow reversal experiments for PN7.5-3 samples.

Viscoelastic phase separation (VPS) can produce a network structure of the minor phase, which needs to be stabilized for designing a heterogeneous structure with desired mechanical and electrical functions. In this work, we investigate the stabilization of the VPS-induced network structure in a dynamically asymmetric PS/PVME blend by incorporation of a SEBS-g-MA block copolymer or dimethyldichlorosilane modified nanosilica. The addition of SEBS-g-MA retards the volume shrinking process and slows down the kinetics of phase separation due to its localization at the PS/PVME interfaces. Consequently, in the later stage of VPS, phase inversion occurs at longer times with respect to the neat blend due to the decreased interfacial tension. In contrast, hydrophobic nanoparticles self-assemble in the bulk of PS-rich phase and restrain the dynamics of polymer chains enhancing the dynamic asymmetry of the system. The efficiency of nanoparticles in controlling the kinetics of phase separation is found to be superior compared to block copolymer-based compatibilizers indicating the significance of chain dynamics. Moreover, beyond a critical nanoparticle volume fraction, phase separation is pinned due to particle percolation within the PS-rich phase, yielding a kinetically trapped VPS-induced network structure.

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We investigated the effects of soft dendritic polyethylene (dPE) nanoparticles on the rheological properties of a linear polystyrene (PS) matrix. The viscosity of PS−dPE nanocomposites is found to exhibit nonmonotonic dependence on the dPE concentration. In particular, with the addition of 1% dPE nanoparticles, we already observe more than 1 order of magnitude reduction in viscosity. The minimum viscosity was observed at 5% nanoparticles. At dPE concentrations higher than 5%, nanocomposite viscosity increases by addition of nanoparticles, yet it remains below the viscosity of PS. Addition of nanoparticles not only influences the terminal relaxation times of the nanocomposites but also affects their whole relaxation spectra. The viscosity of PS−dPE nanocomposites at high temperature is found to reversibly evolve with time, which proves the existence of supramolecular interactions between the PS matrix and the nanoparticles. Atomic force microscopy confirms that dPE nanoparticles are well distributed in the PS matrix, though each component of the nanocomposite exhibits its own glass transition. While the origin of viscosity reduction remains unknown, it cannot be attributed to confinement, free volume effect, change of entanglement density, surface slippage, shear banding, or particle induced shear thinning.