Volume 22, Issue 3

The review is devoted to the fundamental aspects of the reactive processing of thermoplastic polymers. First of all, some reactive processing examples, including polymer grafting (vinyl silane, maleic anhydride) and/or functionalization, bulk polymerization (urethane, lactams, acrylate, ∊-capolactone), polyester modification and new copolymers synthesis, are presented. From a fundamental point of view, the review covers the state of the art in the domains of rheology (specifically modelling of rheo-kinetics), diffusion and mixing in highly viscous reactive or non reactive media. Finally, 1, 2 and 3-D simulation of the reactive extrusion process in twin-screw extruder is reported at the end of the review.

During mixing of a rubber compound containing silica and silane, the mixer is not only used for the dispersion of the filler and other ingredients, but also for a chemical reaction. These two functionalities of the mixer result in opposite processing requirements: A good dispersion is reached by high shearing forces, increasing the compound temperature. The silanization is not dependent on high shearing forces; it is positively influenced by high temperatures, but with an increasing risk of scorch. Another drawback is the equilibrium between the ethanol concentration in the vapor phase in the void space of the mixing chamber and in the rubber phase, which is limiting the reaction rate of the silanization. Devolatilization of the compound is a crucial factor for the efficiency of the silanization reaction. In this article a model for devolatilization of a rubber compound in an internal mixer is developed, including a chemical reaction replenishing the volatile component during the devolatilization process. The model is based on the penetration theory, with the main contribution to the devolatilization being convective mass transfer. The main influencing factors, theoretically deducted and practically verified, are temperature, mixer volume, fill factor, rotor speed, reaction time and partial pressure of the volatile component in the void volume of the mixer.

In the present study, we aim to investigate the basic flow and filling characteristics in the hot embossing filling stage, which depend on the geometry and processing conditions. For this purpose, we have developed a numerical analysis to simulate hot embossing filling using the finite element method and verified the developed program using the existing experimental data. As s basic study to understand hot embossing filling we have chosen a simple rectangular cavity with repeating protruded parts as a computational domain. The filling pattern was found to be significantly influenced by the variation of thickness of polymer substrate for the same stamp geometry, thermal boundary condition, and the embossing time. Filling from the border of the cavity is clearly observed as the thickness of polymer substrate decreases under the equal wall temperature condition. As for the effect of unequal temperature at the stamp and solid base plate, we found that the filling pattern has been affected by the temperature difference between the two surfaces and embossing time. The localized uprising flow results from the thermal boundary condition and subsequent change in the effective thickness of polymer substrate having enough fluidity to deform.

Part cooling parameters such as coolant flow rate and coolant temperature has been shown to have an important influence on the part quality in plastic injection molding. Molders commonly manipulate the coolant flow rate in an unclear manner to adjust part quality and reduce the overall cycle time. Manipulating such parameters effectively can indirectly control part quality when deviations in the injection processing variables occur if it is done in a controlled manner. In this investigation, coolant flow rate is selected to be the manipulated variable that affects an average temperature of the part surface as it cools within the mold cavity. The average part temperature is the controlled variable and its control represents the indirect control of part quality. Experiments were conducted to quantify the effects of coolant flow rate on the part surface temperature demonstrating that it is highly nonlinear and its control would require an advanced control scheme. An adaptive online modeling algorithm that uses information from temperature and flow rate sensors was developed to continuously retune a predictive controller for controlling the part surface temperature. Good control performance was obtained from the adaptive strategy for tracking setpoint changes in the part temperature and when the cooling cycle was reduced from 16 to 14 s.

This study examines the rheological and morphological properties of dynamically vulcanized nanocomposite thermoplastic elastomers (TPV nanocomposites) based on PP/EPDM. Rubber contents of 20, 40, and 60% were used with polypropylene of different viscosities at 2 wt.% of nanoclay. We performed rheological and morphological characterizations on the nanocomposites using X-ray diffraction, transmission electron microscopy, scanning electron microscopy and rheometry in small amplitude oscillatory shear. The effects of polypropylene viscosity, maleic anhydride grafted polypropylene (PPMA), and composition were also investigated. The storage modulus (G) of the TPV nanocomposites (without PPMA) containing 20, 40, and 60% rubber significantly increased in comparison with similar but unfilled samples and also a further increase in the G from the incorporation of the PPMA in the samples. The agglomeration of the clay considerably decreased when the rubber content was increased in the TPV nanocomposites. The yield stress of the prepared TPV nanocomposite, based on a low-viscosity PP, increased more than that of the sample from high viscosity PP. The TPV nanocomposites containing 20, 40 and 60% EPDM exhibited a strong elastic modulus that tended to level off (plateau) at low shear rates. These results were attributed to strong interfacial interactions between the nanoclay and TPV matrix and, also, the existence of the physical three-dimensional network structure formed between the cured rubber particles, as evidenced by the morphological features of the samples. A Carreau-Yasuda law with yield stress and a linear viscoelastic model, taking into account the maximum packing volume () were used to describe the melt linear viscoelastic properties of the TPV nanocomposites.

The co-rotating twin screw extrusion process is widely employed in chemical industries for the processing of complex fluids including various polymers, suspensions, emulsions and gels. Here we propose a new integrated modeling strategy that is based on the numerical analysis of pressure-generating extrusion elements concomitantly with the pressure-losing extrusion elements of the co-rotating twin screw extrusion process for non-Newtonian fluids under nonisothermal conditions. The numerical analysis undertakes three-dimensional (3-D) finite element simulations of any multiple combinations of forwarding and reversing fully-flighted screw elements with other types of elements including kneading discs staggered in the forward or reverse configurations and the die. The abilities of the methodologies in simulating the coupled flow and heat transfer in industrially-relevant mixing sections or pressurization/die shaping are demonstrated with predictions of the degree of fill and typical velocity, deformation rate, stress magnitude, pressure distributions as functions of various operating parameters and basic twin screw extrusion geometries for a viscoplastic type generalized Newtonian fluid.

The crystallization of a polymer melt, taking place during transformation processes, has a great impact on the process itself, mainly because it causes a large increase in the viscosity (hardening). Knowledge of the hardening kinetics is important for modeling and controlling the transformation processes. In this work, first an overview is given of the experimental and modeling work on the hardening of crystallizing polymers. Next, we present isothermal crystallization experiments using differential scanning calorimetry (DSC) and rotational rheometry to measure the dynamic viscosity. The evolution of the relative crystallinity and normalized complex viscosity are correlated by a novel technique which allows simultaneous analysis of several runs, even if they are not carried out at same temperatures; the main requirement with the traditional technique. The technique, described in detail in this paper, provides an experimental relationship between the crystallinity and the hardening, i.e. the increase in the viscosity. Moreover, by measuring the dynamic viscosity at different frequencies, surprisingly, a master curve is obtained which combines the effects of shear rate, temperature and the level of crystallinity.

The functionalization of polypropylene (PP) by 4-carboxybenzene sulfonyl azide (CBSA) was investigated in a batch mixer and the reaction was monitored through FTIR, 1 H-NMR and XPS spectroscopy. The degree of grafting was found to increase initially with azide feed content and subsequently to level off at azide concentrations of 2 wt.%. Experiments performed at different reaction temperatures showed that a maximum degree of grafting was obtained around 190°C. The linear viscoelastic properties the functionalized PPs were also evaluated by oscillatory shear measurements and were found to correlate with the grafting degree results. Finally, the adhesive properties of the functionalized PPs were evaluated through peel tests on aluminum substrates. The peel strength increased with the degree of grafting and it was found to be significantly higher for purified samples than for non-purified ones. Finally, it was demonstrated that the cooling rate of the PP/aluminum laminate specimens had a major effect on the peel strength.