Band 27, Heft 3

A brief review of reactive processing of polyolefins, which are the most widely used polymers today, is given in this paper from the role of flow field in processing and the characterization of the modified chain topologies. The materials are mainly focused on polyethylene (PE), polypropylene (PP) and polyolefin elastomer (POE) here. Aspects of reactions, coupling/crosslinking and scission are discussed both in terms of the mechanism and kinetics under different flow conditions.

In this study, cross-sectional analyses were performed on microcellular injection-molded high-impact polystyrene products. The results confirm that the following five types of layers were formed: Skin layers I (the silver streak layer) and II (a nonfoamed layer), Core layers I (cell diameter, d > 150 μm), II (d < 50 μm), and III (d > 100 μm). As the maximum in-mold pressure (P max ) was increased from 5 to 30 MPa, the thickness of Skin layer II remained nearly constant. However, the foam types in the core layers changed from I and II to II and III or III only, resulting in an increase in cell diameter and a decrease in cell density. The process of cellular structure formation was observed using a glass-inserted mold, which revealed that this process consists of a flow (with a burst of cells at the melt front and the subsequent flow of the melt containing the cells), an end of the filling (involving elastic compression or the dissolution and disappearance of cells formed in the flow stage), and a cooling (new cell generation and growth and cooling solidification). Based on these cross-sectional observations, in concert with melt-pressure measurements and visualizations, we developed a model describing the formation process of Skin layer II and the core layers including a new concept that considers the melt pressure inside the cavity. The following layers are incorporated into the model: Skin layer II: A nonfoamed layer is formed in the area of the melt front where gases diffuse out from within the melt during the filling stage, and this nonfoamed layer moves to from melt front to the surface of the product due to fountain flow. Core layers I and II: A multilayer is formed containing a distribution of cells preserved from the flow stage due to the low compression forces, Core layer III: cells are dissolved in the melt due to strong compression forces at the end of the filling stage and then reform and grow in the cooling stage.

In plastic injection molding, external defects such as flow marks are serious problems. These external defects are known to occur during cavity filling processes inside the mold, and are closely related to resin flow behavior in the flow front area. In this study, the authors propose a new method for visualizing in-mold resin flow behavior using a glass-inserted mold and rotary runner exchange system capable of instantaneously switching two types of melt at the runner just before the gate. This method is capable not only of dynamic visualization, but also static visualization by the observation of cross-sections of a sample, because colored resins switched multiple times at the gate spread in layers inside the sample and freeze. Using this method and general purpose polystyrene, visualization analysis of the flow behavior of inner layer resins near the flow front in simple rectangular cavities was carried out. As a result, it was found that resins reaching the flow front are not exposed at the molded product surface immediately after the fountain-flow process, but remain along the circumference of the flow front for a long period of time, and then stretch out into a thin film-like shape to form the surface of the molded product. In addition, the inner layer resins near the flow front form a converging flow just before reaching the flow front and then form a fountain flow. It was also confirmed that this is a general phenomenon in the fountain-flow process during injection molding regardless of whether the resin is crystalline or noncrystalline. Based on these results, we built a model on the flow of inner layer resins near the flow front of general resins.

The coupled coextrusion calendering process of multilayer thermoplastic sheets has been studied. The structure of the film has been observed, the density of chemical links at the interface and the adhesion between the coextruded layers have been measured. There are some controversial features about the influence of calendering parameters. Several models of increasing complexity are proposed to master the process and its influence on adhesion. A multilayer thermal model accounting for the crystallization kinetics of both polymers allows defining qualitatively the temperature field especially at the interface between the two layers. A multilayer thermo-mechanical model provides quantitative figures on the stress, shear, elongation and temperature fields in the coextruded film and especially at the interface. Relationships between these parameters, density of chemical links at the interface, crystalline structure of the sample and peeling forces are discussed.

Carboxylated Nitrile Butadiene Rubber (XNBR) was reinforced with untreated and silane treated hybrid filler. The hybrid filler was composed of organic layered nanosilicates (NLS) and agro polymer based olive husk powder (OHP). The fabricated composites were inspected with regard to their mechanical and thermal properties. It was found that the silane treated hybrid filler was able to improve the tensile strength at break and the tensile modulus as compared to the control. The overall degree of interaction between the matrix and both the untreated and treated hybrid filler was improved. This was evidenced by the increased degree of curing which is the torque difference (τ max –τ min ) derived from the moving die rheometer (MDR) and the decreased swelling index data. Dynamic mechanical analysis (DMA) revealed that the apparent was the highest in case of the silane treated hybrid filler. The thermogravimetric analysis (TGA) revealed that the thermal stability of the composites improved with the incorporation of the hybrid filler. The attenuated total reflectance (ATR-IR) revealed that dipole-dipole interactions between the various reactive functional groups namely the carboxylic of the XNBR, the hydroxyl group of the agro-polymer and the silanol of the silane agent occurred during the fabrication stage of the composites. Scanning electron microscopy (SEM) showed that the fracture surface of the samples differ after the incorporation of the treated hybrid filler.

Bioplastics from melt-mixing of cassava flour, rice flour and their blends with compositions of between 0/100 and 100/0 %wt were successfully obtained using twin-screw extrusion and compression molding processes. The influence of blend composition on the bioplastic's properties was studied. It was found that the flour blends were uniformly mixed. The tensile properties and dynamic properties of the flour bioplastics were examined. The tensile strength and storage modulus of compression molded bioplastics based on rice flour was greater than those of the cassava flour, but their flexibility was lower. The tensile strength and storage modulus of the flour blend bioplastics increased with increasing rice flour content. The flour bioplastics showed two glass transitions, one corresponding to glycerol rich phase and the other corresponding to plasticized starch. For plasticized flour blends, the glass transitions were not affected by the blend composition. The improvement in the mechanical properties of the bioplastics produced from the cassava/rice flour blend could be explained by an increase in the crystallinity level resulting from the higher concentration of rice flour. Using flour blends derived from cassava and rice flours, the bioplastics developed in this study offer a greater performance while maintaining environmental compatibility and sustainability, which allows for a substitution of tradition bioplastics from cassava starch.

A surrogate-based warpage optimization for injection molding is proposed in this study. The optimization process aims at minimizing the warpage of the injection molding parts in which process parameters, i.e., the mold temperature, melt temperature, injection time, packing time, packing pressure, and cooling time are the design variables. The warpage values are reduced by optimizing the process parameters. A new optimization iteration scheme based on artificial neural network (ANN) combined weighted expected improvement (WEI) is employed to speed up the optimization process and to ensure very rapid and steady convergence. The ANN is used to build an surrogate warpage function for the process parameters, replacing the expensive simulation analysis in the optimization iterations. The adaptive process is executed by the WEI function, which is an infilling sampling criterion. Although the design of experiment (DOE) size is small, this criterion can precisely balance the local and global search and tend to find the global optimal design. As examples, a TV cover and a scanner are investigated. The results show that the proposed approach can effectively reduce the warpage of the injection molding parts.

A set of commercial polyethylenes (three LDPE and three LLDPE) was rheological characterized and processed in a laboratory double bubble extrusion line with the purpose of investigating: i) whether their relative processability could be predicted in the laboratory and ii) the effect of operating and machine variables on processability. Oscillatory shear and extensional measurements were able to differentiate the various materials, who also behaved quite differently upon processing. Those with a stronger shear thinning behaviour, higher elasticity and higher melt strength were the most suited to the process. Bubble stability and thickness uniformity were assumed as the main requirements for processability. The former was estimated by monitoring the time required to stabilize the bubble and examining any variation/oscillation in size/shape. Bubble stability depends on the interaction between various parameters, the most relevant being those related with the film cooling stage, namely the axial position of the air rings, the air flow rate and air velocity. The study was preceded by an assessment of the performance of the re-heating oven and die/calibration/centring, as these parameters could also narrow the practical operating window.

The purpose of the paper is to study the influence of molecular architecture of poly(ethylene terephthalate) (PET) on its ability to be processed by stretch-blow molding, which is not well documented in the literature. To evaluate this process ability, it proposes an original strategy combining laboratory analyses and experiments on a prototype machine. PET copolymers were prepared from three types of comonomers: diethylene glycol (DEG), isophthalic acid (IPA) and trimethylolpropane (TMP). It is first shown, through laboratory experiments, that the nature of the polymer in terms of chain constitution (copolymerization), chain length (intrinsic viscosity) and purity (catalytic residues) greatly affects many properties: melt crystallization, thermal properties, polymer rigidity and drawability. These different properties obviously induce very different behaviours at the different steps of the stretch-blow molding process: injection-molding of the preform (quenchability), heating (IR absorption), stretch-blow (rigidity and drawability). The stretch-blow step has been simulated on a prototype apparatus designed in our laboratory. It has been shown that free blowing can be used to characterize the process ability of the polymer. A statistical analysis has confirmed the great differences between the materials investigated and pointed out the complexity of the material response during blowing.

The aim of this work was to develop polyamide-6/ organic-modified montmorillonite (omMMT) nanocomposites for the production of hollow parts by rotational molding. Particular emphasis was placed on the mechanical and flame retardancy properties needed for the fabrication of vessels for flammable liquids. The morphology of the melt compounded nanocomposites, produced by melt compounding, was investigated by X-ray diffraction measurements (WAXD), and Transmission Electron Microscopy (TEM) showed an exfoliated structure. Rheological measurements were used in order to verify whether the viscosity of materials was adequate for rotational molding. While thermomechanical analysis has revealed that neat PA6 and its nanocomposites were not suitable for rotational molding, due to the very low thermal stability of the polymer, the addition of a thermal stabilizer, shifted the onset of degradation to higher temperatures, thus widening the processing window of both PA6 and PA6 nanocomposites. Large-scale vessel prototypes were obtained by rotational molding of thermo-stabilized PA6 and its nanocomposites, and samples extracted from the rotomolded parts were characterized with respect to physical and mechanical properties. It was found that the PA6 nanocomposites exhibited significant improvements at cone calorimeter tests in comparison with neat PA6.

Nanocomposites based on high density polyethylene (HDPE)/linear low density polyethylene (LLDPE) blend were prepared by melt compounding in a torque rheometer using an organoclay (montmorillonite) as nano-filler and maleic anhydride-grafted linear low density polyethylene (LLDPE-g-MA) as compatibilizer. The effects of five blending protocols on microstructure, crystallinity and rheological properties of the prepared samples were examined. The steady state rheological properties showed that the addition of nanoclay to the HDPE/LLDPE blend increased its shear viscosity at low shear rates changing the behavior of the HDPE/LLDPE matrix to a more pronounced shear thinning behavior. The blending sequence (LLDPE/LLDPE-g-MA/20A)/HDPE (where LLDPE and LLDPE-g-MA were first mixed with organoclay and then this system was later blended with HDPE) showed a lower slope of the log versus log curve and these results can be an indicative that the interactions between the matrix and the organoclay are stronger. The organoclay interlayer spacing and the crystallinity of the polymer domains were also influenced by the blending sequence. The crystallinity was calculated through the mathematical deconvolution of the peaks observed in the WAXD profiles. Overall, the crystallization of HDPE in the blends was hardly influenced by the presence of LLDPE. The blending sequence (LLDPE/LLDPE-g-MA/20A)/HDPE showed lower cristallinity when compared to others blending sequences. On the other hand, it was observed an increase in the organoclay interlayer spacing of this nanocomposite because the intercalation and/or exfoliation process occurs preferentially in the amorphous phase.

The mechanical properties of conjugated-spun and laser drawn poly(ethylene terephthalate) (PET) fibers were investigated. The as-spun fibers used for the laser drawing were made by conjugated melt spinning with the copolymer of p-hydroxybenzoicacid and 2-hydroxy-6-naphthoicacid or polystyrene. The PET fibers prepared by conjugated spinning could be laser drawn to higher draw ratios under lower drawing stresses. The drawn fiber could be re-drawn up to a higher total draw ratio. Thus, a PET fiber having a tensile strength of 1.14 N/tex could be produced.

In the present study, blown films of h-LLDPE, LDPE, and their blends were produced using a twin screw extruder. The tear properties of all films were determined in the machine direction (MD) and the transverse direction (TD). On one hand, similar values of the MD tear-resistance for the two virgin polymers, h-LLDPE and LDPE, were measured to be 100 and 120 kN/m, respectively. On the other hand, the TD tear-resistance value of h-LLDPE was 180 kN/m, four times higher than that of LDPE, 45 kN/m. It was observed that small additions of LDPE (5 to 20 wt.%) to h-LLDPE produced blends with better TD tear-resistance films, 400 kN/m. The main reason for this large increase in tear-resistance was attributed to the morphological changes induced by the addition of the LDPE polymer, as shown by SEM, FTIR, and birefringence techniques.