Effect of processing history on the morphology and properties of polypropylene/thermotropic liquid crystalline polymer blends

Preparation, morphology, and mechanical properties were studied of blends of a thermotropic liquid crystalline polymer (TLCP) with two different grades of polypropylene, one with and one without overlap in processing temperatures, using two different blending methods. The highly viscous grade (PP-1) was of sufficient thermal stability to be blended with the TLCP (Vectra A950) in a single-screw extruder with an Egan mixing section on the screw. The low viscous grade (PP-2) could not be processed at the same temperature as the TLCP because of degradation. Its blends were, therefore, prepared by a special coextrusion technique, i.e. feeding the two components from two separate extruders to a Ross static mixer. In both methods drawing of the extrudate is necessary to obtain satisfactory mechanical properties. The PP-1/TLCP blends had to be extruded twice in order to obtain proper mixing. The morphology of these blends ranges from a pronounced skin-core morphology at low extrudate draw ratio (DR = 3) to a high-aspect ratio fiber/matrix morphology at high draw ratio (DR = 15). The morphology of the PP-2/TLCP blends was always a high-aspect ratio fiber/matrix morphology even at low draw ratios. The TLCP fibers were generated in this coextrusion process under conditions where the viscosity of the dispersed phase was higher than the viscosity of the matrix. Breakup experiments demonstrate that fibers of a thickness of approximately 1 μm disintegrate into droplets within a few seconds at temperatures above the melting point of the TLCP. This is probably the cause of the skin-core morphology obtained with single-screw extrusion. Tensile modulus and strength of all blends increase with extrudate draw ratio. The deformation of the TLCP phase in the drawn blends is less than affine, probably because of slip between the phases. The moduli of the PP-1/TLCP blends as a function of the draw ratio can be described well by a modified Halpin-Tsai equation taking into account both changes in aspect ratio and molecular orientation of the TLCP fibers. The level of reinforcement in the PP-2/TLCP blends is lower than expected, probably because of the low temperature of drawing. This demonstrates a limitation of the coextrusion process: blending at temperatures that are too low reduces mechanical properties.     

The effect of viscosity ratio on the phase inversion of polyamide 66/polypropylene blends

The rheological properties of the blend components are an important parameter in the formation of a blend morphology. The effect of viscosity ratio on the morphology of polyamide 66/polypropylene blends was studied, with primary attention to the phase-inversion behavior and the average particle size of the dispersed phase. The relationship between the mechanical properties and the phase-inversion composition was investigated as well. Noncompatibilized and compatibilized blends having five different viscosity ratios were prepared by twin-screw extrusion. Maleic anhydride-grafted polypropylene was used as the compatibilizer to increase the adhesion between the two polymers and to stabilize the blend morphology. Investigation of the morphology of the blends by microscopy (SEM and TEM) showed that the smaller the viscosity ration (η_PA/η_PP) the smaller was the polyamide 66 concentration at which the phase inversion took place and that polyamide 66 became the continuous phase. The results are in accord with the model of Jordhamo. The compatibilizer induced a sharp reduction of particle size, but did not have a major effect on the phaseinversion point. The tensile and impact properties of the compatibilized blends were found to correlate with the phase inversion. An improvement in the mechanical properties was observed when polyamide 66 provided the matrix phase. © 1994 John Wiley & Sons, Inc.     

The phase inversion and morphology of nylon 1010/polypropylene blends

Noncompatibilized and compatibilized blends of nylon 1010/PP blends having five different viscosity ratios were prepared by melt extrusion. Glycidyl methacrylate-grafted-polypro-pylene (PP-g-GMA) was used as the compatibilizer to enbance the adhesion between the two polymers and to stabilize the blend morphology. The effect of the viscosity ratio on the morphology of nylon 1010/polypropylene blends was investigated, with primary attention to the phase-inversion behavior and the average particle size of the dispersed phase. The relationship between the mechanical properties and the phase-inversion composition was investigated as well. Investigation of the morphology of the blends by microscopy indicated that the smaller the viscosity ratio (ηpp/ηpa) the smaller was the polypropylene concentration at which the phase inversion took place and polypropylene became the continuous phase. The compatibilizer induced a sharp reduction of particle size, but did not have a major effect on the phase-inversion point. An improvement in the mechanical properties was found when nylon 1010 provided the matrix phase. © 1996 John Wiley & Sons, Inc.     

Polymer blend de‐mixing and morphology development of immiscible polymer blends during tube flow

This work is an investigation of morphology and de‐mixing of polymer blends during melt flow through a tube. Morphology is the relative size, shape and location of each distinguishable phase present in a polymer blend. De‐mixing is the shear‐induced migration of different types of polymers away from each other during the flow. The ability to tailor de‐mixing during extrusion can potentially result in a new family of plastics waste recycling processes with mixed waste entering an extruder and separate streams of different polymer types leaving it. Also, control of morphology development can lead to the formation of layered structures without the need for two or more extruders and co‐extrusion. This work is directed at elucidating morphology development and de‐mixing of polymer blends in the most simple process design: melt flow through a tube. Shear‐induced migration was quantitatively shown in various polyethylene‐polypropylene, polypropylene‐nylon 6 and polyethylene‐nylon 6 blends. The migration observed was in accord with the hypothesis that the system tends to minimize its rate of energy dissipation for a fixed flow rate. The ratio of the viscosity of the dispersed phased to that of the continuous phase greatly influenced the morphology of polypropylene‐nylon 6 and polyethylenenylon 6 blends: a droplet‐dispersed phase structure occurred at a high viscosity ratio, whereas a multi‐layer structure resulted at viscosity ratios near unity. Shear‐induced deformation and coalescence contributed to formation of the multi‐layer structure.     

Morphology evolution in PS/LDPE blends in a twin screw extruder: Effects of compatibilizer

In order to understand the mixing in polymer extrusion, the morphology of PS/LDPE blends compatibilized with SEBS was simulated based on the Lee and Park model. Experiments were performed in a co-rotating twin screw extruder and a Haake mixer, and the morphology of the compatibilized blends of various compositions was compared with the non-compatibilized ones. The size of the dispersed phase of the compatibilized blend was smaller than the non-compatibilized one, and the blend of the PE matrix had a smaller size in the dispersed phase than the non-compatibilized one. Simulation results were agreed well with experiments, and the Lee and Park model could be applied in the extrusion analysis of compatibilized polymer blends.     

Morphology development of in situ compatibilized semicrystalline polymer blends in a co-rotating twin-screw extruder

This paper concerns the morphology development of in situ compatibilized semicrystalline polymer blends in a co-rotating, intermeshing twin-screw extruder, using polypropylene (PP) and polyamide 6 (PA-6) blends as model systems. The morphology of in situ compatibilized blends develops much faster that of mechanical ones. The size of the dispersed phase (PA-6) undergoes a 10⁴ fold reduction from a few millimeters to sub-micron during its phase transition from solid pellets to a viscoelastic fluid. The final morphology is reached as soon as the phase transition is completed, which usually requires only a small fraction of the screw length in a co-rotating twin screw extruder. Screw profiles and processing conditions (screw speed, throughput and barrel temperature) control the PA-6's melting location and/or rate, but do not have significant impact on the ultimate morphology and mechanical properties of in situ compatibilized blends. The finding that morphology of PP/PA-6 reactive blend develops rapidly makes it possible to produce compatibilized PP/PA-6 blends by the so-called one-step reactive extrusion. It integrates the traditionally separated free radical grafting of maleic anhydride onto PP and the compatibilization of PP/PA-6 into a single extrusion step.     

Rheology and impact characteristics of compatibilized polypropylene-liquid crystalline polymer composites

Polypropylene-liquid crystalline polymer (PP/LCP) and maleic anhydride compatibilized PP/LCP blends were prepared using the extrusion technique followed by injection molding. The LCP employed was Vectra A950 which consists of 25 mol % of 2,6-hydroxynaphthoic acid and 75 mol % of p-hydroxybenzoic acid. The rheology, morphology, and impact behavior of compatibilized PP/LCP blends were investigated. The rheological measurements showed that the viscosity of LCP is significantly higher than that of the PP at 280°C. This implied that the viscosity ratio of the LCP to the polymer matrix is much larger than unity. Scanning electron microscopy (SEM) observations revealed that the LCP domains are dispersed mainly into elongated ellipsoids in the PP/LCP blends. However, fine fibrils with large aspect ratios were formed in the compatibilized PP/LCP blends containing LCP content ≥ 10 wt %. The development of fine fibrillar morphology in the compatibilized PP/LCP blends had a large influence on the mechanical properties. The Izod impact strength of the PP/LCP blends showed little dependence on the LCP concentrations. On the other hand, the impact strength of the compatibilized PP/LCP blends was dependent on the LCP concentrations. The correlation between the LCP fibrillar morphology and spherulitic structure with the impact properties of the compatibilized PP/LCP blends is discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 521–530, 1998     

Factors influencing microstructure formation in polyblends containing liquid crystalline polymers

Four isotropic polymers, poly(butylene terephthalate) (PBT), polycarbonate (PC), polyethersulfone (PES) and polysulfone (PSU), were blended by extrusion with a thermotropic liquid crystalline polymer (LCP) at different temperatures. The morphology of extrudates was observed by means of scanning electron microscopy and the intrinsic aspect ratio of LCP fibrils and particles separated from matrix resin was measured with an image analysis. Special attention was paid to the LCP fibrillation in these four matrices in a wide temperature range from 270 to 360°C and the internal relations among the effects of processing parameters, such as viscosity ratio, extrusion temperature, and LCP concentration. The results show that the viscosity ratio of the dispersed LCP phase to the continuous phase is a decisive factor determining the formation of LCP fibrils, but its effect closely relates with the LCP content. In the range of viscosity ratios investigated, 0.004 to 6.9, and lower LCP content of 10%, significant fibrillation took place only at viscosity ratios below 0.01. It is predicted that the upper limit of the viscosity ratio for LCP fibrillation will increase with increasing LCP content. A comparison of the morphologies of LCP/PES blends with different LCP concentrations reveals that the LCP phase becomes continuous at a concentration of less than 50%, and high LCP content does not always favor the formation of long and uniform LCP fibrils. The extrusion temperature has a marked effect on the size of the minor LCP domains. For fibril forming systems, the percentage of LCP fibrils with larger aspect ratios increases with increasing extrusion temperatures. All these results are explained by the combined role of deformation and coalescence of the LCP disperesed phase in the blend.     

Rheology and sheet extrusion of Novatein thermoplastic protein/polybutylene adipate-co-terephthalate blends

Novatein is a thermoplastic polymer made from blood meal proteins, but it has rheological properties very different from commodity thermoplastics. Capillary rheometry revealed an apparent time dependent shear viscosity for Novatein, evident from a decreasing pressure drop over time, measured at constant shear rate. However, blending with polybutylene adipate-co-terephthalate (PBAT) reduced the time dependence for uncompatibilized blends and virtually eliminated time dependence for compatibilized blends containing 30 wt % PBAT. Novatein's extensional viscosity is three orders of magnitude more than its shear viscosity and explained the difficulty in sheet extrusion. In contrast, 30% compatibilized blends had an extensional viscosity similar to neat PBAT and was also the only blend that could be successfully sheet extruded. Although uncompatibilized blends at the same or lower PBAT content also had a lower extensional viscosity, they could not be sheet extruded and the difference was the 30% compatibilized blends had a fine PBAT phase structure (co-continuous in this case), which was sufficiently adhered to the Novatein phase. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47977.     

Morphology of injection molded modified poly(phenylene oxide)/polyamide‐6 blends

The morphology of injection molded poly(phenylene oxide)/polyamide‐6 blends was investigated. A distinct skin layer, subskin layer, and core region were found across the part thickness, and the morphology of the skin layer was clearly observed. The shape and size of the dispersed phase depended on the position across the part thickness and the viscosity ratio of the component polymers. For low viscosity ratios, small and large particles coexisted in the subskin layer, implying that both coalescence and breakup of the dispersed phase occurred in that layer. For high viscosity ratios, an intermediate zone, in which little deformation of the dispersed phase occurred, was found between the skin layer and the subskin layer. These findings are expected to help foster understanding of the mechanism of morphology evolution during the filling and cooling stages of the injection molding process.     

Reinforcing performance of recycled PET microfibrils in comparison with liquid crystalline polymer for polypropylene based composite fibers

Recycled polyethylene terephthalate (rPET) used as an alternative reinforcing additive for polypropylene (PP) based composite fibers, compared with liquid crystalline polymer (LCP), was investigated. Both PP-LCP and PP-rPET composites were prepared as fiber using hot drawing process. The effects of draw ratios and compatibilizer dosages on morphology in relation to tensile properties of both types of the composite systems were studied. The variation of draw ratios resulted in much change of stress–strain behavior in compatibilized rPET composite system owing to the obvious difference in morphological change of rPET dispersed phase upon drawing. Tensile strength and extensibility of both composites system were significantly improved with compatibilizer loading. The tensile strength of compatibilized rPET-composite fibers was higher than that of the compatibilized LCP system. The obtained results demonstrated the high potential of rPET as a well-defined reinforcing material for PP based composite fiber under the improved interfacial adhesion promoted by compatibilizer.     

Mechanical and fracture characterization of 50:50 HDPE/PET blends presenting different phase morphologies

Uncompatibilized and compatibilized blends of poly(ethylene terephthalate) (PET) and high‐density polyethylene (HDPE) (50:50 PET/HDPE) have been prepared and characterized. A commercial grade of ethylene/methacrylic acid copolymer was used as compatibilizing agent and added to the blends in two different proportions, 1% and 7%. Compounded blends were processed following three different procedures: compression molding, extrusion, and extrusion followed by annealing. In every case, there is evidence that suggests that HDPE constitutes the matrix and PET is the dispersed phase. The PET phase shape was related to the processing procedure of the blends. PET adopted a globular morphology in the compression molded samples but it took the form of microfibers (microfibrillar‐like reinforced composites) in extruded samples, which were flattened during the postextrusion annealing process. According to the results obtained in tensile and fracture tests, extruded blends having 7% of ethylene/methacrylic acid copolymer appeared as the optimum combination of processing method and compatibilizer content. POLYM. ENG. Sci., 45:354–363, 2005. © 2005 Society of Plastics Engineers     

Effect of LCP and rPET as reinforcing materials on rheology,morphology, and thermal properties of in situ microfibrillar‐reinforced elastomer composites

Microfibrillar‐reinforced elastomer composites based on two dispersed phases, liquid crystalline polymer (LCP) and recycled poly(ethylene terephthalate)(rPET), and styrene‐(ethylene butylene)‐styrene (SEBS) were prepared using extrusion process. The rheological behavior, morphology, and thermal stability of SEBS/LCP and SEBS/rPET blends containing various dispersed phase contents were investigated. All blends and LCP exhibited shear thinning behavior, whereas Newtonian fluid behavior was observed for rPET. The incorporation of both LCP and rPET into SEBS significantly improved the processability by bringing down the melt viscosity of the blend system. The fibrillation of LCP dispersed phase was clearly observed in as‐extruded strand with addition of LCP up to 20–30 wt %. Although the viscosity ratio of SEBS/rPET system is very low (0.03), rPET domains mostly appeared as droplets in as‐extruded strand. The results obtained from thermogravimetric analysis suggested that an addition of LCP and rPET into the elastomer matrix improved the thermal resistance significantly in air but not in nitrogen. The simultaneous DSC profiles revealed that the thermal degradation of all polymers examined were endothermic and exothermic in nitrogen and in air, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Relationship between interfacial tension and dispersed‐phase particle size in polymer blends. I. PP/EPDM

Simple blends with different viscosity ratios of the components as well as compatibilized blends varying both in type and content of compatibilizers were used to study the relation between interfacial tension and dispersed‐phase particle size for PP/EPDM (80/20 wt %) blends in this work. Four compatibilizing systems, poly(ethylene‐co‐methacrylic acid) ionomers (EMA–I), dicumyl peroxide (DCP), DCP combined with EMA–I, and DCP in combination with trimethylol propane triacrylate (TMPTMA), were used. For blends prepared in an internal mixer, a power law relation was found between capillary number and torque ratio of the blends' components. This relation was used to estimate the interfacial tension for the compatibilized blends. The relation between steady‐state torque of the blends as a measure of viscosity and the estimated values of interfacial tension were also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3148–3159, 2002     

Relationship between interfacial tension and dispersed‐phase particle size in polymer blends. II. PP/PA6

Simple blends with different viscosity ratios of the components as well as compatibilized blends varying both in type and content of the compatibilizers were used to study the relation between the interfacial tension and the dispersed‐phase particle size for PP/PA6 (80/20 wt %) blends in this work. Four compatibilizing systems including poly(ethylene‐co‐methacrylic acid) ionomers, a maleic anhydride‐grafted propylene copolymer, maleic anhydride‐grafted polypropylene, and a maleic anhydride‐grafted styrene ethylene butylene copolymer were used. For blends prepared in an internal mixer, a power‐law relation was found between the capillary number and the torque ratio of the blends' components. This relation was used to estimate the interfacial tension for the compatibilized blends. The relation between the steady‐state torque of the blends as a measure of viscosity and the estimated values of interfacial tension were also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 54–63, 2003     

Thermotropic liquid crystalline polymer (Rodrun LC5000)/polypropylene in situ composite films: rheology, morphology, molecular orientation and tensile properties

In situ composite films were prepared by a two-step method. First, polypropylene and thermotropic liquid crystalline polymer (TLCP), Rodrun LC5000 (80 mol% p-hydroxy benzoic acid (HBA)/20 mol% polyethylene terephthalate (PET)), were melt blended in a twin-screw extruder and then fabricated by extrusion through a mini-extruder as cast film. Rheological behavior of the blends, morphology of the extruded strands and films, and tensile properties of the in situ composite films were investigated. Rheological behavior of the blends at 295 °C studied using a plate-and-plate rheometer revealed a substantial reduction of the complex viscosity with increasing TLCP content, and all specimens exhibited shear thinning behavior. Over the angular frequency range of 0.6-200 rad/s, the viscosity ratio (dispersed phase to matrix phase) was found to be very low, in the range of 0.03-0.07. Morphologies of the fracture surfaces of the blend extrudates and the film surfaces etched in permanganic solution were investigated by scanning electron microscope (SEM). The TLCP droplets in the extruded strands were seen with a progressive deformation into fibrillar structure when TLCP content was increased up to 30 wt%. In the extruded films, TLCP fibrils with increasing aspect ratio (length to width) were observed with increasing TLCP concentration. Orientation functions of each component were determined by X-ray diffraction using a novel separation technique. It was observed that the Young's modulus in machine direction of the extruded film was greatly improved with increasing TLCP loading, due to the increase in fiber aspect ratio and also molecular orientation.     

Morphology development of PC/PE blends during compounding in a twin-screw extruder

The morphological development of a polycarbonate/polyethylene (PC/PE) blend in a twin-screw extruder was studied using a scanning electron microscope (SEM). The effects of extrusion temperature, viscosity ratio (the ratio of the viscosity of the dispersed phase to that of the matrix), and the screw configuration on the morphology of the PC/PE blend during the extrusion were discussed in detail. It was found that the morphology of the dispersed particles and the interfacial adhesion between the dispersed phase and matrix were both influenced by the extrusion temperature. The dispersed phase had a spheroidal shape and a small size during the high temperature processing, and an irregular shape and a large size when it was processed at low temperature. The PC phase with a lower viscosity was easier to disperse and also to coalesce. Therefore, the deformation of the low-viscosity dispersed phase during the processing was more intense than that of the high-viscosity dispersed phase. By comparing the effects of the different screw configurations on the morphology development of the PC/PE blend, it was found that the melting and breaking up of the dispersed phase were mainly affected in the initial blending stages by the number of the kneading blocks. While a kneading block with a 90 degree staggering angle was used, the size of the dispersed particles decreased and the long fibers were shortened, the large particles were drawn by the additional kneading zone. Finally, all of these structures were completely changed to the short fibers. POLYM. ENG. SCI., 47:14–25, 2007. © 2006 Society of Plastics Engineers     

Effect of the dispersed phase fraction on particle size in blends with high viscosity ratio

It has been reported that for polymer blends with high viscosity ratio (>1), the size of the dispersed particles decreases with increasing volume fraction of the dispersed phase. In order to explain this effect, an equation was derived for the affine deformation of an imaginary plane of the dispersed phase in stratified two‐phase steady, simple, shear flow. The model predicts that for viscosity ratio >1, the deformation rate increases with volume fraction of the dispersed phase, and the shear stress also increases, leading to an increase of the breakup time. Therefore, the total deformation of the dispersed phase, before breakup, increases with increase of volume fraction, resulting in a decrease of the size of the dispersed phase particles. Accordingly, one can expect that in industrial mixers, the particle size of the blends should decrease as the volume fraction increases, if coalescence is suppressed. Experiments were carried out in a Haake batch mixer, using polyethylene/polyamide‐6 blends compatibilized by adding maleic anhydride grafted polyethylene. Particle size decreased up to 20 wt% polyamide‐6, at 100, 150, and 200 RPM, and increased between 20 and 30 wt%. The decrease of the particle size is mainly due to increased deformation of the dispersed phase. The increase of the particle size above 20 wt% is due to coalescence at high fractions.     

Influence of post‐extrusion parameters on the final morphology of polystyrene/high density polyethylene blends

The deformation of the dispersed phase in polystyrene/high density polyethylene (PS/HDPE) blends produced by ribbon extrusion was studied numerically and experimentally. A mathematical model for the deformation of the dispersed phase in ribbon extrusion processing of polymer blends was developed assuming uniaxial deformation of the ribbon and the equilibrium shapes of the dispersed particles with a pressure balance over a drop. Simulated morphologies as function of the post‐extrusion parameters were obtained and compared with experiments. The analysis of the ribbon extrusion process showed that parameters such as draw ratio (DR) and ribbon‐water contact length (X) significantly influence the ribbon dimensions, the extensional stress, and the stretching force. The results also showed that deformation and coalescence of the dispersed phase in the ribbon extrusion processing of polymer blends increase at higher DR and/or lower X values. The comparison between the model and the experimental morphologies of PS/HDPE produced a good agreement.     

Correlation of viscosity ratio,morphology, and mechanical properties of polyamide 12/natural rubber blends via reactive compatibilization

Natural rubber (NR)-modified polyamide 12 (Nylon12/NR) was produced by melt blending Nylon12 and NR in the presence of polystyrene/maleated natural rubber (PS/MNR) copolymer as a reactive compatibilizer. The influence of compatibilizer loading on viscosity ratio, morphology, and mechanical properties of the blends was investigated. As a consequence of the reactive blend between Nylon12 and maleated NR in PS/MNR, the formation of amide and succinimide linkages was set at rubber-Nylon12 interfaces. Thus the dispersion of rubber particles was improved, and the particle coalescence was prevented so that the fine morphology with good interfacial adhesion was stabilized. This also resulted to enhance the blend viscosity and to lower viscosity ratio. The data revealed strong correlation between low viscosity ratio and fine spherical morphology of the compatibilized blends. An optimum PS/MNR compatibilizer content was at 7 phr to produce good dispersion of small rubber domains (size ≤0.3 μm) in Nylon12 matrix. Thermal properties by DSC revealed that crystallization temperature of Nylon12 was lowered by the presence of NR and crystallinity of Nylon12 was slightly affected by the PS/MNR content. An enhancement of mechanical properties, especially the impact energy was observed without suffering the tensile and flexural properties. Compared to the neat Nylon12, the compatibilized blends showed an increase in impact energy by a factor of 5. This large enhancement is successfully interpreted in term of the toughening effect by rubber phase of suitable dispersed size and the interparticle distance.