Investigation into the morphology and mechanical properties of melt‐drawn filaments from uncompatibilized blends of polystyrene and high‐density polyethylene

Uncompatibilized immiscible blends of polystyrene (PS) and high‐density polyethylene (HDPE) were melt‐processed in a single‐screw extruder fitted with a fine screen mesh and capillary die and were further drawn into filaments to produce near‐nanoscale immiscible domains. The resultant morphologies and mechanical properties were studied for these structures in which load transfer is achieved solely by mechanical linkages between blend domains. The morphology of the blends revealed co‐continuity approximately in the range of 45–47 volume percent PS. The development of a three‐dimensional co‐continuous network in 45 vol% PS, as revealed by morphology observations, was also related to a decrease in extruder output rate in this region, an indicator of the melt interaction of the two phases as co‐continuity is achieved. Image analysis revealed submicron fibrillar structures near the phase inversion composition where domain sizes ranged from 6–220 nm with an average domain size of 90 nm. Tensile modulus increased with increasing PS content (E = 2.7 GPa at 47% PS) over the entire blend range with values greater than the rule of mixtures up to 50% PS. Strain to failure did not seem to be influenced by co‐continuous morphologies and the fine dispersion of PS domains appears to constrain the fundamentally high strain of HDPE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1616–1625, 2007     

Phase continuity detection and phase inversion phenomena in immiscible polypropylene/polystyrene blends with different viscosity ratios

Blends of polypropylene (PP) and polystyrene (PS) were prepared in a twin-screw extruder and studied in a wide range of compositions. Phase continuity was first determined using selective solvent extraction. Subsequently, dynamic stress rheometry and dynamic mechanical analysis were used to detect the co-continuity and phase inversion compositions in the melt and the solid states. It appears that the phase inversion occurs in a domain rather than at a single point. The evaluation of the storage modulus of PP/PS blends in the melt at a constant low frequency gives information about the co-continuity, as far as the onset of co-continuity and phase inversion composition of the PS phase are concerned. The evaluation of the storage modulus and mechanical loss factor at a constant high temperature, or the glass transition temperature intensity allowed to precisely detect the phase inversion composition. The fractionated or bulk crystallization behavior of the crystallizable PP phase in the PP/PS blends can also be used to identify the matrix/dispersed phase or co-continuous phase morphology. Several semi-empirical models using the dynamic viscoelastic properties of blend components have been applied to detect the phase inversion composition. An extensive data set presented, can also be used to guide future modeling.     

Cocontinuous morphologies in polystyrene/ethylene–vinyl acetate blends: The influence of the processing temperature

The influence of the compression‐molding temperature on the range of cocontinuity in polystyrene (PS)/ethylene–vinyl acetate (EVA) copolymer blends was studied. The blends presented a broad range of cocontinuity when compression‐molded at 160°C, and they became narrower when compression‐molded at higher temperatures. A coarsening effect was observed in PS/EVA (60:40 vol %) blends upon compression molding at higher temperature with an increase in the phase size of the cocontinuous structure. Concerning PS/EVA (40:60 vol %) blends, an increase in the mixing and molding temperatures resulted in a change from a cocontinuous morphology to a droplet–matrix morphology. This effect was observed by selective extraction experiments and scanning electron microscopy. The changes in the morphology with the molding conditions affected the storage modulus. An increase in the storage modulus in blends compression‐molded at 160°C was observed as a result of dual‐phase continuity. An EVA copolymer with a higher vinyl acetate content (28 wt %) and a higher melt‐flow index resulted in blends with a broader range of cocontinuity. This effect was more pronounced in blends with lower amounts of PS, that is, when EVA formed the matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 386–398, 2003     

Phase continuity and inversion in polymer blends and simultaneous interpenetrating networks

A semi-empirical expression for predicting phase continuity and inversion in polymer blends and simultaneous interpenetrating networks (SINs) was developed and examined experimentally. A rheological model based on the volume fraction, ?, and viscosity, η, led to the equation as the criteria for dual phase continuity for phases 1 and 2. This relation was evaluated for two systems: a castor oil polyester-urethane/polystyrene SIN, and a mechanical blend of polystyrene and polybutadiene. Literature data was also examined. A gradual phase inversion was found, with a region of dual phase continuity in between. While predictions of phase continuity were confirmed for the mechanical blends, they were not confirmed for the SIN system. This was probably due to rapid gelation at the point of phase inversion.     

Morphology of plastic/rubber blends

Blends of polypropylene (PP) and ethylene-propylene rubber (EPR) and blends of polystyrene (PS) and styrene-butadiene rubber (SBR) were prepared in a laboratory-scale internal mixer at various blend compositions and rotor rates. Blend morphology was studied by means of electron microscopy. For each blend pair under the given processing conditions, the phase inversion process occurred progressively with respect to the variation in blend composition; it is within this composition range of phase inversion that dual-phase continuity was observed. In addition, Characteristic torque values of blends were found to deviate negatively from a linear additivity rule; the composition range of maximum deviation from linear additivity corresponded approximately to the composition range where dual-phase continuity was observed. Sperling's predictive scheme was found to yield acceptable (although not completely satisfactory) estimates for compositions of dual-phase continuity in the present systems. It was also observed that partial cross-linking of SBR during the mechanical blending process, as suggested by the appearance of a cure peak in the torque curve and supported by infrared spectroscopic evidence, resulted in morphological features drastically different from those of the uncured blends.     

Effect of crystallization conditions on spherulitic texture and tensile properties of sPS/PPO blends

In the second study on melt‐miscible syndiotactic polystyrene (sPS) and poly(phenylene oxide) (PPO) blends, the effect of processing conditions on morphology, ultimate tensile properties, and the mode of fracture is reported. Bulk samples of the blends were molded and then crystallized from melt as well as from the quenched state at different temperatures. The spherulitic morphology of the melt‐crystallized blends, observed by scanning electron microscopy, revealed formation of complete, well‐developed spherulites whose texture increased in coarseness with increasing crystallization temperatures. In all the cold‐crystallized blends lamellar bundles formed a meshlike structure whose texture did not vary significantly with crystallization temperature. Depending on the crystallization temperature, 50/50 melt‐crystallized blends showed varying tensile properties and different modes of failure. In the samples with the largest amorphous domain size of 0.6 μm, the amorphous ellipsoids were cold drawn into fibrils during tensile loading and very high tensile strengths were recorded. The tensile properties for the other melt‐crystallized and all cold‐crystallized blends did not vary substantially with the changing crystallization temperature. The micrographs of the fractured surfaces of the melt‐crystallized blends suggested that, although intraspherulitic fracture occurred at low crystallization temperatures, interspherulitic fracture took place at high crystallization temperatures. The correlation of the morphology and mechanical properties suggests that melt‐miscible blends have good interfacial adhesion between phases and that, by varying composition and processing conditions, it might be possible to control amorphous domain sizes, which is critical in achieving better mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1984–1994, 2003     

Evidence for inversion of phase continuity during morphology development in polymer blending

When polymer blends are prepared from a mixture of pellets, the melting order of the components is important in determining the mechanism of morphology development. Here, we show that an inversion of phase continuity occurs during processing when a minor phase component has a softening or melting transition temperature which is lower than the softening temperature of the major phase component. Three 80:20 concentration systems were studied: polyarylate/rubber, polyamide 6,6/polystyrene, and polystyrene/ethylene propylene rubber. Initially, the minor phase was the continuous phase and coated the major phase in all three systems. As the major phase melted, a switching of phase continuity occurred, and in the final blend state, the major phase was the continuous phase. An increase in power input was required during the switching of the dispersed and matrix phases. The compounding process was studied through continuous video monitoring, torque-temperature analysis, and microscopy of quenched samples. A continuity inversion mechanism is proposed. It is found that the initial morphology of the blend consists of sheets of the major phase inside the minor phase. These sheets break up into irregularly shaped particles, which then coalesce around the minor phase. The effects of compatibilization (using reactive polymers or adding a premade diblock) on the rheology and morphology of the blend are also investigated. Interfacial reaction is seen to delay and intensify the inversion of phase continuity, whereas addition of premade diblock does not have any significant effect. The torque increases due to interaction of the major phase domains and due to reactive stabilization of the interface against coalescence, and the contributions of each to the torque can be decoupled.     

Mechanical Properties and Morphology of Nitrile Rubber Toughened Polystyrene

Mechanical properties and morphology of blends of polystyrene and finely powdered (uncrosslinked and crosslinked) nitrile rubber were studied with special reference to the effect of blend ratio. Blends were prepared by melt mixing polystyrene and nitrile rubber in an internal mixer at 180°C in the composition range of 0–20 wt% nitrile rubber. The tensile stress/strain properties and impact strength of the polystyrene/nitrile rubber blends were determined using injection molded test specimens. In comparison to the blends with uncrosslinked nitrile rubber, blends with crosslinked nitrile rubber showed higher tensile strength, elongation at break, Young's modulus, impact strength, flexural strength, and flexural modulus. The enhanced adhesion between the dispersed nitrile rubber phase and the polystyrene matrix results in an increase in mechanical properties. Scanning electron micrographs of the fractured surfaces confirm the enhancement in mechanical properties.     

Influence of diblock copolymer on the morphology and properties of polystyrene/poly(dimethylsiloxane) blends

Blends of polystyrene (PS) and poly(dimethylsiloxane) (PDMS), with and without diblock copolymers (PS‐b‐PDMS), were prepared by melt mixing. The melt rheology behavior of the blends was studied with a capillary rheometer. The morphology of the blends was examined with scanning electron microscopy. The miscibility of the blends was studied with differential scanning calorimetry. The morphology of PS/PDMS blends was modified by the addition of PS‐b‐PDMS copolymers and investigated as a function of the molar mass of the diblock copolymers, viscosity ratios and the processing conditions. As investigated, the observed morphology of the melt‐blended PS/PDMS pair unambiguously supported the interfacial activity of the diblock copolymers. When a few percent of the diblock copolymers blended together with the PS and PDMS homopolymers, the phase size was reduced and the phase dispersion was firmly stabilized against coalescence. The compatibilizing efficiency of the copolymers was strongly dependent on its molar mass. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2747–2757, 2004     

Phase morphology development and melt rheological behavior in nylon 6/polystyrene blends

Phase morphology development in immiscible blends of polystyrene (PS)/nylon 6 was investigated. The blends were prepared by melt blending in a twin‐screw extruder. The influence of the blend ratio, rotation speed of the rotors, and time of mixing on the phase morphology of the blends was carefully analyzed. The morphology of the samples was examined under a scanning electron microscope (SEM) and the SEM micrographs were quantitatively analyzed for domain‐size measurements. From the morphology studies, it is evident that the minor component, whether PS or nylon, forms the dispersed phase, whereas the major component forms the continuous phase. The 50/50 PS/nylon blend exhibits cocontinuous morphology. The continuity of the dispersed phase was estimated quantitatively based on the preferential solvent‐extraction technique, which suggested that both phases are almost continuous at a 50/50 blend composition. The effect of the rotor speed on the blend morphology was investigated. It was observed that the most significant breakdown occurred at an increasing rotor speed from 9 to 20 rpm and, thereafter, the domain size remained almost the same even when the rotor speed was increased. The studies on the influence of the mixing time on the blend morphology indicated that the major breakdown of the dispersed phase occurred at the early stages of mixing. The melt rheological behavior of the blend system was studied using a capillary rheometer. The effect of the blend ratio and the shear stress on the melt viscosity of the system was investigated. Melt viscosity decreased with increase in the shear stress, indicating pseudoplastic behavior. With increase of the weight fraction of PS, the melt viscosity of the system decreased. The negative deviation of the measured viscosity from the additivity rule indicated the immiscibility of the blends. The domain size versus the viscosity ratio showed a minimum value when the viscosities of the two phases were matched, in agreement with Wu's prediction. The morphology of the extrudates was analyzed by SEM. From these observations, it was noted that as the shear rate increased the particle size decreased considerably. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3537–3555, 2002     

Melt rheology of HDPE/EVA blends: The effects of blend ratio,compatibilization, and dynamic vulcanization

The melt rheological behavior of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends has been examined with reference to the effect of blend ratio, shear stress, and temperature. The HDPE/EVA blends exhibit pseudoplastic behavior, and the observed rheological behavior of the blends was correlated with the extrudate morphology. The experimental values of the viscosity were compared with the theoretical models. The effect of maleic‐ and phenolic‐modified PE compatibilizers on the viscosity of H₇₀ blend was analyzed and found that compatibilization did not significantly increase the viscosity. The effect of dynamic vulcanization and temperature on the viscosity was also analyzed. The activation energy of the system decreased with increase in EVA content in the system. The phase continuity and phase inversion points of the blends were theoretically predicted and compared with the experimental values. The melt flow index (MFI) values of the blends were also determined and found that the MFI values decreased with increase in EVA content in the system. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Blends of SBS triblock copolymer with poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polystyrene mixture

Blends of styrene–butadiene–styrene (SBS) or styrene–ethylene/1‐butene–styrene (SEBS) triblock copolymers with a commercial mixture of polystyrene (PS) and poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) were prepared in the melt at different temperatures according to the chemical kind of the copolymer. Although solution‐cast SBS/PPO and SBS/PS blends were already known in the literature, a general and systematic study of the miscibility of the PS/PPO blend with a styrene‐based triblock copolymer in the melt was still missing. The thermal and mechanical behavior of SBS/(PPO/PS) blends was investigated by means of DSC and dynamic thermomechanical analysis (DMTA). The results were then compared to analogous SEBS/(PPO/PS) blends, for which the presence of a saturated olefinic block allowed processing at higher temperatures (220°C instead of 180°C). All the blends were further characterized by SEM and TGA to tentatively relate the observed properties with the blends' morphology and degradation temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2698–2705, 2003     

成型加工中PC/PS微观结构的生成和演化

用扫描电镜(SEM)研究了聚碳酸酯／聚苯乙烯共混物在3种工业级熔融混合加工过程中形态结构的生成和演化。结果表明，共混物双相共连续形态结构的生成和演化强烈地依赖于共混物的组成和混合方法，相转变点的理论预测与试验值有一定的偏差，混合初期体系会形成片状、层叠状和纤维状的形态结构。但由于流动场和界面力的影响，这种片、层状结构不稳定，而纤维状结构易于在高剪切力的情况下出现。     

Investigation on particular morphology of immiscible polyamide 12/polystyrene blends

In this article, a particular phase morphology of immiscible polyamide 12/polystyrene (PA12/PS) blends prepared via in situ anionic ring-opening polymerization of Laurolactam (LL) in the presence of PS was investigated. SEM and FTIR were used to analyze the morphology of the blends. The results showed that PS is dispersed as small droplets in the continuous matrix of PA12 when PS content is less than 5 wt %. When the PS content is higher than 10 wt %, two particular phase morphologies appeared. First, dispersed PS-rich particles with the spherical inclusions of PA12 can be found when PS content is between 10 wt % and 15 wt %. Then, the phase inversion (the phase morphology of the PA12/PS blends changes from the PS dispersed/PA12 matrix to PA12 dispersed/PS matrix system) occurred when PS content is higher than 20 wt %, which is completely different from traditional polymer blends prepared by melt blending. The possible reason for the particular morphology development was illuminated through phase inversion mechanism. Furthermore, the stability of the phase morphologies of the PA12/PS blends was also investigated. SEM showed that the particular morphology is instability, and it will be changed upon annealing at 230°C for 30 min. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on polycarbonate/polystyrene/polycarbonate- graft-polystyrene blends. II. Compatibility and morphology of PC/PS/PC-g-PS blends

A radiation grafted copolymer of polycarbonate (PC) and polystyrene (PS) was used as a compatibilizer of PC/PS melt blends. The compatibility and morphology of PC/PS/PC-g-PS blends were studied by differential scanning calorimetry and scanning electron microscopy. As a consequence of the addition of PC-g-PS, the compatibility of PC/PS blends was improved; the dimensions of the dispersed phases and the interfacial tension between the two phases were reduced. Additionally, stabilization against gross segregation and interfacial adhesion of the blends were also improved by adding PC-g-PS as a compatibilizer. © 1998 SCI.     

Rayleigh散射研究部分相容聚苯乙烯／顺丁橡胶合金相结构

用光散射在线采集与分析方法完成了熔融混炼过程中非相容高分子共混物的形态结构分析。选择了聚苯乙烯／顺丁橡胶合金体系；使用了小角前向光散射和小角背散射(在线)技术，用Debye-Bueche光散射理论的结构参数如相关距离ac、平均弦长l、旋转半径Rg和积分不变量Q表征了共混物中分散相尺度和均匀性，讨论了合金体系的相容性。用扫描电子显微镜测定了共混物中分散相尺寸，并与光散射的结果进行了比较。ac、l和Rg的变化规律与显微镜的结果是一致的。用积分不变量Q研究了共混物的均匀性。     

Properties and morphology of polystyrene and linear low density polyethylene polyblend and polyalloy

A co-rotating twin screw extruder was employed in melt mixing and reactive extrusion of polystyrene/linear low density polyethylene (PS/PE) blends. Blends of PS/PE in the ratio of 9: 1 were prepared under different conditions of shear mixing and with different concentrations of dicurnlyl peroxide (DP) and triallyl isocyanurate (TALC) coupling agent. The Charpy impact strength of unnotched samples of melt blends was found to be lower than that of the polystyrene and was not affected much by the different conditions of melt mixing at different rates of extrusion, screw speeds, and screw configurations. In the case of reaction-extruded blends, the impact strength initially deteriorated with small addition of TAIC/DP, but improved with further increase in the level of TAIC/DP, exceeding that of polystyrene at an optimum concentration. With even further increase in TAIC/DP concentration, the impact strength again decreased. This was attributed to the different extents of coupling reactions of PE-TAIC-PE, PE-TAIC-PS, and PS-TAIC-PS with different levels of TAIC/DP. The interfacial adhesion of the incompatible PS-PE was postulated to be improved by the graft copolymers formed during reactive extrusion. This observation was supported by melt rheology, thermal characterization, molecular weight, and fracture surface morphology studies.     

Melt rheology and morphology of LLDPE/EVA blends: Effect of blend ratio,compatibilization, and dynamic crosslinking

The melt rheological properties of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were investigated with special reference to the effect of blend ratio, temperature, shear rate, compatibilization, and dynamic vulcanization. The melt viscosity of the blends determined with a capillary rheometer is found to decrease with an increase of shear rate, which is an indication of pseudoplastic behavior. The viscosity of the blend was found to be a nonadditive function of the viscosities of the component polymers. A negative deviation was observed because of the interlayer slip between the polar EVA and the nonpolar LLDPE phases. The melt viscosity of these blends decreases with the increased concentration of EVA. The morphology of the extrudate of the blends at different shear rates and blend ratios was studied and the size and distribution of the domains were examined by scanning electron microscopy. The morphology was found to depend on shear rate and blend ratio. Compatibilization of the blends with phenolic‐ and maleic‐modified LLDPE increased the melt viscosity at lower wt % of compatibilizer and then leveled off. Dynamic vulcanization is found to increase the melt viscosity at a lower concentration of DCP. The effect of temperature on melt viscosity of the blends was also studied. Finally, attempts were made to correlate the experimental data on melt viscosity and cocontinuity region with different theoretical models. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3210–3225, 2002     

Formation of phase structure and crystallization behavior in blends containing polystyrene–polyethylene block copolymers

The microphase separation structure in the molten state and the structure formation in crystallization from such ordered melt were investigated for the blends of polystyrene–polyethylene block copolymers (SE) with polystyrene homopolymer (PS) and polyethylene homopolymer (PE) and for the blends consisting of two kinds of SE with different copolymer compositions from each other, using synchrotron small-angle X-ray scattering techniques (SAXS). The copolymer compositions of SE block copolymers employed were 0.34, 0.58 and 0.73 wt. fraction of PE, and their melt morphologies were cylindrical, lamellar and lamellar, respectively. Macrophase separation or the morphology change in the melt occurred depending on the molecular weight and the blend composition, as reported so far. In crystallization from such macrophase-separated and microphase-separated melts, the melt morphology was completely kept for all the blends. Crystallization behavior was also investigated for the blends. The crystallization within the spherical and cylindrical domains surrounded by glassy PS was not observed for SE/PS blends. In the crystallization from the macrophase-separated melt, two exothermal peaks were observed in the DSC measurements, while a single peak was observed for other blends. For the blends with PS, the degree of crystallinity was depressed and the apparent activation energy of crystallization was high, compared to those for the corresponding neat SE. For SE/PE and SE/SE blends, those were changed depending on the blend composition.     

Efficient mixing of polymer blends of extreme viscosity ratio: Elimination of phase inversion via solid‐state shear pulverization

A novel, continuous process, solid‐state shear pulverization (S³P), efficiently mixes blends with different component viscosities. Melt mixing immiscible polymers or like polymers of different molecular weight often requires long processing times. With a batch, intensive melt mixer, a polyethylene (PE)/polystyrene (PS) blend with a viscosity ratio (low to high) of 0.019 required up to 35 min to undergo phase inversion. Phase inversion is associated with a morphological change in which the majority component, the high‐viscosity material in these blends, transforms from the dispersed to the matrix phase, and may be quantified by a change from low to high mixing torque. In contrast, such blends subjected to short‐residence‐time (～3 min) S³P yielded a morphology with a PS matrix and a PE dispersed phase with phase diameters ≤ 1 μm. Thus, S³P directly produces matrix and dispersed phases like those obtained after phase inversion during a melt‐mixing process. This assertion is supported by the similarity in the near‐plateaus in torque obtained in the melt mixer at short times with the pulverized blend and at long times with the non‐pulverized blend. The utility of S³P to overcome problems associated with melt mixing like polymers of extreme viscosity ratio is also shown.