Ultradrawing and crystallization of isotactic polystyrene and blends with atactic polystyrene

Pure isotactic polystyrene (iPS, M_w = 8.89 × 10⁴, M_w/M_n = 4.89) and its blends with an atactic polystyrene (aPS, M_w = 3.9 × 10⁵, M_w/M_n < 1.13) were subjected to draw by solid state coextrusion at 127°C within polyethylene. The content of amorphous iPS in these blends was varied from 100 to 24.4 wt %. The extent of draw-induced crystallization was found to depend on the draw ratio and on iPS concentration. The blend with 24.4% iPS was coextruded in two stages. The highest effective draw ratio (EDR) was 7.6 and 13.7 for one- and two-stage draw, respectively. The highest crystallinity of 33.2% was obtained for pure iPS at the maximum EDR of 7.6. Considerable crystallinity was induced in blends, requiring successively higher draw ratio to reach similar crystallinity with increased aPS content. The tensile modulus increased from 1.5 to 3.2 GPa, independent of iPS concentration. Thermal shrinkage results indicate that the elastic recovery of draw in the blends is near quantitative for an EDR < 8. For pure iPS, extrudate elastic recovery was dramatically altered by the draw-induced crystallinity.     

The supermolecular structure of isotactic polypropylene/atactic polystyrene blends

The supermolecular structure of binary isotactic polypropylene/atactic polystyrene (iPP/PS) injection‐molded blends were studied by wide‐angle X‐ray diffraction, differential scanning calorimetry, and optical microscopy. The combination of different methods gives a possibility of analysis of relation between the phase transformation in polypropylene and crystallization parameters. Effect of compatibilization of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) grafted with maleic anhydride (SEBS‐g‐MA) block copolymers in the iPP/PS blends on the structure, nucleation, crystal growth, solidification, and the phase morphology was analyzed. We found that the β‐crystallization tendency of polypropylene matrix can be enhanced by adding atactic polystyrene. However, the incorporation of SEBS‐g‐MA into iPP/PS blends resulted in an important decrease in β‐content of iPP. It is evident that the presence of compatibilizing agent caused a very significant reduction of the α‐spherulite growth rates and the crystal conversion as well as increases of half‐time crystallization in comparison with the iPP/PS systems. The relation between kinetic parameters of crystallization process and polymorphic structure of iPP in blend systems has been satisfactorily explained. Moreover, a strong effect of processing parameters on the β‐phase formation was observed. The results clearly show that at a higher temperature of mold and lower injection speed, the amount of β‐phase of iPP matrix slightly decreases. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Thermal and structural properties of blends of isotactic with atactic polystyrene

Blends of isotactic polystyrene (iPS) with non-crystallizable atactic polystyrene (aPS) were studied by differential scanning calorimetry and small angle X-ray scattering. The iPS/aPS blends, prepared by solution casting, were found to be miscible in the melt over the entire composition range. Both quenched amorphous and semicrystalline blends exhibit a single, composition-dependent glass transition temperature, depressed from that of either of the homopolymer components. Addition of aPS causes a decrease in crystallinity and in the rigid amorphous fraction, and suppression of the reorganization/recrystallization of iPS during thermal scanning: only one melting peak is observed for blends with larger aPS content. Formation and devitrification of the rigid amorphous fraction of iPS are also affected by aPS addition. The annealing peak, which is due to the relaxation of rigid amorphous fraction in parallel with melting of a tiny amount of crystals, is retarded with an increase of the composition of aPS, resulting in the slow devitrification of RAF in parallel with the melting of large amount of crystals. X-ray scattering shows that the long period in the iPS/aPS blends is greater than in the iPS homopolymer, and long period increases slightly as aPS content increases. Comparison of the volume fraction of phase 1 with the volume fraction crystallinity from DSC suggests that more and more amorphous phase is rejected outside the lamellar stacks as aPS content increases. The effect of aPS addition is to reduce the confinement of the amorphous phase chains. The cooperativity length, ξ_A, which is calculated from thermal analysis of the T_g region, increases with aPS addition. The interlamellar and extra-lamellar amorphous chains both contribute to the glass transition relaxation process.     

Miscibility, crystallization and morphologies of syndiotactic polystyrene blends with isotactic polystyrene and with atactic polystyrene

Two-component blends of differing polystyrene (PS), one syndiotactic (sPS) and the other isotactic (iPS) or atactic (aPS), were discussed. The phase behavior, crystallization and microstructure of binary polystyrene blends of sPS/iPS and sPS/aPS with a specific composition of 5/5 weight ratio were investigated using optical microscopy (OM), differential scanning calorimetry, wide-angle X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM). Based on the kinetics of enthalpy recovery, complete miscibility was found for the sPS/aPS blends where a single recovery peak was obtained, whereas phase separation was concluded for the sPS/iPS blends due to the presence of an additional recovery shoulder indicating the heterogeneity in the molten state. These findings were consistent with OM and SEM observations; sPS/iPS exhibits the dual interconnectivity of phase-separated phases resulting from spinodal decomposition.Both iPS and aPS have the same influence on the sPS crystal structure, i.e., dominant β-form sPS and mixed α-/β-form sPS obtained for melt-crystallization at high and low temperatures respectively, but imperfect α-form sPS developed when cold-crystallized at 175 °C. Co-crystallization of iPS and sPS into the common lattice was not observed regardless the thermal treatments, either cold or melt crystallization. Due to its slow process, crystallization of iPS was found to commence always after the completion of sPS crystallization in one-step crystallization kinetics. Segregation of rejected iPS component during sPS crystallization was extensively observed from TEM and SEM images which showed iPS pockets located between sPS lamellar stacks within spherulites, leading to the interfibrillar segregation, which was similar with that observed in the sPS/aPS blends. The addition of iPS (or aPS) component will reduce the overall crystallization rate of the sPS component and the retardation of crystal growth rates can be simply accounted by a dilution effect, keeping the surface nucleation intact. The phase-separated structure in the sPS/iPS blend shows a negligible effect on sPS crystallization and the signature of phase separation disappears after sPS crystallization. Depending on the relative dimensions of the segregated domains and iPS lamellar nucleus, subsequent crystallization of iPS can proceed to result in a crystalline/crystalline blend, or be inhibited to give a crystalline/amorphous blend morphology similar with that of sPS/aPS blends.     

Directional solidification of isotactic and atactic polypropylene blends

The directional solidification of polypropylene (PP) films results in an oriented semicrystalline microstructure and may offer a method to improve the properties of a product. The directional solidification of isotactic PP samples blended with 0% to 50% atactic PP, by mass, was therefore studied. The effects of composition and processing conditions were monitored to determine how they affect the quality and microstructure of the directionally solidified films. Difficulty was encountered in reproducing testable samples with a unidirectional crystal microstructure. Tensile testing of directionally solidified films was used to quantify the yield strength and elastic modulus of the films. These properties were compared with those of other PP films. The tensile test results do not support the hypothesis that enhanced mechanical properties were produced by directional solidification of the PP films. Improving the sample fabrication method and optimizing the processes involved may, however, lead to directionally solidified PP films with enhanced mechanical properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1516–1528, 2000     

The atactic polystyrene molecular weight effect on the thermal properties and crystal structure of syndiotactic polystyrene/atactic polystyrene blends

This work examined how the molecular weight of atactic polystyrene (aPS) affects the thermal properties and crystal structure of syndiotactic polystyrene (sPS)/aPS blends using differential scanning calorimetry, polarized light microscopy and wide angle X-ray diffraction (WAXD) technique. For comparative purposes, the structure and properties of the parent sPS was also investigated. The experimental results indicated that these blends showed single glass transition temperatures (T_gs), implying the miscibility of these blends in the amorphous state regardless of the aPS molecular weight. The non-isothermal and isothermal melt crystallization of sPS were hindered with the incorporation of aPSs. Moreover, aPS with a lower molecular weight caused a further decrease in the crystallization rate of sPS. Complex melting behavior was observed for parent sPS and its blends as well. The melting temperatures of these blends were lower than those of the parent sPS, and they decreased as the molecular weight of aPS decreased. Compared with the results of the WAXD study, the observed complex melting behavior resulted from the mixed polymorphs (i.e. the α and β forms) along with the melting-recrystallization-remelting of the β form crystals during the heating scans. The degree of melting-recrystallization-remelting phenomenon for each specimen was dependent primarily on how fast the sPS crystals were formed instead of the incorporation of aPSs. Furthermore, the existence of aPS in the blends, especially the lower molecular weight aPS, apparently reduced the possibility of forming the less stable α form in the sPS crystals.     

Plastic deformation and subsequent crystallization of thin films of isotactic/atactic polystyrene (iPS/aPS) blends

Thin films of crystallized and non crystallized isotactic polystyrene (iPS) and its blends with atactic polystyrene (aPS) were deformed below their glass transition temperature T_g. Deformation occurs in a very narrow ‘deformation zone’ (λ = 4 nm) and the deformed material exhibits long range order independent of the crystallinity of the films till concentrations of aPS up to 15%. Films containing more than 20% aPS do not show long range order within the deformed material even after subsequent annealing above T_g. From these results, which were obtained by transmission electron microscopy and electron diffraction, the conclusion is drawn that the molecular processes of crazing in amorphous polymers and the high local deformation of polymer single crystals are obeying similar mechanisms.     

High modulus of isotactic polypropylene attained by coextrusion with atactic polystyrene

Orientation-induced crystallization of crystallizable polymer melts can occur, under certain conditions, during flow through converging channels. Attempts have been made to achieve this phenomenon in a two-phase system, i.e., during simultaneous extrusion of a continuous concentric core of polypropylene within a polystyrene matrix through a conical duct. On one occasion, using Carlona P SY6100 (MFI = 11.0) with Hostyren N2000-V-01 (MFI = 25.0), a highly oriented polypropylene thread with a modulus of 14.6 GPa and a melting point of 178°C was extruded at a die temperature of approximately 170°C and a pressure lower than 40 MPa. It is, in principle, possible to form highly oriented, fiber-like structures as reinforcing elements in a polymer matrix.     

Thermal transitions in cold-crystallized blends of isotactic and static polystyrene

Solution-cast blends of isotactic and atactic polystyrene were stripped of casting solvent and heated above the glass transition temperature to temperatures below the equilibrium melting point of the respective blends to induce the development of crystallinity of the isotactic polystyrene. The samples, maintained at these crystallization temperatures for various times, were subsequently characterized by differential scanning calorimetry. The amount of crystallinity, the crystalline melting point, and the rate of crystallization were determined for each of the blends from the d.s.c. scans. The development of crystallinity, characterized by increased melting points, resulted from annealing at progressively higher temperatures. The maximum rate of crystallization for each of the blends was observed at a temperature corresponding closely to $\text{8}\text{9}$ of the absolute equilibrium melting temperature. The decrease in the melting point of the isotactic polymer, crystallized in the presence of atactic diluent, resulted primarily from weak enthalpic interactions between isotactic and atactic polystyrene homopolymers. Scanning electron photomicroscopy revealed that atactic-rich blends, immersed in n-hexane at 40°C, developed a non-intercommunicating network of microvoids. Similar solvent treatment of isotactic rich blends had little effect on the samples. D.s.c. measurements confirmed recently published results which indicated that n-hexane, at modest temperatures, does not induce the development of crystallinity in isotactic polystyrene.     

Simultaneous presence of positive and negative spherulites in syndiotactic polystyrene and its blends with atactic polystyrene

Crystal growth rates of syndiotactic polystyrene (sPS) and its blends with atactic polystyrene (aPS) at various temperatures (T_c) were measured using a polarized optical microscope (POM). In addition to the positively birefringent spherulites and axilites (P-spherulites and P-axilites) which are predominantly observed, small population of negatively birefringent spherulites (N-spherulites) is also detected in the neat sPS as well as in the sPS/aPS blends at a given T_c. Both P-spherulites and P-axilites possess a similar growth rate, whereas a smaller growth rate is found for N-spherulites at all T_c and samples investigated. Melting behavior of individual P- and N-spherulites was feasibly traced using hot-stage heating and a highly sensitive CCD through the decay of transmitted light intensity under cross-polars. Both P- and N-spherulites demonstrate exactly the same melting behavior under POM, which well corresponds to the differential scanning calorimetry measurements, suggesting no difference in lamellar thickness distribution or crystal perfection within P- and N-spherulites. Lamellar morphologies within spherulites were extensively investigated using transmission electron microscopy (TEM) as well as scanning electron microscopy (SEM). Results obtained from TEM and SEM show that the lamellar stacks within P-spherulites grow radially, whereas those within N-spherulites are packed relatively tangentially. The growth of P-spherulites is associated with the gradual increase of lamellae' lateral dimensions which follows the conventional theory of growth mechanism. However, the measured growth rate of N-spherulites is relevant to the gradual deposition of new lamellar nuclei adjacent to the fold surfaces of already-existing lamellar stacks. The difference in measured growth rate between P- and N-spherulites is attributed to the different energy barrier required to develop stable nuclei. Based on the exhaustive TEM and SEM observations, plausible origin of N-spherulites is provided and discussed as well.     

Isothermal crystallization kinetics and morphology development of isotactic polypropylene blends with atactic polypropylene

The crystallization kinetics and morphology development of pure isotactic polypropylene (iPP) homopolymer and iPP blended with atactic polypropylene (aPP) at different aPP contents and the isothermal crystallization temperatures were studied with differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. The spherulitic morphologies of pure iPP and larger amounts of aPP for iPP blends showed the negative spherulite, whereas that of smaller amounts of aPP for the iPP blends showed a combination of positive and negative spherulites. This indicated that the morphology transition of the spherulite may have been due to changes the crystal forms of iPP in the iPP blends during crystallization. Therefore, with smaller amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends increased with increasing aPP and presented a lower degree of perfection of the γ form coexisting with the α form of iPP during crystallization. However, with larger amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends decreased and reduced the γ‐form crystals with increasing aPP. These results indicate that the aPP molecules hindered the nucleation rate and promoted the molecular motion and growth rate of iPP with smaller amounts of aPP and hindered both the nucleation rate and growth rate of iPP with larger amounts of aPP during isothermal crystallization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1093–1104, 2007     

Effect of prior sample history on n-hexane sorption in glassy polystyrene microspheres

The effect of prior swelling or thermal annealing on the kinetics and apparent equilibria of n-hexane vapour sorption at 30°C in submicron diameter polystyrene microspheres was studied at penetrant activities of 0.75 and 0.10. Preswelling with n-hexane at an activity of 0.90 increased both the rate and the apparent equilibrium of subsequent n-hexane sorption at both the lower activities. Conversely, thermal annealing reduced the sorption rate and apparent equilibrium sorption relative to the measured sorption in the ‘as-received’ sample. Cycling experiments, at the high activity ($\text{p}\text{p}\text{° = 0.75}$), revealed that the effects of the earlier preswelling or thermal history are effectively erased by the first sorption cycle. In contrast, at the lower activity ($\text{p}\text{p}\text{° = 0.10}$), the effects of preswelling or thermal annealing decay more gradually consequent to repeated cycling. The observed convergence of the apparent equilibrium penetrant concentration, in all samples, to a single value upon repeated cycling suggests that a true glassy state equilibrium sorption can be approached by conditioning microsphere samples by the particular cycling histories studied in this work.     

Miscible blends of syndiotactic polystyrene and atactic polystyrene. Part 1. Lamellar morphologies and diluent segregation

Lamellar morphologies of melt-crystallized blends of syndiotactic polystyrene (sPS, weight-average molecular weight ) and atactic polystyrene (aPS, M_w=100k) have been investigated using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). sPS/aPS blends with various compositions were prepared and crystallized isothermally at 250 °C prior to morphological studies. Due to the proximity in the densities of the crystal and amorphous phases, a weak SAXS reflection associated with lamellar microstructure was obtained at room temperature. In addition, strong diffuse scattering at low scattering vectors was evidently observed and its appearance may obscure the intensity maximum associated with the lamellar features, leading to the difficulties in determining the microstructure of the blends. To enhance the density contrast, SAXS intensities at an elevated temperature of 150 °C were measured as well to deduce the morphological results with better precision. Based on the Debye-Bueche theory, the intensities of the diffuse scattering were estimated and subtracted from the observed intensities to obtain the scattering contribution exclusively from the lamellar microstructure. Morphological parameters of the sPS/aPS blends were derived from the one-dimensional correlation function. On addition of aPS, no significant changes in the lamellar thickness have been found and the derived lamellar thicknesses are in good agreement with TEM measurements. Segregation of rejected aPS components during sPS crystallization was evidently observed from TEM images which showed aPS pockets located between sPS lamellar stacks and distributed uniformly in the bulk samples, leading to the interfibrillar segregation.     

Syndiotactic polystyrene‐b‐atactic polypropylene block copolymer alloy as a compatibilizer for syndiotactic polystyrene/isotactic polypropylene blends

A polymeric alloy (SP–A) containing syndiotactic polystyrene (sPS), atactic polypropylene (aPP), and about 66 wt % sPS‐b‐aPP diblock copolymer, was prepared by the sequential feed of monomers in the presence of the half‐titanocene Cp*Ti(OBz)₃ (where Cp* is C₅Me₅ and Bz is PhCH₂), modified methylaluminoxane, and external triisobutylaluminum. The effects of the SP–A alloy as a compatibilizer for sPS and isotactic polypropylene (iPP) blends were evaluated. The blending of sPS and iPP, with and without SP–A, was performed in a single‐screw miniextruder with a side channel that allowed the continuous recycling of materials. The influence of SP–A on the mechanical and thermal properties of the immiscible sPS/iPP blends was investigated over a range of composition. The presence of the SP–A alloy resulted in a significant improvement of the impact strength of the blends compared with that of pure sPS and their pure blends. This improvement was particularly obvious in the sPS/iPP (90/10 wt %) blend containing 5 wt % SP–A. Morphological analysis of the impact‐fractured surface of the ternary blends indicated that the sPS‐b‐aPP diblock copolymer contained in the SP–A alloy acted as an efficient compatibilizer by decreasing the dispersed‐phase iPP particle size, improving the interfacial adhesion, and generating a stable microphase‐separated state. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1596–1605, 2003     

Compatibilizing effect of a diblock copolymer of isotactic polystyrene and isotactic polypropylene in blends of the corresponding homopolymers

A high molecular weight polymer mixture was obtained from a sequential Ziegler–Natta polymerization of styrene and propylene. After removing unwanted homopolymers from the reaction product, the remaining copolymer was subjected to extensive molecular and morphological characterization. The results of these experiments indicate that the purified material is a diblock copolymer of isotactic polystyrene and isotactic polypropylene, with each block having a molecular weight in the range of 225,000 g/mol. This block copolymer was incorporated in varying amounts into blends of isotactic polystyrene and isotactic polypropylene homopolymers. At low concentrations of copolymer (<20 wt %), the diblock functions as a dispersing agent, significantly reducing the size of domains in the heterogeneous blends. At higher copolymer concentrations, a dramatic improvement in the adhesion across the domain boundaries is also observed. The favorable effects of the copolymer on mechanical properties are demonstrated in the results of tensile impact experiments.     

Preparation of isotactic polypropylene/polystyrene blends by diffusion and subsequent polymerization of styrene in isotactic polypropylene pellets

Isotactic polypropylene (iPP) pellets were used to prepare isotactic polypropylene/polystyrene (iPP/PS) blends by diffusion and subsequent polymerization of styrene in water medium, with initiator benzoyl peroxide (BPO) added after diffusion of styrene. Two methods, differencing in whether the excess monomer was removed after diffusion, were used and parameters influencing PS contents were investigated. Diffusion kinetic study showed that the diffusion coefficient at 90 °C is 2.8 times that at 80 °C due to the α relaxation of iPP segments. Investigation on the distribution state of styrene in the mixture before diffusion revealed that most styrene adsorbed on the surface of iPP pellets, and thus the diffusion behavior of styrene into iPP pellets in water medium is similar to that in bulk styrene. Phase morphology of a typical iPP/PS blend showed an average particle size of about 90 nm in the inner part of the iPP pellets. The diametrical distributions of PS showed that styrene can diffuse up to the center of the pellets at 90 °C. It is important to note that the depth of styrene is limited when the initiator BPO is added along with styrene, providing a good explanation for the previously reported ineffective solid-state modification of melt-extruded iPP pellets.     

Effect of particle size on the mechanism controlling n-hexane sorption in glassy polystyrene microspheres

The effect of particle size on the rate-determining transport mechanism controlling n-hexane sorption into polystyrene spheres was determined by monitoring the kinetics of n-hexane vapour absorption in two powder samples of distinctly different narrow particle size distributions. The microspheres differed in mean diameter by a factor of three hundred. In all cases, sorption in the smaller spheres was controlled principally by Fickian diffusion. In contrast, at temperatures and activities which result in relaxation-controlled (Case II) transport in films, the larger spheres (184 μm diameter) sorb by Case II kinetics. Under these identical boundary conditions, however, the small spheres (5340 Å diameter) absorbed n-hexane by Fickian kinetics. Presumably, there is insufficient time or space in the small spheres to develop the step concentration profiles associated with limiting Case II transport. A mathematical model describing Case II sorption in spheres cylinders, and slabs is developed. The kinetics describing absorption in the larger spheres are well described by this analysis. Desorption in all cases is adequately described by concentration-dependent diffusion. Repeated experiments confirmed, moreover, that at identical temperatures and penetrant vapour activities the apparent equilibrium concentration of n-hexane in the small spheres is significantly higher than the corresponding sorption equilibria in the large spheres. Although several possible explanations for this glassy-state anomaly are presented, the most satisfying explanation involves the development of a non-sorbing core in the large spheres consequent to the prior sorption in the surrounding shell. Desorption data are consistent with the notion of partial swelling of large spheres.     

Amorphous phase in atactic polystyrene

Summary Amorphous phase in atactic polystyrene (a-PS) was investigated via its physical aging behavior. It was found that when the samples were quenched rapidly, there were dual amorphous regions with quite different characters: free amorphous region and constrained amorphous region. The former was the normal bulk amorphous region, while the latter was constrained by the internal stress. The dual amorphous regions exhibited as dual endothermic peaks in differential scanning calorimetry (DSC) traces when the samples were physically aged at temperatures well below the glass transition temperature (T_g). The lower peak corresponded to the free amorphous region, and the upper peak to the constrained amorphous region. Received: 10 July 2001/Accepted: 24 July 2001