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.     

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     

Diffusion of disperse dye in atactic polystyrene

Sublimative desorption experiments were carried out on atactic polystyrene containing p-nitroaniline, p-aminoazobenzene, or C.I. Disperse Yellow 7 at 114°–170°C (above the T_g of the polymer). The diffusion coefficient of each dye in the polymer increased monotonically with rise in the desorption temperature. The mode of this change was exactly expressed by a WLF relation having the universal parameters given for amorphous polymers. The value of B_d, defined as the ratio of diffusional penetrant volume to that of a segment of the chain molecule, varied from 0.37 to 0.70 for the different dyes used. It is also shown that the B_d value is related to the logarithmic rotational volume of the dye molecule estimated from a molecular model.     

Orientation in uniaxially stretched plasticized atactic polystyrene

Summary Fourier transform infrared spectroscopy and birefringence measurements have been used to study the changes in molecular orientation which occur on drawing of plasticized as compared to pure polystyrene (PS) at a temperature T=Tg+Cte. No influence of plasticizers on orientation can be detected whatever the interactions between small molecules and PS chains are. Comparison with previous results obtained on PS-poly(vinylmethyl ether) compatible blends confirms the importance of the macromolecular nature of the second component to enhance the friction coefficient leading to higher level of chain orientation.     

Comparison of crystallization kinetics of miscible blends of syndiotactic polystyrene with atactic polystyrene or poly(1,4-dimethyl-p-phenylene oxide)

Crystallization kinetics were characterized by using isothermal differential scanning calorimetry (DSC) analysis on neat semicrystalline syndiotactic polystyrene (s-PS) and its miscible blends with atactic (amorphous) polystyrene (a-PS) or with poly (1,4-dimethyl-p-phenylene oxide) (PPO). The crystallization behavior of neat s-PS polymer was compared to its miscible blends. The results suggest that the crystal growth in melt-crystallized s-PS is nearly of homogeneous nucleation and that the growth pattern of the spherulites is 3-D spherical. The s-PS component in its miscible blends was found to crystallize with similar behavior to that of neat s-PS, but with lower Avrami exponents, suggesting that the nucleation mechanism is likely more heterogeneous with blending.     

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.     

Orientation and relaxation in uniaxially stretched atactic polystyrene

Infra-red measurements of the dichroic ratio of atactic polystyrene absorption bands provide a valuable method of determination of orientation as well as relaxation of chains during stretching. Different strain rates and temperatures of stretching were used. Orientation relaxation was analysed using Lodge's constitutive equation and a master curve was obtained at a reference temperature T₀ = 115°C. Orientation relaxation behaves similarly to mechanical relaxation and a scaling factor of 3.6 × 10^?8 m² N^?1 holds between the two sets of results.     

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     

The Tll (>Tg) transition of atactic polystyrene

Torsional braid analysis (TBA) (～0.3 Hz) and differential thermal analysis (DTA) data are presented for the temperature for the region 0–200°C for two series of atactic polystyrenes with narrow molecular weight distributions: (a) anionic series, M?_n = 600–2×10⁶, M?_w/M?_n ? 1.1; (b) fractionated thermal series, M?_n = 2,000–1.1×10⁵, M?_w/M?_n < 1.25. Preliminary results on bimodal blends are also reported. Heating and cooling cycles were employed with TBA; only the heating mode was used with DTA. In addition to a dynamic mechanical loss peak at T_g, a higher temperature loss peak was also found. Designated the T_ll or liquid–liquid transition (relaxation), its temperature is 1.1 to 1.2 T_g (°K) for polymers with molecular weight below the critical molecular weight (M_c) for chain entanglements. Above M_c ? 35,000, it rises steeply, being ?200°C for M?_n = 110,000. The common dependence of T_g and T_ll on M?_n^?1 below M_c suggests a common molecular origin. The two facts, (a) that T_ll > T_g and (b) that T_ll reflects chain entanglements, further suggest that T_ll involves a longer chain segment length and possibly the entire molecule. Comparison of T_ll versus log M plots with T versus log M isoviscous state plots based on zero-shear melt viscosity data from the literature implies that T_ll measured by the TBA technique corresponds to an isoviscous state of 10⁴–10⁵ poises. The employment of narrow molecular weight polymers is presumably responsible for both the linear variation of the T_ll transition with M?_n^?1 (which suggests a free volume basis for the relaxation) and the form of the variation of the T_ll transition with log M (which suggests an isoviscous basis for the relaxation). The sharpness of the T_ll loss peak by TBA decreases with increasing molecular weight and dispersity. The DTA endothermic event corresponding to T_ll is clearly related to the occurrence of flow since the fused films which result from heating granules to 200°C and cooling to R.T. do not reveal a T_ll on reheating. If a fused film is crushed, a T_ll event is observed on heating. For bimodal blends with M?_n < M_c for both components, the T_ll transition was averaged; with one component less than and one greater than M_c, the T_ll transitions of the components appeared to occur independently at temperatures corresponding to those of the isolated components. In accordance with Ueberreiter and Orthmann, T_g appears to separate a glassy state from a fixed liquid state, whereas T_ll separates the fixed liquid from a true liquid state. Possible molecular interpretations for the T_ll process are discussed. Systematic bodies of data from the literature which indicate the presence of the T_ll process in other polymers are summarized.     

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.     

Glass transition of atactic polystyrene with less chain entanglements

Summary Atactic polystyrene was dissolved and refluxed in benzene keeping the polymer concentration well below the critical concentration C^* value for chain overlap. After rapid freezing of the solution by injecting it directly into liquid nitrogen, the solvent was sublimated so that the expanded chain coils with few entanglements could be obtained. T_g for this material was found to be 11 K lower than the normal polystyrene even after annealing up to 470 K. Comparison of the infrared spectra shows some conformational differences between the freeze-dried and the normal PS. Upon shock-cooling and subsequent freeze-drying, all vibrational bands appear much sharper, indicating an increase in structure regularity.     

Structure development in melt‐spinning syndiotactic polystyrene and comparison to atactic polystyrene

Syndiotactic polystyrene (s‐PS) and atactic polystyrene (a‐PS) were melt‐spun into filaments. The s‐PS filaments exhibited increasing amounts of crystallinity and orientation with increasing drawdown ratio and spinline stress. The a‐PS filaments were amorphous but exhibited birefringence. The birefringence and Hermans orientation factors for a‐PS were proportional to this spinline stress. In ice water and at low drawdown ratios, the s‐PS is glassy or mesomorphic. At higher drawdown ratios and spinline stresses, it crystallized. The crystalline form was the zigzag TTTT hexagonal α‐form. The birefringence and orientation factors of the s‐PS filaments were higher than those of the a‐PS filaments and the difference of the birefringence increased with increasing spinline stress. Mechanical testing results showed that the Young's modulus and tensile strength generally increased with increasing spinline drawdown ratio for both a‐PS and s‐PS filaments. The elongation to break was enhanced for both materials by increased chain orientation. Polym. Eng. Sci. 44:2141–2147, 2004. © 2004 Society of Plastics Engineers.     

Ultradrawing of amorphous polymers by coextrusion illustrated with atactic polystyrene

Films of pure and high-impact atactic polystyrene were prepared by the recently developed technique of solid-state coextrusion. The films were produced at extrusion rates ≥4 cm/min at 126°C with a maximum extrusion draw ratio (EDR) of 11.6. These ultradrawn films are fibrous, have a high birefringence of ?2.24 × 10^?2, and exhibit a 72% elastic recovery. The material has a tensile modulus of ～4–5 GPa and a tensile strength to break of 85 MPa. Thermal analysis suggests a constant T_g.     

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.     

Thermo-mechanical properties of the blend syndiotactic/atactic polystyrene after crystallization of the syndiotactic polystyrene

The thermo-mechanical properties of the blend syndiotactic polystyrene (sPS)/ atactic polystyrene (aPS) are characterized by studying the concentration depending softening behavior with thermo-mechanical analysis (TMA) and the temperature depending Young's modulus for different concentrations with dynamic mechanical analysis (DMA).     

Thermal degradation kinetics of isotactic and atactic polypropylene

The thermal degradation of isotactic and atactic polypropylene was investigated in bulk and in solution. The degradation in bulk was studied with thermogravimetric analysis, and the degradation in solution was studied by the dissolution of the polymer in paraffin oil. The degradation in solution was investigated from 230 to 350°C. The effect of the hydrogen donor on the degradation of the polymer in solution was also studied at 350°C. Continuous distribution kinetics were employed to model the degradation kinetics for the degradation in solution. The rate coefficients were obtained, and the activation energy was calculated from an Arrhenius plot. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2206–2213, 2003     

Fourier transform infrared spectroscopic study of transitions above Tg in atactic polystyrene

Fourier transform infrared spectroscopy (FT-IR) has been applied to the study of the molecular mechanisms of transitions of atactic polystyrene above T_g. Intensity measurements of vibrational modes as a function of temperature revealed two transitions above T_g, which are designated as T_u and T′_u. T′_u is independent of molecular weight as opposed to the molecular weight dependent T_u whose behavior is similar to T_g. Infrared measurements are more sensitive to T′_u than T_u. Conformationally sensitive bands show that T′_u may be related to disruption of local order where there is a negligible barrier to conformational change.     

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.     

Supermolecular structure of gelation of atactic polystyrene/carbon disulphide solutions

In this paper, atactic polystyrene/carbon disulphide (aPS/CS₂) gel-dried film was prepared at low temperature. In such film, ordered structure was formed through stacks of some stereoregular segments by accepting TTGG type conformation, which strongly depended upon the interaction of CS₂ and polymer segments. The dynamics of interaction was studied by measuring FTIR spectra. With increasing temperature, the regular TTGG conformation transferred to less regular gauche TG conformation and the molecular chains relaxed. Received: 18 July 1997/Revised: 2 September 1997/Accepted: 25 September 1997