Solution‐crystallization and related phenomena in 9,9‐dialkyl‐fluorene polymers. I. Crystalline polymer‐solvent compound formation for poly(9,9‐dioctylfluorene)

Polymer‐solvent compound formation, occurring via co‐crystallization of polymer chains and selected small‐molecular species, is demonstrated for the conjugated polymer poly(9,9‐dioctylfluorene) (PFO) and a range of organic solvents. The resulting crystallization and gelation processes in PFO solutions are studied by differential scanning calorimetry, with X‐ray diffraction providing additional information on the resulting microstructure. It is shown that PFO‐solvent compounds comprise an ultra‐regular molecular‐level arrangement of the semiconducting polymer host and small‐molecular solvent guest. Crystals form following adoption of the planar‐zigzag β‐phase chain conformation, which, due to its geometry, creates periodic cavities that accommodate the ordered inclusion of solvent molecules of matching volume. The findings are formalized in terms of nonequilibrium temperature–composition phase diagrams. The potential applications of these compounds and the new functionalities that they might enable are also discussed. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1481–1491     

Spectroscopic properties of poly(9,9‐dioctylfluorene) thin films possessing varied fractions of β‐phase chain segments: enhanced photoluminescence efficiency via conformation structuring

Poly(9,9‐dioctylfluorene) (PFO) is a widely studied blue‐emitting conjugated polymer, the optoelectronic properties of which are strongly affected by the presence of a well‐defined chain‐extended “β‐phase” conformational isomer. In this study, optical and Raman spectroscopy are used to systematically investigate the properties of PFO thin films featuring a varied fraction of β‐phase chain segments. Results show that the photoluminescence quantum efficiency (PLQE) of PFO films is highly sensitive to both the β‐phase fraction and the method by which it was induced. Notably, a PLQE of ～69% is measured for PFO films possessing a ～6% β‐phase fraction induced by immersion in solvent/nonsolvent mixtures; this value is substantially higher than the average PLQE of ～55% recorded for other β‐phase films. Furthermore, a linear relationship is observed between the intensity ratios of selected Raman peaks and the β‐phase fraction determined by commonly used absorption calibrations, suggesting that Raman spectroscopy can be used as an alternative means to quantify the β‐phase fraction. As a specific example, spatial Raman mapping is used to image a mm‐scale β‐phase stripe patterned in a glassy PFO film, with the extracted β‐phase fraction showing excellent agreement with the results of optical spectroscopy. © 2016 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1995–2006     

Micromechanical modeling of anisotropic behavior of oriented semicrystalline polymers

Some manufacturing processes of polymeric materials, such as injection molding or film blowing, cause the final product to be highly anisotropic. In this study, the mechanical behavior of drawn polyethylene (PE) tapes is investigated via micromechanical modeling. An elasto‐viscoplastic micromechanical model, developed within the framework of the so‐called composite inclusion model, is presented to capture the anisotropic behavior of oriented semicrystalline PE. Two different phases, namely amorphous and crystalline (both described by elasto‐viscoplastic constitutive models), are considered at the microstructural level. The initial oriented crystallographic structure of the drawn tapes is taken into account. It was previously shown by Sedighiamiri et al. (Comp. Mater. Sci. 2014, 82, 415) that by only considering the oriented crystallographic structure, it is not possible to capture the macroscopic anisotropic behavior of drawn tapes. The main contribution of this study is the development of an anisotropic model for the amorphous phase within the micromechanical framework. An Eindhoven glassy polymer (EGP)‐based model including different sources of anisotropy, namely anisotropic elasticity, internal stress in the elastic network and anisotropic viscoplasticity, is developed for the amorphous phase and incorporated into the micromechanical model. Comparisons against experimental results reveal remarkable improvements of the model predictions (compared to micromechanical model predictions including isotropic amorphous domains) and thus the significance of the amorphous phase anisotropy on the overall behavior of drawn PE tapes. © 2019 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 378–391     

Effects of molecular characteristics and processing conditions on melt‐drawing behavior of ultrahigh molecular weight polyethylene

The effects of molecular characteristics and processing conditions on melt‐drawing behavior of ultrahigh molecular weight polyethylene (UHMW‐PE) are discussed, based on a combination of in situ X‐ray measurement and stress–strain behavior. The sample films of metallocene‐ and Ziegler‐catalyzed UHMW‐PEs with a similar viscosity average MW of ～10⁷ were prepared by compression molding at 180 °C. Stress profiles recorded at 160 °C above the melting temperature of 135 °C exhibited a plateau stress region for both films. The relative change in the intensities of the amorphous scattering recorded on the equator and on the meridian indicated the orientation of amorphous chains along the draw axis with increasing strain. However, there was a substantial difference in the subsequent crystallization into the hexagonal phase, reflecting the molecular characteristics, that is, MW distribution of each sample film. Rapid crystallization into the hexagonal phase occurred at the beginning point of the plateau stress region in melt‐drawing for metallocene‐catalyzed UHMW‐PE film. In contrast, gradual crystallization into the hexagonal phase occurred at the middle point of the plateau stress region for the Ziegler‐catalyzed film, suggesting an ease of chain slippage during drawing. These results demonstrate that the difference in the MW distribution due to the polymerization catalyst system dominates the phase development mechanism during melt‐drawing. The effect of the processing conditions, that is, the including strain rate and drawing temperature, on the melt‐drawing behavior is also discussed. The obtained results indicate that the traditional temperature–strain rate relationship is effective for transient crystallization in to the hexagonal phase during melt‐drawing, as well as for typically oriented crystallization during ultradrawing in the solid state. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2455–2467, 2006     

The role of segregation in the polarized emission from polyfluorene embedded in a liquid crystal

Polyfluorene (PFO) embedded in a nematic liquid crystal (LC) matrix is investigated. For low PFO weight contents, a homogeneous dispersion is obtained which displays a strong fluorescence anisotropy along the LC director, indicating a significant alignment of the polymeric chains along this direction. Besides, for relatively high PFO weight contents, phase separation takes place. Under these conditions, the sample is composed of micrometer‐sized domains, where the two species are in solution, enclosed by segregated polymeric boundaries. By polarized‐photoluminescence imaging and spectroscopy, it is found that most of the light emission originates from these boundaries and gets strongly pinned along their orientation. Since boundaries are mainly oriented orthogonal to the LC chains, this morphological alignment results in a system in which the orientation of the polarization emission can be predicted and possibly controlled. Conversely, in the homogeneous sample one can obtain a homogeneous emission polarization by controlling the alignment of the LC. These features are potentially relevant for the development of flexible polarization‐sensitive optoelectronic devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1558–1563     

Effects of the structures of polymerizable monomers on the electro‐optical properties of UV cured polymer dispersed liquid crystal films

Polymer dispersed liquid crystal (PDLC) films were prepared by photopolymerization of liquid crystal (LC)/polymerizable monomers/photoinitiator composites. The effects of the structures of the polymerizable monomers on the electro‐optical properties of PDLC films were investigated. It was found that the length of the molecular chain and the rigidity and flexibility of molecules influenced the structure of the polymer network in the PDLC films somewhat, and then affected the electro‐optical properties of the composites accordingly. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1369–1375, 2008     

Molecular orientation study of uniaxially drawn nafion polymer electrolyte membranes utilizing polarized UV–Raman spectra

Nafion® perfluorosulfonic acid polymer electrolyte membranes were uniaxially drawn at a temperature where the α‐relaxation is active. Polarized UV–Raman spectra revealed the anisotropy developed. They strongly suggest that, upon uniaxial drawing, Nafion macromolecular chains are oriented parallel to the drawing axis, while the perfluorinated side chains exhibit a tendency to be oriented perpendicular to the draw axis. The drawing process resulted in the reduction of the membrane thickness in addition to an enhanced mechanical strength along the draw direction, measured with dynamic mechanical analysis. In a parallel study, a preliminary molecular orientation study of uniaxially drawn Teflon samples allowed a better assignment of the Raman bands of Nafion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2509–2517, 2007     

Semicrystalline blends of polyethylene and isotactic polypropylene: Improving mechanical performance by enhancing the interfacial structure

The low‐temperature mechanical behavior of semicrystalline polymer blends is investigated. Isotactic polypropylene (iPP) is blended with both Zeigler–Natta polyethylene (PE) and metallocene PE. Transmission electron microscopy (TEM) on failed tensile bars reveals that the predominate failure mode in the Zeigler–Natta blend is interfacial, while that in the metallocene blend is failure of the iPP matrix. The observed change in failure mode is accompanied by a 40% increase in both tensile toughness and elongation at −10 °C. We argue that crystallite anchoring of interfacially entangled chains is responsible for this dramatic property improvement in the metallocene blend. The interfacial width between PE and iPP melts is approximately 40 Å, allowing significant interfacial entanglement in both blends. TEM micrographs illustrate that the segregation of low molecular weight amorphous material in the Zeigler–Natta blend reduces the number and quality of crystallite anchors as compared with the metallocene blend. The contribution of anchored interfacial structure was further explored by introducing a block copolymer at the PE/iPP interface in the metallocene blend. Small‐angle X‐ray scattering (SAXS) experiments show the block copolymer dilutes the number of crystalline anchors, decoupling the interface. Increasing the interfacial coverage of the block copolymer reduces the number of anchored interfacial chains. At 2% block copolymer loading, the low‐temperature failure mode of the metallocene blend changes from iPP failure to interfacial failure, reducing the blend toughness and elongation to that of the Zeigler–Natta blend. This work demonstrates that anchored interfacial entanglements are a critical factor in designing semicrystalline blends with improved low‐temperature properties. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 108–121, 2000     

Effect of molecular weight of macro‐iniferter on electro‐optical properties of polymer dispersed liquid crystal films prepared by iniferter polymerization

Polymer dispersed liquid crystal (PDLC) films were prepared by a devised method, in which photo‐polymerization induced phase separation in a mixtures of a macro‐iniferter, methyl acrylater, and liquid crystal. The morphology of the obtained PDLC films was examined on a polarized optical microscopy, and the effect of molecular weight of MIs on the electro‐optical properties was deliberately investigated. Decreasing the molecular weight of MIs in the films led to formation of larger liquid crystal droplets and a lower V_th values. V_sat increased and the memory effect decreased because of the increased interface anchoring strength induced by the higher molecular weight of polymer matrices. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1530–1534, 2009     

Quantitative analysis of near surfaces three‐dimensional orientation of polymer chains in PET and PEN films using polarized ATR FTIR spectroscopy

Polarized attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy was utilized to characterize the three‐dimensional orientation of polymer chains near highly anisotropic surfaces generated by uniaxial drawing. A versatile method was proposed to analyze the molecular orientation of the polymers by combining the experimental refractive indices and optimized contact pressure by an anvil for solving the optical contact problem. This method is effective even when changes in the molecular orientation along the thickness direction caused by drawing are remarkable. In addition, this method enables quantitative comparison of the molecular orientation among different polymers in the same coordinate system. From the molecular orientation analysis of poly (ethylene terephthalate) (PET) and poly (ethylene naphthalate) (PEN), it was revealed that this method has a broader range of applications with high accuracy in estimating the molecular orientation of polymers compared with the conventional methods. The significant changes in the molecular orientation caused by uniaxial and biaxial drawing of PET and PEN films were quantitatively analyzed, and the reasons for the significant in‐plane orientation of PEN chains on the film plane are discussed. In addition, the difference in the molecular orientation between both sides of the films was also demonstrated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 870–879, 2010     

Structure and formation mechanism of melt‐drawn highly oriented polymer fibers

Well‐separated and parallel aligned fibers of various polymers have been prepared by a simple but effective melt‐drawing procedure, and their structural features have been studied with field‐emission scanning electron microscopy. The results show that the resulting polymer fibers, with diameters ranging from tens of nanometers to hundreds of nanometers, consist of highly oriented lamellar or fibrillar crystals with the molecular chains aligned in the drawing direction. Scanning electron microscopy images of the drawing process indicate that drawing a thin polymer molten layer at temperature far above its melting point leads to the formation of elongated microcracks. The microcracks embedded in the polymer thin film propagate along the drawing direction and result in the formation of polymer microfibers, which split continuously under high instantaneous stresses and produce well‐separated polymer fibers with diameters on the nanometer scale. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2703–2709, 2004     

Structural anisotropy in friction‐deposited layers of polystyrene

Friction‐deposited layers of atactic polystyrene (PS) on inert and OH‐grafted gold substrates were the subject of this study to establish a relationship between the friction process and the resulting anisotropy of the transferred polymer chains. We show, by using polarization‐modulation infrared reflection‐absorption spectroscopy that the deposited PS chains involve an anisotropy in which PS main backbone is rather perpendicular to the friction support, fact that is surprising when compared with the majority of polymers where the anisotropy is along the sliding direction. Moreover, our calculation of the orientation angles revealed that PS chains are more perpendicular in the transferred layers than in spin‐coated films. This particular anisotropy is probably due to a parallel reorientation of the phenyl ring on the friction support whatever the surface chemistry is. On the other hand, this study was useful to rectify the assignment of infrared bands unclearly reported in the literature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3272–3281, 2006     

Layer structure estimation of three‐dimensional crystal and two‐dimensional molecular film for fluorinated comb copolymers

Comb copolymers containing both hydrogenated and fluorinated side‐chains were prepared by copolymerization using acrylic or methacrylic monomers in several ratios. The crystal structures of these copolymers and layer structures of their organized molecular films were investigated by wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS), and out‐of plane X‐ray diffraction. Further, to selectively estimate the regularity of shorter fluorocarbon side‐chains, organized molecular films of copolymers were investigated by polarized near‐edge X‐ray adsorption fine structure (NEXAFS) spectroscopy. From the results of these measurements, it was inferred that these copolymers formed highly ordered layer structures, and a long spacing was predominantly determined by the arrangement of hydrogenated side‐chains, except in copolymers having extremely high fluorocarbon contents. In the case of the organized molecular films, the fluorinated side‐chains of methacrylate copolymers cannot form a highly ordered arrangement, whereas those of acrylate copolymers were oriented on monolayers. However, in both cases, the hydrogenated side‐chains predominantly formed layer structures in the organized films, and the fluorinated side‐chains did not contribute to the formation of the layer structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 534–546, 2008     

Melt drawing of ultra‐high molecular weight polyethylene: Comparison of Ziegler‐ and metallocene‐catalyzed reactor powders

The drawing behavior of the ultra‐high molecular weight polyethylene (UHMW‐PE) melts has been studied by comparing the stress/strain curves for two types of samples as polymerized using conventional Ziegler and newer metallocene catalyst systems. Two UHMW‐PE samples, having the same viscosity average molecular weight of 3.3 × 10⁶, but different molecular weight distribution, have been drawn from melt at special conditions. The sample films for drawing were prepared by compression molding of reactor powders at 180°C in the melt. Differences in the structural changes during drawing and resultant properties, ascribable to their broad or narrow molecular weight distribution, were estimated from tensile tests, SEM observations, X‐ray measurements and thermal analyses. The metallocene‐catalyzed sample having narrower molecular weight distribution, could be effectively drawn from the melt up to a maximum draw ratio (DR) of 20, significantly lower than that obtained for the Ziegler‐catalyzed sample, ∼ 50. The stress/strain curves on drawing were remarkably influenced by draw conditions, including draw temperature and rate. However, the most effective draw for both was achieved at 150°C and a strain rate of 5 min⁻¹, independent of sample molecular weight distribution. The efficiency of drawing, as evaluated by the resultant tensile properties as a function of DR, was higher for the metallocene‐catalyzed sample having narrower molecular weight distribution. Nevertheless, the maximum achieved tensile modulus and strength for the Ziegler sample, 50–55 and 0.90 GPa, respectively, were significantly higher than those for the metallocene sample, 20 and 0.65 GPa, respectively, reflecting the markedly higher drawability for the former than the latter. The stress/strain behavior indicated that the origin of differences during drawing from the melt could be attributed to the ease of chain relaxation for the lower molecular weight chains in the melt. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1921–1930, 1999     

Oriented crystallization of poly(L‐lactic acid) in uniaxially oriented blends with poly(vinylidene fluoride)

This article describes the oriented crystallization of poly(L ‐lactic acid) (PLLA) in uniaxially oriented blends with poly(vinylidene fluoride) (PVDF). Uniaxially drawn films of PLLA/PVDF blend with fixed ends were heat‐treated in two ways to crystallize PLLA in oriented blend films. The crystal orientation of PLLA depended upon the heat‐treatment process. The crystal c‐axis of the α form crystal of PLLA was highly oriented in the drawing direction in a sample cold‐crystallized at T_c = 120 °C, whereas the tilt‐orientation of the [200]/ [110] axes of PLLA was induced in the sample crystallized at T_c = 120 °C after preheating at T_p = 164.5–168.5 °C. Detailed analysis of the wide‐angle X‐ray diffraction (WAXD) indicated that the [020]/ [310] crystal axes were oriented parallel to the drawing direction, which causes the tilt‐orientation of the [200]/ [110] axes and other crystal axes. Scanning electron microscopy (SEM) suggested that oriented crystallization occurs in the stretched domains of PLLA with diameters of 0.5–2.0 μm in the uniaxially drawn films of PVDF/PLLA = 90/10 blend. Although the mechanism for the oriented crystallization of PLLA was not clear, a possibility was heteroepitaxy of the [200]/[110] axes of the α form crystal of PLLA along the [201]/[111] axes of the β form crystal of PVDF that is induced by lattice matching of d₁₀₀(PLLA) ≈ 5d₂₀₁(PVDF). © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1376–1389, 2008     

Salt concentration dependence of the mechanical properties of LiPF6/poly(propylene glycol) acrylate electrolyte at a graphitic carbon interface: A reactive molecular dynamics study

This reactive molecular dynamics study explores the salt concentration dependence of the viscoelastic and mechanical failure properties of a poly(propylene glycol)/LiPF₆‐based solid polymer electrolyte (SPE) at a graphitic carbon electrode interface. To account for the finite‐size effect of interface‐confined SPE films, the properties of two distinct film thicknesses are compared with the respective bulk properties. Additionally, the effect of uniaxial compression in the interface‐normal direction on free energy profiles of Li‐ion SPE‐desolvation is studied. © 2018 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 718–730     

Preparation and characterization of cellulose and konjac glucomannan blend film from ionic liquid

Blend films from cellulose and konjac glucomannan (KGM) in room temperature ionic liquid 1‐allyl‐3‐methylimidazolium chloride were satisfactorily prepared by coagulating with water. The composition of the blend films was gravimetrically analyzed, and the compatibility of the two natural polymers was characterized by Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction. The results indicate good compatibility and strong interactions between cellulose and KGM, resulting in almost no loss of the water‐soluble KGM from the blend films even after the water coagulating and washing. However, microstructure analyses portrayed phase separations in the blend films, namely, egg‐like new phase particles were embedded in a continuous matrix base (MB). Phase diagram analysis and differential scanning calorimetry of the phase inversion coagulation process suggest that relative low molecular mass part of both cellulose and KGM formed the continuous MB, whereas the egg‐like new phase particles were super patterns of relative high molecular mass of both polymers, which played an important role in strengthening the blend material. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1686–1694, 2009     

Low‐band gap copolymers containing thienothiadiazole units: Synthesis,optical, and electrochemical properties

Novel low‐band gap alternating copolymers consisting of 9,9‐bis(2‐ethylhexyl)fluorene and 4,6‐di(2‐thienyl)thieno[3,4‐c][1,2,5]thiadiazole and its 3,3″‐dialkyl derivatives were synthesized by Suzuki copolymerization reaction, and their photophysical and electrochemical properties were studied. The copolymers possess small optical band gap 1.3–1.4 eV. The absorption covers the whole visible spectral region. The long‐wavelength absorption maxima in thin films located at approximately 750–785 nm are significantly red shifted compared with those in solution, indicating strong intermolecular interactions. The introduction of alkyl chains to the thiophene units increases the molecular weights of soluble fractions and solubility of the final copolymers, leading to the improved processability of thin films. Polymer solutions exhibited solvatochromism and thermochromism, which is strongly supported by the involvement of the alkyl chains. The copolymers exhibited ambipolar redox properties and reversible electrochromic behavior. The electronic properties are influenced only slightly by alkyl substituents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2743–2756, 2010     

Applications of shear‐induced polarized light imaging (SIPLI) technique for mechano‐optical rheology of polymers and soft matter materials

A new experimental method for studying the mechano‐optical rheology of polymeric liquids and soft matter materials is presented. The method is based on a combination of rotational rheology and a recently developed optical technique—shear‐induced polarized light imaging (SIPLI). The method provides a unique opportunity to monitor a complete sample view during rheological measurements in plate–plate and cone‐and‐plate geometry. Applications of the method are presented including simultaneous SIPLI and the rheology of the oriented lamellar phase of block copolymers and liquid crystals as well as a study of the thermally induced reversible transformation of worm‐like micelles to spherical micelles. In addition, a direct relation between the shish formation and the polymer melt viscosity upturn during flow‐induced crystallization of semi‐crystalline polymers is demonstrated. An application of SIPLI for quantitative birefringence measurements is also shown. © 2016 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2151–2170     

Effects of the oriented mesophase on the cold crystallization of syndiotactic polystyrene and its blend with poly(2,6‐dimethyl‐1,4‐phenylene oxide)

The effects of molecular orientation on the crystallization and polymorphic behaviors of syndiotactic polystyrene (sPS) and sPS/poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) blends were studied with wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry. The oriented amorphous films of sPS and sPS/PPO blends were crystallized under constraint at crystallization temperatures ranging from 140 to 240°C. The degree of crystallinity was lower in the cold‐crystallized oriented film than in the cold‐crystallized isotropic film. This was in contrast to the case of the cold crystallization of other polymers such as poly(ethylene terephthalate) and isotactic polystyrene, in which the molecular orientation induced crystallization and accelerated crystal growth. It was thought that the oriented mesophase was obtained in drawn films of sPS and that the crystallization of sPS was suppressed in that phase. The WAXD measurements showed that the crystal phase was more ordered in an sPS/PPO blend than in pure sPS under the same annealing conditions. The crystalline order recovered in the cold‐crystallized sPS/PPO blends in comparison with the cold‐crystallized pure sPS because of the decrease in the mesophase content. The crystal forms depended on the crystallization temperature, blend composition, and molecular orientation. Only the α′‐crystalline form was obtained in cold‐crystallized pure sPS, regardless of molecular orientation, whereas α′, α″, and β′ forms coexisted in the cold‐crystallized sPS/PPO blends prepared at higher crystallization temperatures (200–240°C). The β′‐form content was much lower in the oriented sPS/PPO blend than in the isotropic blend sample at the same temperature and composition. It was concluded that the oriented mesophase suppressed the crystallization of the stable β′ form more than that of the metastable α′ and α″ forms during the cold crystallization of sPS/PPO blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1665–1675, 2003