Orientation of miscible and immiscible polymer blends

Polystyrene (PS) and poly(vinylmethylether) (PVME) were used to study the orientation of miscible and immiscible polymer blends. A miscible blend containing 60 wt% PS was prepared by casting the sample from a benzene solution. The immiscible blend was made by annealing the initially miscible mixture above its lower critical solution temperature for different times and temperatures. Fourier transform infrared spectroscopy and birefringence were used to measure the orientation of PS and PVME, before and after phase separation. Stress-strain curves were also measured for the two types of systems. It was found that the two polymers orient differently and that phase separation induces an increase in the overall orientation of the mixture, in the modulus and in PS orientation. The differences observed between pure PS and PS in the blend were attributed to changes in specific interactions and density of entanglements. The variations with phase separation were attributed to a change in the morphology of the system.     

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.     

Selective localization of multi-wall carbon nanotubes in homopolymer blends and a diblock copolymer. Rheological orientation studies of the final nanocomposites

In this study, pristine as well as polystyrene (PS) and poly(2-vinylpyridine) (P2VP) functionalized multi-wall carbon nanotubes (MWCNTs) were selectively incorporated in homopolymer binary blends of PS/P2VP and diblock copolymer (BCP) of the PS-b-P4VP type [P4VP: poly(4-vinylpyridine)]. Studies on the blends verified the chemical affinity of PS and P2VP grafted MWCNTs to the corresponding phase. Based on the results obtained from the blend systems, MWCNTs were incorporated in a PS-b-P4VP copolymer matrix with lamellar morphology and large amplitude oscillatory shear (LAOS) experiments were performed to achieve orientation of the BCP lamellae. The PS grafted MWCNTs (MWCNT-g-PS) were selectively sequestered in the PS phase and the P2VP grafted MWCNTs (MWCNT-g-P2VP) in the P4VP phase of the diblock copolymer. Unfunctionalized pristine MWCNTs were localized on the PS phase of the blend system and no special preference was observed towards the diblock copolymer PS domains. Small angle X-ray scattering (SAXS) analysis revealed the orientation of the alternating lamellae formed by the diblock copolymer when studied by LAOS. The localization of PS and P2VP grafted MWCNTs on the corresponding blend and BCP phase was also verified by transmission electron microscopy (TEM) studies.     

Oriented PP-PS composites obtained by polymerization of styrene inside oriented PP matrices. I. Dispersion of PS and the composites' orientation

Dispersion of polystyrene (PS) and the molecular orientation of the polypropylene–polystyrene (PP–PS) composites acquired by the in situ polymerization of styrene in the oriented PP matrices were characterized by microscopic observations, birefringence measurements, and differential scanning calorimetry. It has been shown that applied processing of the “envelope” polymerization leads to obtaining oriented composites with large contents and the specific dispersion of PS. Some composites exhibit a substantial gradient of PS concentration and a gradient of molecular orientation, both strongly dependent on the initial structure of the oriented PP matrix. The modification of the PP structure taking place during processing does not disturb the orientation of the matrices deformed to the higher draw ratios. The structural changes of the oriented PP induced by processing are reflected in the shrinkage behavior and mechanical properties discussed in the second part of this paper. © 1993 John Wiley & Sons, Inc.     

Orientation Effect of the Wafer on the Structural Properties of P+ Type Porous Silicon Layers

The structural properties of (111) oriented p⁺ type Porous Silicon (PS) samples are investigated using various X-ray diffraction techniques and compared to (001) p⁺ type PS layer structure. High resolution X-ray diffractometry was used to record rocking curves and reciprocal space maps, giving indications about the crystalline quality of the PS samples as well as about the pore orientation. X-ray diffraction and reflectivity performed on thin PS layers allow to estimate the layer thickness, porosity and roughness of the PS/substrate interface.     

Effect of thermal history on the molecular orientation in polystyrene/poly(vinyl methyl ether) blends

The effect of thermal history on the orientation and relaxation behavior of blends of polystyrene with poly(vinyl methyl ether) (PS/PVME) has been studied using polarization modulation infrared linear dichroism (PM-IRLD) and differential scanning calorimetry (DSC). DSC shows that miscible PS/PVME blends containing 70% of PS can be physically aged at temperatures above their mean glass transition temperature (T_g). PM-IRLD measurements reveal that both components become more oriented upon stretching at 51 °C (8 °C above T_g) if the sample is aged at the deformation temperature prior to stretching. Room-temperature aging can also lead to an increased orientation if the heating time at 51 °C is kept short. Moreover, PS and PVME develop a larger orientation in phase-separated blends than in miscible ones, and their relaxation is hindered. The results have been interpreted considering the morphology of the samples, including the presence of concentration fluctuations in miscible blends, and the effect of the local environment on the rigidity of the chains.     

Fourier transform infra-red study of uniaxially oriented poly(2,6-dimethyl 1,4-phenylene oxide)-atactic polystyrene blends

Infra-red measurements of the dichroic ratio of absorption bands of atactic polystyrene-poly(2,6-dimethyl 1,4-phenylene oxide) blends provide a valuable method to investigate the orientation of the chains of both polymers. The results show that PPO and PS chains orient in a different way when subjected to an uniaxial strain, in spite of the compatible nature of the blend. The PPO orientational behaviour does not depend on PPO concentration in the studied concentration range (0–35%) while PS orientation regularly increases up to 25% PPO then remains constant.     

Injection and compression molding of polystyrene/high-density polyethylene blends—phase morphology and tensile behavior

Processing and compatibilization effects on the phase morphology and the tensile behavior of blends of polystyrene and high-density polyethylene (PS/HDPE) were investigated. As predicted by theory, high shear rates encountered during extrusion blending led to efficient minor phase emulsification in immiscible PS/HDPE blends for which the viscosity ratio approaches unity. Consequently, the emulsifying effect of a styrene/ethylene-butylene/styrene (SEBS) compatibilizer was found to be negligible. In the subsequent molding process, disintegration, shape relaxation and coarsening of the minor phase domains were found to be responsible for the morphological evolution. In the compression molding process, morphological observations showed that the rate of minor phase coarsening followed the predictions of the Ostwald ripening theory, in agreement with the rheological analysis. In the injection molding process, minor phase coarsening was attributed to shear coalescence. Tensile tests performed on compression molded and injection molded blends showed that the mechanical behavior of PS/HDPE blends depend strongly upon the matrix orientation as well as the dispersed phase morphology and orientation. In both postforming operations, compatibilization effects on the morphological stability and the tensile behavior of PS/HDPE blends were found to be dependent upon the composition and the rheological behavior of the blend. Evidence of adhesion between the PS and HDPE phases was observed in the presence of SEBS in HDPE-rich blends.     

The surface orientation of polystyrene measured by liquid contact angle

The surface contact angle of glycerol and of water on polystyrene (PS) films has been found to depend on the extent of uniaxial draw for atactic PS. The contact angle depends on direction for the smooth films of PS drawn by solid state coextrusion. Results as a function of draw ratio to values over 4 on these noncrystalline PS samples, M_w = 6 × 10⁵, have also been interrelated with other measures of orientation such as the anisotropy of surface and bulk properties measured, respectively, by dichroic reflectance infrared spectroscopy and by birefringence.     

Deformation studies of polystyrene/poly(vinyl methyl ether) blends by mechanical-vibrational spectroscopy

We have analyzed the deformation behavior of compatible and incompatible polystyrene (PS) and poly(vinyl methyl ether) (PVME) blends by a combination of mechanical and vibrational spectroscopy. Macroscopic properties and segmental orientation were found to be sensitive to molecular weight, strain rate, and temperature of measurement above the glass-transition temperature. Considerably different orientation functions were found for the PS and PVME components. For the experiments carried out above the T_g of the blends, the deformation behavior measured was consistent with expectations of a rubbery network.     

Energy model of the interfacial slip of polymer blends under steady shear

Interfacial slip at high‐density polyethylene (HDPE)/polystyrene (PS) and high‐impact polystyrene (HIPS)/PS interfaces under steady shear was studied. The multilayer structure and energy model for steady shear proposed by Lam and colleagues was employed. Results indicated that there was no interfacial slip at the HIPS/PS interface. However, interfacial slip was detected for HDPE/PS under steady shear. Small interfacial thickness and weak interactions between HDPE and PS was proposed as the reason for interfacial slip at the HDPE/PS interface. Chain orientation under shear was believed to promote chain disentanglement in the interfacial layer and therefore increase interfacial slip. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1164–1470, 2003     

Characterization of molecular orientation in injection-molded thermoplastics by transmission and reflection infrared spectroscopy

Orientation in injection moldings of polypropylene (PP), polyethylene (PE), polyamide 6 (PA-6), and polystyrene (PS) was investigated by transmission and reflection infrared spectroscopy. Orientation of the surface was measured by the reflection method, the depth profiles of orientation and of the fraction of the crystalline phase were measured by the transmission spectroscopy of microtome sections. The maximum of orientation of PP lies in the subsurface layer (ca. 250 μm); the crystalline phase is oriented more than the amorphous one. The maximum of the depth profile of orientation corresponds to the minimum of the fraction of the crystalline phase in PP. The profile of orientation of PE Is similar; at the beginning (to a depth of about 500 μm) the parallel orientation of the c axis of the crystalline phase is the most distinct one, towards the center the orientation of the a axis passes from the perpendicular to the parallel one. Under the described molding conditions PA-6 is not significantly oriented, the fraction of the crystalline phase increases towards the center of the molding. Unoriented PA-6, the surface layer of which was removed by milling, has a highly oriented surface due to its mechanical treatment. No pronounced orientation of PS was observed under the molding conditions used.     

Craze initiation in glassy polymers: Quantifying the influence of molecular orientation

A study has been made of crazing stress in oriented glassy polystyrene. The aim was to develop a methodology for prediction of crazing stress in glassy polymers with frozen-in molecular orientation. Oriented specimens of two grades of monodisperse polystyrene (PS) and one grade of polydisperse PS were produced by uniaxial melt-drawing and subsequent quenching of compression-moulded bars. Birefringence and crazing stress parallel to the draw direction (in the presence of diethylene glycol) were measured on miniature beam specimens cut from them. The crazing stress increased substantially with orientation, and the magnitude of the increase relaxed approximately on a timescale associated with the longest Rouse time. Specifically, a linear correlation was found, to within experimental scatter, between the increase in crazing stress and the orientation expressed in terms of frozen-in conformational stress, as predicted by the theory of Maestrini and Kramer [13]. The inverse gradient (constant β in the theory) was found to be 0.059 ± 0.002, when inferring the conformational stress from the measured birefringence. Crazing was found to be suppressed in favour of yielding in the most highly oriented specimens, and this could be explained in terms of the differing sensitivities of crazing and yield to molecular orientation.     

A block copolymer nanotemplate for mechanically tunable polarized emission from a conjugated polymer

A polymer blend system consisting of polystyrene grafted onto poly (p-phenylene ethynylene) (PS-g-PPE) and poly (styrene-block-isoprene-block-styrene) triblock copolymer (SIS) yields highly polarized emission due to the unidirectional alignment of the PPE molecules. During the roll casting, the triblock copolymer microphase separates and creates unidirectionally aligned PS cylindrical microdomains in the rubbery PI matrix. PPE, a fluorescent conjugated polymer, was grafted with polystyrene (PS) side chains that enabled sequestration and alignment of these rigid backbone emitter molecules into the PS microdomains of the SIS triblock copolymer. Deforming the thermoplastic elastomer in a direction perpendicular to the orientation direction of the cylinders causes rotation of the PS cylinders and the PPE emitter molecules and affords tunable polarized emission due to re-orientation of the PPE containing PS cylinders as well as film thinning from Poisson effect.     

ABS,PS,PP／PE共混物的声发射研究

报道了ＡＢＳ,ＰＳ,ＰＰ／ＰＥ共混物的声发射研究。探讨了热处理和温度骤变对ＡＢＳ和ＰＳ声发射的影响,考察了ＰＰ／ＰＥ不同共混比的声发射和断裂行为,并且用电镜分析了共混物的取向结构和断面形态。结果表明,声发射与材料内应力的大小关系密切,提出了可以用声发射技术来评价塑料的成型条件的观点,揭示了ＰＰ／ＰＥ共混材料单轴拉伸断裂主要是由分子链高度取向所形成的纤维断裂和滑移造成的。     

Effect of electrical field on dipoles in polymer composites

Orientation of two bipolar compounds embedded in polymer composites was studied. Poly(methyl methacrylate) (PMMA) dissolved in acetone was doped with a cobaltborane derivative of 1,2‐dimethylimidazole and polystyrene (PS) dissolved in toluene was doped with the 3‐(1,2‐dimethyl imidazole)‐borane. To orient the dipoles, the composites were exposed to external electrical field: PMMA composite at the temperature of glass transition (T_g) and PS composite during evaporation of the toluene solvent. The degree of dipole orientation was estimated by the change in relative permittivity (ε) of the resulting composite film. The dependence of the ε on the temperature, frequency, voltage, and dipole concentration was studied. It was found that the dipole's distribution in the composite film was not homogenous. At the T_g, the dipoles in PMMA became oriented by external direct electrical field and the orientation was conserved after cooling to lower temperatures. In a PS‐based composite, the significant permittivity increase was observed already at low‐dopant concentrations. The dipole orientation achieved during solvent evaporation was also permanent and the composite permittivity was an increasing function of the film thickness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 40–45, 2004     

Adhesion Properties of Acrylic Copolymers Modified with Si-Containing Copolymer

We made clear the cause of the increase in peel strength of pressure sensitive (PS) adhesives as a function of contact time, and investigated how to modify PS adhesives to maintain a low and constant peel strength for a long time. It was found that polar groups in the adhesive orient to the interface between the adhesive and the (stainless steel) metal substrate (SUS 304) so as to minimize interfacial free energy during adhesion, and the orientation increased affinity between the adhesive and the metal material and increased the peel strength as a result. The use of modifier which contained both P(MMA-co-SiMA) and PDMS showed an excellent modification effect, although modification with only PDMS or P(MMA-co-SiMA) was not sufficient. It was suggested that PDMS which migrated to the surface was extended uniformly over the surface by PDMS segments of P(MMA-co-SiMA) and that the enriched layer of PDMS on the adhesive surface worked as a barrier to prevent the orientation of polar groups in bulk. Therefore, low and constant peel strength could be achieved.     

Adhesion Properties of Acrylic Copolymers Modified with Si-Containing Copolymer

We made clear the cause of the increase in peel strength of pressure sensitive (PS) adhesives as a function of contact time, and investigated how to modify PS adhesives to maintain a low and constant peel strength for a long time. It was found that polar groups in the adhesive orient to the interface between the adhesive and the (stainless steel) metal substrate (SUS 304) so as to minimize interfacial free energy during adhesion, and the orientation increased affinity between the adhesive and the metal material and increased the peel strength as a result. The use of modifier which contained both P(MMA-co-SiMA) and PDMS showed an excellent modification effect, although modification with only PDMS or P(MMA-co-SiMA) was not sufficient. It was suggested that PDMS which migrated to the surface was extended uniformly over the surface by PDMS segments of P(MMA-co-SiMA) and that the enriched layer of PDMS on the adhesive surface worked as a barrier to prevent the orientation of polar groups in bulk. Therefore, low and constant peel strength could be achieved.     

A simple illustration of structure-properties relationships for short fiber-reinforced thermoplastics

In this paper, a simple theoretical model for elastic properties of short fiber-reinforced thermoplastic (SFRTP) composite systems is described, which considers the effect of two important structural parameters, viz., fiber aspect ratio distribution and fiber orientation distribution. An experimental technique for producing SFRTP samples featuring a fairly uniform fiber orientation is described, and a broad set of experimental results on the mechanical properties of SFRTP systems based on polystyrene (PS) and polyethylene (PE) resins with several fiber loadings is presented. The use of the simple theoretical model to analyze the experimentally-determined elastic properties is discussed.     

Structured latex particles based on natural rubber for high-impact polymer blends

Natural latex (NR) particles, modified with a hard shell of poly(methyl methacrylate) (PMMA) and with a substructure of PMMA (type "NR-M") or polystyrene (type "NR-SM"), were tested as compatibilizers in blends of polycarbonate (of bisphenol A, PC) and PMMA or PS. During melt blending, the modified NR particles were torn apart, from an original size of >0.5 μm down to ≅0.1 μm in diameter. Two different types of particle distribution were observed in the blends: in PC/PMMA/NR-M blends, the NR-M particles were dispersed in the PMMA phase, whereas, in PC/PS/NR-SM blends, the NR-SM particles formed interface layers between PC and PS phase domains. The latter blend morphology, distinguished by continuous rubbery interface layers of NR-SM, turned out to be mechanically excellent in injection-moulded parts. The poor impact strength of PC/PS was raised by an order of magnitude. The effect depends on the orientation in the injection-moulded test bars.