Toughening of immiscible PPE/SAN blends by triblock terpolymers

The mechanical performance of immiscible blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPE) and poly(styrene-co-acrylonitrile) (SAN) and the subsequent influence of compatibilisation by tailored polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock terpolymers (SBM) on the mechanical performance under static and dynamic loads is analysed in detail. A PPE/SAN 60/40 blend was selected as a base system for the compatibilisation experiments. The observed static tensile behaviour is described by micromechanical models and correlated to the blend microstructures as observed by transmission electron microscopy. In most cases, the addition of the SBM triblock terpolymers further enhances the ductility of the blend while only leading to a minor reduction of modulus and strength. Triblock terpolymers with symmetric end blocks, mainly located at the interface between PPE and SAN, led to nearly isotropic specimens. In contrast, SBM materials with a longer polystyrene block predominantly formed micelles in the PPE phase and the blends revealed a highly anisotropic morphology. Comparative investigations of the fatigue crack growth behaviour parallel to the direction of injection also reflected this variation in mechanical anisotropy of the compatibilised blends. A poor toughness and a predominant interfacial failure were observed in the case of the SBM with a long polystyrene block. In contrast, a considerable improvement in properties as a result of pronounced plastic deformations was observed for blends compatibilised by triblock terpolymers with symmetric end blocks. The systematic correlation between morphology and mechanical performance of compatibilised PPE/SAN blends established in this study provides an efficient way for the desired selection of suitable and effective compatibilising agents, ensuring both a superior multiaxial toughness as well as a high strength and modulus of the overall system.     

Compatibilisation of heterogeneous acrylonitrile-butadiene rubber/polystyrene blends by the addition of styrene-acrylonitrile copolymer: effect on morphology and mechanical properties

Compatibility of polystyrene (PS) and acrylonitrile-butadiene rubber (NBR) blend is poor, hence technological compatibilisation was sought by the addition of styrene-acrylonitrile copolymer (SAN). The interfacial activity of SAN was studied as a function of compatibiliser concentration by following the morphology of three different blend series, viz. PS/NBR 30/70, 50/50 and 70/30. Incorporation of SAN into PS/NBR blends improved tensile, tear, hardness and impact properties. Addition of SAN beyond the saturation level (critical micelle concentration) adversely affected the ultimate properties. Attempts were made to understand the conformation of the compatibiliser at the interface. The protocol of mixing was varied, and, its effect on the mechanical properties was investigated. The experimental results were compared with the theoretical predictions of Noolandi and Hong.     

Synthesis and morphological studies of polyisoprene-block-polystyrene-block-poly(vinyl methyl ether) triblock terpolymer

The triblock terpolymer (PI-b-PS-b-PVME) consisting of polyisoprene (PI), polystyrene (PS) and poly(vinyl methyl ether) (PVME) was synthesized by coupling reaction between living PI-b-PS anion and end-chlorinated PVME prepared via living cationic polymerization. This polymer is an amphiphilic block polymer and unique in a sense that it exhibits complex phase behavior because PS and PVME have a lower critical solution temperature (LCST)-type phase diagram while PI and PS (or PVME) have an UCST-type phase diagram. This unique architecture would result in a step-wise microphase separation to form a three-phase microdomain structure. It was observed by transmission electron microscopy with ultrathin sections that the toluene-cast film of PI-b-PS-b-PVME has a two-phase lamellar structure consisting of PI microdomains and mixed PS/PVME microdomains. Applying a drop of water onto the ultrathin sections induced further microphase separation between PS and PVME within the lamellar microdomains resulting in the three-phase structure. Water is a selective solvent for PVME and might have lowered the order-disorder temperature between PS and PVME. This step-wise microphase separation may be a new technique to control microphase-separated structures in triblock terpolymers.     

Compatibilising action of random and triblock copolymers of poly(styrene-butadiene) in polystyrene/polybutadiene blends: A study by electron microscopy, solid state NMR spectroscopy and mechanical measurements

Scanning electron microscopy, solid-state proton NMR spectroscopy and static mechanical analysis have been performed in order to evaluate the compatibilising action of random copolymers of polystyrene and polybutadiene and triblock copolymers of poly(styrene-butadiene-styrene) in incompatible polystyrene/polybutadiene (PS/PB) blends. Scanning electron microscopic examination of the cryofractured and etched surfaces showed high degree of compatibilising action of the triblock copolymers as evidenced by the very sharp decrease of the domain size of the dispersed phase followed by an increase at higher concentrations. This is a clear indication of interfacial saturation. These results were in agreement with the theoretical predictions of Noolandi and Hong. The random copolymer was not effective in compatibilising the system. Solid-state proton NMR experiments were performed on the uncompatibilised and compatibilised blends. The proton spin-lattice relaxation times in the laboratory frame, T₁(H), and in the rotating frame, T_1ρ(H), and spin-spin relaxation times, T₂(H), were carefully measured for the systems. Significant changes were observed for the systems compatibilised with triblock copolymers due to the preferential localisation of the copolymers at the PS/PB interface. However, the random copolymer did not have any compositional drift and is not an effective interface modifier in agreement with microscopy study. The static mechanical properties of the blends have also been analysed. The addition of triblock copolymers increased the mechanical properties of the blends. Finally, attempts have been made to correlate the NMR results with the microstructure and mechanical properties of the blends.     

Properties and morphologies of PVC/nylon terpolymer blends

A new kind of blends of polyvinyl chloride (PVC)/nylon terpolymer was reported in this article. Two compatibilizers were used in this study: one is a terpolymer of ethylene–n‐butyl acrylate–monoxide (EnBACO); the other is terpolymer of EnBACO grafted with maleic anhydride (EnBACO‐g‐MAH). The observation of scanning electron microscope (SEM) reveals that the PVC/nylon terpolymer blends have a two‐phase structure; and the nylon terpolymer phase is the continuous phase, and PVC domains in the PVC/nylon terpolymer/EnBACO‐g‐MAH blends have fine dispersion over a broad range of the PVC/nylon terpolymer ratio. EnBACO‐g‐MAH is more compatible with the nylon terpolymer than EnBACO. EnBACO and EnBACO‐g‐MAH have different effects on the glass transition temperatures of the PVC phase and nylon terpolymer phase in the blends. The notched Izod impact strength, tensile strength, elongation at break, Vicat softening temperature (VST), and melt flow index (MFI) critically depend on PVC/nylon terpolymer ratio, the kinds and concentration of the compatibilizers. The PVC/nylon terpolymer/EnBACO‐g‐MAH blends display a good combination of high toughness, high flowability, and high VST under low load. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2823–2832, 2001     

Influence of the viscosity ratio in PC/SAN blends filled with MWCNTs on the morphological,electrical, and melt rheological properties

Co-continuous polycarbonate (PC)/poly(styrene-acrylonitrile) (SAN) = 60/40 wt.% blends were filled with 1 wt.% multi-walled carbon nanotubes (MWCNTs), which selectively localized within the PC component. To study the influence of the viscosity ratio, PCs with different viscosities were selected resulting in PC/SAN viscosity ratios (at 100 rad/s) between 1.2 and 4.5. With increasing viscosity ratio, smaller blend structures were observed. Furthermore, optical microscopy revealed that the filler dispersion was improved with decreasing PC viscosity. The highest electrical conductivity was achieved for the blend composite with the coarsest morphology, containing the low viscosity PC and having the lowest PC/SAN viscosity ratio. Transmission electron microscopy analysis indicated that for the composite prepared with high viscosity PC, not all of the incorporated MWCNTs were able to localize completely into the PC component. Instead, some MWCNTs were found to be stacked at the interface of the two polymers, indicating that the high PC melt viscosity had a restricting effect on the movement of the MWCNTs. Moreover, with electrical conductive atomic force microscopy, it was proven that small, spherical PC particles, even if filled with CNTs, do not take part in the conductive network of the blend composites. Rheological analyses showed a correlation with the morphological analysis and the electrical conductive behavior of the blend composites. In summary, a lower viscosity ratio between the blend components, in which upon addition due to thermodynamic reasons the CNTs localize (here PC), and the other component (here SAN) is favorable for high electrical conductivity values.     

Miscibility study of polycarbonate and SBS triblock copolymer blends

Polymer blends of Polycarbonate (PC) and Styrene-Butadiene-Styrene triblock (SBS) have been investigated. SBS copolymers have four different styrenic contents, three of which are linear SBS. PC and PS blends are partially miscible as revealed by dynamic mechanical analysis with two clear Tgs near 100–150°C. On the contrary, PC/SBS blends have only one Tg with a left shoulder. Based on the PS domain model of pure SBS, we suggest a micelle model based on the structure when the micelle and absorb PC in the PC/SBS blends. The micelle plays an important role in improving the miscibility. The proposed micelle model has been empolyed to interpret the testing results, such as toughness, impact strength, dynamic mechanical property and SEM morphologies. This proposed micelle model seems a worth-while method to explain the properties of partialtly miscible blends of PC and SBS.     

Thermal,mechanical, and adhesive properties of HDPE/reactive ethylene terpolymer blends

Blends of high‐density polyethylene (HDPE) and a reactive ethylene terpolymer (RET) were developed as a protective coating material for steel. A morphological study with scanning electron microscopy (SEM) indicated that blends of HDPE and RET are immiscible, while high interaction between these two phases was found. Crystallization and thermomechanical behavior of the blends were investigated using differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The crystallinity of HDPE decreased with the incorporation of RET slightly due to the disturbance of the highly viscous RET melt during crystallization. Tensile tests indicated that the addition of RET reduced both strength and modulus but increased the strain‐to‐break. Adhesion to steel substrates was improved with the incorporation of the RET component. An optimum composition of RET loading was detected to be in the range of 25–33 wt %, leading to the best adhesive performance, high tensile strength, and strain‐to‐failure of the blend material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 331–338, 2007     

Polymer blends of PA6 and PPE compatibilized by phenolic novolac epoxy coupler

A commercially available multi-functional epoxy monomer, phenolic novolac epoxy (PNE) resin, has demonstrated to be an effective reactive compatibilizer for the blends of polyamide-6 (PA6) and poly(2,6-dimethyl-1,4-phenylene ether) (PPE). It requires about 1/10 by weight relative to a typical conventional reactive compatibilizer to achieve same level of compatibilization in terms of mechanical property improvements. By acting as a coupler, this multi-functional epoxy can react with PA6 and PPE during melt blending and produces the desirable PA6-co-PNE-co-PPE mixed copolymers at the interface. This in situ-formed copolymer containing PA6 and PPE segments tends to reside at the interface between PA6 and PPE domains to reduce melt interfacial tension and enhance interface adhesion as an efficient compatibilizer of the PA6/PPE blends.     

Compatibilization and properties of SAN/EPDM blends with the addition of coagents

SAN and EPDM are not miscible. In this work, the dry blending of SAN and EPDM using Centrex (acrylonitrile/EPDM/styrene graft copolymer) and EPMMA (EPDM‐g‐Mah) as coagents was studied. Centrex content was used at 6–20 wt %. EPMMA content in the mixture was 20 wt %. The effects of coagent type and content on the mechanical properties and morphology were investigated. SEM micrographs of SAN/EPDM/Centrex and SAN/EPDM/EPMMA blends showed that both Centrex and EPMMA have an effective role in forming a finer morphology. For the ternary blends, the addition of coagent resulted in a significant reduction in the size of the dispersed phase. The mechanical properties of SAN/EPDM/coagent blends were improved significantly in comparison to the simple SAN/EPDM blends. SAN/EPDM/Centrex blends showed higher stress‐at‐break and SAN/EPDM/EPMMA blends showed higher impact strength. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

PBT-b-PEO-b-PBT triblock copolymers: Synthesis,characterization and double-crystalline properties

We demonstrated here a facile method to synthesize novel double crystalline poly(butylene terephthalate)-block-poly(ethylene oxide)-block-poly(butylene terephthalate) (PBT-b-PEO-b-PBT) triblock copolymers by solution ring-opening polymerization (ROP) of cyclic oligo(butylene terephthalate)s (COBTs) using poly(ethylene glycol) (PEG) as macroinitiator and titanium isopropyloxide as catalyst. The structure of copolymers was well characterized by ¹H NMR and GPC. TGA results revealed that the decomposition temperature of PEO in triblock copolymers increased about 30 °C to the same as PBT copolymers, after being end-capped with PBT polymers. These triblock copolymers showed double crystalline properties from PBT and PEO blocks, observed from DSC and WAXD measurements. The melting and crystallization peak temperatures corresponding to PBT blocks increased with PBT content. The crystallization of PBT blocks showed the strong confinement effects on PEO blocks due to covalent linking of PBT blocks with PEO blocks, where the melting and crystallization temperatures and crystallinity corresponding to PEO blocks decreased significantly with increment of PBT content. The confinement effect was also observed by SAXS experiments, where the long distance order between lamella crystals decreases with increasing PBT length. For the triblock copolymer with highest PBT content (PBT₅₄-b-PEO₂₂₇-b-PBT₅₄), this effect shows a 30 °C depression on PEO crystals' melting temperature and 77% on enthalpy, respectively, compared to corresponding PEO homopolymer. The crystal morphology was observed by POM, and amorphous-like spherulites were observed during PBT crystallization.     

Influence of blend composition on the mechanical properties and morphology of PC/ASA/SAN ternary blends

Bisphenol A polycarbonate/acrylonitrile–styrene–acrylic/styrene–acrylonitrile copolymer (PC/ASA/SAN) ternary blends were prepared over a range of compositions via mixing PC, SAN, and ASA copolymer by melt blending. An analysis was made on the mechanical properties and morphology of the blends. Special care was taken to make comparisons of the morphologies and properties of blends with different SAN content. When a small amount SAN was introduced to PC/ASA blends, the dispersion condition of ASA in the matrix was improved and a better integrated mechanical properties was realized. Further increasing the SAN content led to a decrease of impact strength, which was due to the changing of the morphology of the blends and the inherent brittleness of matrix. The study about the effect of ASA content on the properties of PC/ASA/SAN blends showed that the blend with 20 wt% ASA had good mechanical properties.     

Morphology and physical properties of SAN/NBR blends: The effect of AN content and melt viscosity of SAN

To study the effect of dispersed poly(butadiene-co-acrylonitrile) (NBR) rubber size on the physical properties of poly(styrene-co-acrylonitrile) (SAN)/NBR blends, SANs with various melt viscosities and acrylonitrile (AN) contents were examined. The dispersed size of NBR, whose AN content is 30 wt %, was reduced as the melt viscosity of the SAN matrix was increased or as the AN content of the SAN matrix was reduced in the range of 19–32 wt %. As the melt viscosity of the SAN matrix was increased, the damping peak of the NBR phase moved to a higher temperature, and as the AN content of SAN was reduced, the damping peak of the SAN phase moved to a lower temperature. Higher values of impact strength and elongation at break and reduced yield behavior at a low shear rate were observed at a finer dispersion of NBR. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 935–941, 1999     

Crystallization of double crystalline block copolymer/crystalline homopolymer blends: 1. Crystalline morphology

The crystalline morphology formed in binary blends of poly(ε-caprolactone)- block-polyethylene (PCL-b-PE) copolymers and PCL homopolymers has been examined using synchrotron small-angle X-ray scattering (SR-SAXS) and differential scanning calorimetry (DSC) as a function of the homopolymer fraction in the blend. The PE block crystallized first on quenching from a lamellar microdomain structure to set a hard lamellar morphology (PE lamellar morphology) in the blend, followed by the crystallization of PCL chains (i.e., PCL homopolymers + PCL blocks). Two binary blends were studied by considering the miscible state of PCL homopolymers in the microdomain structure: when the PCL homopolymers were uniformly mixed with PCL blocks, they formed a mixed crystal. When the PCL homopolymers were localized between PCL blocks in the microdomain structure, DSC results suggested the possible formation of separate PCL crystals in the PE lamellar morphology. The effect of the advance crystallization of PE blocks on the subsequent crystallization of PCL chains was discussed as compared with the crystalline morphology formed in PCL-block-polybutadiene copolymer/PCL homopolymer blends, where the crystallization of PCL chains started directly from a microdomain structure without forming the hard lamellar morphology.     

Dynamic and static properties of SBS triblock copolymer and their blends

By using a dynamic testing method (Rheovibron), it has been established that for a pure triblock copolymer (styrene-butadiene-styrene, SBS), the morphology is composed of a continuous phase, a dispersed phase and an interphase. The predominance of the phase depends upon whether the polymer is cast from a good or poor solvent for each block. For the blends of SBS with PS and PBd, the interphase occupies a greater fraction as indicated by the fact that its corresponding molecular relaxation temperature range is much broader (10°–80°C) than that of pure SBS (60°–80°C). If the blends of SBS with its corresponding homopolymers are heated at 140°C for 45 min, the fraction of the interphase increases significantly and the onset of molecular relaxation is lowered to ?10°C. The viscosities of SBS and their blends are measured by both dynamic and static methods. Complex viscosities calculated from the dynamic method show transitions similar to those of storage moduli. Viscosities at different temperatures from these two methods are superimposed onto master curves.     

Radiation‐processed polychloroprene‐co‐ethylene–propene diene terpolymer blends: Evaluation of blend morphology,miscibility, and physical properties

The miscibility of polychloroprene rubber (CR) and ethylene–propylene–diene terpolymer rubber (EPDM) was studied over the entire composition range. Different blend compositions of CR and EPDM were prepared by initially mixing on a two‐roll mill and subsequently irradiating to different gamma radiation doses. The blends were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, density measurement, hardness measurement, and solvent permeability analysis. The compatibility of the blends was studied by measuring the glass transition temperature and heat capacity change of the blends. The immiscibility of blends was reflected by the presence of two glass transition temperatures; however, partial miscible domains were observed due to inter diffusion of phases. Permeation data fitted best with the Maxwell's model and indicated that in CR‐EPDM blends, EPDM exists as continuous phase with CR as dispersed phase for lower CR weight fractions and phase inversion occurred in 40–60% CR region. It was observed that CR improved oil resistance of EPDM; however, the effect was prominent for blends of >20% CR content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of compatibilizer on morphology and mechanical properties of TPU/SAN blends

Melt blends of thermoplastic polyurethane (TPU) and Poly(styrene‐co‐acrylonitrile), (SAN) of various compositions were prepared using a two‐roll mill. Two blends of composition 70:30 and 50:50 TPU/SAN were selected for compatibility studies. The compatibility effect of SMA on these incompatible blends was studied. The morphology and physical properties of blends were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Fourier transform infrared spectra (FTIR) and mechanical properties. TPU/SAN/SMA 70:30:5 showed better compatibility than other blend ratios.     

Reactive compatibilization of PET and PPE blends by epoxy couplers

A commercially available tetrafunctional epoxy monomer was demonstrated to be an effective reactive compatibilizer for blends of poly(ethylene terephthalate) (PET) and polyphenylene ether (PPE). It requires about 10–20% by weight of a conventional reactive compatibilizer to achieve the same level of compatibilization in terms of domain size reduction and mechanical property improvement. This epoxy monomer is able to contact and react with PET and PPE simultaneously during high shear extruder blending to form the desirable PET–epoxy–PPE mixed copolymer. This mixed copolymer contains PET and PPE segments that tend to anchor at the interface to act as an efficient compatibilizer of the PET and PPE blends. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 739–753, 1997     

Ionomer compatibilised PA6/EVA blends: mechanical properties and morphological characterisation

The compatibilisation of PA6/EVA blends with the addition of an ionomer on the mechanical properties and morphology were studied as a function of ionomer concentration with the primary aim of enhancing the impact strength of PA6 by EVA. The level of EVA was kept at 20%, which formed the dispersed phase, and the ionomer content was varied from 0 to 1.6 wt%. It was found that notched Izod impact strength of PA6/EVA/ionomer blends increased with the incorporation of ionomer to about three times of the value for uncompatibilised PA6/EVA blends. Further, it was observed that on incorporation of the ionomer the tensile strength also increased significantly. Analysis of the tensile data using predictive theories indicated an enhanced interaction of the dispersed phase and the matrix. SEM studies of cryogenically fractured surfaces indicated a decrease in dispersed phase domain size with the addition of the ionomer, while the impact fractured surfaces of PA6/EVA blends indicated extensive deformation with the formation of rumples indicating increased interfacial adhesion as compared to PA6/EVA blends. An attempt has been made to evaluate the compatibilising efficiency of ionomer in PA6/EVA blends.     

Effect of the type of SAN in SAN/CPE blend: Morphology,mechanical, and rheological properties

The effect of the molecular weight and acrylonitrile (AN) content of the styrene-acylonitrile copolymer (SAN) on the morphology, mechanical, and rheological properties of SAN/chlorinated polyethylene (CPE) blends was studied. The interaction between dispersed particle and matrix is expected to be optimal at the 25% AN content of SAN. Phase inversion from a dispersion to a continuous phase appears to occur above 50 wt % CPE. Mechanical properties increased with molecular weight at a constant AN content of SAN. Morphological, mechanical, and rheological properties were more sensitive to the AN content, rather than the molecular weight of SAN. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 27–36, 1998