Effect of blending sequence on the microstructure and properties of PBT/EVA‐g‐MAH/organoclay ternary nanocomposites

Ternary nanocomposites based on poly(butylene terephthalate) (PBT), maleic anhydride grafted poly(ethylene‐co‐vinyl acetate) (EVA‐g‐MAH), and organically modified montmorllonite (organoclays) were prepared through four different blending sequences in a Haake rheocord mixer: (1) To blend PBT, EVA‐g‐MAH and organoclays in one step; (2) First to prepare EVA‐g‐MAH/organoclay nanocomposite, then mix it with PBT to get the final nanocomposite; (3) To mix PBT with organoclays first, then the PBT/organoclay nanocomposite with EVA‐g‐MAH. (4) To mix organoclays with the PBT/EVA‐g‐MAH blend. The microstructure of the PBT/EVA‐g‐MAH/organoclay ternary hybrids was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). It was found that the blending sequence significantly influences the microstructure of PBT/EVA‐g‐MAH/organoclay ternary hybrids and the dispersion behavior of the organoclays in the polymer matrix. Tensile and impact properties of the hybrids were also studied. The results showed that the mixing sequence (2) gives the best tensile and impact strength due to its fine “sea‐island” morphology of PBT/EVA‐g‐MAH blend and good dispersion of the organoclays in the continuous PBT matrix.     

Effect of EPDM‐g‐MAH on the morphology and properties of PA6/EPDM/HDPE ternary blends

The formation of core‐shell morphology within the dispersed phase was studied for composite droplet polymer‐blend systems comprising a polyamide‐6 matrix, ethylene‐propylene‐diene terpolymer (EPDM) shell and high density polyethylene (HDPE) core. In this article, the effect of EPDM with different molecular weights on the morphology and properties of the blends were studied. To improve the compatibility of the ternary blends, EPDM was modified by grafting with maleic anhydride (EPDM‐g‐MAH). It was found that core‐shell morphology with EPDM‐g‐MAH as shell and HDPE as core and separated dispersion morphology of EPDM‐g‐MAH and HDPE phase were obtained separately in PA6 matrix with different molecular weights of EPDM‐g‐MAH in the blends. DSC measurement indicated that there may be some co‐crystals in the blends due to the formation of core‐shell structure. Mechanical tests showed that PA6/EPDM‐g‐MAH/HDPE ternary blends with the core‐shell morphology exhibited a remarkable rise in the elongation at break. With more perfect core‐shell composite droplets and co‐crystals, the impact strength of the ternary blends could be greatly increased to 51.38 kJ m^?2, almost 10 times higher than that of pure PA6 (5.50 kJ m^?2). POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

High‐frequency welding of thermoplastic LLDPE/PA 6/PE‐g‐MAH ternary blends

High frequency (HF) welding of linear low density polyethylene (LLDPE) melt blends with polyamide 6 (PA6) was done at 27.12 MHz using maleic anhydride grafted polyethylene (PE‐g‐MAH) as compatibilizer. HF welding was not possible for the blends at room temperature, but possible at higher temperatures (50, 80°C) although the maximum relaxation frequency was lower than the operating frequency. Greater dielectric constant, dissipation factor, and welding performance were obtained when PA 6 was premixed with PE‐g‐MAH rather than the one‐shot process where all the components were mixed simultaneously. This was interpreted in terms of lowered viscosity of PA 6 phase, which encapsulates the flow effectively and provides great skin effect. Also, the peeling force of resin–resin was greater than resin–nylon mesh due to the higher melting temperature and vacancy of nylon mesh. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology,thermal behavior,and mechanical properties of PA6/UHMWPE blends with HDPE‐g‐MAH as a compatibilizing agent

A functionalized high‐density polyethylene (HDPE) with maleic anhydride (MAH) was prepared using a reactive extruding method. This copolymer was used as a compatibilizer of blends of polyamide 6 (PA6) and ultrahigh molecular weight polyethylene (UHMWPE). Morphologies were examined by a scanning electron microscope. It was found that the dimension of UHMWPE and HDPE domains in the PA6 matrix decreased dramatically, compared with that of the uncompatibilized blending system. The size of the UHMWPE domains was reduced from 35 μm (PA6/UHMWPE, 80/20) to less than 4 μm (PA6/UHMWPE/HDPE‐g‐MAH, 80/20/20). The tensile strength and Izod impact strength of PA6/UHMWPE/HDPE‐g‐MAH (80/20/20) were 1.5 and 1.6 times as high as those of PA6/UHMWPE (80/20), respectively. This behavior could be attributed to chemical reactions between the anhydride groups of HDPE‐g‐MAH and the terminal amino groups of PA6 in PA6/UHMWPE/HDPE‐g‐MAH blends. Thermal analysis was performed to confirm that the above chemical reactions took place during the blending process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 232–238, 2000     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fractionated crystallization of dispersed PA6 phase of PP/PP‐g‐MAH/PA6 blends

Fractionated crystallization behavior of dispersed PA6 phase in PP/PA6 blends compatibilized with PP‐g‐MAH was investigated by scanning electron microscopy (SEM), differential scanning calorimeter (DSC), polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD) in this work. The lack of usual active heterogeneities in the dispersed droplet was the key factor for the fractionated crystallization of PA6. The crystals formed with less efficient nuclei might contain more defects in the crystal structures than those crystallized with the usual active nuclei. The lower the crystallization temperature, the lesser the perfection of the crystals and the lower crystallinity would be. The fractionated crystallization of PP droplets encapsulated by PA6 domains was also observed. The effect of existing PP‐g‐MAH‐g‐PA6 copolymer located at the interface on the fractionated crystallization could not be detected in this work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3742–3755, 2004     

Melt rheological properties of PBT/SEBS and reactively compatibilized PBT/SEBS/SEBS‐g‐MA polymer blends

Melt rheological properties of PBT/SEBS and PBT/SEBS/SEBS‐g‐MA blends at SEBS volume fraction (Φ_d) = 0.00–0.38 were studied at 240°C, 250°C and 260°C using a capillary rheometer. The compatibilizer SEBS‐g‐MA addition resulted in significant reduction in the dynamic interfacial tension which in turn led to increased phase adhesion. The power law exponent n decreased with increasing Φ_d and increasing temperature for both the compatiblized and uncompatiblized blends. The consistency index of PBT/SEBS increased with increasing Φ_d but were smaller than those of PBT/SEBS/SEBS‐g‐MA blends. Melt elasticity such as die swell and first normal stress difference increased with Φ_d. Variations of first normal stress coefficient function (ψ₁), recoverable shear strain (γ_R), relaxation time (λ), and shear compliance (J_c) values versus shear rate were analyzed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41402.     

Melting behavior,nonisothermal crystallization kinetics,and morphology of PP/nylon 11/EPDM‐g‐MAH blends

The melting behavior, nonisothermal crystallization behavior, and morphology of pure polypropylene (PP) and its blends were investigated by differential scanning calorimetry and polarized optical microscopy. The nonisothermal crystallization kinetics was analyzed using the Avrami equation modified by Jeziorny and the equation combining the Avrami and Ozawa method. The surface fold free energy and the effective activation energy for both PP and its blends were obtained by Hoffman‐Lauritzen theory and Vyazovkin's approach, respectively. The results showed that the presence of nylon 11 hindered the mobility of PP chains but accelerated the overall crystallization rate. The POM observation confirmed that the addition of nylon 11 decreased the spherulites size of PP matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology monitoring of PE/PBT blends by reactive processing

Polyethylene (PE)/poly(butylene terephthalate) (PBT) blends were in situ compatibilized during a processing operation by the addition of a partially hydroxylated ethylene vinyl acetate copolymer (EVAh). This copolymer, obtained from ethylene vinyl acetate (EVA), was as compatible with PE as EVA was before modification. In the presence of EVAh, the dispersion of PBT in the PE matrix was finer, and the interfacial adhesion was improved. These results are relevant for the compatibilization of PE/PBT blends. Moreover, such blends present good toluene barrier properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3568–3577, 2001     

A study on the effects of SEBS‐g‐MAH on the phase morphology and mechanical properties of polypropylene/polycarbonate/SEBS ternary polymer blends

In this work, five ternary blends based on 70% by weight (wt %) of polypropylene (PP) with 30% wt of polycarbonate (PC)/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene)(SEBS) dispersed phase consists of 15 wt % PC and 15 wt % reactive (maleic anhydride grafted) and nonreactive SEBS mixtures at various ratios were prepared in a co‐rotating twin screw extruder. scanning electron microscopy (SEM) micrographs showed that the blends containing only nonreactive SEBS exhibited a fine dispersion of core‐shell particles. With decreasing the SEBS/SEBS‐g‐Maleic Anhydride (MAH) weight ratio, the morphology changed from the core‐shell particles to a mixed of core‐shell, rod‐like and individual particles. This variation in phase morphology affected the thermal and mechanical properties of the blends. DSC results showed that the blends containing only nonreactive SEBS exhibited a minimum in degree of crystallinity due to the homogeneous nucleation of core‐shell particles. Mechanical testing showed that in the SEBS/SEBS‐g‐MAH weight ratio of 50/50, the modulus and impact strength increased compared with the PP matrix while the yield stress had minimum difference with that of PP matrix. These effects could be attributed to the formation of those especial microstructures revealed by the SEM studies. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and properties of polyimide‐g‐nylon 6 and nylon 6‐b‐polyimide‐b‐nylon 6 copolymers

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ε‐caprolactam. Nylon 6‐b‐polyimide‐b‐nylon 6 copolymers were prepared by the use of phenyl 4‐aminobenzoate as an end‐capping agent in the preparation of a series of imide oligomers. The oligomers were then used to activate the anionic polymerization of ε‐caprolactam. In both the graft and copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. All the block copolymers had higher moduli and tensile strengths than those of nylon 6. However, their elongations at break were much lower. The graft copolymers based on 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane displayed elongations comparable to that of nylon 6 and the highest moduli and tensile strengths of all the copolymers. The thermal stability, moisture resistance, and impact strength were dramatically increased by the incorporation of only 5 wt % polyimide into both the graft and block copolymers. The graft and block copolymers also exhibited improved melt processability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 300–308, 2006     

A study of the effect of PP‐g‐MA and SEBS‐g‐MA on the mechanical and morphological properties of polypropylene/nylon 6 blends

The mechanical and morphological properties of polypropylene/nylon 6 blends compatibilized with PP grafted with maleic anhydride (PP‐g‐MA) and styrene/ethene‐co‐butene/styrene grafted with maleic anhydride (SEBS‐g‐MA) are studied using a special version of a factorial design known as extreme vertices. Properties examined include yield stress, modulus, elongation, toughness, impact strength and morphology. Comparisons are made between various treatment combinations (i.e. a variety of blends) and polypropylene homopolymer using various statistical methods including analysis of variance (ANOVA). Scheffe's Test and Duncan's Multiple Range Test. Significant differences were found for yield stress, modulus, elongation, toughness and impact strength for specific treatment combinations versus PP as well as on average. Ternary diagrams are used to plot response surfaces of the measured data illustrating the main effects and interactions involved, while allowing correlations to be made with blend morphology. Indications from test results and analysis of response surfaces show a strong relationship between nylon/compatibilizer ratio and mechanical properties.     

Preparation and properties of compatibilized PVC/SMA‐g‐PA6 blends

The morphology and mechanical properties of PVC/SMA‐g‐PA6 blends were investigated in this paper. Graft to polymer SMA‐g‐PA6 was prepared via a solution graft reaction between SMA and PA6. FTIR test evidences the occurrence of the graft reaction between SMA and PA6. DSC analysis shows that SMA‐g‐PA6 has a lower melting point of 187°C, which may result in a decrease in crystallinity of PA6 and thus enable efficient blending of SMA‐g‐PA6 and PVC. Compatibilization was evidenced by the dramatic increase in mechanical properties, the smaller particle size and finer dispersion of PA6 in PVC matrix, and, further, a cocontinuous morphology at 16 wt % SMA‐g‐PA6 content. SMA‐g‐PA6 from the solution graft reaction can toughen and reinforce PVC material. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 432–439, 2004     

Morphology development of PBT/PE blends during extrusion and its reflection on the rheological properties

In this study, we have investigated morphology evolution of polymer blends during extrusion. By choosing two polymers, high density polyethylene (PE) and poly (1,4‐butylene terephthalate) (PBT), having a large difference in melting temperature, we could control the viscosity ratio of the blend as well as the morphology. The morphology of the dispersed phase evolved from film to fibril and to droplet structure depending on thermal and deformation history. We could maintain the film or fibril structure in a final product by keeping the dispersed phase deformable and rigid enough to avoid the relaxation that is related with instability originating from the interfacial tension. The anisotropic structures (film and fibril) were found to enhance the rheological properties significantly, but in different manners under shear and extensional flow fields. This study shows that diverse morphology can be obtained by controlling processing conditions, and the rheological properties can be dramatically enhanced by morphology control. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1702–1709, 2005     

反应增容PP/PA 6共混体系的形态与性能

采用侧向注入增容剂和直接混合的方法制备了不同配比的聚丙烯(PP)/马来酸酐接枝聚丙烯(PP-g-MAH)/聚酰胺(PA) 6共混物.考察了侧向注入和直接混合2种增容方式对PP/PP-g-MAH/PA 6共混体系形态与性能的影响.结果表明:加入PP-g-MAH可以同时提高PP/PA 6共混体系的刚性和韧性,侧向注入的增容效果尤为明显.侧向注入PP-g-MAH (5 phr) 的复合体系拉伸强度较纯PP提高了23.6%;侧向注入PP-g-MAH (20 phr)的复合体系拉伸断裂应变大于1 000%;PP-g-MAH能有效改善PP/PA 6体系的相容性,提高两相界面结合力,降低分散相粒子尺寸,且侧向注入比直接混合的效果更显著.     

PA 6/EPDM-g-MAH/HDPE三元共混物的形态与力学性能

制备了聚酰胺(PA)6/马来酸酐(MAH)接枝三元乙丙橡胶(EPDM)(EPDM-g-MAH)/高密度聚乙烯(HDPE)三元共混物,采用扫描电子显微镜观察了三元共混物的相形态,研究了注塑过程的二次剪切流动对该三元共混物相形态的影响,以及三元共混物相形态对其力学性能的影响。结果表明:二次剪切流动有利于PA 6/EPDM-g-MAH/HDPE体系向热力学最稳定的壳核结构发生转变。与PA 6/EPDM-g-MAH二元共混物相比,该三元共混物的力学性能得到较大改善,w(EPDM-g-MAH)为15%时,其Izod缺口冲击强度达85.83 kJ/m2,是纯PA 6的9倍,是同等橡胶含量的PA 6/EPDM-g-MAH二元共混物的2倍。     

Study on composition and characteristics of maleated ethylene‐octene copolymer prepared by reactive extrusion on the morphology and properties of polyamide 6/ethylene‐octene copolymer blends

Blends of polyamide 6 (PA6) and elastomeric ethylene‐octene copolymer (EOR), with and without maleated EOR (EOR‐MA) were studied. EOR‐MA with various amounts of grafted MA and gel content were prepared by reactive extrusion. The effects of EOR‐MA characteristics and composition on the morphology, thermal and mechanical properties of the blends were investigated. EOR‐MA was found to promote the toughness efficiency of PA6 remarkably. High impact resistance was achieved by the use of EOR‐MA containing less than 2% gel. The content of MA grafted on EOR‐MA in the range of 0.5%–1.0% gave a similar effect on the blend properties. The blend containing 20% of EOR grafted with 1% MA exhibited twenty times higher impact strength (1000 J/m) than pure PA6 (55 J/m). The presence of EOR‐MA in the blends led not only to a drastic reduction in the dispersed particle size, but also to some changes in fracture mechanisms, thus enhancing the impact resistance of the blends.     

Reactive compatibilization of PP/PBT blends by a mixture of PP‐g‐MA and epoxy resin

In this study, dual compatibilizers composed of the commercially available maleic anhydride‐grafted polypropylene (PP–MA) and a multifunctional epoxy resin were demonstrated to effectively compatibilize the immiscible and incompatible blends of PP and poly(butylene terephthalate) (PBT). The PP–MA with a low MA content is totally miscible with PP to make the PP phase quasi‐functionalized, so that the multifunctional epoxy has the chance to react with PBT and PP–MA simultaneously to form PP–MA‐co‐epoxy‐co‐PBT copolymers at the interface. These desired copolymers are able to anchor along the interface and serve as efficient compatibilizers. The compatibilized blends, depending on the quantity of dual compatibilizers employed, exhibit higher viscosity, finer phase domain, and improved mechanical properties. Epoxy does not show compatibilization effects for the PP/PBT blends without the presence of PP–MA in the blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2272–2285, 2001     

Shape memory properties of polycaprolactone‐based polyurethanes prepared by reactive extrusion

The shape memory properties of polycaprolactone‐based polyurethanes (PCLUs) synthesized via a novel route of reactive extrusion were investigated in terms of the deformation amplitude, temperature, and rate by differential scanning calorimetry (DSC), dynamic mechanical analyzer, and polarized optical microscopy (POM). DSC analysis shows that the crystalline melting temperature and crystallinity of PCLU increased monotonically with increasing the average polymerization degree $ ( \overline {DPn}) $ of poly(ε‐caprolactone) (PCL) block. The retract force increased with increasing the temperature and reached the maximum (6–7 MPa) within 45–55°C. Furthermore, a modified model with two recovery stages was postulated to elucidate the shape memory process, which is visually presented by POM analysis. The two stages of tensile and compressive recovery are distinguished by the inflexion temperature, within 43–48°C and 64–66°C, respectively. The shape fixity is about 60–70% and can be improved to 100% by choosing proper deformation temperature. The tensile deformation recovery ratio was 80–98% due to the water absorption, whereas the compressive deformation recovery ratio was almost 100%. Besides, recovery tests show that the lowest recovery temperature ranged from 24 to 47°C was influenced by the deformation temperature, rate and the PCL block $ ( \overline {DPn}) $ . Thus, the shape memory properties can be adjusted according to different purposes. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013