Fractionated crystallization of compatibilized LDPE/PA6 blends

The paper presents differential scanning calorimetry and electron microscopy of the fractionated crystallization and polydispersity of the dispersed PA6 phase in compatibilized LDPE/PA6 75/25 w/w blends. The compatibilizers used were (i) an acrylic acid functionalized polyethylene, Escor 5001 (EAA); (ii) an ethylene-glycidylmethacrylate copolymer, Lotader GMA AX8840 (EGMA); (iii) a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer comprising 2 wt.% maleic anhydride grafts, Kraton FG 1901X (SEBS-g-MA). The compatibilizer SEBS-g-MA has the strongest reduction effect upon the size of PA-6 droplets. Its implementation provides the best fractionated crystallization. The fractionated crystallization has not been observed for the blend compatibilized with EGMA. The results show that the degree of compatibilization could be evaluated qualitatively by the progress of the fractionated crystallization. So, the three compatibilizers could be rated according to their effectiveness as follows: SEBS-g-MA > EAA > EGMA. The self-nucleation experiments have demonstrated that the lack of active nuclei in the finely dispersed PA6 droplets is the determining factor for the fractionated crystallization at high supercooling, and not the considered absolute particle size. The measurement of the Vickers microhardness of the compatibilized blends confirms that the compatibilizing activity of SEBS-g-MA and EAA is stronger than that of EGMA.     

Microhardness of compatibilized blends of polypropylene with a semiflexible liquid-crystalline polymer

 The Vickers microhardness of blends of isotactic polypropylene and a semiflexible liquid-crystalline polymer (iPP/LCP 90/10 and 80/20 w/w), compatibilized with 2.5, 5 or 10 wt% PP-g-LCP copolymers with different composition has been studied. It has been shown that the microhardness values of uncompatibilized blends are close to the additive ones, while for compatibilized blends a strong positive deviation from additivity has been established. This result is interpreted by the increase in the degree of crystallinity of PP, by the decrease in the surface free energy of PP crystals and by the decrease in the surface free energy of the LC domains when the PP-g-LCP compatibilizer is present. The effect of the composition and concentration of the compatibilizer on the experimental hardness values has also been studied. The values of the microhardness/modulus of elasticity of some of the materials have been obtained. It is demonstrated that according to these values the compatibilized blends take a position closer to the elastic material in the elastic–plastic spectrum than the uncompatibilized blends. The results are interpreted by the compatibilizing efficiency of PP-g-LCP copolymers towards iPP/LCP blends. Received: 18 June 2001 Accepted: 4 October 2001     

Influence of microstructure and deformation behavior on toughening of reactively compatibilized polyamide 6 and poly(ethylene-co-butyl acrylate) blends

Influence of microstructure on impact toughness and fracture behavior of PA6 and EBA blends reactively compatibilized by EBA-g-MAH was quantitatively studied. The reactively compatibilized blends showed better distribution of elastomeric EBA particles in the PA6 matrix and the presence of EBA-g-MAH resulted in considerable reduction of interfacial tension between the component polymers. The interfacial adhesion between the PA6 and EBA phase in the compatibilized blends was enhanced by the interfacial reaction between the amide end-groups of PA6 and maleic anhydride group of EBA-g-MAH compared to uncompatibilized blends. The matrix ligament thickness and particle diameter values were lower than the predicted critical values and were responsible for the ductile behavior of the compatibilized blends. Stress whitening around the notch occurred in all the compatibilized blends which was the major energy dissipation zone in the blends. Matrix shear yielding or plastic flow without crazing was the dominant deformation mechanism in the tough compatibilized blends. There was no sign of shear yielding during impact fracture of the uncompatibilized blends where the elastomeric particles were completely dislodged from the matrix.     

Morphology and mechanical properties of extruded ribbons of LDPE/PA6 blends compatibilized with an ethylene-acrylic acid copolymer

Two grades of low density polyethylene (LDPE) were blended with polyamide-6 (PA) in the 75/25 and 25/75 wt/wt ratios and shaped into ribbons with a Brabender single screw extruder. An ethylene-acrylic acid copolymer (EAA) was used in the 2 phr concentration as a compatibilizer precursor (CP). The morphology of the ribbons and its evolution during high temperature annealing were investigated by scanning electron microscopy (SEM). The results confirmed that EAA does actually behave as a reactive compatibilizer for the LDPE/PA blends. In fact, in the presence of EAA, the interfacial adhesion is improved, the dispersion of the minor phase particles is enhanced and their tendency toward fibrillation is increased, especially for the blends with the higher molar mass LDPE grade. The mechanical properties of the latter blends were found to be considerably enhanced by the addition of EAA, whereas the improvement was relatively modest for the blends with the lower molar mass LDPE. The fracture properties of double end notched samples of the ribbons prepared with the blends containing the lower molar mass LDPE grade were also studied. It was shown that, despite of the increased interfacial adhesion caused by the presence of EAA, the latter plays a measurable positive effect on the fracture properties only for the blends with LDPE as the matrix.     

Reactively and physically compatibilized immiscible polymer blends: stability of the copolymer at the interface

This paper reports on the interfacial behaviour of block and graft copolymers used as compatibilizers in immiscible polymer blends. A limited residence time of the copolymer at the interface has been shown in both reactive blending and blend compatibilization by preformed copolymers. Polystyrene (PS)/polyamide6 (PA6), polyphenylene oxide (PPO)/PA6 and polymethylmethacrylate (PMMA)/PA6 blends have been reactively compatibilized by a styrene-maleic anhydride copolymer SMA. The extent of miscibility of SMA with PS, PPO and PMMA is a key criterion for the stability of the graft copolymer at the interface. For the first 10 to 15 minutes of mixing, the in situ formed copolymer is able to decrease the particle size of the dispersed phase and to prevent it from coalescencing. However, upon increasing mixing time, the copolymer leaves the interface which results in phase coalescence. In PS/LDPE blends compatibilized by preformed PS/hydrogenated polybutadiene (hPB) block copolymers, a tapered diblock stabilizes efficiently a co-continuous two-phase morphology, in contrast to a triblock copolymer that was unable to prevent phase coarsening during annealing at 180°C for 150 minutes.     

The effect of various compatibilizers on thermal,mechanical, and morphological properties of polystyrene/polypropylene blends

The effects of various compatibilizers on thermal, mechanical and morphological properties of 50/50 polypropylene/polystyrene blends were investigated. Various compatibilizers, polystyrene-(ethylene/butylenes/ styrene) (SEBS), ethylene vinyl acetate (EVA), polystyrene-butylene rubber (SBR) and blend of compatibilizers SEBS/PP-g-MAH, EVA/PP-g-MAH, and SBR/PP-g-MAH were used. Differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray scattering, scanning electron microscopy, microhardness, and Izod impact strength were adopted. It was found that the influence of various compatibilizers was appeared on all the properties studied. The properties of the blends compatibilized with SEBS, EVA, and SBR are very distinct from those of blends compatibilized with blend of compatibilizers. Results show that compatibilized blends with the blend of compatibilizers EVA/PP-g-MAH, SBR/PP-g-MAH, and SEBS/PP-g-MAH or SBR were relatively more stable than the uncompatibilized blend and blend compatibilized with SEBS or EVA. The compatibilizer does not only reduce the interfacial tension or increase the phase interfacial adhesion between the immiscible polymers, but greatly affects the degree of crystallinity of blends.

     

Elastic properties of oriented polymers, blends and reinforced composites using the microindentation technique

The elastic behaviour of poly(ethylene terephthalate) (PET) and nylon 6 (PA6), their blends (1:1 by weight) and microfibrillar-reinforced composites of the previously mentioned homopolymers has been investigated by means of load-displacement analysis from indentation experiments. The dependence of the elastic modulus of the homopolymers upon the degree of crystallinity and the crystal size, as derived from indentation experiments, is discussed. A linear correlation between the elastic modulus anisotropy and the microindentation hardness anisotropy values is also found to apply for the oriented materials. The results reveal that the indentation modulus values of the PET/PA6 blends follow the parallel additivity model of the individual components. The use of the additivity law is also shown to provide a value, otherwise not accessible from direct measurements, of the modulus of the microfibrils within the microfibrillar-reinforced composites.     

Raman,X-ray diffraction and differential scanning calorimetry studies of the melt-induced changes in uncompatibilized and compatibilized blends of high-density polyethylene and nylon 12

The crystallinity of non-molten and pre-molten uncompatibilized and compatibilized polymer blends of high density polyethylene (HDPE)/Nylon 12 have been investigated by using FT-Raman spectroscopy, differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD). The FT-Raman, DSC, and WAXD measurements have revealed that the crystallinity of HDPE of both uncompatibilized and compatibilized blends increases upon melting except for the compatibilized blend with the Nylon 12 content of 80 wt%. The degree of the increase is significantly larger for the uncompatibilized blends than the compatibilized blends. The FT-Raman data suggests that the crystallinity of the compatibilized blend with the Nylon 12 content of 80 wt% decreases slightly after melting. It is very likely that the compatibilized polymer blends are well oriented during the melting and molding process by an extruder because of the existence of maleic anhydride (MAH)-grafted copolymer as a compatibilizer. In contrast, it seems that the uncompatibilized polymer blends are not so much oriented and have more amorphous phase in the Nylon 12 rich region before melting. Thus, the melting process induces a recrystallization process.     

Crystallinity and rheology of HDPE/PA12 blends compatibilized with HDPE-alt-MAH

This work studies the crystallinity and rheology of HDPE/PA12 blends compatibilized with 2 wt% of HDPE-alt-MAH. Specimens of HDPE/PA12 blends were extruded and injected into a mold with 75/25, 50/50, and 25/75 HDPE/PA ratios. The Fourier-transform infrared spectroscopy (FTIR) analysis showed that no oxidation reaction occurred in the high-temperature processing and that stronger interactions between the components of the blends occurred in the polyamide's functional groups. The x-ray diffraction (XRD) analysis showed that the crystallinity degree of the blends and the mean crystallite sizes decreased with the addition of PA12 for both blends. The HDPE's lattice parameters were consistent with the values in the literature, whereas for the PA12, it was not possible to fit its lattice parameters. The rheology analysis evaluated the relationship between the shear stress and viscosity and found that the HDPE/PA 75/25 blend was the most pseudoplastic, presenting the best processability under high shear rates.     

The compatibilization effect of ethylene/styrene interpolymer on polystyrene/polyethylene blends

In this study, ethylene/styrene interpolymer (ESI) was used as compatibilizer for the blends of polystyrene (PS) and low‐density polyethylene (LDPE). The mechanical properties including impact, tensile properties, and morphology of the blends were investigated by means of uniaxial tension, instrumented falling‐weight impact measurements, and scanning electron microscopy. Impact measurements indicated that the impact strength of the blends increases slowly with LDPE content up to 40 wt %; thereafter, it increases sharply with increasing LDPE content. The impact energy of the LDPE‐rich blends exceeded that of pure LDPE, implying that the LDPE polymer can be further toughened by the incorporation of brittle PS minor phase in the presence of ESI. Tensile tests showed that the yield strength of the PS/LDPE/ESI blends decreases considerably with increasing LDPE content. However, the elongation at break of the blends tended to increase significantly with increasing LDPE content. The compatibilization efficiency of ESI and polystyrene‐hydrogenated butadiene‐polystyrene triblock copolymers (SEBS) for PS/LDPE 50/50 was further compared. Mechanical properties show that ESI is more effective to achieve a combination of LDPE toughness and PS rigidity than SEBS. The correlation between the impact property and morphology of the ESI‐compatibilized PS/LDPE blends is discussed. The excellent tensile ductility of the LDPE‐rich blends resulted from shield yielding of the matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2136–2146, 2007     

Reactive compatibilization of polyamide‐6 (PA 6)/polybutylene terephthalate (PBT) blends by a multifunctional epoxy resin

A multifunctional epoxy resin has been demonstrated to be an efficient reactive compatibilizer for the incompatible and immiscible blends of polyamide‐6 (PA 6) and polybutylene terephthalate (PBT). The torque measurements give indirect evidence that the reaction between PA and PBT with epoxy has an opportunity to produce an in situ formed copolymer, which can be as an effective compatibilizer to reduce and suppress the size of the disperse phase, and to greatly enhance mechanical properties of PA/PBT blends. The mechanical property improvement is more pronounced in the PA‐rich blends than that in the PBT‐rich blends. The fracture behavior of the blend with less than 0.3 phr compatibilizer is governed by a particle pullout mechanism, whereas shear yielding is dominant in the fracture behavior of the blend with more than 0.3 phr compatibilizer. As the melt and crystallization temperatures of the base polymers are so close, either PA or PBT can be regarded as a mutual nucleating agent to enhance the crystallization on the other component. The presence of compatibilizer and in situ formed copolymer in the compatibilized blends tends to interfere with the crystallization of the base polymers in various blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 23–33, 2000     

HDPE/PA6反应增容体系的形态演化与黏弹行为

采用扫描电子显微镜(SEM)与先进流变扩展系统(ARES),研究了马来酸酐接枝高密度聚乙烯(HDPE-g-MAH)对高密度聚乙烯/尼龙6(HDPE/PA6)共混体系形态结构和黏弹行为的影响.发现HDPE-g-MAH的加入可原位生成尼龙6-高密度聚乙烯接枝共聚物(HDPE-g-PA6),使基体与分散相间的相容性显著改善,且随其添加量的增加两者相容性更好,导致HDPE/PA6体系形态结构变化.研究结果表明,由ARES获得的体系黏弹行为参数随HDPE-g-MAH含量的变化可与由SEM所观察到的微观形貌演化很好关联,动态流变学方法可敏感表征增容剂的加入所引起的HDPE/PA6界面性质变化,且能够反映分子链间相互作用的变化及由此导致的分散相颗粒网络的形成.     

Polymer blends of sPS/PA6 compatibilized by sulfonated syndiotactic polystyrene

Syndiotactic polystyrene (sPS) and polyamide-6 (PA6) are immiscible and incompatible and have been recognized. In this study, sulfonated syndiotactic polystyrene (SsPS-H) is employed as compatibilizer in the blend of sPS/PA6. During melt blending, the sulfonic acid groups of the SsPS-H can interact strongly with the amine end-groups of PA6 through acid-base interaction. In addition, SsPS-H is miscible with sPS when SsPS-H content is less than 20 wt.%. Therefore, the addition of SsPS-H to sPS/PA6 blends reduces the dispersed phase size and improves the adhesion between the phases. The glass transition temperatures of the PA6 component in the compatibilized blends shift progressively towards higher temperature with the content of SsPS-H-12 increase, indicating enhanced compatibility. On the other hand, the progressive lowering of the melting point and crystallization temperatures of PA6 in the blends with increasing SsPS-H contents compared to the incompatibilized blend, provide some insight into the level of interaction between the PA6 and SsPS-H. The compatibilized blends have significantly higher impact strength than the blends without SsPS-H. The best improvement in the impact strength of the blends was achieved with the content of the SsPS-H (11.9 mol%) about 5 wt.%.     

New polyamide - based blends

Among polyamide based blends, PA/PP alloys show interesting technological properties due to low moisture absorption. A model class of PA6/PP homopolymer blends, compatibilized through the addition of PP-g-MA is described in the present work; the experimentally obtained morphologies are related to predictive equations for co-continuity, at given rheological conditions. PP/compatibilizer ratio = 4/1 is found to impart an optimum level of phase dispersion. Moisture absorption, dimensional stability, mechanical properties and morphology are related with blend composition.     

Effect of maleic anhydride-grafted ethylene-propylene rubber on the mechanical, rheological and morphological properties of organoclay reinforced polyamide 6/polypropylene nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic modified montmorillonite (organoclay) were compatibilized with maleic anhydride-grafted ethylene-propylene rubber (EPRgMA). The blends were melt compounded in twin screw extruder followed by injection molding. The mechanical properties of PA6/PP nanocomposites were studied by tensile and flexural tests. The microstructure of the nanocomposite were assessed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The dynamic mechanical properties of the PA6/PP blend-based nanocomposites were analyzed by using a dynamic mechanical thermal analyzer (DMTA). The rheological properties were conducted from plate/plate rheometry via dynamic frequency sweep scans. The melt viscosity in a high shear rate region was performed by using a capillary rheometer. The strength and stiffness of the PA6/PP-based nanocomposites were improved significantly with the incorporation of EPRgMA. Adding EPRgMA to the PA6/PP blends resulted in a finer dispersion of the PP phase. TEM and XRD results revealed that the organoclay was dispersed more homogeneously in the presence of EPRgMA, however, mostly in the PA6 phase of the blends. DMTA results showed that EPRgMA worked as an effective compatibilizer. The storage (G′) and loss moduli (G″) assessed by plate/plate rheometry of PA6/PP blends increased with the incorporation of EPRgMA and organoclay. Furthermore, the apparent shear viscosity of the PA6/PP blend increased significantly for the EPRgMA compatibilized PA6/PP/organoclay nanocomposite. This was traced to the formation of an interphase between PA6 and PP (via PA6-g-EPR) and effective intercalation/exfoliation of the organoclay.     

Influence of Reactive Compatibilization on the Melt Flow Properties and Morphology of Polyamide 6/Styrene-Acrylonitrile Blends

Summary: In this study, we investigate the influence of reactive compatibilization on the rheological properties of polyamide 6/styrene-acrylonitrile (PA 6/SAN) blends in the melt. Linear viscoelastic shear oscillations, simple elongation to a large stretch ratio and subsequent recovery experiments were performed. The morphology of the blends was examined by atomic force microscopy. We prepared three PA 6/SAN blends with different composition ratios of PA 6 and SAN (70/30, 50/50, 30/70) and a constant concentration of the reactive agent. Our experiments revealed that reactive compatibilization significantly increases the complex modulus of PA 6/SAN blends at low frequencies. In particular, the data of the PA 6/SAN 50/50 blend and the PA 6/SAN 30/70 blend indicated that an elastic network between neighbouring PA 6 domains was formed. In simple elongation, the transient elongational viscosity of the blends exceeded the values of the single components. In recovery, the recovered stretch of all blends was larger than the recovered stretch of the pure components. The differences of the blend morphology and of the linear viscoelastic behaviour were qualitatively explained by the asymmetric properties of the reactively compatibilized interface.     

Thermogravimetric and wide angle X-ray diffraction analysis of thermoplastic elastomers from nylon copolymer and EPDM rubber

Nylon copolymer (PA6, 66) and ethylene propylene diene (EPDM) blends with and without compatibilizer were prepared by melt mixing using Brabender Plasticorder. The thermal stability of nylon copolymer (PA6, 66)/ethylene propylene diene rubber (EPDM) blends was studied using thermogravimetric analysis (TGA). The morphology of the blends was investigated using scanning electron microscopy (SEM). In this work, the effects of blend ratio and compatibilisation on thermal stability and crystallinity were investigated. The incorporation of EPDM rubber was found to improve the thermal stability of nylon copolymer. The kinetic parameters of the degradation process were also studied. A good correlation was observed between the thermal properties and phase morphology of the blends. By applying Coats and Redfern method, the activation energies of various blends were derived from the Thermogravimetric curves. The compatibilization of the blends using EPM-g-MA has increased the degradation temperature and decreased the weight loss. EPM-g-MA is an effective compatibilizer as it increases the decomposition temperature and thermal stability of the blends. Crystallinity of various systems has been studied using wide angle X-ray scattering (WAXS). The addition of EPDM decreases the crystallinity of the blend systems.     

Effects of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] on the charge distributions of low‐density polyethylene/polystyrene blends

The effect of the triblock copolymer poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) on the formation of the space charge of immiscible low‐density polyethylene (LDPE)/polystyrene (PS) blends was investigated. Blends of 70/30 (wt %) LDPE/PS were prepared through melt blending in an internal mixer at a blend temperature of 220 °C. The amount of charge that accumulated in the 70% LDPE/30% PS blends decreased when the SEBS content increased up to 10 wt %. For compatibilized and uncompatibilized blends, no significant change in the degree of crystallinity of LDPE in the blends was observed, and so the effect of crystallization on the space charge distribution could be excluded. Morphological observations showed that the addition of SEBS resulted in a domain size reduction of the dispersed PS phase and better interfacial adhesion between the LDPE and PS phases. The location of SEBS at a domain interface enabled charges to migrate from one phase to the other via the domain interface and, therefore, resulted in a significant decrease in the amount of space charge for the LDPE/PS blends with SEBS. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2813–2820, 2004     

新型sPS/PA6/SsPS-H塑料合金的性能和形态结构

研究新型sPS PA6 SsPS H塑料合金的力学性能和微观形态结构 .间规聚苯乙烯 (sPS)的磺化产物磺化间规聚苯乙烯 (SsPS H)的加入明显地改善了sPS PA6(聚酰胺 6)二组分合金的力学性能 ,在sPS PA6 SsPS H重量组成为 80 2 0 5时 ,三组分合金的冲击强度最大 ,为 1 5 6kJ m2 ,约为纯sPS冲击强度的 3倍 DMA和SEM结果表明 ,SsPS H对sPS和PA6共混有良好的增容作用 ,它起到了降低合金的微相尺寸和加强相间界面粘结的作用 .此外 ,FTIR结果还表明SsPS H和PA6之间存在特殊相互作用 ,其作用方式是通过SsPS H的磺酸基将其质子转移给PA6酰胺基的氮     

Miscibility of Semi-flexible Thermotropic Liquid Crystalline Copolyesteramide with Polyamide 66

IntroductionIn sl'tu polymer composites containing liquid crystalline polymers(LCPs) have attractedconsiderable attention in the past'decades['--'j. But the development of in sl'tu composites is restricted by two factors. First, the melting temperatures of thermotropic liquid crystallinepolymers (TLCPs) are generally higher than those of the commodity engineering resins. Athigh processing temperatures, these resins tend to become unstable, thereby, causing seriousproblems during fiber spinn…