Phase morphology and stability of co-continuous (PPE/PS)/PA6 and PS/PA6 blends: effect of rheology and reactive compatibilization

(PPE/PS)/PA6 and PS/PA6 blends were prepared by means of melt-extrusion. They were compatibilized using the reactive styrene-maleic anhydride copolymer with 2 wt% maleic anhydride (SMA2). The effect of compatibilization on the phase inversion and the stability of the resulting co-continuous blend structures were investigated using scanning electron microscopy, dissolution and extraction experiments. The onset of co-continuity shifted towards lower PA6 concentrations according to the change in blend viscosity ratio. The melting order of the components inside the extruder could result in a change in the observed co-continuity interval in slowly developing phase morphologies. The unmodified co-continuous blends were not stable and did break-up into a droplet/matrix type of morphology upon annealing in the melt depending on the blend composition. Although the stability of the threads during annealing improved upon compatibilization because of the lower resulting interfacial tension, the decreased possibility for recombination and coalescence during flow reduced the co-continuous region for the compatibilized blends. It is proposed that a dynamic equilibrium between break-up and recombination phenomena after the initial network formation is necessary to maintain the network structure.     

Flow Characteristics and Dynamic Behavior of Polyamide 6/Acrylonitile Butadiene Styrene (PA6/ABS) Blends

The objective of this research was to investigate the effect of incorporation of maleic anhydride grafted acrylonitrile-butadiene-styrene (ABS-g-MAH) on rheological properties of PA6/ABS blends. Flow properties of the blends were examined by dynamic and capillary rheometers. The dynamic rheological analyses showed an increase in complex viscosity with the incorporation of a compatibilizer. The reduction of tan δ peaks showed enhanced interfacial interaction between PA6 and ABS phase, which resulted in the enhancement of melt strength. The power law index analysis showed that 1.5 wt.% resulted in minimum n and maximum K value for the blends while still retaining the pseudoplastics behavior necessary for plastics processing and prediction for the end use performance of the PA6/ABS blends.     

The morphology and mechanical properties of dynamic packing injection molded PP/PS blends

As a part of long-term project aimed at super polyolefin blends, in this work, we report the mechanical reinforcement and phase morphology of the immiscible blends of polypropylene (PP) and polystyrene (PS) achieved by dynamic packing injection molding (DPIM). The shear stress (achieved by DPIM) and interfacial interaction (obtained by using styrene-butadiene-styrene (SBS) as a compatibilizer) have a great effect on phase morphology thus mechanical properties. The shear-induced morphology with core in the center and oriented zone surrounding the core was observed in the cross-section areas of the samples. The phase inversion was also found to shift towards lower PS content under shear stress, at 70 wt% in the core and 30 wt% in the oriented zone, compared with 80 wt% for static samples (without shear). The tensile strength, tensile modules and impact strength were found largely increase by means of either shear stress or compatibilizer. The PS particle size is greatly reduced with adding of SBS, and the reduced particle size results in greater resistance to deformation, which causes the co-continuous structure at oriented zone change into droplet morphology. The morphology resulting from blending and processing was discussed based on effect of interfacial tension, shear rate, phase viscosity ratio and composition. The observed change of mechanical properties was explained based on the combined effect of phase morphology (droplet-matrix or co-continuous phase) and molecular orientation under shear stress.     

Rheology,morphology, and crystallization behavior of melt‐mixed blends of polyamide6 and acrylonitrile‐butadiene‐styrene: Influence of reactive compatibilizer premixed with multiwall carbon nanotubes

Blends of polyamide6 (PA6) and acrylonitrile butadiene styrene (ABS) were prepared in presence or absence of up to 5 wt % of a reactive compatibilizer [styrene maleic anhydride copolymer (SMA) modified with 5 wt % multiwall carbon nanotubes (MWNT)] by melt‐mixing using conical twin screw microcompounder where the ABS content was varied from 20 to 50 wt %. The melt viscosity of the blends was significantly enhanced in presence of SMA modified by multiwall carbon nanotubes due to the reactive compatibilization, which leads to stabilized interphase in the blends. Furthermore, the presence of MWNT in the compatibilizer phase led to additional increase in viscosity and storage modulus. Morphological studies revealed the presence of either droplet‐dispersed or cocontinuous type depending on the blend compositions. Further, reactive compatibilization led to a significant change in the morphology, namely a structure refining, which was enhanced by MWNT presence as observed from SEM micrographs. DSC crystallization studies indicated a delayed crystallization response of PA6 in presence of ABS presumably due to high melt viscosity of ABS. The crystallization temperature and the degree of crystallinity were strongly dependent on the type of morphology and content of reactive compatibilizer, whereas the presence of MWNT had an additional influence. SAXS studies revealed the formation of thinner and less perfect crystallites of PA6 phase in the blends, which showed cocontinuous morphology. A unique observation of multiple scattering maxima at higher q region has been found in the blends of cocontinuous morphology, which was observed to be successively broadened in presence of the compatibilizer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Morphological,rheological and thermal studies in melt processed compatibilized PA6/ABS/clay nanocomposites

Multicomponent compatibilized blends of polyamide 6 (PA6) and styrene-butadiene-acrylonitrile (ABS) with co-continuous morphology are among commercial alloys with an interesting combination of properties. To further enhance the properties different amounts of nanoclay were incorporated into these blends through a one step melt mixing process. The effect of nanoclay addition on rheological, thermal stability, crystallization and morphological properties of the nanocomposites were investigated and compared with those of the neat blends. The nanoscale dispersion of the clay layers in the blends were confirmed through X-ray diffraction and transmission electron microscopy methods. Rheological investigation indicated an increased viscosity and melt elasticity for the nanocomposite systems. The viscosity of nanocomposites followed a shear thinning flow behavior and decreased with increasing shear rates. The changes in the rheological properties were accompanied by refinement of the co-continuous morphology. For thermal degradation under N₂ atmosphere, the onset and maximum of degradation temperatures for the nanocomposites were as high as the neat blends, while significant improvement in thermal stability (about 60 °C by 3 wt% clay addition) was observed in the air environment. In addition agglomerated clay particles did not significantly affect thermal stability of the polymer matrix. Non-isothermal crystallization results indicated that the clay layers had a retarding effect on the crystal growth rate and facilitated the formation of α crystalline form. In addition no nucleation effect was observed during the crystallization process due to incorporation of nanoclay into the blends.     

Application of styrene‐acrylonitrile random copolymer–polyarylate block copolymer as reactive compatibilizer for polyamide and acrylonitrile‐butadiene‐styrene blends

Styrene‐acrylonitrile random copolymer (SAN) and polyarylate (PAr) block copolymer were applied as a reactive compatibilizer for polyamide‐6 (PA‐6)/acrylonitrile‐butadiene‐styrene (ABS) copolymer blends. The SAN–PAr block copolymer was found to be effective for compatibilization of PA‐6/ABS blends. With the addition of 3.0–5.0 wt % SAN–PAr block copolymer, the ABS‐rich phase could be reduced to a smaller size than 1.0 μm in the 70/30 and 50/50 PA‐6/ABS blends, although it was several microns in the uncompatibilized blends. As a result, for the blends compatibilized with 3–5 wt % block copolymer the impact energy absorption reached the super toughness region in the 70/30 and 50/50 PA‐6/ABS compositions. The compatibilization mechanism of PA‐6/ABS by the SAN–PAr block copolymer was investigated by tetrahydrofuran extraction of the SAN–PAr block copolymer/PA‐6 blends and the model reactions between the block copolymer and low molecular weight compounds. The results of these experiments indicated that the SAN–PAr block copolymer reacted with the PA‐6 during the melt mixing process via an in situ transreaction between the ester units in the PAr chain and the terminal amine in the PA‐6. As a result, SAN–PAr/PA‐6 block copolymers were generated during the melt mixing process. The SAN–PAr block copolymer was supposed to compatibilize the PA‐6 and ABS blend by anchoring the PAr/PA‐6 and SAN chains to the PA‐6 and ABS phases, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2300–2313, 2002     

Effect of maleic anhydride grafted polybutadiene on the compatibility of polyamide 66/acrylonitrile‐butadiene‐styrene copolymer blend

The addition of maleic anhydride grafted polybutadiene (PB‐g‐MAH) can greatly improve the compatibility of polyamide 66 (PA66)/acrylonitrile‐butadiene‐styrene copolymer (ABS) blends. Unlike the commonly used compatibilizers in polyamide/ABS blends, PB‐g‐MAH is compatible with the ABS particles' core phase polybutadiene (PB), rather than the shell styrene‐acrylonitrile (SAN). The compatibility and interaction of the components in the blends were characterized by Fourier transform‐infrared spectra (FTIR), Molau tests, melt flow index (MFI), dynamic mechanical analyses (DMA), and scanning electron microscopic (SEM) observations. The results show that PB‐g‐MAH can react with the amino end groups in PA66 while entangle with the PB phase in ABS. In this way, the compatibilizer anchors at the interface of PA66/ABS blend. The morphology study of the fracture sections before and after tensile test reveals that the ABS particles were dispersed uniformly in the PA66 matrix and the interfacial adhesion between PA66 and ABS was increased significantly. The mechanical properties of the blends thus were enhanced with the improving of the compatibility. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

PA6/LLDPE共混物的制备与增容作用研究

以乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯三元共聚物(E-MA-GMA)为相容剂,用熔融法在双螺杆挤出机上制备了聚酰胺6/线型低密度聚乙烯(PA6/LLDPE)共混物,并加入降解聚乙烯(DPE)来改变LLDPE的黏度。结果表明:加入10 phr E-MA-GMA可以有效降低PA6/LLDPE(80/20)共混物的分散相尺寸;当LLDPE/DPE=19/1时,共混物的复数黏度和储能模量达到最大值;DPE的加入对共混物的拉伸性能没有明显影响,但使其缺口冲击强度下降。     

Hot melt adhesive properties of PA/TPU blends compatibilized by EVA-g-MAH

A new copolyamide (PA52) with good adhesion to aluminum (Al) sheets was synthesized from caprolactam, nylon 66 salt, nylon 1010 salt, and stearic acid, and a series of PA52/TPU blends compatibilized by maleic anhydride-grafted ethylene vinyl acetate (EVA-g-MAH) were prepared for use as hot melt adhesives. In the ternary blends (PA52/EVA-g-MAH/TPU), the weight ratio of PA52 to TPU was kept constant at 50/50 and the amount of EVA-g-MAH was varied at 0, 2, 4, 6, and 8 wt% over the total weight of the blend, respectively. The solubility parameters were taken into account to describe the partial compatibility of PA52/TPU blends. The effects of EVA-g-MAH content on the melt viscosity, morphology, mechanical and thermal properties of ternary blends were systematically investigated, and the adhesion strength of hot melt adhesives based on the ternary blends were determined in terms of 90° peeling strength tests of Al/adhesive/ABS stacks. The results showed that the melt viscosity of ternary blends were greater than that of PA52/TPU blend, and the blend containing 6 wt% EVA-g-MAH exhibited an optimal miscibility behavior and excellent mechanical properties, at the same time, its peeling strength reached the maximum (120 N/25 mm).     

Investigation on the correlation between rheology and morphology of PA6/ABS blends using ethylene acrylate terpolymer as compatibilizer

Phase morphology and rheological behavior of polyamide 6 (PA6)/acrylonitrile butadiene styrene (ABS) polymers blends was studied using scanning electron microscopy and rheometry. The results showed that the phase morphology and rheological properties depends on blend composition. We evaluated the effect of addition of ABS as dispersed phase and EnBACO‐MAH (ethylene n‐butyl acrylate carbon monoxide maleic anhydride) as a compatibilizer on the morphological and rheological behaviors of PA6/ABS blends. It was concluded that there is a good agreement between the results obtained from rheological and morphological studies. As a consequence, addition of the ABS and compatibilizer weight percent led to a significant change in morphological structure and a great mounting in the viscosity as well as the elasticity. The rheological properties results demonstrate that adding compatibilizer to polymer blends led to increasing the crossover point, which shows a transition from a high viscous to a considerably more elastic behavior. Also, the slow transition of relaxation time peak from the peak of the PA6 to the peak of the ABS implies increasing the miscibility of the PA6/ABS blend components by increasing compatibilizer content. In addition, the Carreau–Yasuda model was used to extract information on rheological properties (zero shear viscosity and relaxation time) for PA6/ABS/EnBACO‐MAH blends by fitting the experimental data with this model. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

ABS/SMA/GF复合材料的制备及性能

以丙烯腈-丁二烯-苯乙烯共聚物(ABS)及玻璃纤维(GF)为原料,以苯乙烯-马来酸酐共聚物(SMA)作为界面相容剂,研究界面相容剂对玻璃纤维增强ABS复合材料力学性能及界面粘接的影响.结果表明:加入SMA玻纤增强ABS复合材料的力学性能明显提高;随着玻纤质量分数增加,复合材料的拉伸强度、弯曲强度均逐渐增加,冲击强度下降.     

Effects of polyamide 6 incorporation to the short glass fiber reinforced ABS composites: an interfacial approach

The properties of 30 wt% short glass fiber (SGF) reinforced acrylonitrile-butadiene-styrene (ABS) terpolymer and polyamide 6 (PA6) blends prepared with extrusion were studied using the interfacial adhesion approach. Work of adhesion and interlaminar shear strength values were calculated respectively from experimentally determined interfacial tensions and short beam flexural tests. The adhesion capacities of glass fibers with different surface treatments of organosilanes were evaluated. Among the different silanes tested, γ-aminopropyltrimethoxysilane (APS) was found to be the best coupling agent for the glass fibers, possibly, because of its chemical compatibility with PA6. Tensile test results indicated that increasing amount of PA6 in the polymer matrix improved the strength and stiffness of the composites due to a strong acid–base interaction at the interface. Incorporation of PA6 to the SGF reinforced ABS reduced the melt viscosity, broadened the fiber length distributions and increased the toughness of the composites. Fractographic analysis showed that the incorporation of PA6 enhanced the interactions between glass fibers and the polymeric matrix.     

A facile route for preparing stable co-continuous morphology of LLDPE/PA6 blends with low PA6 content

A facile method is employed to prepare a series of LLDPE/PA6 blends with co-continuous morphology with low PA6 content via reactive extrusion. In these blends, co-continuous morphology is obtained by introducing graft copolymers with both high and low molecular weight trunk chains to the interface simultaneously. Maleic anhydride functionalized polybutadine (PB-g-MAH, and MAH content = 10 wt%) is first melt grafted onto the LLDPE backbones with dicumyl peroxide (DCP) as an initiator. Part of PB-g-MAH is grafted onto LLDPE to form LLDPE-g-PB-g-MAH copolymer. During reactive extrusion, in-situ formed Copolymer II (polybutadiene-graft-polyamide, PB-g-PA6) with a low molecular weight trunk chain (PB) is obtained from the reaction between the maleic anhydride group of free or non-grafted PB-g-MAH and the amino group on PA6 molecules; while Copolymer I (LLDPE-g-PB-g-PA6) is obtained via the reaction between the maleic anhydride group of the grafted PB-g-MAH (i.e., LLDPE-g-PB-g-MAH) and the amino group of PA6. Copolymer I with a high molecular weight trunk chain, LLDPE, should strengthen the interface and favor stress transfer, enabling the deformation of PA6; and Copolymer II (PB-g-PA6) with a low molecular weight trunk chain, PB, facilitates the formation of a flat interface between LLDPE and PA6, thus promoting an elongated PA6 phase. Therefore, co-continuous morphology of LLDPE/PA6 blend is successfully prepared with only 25 wt% PA6 by controlling suitable amounts of Copolymers I and II in the blend.     

Rheological,thermal, and morphological properties of ABS–PA1010 blends

Noncompatibilized and compatibilized ABS–nylon1010 blends were prepared by melt mixing. Polystyrene and glycidyl methacrylate (SG) copolymer was used as a compatibilizer to enhance the interfacial adhesion and to control the morphology. This SG copolymer contains reactive glycidyl groups that are able to react with PA1010 end groups ( NH₂ or  COOH) under melt conditions to form SG‐g‐Nylon copolymer. Effects of the compatibilizer SG on the rheological, thermal, and morphological properties were investigated by capillary rheometer, DSC, and SEM techniques. The compatibilized ABS–PA1010 blend has higher viscosity, lower crystallinity, and smaller phase domain compared to the corresponding noncompatibilized blend. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 683–688, 1999     

Synthesis of functionalized copolymers and their compatibilization effects on acrylonitrile butadiene styrene/poly(butylene terephthalate) blends

In this study, the copolymers of methyl methacrylate-co-glycidyl methacrylate (MGD) with different epoxy contents and molecular weights, the styrene-co-glycidyl methacrylate (SGD) and methyl methacrylate-co-maleic anhydride (MAD) were synthesized. The synthesized copolymers, styrene-co-maleic anhydride (SMA) and styrene-acrylonitrile-co-glycidyl methacrylate (SAG) were used as compatibilizers to enhance the impact strength of the acrylonitrile butadiene styrene/poly(butylene terephthalate) (ABS/PBT). The effects of differences in the structure, reactive group type, and molecular weight of the compatibilizers on the mechanical properties, phase morphology, melt viscosity, thermal stability, and melting temperature of the blend were studied. The results showed that functionalized copolymers were successfully synthesized with high monomer conversions. Addition of the functionalized copolymers increased melt viscosity but did not considerably affect thermal stability, tensile strength, flexural strength and melting temperature of the ABS/PBT blends. The compatibilizers improved the dispersion of the PBT phase and prevented brittle fracture, thereby increasing the impact strength of the blend. Among the studied compositions, the ABS/PBT/MGD-5 blend exhibited the highest impact strength of 25.8 kJ/m² and an appropriate melt flow index of 19.1 g/10 minutes. The compatibilizer should have an appropriate molecular weight to improve the interface bonding force. Regarding the melting viscosity, the reactive group content and compatibilizer dosage should be adjusted to ensure high impact strength.     

Anisotropy and instability of the co-continuous phase morphology in uncompatibilized and reactively compatibilized polypropylene/polystyrene blends

The present work describes the anisotropy and instability observed upon the formation of co-continuous phase morphologies in model polystyrene/polypropylene melt-extruded blends. Uncompatibilized and reactively compatibilized blends using amino-terminated polystyrene, PS-NH₂, and maleic anhydride grafted polypropylene, PP-MAh, reactive precursors were investigated. Differences in phase morphology are discussed based on the viscoelastic properties of the components used, the blend composition and, the type and content of the compatibilizer precursor employed. As expected, for the same polystyrene grade at a concentration in the blend below 20 wt%, a polypropylene matrix having a higher viscosity enables the formation of a more co-continuous phase morphology than a less viscous one, as quantified by solvent extraction. The co-continuous phase morphology developed was found to exhibit a highly elongated structure upon melt flow through the die of the extruder. Isotropic co-continuity, observed inside the barrel of extruder, was transformed into anisotropic phase co-continuity in the form of interconnected infinite strands of the minor phase highly oriented in the extrusion direction.When the blends were thermally annealed, a 50/50 PS/PP co-continuous blend exhibits a substantial phase coarsening from micro- to millimeter scale without alteration of the phase co-continuity. The reactive compatibilization of the polypropylene and the polystyrene phases using 5 wt% PP-graft-PS, reactively in situ generated was able to significantly retard the phase evolution process.     

Effects of mixing protocol on the performance of nanocomposites based on polyamide 6/acrylonitrile–butadiene–styrene blends

Toughening of polyamide 6 (PA6) can be achieved by appropriate addition of an elastomeric matrix phase; however, this leads to a loss of rigidity and mechanical strength. As a result, much research has been directed at obtaining an optimal balance between toughness and rigidity for these thermoplastics. The approach explored here is the formation of nanocomposites from PA6/acrylonitrile–butadiene–styrene (ABS) blends prepared by melt mixing with a modified montmorillonite (Cloisite® 30B) and styrene/maleic anhydride copolymer as a compatibilizer. The effect of the mixing sequence of the components on the morphology and properties is a primary focus. The morphology and mechanical properties of the materials were characterized by X‐ray diffraction, electron microscopy, and tensile and impact testing. Incorporation of the compatibilizer in the PA6/ABS blend increased toughness but decreased rigidity. A significant increase of modulus was observed for the nanocomposite blend compared with the blend or the matrix. This increase was attributed to the exfoliation of organoclay layers in the PA6 matrix phase. It was also observed that the morphology of the ABS dispersed phase was considerably influenced by the mixture sequence. POLYM. ENG. SCI., 52:1909–1919, 2012. © 2012 Society of Plastics Engineers     

Fractionated crystallization in PA6/ABS blends: Influence of a reactive compatibilizer and multiwall carbon nanotubes

The 20/80 blends of polyamide 6 (PA6) and acrylonitrile–butadiene–styrene copolymer (ABS) in the presence of styrene–maleic anhydride copolymer (SMA) and multiwall carbon nanotubes (MWNT) were prepared using melt-mixing technique. Crystallization behavior of the PA6 phase in the blends was studied using DSC, WAXD and SAXS techniques. Blends' morphology was characterized by SEM. We observed fractionated crystallization of PA6 phase in 20/80 PA6/ABS blends. It was also observed that the phenomenon of fractionated crystallization was influenced by the presence of both SMA and MWNT. Blends' morphology revealed the presence of wide domain size distribution of PA6 droplets in the amorphous ABS matrix. On incorporation of either SMA or SMA modified MWNT, the average domain size of PA6 droplets was found to be finer up to 1 wt% SMA modified MWNT. Encapsulation of SMA copolymer layer on the MWNT surface was also evident from SEM micrographs. SAXS analysis revealed the formation of multiple lamellae stacking of PA6 phase in the presence or absence of SMA and MWNT in 20/80 PA6/ABS blends. This was attributed to the formation of less perfect crystallites formed during the cooling of melt at higher degree of supercooling.     

The simultaneous addition of styrene maleic anhydride copolymer and multiwall carbon nanotubes during melt‐mixing on the morphology of binary blends of polyamide6 and acrylonitrile butadiene styrene copolymer

The effect of simultaneous addition of multiwall carbon nanotubes (MWNTs) and a reactive compatibilizer (styrene maleic anhydride copolymer, SMA) during melt‐mixing on the phase morphology of 80/20 (wt/wt) PA6/ABS blend has been investigated. Morphological analysis through scanning and transmission electron microscopic analysis revealed finer morphology of the blends in presence of SMA + MWNTs. Fourier transform infrared spectroscopic analysis indicated the formation of imide bonds during melt‐mixing. Non‐isothermal crystallization studies exhibited the presence of a majority faction of MWNTs in the PA6 phase of 80/20 (wt/wt) PA6/ABS blend in presence of SMA + MWNTs. Rheological analysis, dynamic mechanical thermal analysis, and thermogravimetric analysis have demonstrated the compatibilization action of simultaneous addition of a reactive compatibilizer (SMA copolymer) and MWNTs in PA6/ABS blends. An attempt has been made to investigate the role of simultaneous addition of SMA copolymer and MWNTs on the morphology of 80/20 (wt/wt) PA6/ABS blend through various characterization techniques. POLYM. ENG. SCI., 55:457–465, 2015. © 2014 Society of Plastics Engineers     

PP-g-GMA的制备及其增容PP/PA6共混物的性能

通过熔融接枝反应制备了甲基丙烯酸缩水甘油酯接枝聚丙烯（PP-g-GMA）,并将其作为聚丙烯/聚酰胺6（PP/PA6）共混物的相容剂,研究了PP-g-GMA对PP/PA6共混物的力学性能及形态结构的影响。结果表明,采用滴定法测得PP-g-GMA接枝率为3.35 %;当PP-g-GMA的添加量为4 %（质量分数,下同）和8 %时,PP/PA6/PP-g-GMA共混物的拉伸强度和缺口冲击强度分别较PP/PA6共混物提高了32.4 %和60.4 %;PP-g-GMA显著改善了PP/PA6 共混物的界面相容性,是PP/PA6共混物的有效增容剂。