Polypropylene/polyamide 6/polyethylene-octene elastomer blends. Part 2: volume dilatation during plastic deformation under uniaxial tension

Plastic deformation upon stretching was investigated in ternary blends of polypropylene, polyamide 6 and maleic anhydride-grafted polyethylene-octene elastomer (PP/PA6/POE). A novel video-controlled tensile testing method was utilized, which allows recording simultaneously axial strain, axial stress and volume strain while axial strain-rate is regulated at a constant value even after necking has begun. Increasing the alloying content modifies drastically the original stress-strain properties of PP: yield softening is suppressed and strain hardening is increased. As for the volume strain, which is representative of the overall cavitation process, it is found to decrease with increasing alloying content (apart from a small increase for low alloying content). This unexpected result indicates that the finely dispersed cavities nucleated under tension at the POE interphase of PA6 particles and at isolated POE particles favor the profuse development of plastic shear bands in the PP matrix. As such, it can be considered as an experimental evidence of the synergistic effect of cavitation and shear banding in a structural polymer.     

Polypropylene/polyamide 6/polyethylene-octene elastomer blends. Part 3. Mechanisms of volume dilatation during plastic deformation under uniaxial tension

It has been shown in a previous paper in this series that important dilatation is produced by plastic deformation under tension of neat PP and PP/PA6/POE blends, for which the POE to PA6 concentration ratio equals 1/2. In this work, the detailed mechanisms of this volume change are investigated from electron micrographs (SEM and TEM) obtained in the deformed state. At low alloy content, it is thus observed that dilatation results from decohesion of the PA6 particles from the PP matrix. As the amount of PA6 and POE increases, voids are nucleated preferentially in the thicker POE interphase making a shell around the PA6 particles, and secondarily in isolated POE particles. Unexpectedly, it has been found that the overall volume dilatation decreases with total alloying content. This is interpreted by: (i) the increasing contribution of PA6 that intrinsically deforms with less cavitation than PP, (ii) the post-cavitation rubber-like stretching of POE particles and, (iii) the early formation of a percolating network of shear bands from the diffuse array of voids formed after the yield point. These mechanisms explain the gradual increase of the resistance to impact of the PP/PA6/POE as their alloying content is increased.     

Study on the microstructures and mechanical behaviour of compatibilized polypropylene/polyamide‐6 blends

A series of blends of polypropylene (PP)–polyamide‐6 (PA6) with either reactive polyethylene–octene elastomer (POE) grafted with maleic anhydride (POE‐g‐MA) or with maleated PP (PP‐g‐MA) as compatibilizers were prepared. The microstructures and mechanical properties of the blends were investigated by means of tensile and impact testing and by scanning electron microscopy and transmission electron microscopy. The results indicated that the miscibility of PP–PA6 blends was improved with the addition of POE‐g‐MA and PP‐g‐MA. For the PP/PA6/POE‐g‐MA system, an elastic interfacial POE layer was formed around PA6 particles and the dispersed POE phases were also observed in the PP matrix. Its Izod impact strength was four times that of pure PP matrix, whilst the tensile strength and Young's modulus were almost unchanged. The greatest tensile strength was obtained for PP/PA6/PP‐g‐MA blend, but its Izod impact strength was reduced in comparison with the pure PP matrix. © 2002 Society of Chemical Industry     

PP/PA6共混比例对其水辅助注塑管件性能及微观形态的影响

以聚丙烯 (PP)为基材,聚酰胺6(PA6)为分散相,制备了4种共混比例的PP/PA6复合材料,考察了共混比例对其水辅助注射成型技术（WAIM）管件拉伸强度及微观形态的影响。结果表明,试样拉伸强度随PA6含量增加先减小后增大;近模壁层和近水层的PA6分散相为大长厚比的长条状或长片状,中间层分散相为椭球状,且随PA6含量增加各层分散相有聚集长大的趋势;管件近模壁层和近水层的晶粒小而密且沿流动方向排列,而中间层晶粒相对更粗大;PP只形成了一种晶型,PA6形成了2种晶型;近水层和近模壁层PP结晶度高于中间层;PA6随其含量增加其结晶度有增大的趋势,且近模壁层结晶度较高。     

Rubber‐toughened polypropylene nanocomposite: Effect of polyethylene octene copolymer on mechanical properties and phase morphology

Rubber‐toughened polypropylene (PP)/org‐Montmorillonite (org‐MMT) nanocomposite with polyethylene octene (POE) copolymer were compounded in a twin‐screw extruder at 230°C and injection‐molded. The POE used had 25 wt % 1‐octene content and the weight fraction of POE in the blend was varied in the range of 0–20 wt %. X‐ray diffraction analysis (XRD) revealed that an intercalation org‐MMT silicate layer structure was formed in rubber‐toughened polypropylene nanocomposites (RTPPNC). Izod impact measurements indicated that the addition of POE led to a significant improvement in the impact strength of the RTPPNC, from 6.2 kJ/m² in untoughened PP nanocomposites to 17.8 kJ/m² in RTPPNC containing 20 wt % POE. This shows that the POE elastomer was very effective in converting brittle PP nanocomposites into tough nanocomposites. However, the Young's modulus, tensile strength, flexural modulus, and flexural strength of the blends decreased with respect to the PP nanocomposites, as the weight fraction of POE was increased to 20 wt %. Scanning electron microscopy (SEM) was used for the investigation of the phase morphology and rubber particles size. SEM study revealed a two‐phase morphology where POE, as droplets was dispersed finely and uniformly in the PP matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3441–3450, 2006     

Effect of nanosilica on the co-continuous morphology of polypropylene/polyolefin elastomer blends

This paper reports the effect of nanosilica (SiO₂) on the morphology of co-continuous immiscible polypropylene (PP)/polyolefin elastomer (POE) blends. The unfilled blends display phase inversion and a co-continuous structure at a ratio of 50/50 PP/POE by weight. Upon addition of SiO₂ in the presence of maleated PP compatibilizer a finer structure, consisting of elongated POE particles dispersed within the PP phase is obtained. This transformation is associated to the presence of finely dispersed SiO₂ particles that are localized exclusively within the PP matrix. The impact properties, flexural and Young's moduli of the blends increase significantly, pointing to a synergistic effect arising from the presence of the reinforced PP phase, containing high amounts of the finely dispersed elastomeric phase.     

The effects of SEBS-g-maleic anhydride reaction on the morphology and properties of polypropylene/PA6/SEBS ternary blends

Ternary blends, based on 70% by weight of polypropylene (PP) with 30% by weight of a dispersed phase, consisting of 15% polyamide-6 (PA6) and 15% of a mixture comprising varying ratios of an unreactive poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) triblock copolymer and a reactive maleic anhydride-grafted SEBS-g-MA, were produced via melt blending in a co-rotating twin-screw extruder. TEM revealed the blend containing only non-reactive SEBS to exhibit individual PA6 and SEBS dispersed phases. However, the progressive replacement of SEBS with reactive SEBS-g-MA increased the degree of interfacial reaction between the SEBS and PA6 phases, thus reducing interfacial tension and providing a driving force for encapsulation of the PA6 by the SEBS. Consequently, the dispersed-phase morphology was observed to transform from two separate phases to acorn-type composite particles, then to individual core-shell particles and finally to agglomerates of the core-shell particles. The resultant blends exhibited significant morphology-induced variations in both thermal and mechanical properties. DSC showed that blends in which the diameter of the PA6 particles was reduced to ≤3 μm by the increasing interfacial reaction exhibited fractionated PA6 crystallisation. In general, mechanical testing showed the blends to exhibit inferior low-strain tensile properties (modulus and yield stress) compared to the matrix PP, but superior ultimate tensile properties (stress and strain at break) and impact strength. These changes are discussed with reference to composite models.     

增容剂EAA对PA6／POE共混体系的相态及性能的影响

采用乙烯－丙烯酸共聚物（EAA）作为尼龙6／乙烯－1－辛烯共聚物弹性体（POE）共混体系的增容剂,详细研究了增容剂用量与共混体系的相态、力学性能和流变性能的关系。结果表明相容剂的加入使共混体系的分散性大大改善,分散相POE粒子明显细化,粒子较均匀地分散在PA6连续相中;相容剂的加入使体系韧性明显提高,拉伸强度和弯曲弹性模量下降,加工性能也得到改善,而且当每100份PA6／POE用量为85／15、EAA用量在4月份左右时,其增容作用达到饱和,综合性能达到最优。     

PP/POE/PA6三元共混物相形态的预测及受混炼顺序的影响

引言对聚合物进行共混是改善其性能的重要方法,多元聚合物共混物结合了多种聚合物的优点,具有更多独特的性能,因此对多元尤其是三元共混物的研究越来越多[1-5]。聚合物共混物的相形态对其性能有着决定性的影响[6-9],因而相形态是共混物研究的一个非常重要的方面[9-12]。     

Co-continuous and encapsulated three phase morphologies in uncompatibilized and reactively compatibilized polyamide 6/polypropylene/polystyrene ternary blends using two reactive precursors

Phase morphology development in ternary uncompatibilized and reactively compatibilized blends based on polyamide 6 (PA6), polypropylene (PP) and polystyrene (PS) has been investigated. Reactive compatibilization of the blends has been performed using two reactive precursors; maleic anhydride grafted polypropylene (PP-g-MA) and styrene maleic anhydride copolymer (SMA) for PA6/PP and PA6/PS pairs, respectively. For comparison purposes, uncompatibilized and reactively compatibilized PA6/PP and PA6/PS binary blends, were first investigated. All the blends were melt-blended using a co-rotating twin-screw extruder. The phase morphology investigated using scanning electron microscope (SEM) and selective solvent extraction tests revealed that PA6/PP/PS blends having a weight percent composition of 70/15/15 is constituted from polyamide 6 matrix in which are dispersed composite droplets of PP core encapsulated by PS phase. Whereas, a co-continuous three-phase morphology was formed in the blends having a composition of 40/30/30. This morphology has been significantly affected by the reactive compatibilization. In the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends, PA6 phase was no more continuous but gets finely dispersed in the PS continuous phase. The DSC measurements confirmed the dispersed character of the PA6 phase. Indeed, in the compatibilized PA6/(PP/PP–MA)/(PS/SMA) blends where the PA6 particle size was smaller than 1 μm, the bulk crystallization temperature of PA6 (188 °C) was completely suppressed and a new crystallization peak emerges at a lower temperature of 93 °C as a result of homogeneous nucleation of PA6.     

Melt rheological properties of polypropylene–polyamide6 blends compatibilized with maleic anhydride‐grafted polypropylene

The melt rheological properties of binary uncompatibilized polypropylene–polyamide6 (PP–PA6) blends and ternary blends compatibilized with maleic anhydride‐grafted PP (PP–PP‐g‐MAH–PA6) were studied using a capillary rheometer. The experimental shear viscosities of blends were compared with those calculated from Utracki's relation. The deviation value δ between these two series of data was obtained. In binary PP–PA6 blends, when the compatibility between PP and PA6 was poor, the deformation recovery of dispersed PA6 particles played the dominant role during the capillary flow, the experimental values were smaller than those calculated, and δ was negative. The higher the dispersed phase content, the more deformed the droplets were and the lower the apparent shear viscosity. Also, the absolute value of δ increased with the dispersed phase composition. In ternary PP–PP‐g‐MAH–PA6 systems, when the compatibility between PP and PA6 was enhanced by PP‐g‐MAH, the elongation and break‐up of the dispersed particles played the dominant role, and the experimental values were higher than calculated. It was observed that the higher the dispersion of the PA6 phase, the higher the δ values of the ternary blends and the larger the positive deviation. Unlike uncompatibilized blends, under high shear stress with higher dispersed phase content, the PP‐g‐PA6 copolymer in compatibilized blends was pulled out from the interface and formed independent micelles in the matrix, which resulted in reduced total apparent shear viscosity. The δ value decreased with increasing shear stress. Copyright © 2006 Society of Chemical Industry     

Effect of the compatibilizer on the morphology and properties of dynamically cured PP/POE/epoxy blends

Dynamic vulcanization was successfully applied to epoxy resin reinforced polypropylene (PP)/ethylene‐octene copolymer (POE) blends, and the effects of different compatibilizers on the morphology and properties of dynamically cured PP/POE/epoxy blends were studied. The results show that dynamically cured PP/POE/epoxy blends compatibilized with maleic anhydride‐grafted polypropylene (MAH‐g‐PP) have a three‐phase structure consisting of POE and epoxy particles dispersed in the PP continuous phase, and these blends had improved tensile strength and flexural modulus. While using maleic anhydride‐grafted POE (MAH‐g‐POE) as a compatibilizer, the structure of the core‐shell complex phase and the PP continuous phase showed that epoxy particles could be embedded in MAH‐g‐POE in the blends, and gave rise to an increase in impact strength, while retaining a certain strength and modulus. DSC analysis showed that the epoxy particles in the blends compatibilized with MAH‐g‐PP were more efficient nucleating agents for PP than they were in the blends compatibilized with MAH‐g‐POE. WAXD analysis shows that compatibilization do not disturb the crystalline structure of PP in the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Compatibilization of polypropylene/nylon 6 blends with a polypropylene solid‐phase graft

The compatibilization of polypropylene (PP)/nylon 6 (PA6) blends with a new PP solid‐phase graft copolymer (gPP) was systematically studied. gPP improved the compatibility of PP/PA6 blends efficiently. Because of the reaction between the reactive groups of gPP and the NH₂ end groups of PA6, a PP‐g‐PA6 copolymer was formed as a compatibilizer in the vicinity of the interfaces during the melting extrusion of gPP and PA6. The tensile strength and impact strength of the compatibilized PP/PA6 blends obviously increased in comparison with those of the PP/PA6 mechanical blends, and the amount of gPP and the content of the third monomer during the preparation of gPP affected the mechanical properties of the compatibilized blends. Scanning electron microscopy and transmission electron microscopy indicated that the particle sizes of the dispersed phases of the compatibilized PP/PA6 blends became smaller and that the interfaces became more indistinct in comparison with the mechanical blends. The microcrystal size of PA6 and the crystallinity of the two components of the PP/PA6 blends decreased after compatibilization with gPP. The compatibilized PP/PA6 blends possessed higher pseudoplasticity, melt viscosity, and flow activation energy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 420–427, 2004     

Effect of compatibilization on the properties of polypropylene/polyamide-66 (75/25 wt/wt) blends

Interfacially compatibilized immiscible blends with an isotactic polypropylene matrix (PP) and dispersed polyamide-66 (PA) were prepared by extrusion with anhydride-grafted isotactic PP compatibilizers, one of high-anhydride content (HAC, 2.7 wt % grafted maleic anhydride) and one of low-anhydride content (LAC, 0.2 wt % anhydride). On a weight basis, HAC was more efficient than LAC in dispersing PA to submicron domains, but on a total weight % anhydride basis, both compatibilizers were equally efficient. Both compatibilizers imparted similar tensile strength improvement compared to an uncompatibilized blend. Maximum fracture strain was obtained at similar total anhydride content, but much higher maximum fracture strain was achieved with LAC than with HAC. Good adhesion in an 11.25 wt % LAC blend was seen at the microscale as fibrillar ligaments connecting PA particles to the drawn PP matrix. Interfacial failure was observed in a lower fracture strain composition, 11.25 wt % HAC. © 1994 John Wiley & Sons, Inc.     

新型丙烯-乙烯共聚物增韧聚丙烯的研究

丙烯-乙烯共聚物Vistamaxx（VM）是一种丙烯摩尔含量占70％以上的新型弹性体。用VM增韧聚丙烯（PP），考察了PP／VM共混物的力学性能、微观形态结构以及结晶性能，并与乙烯-辛烯共聚物（POE）与PP的共混体系进行了对比。结果表明，常温下VM增韧效果优于POE，PP／VM体系拉伸性能优于PP／POE体系；VM在PP中表现出比POE更好的分散性；VM具有与PP相同的晶型，VM的加入细化了PP的晶粒。     

制备工艺对PP/PA6/无机纳米粒子复合材料力学性能的影响

在PP/PA6基体中分别添加两种无机纳米粒子(SiO2,TiO2)和5%的接枝POE作为相容剂。采用三种不同的共混工艺制备PP/PA6/纳米粒子复合材料,并对其性能进行了对比分析。通过力学性能测试和SEM照片观测分析了影响复合材料力学性能的因素。结果表明:分步法的制备工艺能够明显提高PP/纳米粒子复合材料的综合力学性能,改善分散相的相容性。并且研究发现:在PP/PA6中添加相同质量分数的纳米TiO2的综合力学性能要优于纳米SiO2。     

Structure and properties of PP/POE/HDPE blends

This work was aimed to counteract the effect of ethylene‐α‐olefin copolymers (POE) by reinforcing the polypropylene (PP)/POE blends with high density polyethylene (HDPE) particles and, thus, achieved a balance between toughness and strength for the PP/POE/HDPE blends. The results showed that addition of HDPE resulted in an increasing wide stress plateau and more ductile fracture behavior. With the increase of HDPE content, the elongation at break of the blends increased rapidly without obvious decrease of yield strength and Young's modulus, and the notched izod impact strength of the blends can reach as high as 63 kJ/m² at 20 wt % HDPE loading. The storage modulus of PP blends increased and the glass transition temperature of each component of the blends shifted close to each other when HDPE was added. The crystallization of HDPE phase led to an increase of the total crystallinity of the blend. With increasing HDPE content, the dispersed POE particle size was obviously decreased, and the interparticle distance was effectively reduced and the blend rearranged into much more and obvious core‐shell structure. The fracture surface also changed from irregular striation to the regularly distant striations, displaying much obvious character of tough fracture. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of SEPS as a novel compatibilizer on the properties and morphology of PP/PC/POE blends

A novel macromolecular compatibilizer, styrene-ethylene-propylene-styrene (SEPS) with high content of styrene, was investigated for the purpose of improving the compatibility of PP (polypropylene)/PC (polycarbonate)/POE (ethylene-octene copolymer) blends. SEPS shows a remarkable compatibilizing effect since it has a particular structure with the EP-compatible aliphatic segments, which is well miscible with the nonpolar PP and olefinic elastomer POE domains, and S-chain segments which exhibit strong affinity with PC because of the similar molecular structure. Its compatibilizing effect was examined in terms of the mechanical, morphological, and thermal properties. The compatibilized PP-based blends represent remarkable improvement in impact strength and balanced tensile strength. When 5 wt % SEPS was added to PP/PC/POE blends (20 wt % POE), the impact strength of the blends was enhanced from 24 to 43 kJ/m² without obvious drop in the tensile strength. Their morphologies show a decreasing and much more homogeneous size of dispersed PC and POE particles through addition of SEPS, and the fracture surface morphologies change from irregular mosaic to the mix of mosaic and striation, and finally the regularly distant striation. The special morphology structure that resulted from the effect of the compatibilizer could be a key for enhancement of toughness and balanced rigidity of the blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyacrylonitrile/Nylon 6 Blends: Preparation and Characterization

Summary: Polyacrylonitrile (PAN) particles with micro‐size ranges (0.15–2 μm) were prepared by emulsion and dispersion polymerizationa and in supercritical carbon dioxide media. The PAN particles were blended with Nylon 6 (PA6) at 220 °C by using a miniature mixer; it was found that melt‐mixing was possible for PAN‐rich compositions as high as 70 wt.‐%. Blends were characterized by scanning electron microscopy, IR, viscosity measurements, differential scanning calorimetry, and dynamic mechanical thermal analysis (DMTA). The size and shape of original PAN particles were retained in PAN/PA6 blends. The useful range to blend PAN particles size was less than 1 μm in terms of shape retention of the PAN particles in blends. Blends with 40 wt.‐% PAN content were found to be melt‐processable. The elastic modulus was higher for PAN/PA6 blends than pure PA6.

SEM photograph of PAN‐SC/PA6 blend with a 40/60 weight ratio.     

Relaxation behavior of polymer blends with complex morphologies: Palierne emulsion model for uncompatibilized and compatibilized PP/PA6 blends

This paper deals with the dynamic rheological behavior of polypropylene/polyamide6 (PP/PA6) uncompatibilized blends and those compatibilized with a maleic anhydride grafted PP (PP/PP-g-MAH/PA6). The terminal relaxation times of the blends predicted by the Palierne emulsion model were compared with those obtained from experimental relaxation time spectra. The Palierne model succeeded well in describing PP/PA6 uncompatibilized blends with relatively low dispersed phase contents (10 wt%) and failed doing so for those of which the dispersed contents were high (30 wt%). It also failed for the compatibilized ones, irrespective of the dispersed phase content (10 or 30 wt%) and whether or not interface relaxation was taken into consideration. In the case of the uncompatibilized blend with high dispersed-phase content, interconnections among inclusions of the dispersed phase were responsible for the failure of the Palierne model. As for the compatiblized blends, in addition to particle interconnections, the existence of emulsion-in-emulsion (EE) structures was another factor responsible for the failure of Palierne model. A methodology was developed to use Palierne emulsion model upon taking into account the effects of the EE structure on the viscosity of the continuous phase and the effective volume fraction of the dispersed phase.