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.     

Plastic damage mechanisms of polypropylene/polyamide 6/polyethelene-octene elastomer blends under cyclic tension

A series of three-phase polymer blends, composed of polypropylene (PP) matrix, polyamide-6 (PA6) fillers and polyethylene-octene elastomer grafted with maleic anhydride (POE-g-MA) modifiers, were designed and manufactured. Their mechanical behavior under cyclic loading-unloading was studied by using a video-controlled testing system named as VideoTraction^© system. It was found that with the increasing PA6 and POE content, the strain hardening became more and more prominent, the volume strain decreased, and the energy dissipated increased. A detailed examination of the cryo-fractured surfaces under SEM was undertaken. The microcavity nucleation, growth and coalescence were observed, and represent the main mechanisms of plastic deformation and damage. The high volume strain comes from the abundant formation of microvoids. On the contrary, the formation of microvoids resulted in relatively smaller quantity of energy dissipation. This result coincides well with the toughening mechanisms of polymer blends revealed by other peoples.     

Microstructures and mechanical properties of polypropylene/polyamide 6/polyethelene-octene elastomer blends

A series of polymer blends were designed and manufactured. They are composed of three phases: polypropylene (PP), polyamide-6 (PA6) and polyethylene-octene elastomer (POE) grafted with maleic anhydride. The weight fraction of PA6 was adjusted from 0 to 40% by increments of 10%, and the weight fraction of POE was systematically half that of PA6. The morphology, essentially made of PA6 particles dispersed in the PP matrix, was characterised by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In the extruded plates prepared with the blends, the shape of the dispersed PA6 particles showed an elongated ellipsoidal shape, whose aspect ratio increased somehow with alloying content. The POE modifier was observed both as a thin interlayer (less than 100 nm thickness) at the PP/PA6 interface, and as a few isolated particles. The elastic modulus and yield stress in tension are nearly constant for PP and blends. By contrast, the notched Izod impact strength increases very much with alloying content. This remarkable effect is interpreted in terms of POE interphase cavitation, enhanced plastic shear deformation and resistance of PA6 particles to crack propagation.     

Polypropylene/elastomer/poly(styrene-co-acrylonitrile) blends: Manifestation of the critical volume fraction of SAN in dynamic mechanical, tensile and impact properties

The effect of the critical volume fraction v_cr of poly(styrene-co-acrylonitrile) (SAN) on the mechanical properties of its blends with rubber-toughened polypropylene (RTPP) containing about 12% grafted ethylene-propylene copolymer was studied. To encompass a wide spectrum of mechanical properties, blend components were selected which are characterized with rather different viscoelastic, tensile and ultimate properties. The SAN volume fraction in blends covers the interval 0∼0.30; concentration dependencies of measured mechanical properties indicate v_cr = 0.13. Experimental data on storage modulus E_b′, loss modulus E_b″, tensile modulus E_b, yield S_yb and tensile S_ub strength are in plausible accord with their simultaneous prediction based on a predictive scheme which operates with a two-parameter equivalent box model and the data on the phase continuity of components obtained from modified equations of the percolation theory. Strain at break, tensile energy to break and total impact energy of blends show a conspicuous drop in the interval 0∼15 % of SAN where SAN forms a discontinuous component; further growth of the SAN fraction accounts for a reduction of the blend ultimate properties to the values typical of brittle polymers.     

Compatibility effect of reactive copolymers on polypropylene/polyamide 6 blends from commingled plastic wastes

We report the compatibility effect on a recycled polypropylene/nylon (75/25) blend processed with reactive copolymers on the basis of morphological, mechanical, and rheological characteristics. Via a scanning electron microscopy investigation, we found improved surface morphologies with regular and fine domains in a recycled polypropylene/nylon (75/25) blend compatibilized with copolymers containing maleic anhydride as a reactive functional group [styrene–(ethylene/butylene)–styrene‐graft‐maleic anhydride copolymer and polypropylene‐graft‐maleic anhydride]. Large increases in both the mechanical and rheological properties with the addition of the styrene–(ethylene/butylene)–styrene‐graft‐maleic anhydride copolymer could be interpreted with respect to a specific structure at the interface, showing a strong interfacial adhesion between recycled polypropylene and nylon. To confirm the existence of this structure, we used various dynamic rheological parameters: the Cox–Merz rule, storage modulus, and phase angle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1188–1193, 2006     

Mechanisms of plastic deformation in biodegradable polylactide/poly(1,4‐cis‐isoprene) blends

Polylactide (PLA), a main representative of biodegradable and made from renewable resources polymers, is surprisingly brittle at ambient temperature. In this article it is investigated how to increase its toughness by a strategy called “rubber toughening” using poly(1,4‐cis‐isoprene), a major component of natural rubber, which is immiscible with PLA, could be well dispersed in PLA matrix and is biodegradable. Immiscible blends of PLA with poly(1,4‐cis‐isoprene) were prepared by melt blending and their properties were studied and optimized. Incorporation of as low as 5 wt % of rubber increased the strain at break of compression molded film during uniaxial drawing, and also improved its tensile impact strength by 80%. The complex mechanism of plastic deformation in the blends leading to improvement of ductility and toughness was revealed. The rubbery particles initiated crazing at the early stages of deformation, as evidenced by transmission and scanning electron microscopy and also by small angle X‐ray scattering. Crazing was immediately followed by cavitation inside rubber particles, which further promoted shear yielding of PLA. The sequence of those mechanisms was proven by microscopic investigation. All three elementary mechanisms acting in the sequence indicated are responsible for surprisingly efficient toughening of PLA by a major component of natural rubber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of crystalline structure and free volume of polyamide 6/nitrile rubber elastomer thermoplastic vulcanizates: Effect of the processing additives

Blends of polyamide 6 and nitrile rubber (PA6/NBR) dynamically vulcanized may generate innovative products for special purposes where both high temperature and chemical resistance are key factors. In this investigation, we show that the crystalline nature of the PA6 can be controlled in terms of its morphological aspects (degree of crystallinity, crystal size, and structure) as a consequence of the presence of NBR and processing additives. Our results indicate that this crystalline control is dependent on the plasticization caused by the processing additives. Furthermore, imide‐like linkage formation was favored in the presence of ethylene‐co‐vinyl acetate (EVA)‐g‐maleic anhydride, resulting in changes in the molecular mobility of the PA6 matrix, crystallization parameters, and viscoelastic properties when compared to the others EVA additives. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45576.     

Synthesis and characterization of monomer‐casting polyamide 6/polymethacrylic ionomer blends

Monomer‐casting polyamide 6 (MCPA6)/polymethacrylic ionomer blends were synthesized by the in situ anionic ring‐opening polymerization of ?‐caprolactam. The polymethacrylic ionomer used in this study was a copolymer of methyl methacrylate and sodium or zinc methacrylate. Because the polymethacrylic ionomer strongly interacted with polyamide 6 (PA6) chains, it influenced the alignment of the polyamide chains. The change in the degree of the order of hydrogen bonding in MCPA6 caused by the addition of the polymethacrylic ionomer was studied with Fourier transform infrared. The change in the interaction between PA6 chains was studied with rheological measurements. The influence of the polymethacrylic ionomer on the crystallization behavior of MCPA6 was also studied with differential scanning calorimetry. The isothermal crystallization and subsequent melting behavior were investigated at the designated temperature. The commonly used Avrami equation was used to fit the primary stage of the isothermal crystallization. The Avrami exponent (n) values were evaluated to be 2 < n < 3 for the neat MCPA6 and MCPA6/polymethacrylic ionomer blends. The polymethacrylic ionomer, acting as a stumbling‐block agent in the blends, decelerated the crystallization rate with the half‐time of crystallization increasing. The polymethacrylic ionomer made the molecular chains of MCPA6 more difficult to crystallize during the isothermal crystallization process. More less perfect crystals formed in the MCPA6/polymethacrylic ionomer blends because of the interaction between the MCPA6 molecular chains and polymethacrylic ionomer. The crystallinity of the blends was depressed by the addition of the polymethacrylic ionomer. The thermal stability was also studied with thermogravimetric analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of polyamide 6/liquid natural rubber blends

This study presents a new approach to toughen Polyamide 6 (PA6) by using a low‐molecular weight liquid natural rubber (LNR). The LNR is prepared by mastication of pale latex crepe in the presence of 0.5 phr Peptizol 7. The PA6/LNR blend samples are characterized in terms melt flow index, hardness, abrasion resistance, impact strength, flexural strength, tensile strength, and thermal properties. The impact strength of PA6 increases by about 67% upon addition of 10% LNR. The percolation model is applied to study of brittle to ductile transition. The percolation threshold for the brittle to ductile transition of the blend was found to be 14.5 wt % LNR, corresponding to the critical volume fraction of the stress volume, V_sc = 0.58, which is consistent with the calculated value of ≈ π/6. The PA6/LNR blends exhibit cavitation and matrix shear yielding, which would be the main contribution to the increases impact strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39750.     

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.     

Synthesis and properties of monomer casting polyamide 6/poly(methyl methacrylate) blends

We successfully synthesized monomer casting polyamide 6 (MCPA6)/poly(methyl methacrylate) (PMMA) blends in two steps: (1) radical polymerization of methyl methacrylate in ?‐caprolactam and (2) anionic ring‐opening polymerization of this ?‐caprolactam solution. The influence of PMMA on the crystallization behavior of MCPA6 was studied with differential scanning calorimetry and X‐ray diffraction, which showed that PMMA could act as a heterogeneous nucleation agent and favored the formation of the γ‐crystalline form. The rheological properties were also studied and indicated that PMMA reduced the interaction between MCPA6 chains by lowering the density of hydrogen bonding. This study used a novel and convenient method to prepare microporous MCPA6/PMMA particles that involved removing the continuous phase. Their surface area and thermal stability were characterized by the Brunauer–Emmett–Teller method and thermogravimetric analysis, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Micromechanical processes and failure phenomena in reactively compatibilized blends of polyamide 6 and styrenic polymers. I. Polyamide 6/acrylonitrile– butadiene–styrene copolymer blends

In this work, in situ investigations of the micromechanical properties of reactively compatibilized blends of polyamide 6 (PA6) and an acrylonitrile–butadiene–styrene copolymer (ABS) were performed with transmission electron microscopy. Three PA6/ABS blends were prepared with a disperse morphology (inclusions of PA6 or ABS) and with a cocontinuous structure. The objective of this work was to study the deformation of the inclusions and the interface between the PA6 phase and the ABS phase. Our transmission electron microscopy investigations revealed that the morphology of the blends was strongly influenced by the asymmetric nature of the interface between PA6 and ABS. In the blends with a PA6 matrix, the interface between PA6 and the ABS inclusions was deformed in tensile deformation under uniaxial loading. A strong influence of the PA6 water content on the (micro)mechanical behavior was observed. Although the “dry” blends behaved in a brittle fashion, the “wet” blends behaved in a ductile fashion with the formation of deformation bands in the matrix (PA6 or ABS), which were initiated by stress concentration at the particles (ABS or PA6, respectively). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Analysis of phase morphology and dynamics of immiscible PP/PA1010 blends and its partial-miscible blends during melt mixing from SEM patterns

The formation and evolution of the phase morphology of polypropylene (PP) with Nylon1010 (PA1010) blends before and after adding the compatibilizer, polypropylene grafted maleic anhydride (PP-g-MAH), during melt mixing are investigated by the pattern analysis of scanning electron microscope (SEM). The average particle diameter DP_AV, characteristic length Λ and the average characteristic length Λm are calculated to discuss the melt mixing process. It is proved, by the figure-estimation theory, that the distribution of Λ is log-normal distribution. Furthermore, the phase morphology during melt mixing is discussed in depth by the parameters of the log-normal distribution. The results demonstrate that the structure of the dispersed phase during melt mixing evolves with dynamical self-similarity through the competition of break-up and coalescence of dispersed phase. A fractal dimension, based on the probability density of the character length, is calculated in this study. The results show that the fractal dimension is an effective parameter to characterize the melt mixing process of polymer blends.     

Micromechanical processes and failure phenomena in reactively compatibilized blends of polyamide 6 and styrenic polymers. II. Polyamide 6/styrene‐acrylonitrile copolymer blends

This work reports on morphological, mechanical, and micromechanical properties of polyamide 6 (PA 6), a styrene‐acrylonitrile copolymer (SAN), and their blends, which were reactively compatibilized using a styrene‐acrylonitrile maleic anhydride (SANMA) terpolymer. Transmission electron microscopy (TEM) investigations revealed the phase morphology of the blends, which is characterized by inclusions of the minor component in the matrix of the major phase. The blend with 50% PA 6 and 50% SAN depicted a cocontinuous morphology. Using a microtensile device for TEM, the samples were deformed under uniaxial loading in the “dry” state (characterized by a zero water content in the PA 6 phase) and in a “wet” state (with water in the PA 6 phase). Whereas the dry blends behaved brittle, the wet blends showed a larger ductility with the formation of deformation bands in the matrix (PA 6 or SAN), which were initiated by stress concentration at the SAN and PA 6 particles, respectively. In the interface of blends with a PA 6 matrix and SAN inclusions, two phenomena were observed: partial cavitation and debonding on the one hand and partial fibrillation on the other hand. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of β-irradiation on mechanical properties of metallocene elastomers/PA6 blends

Binary blends of metallocene polymers with polyamide-6 as dispersed phase and ternary blends with a metallocene-grafted rubber as compatibilizer were prepared and treated by electron beam radiation. Thermal stability and mechanical properties were studied, showing that thermosetting rubbers and thermoplastic elastomers with excellent mechanical properties and thermal stability may be obtained by β-irradiation. The irradiated ternary blends displayed high break elongation values, similar to other thermoplastic rubbers based on EPDM or EPR materials. On the other hand, the Shore D hardness, tensile strength, high-temperature behavior, compression set and reprocessing ability were found to be clearly dependent on the metallocene polymer used as bulk phase and the irradiation dose employed.     

Filler/matrix-debonding and micro-mechanisms of deformation in particulate filled polypropylene composites under tension

Volume strain measurements of particulate filled polypropylene (PP) composites containing different glass beads and talc as filler were carried out in tension as a function of temperature and strain rate to determine the micro-mechanisms of deformation. While local cavitation mechanisms (micro-voiding, crazing, and micro-cracking) and subsequent debonding of the particles dominated as failure mechanisms at high strain rates and at room temperature, a more significant contribution of local shear yielding was observed with a reduced contribution of cavitational mechanisms at low strain rates or at 80 °C. This change in the dominating micro-mechanisms of deformation resulted in smaller volume strains during the tensile loading of the composites than for the respective neat matrix. Moreover, a novel approach is introduced for the detection of debonding using volume strain measurements, which takes into account the dilatational and deviatoric behavior of the neat matrix polymer and the composite. The results are supported by acoustic emission measurements carried out simultaneously on the same specimens.     

Mercapto‐modified copolymers in elastomer blends. IV. The compatibilization of natural rubber/EPDM blends

Ethylene—propylene—diene functionalized with mercapto groups (EPDMSH) was employed as compatibilizing agent for natural rubber (NR)/EPDM blends, resulting in a substantial increase of the ultimate tensile strength of these blends without affecting the elongation at break. There is also a decrease of the curing time with the addition of as low as 2.5 phr of EPDMSH, mainly in NR/EPDM (70:30 wt %) blend, indicating the accelerator effect of this functionalized copolymer. This copolymer also increased the crosslink degree and the gel content. From dynamic mechanical analysis (DMTA), it was demonstrated that EPDMSH improves the covulcanization process. The reactive compatibilization of EPDMSH was demonstrated by the presence of insoluble material in nonvulcanized/compatibilized blends and by its thermogravimetric (TGA) analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2892–2900, 2002; DOI 10.1002/app.10283     

Using organoclay to promote morphology refinement and co-continuity in high-density polyethylene/polyamide 6 blends - Effect of filler content and polymer matrix composition

We investigate the gradual changes of the microstructure of two blends of high-density polyethylene (HDPE) and polyamide 6 (PA6) at opposite composition filled with increasing amounts of an organomodified clay. The filler locates preferentially inside the polyamide phase, bringing about radical alterations in the micron-scale arrangement of the polymer phases. When the host polyamide represents the major constituent, a sudden reduction of the average sizes of the polyethylene droplets was observed upon addition of even low amounts of organoclay. A morphology refinement was also noticed at low filler contents when the particles distributes inside the minor phase. In this case, however, keep increasing the organoclay content eventually results in a high degree of PA6 phase continuity. Rheological analyses reveal that the filler loading at which the polyamide assembles in a continuous network corresponds to the critical threshold for its rheological transition from a liquid- to a gel-like behaviour, which is indicative of the structuring of the filler inside the host PA6. On the basis of this finding, a schematic mechanism is proposed in which the role of the filler in driving the space arrangement of the polymer phases is discussed. Finally, we show that the synergism between the reinforcing action of the filler and its ability to affect the blend microstructure can be exploited in order to enhance relevant technological properties of the materials, such as their high temperature structural integrity.     

Mechanical and thermal characteristics and morphology of polyamide 6/isotactic polypropylene blends in the presence of a β‐nucleating agent

The mechanical and thermal characteristics and morphology of polyamide 6 (PA6)/isotactic polypropylene (iPP) blends (10/90 w/w) prepared with different processing procedures and incorporated with an aryl amide nucleating agent, a kind of β‐nucleating agent (β‐NA) for iPP, were investigated. The yield strength and flexural modulus of the blends decreased as β‐NA was introduced into the blends, whereas the impact strength and elongation at break improved. The crystalline structures of the blends closely depended on (1) the processing conditions and (2) competition between the β‐nucleating effect of β‐NA and the α‐nucleating effect of PA6 for iPP. Scanning electron microscopy, differential scanning calorimetry, and X‐ray diffraction were adopted to reveal the microstructures of the blends. At a low β‐NA content (<0.1 wt %), the α‐phase iPP dominated the blends, whereas the relative content of the β‐phase iPP increased remarkably when the β‐NA content was not less than 0.1 wt %. The processing conditions also showed profound influences on the supermolecular structures of iPP; this resulted in different mechanical properties of the blends. As for PA6, the crystallization behavior and crystalline structure did not exhibit obvious changes, but PA6 did play an important role in the epitaxial crystallization of iPP on PA6. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polyamide 6/ethylene‐butylene elastomer blends generated via anionic polymerization of ε‐caprolactam: Phase morphology and dynamic mechanical behavior

This paper reports about the polymerization of ε‐caprolactam monomer in the presence of low molecular weight hydroxyl or isocyanate end‐capped ethylene‐butylene elastomer (EB) elastomers as a new concept for the development of a submicron phase morphology in polyamide 6 (PA6)/EB blends. The phase morphology, viscoelastic behavior, and impact strength of the polymerization‐designed blends are compared to those of similar blends prepared via melt‐extrusion of PA6 homopolymer and EB elastomer. Polyamide 6 and EB elastomer were compatibilized using a premade triblock copolymer PA6‐b‐EB‐b‐PA6 or a pure EB‐b‐PA6 diblock reactively generated during melt‐blending (extrusion‐prepared blends) or built‐up via anionic polymerization of ε‐caprolactam on initiating ? NCO groups attached to EB chain ends (polymerization‐prepared blends). Two compatibilization approaches were considered for the polymerization‐prepared blends: (i) the addition of a premade PA6‐b‐EB‐b‐PA6 triblock copolymer to the ε‐caprolactam monomer containing nonreactive EB? OH elastomer and (ii) generation in situ of a PA6‐b‐EB diblock using EB? NCO precursor on which polyamide 6 blocks are built‐up via anionic polymerization of ε‐caprolactam. The noncompatibilized blends exhibit a coarse phase morphology, either in the extruded or the polymerization prepared blends. Addition of premade triblock copolymer (PA6‐b‐EB‐b‐PA6) to a EB? OH /ε‐caprolactam dispersion led to a fine EB phase (0.14 μm) in the PA6 matrix after ε‐caprolactam polymerization. The average particle size of the in situ reactively compatibilized polymerization‐prepared blend is about 1 μm. The notched Izod impact strength of the blend compatibilized with premade triblock copolymer was much higher than that of the neat PA6, the noncompatibilized, and the in situ reactively compatibilized polymerization blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2538–2544, 2004