Polypropylene/polyethylene blends as models for high‐impact propylene–ethylene copolymers,part 1: Interaction between rheology and morphology

In this work, composition effects on interfacial tension and morphology of binary polyolefin blends were studied using rheology and electron microscopy. The amount of dispersed phase (5–30 wt %) and its type [ethylene–octene copolymer, linear low‐density polyethylene (LLDPE), and high‐density polyethylene] was varied, and the influence of different matrix materials was also studied by using a polypropylene homopolymer and a ethylene–propylene (EP) random copolymer. The particle size distribution of the blends was determined using micrographs from transmission electron microscopy (TEM). A clear matrix effect on the flow behavior could be found from the viscosity curves of the blends. Analyzing the viscosity of the blends applying the logarithmic mixing rule indicated a partial miscibility of the EP random copolymer with low amounts of the LLDPE in the melt. Micrographs from TEM also showed a clear difference in morphology if the base polymer is changed, with PE lamellae growing out of the inclusions or being present directly embedded in the matrix. To verify these findings, the interfacial tension was determined. The applicability of Palierne's emulsion model was found to be limited for such complex systems, whereas Gramespacher–Meissner analysis led to interfacial tensions comparable with those already reported in the literature. The improved compatibility when changing the matrix polymer from the homopolymer to the random copolymer allows the development of multiphase materials with finer phase structure, which will also result in improved mechanical and optical performance. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of coalescence and interfacial tension on the morphology of PP/HDPE compatibilized blends

In this paper, the compatibilization of polypropylene (PP)/high-density polyethylene (HDPE) blend was studied through morphological and interfacial tension analysis. Three types of compatibilizers were tested: ethylene-propylene-diene copolymer (EPDM), ethylene-vinylacetate copolymer (EVA) and styrene-ethylene/butylene-styrene triblock copolymer (SEBS). The morphology of the blends was studied by scanning electron microscopy. The interfacial tension between the components of the blends was evaluated using small amplitude oscillatory shear analysis. Emulsion curves relating the average radius of the dispersed phase and the interfacial tension to the compatibilizer concentration added to the blend were obtained. It was shown that EPDM was more efficient as an emulsifier for PP/HDPE blend than EVA or SEBS. The relative role of interfacial tension reduction and coalescence reduction to particle size reduction was also addressed. It was observed that the role of coalescence reduction is small, mainly for PP/HDPE (90/10) blends compatibilized by EPDM, EVA or SEBS. The results indicated that the role of coalescence reduction to particle size reduction is lower for blends for which interfacial tension between its components is low at compatibilizer saturation.     

Fracture characteristics and deformation behavior of heterophasic ethylene-propylene copolymers as a function of the dispersed phase composition

The deformation and fracture behavior of in reactor produced heterophasic copolymers, comprising a polypropylene (PP) matrix and an ethylene propylene copolymer (EPC) dispersed phase, have been studied as a function of the dispersed phase composition (ethylene/propylene ratio). Conventional and instrumented Charpy as well as instrumented drop weight tests were employed to quantify the response of the materials to impact loading. Scanning and high-voltage electron microscopy was used for characterization of the deformation mechanisms. Decreasing ethylene content of the EPC led to an enhancement of the matrix/dispersed phase compatibility, reduction of the dispersed phase particle size and therewith to a systematic increase of the impact strength at room temperature and a decrease of the brittle-to-tough transition temperature (T_BTT) of the materials. The low temperature impact strength was predominantly dependent upon the glass transition temperature of the EPC phase. The results are discussed from the viewpoint of interfacial interactions, size and spatial packing of the dispersed phase domains and the observed deformation mechanisms.     

Influence of composition on the linear viscoelastic behavior and morphology of PP/HDPE blends

In this paper the influence of temperature and composition on the dynamic behavior and morphology of polypropylene (PP)/high-density polyethylene (HDPE) blends were studied. The blend composition ranged from 5 to 30 wt% of dispersed phase (HDPE) and the temperatures ranged from 180 to 220 °C. The interfacial tension between PP and HDPE at temperatures of 180, 200 and 220 °C was obtained from fitting Palierne's emulsion model [1] to the experimental data of PP/HDPE blends with different compositions and from the weighted relaxation spectra of PP/HDPE blends with different compositions, following Gramespacher and Meissner [2] analysis. The interfacial tension between PP and HDPE as inferred from the rheological measurements was shown to depend on PP/HDPE blend composition. However, the results indicated that there is a range of PP/HDPE blend composition for which interfacial tension between PP and HDPE is constant. Considering these values, it was shown that interfacial tension between PP and HDPE decreases linearly with increasing temperature.     

Effect of composition on the linear viscoelastic behavior and morphology of PMMA/PS and PMMA/PP blends

Here, the effect of concentration on the morphology and dynamic behavior of polymethylmethacrylate/polystyrene (PMMA/PS), for PS with two different molecular weight, and polymethylmethacrylate/polypropylene (PMMA/PP) blends was studied. The blends concentrations ranged from 5% to 30% of the dispersed phase (PS or PP). The dynamic data were analyzed to study the possibility of inferring the interfacial tension between the components of the blend from their rheological behavior using Palierne [Palierne JF. Rheol Acta 1990;29:204-14] [1] and Bousmina [Bousmina M. Acta 1999;38:73-83] [2] emulsion models. The relaxation spectrum of the blends was also studied. The dynamic behavior of 85/15 PS/PMMA blend were studied as a function of temperature. It was possible to fit both Palierne and Bousmina's emulsion models to the dynamic data of PMMA/PS blends, to obtain the interfacial tension of the blend. This was not the case for PMMA/PP. The relaxation spectrum of both blends was used to obtain the interfacial tension between the components of the blends. The values of interfacial tension calculated were shown to decrease when the concentration of the blends increased. It was shown using morphological analysis that this phenomenon can be attributed to the coalescence of the dispersed phase during dynamic measurements that occurs for large dispersed phase concentration. When the ‘coalesced’ morphology is taken into account in the calculations the interfacial tension inferred from rheological measurement did not depend on the concentration of the blend used. The values of interfacial tension found analyzing the dynamic behavior of one of the PMMA/PS blend were shown to decrease with temperature.     

Relationship between interfacial tension and dispersed‐phase particle size in polymer blends. II. PP/PA6

Simple blends with different viscosity ratios of the components as well as compatibilized blends varying both in type and content of the compatibilizers were used to study the relation between the interfacial tension and the dispersed‐phase particle size for PP/PA6 (80/20 wt %) blends in this work. Four compatibilizing systems including poly(ethylene‐co‐methacrylic acid) ionomers, a maleic anhydride‐grafted propylene copolymer, maleic anhydride‐grafted polypropylene, and a maleic anhydride‐grafted styrene ethylene butylene copolymer were used. For blends prepared in an internal mixer, a power‐law relation was found between the capillary number and the torque ratio of the blends' components. This relation was used to estimate the interfacial tension for the compatibilized blends. The relation between the steady‐state torque of the blends as a measure of viscosity and the estimated values of interfacial tension were also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 54–63, 2003     

乙丙橡胶增韧聚丙烯共混物中橡胶相形态

通过电子扫描电镜(SEM),研究了乙丙橡胶增韧聚丙烯共混物中作为分散相的橡胶粒子的形态。结果表明,在交联剂等助剂的作用下进行过动态硫化的共混物中橡胶相的粒子形状、粒径、粒径分布以及橡胶粒子与连续相聚丙烯所形成的界面形态与单纯的橡塑共混物和PP/EPDM反应器共混物相比有着截然不同的区别。正是由于这些区别,提高了经过动态硫化的共混物的冲击性能。     

Blending PP with PA6 industrial wastes: Effect of the composition and the compatibilization

Blending polypropylene to recycled PA6 industrial wastes at different compositions, with and without compatibilizer PPgMA was produced in a corotating twin screw extruder where, polypropylene acts as the polymer matrix and polyamide as the dispersed phase. Several techniques were used to investigate the morphology, thermal, viscoelastic and tensile properties of these blend. Binary PP/PA6 blends showed the presence of PA6 particles dispersed in the PP continuous phase and exhibited a coarse morphology. Increasing PA6 contents in the blend increased their crystallinity and their size and improved the tensile properties at weak deformation. In addition to compatibilizer PPgMA, the morphology shows lower diameters and a decrease in size of the dispersed PA6 particles. The interfacial adhesion was also improved, as a result of the creation of an interphase that was formed by the interaction between the formed PPgPA6 copolymer in situ and both phases. This interphase induced an improvement in tensile properties. The PPgPA6 copolymer generated by the interphase was identified with DMA analysis thanks to an additional transition in loss modulus curves. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology-processing relationships in polyethylene-polyamide blends

Blends of polyethylene (PE) and polyamide (PA) were prepared by a melt mixing process. The dependence of the number average size A_n of the dispersed phase on hydrodynamic conditions not only of shear rate but also temperature, inter-facial tension, viscosity of the blends (WU's treatment), and dispersed phase concentration were studied. The analysis of PE-PA blend morphology shows A_n to be the result of a balance between coalescence and disruption of the particles in the melt, and to display a strong increase in particle size when the minor component concentration is enhanced. These observations can be explained by a change in the rheology of the system. These assumptions are confirmed by the insertion in the blend of an ethylenemaleic anhydride (EMA) copolymer that yields EMA-g-PA graft copolymer during mechanical processing. Formation of this graft copolymer has been indicated by a strong particle size reduction and its concentration was measured by infrared experiments. The EMA-g-PA copolymer seems to decrease the blend interfacial tension and to deter the coalescence process.     

Rubber-modified epoxies: Interfacial tension and morphology

The interfacial tension between carbomethoxy-terminated butadiene–acrylonitrile copolymers and an epoxy resin as a function of temperature and copolymer composition is investigated. Using a digital image processing technique, the shape of a pendant drop of the epoxy in the copolymer is determined. Analysis of the drop shape is performed by profile discrimination and subsequent robust shape analysis. The data are used to examine the relationship between interfacial tension and particle size of the dispersed copolymer-rich phase in rubber-modified epoxy resins, that are immiscible in the uncured state.     

New polypropylene blends toughened by polypropylene/poly(ethylene-co-propylene) in-reactor alloy: Compositional and morphological influence on mechanical properties

A new toughening agent, polypropylene/poly(ethylene-co-propylene) in-reactor alloy (EP-P), has been adopted to modify isotactic polypropylene (PP) in present study. Systematic investigation has been performed on the inter-compositional interaction, crystalline structure, and phase morphology of a series of PP/EP-P blends. It has been found that the PP component from EP-P is thoroughly miscible with neat PP and they together serve as the matrix of the PP/EP-P blends, while the ethylene-propylene random copolymers (EPR) act as the dispersed phase. The ethylene-propylene segmented copolymers (EPS), behaving as the compatibilizer between the EPR dispersed phase and PP matrix, strengthen mutual incorporation and effective diffusion of the amorphous PP segments and the EPR molecules. Based on the in-depth understanding of the crystalline structure and phase morphology, the correlation between morphological structure and mechanical properties has been established. The excellent impact toughness of PP/EP-P blends with higher EP-P content is mainly attributed to the small PP crystallites scattered in the blends and the well dispersed EP copolymer domains in PP matrix.     

New synthesis methods for polypropylene‐co‐ethylene‐propylene rubber

In this research, the reinforcement of polypropylene (PP) was studied using a new method that is more practical for synthesizing polypropylene‐block‐poly(ethylene‐propylene) copolymer (PP‐co‐EP), which can be used as a rubber toughening agent. This copolymer (PP‐co‐EP) could be synthesized by varying the feed condition and changing the feed gas in the batch reactor system using Ziegler–Natta catalysts system at a copolymerization temperature of 10°C. The ¹³C‐NMR tested by a 21.61‐ppm resonance peak indicated the incorporation of ethylene to propylene chains that could build up the microstructure of the block copolymer chain. Differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and dynamic mechanical analysis (DMA) results also confirmed these conclusions. Under these conditions, the morphology of copolymer trapped in PP matrix could be observed and the copolymer T_g would decrease when the amount of PP‐co‐EP was increased. DMA study also showed that PP‐co‐EP is good for the polypropylene reinforcement at low temperature. Moreover, the PP‐co‐EP content has an effect on the crystallinity and morphology of polymer blend, i.e., the crystallinity of polymer decreased when the PP‐co‐EP content increased, but tougher mechanical properties at low temperature were observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3609–3616, 2007     

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.     

Blends of polypropylene with solid silicone additive

Blends of polypropylene (PP) and silicone masterbatch (SMB_PP)—a commercial formulation consisting of an ultrahigh molecular weigh polydimethylsiloxane (PDMS) dispersed in PP—were prepared by melt mixing in an internal mixer. Four binary blends with different SMB_PP content and two ternary blends containing silane‐grafted polypropylenes (PP‐VTES) of different VTES content as compatibilizer were produced. The blends were analyzed by melting flow rate, rotational rheometry, scanning electron microscopy, and differential scanning calorimetry (DSC). In all blends, the SMB_PP remained as dispersed phase in the continuous PP matrix. The addition of PP‐VTES reduced significantly the size of the SMB_PP domains. Rheological and morphological data strongly indicate that the PP‐VTES acts only by lowering the interfacial tension of the system without generating strong interaction between SMB_PP domains and the PP matrix. The dimensions of the SMB_PP domains and the interfacial energy were observed to determine the characteristics of the pseudoplastic behavior of the blends in the melt state. For both binary and ternary blends, the SMB_PP domains showed nucleating effect leading to an increase of the degree of crystallinity. However, the decrease in the interfacial energy and viscosity promoted by the addition of PP‐VTES to the system led to a more intense nucleating effect and to an increase of crystallization, melting temperatures, and melting enthalpy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 226–233, 2007     

Influence of compatibilizers on the rheological,mechanical, and morphological properties of epoxidized natural rubber/polypropylene thermoplastic vulcanizates

In polymeric materials combining desirable properties, compatibility between constituent components of incompatible blends is necessary. The influence of two types of blend compatibilizers, a graft copolymer of maleic anhydride and polypropylene (PP) and phenolic‐modified PP, on the rheological, mechanical, and morphological properties of epoxidized natural rubber/PP thermoplastic vulcanizates was investigated at varied concentrations. All properties improved in a range of loading levels of compatibilizers at 0–7.5 wt % of PP. This was attributed to a chemical interaction between the different phases caused by the functionalized compatibilizers. Increasing chemical interaction between interfaces improved the interfacial tension and led to a microscale size of the dispersion. A decreasing trend in the properties was observed at compatibilizer levels higher than 7.5 wt % of PP because of segregation, which led to a third blend component dispersed in the PP matrix. The compatibilizers behaved as lubricants in the polymer melt flow. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Phase morphology development in a low interfacial tension immiscible polyolefin blend during die extrusion and melt spinning

We describe the development of phase morphology in polypropylene (PP)/ethylene–butene copolymer (EBM) blends in both extrusion through dies and in subsequent melt spinning to form filaments. This immiscible blend has a very low interfacial tension around 0.69 dynes/cm. In the die extrusion process, at low extrusion rates, the dispersed PP phase was sheared into fibrils; at higher extrusion rates, the PP fibrils formed an encapsulation layer near the die wall first, then it broke into droplets because of both interfacial tension and long residence time. These droplets agglomerated together to form a network. In melt spinning, the dispersed phase was also drawn down into fibrils, which coalesced into a continuous layer on the outer surface of the filaments at higher drawdown rates. POLYM. ENG. SCI., 50:1969–1977, 2010. © 2010 Society of Plastics Engineers     

Blends of thermoplastic polyurethane and polypropylene. I. Mechanical and phase behavior

Pure thermoplastic polyurethane (TPU), polypropylene (PP), and TPU/PP blends with different weight ratios prepared in a twin‐screw extruder were investigated by dynamic mechanical analysis (DMA), the universal tester for mechanical investigation, and by wide‐angle X‐ray diffraction (WAXD). The addition of PP above 20 wt % to the TPU stepwise changed the ductility and Young's modulus, i.e., apparently a kind of ductile → brittle transition occurred between TPU/PP 80/20 and TPU/PP 60/40 blends. This fact and the result of analysis of WAXD curves indicated matrix → dispersed phase inversion in this concentration region. TPU melt enabled easier migration of the PP chains and prolonged crystallization of PP matrix during solidification process affecting thus crystallite size, orientation, and crystallinity. In accordance to this fact, DMA results indicated partial miscibility of PP with polyurethane in the TPU/PP blends due to the lack of interfacial interaction and adhesion between the nonpolar crystalline PP and polar TPU phases. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 3980–3985, 2007     

Rubber toughening in polypropylene: A review

The recent advances in the studies of the toughening methods and theories of polypropylene (PP)–elastomer blends are reviewed in the present article. Inclusions are key to toughening PP; they can play the role of agent‐induced crazing, cause shear yielding of the matrix around them, and end the propagation of cracks. The major theories interpreting the toughening mechanisms of the blends are: multiple crazing, damage competition theory, shear‐yielding theory, microvoids, and cavitation theories. The factors affecting the toughening effect are relatively complicated. Therefore, these theories have been verified only in some cases when they have been applied in relevant conditions. To achieve the objective of better toughening, it is important to improve the uniform distribution of dispersed‐phase particle size and suitable filler size, as well as improving the dispersion of the inclusions formed in the matrix; in addition the matrix materials or fillers must be functional with suitable modifier in order to enhance the interfacial adhesion or to improve the interfacial morphological structure between the filler and matrix. However, the exact toughening mechanisms for PP–rubber blends have to be studied further because of complications resulting from the crystallinity of the matrix. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 409–417, 2000     

Correlation of rheology and morphology and estimation of interfacial tension of immiscible COC/EVA blends

Rheology and morphology of cyclic olefin copolymer (COC) / ethylene vinyl acetate copolymer (EVA) immiscible blends with droplet and co-continuous morphologies were experimentally examined and theoretically analyzed using emulsion and micromechanical models. The blends showed an asymmetric phase diagram in which the EVA-rich blends had smaller dispersed size domains as compared to the COC-rich blends. This could be explained based on the higher melt elasticity and viscosity of COC as compared to EVA determined by the rheological investigations. The rheological tools were used to investigate the miscibility of the blends. From the melt viscosity data it is found that the COC/EVA blends show a positive deviation behavior at all compositions which is a hint for strong interaction between the COC and EVA. Analysis of Cole-Cole and Han diagrams revealed that COC/EVA blends, at high EVA contents, were more compatible than COC-rich blends. For the droplet morphology, Palierne model was more successful but, by increasing the dispersed phase content some deviation was observed. In the co-continuous region, the Coran model was in good correspondence with the experimental data as compared to the Veenstra’s model. The storage and loss modulus of EVA-rich blends had a better correspondence with the Palierne model than the COC-rich blends which further confirmed the morphological findings. Interfacial tension calculated for the COC/EVA blends using the Palierne model, were about 1.2 and 15 mN/m² for EVA-rich (10/90) and COC-rich blends (90/10), respectively. In both EVA-rich and COC-rich systems the interfacial tension increased with increasing the dispersed phase content.     

PET/PP blending by using PP‐g‐MA synthesized by solid phase

In attempts to improve the compatibility of polypropylene (PP) with polyethylene terephthalate (PET), a maleic anhydride grafted PP (PP‐g‐MA) was evaluated as a compatibilizer in a blend of 30/70 wt % PP/PET. PP‐g‐MA was produced from isotactic homopolymer PP utilizing the technique of solid phase graft copolymerization. Qualitative confirmations of the grafting were made by Fourier transform infrared spectroscopy (FTIR). Three different weight percent of compatibilizer, PP‐g‐MA, i.e., 5, 10, and 15 wt % have been used in PP/PET blends. The compatibilizing efficiency for PP/PET blend was examined using differential scanning calorimetry (DSC), optical microscopy (OM), scanning electron microscopy (SEM) of crycrofractured surfaces, and energy dispersive X‐ray spectrum (EDAX). The results show that the grafted PP promotes a fine dispersed phase morphology, improves processability, and modifies the crystallization behavior of the polyester component. These effects are attributed to enhance phase interaction resulting in reduced interfacial tension. Also, the results show that the compatibilizing effects of the three amounts of grafted PP in blend are different and dependent on the amount used. Adding 10 wt % of compatibilizer into blend produced the finest dispersed morphology. Elemental analysis results show that PP is matrix. DSC determination revealed that the melting temperature (T_m) of the PET component declined to some extent by comparison with neat PET. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 3986–3993, 2007