Polypropylene/metallocene ethylene‐octene copolymer blends with a bimodal particle size distribution: Mechanical properties and their controlling factors

Blends of polypropylene homopolymer (PP) and metallocene produced ethylene‐octene copolymer (EOR) with a bimodal particle size distribution were investigated. The aim of the work was to study the influences of EOR characteristics and its concentration on the tensile and impact properties of the blends. The matrix ligament thickness between rubber particles was measured and compared to those predicted using the theoretical models. The relationships between blend morphology and impact property were reported. It was found that the content of comonomer and molecular weight of the EOR as well as its concentration in the blends were the major factors controlling the tensile and impact properties of the blends. These factors became ineffective to impact property when the ligament thickness of the matrix was larger than the critical value (T ～0.3–0.4 μm). To achieve blends of high impact strength, the ligament thickness between rubber particles should be smaller than the critical value, and for a certain ligament thickness, EOR with high octene content and high molecular weight was preferred. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2412–2418, 2002     

A generalized criterion for rubber toughening: The critical matrix ligament thickness

The thickness of matrix ligament is shown to be the single parameter determining whether a polymer/rubber blend will be tough or brittle. The matrix ligament is defined as the region of the matrix between two neighboring rubber particles. Specifically, the ligament thickness is the surface-to-surface interparticle distance. When the average ligament thickness is smaller than a critical value, a blend will be tough; when greater, it will be brittle. In other words, a sharp brittle–tough transition occurs at the critical ligament thickness. This critical parameter is independent of rubber volume fraction and particle size, and is characteristic of the matrix for a given mode, temperature and rate of deformation. What is important is the matrix ligament, not rubber particles. The single matrix parameter explains the effects of phase morphology, rubber volume fraction, particle size, particle-size polydispersity, and particle flocculation on toughness.     

Development of dispersed phase size and its dependence on processing parameters

Through measurement of phase dimension via laser scattering, phase morphology development in immiscible blends of polyamide 12/poly(ethylene glycol) (PEG) with an extremely high viscosity ratio was investigated. The blends were prepared by melt blending in a batch mixer. The objective was to examine the influence of mixing time, rotor speed, as well as blending temperature on the size distribution of the minor phase. It is of interest that the breakup process of the dispersed PA 12 phase was observed for the blend systems even for extremely high viscosity ratios of ≤ 10²–10³. Mixing time had a significant effect on the development of dispersed phase size distribution. It was found that the bulk of particle size reduction took place very early in the mixing process, and very small droplets with a diameter of 0.1–10 μm were produced. The number of small particles then decreased, resulting in a larger average particle size. With further prolonged mixing, the particle size levels off. The particle size and its distribution were also found to be sensitive to the rotor speed. The average particle size decreased with increased rotor speed. The effect of blending temperature on size and size distribution, which has seldom been studied, was also examined in this work. When the blending temperature altered from 190°C to 220°C, the size and its distribution of the dispersed phase varied considerably, and the change of viscosity ratio was found to be the key factor affecting the dispersed phase size. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3201–3211, 2006     

Study on morphology of ternary polymer blends. I. Effects of melt viscosity and interfacial interaction

The morphology of some ternary blends was investigated. In all of the blends polypropylene, as the major phase, was blended with two different minor phases, ethylene–propylene–diene terpolymer (EPDM) or ethylene–propylene–rubber (EPR) as the first minor phase and high‐density polyethylene (HDPE) or polystyrene (PS) as the second minor phase. All the blends were investigated in a constant composition of 70/15/15 wt %. Theoretical models predict that the dispersed phase of a multiphase polymer blend will either form an encapsulation‐type phase morphology or phases will remain separately dispersed, depending on which morphology has the lower free energy or positive spreading coefficient. Interfacial interaction between phases was found to play a significant role in determining the type of morphology of these blend systems. A core–shell‐type morphology for HDPE encapsulated by rubber was obtained for PP/rubber/PE ternary blends, whereas PP/rubber/PS blends showed a separately dispersed type of morphology. These results were found to be in good agreement with the theoretical predictions. Steady‐state torque for each component was used to study the effect of melt viscosity ratio on the morphology of the blends. It was found that the torque ratios affect only the size of the dispersed phases and have no appreciable influence on the type of morphology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1129–1137, 2001     

Effect of the composition on the phase size in immiscible blends with the viscosity ratio close to unity

The influence of the composition and interfacial tension on the phase size in immiscible polymer blends with a viscosity ratio close to unity has been investigated with poly(methyl methacrylate)/poly(ethylene terephthalate) blends and data from various works. For all the blends considered, the dispersed particle diameter (d) is proportional to the interfacial tension of the system. When the dispersed‐phase content (?) is below 1%, there is minimal change of d with increasing ?. When ? is between 1 and 20%, d is proportional to ?^0.4. It seems that the processing conditions do not influence the morphology significantly for blend systems with a viscosity ratio close to unity.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1791–1799, 2003     

Influence of microstructure and flexibility of maleated styrene-b-(ethylene-co-butylene)-b-styrene rubber on the mechanical properties of polyamide 12

The present investigation deals with the mechanical and morphological properties of binary polyamide 12/maleic anhydride-grafted styrene-b-(ethylene-co-butylene)-b-styrene rubber (PA12/SEBS-g-MA) blends at varying dispersed phase (SEBS-g-MA) concentrations. Tensile behavior, impact strength and crystallinity of these blend systems were evaluated. Influence of microstructure, dispersed phase particle size, and ligament thickness on the impact toughness of the blend was studied. DSC data indicated an increase in crystallinity of PA12 in the blends. Tensile modulus and strength decreased while impact strength and elongation-at-break increased with the elastomer concentration. The enhanced properties were supported by interphase adhesion between the grafted maleic groups of rubber with polar moiety of polyamide 12. Analysis of the tensile data employing simple theoretical models showed the variation of stress concentration effect with blend composition.     

Relationships among blending conditions,size of dispersed phase,and oil resistance in natural rubber and nitrile rubber blends

The rheological properties, morphology, and oil resistance in natural rubber and nitrile‐butadiene rubber (NR/NBR) blends are investigated as functions of the blending conditions. It is found that the Mooney viscosity of the blends depends more strongly on the blending time than the rotor speed. The size of the NR dispersed phase is approximately independent of the rotor speed, but it decreases with increasing blending time up to 25 min. With a further increase in the blending time the NR dispersed phase size decreases. The results for the relative tensile strength, which is an indicator of oil resistance, are in agreement with those of the blend morphology, indicating that the oil resistance in a 20/80 NR/NBR blend strongly depends on the phase morphology of the blend. The smaller the size of NR dispersed phase, the higher the blend resistance to oil. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1232–1237, 2001     

Influence of solvent contents on the rubber‐phase particle size distribution of high‐impact polystyrene

High‐impact polystyrene (HIPS) was prepared by the bulk or low‐solvent polymerization of styrene in the presence of dissolved rubber and characterized to measure the dispersed particle size of the rubber phase. Before preparation, the prepolymerization time was established by measuring the evolution of particle size distribution of the dispersed phase as a function of reaction time. The measurement technique by laser light scattering was found to be efficient enough not only to lead to the right prepolymerization time but also to predict rubber‐phase particle size distribution. Polymerization experiments were then conducted to investigate the effect of solvent contents on the particle size distribution of the rubber phase, in which ethylbenzene was introduced as a solvent at levels of 0, 3, 10, and 15%. As the solvent content increased, the size of rubber‐phase particles initially increased, reaching a maximum, and then decreased. It is speculated that a decrease in the molecular weight of the matrix, a decrease in the viscosity ratio between polybutadiene to polystyrene phases, and a change in rubber morphology all contributed to the change in the rubber particle size of HIPS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3672–3679, 2003     

Study of carbon black distribution in BR/NBR blends based on damping properties: Influences of carbon black particle size,filler, and rubber polarity

Effects of filler and rubber polarity on the distribution of filler in butadiene/nitrile rubber (BR/NBR) blends were investigated, using the dynamic mechanical thermal analysis technique. As 30-phr filler is added, the reduction in heights of damping peaks (tan δ_max), attributed to the dilution effect, was observed. It was also found that the BR phase in the blends, compared to the NBR phase, is more preferential for small- and large-particle size carbon blacks to reside, probably because of the lower viscosity and lower polarity of the BR phase. The addition of silica instead of carbon black leads to an increase in filler migration to the NBR in the 20/80 BR/NBR blend, which is attributed to the strong silica–NBR interaction. In addition, an increase in NBR polarity promotes carbon black migration to the BR phase. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3198–3203, 2001     

Correlation of viscosity ratio,morphology, and mechanical properties of polyamide 12/natural rubber blends via reactive compatibilization

Natural rubber (NR)-modified polyamide 12 (Nylon12/NR) was produced by melt blending Nylon12 and NR in the presence of polystyrene/maleated natural rubber (PS/MNR) copolymer as a reactive compatibilizer. The influence of compatibilizer loading on viscosity ratio, morphology, and mechanical properties of the blends was investigated. As a consequence of the reactive blend between Nylon12 and maleated NR in PS/MNR, the formation of amide and succinimide linkages was set at rubber-Nylon12 interfaces. Thus the dispersion of rubber particles was improved, and the particle coalescence was prevented so that the fine morphology with good interfacial adhesion was stabilized. This also resulted to enhance the blend viscosity and to lower viscosity ratio. The data revealed strong correlation between low viscosity ratio and fine spherical morphology of the compatibilized blends. An optimum PS/MNR compatibilizer content was at 7 phr to produce good dispersion of small rubber domains (size ≤0.3 μm) in Nylon12 matrix. Thermal properties by DSC revealed that crystallization temperature of Nylon12 was lowered by the presence of NR and crystallinity of Nylon12 was slightly affected by the PS/MNR content. An enhancement of mechanical properties, especially the impact energy was observed without suffering the tensile and flexural properties. Compared to the neat Nylon12, the compatibilized blends showed an increase in impact energy by a factor of 5. This large enhancement is successfully interpreted in term of the toughening effect by rubber phase of suitable dispersed size and the interparticle distance.     

Influence of rubber particle size on mechanical properties of polypropylene–SEBS blends

Isotactic polypropylene blends with 0–20 vol % thermoplastic elastomers were prepared to study the influence of elastomer particle size on mechanical properties. Polystyrene-block-poly(ethene-co-but-1-ene)-block-polystyrene (SEBS) was used as thermoplastic elastomer. SEBS particle size, determined by means of transmission electron and atomic force microscopy, was varied by using polypropylene and SEBS of different molecular weight. With increasing polypropylene molecular weight and, consequently, melt viscosity and decreasing SEBS molecular weight, SEBS particle size decreases. Impact strength of pure polypropylene is almost independent of molecular weight, whereas impact strength of polypropylene blends increases strongly with increasing polypropylene molecular weight. The observed sharp brittle–tough transition is caused by micromechanical processes, mostly shear yielding, especially occurring below a critical interparticle distance. The interparticle distance is decreasing with decreasing SEBS particle size and increasing volume fraction. If the polypropylene matrix ligament between the SEBS particles is thinner than 0.27 μm, the blends become ductile. Stiffness and yield stress of polypropylene and polypropylene blends increase with increasing polypropylene molecular weight in the same extent, and are consequently only dependent on matrix properties and not on SEBS particle size. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1891–1901, 1998     

Melt rheology and morphology of uncompatibilized and in situ compatibilized nylon‐6/ethylene propylene rubber blends

Melt rheology and morphology of nylon‐6/ethylene propylene rubber (EPR) blends were studied as a function of composition, temperature, and compatibilizer loading. Uncompatibilized blends with higher nylon‐6 content (N90 and N95) and rubber content (N5 and N10) had viscosities approximately intermediate between those of the component polymers. A very clear negative deviation was observed in the viscosity–composition curve over the entire shear rate range studied for blends having composition N30, N50, and N70. This was associated with the interlayer slip resulting from the high‐level incompatibility between the component polymers. The lack of compatibility was confirmed by fracture surface morphology, given that the dispersed domains showed no sign of adhesion to the matrix. The phase morphology studies indicated that EPR was dispersed as spherical inclusions in the nylon matrix up to 30 wt % of its concentration. A cocontinuous morphology was observed between 30 and 50 wt % nylon and a phase inversion beyond 70 wt % nylon. Various models based on viscosity ratios were used to predict the region of phase inversion. Experiments were also carried out on in situ compatibilization using maleic anhydride–modified EPR (EPR‐g‐MA). In this reactive compatibilization strategy, the maleic anhydride groups of modified EPR reacted with the amino end groups of nylon. This reaction produced a graft copolymer at the blend interface, which in fact acted as the compatibilizer. The viscosity of the blend was found to increase when a few percent of modified EPR was added; at higher concentrations the viscosity leveled off, indicating a high level of interaction at the interface. Morphological investigations indicated that the size of the dispersed phase initially decreased when a few percent of the graft copolymer was added followed by a clear leveling off at higher concentration. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 252–264, 2004     

Studies on the melt flow behavior of thermoplastic elastomers from polypropylene—Natural rubber blends

The melt flow behavior of thermoplastic polypropylenenatural rubber blends has been evaluated with specific reference to the effects of blend ratio, extent of dynamic crosslinking of the rubber phase and temperature, on viscosity, flow behavior index, and deformation of the extrudate. The proportion of rubber in the blend and the extent of dynamic crosslinking of the rubber phase were found to have profound influence on the viscosity of the blends at lower shear stresses. But at higher shear stresses, the effect of blend ratio on viscosity was comparatively less for the uncrosslinked blends than that for the crosslinked blends. At lower shear stress, the viscosity of the blend increased with increase in degree of crosslinking but at higher shear stress, the effect of crosslinking on viscosity was found to vary depending on the ratio of the plastic and rubber components in the blend. The deformation of the extrudates was also very much dependent on both blend ratio and degree of crosslinking.     

Carbon black filled powdered natural rubber: Preparation,particle size distribution,mechanical properties,and structures

Carbon black (HAF) filled powdered natural rubber (P(NR/HAF)) was prepared and the particle size distribution, mechanical properties, and micromorphology of P(NR/HAF) were studied. A carbon black–rubber latex coagulation method was developed for preparing carbon black filled free‐flowing, noncontact staining NR powders with particle diameter less than 0.9 mm. A powdering mechanism model was put forward to describe the powdering process, which shows that the key technical points consist in the surfactant with good emulsification properties and the polymer coating resin with good film forming properties. SEM analysis shows that carbon black and rubber matrix have formed a macroscopic homogenization in the P(NR/HAF) particles without contact staining, and carbon black particles are well dispersed in rubber matrix with diameter of about 50–150 nm. P(NR/HAF) vulcanizate showed better mechanical properties than bale natural rubber/carbon black blends (NR/HAF) and simple NR latex/carbon black blends (NRL/HAF), which depends primarily upon the absence of free carbon black, the fine dispersion of filler on the rubber matrix, and the better interaction between carbon black and rubber matrix due to the proper preparation condition of noncontact staining carbon black filled powdered NR. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1763–1774, 2006     

The phase inversion and morphology of nylon 1010/polypropylene blends

Noncompatibilized and compatibilized blends of nylon 1010/PP blends having five different viscosity ratios were prepared by melt extrusion. Glycidyl methacrylate-grafted-polypro-pylene (PP-g-GMA) was used as the compatibilizer to enbance the adhesion between the two polymers and to stabilize the blend morphology. The effect of the viscosity ratio on the morphology of nylon 1010/polypropylene blends was investigated, with primary attention to the phase-inversion behavior and the average particle size of the dispersed phase. The relationship between the mechanical properties and the phase-inversion composition was investigated as well. Investigation of the morphology of the blends by microscopy indicated that the smaller the viscosity ratio (ηpp/ηpa) the smaller was the polypropylene concentration at which the phase inversion took place and polypropylene became the continuous phase. The compatibilizer induced a sharp reduction of particle size, but did not have a major effect on the phase-inversion point. An improvement in the mechanical properties was found when nylon 1010 provided the matrix phase. © 1996 John Wiley & Sons, Inc.     

Toughening of polyvinylchloride by methyl methacrylate–butadiene–styrene core–shell rubber particles: Influence of rubber particle size

An analysis was made on the effects of rubber particle size on the mechanical properties and deformation mechanisms of transparent polyvinyl chloride (PVC) blends containing core–shell methyl methacrylate–butadiene–styrene (MBS) impact modifiers. The critical interparticle distance was found not to be the criterion for the brittle‐ductile transition in the blends. In tensile tests, the blends with larger (100–280 nm) rubber particles exhibited intense stress‐whitening, while one blend with small (83 nm) rubber particles showed only slight stress‐whitening. These differences were due to an increase in resistance to cavitation with decreasing rubber particle size. Transmission electron microscopy studies on blends with a bimodal distribution of particle sizes showed that in the whitened zone of Izod specimens the larger rubber particles cavitated and expanded on yielding, while the smaller particles remained intact. However, Izod test results showed that small MBS rubber particles can toughen the PVC matrix very effectively, especially at low temperatures and at low rubber concentrations. The deformation mechanisms responsible for these effects were discussed. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Macromolecular modification of EPDM: Wettability,miscibility, and morphology study

The present investigation deals with studies on wettability, miscibility, and morphology of the macromolecularly modified EPDM. Two different maleated EPDM rubbers (grafted rubber) were chosen (0.5 and 1% maleation) for such modification and they were used in various proportions. Wettability of the rubber substrate, as observed from dynamic contact angle measurement, was improved using these grafted rubbers. Results of X‐ray photoelectron spectroscopy showed an increase in oxygen level with higher levels of grafted rubber in the blends. Morphology study by transmission electron microscopy showed a smaller domain size for the blend with higher maleic anhydride content in the grafted rubber. The viscosity versus blend ratio results showed a negative deviation behavior for blends with 1% grafted rubber, whereas a positive negative deviation behavior was observed in blends with 0.5% grafted EPDM. As the strength of interaction increased, the glass transition shifted to a higher temperature. All blends were heterogeneous, as indicated by different degrees of dispersion. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2647–2661, 2001     

Complex processing–morphology interrelationships during the reactive compatibilization of blends of poly(butylene terephthalate) with epoxide‐ containing rubber

Reactive processing of blends of poly(butylene terephthalate) (PBT) with the ethene–(methyl acrylate)–(glycidyl methacrylate) terpolymer (E–MA–GMA) is known to present a very complex reactivity since two competitive reactions take place spontaneously during melt blending, that is, blend compatibilization and rubber‐phase crosslinking. In this article, the effects of several processing parameters, such as the shear rate, the processing temperature, and the matrix viscosity, on the reactive processing of those blends were investigated in terms of the blend morphology and of the amount of copolymer formed at the blend interface. It was shown that the morphology development could be divided in two successive regimes: In the early stages of the mixing process, the particle size is essentially determined by the physical dispersion process, that is, breakup and coalescence, while, at longer mixing times, a further decrease in particle size is obtained as a result of the compatibilization reactions. The shift between the two regimes is progressive and intimately related to the processing conditions. Despite such a complexity, not only the blend morphology but also the elastic properties of the rubber particles can be controlled in a broad range by an adequate adjustment of the relative kinetics between both physical and chemical processes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 703–718, 2004     

Replacement of virgin rubbers by waste ground vulcanizates in blends of silicone rubber and fluororubber based on tetrafluoroethylene/propylene/vinylidene fluoride terpolymer

This study reports the results of investigations on blends of silicone rubber and fluororubber based on tetrafluoroethylene/propylene/vinylidene fluoride terpolymer and the effects of replacement of silicone rubber and/or fluororubber in their 50/50 blend by the respective vulcanizate powders of known compositions. To simulate the aging condition of factory wastes, the silicone rubber or fluororubber vulcanizates were aged for 72 h at 200°C and then converted into powder by mechanical grinding. The fluororubber vulcanizate powder (FVP), mostly spherical in shape with average diameter varying between 2 and 10 μm, exists in a highly aggregated state displaying chainlike structures that, however, break down during blending with virgin rubbers. The silicone rubber vulcanizate powder (SVP) is irregular in shape, with larger particles in the range of 30–100 μm, and the smaller particles exist in highly aggregated chainlike structures, as in the case of FVP, which break down during milling to mostly spherical particles of 2–10 μm in diameter. Measurements of physical properties reveal that the blends of silicone rubber and fluororubber are technologically compatible. SEM photomicrographs of THF‐etched samples show the biphasic structure of the blends, in which the fluororubber forms the dispersed phase in a continuous silicone rubber matrix of lower viscosity. Replacement of silicone rubber in the 50/50 silicone rubber/fluororubber blend by its vulcanizate powder (SVP) increases the Mooney viscosity, but replacement of fluororubber in the blend by its vulcanizate powder (FVP) has little effect on the Mooney viscosity. Monsanto rheometric studies reveal that replacement of silicone rubber by SVP or fluororubber by FVP in the 50/50 silicone rubber/fluororubber blend increases the minimum rheometric torque but decreases the maximum torque, and the effect is more pronounced in the case of SVP. Furthermore, the replacement of silicone rubber in the blend by SVP causes a decline in the physical properties (25% replacement causing about 10% decline in properties, for example), whereas even 75% replacement of fluororubber by FVP has little effect on the physical properties. When both silicone rubber and fluororubber are partially replaced by SVP and FVP in the same blend, properties of the resulting blend composition are controlled more by SVP incorporation, whereas fluororubber replacement has only a marginal effect on blend properties. It is evident from dynamic mechanical spectra that the blends are immiscible in all compositions and addition of SVP or FVP does not affect the glass–rubber transitions of the constituent polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2326–2341, 2001     

Morphology and mechanical properties of blends of thermoplastic polyurethane and polyolefins

Polyolefins (PO) were melt mixed with thermoplastic polyurethane (TPU) in a 20 : 80 weight ratio with or without compatibilizer containing 0.5 wt % of maleic anhydride. Effects of component viscosities on morphology and on mechanical properties of the blend were studied by scanning electron microscope (SEM), tensile property analysis, and dynamic mechanical analysis (DMA). It was found that the disperse particle size of compatibilizer‐free blends decreased with the decreasing viscosity ratio of the disperse phase to TPU. The efficiency of the compatibilizer in reducing the particle size varied with viscosity ratios of the disperse phase to compatibilizer. However, the particle size did not decrease with the decreasing viscosity ratio monotonically. With lower viscosity ratio, addition of 5 wt % compatibilizer resulted in a greater reduction of particle size and less loss in the tensile properties as compared to the TPU matrix. For the polyethene (PE) that has the lowest viscosity value among all the POs, its size in the blend was stabilized with the addition of compatibilizer and no compatibilization was detected by DMA and by tensile property analysis. The mobility of the disperse phase and compatibilizer and the dispersion competition between them seemed important. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 875–883, 2006