Theory of coalescence in immiscible polymer blends

The theory of coalescence in melts of polymer blends was derived on the basis of the Smoluchowski theory for colloid systems. An approximation for a flux of particles used for solutions of colloids in water was analyzed. It is shown that this approximation cannot be used for polymer blends, and an approximation is suggested that could be justifiably used for them. A system of equations was derived for the time dependence of the number of individual i-mers, using the relation suggested for the diffusion flux of particles. In an approximation of the uniform increase in particle size, equations were found for the time dependence of the number of particles, the average radius of the particle, and the interface area in the volume unit of the blend. The suggested theory predicts measurable coalescence in considerably more viscous systems than mechanically applied relations of the Smoluchowski theory for aqueous colloid solutions.     

Effect of addition protocol on mixing in miscible and immiscible polymer blends

The effects of the addition protocol are investigated for very‐low‐viscosity‐ratio model miscible and immiscible blends consisting of two polyethylenes (PE) and polystyrene (PS)/polyethylene (PE), respectively, are investigated. Miscible and immiscible blends with a matched viscosity ratio of 0.003 are compounded using three different addition protocols: simultaneous solids addition; sequential solids addition; and sequential liquids addition. These protocols correspond to addition of a solid additive to the feed hopper of an extruder; addition of a solid additive into the melting zone in an extruder; and addition of a liquid additive into the melting zone of an extruder. Both of these blends are shown to exhibit phase‐inversion‐like behaviors using a simultaneous solids addition protocol, regardless of concentration. Using either of the sequential addition protocols results in macroscopic segregation of the minor‐phase material to high‐shear‐rate regions of the mixer, delaying mixing. At long mixing times, however, all three protocols achieve a similar dispersed droplet morphology. Furthermore, the simultaneous solids addition protocol is shown to be the least energetically intensive, and the simultaneous solids requires the least amount of time of the three protocols to achieve maximum mixing torque for blends consisting of 20 wt% minor phase.     

Morphology development in immiscible polymer blends

This paper presents the results obtained using a new method for analyzing polymer blend morphologies. The method is based on the selective solubilization of the matrix followed by a separation of the dispersed phase in suspension by filtering. A suspension of the nodular part going through the filter is obtained and can be analyzed with a particle counter. The other part of the dispersed phase retained by the filter is constituted of fibers. The average droplet diameters were compared with those obtained using a Scanning Electron Microscope on fracture surfaces for different compositions and flow conditions. The average diameter obtained with the counter technique increases with the dispersed phase content up to an optimum where simultaneously a decrease in the mean diameter and an increase of the fibrillar part are observed, which means that there is a concentration range where these two types of morphologies are present in the blends. The results indicates that the stability of the fibrillar part seems to determine whether the blend morphology will evolve into nodules by the Rayleigh mechanism or into phase inversion by coalescence of stable fibers.     

Morphology evolution during cooling of quiescent immiscible polymer blends: matrix crystallization effect on the dispersed phase coalescence

The influence of the matrix crystallization on the coalescence of the dispersed phase particles, in quiescent immiscible polymer blends, is a topic that is scientifically addressed scarcely. The coarsening of the phase structure that is induced by the matrix crystallizing domains was studied using the well-established system comprising a polypropylene and an ethylene–propylene rubber (PP/EPR blends). This subject is of great importance as the effectiveness in the toughening of PP is directly determined by the EPR particle size. Cooling experiments were commenced for resolving the correlation among the imposed cooling conditions, the formed matrix crystalline morphology, and the coalescence of the dispersed phase particles. A confirmation of the profound effect of the PP crystallization on the coalescence of EPR particles was undoubtedly obtained. The contribution of the crystallization to the coalescence of the dispersed phase particles is largest at a finite rate of cooling. A thorough discussion regarding the observed effects, encompassing a potential rejection or an engulfing of the dispersed phase particles by the growing crystallites, was undertaken.     

Orientation of miscible and immiscible polymer blends

Polystyrene (PS) and poly(vinylmethylether) (PVME) were used to study the orientation of miscible and immiscible polymer blends. A miscible blend containing 60 wt% PS was prepared by casting the sample from a benzene solution. The immiscible blend was made by annealing the initially miscible mixture above its lower critical solution temperature for different times and temperatures. Fourier transform infrared spectroscopy and birefringence were used to measure the orientation of PS and PVME, before and after phase separation. Stress-strain curves were also measured for the two types of systems. It was found that the two polymers orient differently and that phase separation induces an increase in the overall orientation of the mixture, in the modulus and in PS orientation. The differences observed between pure PS and PS in the blend were attributed to changes in specific interactions and density of entanglements. The variations with phase separation were attributed to a change in the morphology of the system.     

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.     

Co-phase continuity in immiscible binary polymer blends

Methods of microscopic observation and macroscopic characterization have been developed for determining the co-phase continuity in immiscible binary blends. After selective dissolution of the component polymers, the morphologies of microscopic observation are consistent with the results of macroscopic observation and weight percentage determination. By using these methods, the relationship between co-phase continuity, composition and blending time has been explored for two immiscible binary polyblends with different viscosity ratios (λ), polyamide 6/polyethersulfone (PA/PES, λ = 0.03) and poly(butylene terephthalate)/polystyrene (PBT/PS, λ = 1). Both blend systems show a similar dependence of co-phase continuity on the composition and mixing time. That is at short mixing time (for example, 2 minutes), the co-phase continuity takes place in a wide composition range. With increasing blending time, the composition range of co-phase continuity becomes narrow, and finally shrinks to one point. After a long enough mixing time the co-phase continuity region will occur only at a volume fraction of

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, no matter what the viscosity ratio of the blend is. © 1997 Elsevier Science Ltd.     

In situ compatibilized polymer blends of phenoxy and ABS

The combination of styrene-acrylonitrile-glycidyl methacrylate (SAG) reactive copolymer and sodium lauryl sulfonate catalyst is able to function as an effective in situ compatibilizer for the otherwise immiscible and incompatible polymer blends of phenoxy and acrylonitrile-butadiene-styrene (ABS). The copolymer formed from the reaction between phenoxy and SAG under melt blending conditions tends to reduce interfacial tension in the melt and results in finer morphological domains of the blends. The presence of this in situ formed compatibilizer also raises the interphase adhesion of the blends and results in significant improvements in mechanical properties. © 1994 John Wiley & Sons, Inc.     

Nonuniformity of phase structure in immiscible polymer blends

This article is focused on the phase structure development in immiscible polymer blends during melt mixing. Nonuniformity of the phase structure, i.e., the coexistence of areas containing particles with markedly different size distribution, was detected in quenched and compression molded samples of a number of various blends prepared by long and intensive mixing in the chamber of a Plasticorder. The same effect was found also for polystyrene/polyamide blends prepared in a twin‐screw extruder. It was shown that neglecting nonuniformity of the phase structure can lead to considerable error in evaluation of the effect of system parameters on the blend morphology. The reasons for the effect were discussed and it was found that inhomogeneous flow field in mixers is a plausible explanation of the nonuniform phase structure. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Investigation of interfacial slip in immiscible polymer blends

In this study, we investigated an interfacial slip phenomenon occurring in immiscible polymer blends. We chose a binary polymer blend in which the interaction parameter, χ, between the component polymers is high, and thus the interface is thin and entanglement is weak. It was observed that the negative viscosity deviation (NVD) of the blends is large, which might be attributable to interfacial slippage between the interfaces. It was also observed that incorporation of a compatibilizer in the blends significantly reduced the NVD, via suppression of interfacial slip due to increased interfacial strength. We carried out a specially designed experiment to verify that interfacial slip is indeed responsible for the NVD. We prepared several blend samples having different phase sizes ranging from 50 ∼ 5 μm, and evaluated the shear stress vs. shear rate relationships of the samples using a capillary rheometer. We observed that the viscosities of the samples decreased as the phase sizes decreased, which is strong evidence of the occurrence of interfacial slip.     

The rheological behavior of immiscible polymer blends

The complex shear modulus of immiscible polymer blends was measured by a frequency sweep experiment for polystyrene (PS)/low density polyethylene (LDPE) and poly(methylmethacrylate) (PMMA)/LDPE blends at constant composition (13.5/86.5 vol %) and compared with the prediction model of Palierne. Different morphologies of each blend were also prepared using a rheometer with a constant shear rate and different strain. There was morphological dependency on the complex shear modulus at constant temperature. However, this dependency disappeared at specific temperatures in the frequency sweep experiment. There seemed to be a specific temperature like critical flow temperature (T_cf) of amorphous polymer. The difference in morphology affected the complex shear modulus of blends below the specific temperature, T_cf, but did play a major role in determining the complex shear modulus of blends at over specific temperature. A new method may be needed to determine the critical flow temperature of an amorphous polymer via the measurement of a complex shear modulus for immiscible polymer blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 917–924, 2002     

Morphology and deformation of compatibilized polystyrene low density polyethylene blends

This investigation deals with the morphology and tensile behavior of polystyrene/low density polyethylene blends compatibilized by hydrogenated styrene‐b‐butadiene‐b‐styrene triblock copolymer. The stress‐strain measurements indicate that blends with excellent toughness were achieved, due to the compatibilizing role of the triblock copolymer in the system. The morphology of the blends was observed by scanning electron microscopy (SEM), and the results show that the state of polystyrene changes from continuous phase to dispersed phase with increasing LDPE content. The correlation between mechanical properties and morphology is discussed. The morphologies of the tensile bars were also examined by SEM, and the deformation mechanisms of the blend were further analysed according to fractography. © 1999 Society of Chemical Industry     

Compatibilization and morphology development of immiscible ternary polymer blends

We report a novel and effective strategy that compatibilizes three immiscible polymers, polyolefins, styrene polymers, and engineering plastics, achieved by using a polyolefin-based multi-phase compatibilizer. Compatibilizing effect and morphology development are investigated in a model ternary immiscible polymer blends consisting of polypropylene (PP)/polystyrene(PS)/polyamide(PA6) and a multi-phase compatibilizer (PP-g-(MAH-co-St) as prepared by maleic anhydride (MAH) and styrene (St) dual monomers melt grafting PP. Scanning electron microscopy (SEM) results indicate that, as a multi-phase compatibilizer, PP-g-(MAH-co-St) shows effective compatibilization in the PP/PS/PA6 blends. The particle size of both PS and PA6 is greatly decreased due to the addition of multi-phase compatibilizer, while the interfacial adhesion in immiscible pairs is increased. This good compatibilizing effect is promising for developing a new, technologically attractive method for achieving compatibilization of immiscible multi-component polymer blends as well as for recycling and reusing of such blends. For phase morphology development, the morphology of PP/PS/PA6 (70/15/15) uncompatibilized blend reveals that the blend is constituted from PP matrix in which are dispersed composite droplets of PA6 core encapsulated by PS phase. Whereas, the compatibilized blend shows the three components strongly interact with each other, i.e. multi-phase compatibilizer has good compatibilization between the various immiscible pairs. For the 40/30/30 blend, the morphology changed from a three-phase co-continuous morphology (uncompatibilized) to the dispersed droplets of PA6 and PS in the PP matrix (compatibilized).     

Shear-induced fractal morphology of immiscible reactive polymer blends

The origin of shear-induced morphology of two-component immiscible reactive polymer blends is studied by the example of grafting and crosslinking multilayer systems of statistic terpolymer of ethylene, butyl acrylate, and maleic anhydride and statistic copolymers including polyamide and acid groups terminated by acid and/or amine groups. It is found that in contrast to the non-reactive system, the reactive polymer blends display pronounced hydrodynamic instabilities followed by the formation of branched fingers. The observed morphologies are shown to evolve towards the fractal structures. Their fractal dimensions depend on the type of chemical interactions between the blend components resulting either in grafted or crosslinked interfaces. It is shown that the obtained morphologies resemble the Laplacian growth patterns. A simple model of the interface chemical modifications is discussed to explain a physical origin of the observed shear-induced finger instability.     

The effect of mixing time on the morphology of immiscible polymer blends

The effect of mixing time on the morphology, with the viscosity ratio and composition as parameters in the mixing process, was studied for two immiscible binary polyblend systems, polyamide/polyethersulfone (PA/PES) and poly(butylene terephthalate)/polystyrene (PBT/PS), by selective dissolution followed by macroscopic and microscopic observations. At a short mixing time, the morphology of each phase depends not only on the composition, but also on the viscosity difference of two phases, shown by the results of PA/PES blends with a viscosity ratio of 0.03. The lower viscous phase (PA) forms particles, fibrils, and layers successively with its increasing content and becomes a continuous one at low concentrations as the minor phase, while the high viscous phase (PES) appears mainly in the form of particles and directly becomes a continuous one at high concentrations. With increasing mixing time, the effect of the viscosity ratio becomes less and the morphology is determined mainly by the volume fraction of each phase. Particles are the final morphology of the minor phase. Only at a viscosity ratio of unity is the morphological development of two phases (PBT and PS) with mixing time the same, and any one of these two components is in the form of particles when it is the minor phase. At the composition near 50/50, fibrillar or continuous structure may coexist for both phases. The composition range of co-phase continuity is decided not only by the viscosity ratio but also by the mixing time. With increasing mixing time, this range becomes narrower and finally occurs at volume fraction of 50/50, no longer affected by the viscosity ratio. © 1996 John Wiley & Sons, Inc.     

Engineering properties of compatibilized polypropylene/liquid crystalline polymer blends

Polypropylene (PP) and Vectra A950, a thermotropic liquid crystalline polymer (LCP), blends were prepared in a single‐screw extruder with the variation in Vectra A950 content in presence of fixed amount (2%, with respect to PP and LCP mixture as a whole) of ethylene‐acrylic acid (EAA) copolymer as a compatibilizer. Mechanical analysis of the compatibilized blends within the range of LCP incorporations under study (2–10%) indicated pronounced improvement in the moduli, ultimate tensile strength (UTS), and hardness. Fourier transform infrared (FTIR) spectroscopy studies revealed the presence of strong interaction through H‐bonding between the segments of Vectra A950 and the compatibilizer EAA. Morphological studies performed by scanning electron microscopy (SEM) manifested the development of fine fibrillar morphology in the compatibilized PP/Vectra A950 blends, which had large influence on the mechanical properties. Differential scanning calorimetry studies showed an initial drop of the melting point of PP in the presence of EAA followed by enhancement of the same in presence of Vectra A950. TGA showed an increase in the thermal stability for all blends with respect to matrix polymer PP. Rheological studies showed that a very small quantity of Vectra A 950 was capable of reducing the melt viscosity of PP particularly in the lower shear rate region and hence facilitated processibility of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology study of immiscible polymer blends in a vane extruder

This study reports the morphology development of polymer blends in a novel vane extruder in which polymer mainly suffers from elongational deformation field. Rapidly cooled samples of polypropylene/polystyrene (PP/PS) are collected in the vane extruder after stable extrusion. Furthermore, the shape and size of the dispersed phase from initial to final stages are analyzed. In addition, in order to compare the final size of the dispersed phase, different immiscible blends, including polypropylene/polyamide and PP/PS, are prepared by vane extruder and twin‐screw extruder, respectively. The results show that the dispersed phase is made to change rapidly from stretched striations to droplets under the strong elongational deformation field in the vane extruder. Furthermore, the droplet size of dispersed phase of blends prepared by vane extruder is much smaller than that prepared by twin‐screw extruder, indicating that the vane extruder is more efficient in mixing for immiscible polymer blends. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Water extraction of polyethyloxazoline from miscible and immiscible polymer blends

Blends of water-soluble polyethyloxazoline (PEOx) with a series of hydrophobic styreneacrylonitrile copolymers (SAN) of varying AN contents were immersed in water to determine the kinetics of water swelling and the extent of PEOx extraction. Copolymers containing 25 and 40% by weight of AN form miscible blends with PEOx; those containing higher and lower amounts of AN form immiscible mixtures with PEOx. A high degree of PEOx extraction was observed for the immiscible blends as expected, whereas surprisingly little PEOx was extracted from the miscible blends over periods up to 2 years in spite of a high degree of water swelling. Similar behavior has been noted for other blends of hydrophobic and hydrophilic polymers. In the present system, thermal analysis revealed that the sorption of large amounts of water induces a microphase separation of the two miscible polymers to form microdomains of SAN in which, evidently, segments of PEOx are entrapped to form physical cross-links that preclude disintegration of the sample and extraction of the PEOx whose phase is highly swollen by the sorbed water. It is proposed that a similar situation probably occurs for other blend systems exhibiting such behavior.     

The effect of mixing history on the morphology of immiscible polymer blends

A laboratory prototype tester was used to systematically study the effects of geometrical and operational variables on the mixing of two immiscible polymer melts. Results verify that the number of passages is a dominant variable in dispersive mixing. The development of micromorphology in a controlled fashion was studied extensively and backed up with a finite element simulation of the flow in the tester geometry. Complex deformational fields in the laboratory mixer are evident from the highly deformed dispersed phase morphologies.