Evaluating PE/PLA interfacial tension using ternary immiscible polymer blends

Blending with ethylene-based flexible polymers such as polyethylene (PE) is one of the strategies to toughen poly(lactic acid) (PLA), an inherently brittle biodegradable plastic enjoying growing demands worldwide. Interfacial tension plays a crucial role in blend formulation. Yet several literature reports on the PE/PLA interfacial tension contradict each other, giving ~5 mN/m and ~11 mN/m. In this work, we demonstrate that the PE/PLA interfacial tension is at least 9 mN/m. We use a cocontinuous PE/polystyrene (PS)/PLA ternary blend. Scanning electron microscopy (SEM) revealed complete wetting morphology with PS phase separating PE and PLA phases in the ternary blend. In addition, the complete wetting behavior was maintained at a PS volume fraction as low as 3%. This morphology together with the Harkins equation, indicate that the PE/PLA interfacial tension is higher than 10.5 ± 1.4 mN/m at 180°C.     

Interfacial lubricating effect in phase coarsening of polyethylene/polycaprolactone/polyethylene oxide tri-continuous polymer blends

This work aims at studying the mechanism involved in the phase coarsening of ternary tri-continuous polymer blends. To this aim, the phase coarsening behaviors of a co-continuous polyethylene (PE)/polyethylene oxide (PEO) blend, and a tri-continuous PE/polycaprolactone (PCL)/PEO blend during the quiescent annealing process are studied. Rheological characterization showed that the zero-shear viscosities of PE and PCL phases were similar but much less than the zero-shear viscosity of the PEO phase. The evolution of the microstructure of the blends during annealing was characterized using a characteristic length scale (λ). It was found that λ in both co- and tri-continuous blends increased linearly in the early stages of annealing but the phase coarsening rate decreased in both systems at longer annealing times. In general, the tri-continuous blend showed much faster phase coarsening rate. The effects of kinetic and thermodynamic parameters on the observed phase coarsening behaviors are discussed in detail. A new lubricating mechanism is proposed in which the deformation of the PCL layer between PE and PEO phases reduces the effect of high viscosity of the PEO phase and increases the phase coarsening rate in ternary blends. The obtained results provide a new insight into the role of the middle layer in tri-continuous polymer blends on controlling the phase morphology of these systems.     

Interfacial coarsening of ternary polymer blends with partial and complete wetting structures

The coarsening of polymer mixtures is an important route towards major morphology modification in multiphase polymer systems. To date however the coarsening of ternary systems has not been significantly examined. In this study the phase coarsening mechanism via annealing for partial wetting, and complete wetting morphologies in ternary polymer blends is characterized. This is a route towards the examination of interfacial coarsening in polymer blends since ternary partially wet systems involve the presence of interfacial droplets while completely wet ternary systems are comprised of a complete interfacial layer. A partial wetting type of morphology is obtained for polybutylene succinate (PBS)/poly(lactic acid) (PLA)/polycaprolactone (PCL). Three different compositions for that system with composition ratios of ?_(PBS/PLA) = 1.5; ?_(PBS/PLA) = 3; and ?_(PBS/PLA) = 10 are prepared to show the effect of the concentration of the self-assembled PLA droplets located at the interface of PBS/PCL. As the concentration of PLA decreases, the growth rate of the PLA phase during the annealing process sharply decreases due to a significant increase of the “surface to volume ratio” of the PLA droplets required in order to cover the interface. In this case, due to the short inter-droplet distances between PLA droplets at the interface, coalescence is controlled by the drainage time. This mechanism is confirmed by the observation of a linear relationship between the third power of droplet size and annealing time. For the 37.5%PBS/12.5%PLA/50%PCL blend, the conservation of interfacial-angles confirms that the annealing time has no effect on the angle values between phases, as predicted by Harkins spreading theory.     

Morphological effects on glass transition behavior in selected immiscible blends of amorphous and semicrystalline polymers

The effects uncompatibilized immiscible polymer blend compositions on the T_g of the amorphous polymer were studied in the systems polystyrene/polypropylene (PS/PP), polystyrene/high density polyethylene (PS/PE) and polycarbonate/high density polyethylene (PC/PE). In the two similar systems of PS/PP and PS/PE, the T_g of PS increased with decreasing PS percentage in the blends. This variation in glass transition is attributed to the polymer domain interactions resulting from the different morphologies of various blend compositions. Experiments were conducted to study these effects by preparing blends with various polymers that varied the relationship between the T_g of the amorphous polymer and the crystallization behavior of the semicrystalline polymer. Results show that the variation in amorphous component T_g with composition depends strongly on the physical state of the semicrystalline domains. Whereas the T_g of PS in PS/PE blends changed with composition, the T_g of PC in the PC/PE blend did not change with composition.     

Mechanical Properties and Morphology of Ternary PP/EPDM/PE Blends

The ternary blends of high‐density polyethylene (PE), EPDM terpolymer and polypropylene (PP) have been used as a model low interfacial tension system to study encapsulation dynamics in ternary blends and their relation to the blends' mechanical properties. It was found that the modulus, tensile strength and impact resistance can be improved by PE addition if the PE is localized within the EPDM phase. A range of blend morphology was found depending on the PE viscosity and polymer incorporation sequence in the twin‐screw extruder. In the most favorable sequence, PE and EPDM were mixed together prior to their dispersion in the PP matrix. This practice resulted in a 50% increase in impact resistance when compared to mixing the three components in a single‐step.     

Modified interfacial tensions measured in situ in ternary polymer blends demonstrating partial wetting

An in situ Neumann triangle-focused ion beam-atomic force microscopy (NT-FIB-AFM) method has been used to measure modified PS/HDPE interfacial tensions in ternary PS/PP/HDPE blends prepared by melt mixing and demonstrating partial wetting. The ternary blend was modified with SEB, SB and SEBS copolymers. Results related to the position of the PS droplet at the interface show that a symmetrical diblock copolymer is somewhat more efficient in decreasing the interfacial tension compared to an asymmetrical one of similar molecular weight, while the SEBS triblock copolymer appears to have no effect at all. Using the NT-FIB-AFM method, the lowest modified PS/HDPE interfacial tension is 3.0 ± 0.4 mN/m for the symmetric diblock, compared to 4.2 ± 0.6 mN/m (N = 34) for the unmodified interface. This corresponds to an apparent areal density in SEB copolymer equal to 0.16 ± 0.03 molecules/nm², which is near reported saturation values. By varying the concentration of the copolymer, an emulsification curve reporting the value of the PS/HDPE modified interfacial tension as a function of the apparent areal density of the copolymer at the PS/HDPE interface has been obtained. The interfacial tension values obtained by the NT-FIB-AFM approach are significantly higher than the 0.5 ± 0.2 mN/m (N = 3) result obtained by using the classical breaking thread method with the same materials. This discrepancy does not appear to be due to a poor migration of the copolymer to the PS/HDPE interface, but could instead be attributed to the interfacial elasticity of the compatibilized interface, a phenomena that has not been accounted for so far in experimental studies on the morphology of compatibilized multicomponent polymer blends.     

Factors influencing encapsulation behavior in composite droplet-type polymer blends

In this study the influence of the molecular weight of the dispersed phase components on encapsulation effects in the composite droplet phase was examined for high density polyethylene (HDPE)/PS/PMMA ternary blends. Three different blends composed of various PS and PMMA materials dispersed in an HDPE matrix were prepared using an internal mixer. The morphology was studied by light and electron microscopy. Current models used for predicting encapsulation effects and composite droplet formation in ternary systems (based on static interfacial tension) predict in all cases that PS will encapsulate the PMMA. However, in one case, an unexpected encapsulation of PS by PMMA was observed. It was found that arguments based on the effect of viscosity ratio or the absolute viscosity of the different dispersed phases do not explain that discrepancy. In addition, the reversal of that latter composite droplet morphology from PMMA encapsulating PS to PS encapsulating PMMA was observed upon annealing treatment. Considering all the above, a conceptual model was developed to predict encapsulation effects in composite droplet type systems based on the use of a dynamic interfacial tension (i.e. taking into account the elasticity of the polymer components). Calculations based on the dynamic interfacial tension model, using elasticities based on constant shear stress, were able to account for all of the observed encapsulation effects in this study.     

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     

Role of block copolymer on the coarsening of morphology in polymer blend: Effect of micelles

The reactive compatibilization of polystyrene/ethylene‐α‐octene copolymer (PS/POE) blend via Friedel–Crafts alkylation reaction was investigated by rheology and electron microscope. It was found that the graft copolymer formed from interfacial reaction reduced the domain size and decreased the coarsening rate of morphology. The reduction of the interfacial tension is very limited according to the mean field theory even assuming that all block copolymer stays on the interface. With the help of self‐consistent field theory and rheological constitutive models, the distribution of graft copolymer was successfully estimated. It was found that large amount of copolymer had detached from the interfaces and formed micelles in the matrix. Both the block copolymer micelles in matrix and the block copolymers at the interface contribute to the suppression of coarsening in polymer blend, but play their roles at different stages of droplet coalescence. In droplet morphology, the micelles mainly hinder the approaching of droplets. © 2014 American Institute of Chemical Engineers AIChE J, 61: 285–295, 2015     

Study on morphology of ternary polymer blends. II. Effect of composition

The composition effect on morphology of polypropylene/ethylene–propylene–diene terpolymer/polyethylene (PP/EPDM/PE) and polypropylene/ethylene–propylene–diene terpolymer/polystyrene (PP/EPDM/PS) ternary blends has been investigated. In all of the blends, polypropylene as the major phase was blended with two minor phases, that is, EPDM and PE or PS. From morphological studies using the SEM technique a core–shell morphology for PP/EPDM/PE and separated dispersed morphology for PP/EPDM/PS were observed. These results were found to be in agreement with the theoretical predictions. The composition of components affected only the size of dispersed phases and had no appreciable effect on the type of morphology. The size of each dispersed phase, whether it forms core or shell or disperses separately in matrix, can be related directly to its composition in the blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1138–1146, 2001     

The effect of interface characteristics on the morphology,rheology and thermal behavior of three‐component polymer alloys

Immiscible polymer blends are interesting multiphase host systems for fillers. Such systems exhibit, within a certain composition limits, either a separate dispersion of the two minor phases or a dispersion of encapsulated filler particles within the minor polymer phase. Both thermodynamic (e.g. interfacial tension) and kinetic (e.g. relative viscosity) considerations determine the morphology developed during the blending process. The effect of interfacial characteristics on the structure‐property relationships of ternary polymer alloys and blends comprising polypropylene (PP), ethylene‐vinyl alcohol copolymer (EVOH) and glass beads (GB), or fibers (GF), was investigated. The system studied was based on a binary PP/EVOH immiscible blend, representing a blend of a semi‐crystalline apolar polymer with a semicrystalline highly polar copolymer. Modification of the interfacial properties was obtained through using silane coupling agents for the EVOH/glass interface and compatibilization using a maleic anhydride grafted PP (MA‐g‐PP) for the PP/EVOH interface. The compatibilizer was added in a procedure aimed to preserves the encapsulated EVOH/glass structure. Blends were prepared by melt extrusion compounding and specimens by injection molding. The morphology was characterized using scanning electron microscopy (SEM) and high resolution SEM (HRSEM), the shear viscosity by capillary rheometry and the thermal behavior using differential scanning calorimetry (DSC). The system studied consisted of filler particles encapsulated by EVOH, with some of the minor EVOH component separately dispersed within the PP matrix. Modification of the interfaces resulted in unique morphologies. The aminosilane glass surface treatment enhanced the encapsulation in the ternary [PP/EVOH]GB blends, resulting in an encapsulated morphology with no separtely dispersed EVOH particles. The addition of a MA‐g‐PP compatibilizer preserves the encapsulated morphology in the ternary blends with some finely dispersed EVOH particles and enhanced PP/EVOH interphase interactions. The viscosity of the binary and ternary blends was closely related to the blend's morphology and the level of shear rate. The treated glass surfaces showed increased viscosity compared to the cleaned glass surfaces in both GB and GF containing ternary blends. Both EVOH and glass serve as nucleating agents for the PP matrix, affecting its crystallization process but not its crystalline structure. The aminosilane glass surface treatment completely inhibited the EVOH crystallization process in the ternary blend. In summary, the structure of the multicomponent blends studied has a significant effect on their behavior as depicted by the rheological and thermal behavior. The structure‐performance relationships in the three‐component blends can be controlled and varied.     

Development of phase morphology in incompatible polymer blends during mixing and its variation in extrusion

An experimental study of the development of phase morphology in incompatible polymer melt blends of polyethylene/polystyrene (PE/PS), polyethylene/polycarbonate (PE/PC), and polyethylene/nylon-6 (PE/N6) is presented. Different temperatures (180°C, 240°C) of mixing and polyethylene molecular- weight levels were used in the PE/PS studies. Little variation in the cross-sectional phase morphology of the PE/PS extrudates was observed with these variables, though the morphology became finer with increased shear rate/stress in capillary die flow. Variations in the longitudinal morphology are observed with continuous filaments of dispersed phase only arising when the dispersed phase has an equal or lower viscosity than the continuous phase. The PE/N6 and PE/PC, especially the former, give coarser morphologies when the N6 and PC are the continuous phases. This was attributed to larger inter-facial tensions. The effect of viscoelasticity was also discussed.     

Morphological states for a ternary polymer blend demonstrating complete wetting

For the most part, ternary polymer blends demonstrate complete wetting behavior. Conceptually, this is the state where one of the components will always tend to completely separate the other two and from a thermodynamic viewpoint is described as the case where two of the three possible binary spreading coefficients are negative and the other is positive, as defined by Harkins spreading theory. This work examines the complete range of morphological states possible for such a system over the entire ternary composition diagram as prepared by melt mixing. A ternary polymer blend comprised of high-density polyethylene (HDPE), polystyrene (PS), and poly(methyl methacrylate) (PMMA) is selected as a model system demonstrating complete wetting and four sub-categories of morphologies can be identified including: a) matrix/core-shell dispersed phase; b) tri-continuous; c) matrix/two separate dispersed phases, and d) bi-continuous/dispersed phase morphologies. Electron microscopy as well as a technique based on the combination of focused ion beam irradiation and atomic force microscopy are used to clearly illustrate and identify the various phases. Solvent extraction/gravimetry is used to examine the extent of continuity of the systems so as to effectively identify regions of high continuity. Triangular compositional diagrams are used to distinguish these various morphological regions and the results are interpreted in light of the interfacial tension of the various binary combinations and their subsequent spreading coefficients. The effect of the molecular weight and of viscosity ratio on the phase size of the various structures is also considered.     

Compatibilization of PE/PS and PE/PP blends. I. Effect of processing conditions and formulation

The objective of this work was to study the effectiveness of low‐cost commercial compatibilizers and several processes (internal mixer, single‐ and twin‐screw extruders) for two types of plastic blends: high‐density polyethylene/polypropylene and high‐density polyethylene/polystyrene blends, to gain insight into the recycling of wastes from those frequently encountered mixed plastics. Blends going from a pure A to a pure B component, with and without a compatibilizer, were prepared using an internal mixer, a corotating twin‐screw extruder, as well as a single‐screw extruder to follow an industrial‐convenient process. In both cases, the analyses of blend morphologies highlighted the poor adherence between the two phases in the uncompatibilized blends. Compatibilized blends display better adherence between phases and the ability to process blends made from both single‐ and twin‐screw extruders. When adding a compatibilizer, the viscosity of each blend (PE/PP or PE/PS) increased due to a better adhesion of the phases. Charpy impact tests showed that the presence of the compatibilizer in PE/PS blends increased their impact properties. Indeed, the improvement of the adhesion between the two phases enabled stress transfer at the interface. A single‐screw extruder seems to be efficient as a processing method on an industrial scale when a compatibilizer is used. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2475–2484, 2003     

Morphology and rheology of immiscible polymer blends filled with silica nanoparticles

The effect of silica nanoparticles on the morphology and the rheological properties of an immiscible polymer blend (polypropylene/polystyrene, PP/PS 70/30) was investigated. Two types of pyrogenic nanosilica were used: a hydrophilic silica with a specific surface area of 200 m²/g and a hydrophobic silica having a specific surface area of 150 m²/g. First, a significant reduction in the PS droplet volume radius, from 3.25 to nearly 1 μm for filled blends with 3 wt% silica, was observed. More interestingly, image analysis of the micrographs proved that the hydrophilic silica tends to confine in the PS phase whereas hydrophobic one was located in the PP phase and at the PP/PS interface (interphase thickness ≈ 100-200 nm). Furthermore, a migration of hydrophilic silica from PP phase toward PS domains was observed.An analysis of the rheological experimental data was based on the framework of the Palierne model, extended to filled immiscible blends. Due to the partition of silica particles in the two phases and its influence on the viscosity ratio, limited cases have been investigated. The rheological data obtained with the hydrophobic silica were more difficult to model since the existence of a thick interphase cannot be taken into account by the model. Finally, the hypothesis that hydrophilic silica is homogeneously dispersed in PS droplets and that hydrophobic silica is dispersed in PP matrix was much closer to the actual situation. It can be then concluded that stabilization mechanism of PP/PS blend by hydrophilic silica is the reduction in the interfacial tension whereas hydrophobic silica acts as a rigid layer preventing the coalescence of PS droplets.     

Enhancing the mechanical,morphological, and rheological behavior of polyethylene/polypropylene blends with maleic anhydride-grafted polyethylene

This is the first study to showcase the use of maleic anhydride-grafted polyethylene (MAPE) to compatibilize polyethylene (PE)-rich blends, where polypropylene (PP) represents the minor phase. By first mixing PP with MAPE, and then adding PE, MAPE was assumed to be localized at the PE/PP interface. Microscopy analysis confirmed that MAPE led to a remarkably fine PE/PP/MAPE morphology, with PP being uniformly dispersed into PE and having an average diameter 267% smaller than that in the PE/PP blend. According to mechanical and rheological tests, this translated into a 14%, 20%, and 14% enhancement of tensile strength, tensile modulus, and tensile toughness, respectively, as well as a 10% and 20% drop in PE/PP viscosity mismatch and interfacial tension, respectively. Finally, PE/PP/MAPE tensile toughness and elongation at break were greater than those of virgin PP, while PE/PP/MAPE strength and stiffness were similar to the ones of neat PP. Therefore, this study provides industries with the possibility to utilize products rich in PE instead of those made of more expensive PP, while still keeping the level of performance high; hence, creating a paradigm shift in the development of advanced lightweight polyolefin materials with tuned functionalities.     

The role of organically modified layered silicate in the breakup and coalescence of droplets in PBT/PE blends

In this study, we investigated the effect of organically modified nanoclay (organoclay) on the morphology of immiscible polymer blends (PBT/PE) with various compositions of PBT ranging from 1 to 90 wt%. When a small amount of organoclay between 1 and 3 phr is added to the blend, the thin clay tactoids of the thickness of the order of 10 nm are located at the interface between PBT and PE phase. As its content is increased, the additional organoclay positions in a specific component depending on its affinity with the component. The addition of a small amount of organoclay results in the effective size reduction for PBT/PE blend. The organoclay located at the interface forms the interfacial phase with a non-homogeneous distribution of clay along the interface and changes the interfacial tension, which result in the coalescence suppression of the droplets. Rigid organoclay with a high aspect ratio allows the blend morphology with long-term thermal stability by suppressing the Brownian motion. This ability of the organoclay to suppress the coalescence of the droplets effectively reduces the droplet size. On the other hand, additional organoclay results in the rheological properties of particular component being increased, which means the change in the viscosity ratio. The change in the viscosity ratio, together with the coalescence suppression effect, affects the determination of the droplet size, depending on the location of the organoclay. Therefore, the organoclay suppresses the coalescence of the droplets at the interface, while simultaneously influencing the breakup of the droplets due to the change of viscosity ratio.     

The Use of Ethylene/Propylene Copolymers as Compatibilizers for Recycled Polyolefin Blends

Compatibilizing effects of ethylene/propylene (EPR) diblock copolymers on the morphology and mechanical properties of immiscible blends produced from recycled low‐density polyethylene (PE‐LD) and high‐density polyethylene (PE‐HD) with 20 wt.‐% of recycled poly(propylene) (PP) were investigated. Two different EPR block copolymers which differ in ethylene monomer unit content were applied to act as interfacial agents. The morphology of the studied blends was observed by scanning‐ (SEM) and transmission electron microscopy (TEM). It was found that both EPR copolymers were efficient in reducing the size of the dispersed phase and improving adhesion between PE and PP phases. Addition of 10 wt.‐% of EPR caused the formation of the interfacial layer surrounding dispersed PP particles with the occurrence of PE‐LD lamellae interpenetration into the layer. Tensile properties (elongation at yield, yield stress, elongation at break, Young's modulus) and notched impact strength were measured as a function of blend composition and chemical structure of EPR. It was found that the EPR with a higher content of ethylene monomer units was a more efficient compatibilizer, especially for the modification of PE‐LD/PP 80/20 blend. Notched impact strength and ductility were greatly improved due to the morphological changes and increased interfacial adhesion as a result of the EPR localization between the phases. No significant improvements of mechanical properties for recycled PE‐HD/PP 80/20 blend were observed by the addition of selected block copolymers.     

Strategies for interfacial localization of graphene/polyethylene-based cocontinuous blends for electrical percolation

We have investigated melt blending approaches to interfacial localization of few-layer graphene in cocontinuous polymer blends with polyethylene as one of the components. When linear low-density polyethylene (LLDPE)/polypropylene (PP) or high-density polyethylene (HDPE)/polylactic acid (PLA) and graphene were mixed all together, graphene preferred polyethylene over PP or PLA. When PP and graphene were premixed and blended with polyethylene, some graphene was trapped at the blend interface but not enough to cover the large interfacial area. In contrast, an ultralow electrical percolation was achieved (< 0.1 vol%) in HDPE/PLA blend due to smaller interfacial area. In another approach, polystyrene was added as a tertiary minor component to HDPE/PLA blends. This continuous interfacial layer containing graphene led to a low electrical percolation threshold (< 0.2 vol%). From these investigations, we suggest general ways to reduce a percolation threshold by kinetic control of the morphology of cocontinuous polymer blends.     

PC／PE共混体系中增容剂最佳用量的确定

本文以聚碳酸酯（ＰＣ）／聚乙烯（ＰＥ）／聚乙烯蜡接技马来酸酐（ＰＥＷ－ｇ－ＭＡＨ）三元共混物为体系，研究了第三组份增容剂ＰＥＷ－ｇ－ＭＡＨ用量。共混物两相之间界面张力和共混物力学性能之间的相互关系。论证了通过测量高聚物之间界面张力来确定第三组份增容剂的最佳用量的技术途径。