Viscoelastic properties and interfacial tension of polystyrene–polyethylene blends

The linear viscoelastic properties of polystyrene polyethylene (PS/PE) blends have been investigated in the molten state. For concentrations of the dispersed phase equal to 30 vol %, the blends exhibited a droplet‐matrix morphology with a volume‐average diameter of 5.5 μm for a 70/30 PS/PE blend at 200 °C and 14.7 μm for a 30/70 PS/PE blend at 230 °C. Enhanced elasticity (G′) for both blends, in the terminal zone, compared to the modulus of the matrix (PS and PE, respectively) was observed. This is related to the deformation of the droplets in the matrix phase and hence to the interfacial forces between the blend components. The results for these uncompatibilized blends are shown to be in agreement with the predictions of the emulsion model of Palierne. These predictions were used to obtain the interfacial tension between PS and PE, which was found to be between 2 and 5 mN/m at 200 °C and 4 ± 1 mN/m at 230 °C. Independent interfacial tension measurements using the breaking‐thread method resulted in a value of 4.7 mN/m and 4.1 mN/m at 200 °C and 230 °C for the respective blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1359–1368, 2000     

Interfacial tension and acid‐base approaches to polymer interactions

A significant correlation has been shown to exist between the interfacial tension of polymer pairs and their acid‐base pair interaction. The relationship is inverse, with interfacial tensions decreasing as acid‐base interactions increase. Interfacial tensions, frequently used as an indicator of polymer compatibility, were measured by the breaking thread method at temperatures in the vicinity of 200 °C. Acid‐base pair interaction values were measured by inverse gas chromatography over wide temperature ranges. The observed correlation confirms the important contribution made by short‐range, acid‐base interactions to the observed value of interfacial tension and supports the prediction of equations based on fundamental definitions of surface forces. A collateral finding of this work is the decrease of acid‐base functionality with rising temperature for all polymers studied. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2096–2104, 2000     

The influence of partial emulsification on coalescence suppression and interfacial tension reduction in PP/PET blends

This study examines how the relative role of coalescence suppression and interfacial tension reduction influence the particle size at various levels of in situ compatibilization. The polymers studied are polyethylene terephthalate (PET) as matrix and a polypropylene (PP) as dispersed phase compatibilized by a triblock copolymer of poly(styrene–hydrogenated butadiene–styrene) (SEBS) grafted with maleic anhydride. The interfacial tension was studied by the breaking‐thread method, and it was used along with the morphology to characterize the emulsification efficacy of the copolymers. By modifying the concentration of MA grafted on the SEBS, different levels of emulsification of the blends were obtained. A comparison of 1/99 and 10/90 PP/PET blends compatibilized by SEBS‐g‐MA allows one to distinguish the relative role of interfacial tension and coalescence suppression in diminishing particle size. It is shown that varying degrees of residual coalescence remain, depending on the level of %MA in the copolymer. A detailed study of the 2%MA system below interfacial saturation was carried out to shed further light on the dependence of coalescence suppression on emulsification level and interfacial coverage. After separating out the contribution of interfacial tension on particle size reduction, it is shown that coalescence suppression for this system increases gradually with areal density of modifier at the interface right up to the region of interfacial saturation. Finally, the interfacial and morphological data were used to test the ability of the Lee and Park model to describe coalescence in polymer blends. Reasonable agreement was found between the parameter c₁, describing the coalescence in that model, and the trends related to residual coalescence from this study. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 939–951, 1999     

Inequalities for Stationary Poisson Cuboid Processes

A cuboid is a rectangular parallelepipedon. By the notion “stationary Poisson cuboid process” we understand a stationary Poisson hyperplane process which divides the Euclidean space ?^d into cuboids. It is equivalent to speak of a stationary Poisson cuboid tessellation. The distributions of volume and total edge length of the typical cuboid and the origin-cuboid of a stationary Poisson cuboid process are considered. It is shown that these distributions become minimal, in the sense of a specific order relation, in the case of quasi-isotropy. A possible connection to a more general problem, treated in [6], is also discussed.     

Influence of the efficacy of interfacial modification on the coarsening of cocontinuous PS/HDPE blends during quiescent annealing

This article studies the quiescent annealing of three different cocontinuous polystyrene/high‐density polyethylene blends modified with two types of interfacial agents of widely different efficacies. Quantitative analysis of phase growth was obtained using mercury porosimetry. In a previous work, it was shown that one of these modifiers, a symmetrical diblock copolymer, has a high affinity for the interface and demonstrates virtually no micelle formation prior to saturation of the blend interface. The other modifier, a hydrogenated SEBS of 70/30 composition, forms micelles at elevated concentrations of modifier. In this study, it is shown that the cocontinuous phase size grows linearly without modifier, whereas the addition of both interfacial modifiers significantly suppresses the PE/PS phase coarsening and results in nonlinear phase growth behavior. The effect of the diblock copolymer on suppressing coarsening, however, is much more effective than that for the triblock case clearly supporting the tendency toward micelle formation for that latter modifier. In the case of unmodified PE/PS, the driving force for capillary pressure effects is so high that it is the capillary instability phenomena that dominate the coarsening and hence result in a linear growth of pore size with annealing time. When interfacial modifiers are added, the influence of reduced interfacial tension and lower pore size polydispersity significantly diminishes both capillary pressure effects and capillary instability phenomena. In that case, capillary pressure becomes the main rate determining step resulting in a nonlinear dependence of pore size with annealing time. It is shown that both the viscosity of the phases and the temperature of annealing can strongly influence coarsening behavior at low levels of interfacial modifier. Under all those conditions, however, nonlinear phase growth for the partially compatibilized system was maintained. These results clearly show that careful quantitative coarsening experiments using mercury porosimetry can be used as a tool to analyze the efficacy of interfacial modifiers for highly continuous or cocontinuous systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 711–721, 2006     

Impact fracture behavior of nylon-6/ABS blends

Tensile and impact properties of uncompatibilized nylon-6/ABS blends have been studied over the entire range of compositions. The blends were prepared by extrusion and, subsequently, injection molded into tensile specimens and rectangular plaques. The impact fracture performance was characterized using recently proposed models based on fracture mechanics, for various fracture behaviors. The results showed that nylon-6 breaks in a brittle manner. With the addition of ABS, the blend exhibits the same behavior with a slightly lower impact resistance up to about 60 wt %. A sudden jump in the value of impact fracture energy is observed around 70 wt % ABS with a brittle—ductile transition in the mechanism of fracture. The transition in fracture mechanisms is confirmed through observation of the fracture surfaces by scanning electron microscopy (SEM). Tensile tests showed that the elongation at break increases only slightly between 0 and 50% ABS content, but a significant jump occurs around 70% ABS, reaching a 6-fold increase in comparison to that of the pure components. SEM observation of etched samples shows that a cocontinuous morphology occurs around 70 wt % ABS. The peak observed for the elongation at break and the jump in impact performance, as well as the onset of brittle–ductile transition, are attributed to this morphological effect. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2583–2592, 1997     

Cocontinuity and phase inversion in HDPE/PS blends: Influence of interfacial modification and elasticity

In this work the level of continuity and cocontinuity for blends of HDPE/PS prepared on a twin-screw extruder have been studied by both morphology and dissolution studies. Addition of SEBS as an interfacial modifier results in a shift of the percolation threshold for dispersed PS to higher concentrations. The region of phase inversion, however, is maintained at 70% PS. The shift in the percolation threshold to higher values is related to reduced elongation of the PS dispersed phase after interfacial compatibilization. These results indicate that an interfacial modifier significantly influences percolation phenomena without shifting the region of phase inversion. Models based on viscosity ratio have failed to predict the region of phase inversion in this study. Elastic effects are shown to be able to describe the basic tendencies. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1889–1899, 1998     

Stability of the co‐continuous morphology during melt mixing for poly(ε‐caprolactone)/polystyrene blends

Over the last 10 years, research into co‐continuous polymer blends has been intense. Despite these efforts, there are very few detailed studies on the stability of this complex morphology. In this work, blends of poly(ε‐caprolactone) and polystyrene were melt‐mixed in an internal mixer for time intervals of 0.5–120 min at set temperatures of 140 and 170 °C, and the effect of the mixing time on the co‐continuous morphology was studied. This blend system was chosen because each component could be selectively dissolved and this allowed for a complete study of the co‐continuous region. The phase continuity was measured with a solvent‐extraction gravimetric technique, and the concentration range for co‐continuity was determined. The phase size and phase size distribution were obtained with the mercury intrusion porosimetry technique. The results indicate that the co‐continuous morphology forms very early in the mixing process and achieves a stable morphology within the first 5 min of mixing for virtually all the co‐continuous compositions. For all cases studied, the co‐continuous morphology remains unchanged over mixing times as long as 1–2 h. These results support the notion of a stable steady‐state formation of co‐continuous morphologies during melt mixing similar to that observed for matrix/dispersed phase type blends. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 864–872, 2007     

Morphological stability,interfacial tension,and dual-phase continuity in polystyrene-polyethylene blends

The morphological stability of polystyrene high-density polyethylene (PS/PE) blend is investigated in the region of dual-phase continuity. The effect of the addition of a triblock SEBS copolymer to the blends on the stability of these morphologies, is examined. The results show that the morphology of the unmodified blends changes from co-continuous to droplet matrix for PS-rich blends whereas the morphology of a 50/50 blend maintains continuity but coarsened significantly upon annealing at 200°C. In the presence of the copolymer, these morphologies are much more stable. Selective solvent extraction of polystyrene in di-ethyl ether reveals that the level of PS continuity in the 50/50 blend is higher for the unmodified system than for the modified one. Upon annealing, the level of PS continuity significantly increases for the unmodified 50/50 PS/PE blend. The effect of the copolymer content in the blend on the interfacial tension between the two components is also investigated using the breaking thread method. The interfacial tension is found to be reduced from 5.6 to 1.1 mN/m by the addition of 20 parts of the copolymer to the blend. © 1997 John Wiley & Sons, Inc.     

The relative role of coalescence and interfacial tension in controlling dispersed phase size reduction during the compatibilization of polyethylene terephthalate/polypropylene blends

The breaking thread and the sessile drop methods have been used to evaluate the interfacial tension between a polypropylene (PP) and a polyethylene-terephthalate (PET). An excellent correlation was found between the two. The breaking thread technique was then used to evaluate the interfacial tension of these blends at various levels of a styrene-ethylene butylene-styrene grafted with maleic anhydride (SEBS-g-MA) compatibilizer. In order to evaluate the relative roles of coalescence and interfacial tension in controlling dispersed phase size reduction during compatibilization, the morphology of PP/PET 1/99 and 10/90 blends compatibilized by a SEBS-g-MA were studied and compared. The samples were prepared in a Brabender mixer. For the 10/90 blend, the addition of the compatibilizer leads to a typical emulsification curve, and a decrease in dispersed phase size of 3.4 times is observed. For the 1/99 blend, a 1.7 times reduction in particle size is observed. In the latter case, this decrease can only be attributed to the decrease of the interfacial tension. It is evident from these results that the drop in particle size for the 10/90 PP/PET blend after compatibilization is almost equally due to diminished coalescence and interfacial tension reduction. These results were corroborated with the interfacial tension data in the presence of the copolymer. A direct relationship between the drop in dispersed phase size for the 1/99 PP/PET blend and the interfacial tension reduction was found for this predominantly shear mixing device. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2271–2280, 1997