The effect of interface characteristics on the static and dynamic mechanical properties of three‐component polymer alloys

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 systems studied were based on a binary PP/EVOH immiscible blend, representing a blend of a semi‐crystalline apolar polymer with a semi‐crystalline highly polar copolymer. The ternary systems studied consisted of filler particles encapsulated by EVOH, with some of the minor EVOH component separately dispersed within the PP matrix. Modification of the interfacial properties was done 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. Both glass fillers increased the dynamic modulus and decreased the damping of the neat polymers and of their binary blends, especially in the rubbery region. GF has a more profound effect on both the modulus and the damping. Glass surface treatments and compatibilization have only a marginal effect on the dynamic mechanical behavior of the ternary blends. Yet, compatibilization shifted the polymers' T_gS to higher temperatures. Both glass fillers increased the elastic modulus of the binary blends, where GF performed better than GB as a reinforcing agent. GF slightly increased the strength of the binary blends while, GB reduced it. Both fillers reduced the ductility of the binary blends. The blends' mechanical properties were related to the morphology and their components' crystallinity. The compatibilizer increases both stiffness and strength and reduces deformability.     

Interface modification and characterization in three‐component polymer blends

The effect of interface characteristics on the properties of three‐component polymer blends comprising PP/EVOH/mica and PP/EVOH/glass beads (GB) was investigated (polypropylene‐PP, ethylene‐vinylalcohol‐EVOH). The systems selected are based on the binary PP/EVOH immiscible blend representing a semi‐crystalline apolar polymer (PP) and a semi‐crystalline highly polar copolymer (EVOH), where PP serves as the matrix. A series of the binary and three‐component blends with varying compositions was chosen to study the effect of the molding procedure, i.e. compression versus injection molding. The structures observed by SEM analysis consisted of the filler particles engulfed by the EVOH phase, with some of the minor EVOH component dispersed within the PP matrix. The effects of silane treatment (GB/EVOH interface) and compatibilization, using a maleated‐PP compatibilizer (PP/EVOH interface), were studied in relation to the generated structured and properties. The compatibilizer was added in a unique procedure by which the encapsulated GB/EVOH structures were preserved. The characterization methods used included morphology by Scanning Electron Microscopy, thermal properties and crystallization behavior by Differential Scanning Calorimetry, mechanical properties by tensile testing, and dynamic characteristics by Dynamic Mechanical Thermal Analysis. The work has shown that structure‐performance relationships in the three‐component blends can be varied and controlled.     

Rheological behavior of polyester blend and mechanical properties of the polypropylene–polyester blend fibers

The article deals with method of preparation, rheological properties, phase structure, and morphology of binary blend of poly(ethylene terephthalate) (PET)/poly(butylene terephthalate) (PBT) and ternary blends of polypropylene (PP)/(PET/PBT). The ternary blend of PET/PBT (PES) containing 30 wt % of PP is used as a final polymer additive (FPA) for blending with PP and subsequent spinning. In addition commercial montane (polyester) wax Licowax E (LiE) was used as a compatibilizer for spinning process enhancement. The PP/PES blend fibers containing 8 wt % of polyester as dispersed phase were prepared in a two‐step procedure: preparation of FPA using laboratory twin‐screw extruder and spinning of the PP/PES blend fibers after blending PP and FPA, using a laboratory spinning equipment. DSC analysis was used for investigation of the phase structure of the PES components and selected blends. Finally, the mechanical properties of the blend fibers were analyzed. It has been found that viscosity of the PET/PBT blends is strongly influenced by the presence of the major component. In addition, the major component suppresses crystallinity of the minor component phase up to a concentration of 30 wt %. PBT as major component in dispersed PES phase increases viscosity of the PET/PBT blend melts and increases the tensile strength of the PP/PES blend fibers. The impact of the compatibilizer on the uniformity of phase dispersion of PP/PES blend fibers was demonstrated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4222–4227, 2006     

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).     

Effect of blend ratio on bulk properties and matrix-fibril morphology of polypropylene/nylon 6 polyblend fibers

Ternary blends of polypropylene (PP), nylon 6 (N6) and polypropylene grafted with maleic anhydride (PP/N6/PP-g-MAH) as compatibilizer with up to 50 wt% of N6 were investigated. PP-g-MAH content was varied from 2.5 to 10%. Blends of the two polymers PP/N6 (80/20) without the compatibilizer were also prepared using an internal batch mixer and studied. The ternary blends showed different rheological properties at low and high shear rates. The difference depended on the amount of N6 dispersed phase. Co-continuous morphology was observed for the blend containing 50% N6. This blend also exhibited higher viscosity at low shear rate and lower viscosity at high shear rates than the value calculated by the simple rule of mixture. At higher shear rates, viscosity was lower than that given by the rule of mixture for all blend ratios. An increase in viscosity was observed in the 80/20 PP/N6 blend after the concentration of the interfacial agent (PP-g-MAH) was increased. Polyblends containing up to 30% N6 could be successfully melt spun into fibers. DSC results showed that dispersed and matrix phases in the fiber maintained crystallinity comparable to or better than the corresponding values found in the neat fibers. The dispersed phase was found to contain fibrils. By using SEM and LSCM analyses we were able to show that the N6 droplets coalesced during melt spinning which led to the development of fibrillar morphology.     

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     

Rheology‐morphology correlation in PET/PP blends: Influence of type of compatibilizer

Rheological and morphological properties of melt processed poly(ethylene terephthalate) (PET)/polypropylene (PP) blends are presented. Two types of compatibilizer namely, PP‐g‐MA <MA= maleic anhydtide> and Elvaloy PTW, an n‐butyl acrylate glycidyl methacrylate ethylene terpolymers, were incorporated at different levels to the PET/PP blend system. Scanning electron microscopy revealed that the dispersed particle sizes were smaller in PET‐rich blends than PP‐rich blends. With increasing compatibilizer level, the refinement of morphology was observed in both the systems. However, the blends compatibilized with PTW showed a more refined (smaller) particle size, and at high PTW content (10 wt%), the morphology changed towards monophasic. The significant changes in morphology were attributed to the highly reactive nature of PTW. Investigation of rheological properties revealed that the viscosity of the PET/PP blends followed typical trends based on mixing rule, which calculates the properties of blends based on a linear average. Incorporation of PP‐g‐MA into the blends resulted in a negative deviation in the viscosity of the system with respect to that of the neat blend. With increasing PP‐g‐MA level, the deviation became more pronounced. Although incorporation of the compatibilizer into the PET/PP blends refined the morphology, it led to a drastic drop of viscosity, which could be attributed to inherently lower molecular weight of the compatibilizer. In the case of the blends compatibilized by PTW, a strong positive deviation in rheological properties was observed that confirmed the stronger interaction between the blend components due to reactive compatibilization process, which led to the more refined morphology in this series of blends. J. VINYL ADDIT. TECHNOL., 19:25–30, 2013. © 2013 Society of Plastics Engineers     

Study on morphology and viscoelastic properties of PP/PET/SEBS ternary blend and their fibers

The morphology development of polypropylene (PP)/polyethylene terephthalate (PET)/styrene‐ethylene‐butylene‐styrene (SEBS) ternary blends and their fibers were studied by means of scanning electron microscopy (SEM) in conjunction with the melt linear viscoelastic measurements. The morphology of the blends was also predicted by using Harkin's spreading coefficient approach. The samples varying in composition with PP as the major phase and PET and SEBS as the minor phases were considered. Although SEM of the binary blends showed matrix‐dispersed type morphology, the ternary blend samples exhibited a morphological feature in which the dispersed phase formed aggregates consisting of both PET and SEBS particles distributed in the PP matrix. The SEM of the blend samples containing 30 and 40 wt % of total dispersed phase showed an agglomerated structure formed between the aggregates. The SEM of the PP/PET binary fiber blends showed long well‐oriented microfibrils of PET whereas in the ternary blends, the microfibrils were found to have lower aspect ratio with a fraction of the SEBS stuck on the microfibril fracture surfaces. These results were attributed to a core‐shell type morphology in which the PET and SEBS formed the core‐shells distributed in the matrix. The melt viscoelastic behavior of the ternary blends containing less than 30 wt % of the total dispersed phase was found to be similar to the matrix and binary blend samples whereas the samples containing 30 and 40 wt % of dispersed phases exhibited a pronounced viscosity upturn and nonterminal storage modulus in low frequency range. These results were found to be in good agreement with the morphological results. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The morphology of hyperbranched polymer compatibilized polypropylene/polyamide 6 blends

The influence of hyperbranched polymer grafted polypropylene (PP‐HBP) on the morphology of polypropylene (PP)/polyamide 6 (PA6) blends has been investigated. The final morphology was strongly influenced by the PP‐HBP compatibilizer concentration. At low concentrations, PP‐HBP acts as an emulsifying agent, reducing the size of the dispersed phase and preventing coalescence. This is due to the high reactivity and diffusitivity of PP‐HBP rapidly forming a high density of copolymers at the interface. Compared to the use of maleic anhydride grafted PP (PP‐MAH) at identical concentrations, PP‐HBP yielded a smaller dispersed phase particle size. Therefore, PP‐HBP allows the use of less compatibilizer to obtain identical morphologies. At higher compatibilizer concentrations, it has been shown that the PP‐HBP efficiently stabilizes the interface and inhibits both coalescence and breakup of the PA6 droplets. The high concentration of reactive sites and the ability of PP‐HBP to react with both chain‐ends of PA6 suggest that interfacial stabilization occurs because of the formation of a partly crosslinked interface. The interfacial stabilization effects generated by PP‐HBP should allow one to control the morphology of polymer blends in order to create specific functional morphologies.     

Polymer encapsulation of glass filler in ternary PP/PA-6/glass blends

The morphology and rheology of ternary isotactic polypropylene (PP)/polyamide-6 (PA-6)/glass blends is investigated and contrasted with the behavior of two-component (binary) PP/PA-6 blends. Injection molded samples of binary blends exhibit an interlayer slip morphology for both PP and PA-6 as the matrix and the blend shear viscosity is lower than expected from a rule of mixtures. The morphology of ternary blends is dependent on the choice of the matrix phase. In ternary blends with a PA-6 matrix, the PP domains and glass fibers are separately dispersed within the matrix. In ternary blends with a PP matrix, the PA-6 is mainly found surrounding (encapsulating) the glass fibers, and the extent of the interlayer slip morphology is reduced. Variations in glass surface treatment, blending time, and order of addition did not affect the rapid encapsulation of glass by the PA-6. A reduction in blending temperature, below the peak PA-6 melting temperature, hinders encapsulation.     

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.     

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

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

Functionalized elastomeric compatibilizer in PA 6/PP blends and binary interactions between compatibilizer and polymer

Superior impact properties were obtained when maleic anhydride grafted styrene ethylene/butylene styrene block copolymer (SEBS-g-MAH) was used as a compatibilizer in blends of polyamide 6 (PA 6) and isotactic polypropylene (PP), where polyamide was the majority phase and polypropylene the minority phase. The optimum impact properties were achieved when the weight relation PA:PP was 80:20 and 10 wt% SEBS-g-MAH was added. The blend morphology was systematically investigated. Transmission electron microscopy (TEM) indicated that the compatibilizer forms a cellular structure in the PA phase in addition to acting as an interfacial agent between the two polymer phases. In this cellular-like morphology the compatibilizer appears to form the continuous phase, while polyamide and polypropylene form separate dispersions. In microscopy, PA appeared as a fine dispersion and PP as a coarse dispersion. The mechanical properties indicated that in fact PA, too, is continuous, and the blend can be interpreted as possessing a modified semi-interpenetrating network (IPN) structure with separate secondary dispersion of PP. The coarser PP dispersion plays an essential role in impact modification. Binary blends of the compatibilizer and one blend component were also investigated separately. The same cellular structure was observed in the binary PA/SEBS-g-MAH blends, and SEBS-g-MAH again appeared to form the continuous phase when the elastomer concentration was at least 10 to 20 wt%. By contrast, in PP/SEBS-g-MAH only conventional dispersion of elastomeric SEBS-g-MAH was observed up to 40 wt% elastomer. Impact strength was improved and the elastic modulus was lowered in both PA/SEBS-g-MAH and PP/SEBS-g-MAH blends when the elastomer content was increased. The changes in modulus indicate that the semi-IPN-like structure is formed in the binary PA/SEBS-g-MAH blends as well as in the ternary structure.     

Linear viscoelastic behavior of compatibilized PMMA/PP blends

In this work, the morphology and linear viscoelastic behavior of PMMA/PP blends to which a graft copolymer PP‐g‐PMMA has been added was studied. The copolymer concentration varied from 1 to 10 wt % relative to the dispersed phase concentration. The rheological data were used to infer the interfacial tension between the blended components. It was observed that PP‐g‐PMMA was effective as a compatibilizer for PMMA/PP blends. For PP‐g‐PMMA concentration added below the critical concentration of interface saturation, two rheological behaviors were observed depending on the blend concentration: for 70/30 blend, the storage modulus, at low frequencies, increased as compared to the one of the unmodified blend; for 90/10 blend, it decreased. For 90/10 blend, the relaxation spectrum presented an interfacial relaxation time related to the presence of the compatibilizer (τ_β). For PP‐g‐PMMA concentrations added above the critical concentration of interface saturation, the storage modulus of all blends increased as compared with the one of the unmodified blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

PP/EVOH/PA6共混物的性能研究

以聚丙烯接枝马来酸酐(PP-g-MAH)为相容剂,制备了聚丙烯(PP)/乙烯-乙烯醇共聚物(EVOH/)聚酰胺6(PA6)共混物,研究了PP/EVOH/PA6三元共混物的相容性、流变性能、阻隔性能、力学性能、热性能及形态结构。结果表明:相容剂与EVOH和PA6间发生了反应,提高了共混物的相容性;相容剂的加入提高了PP、EVOH、PA6的结晶温度,增强了PP与EVOH和PA6间的黏合力,降低了界面张力;EVOH占EVOH/PA6总量68%的三元共混物吸油率最小,当相容剂用量为5份时,PP/EVOH/PA6三元共混物吸油率比PP/EVOH二元共混物降低了8%。     

The effect of maleated compatibilizers on the structure and properties of EVOH/clay nanocomposites

The effect of compatibilizers on the blending torque, crystallization behavior, intercalation level, thermal stability and morphology of EVOH/treated clay systems was investigated. Maleic anhydride‐grafted ethylene vinyl acetate (EVA‐g‐MA) or maleic anhydride‐grafted linear low density polyethylene (LLDPE‐g‐MA) were used as compatibilizers of EVOH with clay, in various concentrations (1, 5 and 10 wt%). The blends were processed using Brabender Plastograph and characterized by XRD, SEM, DSC, DMTA and TGA. X‐ray diffraction shows advanced intercalation within the galleries when the compatibilizers were added. Unique results were obtained for the EVOH/clay/compatibilizer systems, owing to a high level of interaction developed in these systems, which plays a major role. Thermal analysis showed that with increasing compatibilizer content, lower crystallinity levels result, until at a certain content no crystallization has taken place. Significantly higher viscosity levels were obtained for the EVOH/clay blends compared to the neat polymer, as seen by a dramatic torque increase when processed in the Brabender machine. The DMTA spectra showed lower T_g values for the compatibilized nanocomposites compared to the neat EVOH and the uncompatibilized composites. Storage modulus was higher compared to the uncompatibilized EVOH/clay blend when EVA‐g‐MA compatibilizer was added (at all concentrations), and only at low contents of LLDPE‐g‐MA. TGA results show significant improvement of the blends thermal stability compared to the neat EVOH, and to the uncompatibilized blend, indicating an advanced intercalation.     

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.     

Compatibilization of PP/PBT and PP/PA6 blends with a new oxazoline-functionalized polypropylene

Summary Aim of this work was to study the effectiveness of a novel oxazoline-functionalized polypropylene as a compatibilizer for PP/PBT and PP/PA6 blends. This polypropylene-based compatibilizer mixes well with the polypropylene and is capable of reacting with the carboxylic and amine end groups of PBT and PA6. Significant improvements in blend toughness were achieved without reduction in strength and stiffness. These effects were related to stabilized morphology of finely dispersed minor phase well attached to the matrix. The enhanced interfacial interactions between the two phases, in particular at high PBT content were evidenced by increased melt viscosity.     

Comparison of olefin copolymers as compatibilizers for polypropylene and high‐density polyethylene

Some polyolefin elastomers were compared as compatibilizers for blends of polypropylene (PP) with 30 wt % high‐density polyethylene (HDPE). The compatibilizers included a multiblock ethylene–octene copolymer (OBC), two statistical ethylene–octene copolymers (EO), two propylene–ethylene copolymers (P/E), and a styrenic block copolymer (SBC). Examination of the blend morphology by AFM showed that the compatibilizer was preferentially located at the interface between the PP matrix and the dispersed HDPE particles. The brittle‐to‐ductile (BD) transition was determined from the temperature dependence of the blend toughness, which was taken as the area under the stress–strain curve. All the compatibilized blends had lower BD temperature than PP. However, the blend compatibilized with OBC had the best combination of low BD temperature and high toughness. Examination of the deformed blends by scanning electron microscopy revealed that in the best blends, the compatibilizer provided sufficient interfacial adhesion so that the HDPE domains were able to yield and draw along with the PP matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009