Processability and thermal properties of blends of high density polyethylene,poly (ethylene terephthalate), and ethyl vinyl acetate compatibilizer

Because of differences in chemical structure and rheological characteristics, high density polyethylene (HDPE) and poly(ethylene terephthalate) (PET) are incompatible when blended during recycling of PET soft drink bottles. To improve the properties of the blends, ethylene vinyl acetate copolymer (EVA) was used as a compatibilizer. Based on torque rheometer tests, the higher the concentration of PET in the blends, the higher the initial loading torque. Blends of 50% HDPE and 50% PET had the lowest equilibrium torque. Equilibrium torque was highest at 5% EVA. The presence of EVA made only a slight difference in the glass transition temperatures of HDPE/PET blends. Higher EVA content in the blend resulted in a lower melting endotherm. Thermogravimetric analysis showed that thermal stability was independent of EVA content; but the more PET in the blend, the lower the final weight loss.     

Chemistry of the ternary blends of poly(ethylene terephthalate), bisphenol-a-polycarbonate,and polypropylene

Poly(ethylene terephthalate) (PET) and bisphenol-a-polycarbonate (PC) are known to form a miscible blend whereas ternary blends of PET, PC, and polypropylene (PP) form two phases. This is based on the considerations of various chemical events which may occur in these systems. The role of ester-carbonate interchange reactions during melt mixing and fabricating is found to be unimportant. Differential scanning calorimetric analysis of the ternary blends shows that there appears to occur an exothermic transition in the heating mode of the instrument. This exothermic event was found to be suppressed considerably by incorporating suitable additives into the system. Degradation reactions studied by thermogravimetric analysis and a dilute solution viscometric technique reveal that there exists some kind of interaction among the components even with the immiscible PP component.     

Antistatic performance and morphological observation of ternary blends of poly(ethylene terephthalate), poly(ether esteramide), and ionomers

Blends of poly(ethylene terephthalate) (PET) and poly (ether esteramide) (PEEA), which is known as an ion conductive polymer, were prepared by melt mixing using a twin screw extruder. Antistatic performance of the molded plaques and the effects of adding ionomers such as lithium neutralized poly(ethylene‐co‐methacrylic acid) copolymer(E/MAA‐Li), magnesium neutralized poly(ethylene‐co‐methacrylic acid) copolymer(E/MAA‐Mg), and zinc neutralized poly(ethylene‐co‐methacrylic acid) copolymer (E/MAA‐Zn) were investigated. Antistatic effect of adding poly(ethylene‐co‐methacrylic acid) copolymer(E/MAA) and polystyrene, and poly(ethylene naphthalate) (PEN) into PET/PEEA blends were also investigated. Here we confirmed that lithium ionomer worked the most effectively in those blend systems. We also confirmed that E/MAA worked to enhance the antistatic performance of PET/PEEA blends. Morphological study of these ternary blends system was conducted by TEM. Specific interaction between PEEA and E/MAA‐Li, and E/MAA were observed. Those ionomers and copolymer domains were encapsulated by PEEA, which could increase the surface area of PEEA in PET matrix. This encapsulation effect explains the unexpected synergy for the static dissipation performance on addition of ionomers and E/MAA to PET/PEEA blends. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) blends

Blends composed of poly(ethylene terephthalate) (PET) as the majority component and poly(ethylene naphthalate)(PEN) as the minority component were melt-mixed in a single screw extruder at various PET/PEN compound ratios. Tensile and flexural test results reveal a good PET/PEN composition dependence, indicating that the compatibility of the blends is effective in a macrodomain. In thermal tests, single transitions for T_g, T_m and T_c (crystallization temperature), respectively, are observed from DSC as well as single T_g from DMA except for 50/50 blends. These results suggests that the compatibility is sufficient down to the submicron level. Moreover, isothermal DSC tests along with Avrami analysis indicate that PET's crystallization is significantly retarded when blended with PEN. Results in this study demonstrate that PEN is a highly promising additive to improve PET's spinnability at high speeds.     

Deformation and morphology development of poly(ethylene terephthalate)/polyethylene and polycarbonate/polyethylene blends with high interfacial contact during elongation

Immiscible blends of poly(ethylene terephthalate) (PET)/polyethylene (PE) and polycarbonate (PC)/PE were examined to study the influence of the high interfacial contact (pseudo‐adhesion) on the mechanical properties and the morphology developed during elongation. The high interfacial contact resulted from the contraction difference of the two polymers during cooling from the processing temperature to room temperature. As a result of the pseudo‐adhesion, the tensile strength and modulus of the PET/PE and PC/PE blends increased steadily with the increase of PET and PC concentration. In PC/PE blends, numerous PC microfibers were formed in‐situ, while in PET/PE blends, slippage took place between the PET particles and the matrix. Moreover, the macroscopic morphology development of both blends upon elongation was quite different. For PET/PE blend, necking was initiated at one point close to the non‐gate end of the specimen, and then propagated uniformly from this point. For the PC/PE blend, necking‐initating sites and propagation were irregular, and consequently the whole tested zone was deformed. The recoil of partially elongated specimens indicated that the recoverability of the PC/PE blend is higher than that of the PET/PE blend. Polym. Eng. Sci. 44:1561–1570, 2004. © 2004 Society of Plastics Engineers.     

Thermal properties and morphology of recycled poly(ethylene terephthalate)/maleic anhydride grafted linear low‐density polyethylene blends

Properties of recycled Poly(ethylene terephthalate) were greatly improved. Recycled PET was blended with LLDPE‐g‐MA by low‐temperature solid‐state extrusion. Mechanical properties of the blends were affected obviously by the added LLDPE‐g‐MA. Elongation at break reaches 352.8% when the blend contains 10 wt % LLDPE‐g‐MA. Crystallization behavior of PET phase was affected by LLDPE‐g‐MA content. Crystallinity of PET decreased with the increase of LLDPE‐g‐MA content. FTIR testified that maleic anhydride group in LLDPE‐g‐MA reacted with the end hydroxyl groups of PET and PET‐co‐LLDPE‐g‐MA copolymers were in situ synthesized. SEM micrographs display that LLDPE‐g‐MA phase and PET phase are incompatible and the compatibility of the blends can be improved by the forming of PET‐co‐LLDPE‐g‐MA copolymer. LLDPE‐g‐MA content was less, the LLDPE‐g‐MA phase dispersed in PET matrix fine. With the increase of LLDPE‐g‐MA content, the morphology of dispersed LLDPE‐g‐MA phase changed from spherule to cigar bar, then to irregular spherule. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical compatibilization of high density polyethylene–poly(ethylene terephthalate) blends

Blends of high density polyethylene (HDPE) and poly(ethylene terephthalate) (PET) exhibit extremely poor mechanical properties owing to the incompatibility of these two polymers. Such blends, however, would result from the reprocessing of certain carbonated beverage bottles. Addition of small amounts of a commercially available triblock copolymer greatly improved the ductility of these incompatible blends, whereas addition of an ethylene–propylene elastomer did not. The results are discussed in terms of phase morphology and interfacial adhesion among the various components.     

Deformation of doubly oriented polyethylene,nylon 66 and poly(ethylene terephthalate)

Doubly oriented specimens of high density polyethylene (HDPE), nylon 66 and poly(ethylene terephthalate) (PET) were re-stretched along a direction perpendicular to the molecular chain axis at temperatures ranging between room temperature and the respective polymer melting points. Brittle failure was observed for PE samples at all the test temperatures with no significant amount of plastic deformation; whereas, for both PET and nylon 66 samples, ductile deformation was observed at elevated temperatures with plastic strain of >400%. The ductile deformation of nylon 66 and PET occurred with an anisotropic change in the cross-sectional dimensions of the specimen, the reduction taking place predominantly in only one lateral direction. The morphological change accompanying the drawing of the doubly oriented PET and nylon 66 material was examined by using X-ray and optical methods. The implications of the difference in deformation behaviour with respect to the morphological differences among oriented PE, PET and nylon 66 materials are discussed.     

Recycled poly(ethylene terephthalate)/linear low‐density polyethylene blends through physical processing

Poly(styrene‐ethylene/butylene‐styrene) (SEBS) was used as a compatibilizer to improve the thermal and mechanical properties of recycled poly(ethylene terephthalate)/linear low‐density polyethylene (R‐PET/LLDPE) blends. The blends compatibilized with 0–20 wt % SEBS were prepared by low‐temperature solid‐state extrusion. The effect of SEBS content was investigated using scanning electron microscope, differential scanning calorimeter, dynamic mechanical analysis (DMA), and mechanical property testing. Morphology observation showed that the addition of 10 wt % SEBS led to the deformation of dispersed phase from spherical to fibrous structure, and microfibrils were formed at the interface between two phases in the compatibilized blends. Both differential scanning calorimeter and DMA results revealed that the blend with 20 wt % SEBS showed better compatibility between PET and LLDPE than other blends studied. The addition of 20 wt % of SEBS obviously improved the crystallizibility of PET as well as the modulus of the blends. DMA analysis also showed that the interaction between SEBS and two other components enhanced at high temperature above 130°C. The impact strength of the blend with 20 wt % SEBS increased of 93.2% with respect to the blend without SEBS, accompanied by only a 28.7% tensile strength decrease. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Improving low‐density polyethylene/poly(ethylene terephthalate) blends with graft copolymers

Blends of low‐density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) were prepared with different weight compositions with a plasticorder at 240°C at a rotor speed of 64 rpm for 10 min. The physicomechanical properties of the prepared blends were investigated with special reference to the effects of the blend ratio. Graft copolymers, that is, LDPE‐grafted acrylic acid and LDPE‐grafted acrylonitrile, were prepared with γ‐irradiation. The copolymers were melt‐mixed in various contents (i.e., 3, 5, 7, and 9 phr) with a LDPE/PET blend with a weight ratio of 75/25 and used as compatibilizers. The effect of the compatibilizer contents on the physicomechanical properties and equilibrium swelling of the binary blend was investigated. With an increase in the compatibilizer content up to 7 phr, the blend showed an improvement in the physicomechanical properties and reduced equilibrium swelling in comparison with the uncompatibilized one. The addition of a compatibilizer beyond 7 phr did not improve the blend properties any further. The efficiency of the compatibilizers (7 phr) was also evaluated by studies of the phase morphology (scanning electron microscopy) and thermal properties (differential scanning calorimetry and thermogravimetric analysis). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactive compatibilization and properties of recycled poly(ethylene terephthalate)/polyethylene blends

Summary Blends of recycled poly(ethylene terephthalate) (R-PET) and high-density polyethylene (R-PE), obtained from post-consumer packaging materials, were prepared both by melt mixing and extrusion processes and compatibilized by addition of various copolymers containing functional reactive groups, such as maleic anhydride, acrylic acid and glycidyl methacrylate. The effect of the type and concentration of compatibilizer, as well as the mixing conditions, on the phase morphology, thermal behaviour, rheological and mechanical properties of the blends was investigated. The results indicated that addition (5÷10 pph) of ethylene-co-glycidyl methacrylate copolymer (E-GMA) allows for a marked improvement of processability and physical/mechanical performances of R-PET/R-PE blends. Received: 1 March 2001/Revised version: 15 November 2001/ Accepted: 28 January 2002     

Melting and solidification behavior of blends of high density polyethylene with poly(butylene terephthalate)

This study focuses on the effect of various processing and cooling conditions upon the subsequent melting and solidification behavior of blends of poly(butylene terephthalate) (PBT) and high density polyethylene (HDPE). Differential scanning calorimetry (DSC) measurements have shown that the crystallization of reprocessed PBT is different from the crystallization behavior of virgin samples. Two melting endotherms for PBT were observed for reprocessed PBT and for PBT-PE blends. The nature of each PBT peak is discussed in relation to processing history, solidification conditions, and composition. The presence of two crystallization peaks for the PE component in blends of PE and PBT are thought to be associated with the restriction of molecular motion of PE in the presence of the second component. The relative magnitudes of the two exotherms of PE vary with composition and cooling rate during solidification.     

Morphological origin of super toughness in poly(ethylene terephthalate)/polyethylene blends

A compatibilization strategy for poly(ethylene terephthalate) (PET) and polyethylene (PE) blends to achieve high toughness is described. Maleic anhydride functionalized styrene–ethylene–butylene–styrene (MA-g-SEBS) block copolymer at 20 pph was found to produce an intricate multidomain morphology in which the two major components (50% PE, 50% PET) and the compatibilizer coexist on a hierarchal order. A portion of the PET was dispersed as interconnected rodlike domains oriented along the injection direction. The rest of the PET and the PE constituted beadlike nano domains which served as the matrix. The blend at all these morphological levels responded to deformation in a cooperative fashion giving rise to a super tough material. That is, a blend whose elongation at break (600%) was superior to its two major components (90% for PET and 300% for PE). © 1993 John Wiley & Sons, Inc.     

High-impact poly(ethylene terephthalate) blends

Rubbers of different kind were tested as toughening agents of poly(ethylene terephthalate) (PET), noting significant morphological and mechanical differences. In particular, good results were obtained by using an ethylene–ethyl acrylate–glycidyl methacrylate copolymer. The resulting blend evidenced good particle distribution, and the latter was related to chemical interactions between the rubber epoxy groups and PET terminal groups, including the effect of low molecular weight and polymeric amine catalysts, and to extrusion conditions. © 1995 John Wiley & Sons, Inc.     

A comparison of the flow behavior of linear polyethylene,poly(butylene terephthalate), and poly(ethylene terephthalate)

The viscous and elastic properties of linear high density polyethylene (HDPE), poly(butylene terephthalate) (PBT), and poly(ethylene terephthalate) (PET) are investigated using an Instron capillary rheometer and the Philippoff–Gaskins–Bagley analysis. The viscous properties studied are the shear viscosity and the constant shear rate activation energy and the elastic properties studied are the entrance pressure drop and the end correction. The variables are shear rate and temperature. The order of decreasing viscosity is HDPE>PET>PBT; the order of decreasing activation energy is PB>PET>HDPE; the order of decreasing entrance pressure drop is HDPE>PET>PBT; and the order of decreasing end correction is PBT>PET>HDPE. As temperature increases, both viscosity and entrance pressure drop decrease. The observed behavior is discussed in terms of the difference in number of terephthalic acid moities in the polymer chains and in terms of oligomer plasticization.     

Improving poly(ethylene terephthalate)/high-density polyethylene blends by using graft copolymers

The synthesis and the application of graft copolymers prepared from ozonized polyethylene (HDPE) are described. The homopolymer was treated with ozone and then copolymerized with monomers, such as methyl methacrylate, hydroxy ethyl methacrylate, glycidyl methacrylate, maleic anhydride, and ethyl acrylate. The products were used as compatibilizers in HDPE/PET [poly(ethylene terephthate)] blends. The mechanical properties and the influence of graft comonomers are described. The copolymers were characterized by the grafting rate and FTIR spectroscopy.     

Properties of ultrasound-assisted blends of poly(ethylene terephthalate) with polycarbonate

This study investigated the effect of ultrasound irradiation on blends of polyethylene terephtalate (PET) and polycarbonate (PC). The blends of PET/PC were prepared by a twin-screw extruder with an attached ultrasonic device. Thermal, rheological, and mechanical properties and morphology of the blends with and without sonication have been analyzed. The two distinct T_gs of the blends measured by DSC showed immiscibility over all compositions. The theoretical PET content that is miscible in PC-rich phase calculated using the Fox equation showed that ultrasonic waves made the blends more miscible. From mechanical test results, when sonication was not applied, the 20/80 blend was the most miscible composition. At that composition, the impact strength of sonicated blend was surprisingly high. It was believed to be due to the enhancement of compatibility by a reaction such as transesterification. The results from the morphology of the 20/80 sonicated blend were in agreement with DSC and impact test results.     

Reactive compatibilization of poly(butylene terephthalate)/low‐density polyethylene and poly(butylene terephthalate)/ethylene propylene diene rubber blends with a bismaleimide

The reactive compatibilization effect of a small molecule, bismaleimide (BMI), on poly(butylene terephthalate) (PBT)/low‐density polyethylene (LDPE) and PBT/ethylene propylene diene (EPDM) rubber blends were investigated. All the blends were prepared by melt blending in the mixing chamber of a Haake Rheocord. The particle size of dispersed phase was reduced by >ten times by adding 1.2 wt % of BMI as observed with scanning electron microscopy. The torque‐time curve recorded during mixing showed that the addition of BMI leads to a significant increase in the viscosity of PBT, LDPE, EPDM, and the blends. This indicates that a chemical reaction has taken place. It was confirmed that free radicals are involved in the reactions because the addition of a stabilizer to the blends has removed all the compatibilizing effect, and the torque‐time curve does not show any increase in viscosity. A possible mechanism of compatibilization is proposed. The shear forces during melt mixing cause the rupture of chemical bond in the polymers, which form macroradicals of PBT, LDPE, or EPDM. These macroradicals react with BMI to form PBT‐BMI‐LDPE or PBT‐BMI‐EPDM copolymers. These in situ‐formed copolymers act as compatibilizers to give a significant refinement of the blend morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2049–2057, 1999     

Crystallization in blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Blends composed of poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) were melt-mixed in a Brabender cam mixer at different mixing speeds. The glass transition (T_g) and the crystallization behavior of the blends from glassy state were studied using DSC. It was found that although the blends had the same composition and exhibited the similar T_g, their properties of crystallization could be different; some exhibited a single crystallization peak and some exhibited multiple crystallization peaks depending upon experimental conditions. Results indicated that the behavior of crystallization from glassy state were influenced by entanglement and transesterification of chains. The crystallization time values were obtained over a wide range of crystallization temperature. From curve fitting, the crystallization time values and the temperature, at which the crystallization rate reaches the maximum, were found.     

Morphology and barrier mechanism of biaxially oriented poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

To improve the barrier properties of poly(ethylene terephthalate) (PET), PET/poly(ethylene 2,6‐naphthalate) (PEN) blends with different concentrations of PEN were prepared and were then processed into biaxially oriented PET/PEN films. The air permeability of bioriented films of pure PET, pure PEN, and PET/PEN blends were tested by the differential pressure method. The morphology of the blends was studied by scanning electron microscopy (SEM) observation of the impact fracture surfaces of extruded PET/PEN samples, and the morphology of the films was also investigated by SEM. The results of the study indicated that PEN could effectively improve the barrier properties of PET, and the barrier properties of the PET/PEN blends improved with increasing PEN concentration. When the PEN concentration was equal to or less than 30%, as in this study, the PET/PEN blends were phase‐separated; that is, PET formed the continuous phase, whereas PEN formed a dispersed phase of particles, and the interface was firmly integrated because of transesterification. After the PET/PEN blends were bioriented, the PET matrix contained a PEN microstructure consisting of parallel and extended, separate layers. This multilayer microstructure was characterized by microcontinuity, which resulted in improved barrier properties because air permeation was delayed as the air had to detour around the PEN layer structure. At a constant PEN concentration, the more extended the PEN layers were, the better the barrier properties were of the PET/PEN blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1309–1316, 2006