增容剂对PP/PET原位微纤化共混物的影响

通过"熔融挤出-热拉伸-淬冷"的方法制备了原位微纤化共混物。采用扫描电镜、差示扫描量热仪和力学性能测试等方法研究了增容剂PP-g-GMA含量对共混物微观形态、力学性能和结晶性能的影响。结果表明,增容剂的加入可明显提高两相相容性,改善界面效果,明显降低拉伸前初始粒子的尺寸,但同时使拉伸后形成的微纤呈现一定的损坏,长径比有所降低。增容剂可以明显改善微纤化共混物力学性能,当其含量为2 %（质量分数,下同）时拉伸强度比未增容试样提高了11.0 %,弯曲强度都提高了11.3 %;当其含量为6 %时冲击强度也比未增容共混物提高了34.5 %。此外,PET微纤对PP有很好的异相成核作用,使其结晶温度提高了16.3 ℃,结晶时间为纯PP的32 %左右,而增容剂的加入使共混物中PP的结晶时间延长。     

Morphology and Mechanical Properties of Normal Blends and In-Situ Microfibrillar Composites from Low-Density Polyethylene and Poly(ethylene terephthalate)

In this work, normal blends, microfibrillar blends and composites were prepared from low density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) in 85/15 and 75/25 w/w% ratio in the presence and absence of a compatibilizer polyethylene grafted with maleic anhydride (PE-g-MA). The microfibrillar composites (MFCs) were prepared using extrusion – drawing – isotropization technique. The morphology development of the microfibrillar blends and composites was studied using scanning electron microscopy (SEM). The presence of 5 wt% PE-g-MA compatibilizer affected the continuity of the fibrils differently in 75/25 and 85/15 w/w% microfibrillar blends. In the case of normal blends the addition of compatibiliser reduced the size of the dispersed PET phase. The presence of PET microfibrils improved the tensile properties of the microfibrillar composites. The normal blends exhibited a relatively ductile failure during tensile loading in comparison with the microfibrillar composites. The microfibrillar nature of the dispersed phase was found to improve the stiffness of the composite rather than their impact strength.     

Morphology development and non isothermal crystallization behaviour of drawn blends and microfibrillar composites from PP and PET

Microfibrillar composites (MFC) were prepared from the blends of polypropylene (PP) and poly (ethylene terephthalate) (PET) at a fixed weight ratio of 85/15. The blending of the mixture was carried out in a single screw extruder, followed by continuous drawing at a stretch (draw) ratio 5. The stretched blends were converted into MFC by injection moulding. Scanning electron microscopy (SEM) studies showed that the extruded blends were isotropic, but both phases possessed highly oriented fibrils in the stretched blends, which were generated insitu during drawing. The PET fibrils were found to be randomly distributed in the PP matrix after injection moulding. The non isothermal crystallization behaviour of the as extruded blend, stretched blend and MFC was compared. The analysis of the crystallization temperature and time characteristics revealed that the PET fibrils in the stretched blend had a greater nucleating effect for the crystallization of PP than the spherical PET particles in the as extruded blend and short PET fibrils in the MFC.     

In situ fibrillation of isotactic polypropylene in ethylene-vinyl acetate: Toward enhanced rheological and mechanical properties

In situ microfibrillar reinforced composites with ethylene-vinyl acetate (EVA) as matrix and isotactic polypropylene (iPP) as dispersed fibrils were successfully fabricated by multistage stretching extrusion with an assembly of laminating-multiplying elements (LMEs). Four types of EVA with different apparent viscosity were utilized to study the influence of viscosity ratio on the morphology and mechanical properties of EVA/iPP in situ microfibrillar blends. The scanning electron micrographs revealed that the dividing–multiplying processes in LMEs could effectively transform the morphology of iPP phase into microfibrils and the morphology of iPP microfibrils strongly depended on the viscosity ratio. Higher viscosity ratio was favorable for formation of finer microfibrils with narrower diameter distribution. The morphology development of iPP with different viscosity ratio greatly affected the rheological and mechanical properties of EVA/iPP blends. The dynamic rheological results shown that the iPP microfibrils were helpful to increase the storage modulus and loss modulus. The tensile test indicated that the mechanical properties of EVA/iPP blends were controlled by the morphology of iPP phase and the polarity of EVA matrix. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47557.     

In situ poly(ethylene terephthalate) microfibers- and shear-induced non-isothermal crystallization of isotactic polypropylene by on-line small angle X-ray scattering

In situ microfibrillar reinforced blend (MRB) based on poly(ethylene terephthalate) (PET) and isotactic polypropylene (iPP) was elaborated by a slit die extrusion, hot stretching, and quenching process. The scanning electronic microscopic images show well-developed PET microfibers in the blends. The on-line small angle X-ray scattering (SAXS) test shows that PET microfibers have high nucleation for iPP crystallization. At the same time, after shear, neat iPP and microfibrillar blend both can faster crystallization rate. Three nucleation origins are proposed in microfibrillar reinforced blends under shear flow field: (a) the classical row nuclei model, (b) fiber nuclei and (c) nuclei induced by fiber assistant alignment. The polarized optical microscopic images indicate that, during the non-isothermal crystallization at a cooling rate of 10 °C/min from 200 °C to room temperature, the neat iPP forms common spherulites, while the diluted microfibrillar blend with 1 wt% of PET has a typical transcrystalline structure.     

挤出加工方法对制备PP/PET原位微纤共混物微观形态的影响

分别使用双螺杆挤出机、配备不同结构螺杆或强剪切机头的单螺杆挤出机对聚丙烯(PP)/聚对苯二甲酸乙二醇酯(PET)进行熔融共混挤出,并用扫描电子显微镜观察了产物的微观形态。结果表明,使用双螺杆挤出机或使用配备三段式螺杆的单螺杆挤出机挤出PP/PET,只能制备出PET以球状形态均匀分散在PP连续相中的共混物,不含有任何微纤;使用配备有头部直槽混炼件的单螺杆挤出机挤出PP/PET,部分PET会形成短而粗的微纤;采用熔融挤出热拉伸淬冷法挤出PP/PET,可生产出微纤直径约为5 μm、长径比超过20的原位微纤共混物;采用强剪切机头及头部配备有直槽混炼件螺杆的单螺杆挤出机挤出PP/PET,可生产出微纤直径约为5~7 μm、长径比超过20的原位微纤共混物,且该方法操作简单、辅助设备少、具有工业可行性。     

Melting,crystallization behaviors,and nonisothermal crystallization kinetics of PET/PTT/PBT ternary blends

The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (T_g) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t_1/2 and the parameters Z_c showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Morphology and electrical properties of carbon black/poly(ethylene terephthalate)/polypropylene composite

This work attempts to develop a carbon black (CB) filled conductive polymer composite based on poly(ethylene terephthalate) (PET) and polypropylene (PP). The process follows by localizing the CB particles in the minor phase (PET), and then the conductive masterbatch was elongated to form conductive microfibrils in PP matrix during melt extrusion process. After compression molding, a fine conductive three‐dimensional microfibrillar network is constructed. For comparison purpose, CB, PET, and PP are mixed using different pattern. The morphology and the volume resistivity of the obtained composites are evaluated. Electrical conductivity investigation shows that the percolation threshold and resistivity values are dependent on the CB concentration. The best morphological observation shows that the PET phases forms well‐defined microfibrils, and CB particles overwhelmingly localize in the surfaces of the PET microfibrils, which led to a very low percolation threshold, i.e., 4.5 phr, and a reasonable conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

In situ polymer/polymer composites from poly(ethylene terephthalate), polyamide-6, and polyamide-66 blends

In situ reinforced binary and ternary polymer/polymer composites are obtained by the melt blending of poly(ethylene terephthalate) (PET), polyamide-6 (PA-6), and polyamide-66 (PA-66) in an extruder in the presence of a catalyst, followed by drawing of the extrudate and annealing of the drawn blends. The blends were studied by DSC, X-ray, SEM, and mechanical testing. After drawing, all the components were found to be oriented, forming microfibrils with diameters of about 1–2 μm. The chemical nature of the homopolymers affects the blends' morphologies; while the PA-66/PA-6 blend is homogeneous, phase separation is established in the case of PET/PA-6. The decrease in the enthalpy of melting of the blend components as well as the depression of their peaks of crystallization from the melt, compared to pure homopolymers, are indications that block copolymers have been formed via interchange reactions during the blending process. On the one hand, these copolymers improve the compatibility of the homopolymers, and on the other hand, they alter the chemical composition of the blends. After thermal treatment at 245°C, i.e., above the T_m of PA-6, the latter undergoes some disorientation, while PET and PA-66 retain their microfibrillar shape, and in this way, a compositelike structure is created. The presence of chemical bonds between the separate phases via copolymers favors the cocrystallization of PA-66 and PA-6 as well as the cooperative crystallization of PET, PA-6, and PA-66, both modes fostering improved compatibility (adhesion) of the blend components. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 723–737, 1998     

Oriented monofilaments from blends of poly(ethylene terephthalate) and polypropylene

Poly(ethylene terephthalate) and polypropylene are considered, to be incompatible by the usual criteria for polymer blends. Sheath/core filaments of these polymers could not be oriented because of poor adhesion of the base polymers. Melt blends of the two polymers with 30 and 50 weight percent polypropylene produced useful, oriented monofilaments. Tensile and dynamic mechanical properties of these filaments indicate that the structures consist of interlocked microfibrillar domains of the polyester and polyolefim. The glass transition region of poly(ethylene terephthalate) is not affected by admixture with polypropylene. A fine mutual dispersion of the two polymers was possible because the melt viscosities of the ingredients were reasonably well matched under the conditions of mixing. The melt viscosity and elasticity of blends were lower than those of either component as expected if the two polymers are immiscible. Monofilament extrusion and melt flow measurements were made with a one-half inch single screw extruder.     

Electrically Conductive Carbon Black/Poly(Ethylene Terephthalate)/Polyethylene Microfibrillar Composite: The influence of CaCO3 Nanoparticles

The influence of a complex filler system on the electrical properties of a microfibrillar conductive polymer composite (MCPC) is discussed. By adding insulating filler, nano-CaCO₃, to carbon black (CB)-filled MCPC, the morphology of the poly(ethylene terephthalate) (PET) microfibrillar phase was tailored according to the ratio of CB/nano-CaCO₃, and so were the electrical properties of MCPC. It was found that nano-CaCO₃ did not influence electrical properties in a monotone way. With an increase in nano-CaCO₃ content, on one hand, the surface of the microfibrils became smoother, which jeopardized the conductivity of the MCPC. At the same time, the nano-CaCO₃ particles substituted for the CB particles on the surface of the microfibrils and further decreased conductivity. On the other hand, longer and better-defined microfibrils could form, which enhanced the conductive network and increased the conductivity of the MCPC. As a result, the percolation threshold changed little compared to the common CB-filled MCPC.     

Effect of microfiber reinforcement on the morphology,electrical, and mechanical properties of the polyethylene/poly(ethylene terephthalate)/carbon nanotube composites

In situ microfiber reinforced conductive polymer composites consisting of high‐density polyethylene (HDPE), poly(ethylene terephthalate) (PET), and multiwalled carbon nanotube (CNT) were prepared in a twin screw extruder followed by hot stretching of PET/CNT phase in HDPE matrix. For comparison purposes, the HDPE/PET blends and HDPE/PET/CNT composites were also produced without hot stretching. Extrusion process parameters, hot‐stretching speed, and CNT amount in the composites were kept constant during the experiments. Effects of PET content and molding temperature on the morphology, electrical, and mechanical properties of the composites were investigated. Morphological observations showed that PET/CNT microfibers were successfully formed in HDPE phase. Electrical conductivities of the microfibrillar composites were in semi‐conductor range at 0.5 wt% CNT content. Microfiber reinforcement improved the tensile strength of the microfibrillar HDPE/PET/CNT composites in comparison to that of HDPE/PET blends and HDPE/PET/CNT composites prepared without hot stretching. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Crystalline morphology of isotactic polypropylene (iPP) in injection molded poly(ethylene terephthalate) (PET)/iPP microfibrillar blends

The poly(ethylene terephthalate) (PET)/isotactic polypropylene (iPP) in situ microfibrillar blends have been prepared through a “slit die extrusion-hot stretch-quenching” process, in which PET assumes microfibrils with 0.5-15 μm in diameter depending on the hot stretching ratios (HSR, the area of the transverse section of the die to the area of the transverse section of the extrudate). The injection molded specimens of virgin iPP and the PET/iPP blends were prepared by conventional injection molding (CIM) and by shear controlled orientation injection molding (SCORIM), respectively. The effect of shear stress and PET phase with different shape on superstructures and their distribution of injection molded microfibrillar samples were investigated by means of small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS). The shear (or elongational) flow during CIM and SCORIM can induce oriented lamellae (i.e. kebabs induced by shish). The shish-kebab structure appears not only in the skin and intermediated layers of CIM samples, but also in the whole region of SCORIM samples. For the neat iPP samples, a more “stretched” shish-kebab structure with higher orientation degree can be obtained in the interior region (intermediate and core layers) by the SCORIM method; moreover, the SCORIM can result in the growth of β-form crystal both in intermediate layer and in core layer, which only appears in intermediate layer of the neat iPP samples obtained by CIM. For the PET/iPP blends, interestingly, the addition of microfibrils as well as their aspect ratios can affect the orientation degree of kebabs only in the intermediate layers, and the addition of microfibrils with a low aspect ratio can bring out a considerable increase in the orientation degree of kebabs along the flow direction. However, for the SCORIM, the addition of microfibrils seems to be a minor effect on the orientation degree of kebabs, and it tends to hamper the formation of a more “stretched” shish-kebab structure and suppresses the growth of β-form crystal distinctly. Furthermore, It appears from experiment that γ-form crystals can grow successfully in this oriented iPP melt with the synergistic effect of shear and pressure only when the growth of β crystals can be restrained by some factors, such as the PET dispersed phase and thermal conditions (cooling rate).     

The impact performance of thermoplastic sheet composites

Sheet composites of polypropylene and poly(ethylene terephthalate) were produced by melt consolidation of alternating layers of polymer films and random glass fiber mats. The composites had a nominal glass content of 50 wt% (～30 vol%). The sheets were stamped into a complex part from which test specimens were machined, and mechanical properties determined. Flexural strengths as high as 159 MPa were recorded for polypropylene composites and 313 MPa for poly(ethylene terephthalate) composites. The flexural modulus of the polypropylene composites reached 9.1 MPa, whereas the modulus of the stiffest poly(ethylene terephthalate) composite was 15 GPa. The impact properties of the composites were equally high. Polypropylene composites absorbed up to 257 J/cm during an instrumented falling dart impact test. Poly(ethylene terephthalate) composites absorbed as much as 116 J/cm in the same test.     

Rheological behavior comparison between PET/HDPE and PC/HDPE microfibrillar blends

The rheological behaviors of in situ microfibrillar blends, including a typical semicrystalline/semicrystalline (polyethylene terephthalate (PET)/high‐density polyethylene (HDPE)) and a typical amorphous/semicrystalline (polycarbonate (PC)/HDPE) polymer blend were investigated in this study. PET and PC microfibrils exhibit different influences on the rheological behaviors of microfibrillar blends. The viscosity of the microfibrillar blends increases with increased PET and PC concentrations. Surprisingly, the length/diameter ratio of the microfibrils as a result of the hot stretch ratio (HSR) has an opposite influence on the rheological behavior of the two microfibrillar blends. The stretched PET/HDPE blend exhibits higher viscosity than the unstretched counterpart, while the stretched PC/HDPE blend exhibits lower viscosity than the unstretched blend. The data obtained in this study will be helpful for constructing a technical foundation for the recycling and utilization of PET, PC, and HDPE waste mixtures by manufacturing microfibrillar blends in the future. POLYM. ENG. SCI., 45:1231–1238, 2005. © 2005 Society of Plastics Engineers     

Mechanical and fracture characterization of 50:50 HDPE/PET blends presenting different phase morphologies

Uncompatibilized and compatibilized blends of poly(ethylene terephthalate) (PET) and high‐density polyethylene (HDPE) (50:50 PET/HDPE) have been prepared and characterized. A commercial grade of ethylene/methacrylic acid copolymer was used as compatibilizing agent and added to the blends in two different proportions, 1% and 7%. Compounded blends were processed following three different procedures: compression molding, extrusion, and extrusion followed by annealing. In every case, there is evidence that suggests that HDPE constitutes the matrix and PET is the dispersed phase. The PET phase shape was related to the processing procedure of the blends. PET adopted a globular morphology in the compression molded samples but it took the form of microfibers (microfibrillar‐like reinforced composites) in extruded samples, which were flattened during the postextrusion annealing process. According to the results obtained in tensile and fracture tests, extruded blends having 7% of ethylene/methacrylic acid copolymer appeared as the optimum combination of processing method and compatibilizer content. POLYM. ENG. Sci., 45:354–363, 2005. © 2005 Society of Plastics Engineers     

Crystallization of oriented isotactic polypropylene (iPP) in the presence of in situ poly(ethylene terephthalate) (PET) microfibrils

The present article reports the nonisothermal crystallization process and morphological evolution of oriented iPP melt with and without in situ poly(ethylene terephthalate) (PET) microfibrils. The bars of neat iPP and PET/iPP microfibrillar blend were fabricated by shear controlled orientation injection molding (SCORIM), which exhibit the oriented crystalline structure (shish-kebab), especially in the skin layer. The skin layer was annealed at just above its melting temperature (175 °C) for a relatively short duration (5 min) to preserve a certain level of oriented iPP molecules. It was found that the existence of ordered clusters (i.e. oriented iPP molecular aggregates) leads to the primary nucleation at higher onset crystallization temperature, and formation of the fibril-like crystalline morphology. However, the overall crystallization rate decreases as a result that the relatively high crystallization temperature restrains the secondary nucleation. With the existence of PET microfibrils, the heterogeneous nucleation distinctly occurs in the unoriented iPP melt and results in the increase of crystallization peak temperature and overall crystallization rate, for the first time, we observed that the onset crystallization temperature has been enhanced further with addition of PET microfibrils in the oriented iPP melt, indicating the synergistic effect of row nucleation and heterogeneous nucleation under quiescent condition.     

增容作用对PP/PA6原位微纤复合材料形貌及性能的影响

以马来酸酐接枝聚丙烯(PP-g-MAH)为增容剂,采用熔融挤出-热拉伸法制备了聚丙烯(PP)/聚酰胺6(PA6)/PP-g-MAH原位微纤复合材料.研究了复合材料的微观相形态以及结晶、流变和力学性能.结果表明,加入0.5％(质量分数,下同)的PP-g-MAH有利于大长径比PA6微纤的形成;而当PP-g-MAH的含量继续...     

Microstructure and crystallization of melt‐mixed poly(ethylene terephthalate)/poly(ethylene isophthalate) blends

Physical blends of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), abbreviated PET/PEI (80/20) blends, and of PET and a random poly(ethylene terephthalate‐co‐isophthalate) copolymer containing 40% ethylene isophthalate (PET₆₀I₄₀), abbreviated PET/PET₆₀I₄₀ (50/50) blends, were melt‐mixed at 270°C for different reactive blending times to give a series of copolymers containing 20 mol % of ethylene isophthalic units with different degrees of randomness. ¹³C‐NMR spectroscopy precisely determined the microstructure of the blends. The thermal and mechanical properties of the blends were evaluated by DSC and tensile assays, and the obtained results were compared with those obtained for PET and a statistically random PETI copolymer with the same composition. The microstructure of the blends gradually changed from a physical blend into a block copolymer, and finally into a random copolymer with the advance of transreaction time. The melting temperature and enthalpy of the blends decreased with the progress of melt‐mixing. Isothermal crystallization studies carried out on molten samples revealed the same trend for the crystallization rate. The effect of reaction time on crystallizability was more pronounced in the case of the PET/PET₆₀I₄₀ (50/50) blends. The Young's modulus of the melt‐mixed blends was comparable to that of PET, whereas the maximum tensile stress decreased with respect to that of PET. All blend samples showed a noticeable brittleness. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3076–3086, 2003     

Recyclability of In Situ Microfibrillar Poly(ethylene terephthalate)/High‐Density Polyethylene Blends

Repetitive processing was employed to assess the recyclability of in situ microfibrillar poly(ethylene terephthalate) (PET)/high‐density polyethylene (HDPE) blends which were fabricated through a “rectangular slit die extrusion–hot stretching–quenching” process. For comparison, the conventional PET/HDPE blends were also obtained using the same processing operation but without hot stretching. The morphological observation indicated that slit die extrusion and hot stretching successfully made the dispersed PET phase deform in situ into well‐defined microfibrils. The average diameter of the microfibrils increased with the processing cycles. The rheological properties obtained from the parallel‐plate dynamic rheometer suggested that the microfibrillar blends have higher viscosity and viscoelastic moduli (storage and loss moduli) as well as better flow stability than the conventional PET/HDPE blend. More importantly, with the increase in the processing cycles, an increase in yield strength and unchanged tensile modulus were observed for in situ microfibrillar blends, while a decrease in these properties for conventional blend, indicating that the in situ microfibrillar PET/HDPE blends have promising recycling potential.