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     

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.

     

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.     

Morphology and mechanical properties of poly (phenylene sulfide)/isotactic polypropylene in situ microfibrillar blends

The morphology and mechanical properties of the in situ microfibrillar blend based on isotactic polypropylene (iPP) and poly (phenylene sulfide) (PPS) were examined. The microfibrillar PPS/iPP blend was prepared through a slit‐die extrusion, hot stretching, and water quenching process. Morphological observation indicated that the well‐defined PPS microfibrils were achieved by the method used in this study, which provided a promising method for both PPS and PP recycling. The morphology study showed that the minimum diameter of PPS phase was independent of PPS concentration. The diameter of most PPS fibrils in the microfibrillar blend was unexpectedly comparable to that of the PPS particles in the common blend at the same PPS content. The tensile strength of microfibrillar blend was higher than that of common blend, indicating the mechanical enhancement of microfibrillar processing to the PPS/iPP blend. The tensile strength of the microfibrillar blend also increased with stretching. POLYM. ENG. SCI., 45:1303–1311, 2005. © 2005 Society of Plastics Engineers     

UHMWPE/HDPE共混物的流动性及力学性能的研究

采用不同MFR的HDPE与UHMWPE进行熔体共混。结果表明UHMWPE／HDPE共混物流动性和力学性能的变化受体系组成、熔体粘度比等因素的影响较大。HDPE的MFR过高、过低或用量过多，均不利于共混物流动性及综合力学性能的改善。当HDPE作为分散相时，易于实现向UHMWPE高粘弹粒子的渗透、分散及结合，共混物的．MFR及拉伸屈服强度、断裂强度、断裂伸长率均比UHMWPE有提高，共混物表现出协同效应；当UHMWPE为分散相或二者熔体粘度比差异过大时，混合效果变差，共混物综合力学性能下降；在某些中间配比下，二者表现出增链缠结效应，共混物MFR明显降低。     

制备HDPE/PA-6阻隔性共混合金工艺条件的研究

本文通过测试HDPE、PA 6的流变性能、共混合金的溶剂透过率和PCM,研究了制得阻隔性层状HDPE/PA 6共混合金工艺条件,如加工温度、剪切速率和混合时间等。结果表明:改变加工温度可以调节HDPE/PA 6共混组成粘度比,当PA 6与HDPE的粘度比较大时,能得到PA 6相呈层状分布结构的阻隔性共混合金;剪切作用有利于共混体系两相的分散,适当的剪切速率有利于使PA 6相形成层状结构。较高的剪切速率使PA 6相尺寸减,分散更均匀,但对提高共混物的阻隔性不利;较短的混合时间可以获得具有阻隔性的HDPE/PA 6共混合金体系     

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.     

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     

Morphology and Tensile Strength Prediction of in situ Microfibrillar Poly(ethylene terephthalate)/Polyethylene Blends Fabricated via Slit‐Die Extrusion‐Hot Stretching‐Quenching

Summary: In situ microfibrillar poly(ethylene terephthalate) (PET)/polyethylene blends (MRB) were successfully fabricated by slit‐die extrusion‐hot stretching‐quenching. The morphology of this new material is mainly influenced by the composition and the hot stretching. Appropriate PET concentrations and a comparatively high hot stretching ratio could facilitate the fibrillation of PET domains during processing. The expression employed for prediction of the tensile strength for the microfibrillar blend was proved to be desirable. The prediction was, generally, in agreement with the experimental results, although the values of some parameters were approximated.

SEM micrograph of the cryofractured surface of the in situ microfibrillar PET/PE blend after injection molding.     

Morphologies and properties of polycarbonate/polyethylene in situ microfibrillar composites prepared through multistage stretching extrusion

The sheets of polycarbonate (PC)/polyethylene (PE) in situ microfibrillar composites are successfully prepared directly through multistage stretching extrusion with an assembly of laminating‐multiplying elements (LMEs) instead of the secondary processing. The morphological development of the PC dispersed phase in PE matrix with increasing the number of LMEs during multistage stretching extrusion investigated by scanning electron microscope shows that core‐skin structure of the microfibrillar PC/PE composites during multistage stretching extrusion with 4 LMEs is weakened, and the diameter of the PC microfibrils is relatively more uniform, indicating that the shear field in LMEs greatly affects the morphology of PC dispersed phase in PE matrix. The tensile, crystalline, melting, orientation and rheological behavior of the PC/PE microfibrillar composites are also investigated. The results show that the PC microfibrils are helpful to increase complex viscosity and yield stress of the PE/PC composites. In addition, it is found that the glass transition temperature of PC in PE matrix reduced with increasing the number of LMEs during dynamic rheological testing. It is coincided with the results of DSC analysis of the PC/PE composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40108.     

增容剂对HDPE/PC共混体系性能的影响

系统研究了增容剂（LDPE-g-DABPA)对高密度聚乙烯（HDPE）／聚碳酸酯（PC）共混体系形态及拉伸性能、冲击性能、热性能、流动性能的影响，确定了增容剂的最佳用量。结果表明，在HDPE／PC／LDPE-g-DABPA为85／15／16时，体系拉伸强度没有变化，而冲击强度由未增容的13．86kJ/m增加到55．31kJ/m，提高了3倍，MFR由1．65g/10min增加到2．16g/10min，用裂纹扩展功（G1c)评价LDPE-g-DABPA的增容效果，结果表明，体系的G1c由增容前的0．0955J增加到0．2025J，说明LDPE-g-DABPA有良好的增容作用。     

PP/HDPE共混体系毛细管流变性能研究

用毛细管流变仪对以马来酸酐接枝聚丙烯(PP-g-MAH)为相容剂的聚丙烯/高密度聚乙烯(PP/HDPE)共混体系的流变性能进行研究。研究发现,PP/HDPE共混体系属于假塑性流体;随着剪切速率的增加,表观黏度下降;PP-g-MAH的加入降低了共混体系的表观黏度;HDPE与PP的非牛顿指数在低剪切速率区与适宜温度下适用于幂律方程的经验公式;HDPE与PP共混后,HDPE含量越低,体系出现壁面滑移的临界剪切速率越高,可加工性能越好。     

高韧性和高流动性PP／EPDM共混材料的研制

研究了乙丙橡胶的门尼粘度和结晶性对聚丙烯增韧效果的影响，结果表明，高门尼粘度，部分结晶性橡胶在获得较好韧性的同时不保持较高的刚性，但流动性较差，通过加入ＨＤＰＥ能在复合增韧的同时提高共混物的流动性，添加少量油酸酰胺和硬脂酰胺敢能适当提高共混物的流动性，采用过氧化物降解聚丙烯可以显著提高共混物的流动性，但韧性明显下降，采用可控降解和动态硫化相结合的技术是在得到高韧性，高流动性共混ＰＰ的有效途径。     

In situ fiber composites based on metallocene polyethylene matrices

Binary blends of metallocene polyethylenes with polyethylenes and polypropylene were made in a co‐rotating twin‐screw extruder. A stretching process was carried out afterwards in the melt state at the extruder's exit to study the effect of the induced orientation on their thermal and tensile properties. Capillary rheometry was performed to the neat polymers to determine the viscosity ratios of the blend components as a function of the shear rate. SEM and Micro‐Raman analyses were done to study the morphology of the stretched and nonstretched blends. As expected, an increase in the modulus and tensile stress was obtained through blending. Additionally, the elastomeric behavior of the metallocene polyethylene (mPE) sample is observed in all blends and it was not lost through blending. Nevertheless, all blends without stretching exhibited a negative deviation of the linear additivity rule of blending. The stretching of the blends made with metallocene polyethylenes as matrices and other types of PEs as dispersed phase did not improve the tensile properties, although some differences in the dispersed phases were found by DSC, and microfibrils could be seen in the drawn mPE/HDPE blend. However, blending with PP produced an improvement in the modulus and tensile stress of the drawn samples in comparison to their undrawn counterpart. The tensile stresses of PP blends are more sensitive to the drawing process than the modulus, which can be attributed to the appearance of large fibril fractions during this process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Inhibited transesterification and enhanced fibrillation of TLCP by nano-SiO2 in polycarbonate matrix

Hybrid composites composed of a thermotropic liquid crystalline polymer (TLCP), nano-SiO₂ and polycarbonate (PC) were prepared by melt blending in a twin-screw extruder. Infrared spectroscopy analysis indicated that the transesterification between PC and TLCP molecules during melt blending was significantly reduced in TLCP/PC blends filled with nano-SiO₂, compared to the unfilled TLCP/PC one. Scanning electron microscopy (SEM) observation showed that better compatibility and finer TLCP dispersion were reached in the unfilled blend, which made the fibrillation of TLCP difficult in capillary flow even at high shear rate. In contrast to this, well-developed TLCP fibrils were formed by capillary flow in nano-SiO₂ filled TLCP/PC blends. By increasing the nano-SiO₂ concentration and shear rate, the fibrillation of TLCP was significantly enhanced. Thermodynamically the interfacial tension between these components and dynamically the viscosity ratio of TLCP to PC were used to investigate the mechanism of nano-SiO₂ in inhibiting the transesterification and enhancing the fibrillation of TLCP droplets in these hybrid composites.     

The viscosity reducing effects of very low concentrations of a thermotropic copolyester in a matrix of HDPE

A thermotropic liquid crystalline polymer (TLCP), denoted as TLCP(1), was used as a processing aid for high density polyethylene (HDPE). The TLCP was a copolyester of hydroxybenzoic acid, hydroquinone and sebacic acid and was blended with HDPE to give 0.2, 0.5 and 2 wt% TLCP(1) blends. At a temperature of 185°C, when TLCP(1) is in the nematic regime, the processing window for HDPE was increased tenfold from a maximum shear rate of 100 s^?1 for pure HDPE to 1170 s^?1 for a 2 wt% TLCP(1) blend. There were large viscosity reductions of between 85% and 90% compared with the pure HDPE when the blended material was used at a wall shear stress value of approximately 2.4 × 10⁵ Pa. This viscosity reduction was attributed to the TLCP(1) droplets changing shape from spheres to slender fibrils under shear flows.     

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。     

High-Density Polyethylene-Ethylene Propylene Rubber-Based Thermoplastic Elastomer: A Mechanical Modeling,Thermal and Rheological Study

The present investigation deals with the mechanical, thermal and rheological properties of binary HDPE/EPR blends at various dispersed phase (EPR) concentrations. The effects of EPR concentration on tensile, impact properties of the pure HDPE and HDPE/EPR blends were studied. Analysis of the tensile data in terms of various theoretical models revealed the variation of stress concentration effect with blend composition. Rheological study was carried out to investigate the change in viscosity with shear rate. DSC results show decrease in percent crystallinity of HDPE upon incorporation of EPR except at 20 wt% rubber concentrations wherein the percent crystallinity has shown marginal increment.     

Mechanical properties of the rubber-toughened polymer blends of polycarbonate (PC) and poly(ethylene terephthalate) (PET)

The intrinsically impact-brittle PC/PET blends can be effectively toughened, in terms of lower ductile brittle transition temperature (DBTT) and reduced notch sensitivity, by incorporating butylacrylate core-shell rubber. The rubber particles are distributed exclusively in the PC phase. Varying the PC melt flow rate (MFR) is more important than varying the PET I.V. to vary the low temperature toughness of the blends. PC with MFR = 3 is essential to produce the toughest PC/PET/rubber blend. The presence of rubber slightly relieves the strain rate sensitivity on yield stress increase. Lower MFR PC in the blend results in smaller activation volume and, therefore, higher strain rate sensitivity, because a greater number of chain segments are involved in the cooperative movement during yielding. Two separate modes, localized and mass shear yielding, work simultaneously in the rubber toughening mechanism. The plane-strain localized shear yielding dominates the toughening mechanism at lower temperatures and brittle failure, while the plane-stress mass shear yielding dominates at higher temperatures and ductile failure. The critical precrack plastic zone volume has been used to interpret the observed phenomenon. © 1994 John Wiley & Sons, Inc.     

Rheological properties and crystalline structure of the dynamically cured EPDM and PP/HDPE ternary blends

The rheological properties and crystalline structure of the polyolefin ternary blends of EPDM/polypropylene/high density polyethylene were studied. Blends were prepared in a laboratory internal mixer by two different methods. In blend–cure process, blending and curing were performed simultaneously and EPDM was cured by dicumyl peroxide (DCP) in the presence of PP/HDPE under shear. The cure–blend was to cure EPDM alone first under shear (dynamic curing) and then mix the cured EPDM with PP and HDPE. The effect of DCP concentration, intensity of the shear mixing, and the rubber/plastic composition were studied using capillary rheometer and X-ray diffractometer. The PP-rich ternary blends showed the effect of the mechanooxidative degradation of PP by shear and peroxide. The melt viscosity increased with increasing DCP concentration in blends of EPDM-rich compositions. X-ray diffraction studies revealed that the inclusion of 25 wt % of linear EPDM in the PP/HDPE mixture for the PP-rich ternary blends changed the crystal structure of polypropylene component in the ternary blends. However, the dynamic curing did not alter the crystal structure of PP or HDPE in the blends.