In Situ Microfibril Structure in Incompatible Isotactic Polypropylene/Polylactic Acid Blends Controlled By Viscosity Ratio

In situ microfibril structure can significantly improve the mechanical properties of incompatible blends. In this work, the in situ microfibrils were constructed in isotactic polypropylene/polylactic acid (iPP/PLA) blends by direct injection molding process, and the effect of viscosity ratio on the morphology was systematically analyzed. The results of scanning electron microscope and rheology show that the viscosity ratio plays a decisive role in the formation of in situ microfibrils. When the viscosity ratio of PLA/iPP is near 1, deformation and microfibrillation of PLA particles can be conducted due to the larger and more uniform distributed PLA domains as well as stronger viscous drag forces. However, irregular cylinders are observed when the viscosity ratio is far lower than 1. The poor deformation ability of PLA particles should be attributed to the much smaller size and weaker viscous drag forces. The well-defined PLA microfibrils are conducive to avoid damage at the interface, and play a significant role in the enhancement of tensile strength and modulus. This work can simplify the traditional preparation process, construct in situ microfibrils directly by using conventional melt processing techniques and provide a new ideal for the high performance of incompatible polymer blends. POLYM. ENG. SCI., 60:832–840, 2020. © 2020 Society of Plastics Engineers     

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.     

In situ fibrillation of poly(trimethylene terephthalate) in polyolefin elastomer through multistage stretching extrusion

Polyolefin elastomer (POE)/poly(trimethylene terephthalate) (PTT) microfibrillar composites (MFCs) were successfully fabricated by multistage stretching extrusion with an assembly of laminating‐multiplying elements (LMEs). The morphologies of these novel materials were greatly influenced by the compositions. The number of microfibrils increased with increasing PTT concentration, as revealed by scanning electron microscopy. The tensile strength was the highest along the extrusion direction at the weight ratio of 85/15. Moreover, dynamic rheological results showed that the storage modulus, loss modulus, and complex viscosity were the highest while the tan δ was the lowest for MFCs prepared at the weight ratio 85/15 compared with the neat POE, especially at low frequency (ω < 1 rad/s). In addition, the PTT microfibrils had more effect on the rheological properties compared to the PTT particles. However, the differences became negligible at high frequency (ω > 100 rad/s). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43797.     

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     

Effect of dispersed phase on the morphology of in situ microfibrils and the viscoelastic properties of its composite via direct extrusion

A triangle arrayed triple‐screw extruder was used to prepare in situ polypropylene (PP) microfibrillar composites (MFCs) by direct extrusion, in which polyamide 6,6 (PA66) and poly(butylene terephthalate) (PBT) were used as dispersed phases while PP as matrix phase. The morphological evolution of the dispersed phase were investigated by SEM through taking samples along the extruder from different positions. The results showed that the fibrillating mechanism of PA66 was entirely different from that of PBT. Dynamic oscillatory shear rheological properties were used to analyze the effect of different types of in situ microfibrils on the rheological properties of MFCs. The obtained results showed that the storage modulus and complex viscosity of both PP/PA66 and PP/PBT MFCs were improved with increasing fibrillar aspect ratios. The loss tangent tan δ at low frequencies decreased with the increase of fibrillar aspect ratio. Moreover, the gel point concentration of PP/PA66 composite was lower than that of PP/PBT composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46286.     

Dispersed microfibril‐dominated deformation and fracture behaviors of linear low density polyethylene/isotactic polypropylene blends

Linear low density polyethylene/isotactic polypropylene (LLDPE/iPP) blends, with oriented microfibrils of iPP dispersed in the nearly isotropic LLDPE matrix, has been prepared via melt extrusion drawing and subsequent thermal treatment at 160°C to melt LLDPE matrix. The presence of oriented microfibrils of iPP in the LLDPE/iPP blends not only promotes the homogenous deformation, with no drop of nominal stress around yield point, but also enhances the fracture toughness significantly. The specific Essential Work of Fracture w_e, which is a pure crack resistance parameter per ligament area unit, is 24.7 and 33.6 N/mm for the blends with 15 and 30 wt % microfibrils of iPP, respectively. Moreover, with the deduced deformation parameters, such as true yield stress and strain hardening modulus, the relationship between deformation parameters and fracture toughness is explored. It is demonstrated that the fracture toughness can be well correlated with the ratio of true yield stress to strain hardening modulus σ_ty/G, and either a decrease in yield stress or an increase in strain hardening can improve fracture toughness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1291–1298, 2007     

EVA熔体流动速率对PLA/EVA共混物性能的影响

通过熔融共混法制备了聚乳酸（PLA）/乙烯-乙酸乙烯酯共聚物（EVA）共混物,采用SEM、DSC、旋转流变仪等研究了VA质量分数为28%,熔体流动速率（MFR）不同的EVA对PLA/EVA共混物性能的影响。结果表明,EVA熔体流动速率越小,其在PLA基体中分散越均匀,EVA颗粒粒径也越小。共混物的结晶度随EVA熔体流动速率的增大而增大,但PLA的玻璃化转变温度（Tg）基本不受EVA的影响。PLA/EVA共混物的复数黏度和储能模量均随EVA的熔体流动速率的增高而减小。力学性能测试结果表明,当EVA的质量分数为15%时,PLA的断裂伸长率明显升高,冲击强度约是纯PLA的2倍。     

Morphology and Rheological Behaviors of Polycarbonate/High Density Polyethylene in situ Microfibrillar Blends

Summary: Polycarbonate (PC)/high density polyethylene (HDPE) in situ microfibrillar blends were fabricated by a slit die extrusion, hot stretching, and quenching process. Despite PC and HDPE having a high viscosity ratio, which is usually disadvantageous to fibrillation, the morphological observation indicated that the blends had well‐defined PC microfibrils. The size and amount of the PC fibrils were nonuniform through the thickness of the extrudate, and were also affected by the PC concentration and hot stretch ratio. There were coarse and dense fibrils in the core zone, while these fibrils became finer and reduced in number toward the surface. The melt flow rate (MFR) of the PC/HDPE microfibrillar blend decreased with the increase of PC concentration, but increased with the larger hot stretching rate (or hot stretching ratio, HSR). Besides, it was found that the fibrillar blend had better flowability than the common blend with spherical particles at the same PC concentration. Temperature was also an important factor influencing the MFR due to the temperature dependence of PC and HDPE viscosity, and the PC phase morphology. The PC microfibrils could not be preserved beyond 230 °C and transformed into spherical particles. The rheological behaviors at various shear rates were studied by capillary rheometer. The orientation of PC fibrils and HDPE molecules with higher shear rate led to a decrease in the viscosity of microfibrillar blend. The data obtained in this study can help construct the technical foundation for recycling and utilization of PC and HDPE waste by manufacture of microfibrillar blends in future work.

SEM micrograph of the PC/HDPE microfibrillar blend.     

Microscopic morphology,rheological behavior,and mechanical properties of polymers: Recycled acrylonitrile-butadiene-styrene/polybutylene terephthalate blends

In this study, styrene-acrylonitrile-glycidyl methacrylate (SAG) series copolymers were specially designed for producing the recycled acrylonitrile-butadiene-styrene (rABS)/poly(butylene terephthalate) (PBT)/SAG blends, which were prepared through the process of continuous melt blending and batch feeding. The effects of viscosity composition, SAG chemical composition, and SAG content on the morphology, and rheological and mechanical properties of the blends have been investigated. As demonstrated by morphological observation, the variety of viscosity composition of the blends affects the size of dispersed PBT droplets. Moreover, high viscosity of rABS matrix seems to facilitate the formation of smaller dispersed phase size of blends. Various SAG chemical compositions have different stabilities on the morphology of the blends, which affects the deformation, fragmentation, and coalescence of dispersed phase droplets. In addition, a finer phase morphology can be achieved when the density distribution of epoxy group is optimal in SAG copolymer. Rheological characterization manifested that the rheological properties of the blends depends strongly on its composition and structure, while the crosslinking degree is associated with the concentration of reactive groups and extent of reaction. Thereby, the rheological behavior of the blends during processing can be controlled by changing the reactive sequence and adding the quantity of epoxy group. The test on mechanical properties verified that a recycled product with excellent performance can be obtained by altering processing methods and the blends formula, which may be further applied to the 3D printing materials required by fused deposition modeling technology. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48310.     

Blends of photovoltaic-grade ethylene–vinylacetate copolymers and low-density ethylene–octene copolymers,their morphology and their thermal,mechanical, and rheological properties

Blends of photovoltaic-grade ethylene–vinyl acetate copolymer (EVA), defined by high VA-content and low crystallinity, and low-density ethylene–octene copolymer (EO) have been investigated with regard to their processing, thermal and mechanical properties as well as their morphology. It was found that the amount of EO in the blend has a strong influence on the shear thinning behavior, melt viscosity and therefore the required extrusion temperature and resulting ability to incorporate temperature-sensitive additives like a peroxidic crosslinking agent. A phase separated morphology was found for all blend compositions, though partial miscibility leading to co-crystallization was observed for EVA rich blends. EO rich blends show lower glass transition and higher melting point compared to neat EVA and exhibit higher elastic modulus at elevated temperatures as well as greater elongation at break during tensile testing while the light transmission is diminished. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47714.     

Viscoelasticity and morphology of poly(ethylene‐co‐vinyl acetate)/polyisobutylene blends

Blends of an ethylene/vinyl acetate copolymer (EVA) and polyisobutylene of various compositions were prepared by mechanical mixing at a temperature above the melting point of EVA (T_m^EVA) but below the upper critical solution temperature of 170°C for given blends. The rheological properties of the components and blends were studied in the region of small‐amplitude oscillating deformation at temperatures above and below T_m^EVA in the frequency range of 0.01–100 rad/s. At temperatures lower than T_m^EVA, the rheological properties were determined by the existence of the yield stress. With diminishing frequency, the viscosity increased, and the plateau in the relaxation spectrum at low frequencies broadened. The morphology of the blends depended on the conditions of sample heating. The introduction of a finely dispersed filler into the blends led to an anomalous drop in the viscosity. The morphology of the systems that arose by mechanical blending of the molten components was the important factor in the rheological behavior. The observed effects were examined in the framework of the concept of structural networks formed in melts by nonmelted crystallites of EVA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2700–2707, 2006     

Properties of uncompatibilized and compatibilized poly(butylene terephthalate)–LLDPE blends

In this work, blends of poly(butylene terephthalate) (PBT) and linear low‐density polyethylene (LLDPE) were prepared. LLDPE was used as an impact modifier. Since the system was found to be incompatible, compatibilization was sought for by the addition of the following two types of functionalized polyethylene: ethylene vinylacetate copolymer (EVA) and maleic anhydride‐grafted EVA copolymer (EVA‐g‐MAH). The effects of the compatibilizers on the rheological and mechanical properties of the blends have been also quantitatively investigated. The impact strength of the PBT–LLDPE binary blends slightly increased at a lower concentration of LLDPE but increased remarkably above a concentration of 60 wt % of LLDPE. The morphology of the blends showed that the LLDPE particles had dispersed in the PBT matrix below 40 wt % of LLDPE, while, at 60 wt % of LLDPE, a co‐continuous morphology was obtained, which could explain the increase of the impact strength of the blend. Generally, the mechanical strength was decreased by adding LLDPE to PBT. Addition of EVA or EVA‐g‐MAH as a compatibilizer to PBT–LLDPE (70/30) blend considerably improved the impact strength of the blend without significantly sacrificing the tensile and the flexural strength. More improvement in those mechanical properties was observed in the case of the EVA‐g‐MAH system than for the EVA system. A larger viscosity increase was also observed in the case of the EVA‐g‐MAH than EVA. This may be due to interaction of the EVA‐g‐MAH with PBT. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 989–997, 1999     

Self‐reinforcing elastomer composites based on polyolefinic thermoplastic elastomer and thermotropic liquid crystalline polymer

In situ reinforcing elastomer composites based on Santoprene thermoplastic elastomer, a polymerized polyolefin compound of ethylene–propylene–diene monomer/polypropylene, and a thermotropic liquid crystalline polymer (TLCP), Rodrun LC3000, were prepared using a single‐screw extruder. The rheological behavior, morphology, mechanical, and thermal properties of the blends containing various LC3000 contents were investigated. All neat components and their blends exhibited shear thinning behavior. With increasing TLCP content, processability became easier because of the decrease in melt viscosity of the blends. Despite the viscosity ratio of dispersed phase to the matrix phase for the blend system is lower than 0.14, most of TLCP domains in the blends containing 5–10 wt % LC3000 appeared as droplets. At 20 wt % LC3000 or more, the domain size of TLCP became larger because of the coalescence of liquid TLCP threads that occurred during extrusion. The addition of LC3000 into the elastomer matrix enhanced the initial tensile modulus considerably whereas the extensibility of the blends remarkably decreased with addition of high TLCP level (>.20 wt %). The incorporation of LC3000 into Santoprene slightly improved the thermal resistance both in nitrogen and in air. Dynamic mechanical analysis results clearly showed an enhancement in dynamic moduli for the blends with 20–30 wt % LC3000. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheological and physical properties of in situ composite based on liquid crystalline polymer and poly(ethylene 2,6‐naphthalate) blends

The in situ composites based on poly(ethylene 2,6‐naphthalate) (PEN) and liquid crystalline polymer (LCP) were investigated in terms of thermal, rheological, and mechanical properties, and morphology. Inclusion of LCP enhanced the crystallization rate and tensile modulus of the PEN matrix, although it decreased the tensile strength in the PEN‐rich phase. The orientation effect of this blend system was composition and spin draw ratio dependent, which was examined by Instron tensile test. Further, the addition of dibutyltindilaurate (DBTDL) as a reaction catalyst was found to increase the viscosity of the blends, enhance its adhesion between the dispersed LCP phases and matrix, and led to an increase of mechanical properties of two immiscible blends. Hence DBTDL is helpful in producing a reactive compatibilizer by reactive extrusion at the interface of this LCP reinforced polyester blend system. The optimum catalyst amount turned out to be about 500 ppm, when the reaction proceeded in the 75/25 PEN/LCP blend system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2448–2456, 1999     

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     

In‐situ ultrasonic compatibilization of unvulcanized and dynamically vulcanized PP/EPDM blends

Dynamically vulcanized PP/EPDM blends were treated by high‐intensity ultrasonic waves during extrusion. These blends were compared with unvulcanized PP/EPDM blends that were treated by ultrasound during extrusion and then dynamically vulcanized. Die pressure and power consumption were measured. The effects of different gap sizes, ratio of components, and number of ultrasonic horns were investigated. The rheological properties, morphology and mechanical properties of the blends with and without ultrasonic treatment were compared. The results obtained indicated that ultrasonic treatment induced thermo‐mechanical degradation, causing enhanced molecular transport and chemical reactions at the interfaces, thus leading to in‐situ compatibilization, which is evident by the morphological and mechanical property studies. Processing conditions were established for enhanced in‐situ compatibilization of the PP/EPDM blends that were either originally dynamically vulcanized and then ultrasonically treated or first treated and then dynamically vulcanized. Polym. Eng. Sci. 44:2019–2028, 2004. © 2004 Society of Plastics Engineers.     

In situ microfibrillar‐reinforced composites of isotactic polypropylene/recycled poly(ethylene terephthalate) system and effect of compatibilizer

Recycled poly(ethylene terephthalate) from waste bottles (hereafter, rPET) was used as an reinforcing material for isotactic polypropylene (iPP) based on the concept of in situ microfibrillar‐reinforced composites (iMFCs). Microfibers of rPET were successfully generated during melt‐extrusion and subsequent drawing and preserved in the final injection‐molded specimens. The effects of draw ratio, initial size of ground rPET flakes, and rPET content on morphological appearance of the extrudates and the as‐formed rPET fibers and mechanical properties of the as‐prepared iMFCs were investigated. The results showed that diameters of the as‐formed rPET fibers decreased with increasing draw ratio, and the initial size of ground rPET flakes did not affect the final diameters of the as‐formed rPET fibers nor the mechanical properties of the as‐prepared iMFCs. Flexural modulus, tensile modulus, and tensile strength of iPP/rPET iMFCs were improved by the presence of rPET microfibers and further improvement could be achieved by the addition of maleic anhydride‐grafted iPP (PP‐g‐MA), which was used as the compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1173–1181, 2006     

Morphology, rheology and dynamic mechanical properties of PP/EVA/clay nanocomposites

This paper reports on morphology, rheology and dynamic mechanical properties of polypropylene (PP)/ethylene vinyl acetate (EVA) copolymer/clay nanocomposite system prepared via a single step melt compounding process using a twin screw micro-compounder. Scanning electron microscopic (SEM) investigations revealed that the dispersed phase droplet size was reduced with incorporation of an organo-modified montmorillonite (OMMT). This reduction was more significant in presence of a maleated PP (PP-g-MAH) used as compatibilizer. Phase inversion in the compatibilized blends caused a further decrease in PP droplet size. The OMMT gallery spacing was higher in nanocomposites with EVA as matrix which could be attributed to higher tendency of OMMT nanoparticles towards EVA rather than PP. This enhanced tendency was confirmed by rheological analysis too. Transmission electron microscopy (TEM) results also showed that the majority of OMMT nanoparticles were localized on the interface and within EVA droplets. According to dynamic mechanical analysis, the compatibilized nanocomposites showed higher storage and loss moduli due to better dispersion of OMMT layers. The modulus enhancement of nanocomposites as a function of OMMT volume fraction was modeled by Halpin-Tsai’s-Nielsen expression of modulus for nanocomposites. The results of modeling suggested that the aspect ratio of the intercalated OMMT, in the form of Einstein coefficient (K _E), plays a determining role in the modulus enhancement of nanocomposites.     

Correlation between the morphology and dynamic mechanical properties of ethylene vinyl acetate/linear low‐density polyethylene blends: Effects of the blend ratio and compatibilization

The effects of the blend composition and compatibilization on the morphology of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were studied. The blends showed dispersed/matrix and cocontinuous phase morphologies that depended on the composition. The blends had a cocontinuous morphology at an EVA concentration of 40–60%. The addition of the compatibilizer first decreased the domain size of the dispersed phase, which then leveled off. Two types of compatibilizers were added to the polymer/polymer interface: linear low‐density polyethylene‐g‐maleic anhydride and LLDPE‐g phenolic resin. Noolandi's theory was in agreement with the experimental data. The conformation of the compatibilizer at the blend interface could be predicted by the calculation of the area occupied by the compatibilizer molecule at the interface. The effects of the blend ratio and compatibilization on the dynamic mechanical properties of the blends were analyzed from ?60°C to +35°C. The experiments were performed over a series of frequencies. The area under the curve of the loss modulus versus the temperature was higher than the values obtained by group contribution analysis. The loss tangent curve showed a peak corresponding to the glass transition of EVA, indicating the incompatibility of the blend system. The damping characteristics of the blends increased with increasing EVA content because of the decrease in the crystalline volume of the system. Attempts were made to correlate the observed viscoelastic properties of the blends with the morphology. Various composite models were used to model the dynamic mechanical data. Compatibilization increased the storage modulus of the system because of the fine dispersion of EVA domains in the LLDPE matrix, which provided increased interfacial interaction. Better compatibilization was effected at a 0.5–1% loading of the compatibilizer. This was in full agreement with the dynamic mechanical spectroscopy data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4526–4538, 2006     

Study on the morphology and properties of metallocene polyethylene and ethylene/vinyl acetate blends

Two commercial polymer materials, metallocene linear low density polyethylene (m‐LLDPE) and ethylene/vinyl acetate copolymer (EVA) have been used to form binary blends of various compositions. The mechanical properties, morphology, rheological behavior, dynamic mechanical properties, and crystallization of m‐LLDPE/EVA blends were investigated. It was found that with the addition of EVA, the fluidity and processability of m‐LLDPE were significantly improved, and the introduction of polar groups in this system showed no significant changes in mechanical properties at lower EVA content. As verified by morphology observation and differential scanning calorimetry analysis, miscible blends were formed within certain weight ratios. Dynamic mechanical property studies showed that flexibility of the blends was enhanced in comparion with pure m‐LLDPE, where the peak value of loss modulus shifted to lower temperature and its intensity was enhanced as EVA content increased, indicating the existence of more amorphous regions in the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 905–910, 2004