The influence of matrix viscosity on properties of polypropylene/polyaniline composite fibers—Rheological,electrical, and mechanical characteristics

Electrically conductive composites containing polypropylene (PP) and polyaniline (PANI) were prepared using PP with three different melt flow rates (MFRs) and a commercial PANI‐complex in proportions of 80% by weight and 20%, respectively. Composite blends were melt‐spun to fibers under different solid‐state draw ratios. Rheological studies of dynamic viscosity, as well as the storage modulus and loss modulus showed that the prepared PANI‐complex/PP blends exhibit different dynamic rheological behavior, depending on the PP used. This confirms the blends' morphological differences. PP matrix viscosity was found to play an important role in the electrical properties of the prepared fibers. Fibers prepared using the matrix with the lowest viscosity, showed a larger dispersed phase size in the cross‐sectional SEM micrographs, maximum conductivity observed at higher draw ratios and a more linear resistance–voltage relationship than those of the fibers prepared using the higher viscosity matrices. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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

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

Melt rheological properties of polypropylene–polyamide6 blends compatibilized with maleic anhydride‐grafted polypropylene

The melt rheological properties of binary uncompatibilized polypropylene–polyamide6 (PP–PA6) blends and ternary blends compatibilized with maleic anhydride‐grafted PP (PP–PP‐g‐MAH–PA6) were studied using a capillary rheometer. The experimental shear viscosities of blends were compared with those calculated from Utracki's relation. The deviation value δ between these two series of data was obtained. In binary PP–PA6 blends, when the compatibility between PP and PA6 was poor, the deformation recovery of dispersed PA6 particles played the dominant role during the capillary flow, the experimental values were smaller than those calculated, and δ was negative. The higher the dispersed phase content, the more deformed the droplets were and the lower the apparent shear viscosity. Also, the absolute value of δ increased with the dispersed phase composition. In ternary PP–PP‐g‐MAH–PA6 systems, when the compatibility between PP and PA6 was enhanced by PP‐g‐MAH, the elongation and break‐up of the dispersed particles played the dominant role, and the experimental values were higher than calculated. It was observed that the higher the dispersion of the PA6 phase, the higher the δ values of the ternary blends and the larger the positive deviation. Unlike uncompatibilized blends, under high shear stress with higher dispersed phase content, the PP‐g‐PA6 copolymer in compatibilized blends was pulled out from the interface and formed independent micelles in the matrix, which resulted in reduced total apparent shear viscosity. The δ value decreased with increasing shear stress. Copyright © 2006 Society of Chemical Industry     

Effects of the viscosity ratio on polyolefin ternary blends

Polyolefin binary and ternary blends were prepared from polypropylene (PP), an ethylene–α‐olefin copolymer (mPE), and high‐density polyethylene (HDPE) on the basis of the viscosity ratio of the dispersed phase to the continuous phase. In PP/mPE/HDPE blends, fibrils were observed when the dispersed‐phase (mPE/HDPE) viscosity was less than that of PP, or when the viscosity of mPE was less than that of PP, although the viscosity of mPE/HDPE was greater than that of PP. The notched impact strength and mechanical properties such as the yield strength, flexural modulus, and hardness of PP/mPE binary blends further increased with the addition of HDPE according to the type of HDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4027–4036, 2004     

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

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

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

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

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

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

Effect of nano‐silica filler on the rheological and morphological properties of polypropylene/liquid‐crystalline polymer blends

A fumed hydrophilic nano‐silica‐filled polypropylene (PP) composite was blended with a liquid‐crystalline polymer (LCP; Rodrun LC5000). The preblended polymer blend was extruded through a capillary die; this was followed by a series of rheological and morphological characterizations. The viscosity of the PP matrix increased with the addition of the hydrophilic nano‐silica. At shear rates between 50 and 200 s^?1, the composite displays marked shear‐thinning characteristics. However, the incorporation of LC5000 in the PP composite eliminated the shear‐thinning characteristic, which suggests that LC5000 destroyed the agglomerated nano‐silica network in the PP matrix. Although the viscosity ratio of LCP/PP was reduced after the addition of nano‐silica fillers, the LCP phases existed as droplets and ellipsoids. The nano‐silicas were concentrated in the LC5000 phase, which hindered the formation of LCP fibers when processed at high shear deformation. We carried out surface modification of the hydrophilic nano‐silica to investigate the effect of modified nano‐silica (M‐silica) on the morphology of the PP/LC5000 blend system. Ethanol was successfully grafted onto the nano‐silica surface with a controlled grafting ratio. The viscosity was reduced for PP filled with ethanol‐M‐silica when compared to the system filled with untreated hydrophilic nano‐silica. The LC5000 in the (PP/M‐silica)/LC5000 blend existed mainly in the form of fibrils. At high shear rates (e.g., 3000 s^?1), the LC5000 fibril network was formed at the skin region of the extrudates. The exclusion of nano‐silica in the LC5000 phase and the increased viscosity of the matrix were responsible for the morphological changes of the LCP phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1484–1492, 2003     

The effect of interface characteristics on the morphology,rheology and thermal behavior of three‐component polymer alloys

Immiscible polymer blends are interesting multiphase host systems for fillers. Such systems exhibit, within a certain composition limits, either a separate dispersion of the two minor phases or a dispersion of encapsulated filler particles within the minor polymer phase. Both thermodynamic (e.g. interfacial tension) and kinetic (e.g. relative viscosity) considerations determine the morphology developed during the blending process. The effect of interfacial characteristics on the structure‐property relationships of ternary polymer alloys and blends comprising polypropylene (PP), ethylene‐vinyl alcohol copolymer (EVOH) and glass beads (GB), or fibers (GF), was investigated. The system studied was based on a binary PP/EVOH immiscible blend, representing a blend of a semi‐crystalline apolar polymer with a semicrystalline highly polar copolymer. Modification of the interfacial properties was obtained through using silane coupling agents for the EVOH/glass interface and compatibilization using a maleic anhydride grafted PP (MA‐g‐PP) for the PP/EVOH interface. The compatibilizer was added in a procedure aimed to preserves the encapsulated EVOH/glass structure. Blends were prepared by melt extrusion compounding and specimens by injection molding. The morphology was characterized using scanning electron microscopy (SEM) and high resolution SEM (HRSEM), the shear viscosity by capillary rheometry and the thermal behavior using differential scanning calorimetry (DSC). The system studied consisted of filler particles encapsulated by EVOH, with some of the minor EVOH component separately dispersed within the PP matrix. Modification of the interfaces resulted in unique morphologies. The aminosilane glass surface treatment enhanced the encapsulation in the ternary [PP/EVOH]GB blends, resulting in an encapsulated morphology with no separtely dispersed EVOH particles. The addition of a MA‐g‐PP compatibilizer preserves the encapsulated morphology in the ternary blends with some finely dispersed EVOH particles and enhanced PP/EVOH interphase interactions. The viscosity of the binary and ternary blends was closely related to the blend's morphology and the level of shear rate. The treated glass surfaces showed increased viscosity compared to the cleaned glass surfaces in both GB and GF containing ternary blends. Both EVOH and glass serve as nucleating agents for the PP matrix, affecting its crystallization process but not its crystalline structure. The aminosilane glass surface treatment completely inhibited the EVOH crystallization process in the ternary blend. In summary, the structure of the multicomponent blends studied has a significant effect on their behavior as depicted by the rheological and thermal behavior. The structure‐performance relationships in the three‐component blends can be controlled and varied.     

From polymer blends to in situ polymer/polymer composites: Morphology control and mechanical properties

In situ polymer/polymer short fiber composites were generated by a two‐step process. In the first step, a polyamide (PA) dispersed phase is blended with a polypropylene (PP) matrix in a twin‐screw extruder at a temperature at which both polymers are in molten state. The extrudate was then stretched at the die exit to generate long and thin fibers of PA in the PP matrix well oriented in the direction of flow. Adhesion between the phases was promoted by addition of PP grafted with maleic anhydride (PP‐g‐MA). During the second step, the chopped extrudates were molded by injection or compression molding at a temperature at which PA in the form of fibers is in the solid state and the PP matrix is molten. The control of the formation of such ultrafine fibers was obtained by quantitative analyses for the deformation of the minor PA‐phase during twin‐screw extrusion and stretching at the exit of the die that involve both shear and extensional flows. Morphology and mechanical properties of such polymer/polymer composites were compared to equivalent blends with dispersed spherical particles‐type morphology prepared in a batch mixer device.     

A novel combination of sandwich and co‐continuous structure based on polypropylene and styrene‐butadiene‐styrene block copolymer formed with wide range of polypropylene content

The styrene–butadiene–styrene block copolymer (SBS)/polypropylene (PP) blends with a unique sandwich layered co‐continuous structure were prepared by melt compounding. Differing from single conventional co‐continuous and sandwich structure, this structure was formed, where pure PP and co‐continuous SBS/PP phase acting as the face sheets and core. Even though the volume content was 20 or 10 vol %, PP always amazingly formed a continuous phase in SBS/PP blends, whereas the morphology of SBS phase relatively changed from dispersed particles to continuous network as its content increased to 50 vol %. For immiscible SBS/PP blends, due to the huge difference of complex viscosity and surface tension between SBS and PP, a pure PP layer existed on the surface of blends which can be ascribed to the PP enrichment. Herein, the structure of blends with more than 50 vol % SBS was presented as sandwich layered co‐continuous structure by combining the pure PP layer and co‐continuous structure. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46580.     

Reactive melt modification of polypropylene with a crosslinkable polyester

Melt blending of polypropylene (PP) with a low molecular weight (MW) crosslinkable unsaturated polyester (UP) was studied in a batch mixer and a twin‐screw extruder in the presence of peroxide (POX) free radical initiator. Competing degradation and crosslinking reactions of the peroxide with the blend components leading to significant change in their viscosity ratio were studied and controlled during the blending process. Rheological studies show that depending on the process conditions some reacted PP/UP blends have a pronounced suspension behavior due to the presence of the dispersed polyester gel particles in a low MW PP matrix. It is also evident from SEM analysis that the reacted blends have a more uniform and finer morphology than the unreacted ones. The blends are also characterized by FTIR, which strongly suggests the presence of “block” or “graft” PP‐UP structures that may enhance phase interaction and promote compatibility in the reacted PP/UP blends. Such blends are considered as suitable compatibilizers of PP/high MW thermoplastic polyester blends and as modifiers for low density extrusion foaming of similar blends.     

Structured polymer blends: 2. Processing of polypropylene/EDPM blends: controlled rheology and morphology fixation via electron beam irradiation

Electron beam irradiation has been used to improve the processability of polypropylene/ethylene-propylenediene monomer (PP/EPDM) blends (controlled rheology) in combination with fixation of morphology by inducing crosslinks in the dispersed EPDM phase. An optimum morphology for impact toughening has been obtained via extrusion-blending high molecular weight PP with EPDM. Upon irradiation before subsequent processing (injection moulding) this morphology is fixated, whereas the viscosity of the blend decreases as a result of chain scission of the PP matrix. Impact strength and elongation at break of these irradiated blends are better than those of blends of low molecular weight PP with EPDM, which possess comparable overall viscosity.     

Morphology prediction and the effect of core‐shell structure on the rheological behavior of PP/EPDM/HDPE ternary blends

In this work, the morphologies of polypropylene (PP)/ethylene‐propylene‐diene (EPDM) rubber/high density polyethylene (HDPE) 70/20/10 blends were studied and compared with the predictions of the spreading coefficient and minimum free energy models. The interfacial tension of PP/HDPE, PP/EPDM, and HDPE/EPDM blends were obtained by fitting the experimental dynamic storage modulus data to Palierne's theory. The prediction results showed core‐shell morphology (core of HDPE and shell of EPDM) in PP matrix. The PP/EPDM/HDPE blends were respectively prepared by direct extrusion and lateral injection method. Core‐shell morphology (core of HDPE and shell of EPDM) could be obtained with direct extrusion corresponding to the predicted morphology. The morphology of PP/EPDM/HDPE blends could be effectively controlled by lateral injection method. For PP/EPDM/HDPE blend prepared by lateral injection method, HDPE and EPDM phase were dispersed independently in PP matrix. It was found that the different morphology of PP/EPDM/HDPE blends prepared by two methods showed different rheological behavior. When the core‐shell morphology (core of HDPE and shell of EPDM) appeared, the EPDM shell could confine the deformation of HDPE core significantly, so the interfacial energy contribution of dispersed phase on the storage modulus of blends would be weaken in the low frequency region. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Investigation of rheology and morphology to follow physical fibrillar network evolution through fiber spinning of PP/PA6 blend fiber

This work is aimed at investigating the influence of fibrillar morphology of deformed Polyamide 6 (PA6) droplets dispersed in Polypropylene (PP) matrix on the melt viscoelastic behavior of their blends. The blends of PP with various amounts of PA6 (1%, 6%, 10%, and 20%) were prepared by melt mixing in a co‐rotating twin screw extruder and fibrillated by fiber spinning process. Scanning Electron Microscopy revealed that the PA6 spherical droplets form fibrillar inclusions after fiber spinning. The steady and transient shear rheological responses of samples were evaluated in both linear and nonlinear ranges of deformation. Non‐terminal behavior of storage modulus at low frequency appeared as a typical characteristic of fibrillar morphology whose width and value depend on fibril growth. Storage modulus and complex viscosity of the blends containing PA6 fibrillated structure were remarkably enhanced compared to as‐extruded samples. The fibrillar‐induced elasticity of the fibers is a distinguishable behavior which was revealed by conducting transient stress and creep‐recovery measurements and upon appearing mature fibrils, elasticity of the polymer blend fibers increased significantly. POLYM. ENG. SCI., 58:1251–1260, 2018. © 2017 Society of Plastics Engineers     

A method to control the dispersion of carbon black in an immiscible polymer blend

The dispersion of carbon black (CB) in an immiscible polymer blend of poly‐(methyl methacrylate) (PMMA) and polypropylene (PP) was studied as the viscosity of PMMA increased. It was found that the dispersion of carbon black was strongly influenced by the viscosity of PMMA. The CB was dispersed in the PMMA phase when the viscosities of PMMA and PP are comparable, as predicted by Sumita's model. As the viscosity of PMMA increases, the CB was found to be located at the interface between the PMMA and PP phases. On further increase in the viscosity of PMMA, the CB was found to be dispersed in the PP phase. In addition, the CB dispersion in the PP/PMMA blends can significantly influence the positive temperature coefficient (PTC) intensity of the blends.     

The influence of matrix viscosity and composition on the morphology,rheology, and mechanical properties of thermoplastic elastomer nanocomposites based on EPDM/PP

The morphological and rheological properties of thermoplastic elastomer nanocomposites (TPE nanocomposites) were studied using different viscosities of polypropylene (PP) and ethylene‐propylene‐diene monomer (EPDM) rubber content (20, 40, 60 wt%). The components, namely EPDM, PP, Cloisite 15A, and maleic anhydride‐modified PP as compatibilizer, were compounded by a one‐step melt mixing process in a laboratory internal mixer. The structure of the nanocomposites was characterized with X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, and rheometry in small amplitude oscillatory shear. The distribution state of the clay between the two phases (PP and EPDM) was found to be dependent on the viscosity ratio of PP to EPDM. In the nanocomposites prepared based on low viscosity PP (LVP) and EPDM, the clay was mostly dispersed into the PP phase and the size of the dispersed rubber particles decreased in comparison with unfilled but otherwise similar blends. However, the dispersed elastomer droplet size in the high viscosity PP (HVP) blends containing 40 and 60% EPDM increased with the introduction of the clay. For TPE nanocomposites, the dependence of the storage modulus (G′) on angular frequency (ω) followed a clear nonterminal behavior. The increase in the storage modulus and the decrease in the terminal zone slope of the elastic modulus curve were found to be larger in the LVP nanocomposite in comparison with the HVP sample. The yield stress of nanoclay‐filled blends prepared with LVP increased more than that of HVP samples. The tensile modulus improved for all nanocomposites but a higher percentage of increase was observed in the case of LVP samples. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Viscosity effect in polyolefin ternary blends and composites

Ternary blends of PP (80) /rubber (EPM, EPDM) (10) / PE (10) and PP (80) / rubber (10) / CaCO₃ (10) composites were prepared in a twin-screw extruder. With polyethylene (PE) viscosity comparable to, or higher than that of rubber, the dispersed phase formed a reticulate structure with reduced size. On the contrary, when the viscosity of PE was significantly lower than that of rubber, the dispersed phase formed almost homogeneous morphology. With reticulate morphology, PE crystallinity content, hardness, modulus, and elongation at break of the ternary blend increased. In polypropylene (PP) / rubber / CaCO₃ composites, better dispersion of CaCO₃ in the PP matrix was obtained when the viscosity of rubber was significantly higher than that of matrix. With better dispersion, hardness and tensile properties were improved, but the impact strength more or less decreased. © 1993 John Wiley & Sons, Inc.     

Thermal behavior and morphological and rheological properties of polypropylene and novel elastomeric ethylene copolymer blends

The thermal behavior including melting and crystallization behavior and morphological and rheological properties of the blends based on an isotactic polypropylene and a novel maleated elastomeric ethylene copolymer were investigated in this work. The addition of an elastomer to polypropylene (PP) was found not to change the PP crystalline structure significantly when cooled quickly from the melt. On recrystallization at a lower cooling rate, the elastomer promotes the formation of β?pseudohexagonal PP in PP‐rich blends. In elastomer‐rich compositions, heterogeneous nucleation is hindered and homogeneous nucleation takes place. These phenomena are revealed by morphology observation: that, with increasing of the elastomer content, the system undergoes PP continuous, dual‐phase continuity and PP‐dispersed morphologies. The blend viscosity at a low shear rate range increases continuously with increasing elastomer content and shows positive deviations from the additivity rule. In the terminal zone, the dynamic storage modulus of the blends shows positive deviation from the simple mixing rule and the maximum deviation lies in the composition range of dual‐phase continuity which could be caused by a large increase in the interfacial tension. The Cox–Merz rule does not hold for the blends because of the two‐phase heterogeneous structure and its variation in steady and oscillatory shear flow. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3430–3439, 2002