Melt electrospinning from poly(L‐lactide) rods coated with poly(ethylene‐co‐vinyl alcohol)

Rodlike poly(L ‐lactide) (PLLA) samples coated with poly(ethylene‐co‐vinyl alcohol) (EVOH) were made. Fibers were produced from these rodlike samples by using a melt electrospinning system equipped with a laser irradiating device, and the effects of EVOH content and the processing parameters of the melt electrospinning on fiber diameters were investigated. We also studied the fiber formation mechanism from the rods during the laser melt electrospinning process. The following conclusions were reached: (i) coating of EVOH on PLLA rods has a remarkable effect on decreasing fiber diameter from 3 μm to around 1 μm; (ii) increases in the electric field strength and temperature of spinning space decrease the average diameter of fibers produced from pure PLLA rods, and longer collector distance leads to lager PLLA fiber diameter; and (iii) the migration of PLLA component from the core to the surface of electrospun fibers takes place during the fiber formation process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

High flux nanofibrous composite microfiltration membrane prepared by melt blending extrusion: Application in liquid filtration

High flux PP/EVOH nanofibrous composite microfiltration membrane (P/E‐NCMM) based on polypropylene (PP) (575 nm) and polyethylene‐co‐polyvinyl alcohol (EVOH) nanofibers (248 nm) with low operation pressure for liquid filtration was fabricated by melt blending extrusion. PP nanofibers as the scaffold played a supporting role, and EVOH nanofibers filled in the PP nanofibers network structure narrowed the pore size and improved the wettability. Taking advantages of PP and EVOH nanofibers, the nanofibrous composite membrane created fascinating features for liquid filtration. The experimental results showed that the P/E‐NCMM had high average pure water flux at low operating pressure. The P/E‐NCMM with 30 wt % PP nanofibers showed high water flux [450.9 L/(m² h)] even at very low feeding pressure (0.05 MPa) with above 95% retention for TiO₂ suspension. The results indicated that the P/E‐NCMM prepared by this method had great potential for the application in liquid filtration. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43585.     

Enhanced foamability of isotactic polypropylene composites by polypropylene‐graft‐carbon nanotube

In this article, utilizing a nucleophilic substitution reaction between epoxy group in polypropylene‐graft‐glycidyl methacrylate (PP‐g‐GMA) and carboxyl groups in oxidized carbon nanotubes (O‐CNTs), PP‐g‐CNT was fabricated for reinforcing the interfacial adhesion between CNTs and polypropylene (PP) matrix, favoring the enhancement of melt strength and elastic modulus, i.e., enhancing the foaming ability of PP composites. Cellular structure and thermo‐mechanical properties of PP foams were characterized by scanning electron microscopy and dynamic mechanical analysis, respectively. The average cell diameter of PP foams decreased from 289.2 (PP‐g‐GMA) to 96.7 μm (PP‐g‐CNT foams with 2.0 wt % O‐CNT) and the distribution of cell size also became more uniform. The storage modulus of PP‐g‐CNT foams increased by nearly 62.5% at ?40°C, compared with that of PP‐g‐GMA foams. This work also provided a new procedure for improving the foam ability and thermo‐mechanical property of PP composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 961‐968, 2013     

Development and performance study of polypropylene/polyester bicomponent melt‐blowns for filtration

In this study, a new type of polypropylene (PP)/polyester (PET) bicomponent melt‐blown (bi‐MB) for filtration was developed through the melt‐blowing process with raw materials of melt‐blown (MB)‐grade PP and PET chips. The structure, porosity, and filtration performance of the bi‐MBs were tested through relevant instruments. The results show that the average fiber diameter in the bi‐MBs was 2–3.5 μm, the average pore size was 12.3–15.6 μm, and the porosity was 90–94%. The results also show that the filtration efficiency of the bi‐MBs was much higher than that of monocomponent PP MBs. It reached the highest value of 97.34% when the PP/PET ratio was 50/50 and could be used as high‐performance filter media. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Rheological behaviors of glass bead‐ and wollastonite‐filled polypropylene composites modified with thermoplastic elastomers

Steady‐ and oscillatory‐shear rheological behaviors of polypropylene/glass bead (PP/GB) and PP/wollastonite (PP/W) melts modified with thermoplastic elastomers, poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) copolymer (SEBS) and the corresponding block copolymer grafted with maleic anhydride (SEBS‐g‐MA), were examined by means of a parallel‐plate rheometer. With adding the elastomers (SEBS and SEBS‐g‐MA) and fillers (spherical GB and acicular W) to PP, viscosity especially at low shear rates and shear‐thinning flow behavior at high shear rates were pronounced as evidenced quantitatively by Carreau–Yasuda (CY) parameters, but Cox–Merz analogy became weakened. Besides, melt‐elasticity in terminal region and relaxation time (t_c) in crossing point increased, indicating an enhancement in quasi‐solid behavior of molten PP. Comparing with the elastomers, rheological behaviors of molten PP were more influenced with adding the rigid fillers, especially with W due to distinct acicular shape of W particles. SEBS‐g‐MA elastomer more affected rheological behaviors of the ternary composites than SEBS elastomer, implying that SEBS elastomer and the filler particles behaved individually (i.e., development of separate microstructure) in (PP/GB)/SEBS and (PP/W)/SEBS ternary composites, but core‐shell microstructure developed with strong interfacial adhesion by adding SEBS‐g‐MA elastomer, and the filler particles encapsulated with the thick SEBS‐g‐MA elastomer interlayer (i.e., core‐shell particles) acted like neither big elastomer particles nor like individual rigid particles in melt‐state. Moreover, effects of SEBS‐g‐MA elastomer reached a maximum on rheological behaviors of (PP/W)/SEBS‐g‐MA ternary composite, indicating a synergy between core‐shell microstructure and acicular W particles. Correlations between oscillatory‐shear flow properties and microstructures of the blends and composites were evaluated using Cole–Cole (CC), Han–Chuang (HC), and van Gurp–Palmen (vGP) plots. COMPOS., 2012. © 2012 Society of Plastics     

Study of multi‐monomer melt‐grafting onto polypropylene in an extruder

Free‐radical melt‐grafting of the dual‐monomer systems glycidyl methacrylate–styrene (GMA‐St) and hydroxyethyl methacrylate–styrene (HEMA‐St) onto polypropylene (PP) has been studied using a single‐screw extruder. For single monomer grafting systems, degradation of PP was unavoidable and deterioration of the mechanical properties of the grafted PP subsequently occurred because of β‐scission of PP chains during the free‐radical melt‐grafting process. However, for the dual‐monomer systems, it is shown that the addition of styrene as a comonomer can significantly enhance the GMA or HEMA grafting levels on PP and reduce the extent of β‐scission of PP backbone. It has been found that the grafting degree of dual‐monomer melt‐grafted PP, such as PP‐g‐(GMA‐co‐St) or PP‐g‐(HEMA‐co‐St), is about quadruple that of single‐monomer grafted PP for the same monomer and dicumyl peroxide concentrations. Moreover, the melt flow rate of the dual‐monomer grafted PP is smaller than that of the unmodified PP. Hence, PP not only was endowed with higher polarity, but also kept its good mechanical properties. © 2000 Society of Chemical Industry     

Morphological,thermal, rheological,and mechanical properties of PP/EVOH blends compatibilized with PP‐g‐IA

We prepared some blends of polypropylene (PP) and ethylene vinyl alcohol (EVOH) with and without a compatibilizer. As a new compatibilizer, we synthesized polypropylene grafted with itaconic acid (PP‐g‐IA) using Brabender mixing system. We investigated the morphological, thermal, rheological, and mechanical properties of a compatibilized blends (PP/EVOH/PP‐g‐IA) and not compatibilized blends (PP/EVOH). Our experiments showed that carboxylic acid groups in PP‐g‐IA and hydroxyl group in EVOH formed strong in situ hydrogen bond in the compatibilized blends, resulting in better morphological and mechanical properties of the compatibilized blends than those of not compatibilized blends. POLYM. ENG. SCI., 56:1240–1247, 2016. © 2016 Society of Plastics Engineers     

Isothermal crystallization kinetics of polypropylene in melt‐mixed composites of polypropylene and multi‐walled carbon nanotubes

The isothermal crystallization behaviour of the polypropylene (PP) phase in PP/multi‐walled carbon nanotubes (MWCNTs) composites has been investigated via differential scanning calorimetric analysis, which showed the influence of the varying dispersion level of MWCNTs in the respective PP matrix. PP/MWCNTs composites were prepared via melt‐blending technique, wherein two different grades of MWCNTs of varying average “agglomerate” size and varying entanglements (N‐MWCNTs and D‐MWCNTs) were utilized. Furthermore, the influence of melt‐viscosity of the PP phase was investigated on the crystallization kinetics of the PP/MWCNTs composites. Heterogeneous nucleation ability of MWCNTs has resulted in a decrease in half time of crystallization (t _1/2) from ～14 min for pure PP to ～6 min for PP/N‐MWCNTs and ～11 min for PP/D‐MWCNTs composites at 1 wt% of MWCNTs at 132 °C. Overall rate of crystallization (k) has significantly increased to 4.9 × 10^?2 min^?1 for PP/N‐MWCNTs composite as compared with 6.2 × 10^?3 min^?1 for PP/D‐MWCNTs composite at 0.5 wt% of MWCNTs at 132 °C. Moreover, the effect of a novel organic modifier, Li‐salt of 6‐amino hexanoic acid along with a compatibilizer (PP‐g‐MA) has also been investigated on the crystallization kinetics of the PP phase in PP/MWCNTs composites. POLYM. ENG. SCI., 57:1136–1146, 2017. © 2017 Society of Plastics Engineers     

Enhanced mechanical properties and bactericidal activity of polypropylene nanocomposite with dual‐function silica–silver core‐shell nanoparticles

Dual‐function silica–silver core‐shell (SiO₂@Ag) nanoparticles (NPs) with the core diameter of 17 ± 2 nm and the shell thickness of about 1.5 nm were produced using a green chemistry. The SiO₂@Ag NPs were tested in vitro against gram‐positive Staphylococcus aureus (S. aureus) and gram‐negative Escherichia coli (E. coli), both of which are human pathogens. Minimal inhibitory concentrations of the SiO₂@Ag NPs based on Ag content are 4 and 10 μg mL^?1 against S. aureus and E. coli, respectively. These values are similar to those of Ag NPs. SiO₂@Ag NPs were for the first time incorporated to a commodity polypropylene (PP) polymer. This yielded an advanced multifunctional polymer using current compounding technologies i.e., melt blending by twin‐screw extruder and solvent (toluene) blending. The composite containing 5 wt % SiO₂@Ag NPs (0.05 wt % Ag) exhibited efficient bactericidal activity with over 99.99% reduction in bacterial cell viability and significantly improved the flexural modulus of the PP. Anodic stripping voltammetry, used to investigate the antibacterial mechanism of the composite, indicated that a bactericidal Ag⁺ agent was released from the composite in an aqueous environment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhancing antibacterial properties of polypropylene/Cu‐loaded montmorillonite nanocomposite filaments through sheath–core morphology

Polypropylene (PP) loaded with copper‐exchanged montmorillonite (Cu‐MMT) nanocomposite filaments and films with excellent antimicrobial activity have been reported for the first time. A sheath–core morphology filament in which only the sheath contains Cu‐MMT was prepared for maximizing bioactivity. Sodium MMT clay was modified to acid‐activated MMT and further to Cu‐MMT via an ion exchange process. The exchange operation was confirmed using wide‐angle X‐ray diffraction and energy‐dispersive X‐ray spectroscopy (EDX) which suggested increased interlayer spacing and confirmed the loading of copper in Cu‐MMT. Further, Cu‐MMT was melt‐mixed in PP in the form of PP/Cu‐MMT nanocomposite filament, film and sheath–core morphology PP/Cu‐MMT nanocomposite filament. The surface morphology and elemental composition of the nanocomposites were studied using scanning electron microscopy coupled with EDX. Transmission electron micrographs were obtained to understand the dispersion characteristics of Cu‐MMT phase in PP. X‐ray diffraction analysis of nanocomposites suggested increased crystallinity at lower loading due to heterogeneous nucleating action of MMT. The PP nanocomposite filaments and films were tested for antimicrobial activity against Gram‐negative bacterium Escherichia coli, which is the main pathogenic bacterium found abundantly in water, and were found to exhibit excellent antimicrobial activity. © 2018 Society of Chemical Industry     

Novel multimonomer‐grafted polypropylene preparation and application in polypropylene/poly(vinyl chloride) blends

A novel grafted polymer was prepared in one step through free‐radical melt grafting in a single‐screw extruder. It was shown that the addition of styrene (St) to the melt‐grafting system as a comonomer could significantly enhance the grafting degree of methyl methacrylate (MMA) onto polypropylene (PP) and reduce the degradation of the PP matrix by means of Fourier transform infrared and melt flow rate testing, respectively. Then, the potential of using multimonomer‐grafted PP, which was designated PP‐g‐(St‐co‐MMA), as the compatibilizer in PP/poly(vinyl chloride) (PVC) blends was also examined. In comparison with PP/PVC blends, the average size of the dispersed phase was greatly reduced in grafted polypropylene (gPP)/PVC blends because of the addition of the PP‐g‐(St‐co‐MMA) graft copolymer. The tensile strength of the gPP/PVC blends increased significantly, and the impact strength was unchanged from that of the pure PP/PVC blends. The results of differential scanning calorimetry and scanning electron microscopy suggested that the compatibility of the PP/PVC blends was improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Compatibilization of intumescent flame retardant/polypropylene composites based on α‐methacrylic acid grafted polypropylene

A phosphoric acid–pentaerythritol–melamine copolymer was selected as an intumescent flame retardant (IFR). The influence of α‐methacrylic acid grafted polypropylene (PP‐g‐MAA) on the properties and compatibility of IFR/PP composites was studied. The results obtained from mechanical tests and scanning electron microscopy showed that PP‐g‐MAA was a true coupling agent for IFR/PP blends, but it did not change the necessary flame retardancy. The cocrystallization between bulk PP and PP segments of PP‐g‐MAA was proved by wide‐angle X‐ray diffraction analysis. A flow test showed that the flow behaviors of composites in the melt were those of a pseudoplastic liquid and it was very small for PP‐g‐MAA and affected the rheological behavior of the PP/IFR composite. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3128–3132, 2002; DOI 10.1002/app.10099     

Physical and mechanical properties of Al(OH)3/polypropylene composites modified by in situ‐functionalized polypropylene

Al(OH)₃/polypropylene (PP) composites modified by in situ‐functionalized polypropylene (FPP) were prepared by a one‐step melt‐extrusion process. The effect of in situ FPP on the crystallization and melting behavior, melt‐flow index, limiting oxygen index, thermal degradation, mechanical properties, and fracture morphology of Al(OH)₃/PP composites was studied. Formation of in situ FPP resulted in a decreased crystallization temperature and melting point of PP in the composites, an increased melt‐flow index, and improved tensile and flexural strengths of Al(OH)₃/PP composites, whereas the thermal degradation behavior and limiting oxygen index was not been influenced. The impact strength of the Al(OH)₃/PP composites modified by in situ FPP depended upon the content of the initiator, dicumyl peroxide, and the monomer, acrylic acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2850–2857, 2002; DOI 10.1002/app.10269     

Production of hyaluronic‐acid‐based cell‐enclosing microparticles and microcapsules via enzymatic reaction using a microfluidic system

This article describes the preparation of cell‐enclosing hyaluronic acid (HA) microparticles with solid core and microcapsules with liquid core through cell‐friendly horseradish peroxidase (HRP)‐catalyzed hydrogelation. The spherical vehicles were made from HA derivative possessing phenolic hydroxyl moieties (HA‐Ph) cross‐linkable through the enzymatic reaction by extruding cell‐suspending HA‐Ph aqueous solution containing HRP from a needle of 180 μm in inner diameter into the ambient coaxial flow of liquid paraffin containing H₂O₂ in a microtubule of 600 μm in diameter. By altering the flow rate of liquid paraffin, the diameters of gelatin and HA‐Ph microparticles were varied in the range of 120–220 μm and 100–300 μm, respectively. The viability of the enclosed human hepatoma HepG2 cells in the HA‐Ph microparticles of 180 μm in diameter was 94.2 ± 2.3%. The growth of the enclosed HepG2 cells was enhanced by decreasing the HRP concentration. The microcapsules of 200 μm in diameter were obtained by extruding HA‐Ph aqueous solution containing thermally liquefiable cell‐enclosing gelatin microparticles of 150 μm in diameter using the same microfluidic system. The enclosed cells grew and filled the cavity within 10 days. Spherical tissues covered with a heterogeneous cell layer were obtained by degrading the microcapsule membrane using hyaluronidase after covering the surface with a heterogeneous cell layer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43107.     

Properties of microinjection‐molded polypropylene/graphite composites

In this study, polypropylene (PP) composites filled with two different types of graphite particles, that is, flake‐shaped synthetic graphite (SG) and low‐temperature expandable graphite (LTEG), were prepared by melt blending, followed by microinjection molding (μIM). The microparts had three consecutive zones with decreasing thickness along the flow direction (FD). Results showed that, in addition to the larger particle size, the in situ exfoliation of LTEG during melt processing is crucial to the overall enhancement of electrical conductivity when compared with their SG‐containing counterparts, as corroborated by morphology observations. Moreover, the preferential alignment of conductive particles favors the construction of conductive pathways along the FD. The melting and crystallization behavior for PP, PP/LTEG, and PP/SG materials, and samples from each section of the corresponding microparts were evaluated by differential scanning calorimetry. Results indicated that both the addition of graphite particles and the typical thermomechanical history of μIM (i.e., high shearing and cooling rates) experienced in different sections of the three‐step microparts influence the melting and crystallization behavior of the composites. POLYM. ENG. SCI., 59:1560–1569 2019. © 2019 Society of Plastics Engineers     

Isotactic polypropylene hollow microfibers prepared by CO2 laser‐thinning

An isotactic polypropylene hollow microfiber was continuously produced by using a carbon dioxide (CO₂) laser‐thinning method. To prepare the hollow microfiber continuously, the apparatus used for the thinning of the solid fiber was improved so that the laser can circularly irradiate to the hollow fiber. Original hollow fiber with an outside diameter (OD) of 450 μm and an internal diameter (ID) of 250 μm was spun by using a melt spinning machine with a specially designed spinneret to produce the hollow fiber. An as‐spun hollow fiber was laser‐heated under various conditions, and the OD and the ID decreased with increasing the winding speed. For example, when the hollow microfiber obtained by irradiating the CO₂ laser to the original hollow fiber supplied at 0.30 m min^?1 was wound up at 800 m min^?1, the obtained hollow microfiber had an OD of 6.3 μm and an ID of 2.2 μm. The draw ratio calculated from the supplying and the winding speeds was 2667‐fold. The hollow microfibers obtained under various conditions had the hollowness in the range of 20–30%. The wide‐angle X‐ray diffraction patterns of the hollow microfibers showed the existence of the highly oriented crystallites. Further, the OD and ID decreased, and the hollowness increased by drawing hollow microfiber obtained with the laser‐thinning. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2600–2607, 2006     

Blends of polypropylene with poly(cis‐butadiene) rubber. II. Small‐angle X‐ray scattering studies of the phase structure of immiscible blends of polypropylene with poly(cis‐butadiene) rubber

Pressed films of the blends of polypropylene (PP) with poly(cis‐butadiene) rubber (PcBR) were studied by IR spectra, small‐angle X‐ray scattering, and scanning electron microscopy. The problem of the interaction between different macromolecules in the blends of PP/PcBR is discussed by melt‐mixing at a temperature of 210°C using IR. X‐ray scattering from the relation of the phase was analyzed using Porod's law, and the interface layer thickness was calculated. The immiscibility of the blends of PP/PcBR was proved. The structure parameters, the correlation distance a_c, average chord lengths l?, and radius of gyration R?_g were obtained by the Debye–Buech statistical theory of scattering. Porod's index was calculated and the shape of the dispersed phase is discussed in relation to Porod's index in the blends. The morphology and structure of the blends were investigated by scanning electron microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2088–2094, 2002     

Multiwalled carbon nanotubes‐based polypropylene composites: Influence of interfacial interaction on the crystallization behavior of polypropylene

Composites of polypropylene (PP) and multi‐walled carbon nanotubes (MWCNTs) were prepared via melt‐mixing utilizing Li‐salt of 6‐amino heaxanoic acid (Li‐AHA) modified MWCNTs in the presence of a compatibilizer (polypropylene‐g‐maleic anhydride; PP‐g‐MA). Improved interaction between the anhydride group of PP‐g‐MA and the amine functionality of Li‐AHA was confirmed via FTIR and Raman spectroscopic analysis. A higher glass transition temperature (T_g) of the PP phase has been observed in these composites as compared to pristine MWCNTs‐based composites. The crystallization temperature (T_c) of the PP phase was increased as a function of pristine MWCNTs concentration in PP/MWCNTs composites indicating hetero‐nucleating action of MWCNTs. However, T_c value was decreased in the presence of Li‐AHA modified MWCNTs indicating the adsorbed Li‐AHA on the MWCNTs surface. Moreover, T_c value was higher in the presence of Li‐AHA modified MWCNTs with PP‐g‐MA as compared to that of without PP‐g‐MA, suggesting the desorbed Li‐AHA from the MWCNTs surface due to melt‐interfacial reaction. Further, MWCNTs were extracted by hot vacuum filtration technique from PP/MWCNTs composites containing Li‐AHA and PP‐g‐MA. The isothermal crystallization kinetics showed a variation in crystallization behavior of the PP phase in the corresponding composites as compared to the “extracted MWCNTs.” POLYM. ENG. SCI., 57:183–196, 2017. © 2016 Society of Plastics Engineers     

Isotactic polypropylene microfiber prepared by carbon dioxide laser‐heating

An isotactic polypropylene (i‐PP) microfiber was obtained by irradiating a carbon dioxide laser to previously drawn fibers. To prepare the thinner i‐PP microfiber, it is necessary to previously draw original i‐PP fibers under an applied tension of 7.8 MPa at a drawing temperature of 140°C. The drawn fiber was heated under an applied tension of 0.3 MPa using the laser operated at a power density of 39.6 W cm^?2. The thinnest i‐PP microfiber obtained under optimum conditions had a diameter of 1.8 μm and a birefringence of 30 × 10^?3. Its draw ratio estimated from the diameter reached 51,630. It is so far impossible to achieve such a high draw ratio by any drawing. The wide‐angle X‐ray diffraction photograph of the microfiber shows the existence of the oriented crystallites. Laser‐heating allows easier fabrication of microfibers compared with the conventional technology such as the conjugate spinning. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1534–1539, 2004