Novel fabrication of magnetic thermoplastic nanofibers via melt extrusion of immiscible blends

A novel technique of fabricating magnetic thermoplastic nanofibers by the control of the phase separation of immiscible polymer blends during melt extrusion was presented. The magnetic poly(vinyl alcohol‐co‐ethylene) (PVA‐co‐PE)/Fe₃O₄ composite nanofibers were prepared via the melt extrusion of cellulose acetate butyrate matrix and PVA‐co‐PE preloaded with different amounts of Fe₃O₄ nanoparticles. The morphologies of magnetic composite nanofibers were characterized by scanning electron microscopy. The uniform dispersion of Fe₃O₄ nanoparticles in nanofiber matrixes and crystal structures were confirmed using transmission electron microscopy and wide angle X‐ray diffraction. Thermogravimetric analysis was employed to quantify the exact loading amount of Fe₃O₄ nanoparticles in the composite nanofibers. The magnetic measurements showed that composite nanofibers displayed superparamagnetic behavior at room temperature. With increasing content of Fe₃O₄ nanoparticles, the saturation magnetization of the magnetic composite nanofiber significantly improved. The prepared magnetic composite nanofibers might have found potential applications in the sensors and bio‐molecular separation fields. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of AB and ABA block copolymers as compatibilizers in nylon 6/polycarbonate blends

Nylon 6 (Ny6) and Bisphenol A polycarbonate (PC) are immiscible and form biphasic blends. To improve the compatibility of Ny6 and PC several ABA and AB Ny6/PC block copolymers were synthesized, and their compatibilizing behavior on the blends were tested. Block copolymers were prepared by reacting monoamino- or diamino-terminated Ny6 homopolymers with high molecular weight PC at 130°C in anhydrous DMSO. The reaction of diamino- and monoamino-terminated Ny6 with polycarbonate produces block copolymers of the type PC-Ny6-PC (ABA) and PC-Ny6 (AB), respectively, plus a certain amount of unconverted PC degradated to lower molecular weights. To separate the block copolymer from the unconverted PC, a selective fractionation with tetrahydrofuran (THF) and trifluoroethanol (TFE) was carried out. Three different fractions were obtained: THF-soluble fraction, TFE-soluble fraction, and the TFE-insoluble fraction. The scanning electron microscopy (SEM) analysis of a 75/25 (wt/wt) Ny6/PC blend added with 2% of ABA or AB block copolymers, showed the presence of smaller PC particles more adherent to the polyamide matrix, with respect to the same blend nonadded, which is clearly biphasic. The size of the PC particles decreases from ABA to AB compatibilized blends and the adhesion with the matrix is increases in the same way. © 1996 John Wiley & Sons, Inc.     

Reactive compatibilization of blends of PET and PP modified by GMA grafting

The melt radical grafting of glycidyl methacrylate (GMA) onto isotactic polypropylene (PP) was carried out in Brabender internal mixer and the influence of reaction procedure, radical initiator concentration and addition of co-monomer (styrene) on the grafting efficiency was examined. The viscosity, the thermal behaviour and melt rheology of PP-g-GMA samples was then analysed as a function of grafted GMA content. Blends of poly(ethylene terephthalate) (PET) with PP and PP-g-GMA (5.2 wt% GMA), prepared in internal mixer, were characterised by SEM, DSC and melt viscosimetry. The morphological analysis of PET/PP-g-GMA blends (80/20, 50/50 w/w) pointed out a marked improvement of phase dispersion (with particle size of about 0.6 μm for 80/20 blend) and interfacial adhesion, as compared to non-compatibilized PET/PP blend. The results of mixing torque and thermal analysis supported the occurrence of in-situ compatibilization reaction between epoxy groups of GMA modified PP and carboxyl end-groups of PET in the melt.     

Morphology of nylon 6/polypropylene blends compatibilized with maleated polypropylene

Transmission electron microscopy (TEM) was used to examine the morphology of blends of nylon 6 and polypropylene (PP) containing various maleated polypropylenes (PP-g-MA). The size of the dispersed polypropylene particles decreases as the content of maleic anhydride in the PP-g-MA increases for binary blends of nylon 6 and the maleated polypropylenes. Ternary blends of nylon 6, PP, and PP-g-MA show morphologies that depend on the content of maleic anhydride of the PP-g-MA and on the miscibility of PP and PP-g-MA. Blends where PP and PP-g-MA are immiscible show a bimodal distribution of particle sizes. Miscibility of the PP and PP-g-MA was determined by TEM using a special staining technique. Experimental observations of miscibility were further corroborated by thermodynamic calculations. The morphology of the ternary blends was also found to be dependent on the ratio of PP/PP-g-MA. By changing this ratio it was possible to induce drastic changes of morphology, going from a continuous nylon 6 phase to a continuous PP phase at a fixed composition. The mechanical properties of these blends were found to be dependent on their morphology. ©1995 John Wiley & Sons, Inc.     

Rheological,mechanical and morphological properties of thermoplastic vulcanizates based on NR‐g‐PMMA/PMMA blends

Graft copolymer of natural rubber and poly(methyl methacrylate) (NR‐g‐PMMA) was prepared using semi‐batch emulsion polymerization technique via bipolar redox initiation system. It was found that the grafted PMMA increased with the increase of methyl methacrylate (MMA) concentration used in the graft copolymerization. The NR‐g‐PMMA was later used to prepare thermoplastic vulcanizates (TPVs) by blending with PMMA through dynamic vulcanization technique. Conventional vulcanization (CV) and efficient sulphur vulcanization (EV) systems were studied. It was found that the CV system provided polymer melt with lower shear stress and viscosity at a given shear rate. This causes ease of processability of the TPVs via extrusion and injection molding processes. Furthermore, the TPVs with the CV system showed higher ultimate tensile strength and elongation. The results correspond to the morphological properties of the TPVs. That is, finer dispersion of the small vulcanized rubber particles were observed in the PMMA matrix. Various blend ratios of the NR‐g‐PMMA/PMMA blends using various types of NR‐g‐PMMA (i.e. prepared using various percentage molar ratios of NR and MMA) were later studied via dynamic vulcanization by a conventional sulphur vulcanization system. It was found that increasing the level of PMMA caused increasing trend of the tensile strength and hardness properties but decreasing level of elongation properties. Increasing level of the grafted PMMA in NR molecules showed the same trend of mechanical properties as in the case of increasing concentration of PMMA used as a blend component. From morphological studies, two phase morphologies were observed with a continuous PMMA phase and dispersed elastomeric phase. It was also found that more finely dispersed elastomeric phase was obtained with increasing the grafted PMMA in the NR molecules. Copyright © 2005 John Wiley & Sons, Ltd.     

Molecular weight segregation induced by interfacial melt reactivity in polyamide 6/reactive rubber blends

Polyamide 6 (PA) and ethylene-propylene rubber with maleic functionality (EPMA) were blended in a batch mixer. EPMA anhydride groups react with amine chain ends of polyamide and form a grafted copolymer at the interface. The molecular weights of the grafted PA and of the free PA were measured. The molecular weight of the free PA decreases during the processing. This effect is due to the hydrolysis of the PA consecutively to its reaction with anhydride groups. The molecular weight of both grafted and free polyamide decreases during the processing. Moreover, the molecular weight of the grafted PA is lower than that of the free PA. At constant mixing time, a high conversion level produces grafted PA with a higher molecular weight. This is the result of molecular weight segregation for interfacial reaction. Small molecules react faster at the interface than larger ones. If we compare experimental results with model predictions, two segregation regimes are observed. For high shear and low EPMA concentrations, dispersion is very fast; the segregation only depends on molecular elasticity. In this case, the best correlation between model and experiment is obtained for low interfacial thicknesses. For low shear, or for EPMA concentrations close to the phase inversion composition, the segregation is more noticeable, which is mainly due to the diffusion of macromolecules through the brush of already grafted molecules. In this case, there is a clear competition between the compatibilization and the grafting reaction. Molecular weight segregation gives low ratio of the grafted PA molecular weight to the free PA molecular weight. This is detrimental to interfacial properties of the grafted copolymer formed by melt reactivity. Strategies are developed to improve this ratio in order to investigate its influence on the mechanical properties. © 1995 John Wiley & Sons, Inc.     

Reactivity of functional SAN toward coreactive EPR‐g‐MA at planar interface

The grafting kinetics of reactive poly(styrene‐co‐acrylonitrile) (SAN) onto EPR‐g‐MA was studied under isothermal conditions, at the planar interface of an SAN/ethylene‐propylene rubber (EPR) bilayer film in relation to the type of reactive groups, NH₂ versus carbamate (which is an amine precursor), attached to SAN. The amount of SAN chemically bound to EPR chains at the interface was estimated by selectively washing off the unreacted SAN chains before X‐ray photon spectroscopic analysis of the released surface. It is clear that the mutual reactivity of the reactive groups, i.e., the NH₂–MA pair versus the carbamate–MA pair, has a decisive effect on the amount of SAN that reacts with EPR‐g‐MA at the interface. In case of SAN‐carb, the grafting reaction is controlled by the thermolysis of the carbamate groups into primary amines. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3682–3689, 2000     

Chemical and morphological evolution of PA‐6/Epm/Epm‐g‐MA blends in a twin screw extruder

Chemical conversion and morphological evolution of PA‐6/EPM/EPM‐g‐MA blends along a twin screw extruder were monitored by quickly collecting small samples from the melt at specific barrel locations. The results show that the MA content of all blends decreases drastically in the first zone of the extruder, i.e., upon melting of the blend components. Significant changes in morphology are also observed at this stage. A correlation between chemistry and morphology could thus be established. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1311–1320, 1999     

Influence of hyperbranched polymers on the interfacial tension of polypropylene/polyamide‐6 blends

The compatibilizing effect of polypropylene (PP) grafted with hyperbranched polymers (PP–HBP) has been investigated in PP/polyamide‐6 (PA‐6) blends. Because of its high reactivity and diffusitivity, PP–HBP has been shown to be a more effective compatibilizer in decreasing the interfacial tension than the commonly used maleic anhydride–grafted polypropylene (PP–MAH). This article describes the influence of PP–HBP and PP–MAH on the interfacial tension between PP and PA‐6, as measured by the deformed drop‐retraction method (DDRM). Overall, PP–HBP yielded lower interfacial tension values between PP and PA‐6, which resulted in a finer particle size of the secondary phase. The time dependence of the interfacial tension can be monitored by DDRM, enabling evaluation of the diffusitivity and reactivity of the compatibilizer. A model based on particle coarsening has been developed to describe the time dependence of the interfacial tension. This model showed that the diffusitivity and reactivity for PP–HBP was higher than that of PP–MAH. Therefore, PP–HBP has strong potential as a compatibilizer in diffusitivity‐dependant processes such as film coextrusion and fusion bonding. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2069–2077, 1999     

Morphology of reactive PP/PS blends with hyperbranched polymers

To study the efficiency of different mechanism for reactive compatibilization of polypropylene/polystyrene (PP/PS) blends main chain or terminal functionalized PP and terminal functionalized PS have been synthesized by different methods. While the in-situ block and graft copolymer formation results in finer phase morphologies compared to the corresponding non-reactive blends, the morphology development in the ternary blend system PP/PS + HBP (hyperbranched polymer) is a very complex process. HBP with carboxylic acid endgroups reacts preferably with the reactive sites of the oxazoline functionalized PS (PS-Ox) and locates mainly within the dispersed PS-Ox phase. A bimodal size distribution of the PS-Ox particles within the oxazoline modified PP (PP-Ox) matrix phase is observed with big PS-Ox particles (containing the HBP as dispersed phase) and small PS-Ox particles similar in size like the unimodal distributed particles in the non-reactive PP-Ox/PS-Ox blends. Factors influencing the morphology are discussed.     

Size‐Dependent Interfacial Tension of Polymer Blends with Broad Composition Polydispersity

The surface tension as a function of system size of a pure blend with chemically polydisperse compatibilizer is investigated by simulation. The main finding is that such compatibilizers adsorb readily at the interface between the bulk phases giving rise to very broad interfacial zones. This phenomenon leads to a marked size dependence of the interfacial tension. However the adsorption only leads to a decrease of 40% of the interfacial tension of the blend without compatibilizer. The limited effect on interfacial tension is explained by the observation that a considerable fraction of the compatibilizing chains do not contribute to the interfacial tension, instead these chains become part of an inhomogeneous phase with extensive thermodynamic properties.

     

Reactive compatibilization of epoxy/polyorganosiloxane blends

A new thermoset material based on DGEBA with polyaminosiloxane curing agents is presented. The system shows reaction-induced compatibilization which prevents coalescence of polysiloxane and DGEBA rich domains, leading to gradient structured morphologies. The influence of curing temperature and/or chemical nature of the siloxane on the morphology and surface microhardness were examined. When siloxane is pre-reacted with epoxypropylphenylether (EPPE), a more homogeneous material is obtained. Microhardness profiles on the material are strongly influenced by the extension of the compositional gradients.     

Thermooxidative stability of hot melt adhesives based on metallocene polyolefins grafted with polar acrylic acid moieties

The present paper describes the thermal oxidation of a mixture applied as hot melt adhesive and particularly of its essential polymeric component ethylene-propylene copolymer Licocene 2602 either virgin or grafted by acrylic acid. Chemiluminescence in oxygen under both nonisothermal and isothermal conditions was used as the tool for evaluation of oxidation stability of samples. The effect of various concentrations of stabiliser Naugard XL1 acting as a metal deactivator and phenolic antioxidant was also determined and the antioxidant selected was found to be an efficient thermooxidative stabiliser. The results appear to be of importance for practical multiple application of hot melt adhesives to be used for binding books.     

Specific interactions and phase behavior of ternary poly(2‐vinylpyridine)/poly(N‐vinyl‐2‐pyrrolidone)/bisphenol A blends

Hydrogen‐bonding interactions between bisphenol A (BPA) and two proton‐accepting polymers, poly(2‐vinylpyridine) (P2VPy) and poly(N‐vinyl‐2‐pyrrolidone) (PVP), were examined by Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The Flory–Huggins interaction‐energy densities of BPA/P2VPy and BPA/PVP blends were determined by the melting point depression method. The interaction parameters for both BPA/P2VPy and BPA/PVP blend systems were negative, demonstrating the miscibility of BPA with P2VPy as well as PVP. The miscibility of ternary BPA/P2VPy/PVP blends was examined by DSC, optical observation, and solid‐state nuclear magnetic resonance spectroscopy. The experimental phase behavior of the ternary blend system agreed with the spinodal phase‐separation boundary calculated using the determined interaction‐energy densities. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1125–1134, 2002     

The early stage of the morphology development of immiscible polymer blends during melt blending: Compatibilized vs. uncompatibilized blends

The early stage of the morphology development has been studied for the blending of two immiscible polymers. Controlled experiments were carried out in a batch mixer in such a way that the rate of melting was low enough to follow up the morphology development of dilute and concentrated systems. For a dilute or semidilute polypropylene and polyamide 6 (PP/PA6) blend with 0.5, 5, or 10 wt % PA6, particles formed in the very early stage of melt blending were very small, of the order of 0.25 to 0.3 μm in radius. They immediately began to grow in size when no compatibilizer was added, indicative of coalescence even in the very early stage of melt blending and/or in very dilute systems (0.5 wt % PA6). Further growth of the particles was eliminated with the introduction of a graft copolymer compatibilizer providing evidence of the stabilizing effect of the copolymer from the very beginning of melting blending. However, the behavior of the morphology development of a concentrated PP/PA6 (80/20) system was similar to that reported in the literature. The average radius of the particles of the uncompatibilized blend decreased with increasing mixing time, whereas that of the compatibilized blend remained almost constant during mixing. The most favorable conditions to obtain a fine morphology seems to be the following: rate of melting/plastification of pellets < rate of dispersion (deformation + breakup) of the polymer melt to small particles < rate of stabilization (with an adequate copolymer). © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 601–610, 2001     

Compatibilized blends of thermoplastic polyurethane (TPU) and polypropylene

Compatibilized blends of thermoplastic polyurethane (TPU) and polypropylene (PP) were developed using amine (primary or secondary) functionalized PP's (PP-g-NH₂ or PP-g-NHR). The strategy of reactive compatibilization is based on fast reactions between amine functional groups and urethane linkages or traces of free isocyanates released by thermal degradation of TPU. Excellent compatibilization between TPU and PP was confirmed by rheological, morphological, and mechanical properties. Much finer domain size, higher interfacial adhesion, and more stable morphologies were clearly observed by scanning electron microscopy. Significant improvements in the overall mechanical properties (tensile, tear, abrasion) imply significantly more reaction between TPU and PP phases in the two TPU/PP blends containing PP-g-NH₂ or PP-g-NHR than a TPU/PP blend using PP-g-MA as a compatibilizing agent.     

Melt rheology and morphology of thermoplastic elastomers from polyethylene/nitrile‐rubber blends: The effect of blend ratio,reactive compatibilization,and dynamic vulcanization

A study of the melt‐rheological behavior of thermoplastic elastomers from high‐density polyethylene and acrylonitrile butadiene rubber (NBR) blends was carried out in a capillary rheometer. The effect of the blend ratio and shear rate on the melt viscosity reveals that the viscosity decreases with the shear rate but increases with NBR content. Compatibilization by maleic anhydride modified polyethylene has no significant effect on the blend viscosity, but a finer dispersion of the rubber is obtained, as is evident from scanning electron micrographs. The melt‐elasticity parameters, such as the die swell, principal normal stress difference, recoverable shear strain, and elastic shear modulus of the blends, were also evaluated. The effect of annealing on the morphology of the extrudate reveals that annealing in the extruder barrel results in the coalescence of rubber particles in the case of the incompatible blends, whereas the tendency toward agglomeration is somewhat suppressed in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1104–1122, 2000     

Reactive compatibilization of nylon copolymer/EPDM blends: experimental aspects and their comparison with theory

In situ reactive compatibilization was first time applied to a low melting nylon (nylon 6 and 66 copolymer) and EPDM blend system. The effects of in situ compatibilization and concentration of compatibilizer on the morphology and mechanical properties of nylon/EPDM blends have been investigated. The influence of EPM‐g‐MA on the phase morphology was examined by the scanning electron microscopy (SEM) after preferential extraction of the minor phase. The SEM micrographs were quantitatively analyzed for domain size measurements. The compatibilizer concentrations used were 0, 1, 2.5, 5, and 10 wt%. The graft copolymer (nylon‐g‐EPM) formed at the interface showed relatively high emulsifying activity. A maximum phase size reduction was observed when 2.5 wt% of compatibilizer was added to the blend system. This was followed by a leveling‐off at higher loadings indicating interfacial saturation. The conformation of the compatibilizer at the interface was deduced based on the area occupied by the compatibilizer at the blend interface. The experimental compatibilization results were compared with theoretical predictions of Noolandi and Hong. It was concluded that the molecular state of compatibilizer at interface changes with concentration. The in situ compatibilized blends showed considerable improvement in mechanical properties. Measurement of tensile properties shows increased elongation as well as enhanced modulus and strength up on compatibilization. At higher concentrations of compatibilizer, a leveling‐off of the tensile properties was observed. A good correlation has been observed between the mechanical properties and morphological parameters. Copyright © 2007 John Wiley & Sons, Ltd.     

Formation and compatibilizing effect of the grafted copolymer in the reactive blending of 2-diethylsuccinate containing polyolefins with poly-ϵ-caprolactam (nylon-6)

The intermolecular reaction and its role in determining the partial compatibility between diethylsuccinate containing linear low-density polyethylene or ethylene propylene copolymer and poly-ϵ-caprolactam (PA6) has been investigated in the melt using a Brabender mixer. The reaction product has been submitted to selective solvent extraction with formic acid and n-heptane; the characterization of the two extracted fractions and the insoluble residue has demonstrated the formation of a polyolefin–nylon (PO–PA6) grafted copolymer. The formation of grafted copolymer has an evident effect on the compatibilization of the two original polymers, indeed the differential scanning calorimetry analysis shows a remarkable decrease of temperature and enthalpy of PA6 crystallization. Moreover scanning electron microscopy micrographs show clear evidence of size reduction of PA6 domains associated with improved interface interactions. © 1998 John Wiley & Sons, Ltd.     

Fabrication of helical microfibers from melt blown polymer blends

Helical fibers in micro/nanoscale resembling plant tendrils have been of increasing interest due to their unique characteristics. Fabrication of helical microfibers from polymer blends using melt blowing technique is reported in this study. An elastomeric and a stiff polymer are chosen as the raw materials, and a designed swirl‐die melt‐blowing device is used to prepare the microfibrous nonwovens. Focusing on the interfacial interaction between the polymer components induced by the polymer structure and intrinsic properties, airflow field characteristics, and processing parameters, we explore the effects of various parameters on helical fiber formation. Differential scanning calorimeter is employed to examine the rigidity of polymer chains, and the three‐dimensional airflow field simulation is carried out to reveal the airflow field characteristics. This work can provide a promising technique for producing stretchable microfibrous materials which have potential applications in field such as filtration materials and oil sorbents. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 970–977