Preparation and characterization of electrospun ultrafine polyamide‐6 nanofibers

We report on the preparation and characterization of ultrafine polyamide‐6 nanofibers by the electrospinning technique. The effect of electrospinning on the formation of ultrafine polyamide‐6 nanofiber structure was examined. The morphological and structural characterizations and thermal properties of the ultrafine polyamide‐6 nanofibers were investigated in comparison with bulk polyamide‐6 pellets. In order to accurately characterize the ultrafine polyamide‐6 nanofiber structure by direct identification of mass resolved components, we performed matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry. Field emission scanning electron microscopy images revealed the presence of ultrafine polyamide‐6 nanofibers bound between the main fibers. The diameter of the polyamide‐6 nanofibers was observed to be in the range 75–110 nm, whereas the ultrafine structures consisted of regularly distributed very fine nanofibers with diameters of about 9–28 nm. The MALDI‐TOF spectra showed the presence of protonated and sodiated ions that were assigned to polyamide‐6 chains. Copyright © 2011 Society of Chemical Industry     

Mechanical characterization of toughened polyamide‐6 blends with metallocene copolymers

The effectiveness as impact modifier of two in situ maleated metallocene copolymers, a metallocene polyethylene, (mPE1) and a metallocene ethylene‐propylene (mEPDM) and three commercial maleated copolymers (mPE2‐g‐MA, EPDM‐g‐MA, and mEPR‐g‐MA) were studied in binary and ternary blends carried out in an intermeshing corotating twin‐screw extruder with polyamide‐6 (PA) as matrix (80 wt %). Also, the effects of the grafting degree, viscosity ratio, and crystallinity of the dispersed phases on the morphological and mechanical properties of the blends were investigated. A significant improvement of the compatibility of these grafted copolymers with PA6 was shown by FTIR spectroscopy, capillary rheometry, and scanning electron microscopy (SEM) in all reactive blends. The tensile strength values of the mEPR‐g‐MA/PA2 binary blend showed the highest strain hardening. The results obtained in this work indicated that the effectiveness of the grafted copolymers as impact modifier depends on the morphology of the blends and a combination of tensile properties of the blend components such as Young's modulus, Poisson ratio, and break stress. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of star‐branched polyisobutylene with SIpS triblock copolymer core

Well‐defined polystyrene‐b‐polyisoprene‐b‐polystyrene (SIpS) triblock copolymers with different microstructures were synthesized by living anionic polymerization. The synthesis of star‐branched polyisobutylene (PIB) was accomplished by the cationic polymerization in 2‐chloro‐2,4,4‐trimethylpentane/titanium tetrachloride/SIpS triblock copolymer/2,6‐di‐tert‐butylpyridine initiating system. The double bonds in SIpS triblock copolymer were activated as starting points for isobutylene polymerization. The formation of star‐branched architecture was demonstrated by size‐exclusion chromatography with quadruple detection: refractive index, multiangle laser light scattering, viscometric, and ultraviolet detectors. SIpS triblock copolymer with high 3,4‐PIp content is more reactive than that with high 1,4‐PIp content in cationic initiating stage. The yields of star‐branched PIB were remarkably dependent on the reaction time of TMP⁺ with SIpS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

In situ polymerization and characterization of polyamide‐6/silica nanocomposites derived from water glass

Polyamide‐6/silica nanocomposites were prepared via an in situ polymerization route using silicic acid as the precursor of silica, which was extracted from water glass. Scanning electron microscopy observations showed that the silica particles were well dispersed in the polyamide‐6 matrix on the nanometer scale, which demonstrated that this method could effectively avoid agglomeration of the inorganic particles. The coupling agent, (γ‐aminopropyl) triethoxysilane, was added to introduce interfacial interactions between the silica and the polymer matrix, which led to an increased graft of polymer on the silica surface and made the material display higher performance. It was found that the incorporation of the inorganic component significantly increased the melt viscosity, tensile strength, Young's modulus, thermal decomposition temperature, glass transition temperature and Vicat softening temperature of the polyamide‐6 resin. The reinforcement of the silica particles was clearly demonstrated. Copyright © 2004 Society of Chemical Industry     

Preparation and characterization of polyamide‐leather wastes polymer composites

Chrome tanning of leather improves its appearance, but at the same time, it emits both solid and liquid wastes. These solid wastes mainly after shaving process present in large amount causing hazard to the environment. Leather wastes were disintegrated to prepare hide powder and mixed with polyamide (nylon 6) in different ratios. The physical, mechanical and thermal properties of different composites were investigated, which showed enhancement in physical characters but decreasing in mechanical properties. The charred residue increases by increasing the presence of leather waste filler. Morphological studies were performed on the fractured surface of composites showed uniform and fine particles dispersion. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Innovative polyamide‐based packaging of fresh meat

Innovative polymeric films based on blends of nylon 6 and ethylene‐co‐vinyl alcohol, previously tested by contact with the simulating fat‐containing foods, were further tested as packaging for fresh minced meat. As quality attributes for the shelf‐life evaluation, the microbiological parameters and some chemical–physical parameters were chosen. The changes that occurred during the evaluation period of 6 days were monitored by several means on both the polymer films and the fresh meat. The results suggest that the barrier properties of the polymeric films were shown to play a determinant role in the lipid oxidation, thus confirming the previous evaluation of the simulating foods. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 23–29, 2004     

Effects of olefin‐based compatibilizers on the morphology,thermal and mechanical properties of ABS/polyamide‐6 blends

In this study, commercially available epoxidized and maleated olefinic copolymers, EMA‐GMA (ethylene‐methyl acrylate‐glycidyl methacrylate) and EnBACO‐MAH (ethylene‐n butyl acrylate‐carbon monoxide‐maleic anhydride), were used at 0, 5, and 10% by weight to compatibilize the blend composed of ABS (acrylonitrile‐butadiene‐styrene) terpolymer and PA6 (polyamide 6). Compatibilizing performance of these two olefinic polymers was investigated from blend morphologies, thermal and mechanical properties as a function of blend composition, and compatibilizer loading level. Scanning electron microscopy (SEM) studies showed that incorporation of compatibilizer resulted in a fine morphology with reduced dispersed particle diameter at the presence of 5% compatibilizer. The crystallization behavior of PA6 phase in the blends was explored for selected blend compositions by differential scanning calorimetry (DSC). At high compatibilizer level a decrease in the degree of crystallization was observed. In 10% compatibilizer containing blends, formation of γ‐crystals was observed contrary to other compatibilizer compositions. The behavior of the compatibilized blend system in tensile testing showed the negative effect of using excess compatibilizer. Different trends in yield strengths and strain at break values were observed depending on compatibilizer type, loading level, and blend composition. With 5% EnBACO‐MAH, the blend toughness was observed to be the highest at room temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 926–935, 2007     

Electrospun polyamide‐6 membranes containing titanium dioxide as photocatalyst

Electrospun polyamide‐6 membranes containing titanium dioxide (TiO₂) photocatalyst were prepared and characterized. By tailoring the electrospinning parameters it was possible to obtain membranes having two different thicknesses, namely 5 and 20 µm, in which TiO₂ particles were homogeneously dispersed. As a comparison, hybrid films made with polyamide‐6 matrix and TiO₂ filler were successfully produced, with inorganic/organic ratios of 10 and 20 wt%. The photocatalytic activity of both hybrid systems was evaluated by following the degradation of methylene blue as a target molecule as a function of UV irradiation time. A smoother degradation was recorded for the electrospun membranes with respect to the hybrid films probably due to a less exposed surface because of the highly porous structure. Even if a longer photodegradation time was necessary, the degradation of the dye was successfully achieved. Copyright © 2010 Society of Chemical Industry     

Toughening and compatibilization of polypropylene/polyamide‐6 blends with a maleated–grafted ethylene‐co‐vinyl acetate

In this article, maleated–grafted ethylene‐co‐vinyl acetate (EVA‐g‐MA) was used as the interfacial modifier for polypropylene/polyamide‐6 (PP/PA6) blends, and effects of its concentration on the mechanical properties and the morphology of blends were investigated. It was found that the addition of EVA‐g‐MA improved the compatibility between PP and PA6 and resulted in a finer dispersion of dispersed PA6 phase. In comparison with uncompatibilized PP/PA6 blend, a significant reduction in the size of dispersed PA6 domain was observed. Toluene‐etched micrographs confirmed the formation of interfacial copolymers. Mechanical measurement revealed that the addition of EVA‐g‐MA markedly improved the impact toughness of PP/PA6 blend. Fractograph micrographs revealed that matrix shear yielding began to occur when EVA‐g‐MA concentration was increased upto 18 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3300–3307, 2006     

Morphology and mechanical properties of polyamide‐6/K resin blends

Mechanical properties and morphological studies of compatibilized blends of polyamide‐6 (PA‐6)/K resin grafted with maleic anhydride (K‐g‐MAH) and PA‐6/K resin/K‐g‐MAH were investigated as functions of K resin/K‐g‐MAH and dispersed phase K resin concentrations, and all the blends were prepared using twin screw extruder followed by injection molding. Scanning electron microscopy (SEM) were used to assess the fracture surface morphology and the dispersion of the K resin in PA‐6 continuous phase, the results showing extensive deformation in presence of K‐g‐MAH, whereas, uncompatibilized PA‐6/K resin blends show dislodging of K resin domains from the PA‐6 matrix. Dynamic mechanical thermal analysis (DMTA) test reveals the partially miscibility of PA‐6 with K‐g‐MAH, and differential scanning calorimetry (DSC) results further identified that the introduction of K‐g‐MAH greatly improved the miscibility between PA‐6 and K resin. The mechanical properties of PA‐6/K resin blends and K‐g‐MAH were studied through bending, tensile, and impact properties. The Izod notch impact strength of PA‐6/K‐g‐MAH blends increase with the addition of K‐g‐MAH, when the K‐g‐MAH content adds up to 20 wt %, the impact strength is as more than 6.2 times as pure PA‐6, and accompanied with small decrease in the tensile and bending strength less than 12.9% and 17.5%, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of flame‐retardant melamine cyanurate/polyamide 6 nanocomposites by in situ polymerization

This article focuses on an improved method, i.e., improved in situ polymerization of ε‐caprolactam in the presence of melamine derivatives to prepare flame‐retardant melamine cyanurate/polyamide 6 (MCA/PA6) nanocomposites. The chemical structures of these synthetic flame retardant composites are characterized by Fourier‐transform infrared spectroscopy and X‐ray diffraction. Morphologies, mechanical properties, and thermal properties also are investigated by the use of transmission electron microscopy, mechanical testing apparatus, differential scanning calorimetry, and thermogravimetric analysis, respectively. Through transmission electron microscopy photographs, it can be found that the in situ‐formed MCA nanoparticles with diametric size of less than 50 nm are nanoscaled, highly uniformly dispersed in the PA6 matrix. These nanocomposites, which have good mechanical properties, can reach UL‐94 V‐0 rating at 1.6‐mm thickness even at a relatively low MCA loading level. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

In‐process ultrasonic measurements of orientation and disorientation relaxation of high‐density polyethylene/polyamide‐6 composites with compatibilizer

The relaxation processes of orientation and disorientation of melts of high‐density polyethylene (HDPE) and polyamide‐6 (PA6) blends compatibilized with a compatibilizer precursor (CP) of HDPE‐grafted maleic anhydride (HDPE‐g‐MAH) were investigated in a restricted channel using real‐time ultrasonic technique. The experimental results showed that the evolution of ultrasonic velocity of HDPE/PA6 blends during the orientation or disorientation processes could be described by the exponential equation from which the maximum orientation degree and relaxation time could be obtained. Subsequently, the effects of CP on the relaxation processes of orientation and disorientation were studied. In addition, the relations of the CP content and the morphology and viscosity were investigated by scanning electron microscope analysis and rheological tests. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Investigation of thermal degradation and flammability of polyamide‐6 and polyamide‐6 nanocomposites

In this paper, polyamide‐6 and polyamide‐6 nanocomposites were prepared by direct melt intercalation technique. The thermal degradation behavior of both polyamide‐6 and polyamide‐6 clay nanocomposites has been studied. The apparent activation energy of the nanocomposites is almost the same with that of pure polymer under nitrogen, but the apparent activation energy of the nanocomposites is greatly enhanced in air atmosphere. This increasing trend coincides with the thermal analysis and the cone calorimeter results, which may suggest that the polymer/clay nanocomposites have a higher thermal stability and lower flammability. The kinetic analysis also indicates that the pyrolytic degradation and the thermal oxidative degradation of PA6 and PA6/OMT nanocomposites are two kinds of different reaction models. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2297–2303, 2007     

Study on morphology of compatibilized poly (vinyl chloride)/ultrafine polyamide‐6 blends by styrene–maleic anhydride

Ultrafine polyamide‐6 (UPA6) with a size of 4–8 μm was prepared via jet‐milling. Blends of poly (vinyl chloride) (PVC) and UPA6 using a reactive copolymer styrene–maleic anhydride (SMA‐18%) were prepared. The change in morphology and structure of the blends were studied using differential scanning calorimetry, scanning electron microscopy, and X‐ray diffraction. The blend behavior was also determined experimentally using dynamic mechanical analysis. Contrasted to the original PA6, the crystallinity of the UPA6 decreased, the size of its crystallites were reduced, and its melting point decreased to 175°C. In all blends, PVC formed the continuous matrix phase. SMA is miscible with PVC and tends to be dissolved in the PVC phase during the earlier stages of blending. The dissolved SMA has the opportunity to react with PA6 at the interface to form the desirable SMA‐g‐PA6 copolymer. This in situ formed SMA‐g‐PA6 graft copolymer tends to anchor along the interface to reduce the interfacial tension and results in finer phase domains. Cocrystallity existed in PVC/(UPA6/SMA) at a ratio of 82/(18/5). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 850–854, 2005     

Effect of moisture and filler content on the structural,thermal and dielectric properties of polyamide‐6/boehmite alumina nanocomposites

Polyamide‐6 (PA‐6)/boehmite alumina (BA) nanocomposites were prepared via direct melt compounding. Structural, thermal and dielectric properties of ‘as‐received’ (including moisture) and ‘dried’ (thermally treated) specimens were examined. The BA nanofiller was homogeneously dispersed in the PA‐6 matrix. XRD and FTIR revealed that crystallization of PA‐6 in the γ phase was favoured over α phase with increasing BA content. The crystallinity index (CI) and the percentage of α and γ phases were also evaluated. Dried specimens exhibited a lower CI than as‐received specimens while the CI decreased with the addition of filler. Broadband dielectric spectroscopy revealed the presence of γ, β and α relaxations, the Maxwell–Wagner–Sillars effect and the contribution of conductivity relaxation in the as‐received samples. The drying procedure unmasked a double feature of both β and α modes. The results of the complementary techniques were analysed and the effects of moisture and/or the incorporation of BA nanofiller on the microstructure of the PA‐6 matrix are disclosed. © 2019 Society of Chemical Industry     

Studies on polyamide‐6/polyolefin blend system compatibilized with epoxidized natural rubber

Infrared spectra of polyamide‐6 (PA6) with and without epoxidized natural rubber (ENR) are presented. The influence of ENR used as a compatibilizer on the morphologies, crystallizability, mechanical properties, and thermal behavior of the polyamide‐6/polyolefins (PO) blends are studied. The infrared spectra suggest that under normal processing conditions, the carboxyl end groups of PA6 could chemically react in situ with the epoxy groups of ENR, and ester groups are created. This means that the PA6‐ENR grafting copolymer could be obtained during processing. All the morphological characterizations and thermal analyses show that the compatibility of PA6/PO blends is obviously improved by ENR because the copolymer increases the interaction between PA6 and PO. It is also found that the toughness of PA6/PO blends increase significantly after using ENR, while the tensile strength and the softening temperature of PA6/PO blends have almost no change. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 398–403, 2003     

Synthesis and characteristics of thermoplastic elastomer based on polyamide‐6

A new class of polyether amide thermoplastic elastomers (TPAE) was synthesized via a three‐step polymerization route. In the first step a binary carboxyl terminated polyamide‐6 (PA6) with relatively low number‐average molecular weight was prepared via a caprolactam hydrolytic ring‐opening process. 4,4′‐Diphenylmethane diisocyanate (MDI) was reacted with the PA6 to produce PA6–MDI hard segments in the second step. Chain extension of the hard segments with poly(tetramethylene glycol) was the last step to furnish a series of new TPAEs. Structural characterization, physical properties and the effects of reaction conditions on the properties of the copolymer were investigated by infrared spectroscopy, ¹H nuclear magnetic resonance spectroscopy and other analytical techniques. Possible side reactions and phase separation are reported. Copyright © 2011 Society of Chemical Industry     

Effects of microcompounding process parameters on the properties of ABS/polyamide‐6 blends based nanocomposites

Melt intercalation method was applied to produce acrylonitrile‐butadiene‐styrene/polyamide‐6 (ABS/PA6) blends based organoclay nanocomposites using a conical twin‐screw microcompounder. The blend was compatibilized using a maleated olefinic copolymer. The effects of microcompounding conditions such as screw speed, screw rotation‐mode (co‐ or counter‐), and material parameters such as blend composition and clay loading level on the morphology of the blends, dispersibility of nanoparticles, and mechanical properties were investigated. Furthermore, corotating screws were modified to achieve elongational flow which is efficient for obtaining dispersive mixing. The morphology was examined by SEM analysis after preferential extraction of the minor phase. Subsequently, the SEM micrographs were quantitatively analyzed using image analyzer software. The morphology of the blends indicated that processing with counter‐rotation at a given screw speed yielded coarser morphology than that of processed with corotation. X‐ray diffraction analysis showed that highest level of exfoliation is observed with increasing PA6 content, at 200 rpm of screw speed and in corotation mode. Also, the effects of screw speed, screw rotation mode, and screw modification were discussed in terms of XRD responses of the nanocomposites. The aspect ratio of the clay particles which were measured by performing image analysis on TEM micrographs exhibited a variation with processing conditions and they are in accordance with the modulus of the nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structure,mechanical, and fracture properties of nanoreinforced and HNBR‐toughened polyamide‐6

Hydrogenated nitrile rubber (HNBR) and synthetic nanofillers, viz. water‐swellable sodium fluorohectorite (FH) and water dispersible boehmite alumina (BA), were used to toughen and reinforce polyamide‐6 (PA‐6). FH and BA were introduced in HNBR latex that was dried prior to melt mixing with PA‐6. Binary blend (PA‐6/HNBR) and ternary nanocomposites (PA‐6/HNBR/nanofiller) were produced and their structure–property relationships studied. HNBR was coarsely and microscale dispersed in PA‐6. FH, slightly intercalated, was present in PA‐6 and in the PA‐6/HNBR interphase, whereas BA was mostly located in the HNBR droplets. HNBR improved the ductility of the PA‐6/HNBR blend at cost of stiffness and strength. The fracture toughness and energy, determined on notched Charpy specimens at different temperatures (T = ?30°C, room temperature, and T = 80°C) were improved by blending with HNBR at 9 wt %. Additional incorporation of the nanofillers in 2.5 wt % enhanced the stiffness and strength of the PA‐6/HNBR blend but reduced its ductility. The fracture toughness of the ternary nanocomposites was between those of PA‐6 and PA‐6/HNBR, whereas their fracture energy fairly agreed with that of the parent PA‐6. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of novolac‐based char former: Silicon‐containing phenolic resin and its synergistic action with magnesium hydroxide in polyamide‐6

Novel novolac‐based char former silicon‐containing phenolic resin (SCPR) was synthesized by the reaction of novolac with γ‐aminopropyltriethoxysilane in ethanol via a dehydration reaction, and the synthesized SCPR was characterized by Fourier transform infrared (FT‐IR) spectra, proton nuclear magnetic resonance (¹H NMR) spectroscopy, and thermogravimetric analysis (TGA). Serving as a synergist of magnesium hydroxide (MH) for the flame retardancy of polyamide 6 (PA6), it shows that the introduction of silicon in the structure of novolac molecule can greatly increase the charring performance of phenolic resin, and effectively eliminate the melt drips of PA6, thus improving the flame retardancy of the PA6. Compared with conventional novolac, the thermal oxidative stability of SCPR was obviously enhanced in the presence of MH due to the decrease of phenol hydroxide groups sensitive to oxidation, as well as the high energy Si–O bond introduced in the molecular structure. Copyright © 2010 John Wiley & Sons, Ltd.