Solid‐phase extrusion of polyamide‐6 by using combined deformation schemes

Potentialities of new combined deformation schemes, including the solid state extrusion through conical die (ED) and equal‐channel multiple angle extrusion (ECMAE) implemented in different sequence to modify structure and properties of semicrystalline polymers, have been studied for polyamide‐6 as an example. It is shown that deformation by the ED‐ECMAE scheme gives the best complex of physical and mechanical properties. A significant improvement in elastic and strength properties of polyamide‐6 with the conserved high level of plastic characteristics has been observed. There was only a slight anisotropy and dispersion of microhardness across the extrudates. A more uniform oriented structure with lamellae orientation along extrudate's axis has been formed in semicrystalline polymer because the ED‐ECMAE scheme implementation. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

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     

Bulk fatigue damage evolution in polyamide‐6 and in a polyamide‐6 nanocomposite

The mechanical response of a polyamide‐6 montmorillonite clay nanocomposite and of a polyamide‐6 was monitored during axial fatigue tests performed at R‐ratios of 0.1 and −1. For both materials, two transitions were usually observed in the evolution of all the stress‐strain‐time parameters studied after similar numbers of loading cycles, suggesting interrelationships between the mechanisms of molecular reorganization. Fatigue test monitoring indicated an initial decrease in the storage modulus and a subsequent trend for this modulus to increase, especially in polyamide‐6. During all tests, a partially recoverable strain was accumulated because of viscoelastic deformation. Nanoparticles reduced this strain in the initial cyclic straining regime but not in the last regime, probably because such particles cannot inhibit viscoelastic events constrained in a volume larger than their interaction volume within the matrix. Based on the accumulated volume variation measured, the nucleation and growth of microvoids can be expected to occur in the last cyclic straining regime. POLYM. COMPOS., 26:636–646, 2005. © 2005 Society of Plastics Engineers     

Spatial orientation of nanoclay and crystallite in microcellular injection molded polyamide‐6 nanocomposites

Three different types of characteristic structures‐microcells, nanoclay, and crystallite lamella‐exist in injection molded polyamide‐6 microcellular nanocomposites. These structures are in completely different scales. The spatial orientation of these microscale structures crucially determines the material's bulk properties. Based on scanning electron microscopy, transmission electron microscopy, and two‐dimensional X‐ray diffractometry measurements, it was found that the nanoclay and the crystallite formed special geometric structures around the microcells and near the part skins. The nanoclay platelets lay almost parallel to the surfaces of the molded parts. Preferred orientation of the crystallites was induced by the presence of the nanoclay. A molecular‐based model is proposed to describe the structural hierarchy and correlations among the microcells, nanoclay, and crystallite lamella. From the small‐angle X‐ray scattering experiments, it was found that microcellular injection molding produces relatively smaller crystallite lamella than that of conventional injection molding, and that for both solid and microcellular neat resin parts the crystallite lamella thickness at the part skin is smaller than that at the core. Polarized optical microscopy results also indicated that the size of crystallites in the microcellular neat resin and nanocomposite parts is smaller than that in the corresponding solid parts. POLYM. ENG. SCI., 47:765–779, 2007. © 2007 Society of Plastics Engineers     

Glass fiber reinforced polyamide‐6 nanocomposites

Polyamide 6 nanocomposites (PA6/NC) are novel type of composite materials comprising extremely thin, “nanometer scale” dispersions of smectitic silicate platelets. We prepared such PA6/NC materials via a melt compounding technique using suitably organomodified montmorillonite or hectorite type clays. The high surface to volume ratio of such thin silicate dispersions in PA6/NC leads to a high reinforcement efficiency even at 2 to 5 wt% of clay, achieving high specific modulus, strength and heat distortion temperature under load (DTUL). In addition, the platelet orientation and their surface nucleation effects seem to promote a faster crystallization and higher crystallinity in PA‐6/NC (particularly at the surface and in thin‐wall injection moldings), as compared to the standard PA‐6. Such morphological features in PA‐6/NC also result in improved moisture resistance. Recognizing these benefits, we investigated the use of PA‐6/NC as a matrix for making both short and long glass fiber (GF) reinforced composites. Significant improvements in modulus were achievable in both the dry and the moisture conditioned state for PA‐6/NC compared to standard PA‐6, at any given level of glass fiber reinforcement. In general a small amount (3‐4 wt%) of the nanometer scale dispersed clay is capable of replacing up to 40 wt% of a standard mineral filler or 10‐15 wt% of glass fiber in PA‐6 composites to give equivalent stiffness at a lower density or a lower part weight advantage. In addition, improved moisture resistance, permeation barrier and fast crystallization/mold cycle time contribute to the usefulness of such composites.     

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     

Biaxial orientation of linear polyethylenes using the compressive deformation process

The tensile properties of three grades of linear polyethylene were enhanced by a factor of as much as 15 using a melt/solid phase compressive deformation process that produced equi-biaxial planar orientation in the sheet. Ultra high molecular weight polyethylene with planar isotropy and an in-plane modulus of 10 GPa and a tensile strength of 330 MPa was produced using this method. It was found that the molecular weight had a significant influence on the optimum processing temperature, the ultimate biaxial deformation ratio and hence the ultimate tensile properties. High density polyethylene processed under ideal conditions had a tensile modulus of 2.3 GPa and a tensile strength of 250 MPa. The tensile strength increased linearly with increasing biaxial deformation ratio and the tensile modulus increased non-linearly with increasing biaxial deformation ratio. The deformation rate and the dwell time did not have a significant effect on the tensile properties. Shrinkage tests showed that biaxial deformation was less effective than uniaxial deformation in inducing orientation of the polymer chains, however differential scanning calorimetry results were consistent with the presence of extended chain crystals in very highly oriented ultra high molecular weight polyethylene sheets.     

Study of injection molded microcellular polyamide‐6 nanocomposites

This study aims to explore the processing benefits and property improvements of combining nanocomposites with microcellular injection molding. The microcellular nanocomposite processing was performed on an injection‐molding machine equipped with a commercially available supercritical fluid (SCF) system. The molded samples produced based on the Design of Experiments (DOE) matrices were subjected to tensile testing, impact testing, Dynamic Mechanical Analysis (DMA), and Scanning Electron Microscope (SEM) analyses. Molding conditions and nano‐clays have been found to have profound effects on the cell structures and mechanical properties of polyamide‐6 (PA‐6) base resin and nanocomposite samples. The results show that microcellular nanocomposite samples exhibit smaller cell size and uniform cell distribution as well as higher tensile strength compared to the corresponding base PA‐6 microcellular samples. Among the molding parameters studied, shot size has the most significant effect on cell size, cell density, and tensile strength. Fractographic study reveals evidence of different modes of failure and different regions of fractured structure depending on the molding conditions. Polym. Eng. Sci. 44:673–686, 2004. © 2004 Society of Plastics Engineers.     

Biaxial orientation in LLDPE films: Comparison of infrared spectroscopy,X‐ray pole figures,and birefringence techniques

In this study, linear low‐density polyethylene films were produced using different processes (film blowing and biaxial orientation) and processing conditions. The orientation of the films was characterized in terms of their biaxial crystalline, amorphous, and global orientation factors using birefringence, tilted incidence polarized Fourier Transform Infrared Spectroscopy (FTIR), and X‐ray diffraction pole figures. Evaluation of a simplified FTIR procedure without the use of the tilted method for the determination of crystalline orientation factors proposed in the literature is also evaluated and assessed. The results indicate that FTIR overestimate the crystalline orientation factors, particularly for the crystalline a‐axis. Significant discrepancies are also observed for the b‐axis orientation, which may be due to an overlap of the amorphous phase contribution. Those differences are larger for films with low orientation, such as blown films. Amorphous phase orientation from FTIR depends on the band used and is not necessarily in agreement with that determined from the combination of X‐ray and birefringence. The simplified FTIR procedure is proven to be inadequate in the case of linear low‐density polyethylene blown films studied having a random lamellar crystalline morphology. POLYM. ENG. SCI. 46:1182–1189, 2006. © 2006 Society of Plastics Engineers.     

Effect of biodiesel on polyamide‐6‐based polymers

Biodiesel is considered one of the best alternative fuel sources in the transportation industry, but it has shown aggressive characteristics on materials that are used in fuel storage and delivery systems in vehicles. In this study, the effect of biodiesel (B100) on the properties of two polyamide‐6‐based semicrystalline polymers was studied and compared with that of diesel and a 20/80 blend of biodiesel and diesel (B20). Experiments were conducted using room temperature immersion tests in the three fuels for 720 h followed by postimmersion thermal and mechanical tests. In all three fuels, the polymers exhibited non‐Fickian weight increase during immersion and did not achieve equilibrium level of absorption in 720 h. The glass transition temperature (T_g), yield and tensile strengths, storage modulus, and peak tan δ decreased after immersion, while the degree of crystallinity and loss modulus increased. Fourier transform infrared spectroscopy study showed that no chemical changes occurred due to immersion. It is concluded that all three fuels absorbed into the polymers acted as plasticizers which caused the observed changes in the properties of the two polymers investigated in this research. POLYM. ENG. SCI., 59:1445–1454 2019. © 2019 Society of Plastics Engineers     

A new method to prepare low melting point polyamide‐6 and study crystallization behavior of polyamide‐6/calcium chloride complex by rheological method

A new method to prepare low melting point polyamide‐6 (LPA6) by complex reaction of calcium chloride (CaCl₂) and polyamide‐6 (PA6) in a co‐rotating twin screw extruder was reported. We employed a new rheological method to study the crystallization behavior of PA6/CaCl₂ complex and the mechanism of confined crystallization of PA6. Compared with differential scanning calorimetry (DSC), this method was more capable of detecting crystalline information. What's more, it was also an effective method for studying mechanism of confined crystallization. From the results of X‐ray diffraction, DSC, infrared spectroscopy, rheology, and mechanical properties, the complex reaction of CaCl₂ with the carbonyl oxygen atom in the amide group disrupted the intermolecular hydrogen bonding and confined the mobility of PA6 molecules. This could significantly reduce the crystallinity and melting temperature of PA6, and improve tensile strength and notched Izod impact strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41513.     

Preparation and characterization of polyamide‐6 with three‐branched chains

With trimesinic acid as a molecular weight regulator, the hydrolytic polymerization of ?‐caprolactam was carried out, and nylon‐6 or polyamide‐6 with three‐branched chains was obtained. Through a systematic study of the effects of conditions such as the reaction time and concentration of trimesinic acid on the polymerization, we found that the conversion of caprolactam was almost insensitive to the initial concentrations of the regulators, but the relative viscosity of the polymer decreased with increasing trimesinic acid. Characterization investigations showed that differential scanning calorimetry curves changed from a single peak for normal nylon‐6 to one main peak and one shoulder or one small peak for the branched polymer; the melting point of the star‐shaped nylon‐6 decreased with an increasing amount of trimesinic acid, whereas its crystallization temperature was higher than that of linear‐chain nylon‐6. A wide‐angle X‐ray diffraction study indicated that the crystal structure of the star‐shaped nylon‐6 still belonged to the α form, and the crystallizability of the branched polymer with an elevated amount of trimesinic acid during polymerization did not seem to be weakened; the characteristic absorption of infrared spectra provided indirect evidence for the existence of branched chains in the polymer. Moreover, the mechanical properties of star‐shaped nylon‐6 and linear‐chain nylon‐6 were compared. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3184–3193, 2001     

Mechanical and electrical properties of polyamide‐6‐based nanocomposites reinforced by fulleroid fillers

The effect of the fulleroid fillers (fullerene C₆₀, mixture of C₆₀/C₇₀ and fulleroids soot) on mechanical, tribological, and electrical properties of the nanocomposites based on polyamide‐6 (PA6) was investigated. The nanocomposites were prepared by in situ polymerization. Both the tensile modulus and tensile strength of polymer composites were improved up to 15% with loading of 0.001–0.1 wt% of fulleroids materials. For nanocomposites with fulleroid fillers, the friction coefficients were practically two times as lower that of neat PA6. Electrical volume resistivity of composites decreases at loading of fulleroid fillers. The minimal electrical volume resistance was about 10⁷ Ω cm at 0.1 wt% loading of fullerene soot. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

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     

Impact modified polyamide‐6/organoclay nanocomposites: Processing and characterization

The effects of melt state compounding of ethylene‐butyl acrylate‐maleic anhydride (E‐BA‐MAH) terpolymer and/or three types of organoclays (Cloisite® 15A, 25A, and 30B) on thermal and mechanical properties and morphology of polyamide‐6 are investigated. E‐BA‐MAH formed spherical domains in the materials to which it is added, and increased the impact strength, whereas the organoclays decreased the impact strength. In general, the organoclays increased the tensile strength (except for Cloisite 15A), Young's modulus and elongation at break, but the addition of E‐BA‐MAH had the opposite effect. XRD patterns showed that the interlayer spacing for the organoclays Cloisite 25A and Cloisite 30B increased in both polyamide‐6/organoclay binary nanocomposites and in polyamide‐6/organoclay/impact modifier ternary systems. TEM analysis showed that exfoliated‐intercalated nanocomposites were formed. The crystallinities of polyamide‐6/organoclay nanocomposites were in general lower than that of polyamide‐6 (except for Cloisite 15A). In ternary nanocomposites, crystallinities generally were lower than those of polyamide‐6/organoclay nanocomposites. Cloisite 15A containing ternary nanocomposites had higher tensile and impact strengths and Young's modulus than the ternary nanocomposites prepared with Cloisite 25A and Cloisite 30B, owing to its surface hydrophobicity and compatibility with the impact modifier. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Crystallization and thermal behavior of microcellular injection‐molded polyamide‐6 nanocomposites

This article presents the effects of nanoclay and supercritical nitrogen on the crystallization and thermal behavior of microcellular injection‐molded polyamide‐6 (PA6) nanocomposites with 5 and 7.5 wt% nanoclay. Differential scanning calorimetry (DSC), X‐ray diffractometry (XRD), and polarized optical microscopy (POM) were used to characterize the thermal behavior and crystalline structure. The isothermal and nonisothermal crystallization kinetics of neat resin and its corresponding nanocomposite samples were analyzed using the Avrami and Ozawa equations, respectively. The activation energies determined using the Arrhenius equation for isothermal crystallization and the Kissinger equation for nonisothermal crystallization were comparable. The specimen thickness had a significant influence on the nonisothermal crystallization especially at high scanning rates. Nanocomposites with an optimal amount of nanoclay possessed the highest crystallization rate and a higher level of nucleation activity. The nanoclay increased the magnitude of the activation energy but decreased the overall crystallinity. The dissolved SCF did not alter the crystalline structure significantly. In contrast with conventionally injection‐molded solid counterparts, microcellular neat resin parts and microcellular nanocomposite parts were found to have lower crystallinity in the core and higher crystallinity near the skin. POLYM. ENG. SCI., 46:904–918, 2006. © 2006 Society of Plastics Engineers     

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     

Biaxial orientation of polypropylene by hydrostatic solid state extrusion. Part III: Mechanical properties and deformation mechanisms

The deformation of biaxially oriented polypropylene sheet produced by the BeXor process has been examined in terms of the hierarchical solid state structure described previously. The mechanical properties have been examined over a range of temperatures and strain rates. The anisotropic nature of uniaxial tensile deformation was analyzed from simultaneous measurements of longitudinal extension and lateral contraction in the width and thickness directions, by determining the shape of uniaxially deformed spherulites, and by examining fracture surfaces in the scanning electron microscope (SEM). It was determined that deformation proceeds by elastic extension of the amorphous network and plastic shear deformation of the crystalline regions in the plane of the sheet, and in the thickness dimension, by voiding with induced fibrillation. It is suggested that the property improvements, particularly at low temperatures and high strain rates, which are achieved by the BeXor process, result from changes in the hierarchical structure at the size scale of the crystalline lamellae. Specifically it appears that the small crystalline blocks formed by breakup and recrystallization of lamellae are more easily deformed than the original large coherent lamellae.     

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