Mechanical behavior of films of miscible polyamide 6/polyamide 6I‐6T blends

The deformation behavior of miscible PA6/aPA blends films under uniaxial and biaxial tensile drawing has been investigated in relation to blend composition. Whatever be the composition, the initial crystalline structure is ill‐ordered and no evidence of spherulitic morphology was shown. At temperatures beyond the activation of the viscoelastic α relaxation, a ductility improvement upon addition of aPA has been revealed in both uniaxial and biaxial stretching. The decrease in the yield stress with increasing aPA content mainly originates from the reduction in crystal fraction. Regarding the observed evolution in ultimate drawability and strain hardening upon addition of aPA, the latter component of the blend is considered to act as a diluent of the macromolecular network, and the experimental data are fairly well accounted for according to Graessley's theory. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1690–1701, 2006     

Preparation and nonisothermal crystallization behavior of polyamide 6/montmorillonite nanocomposites

Polyamide 6 (PA6)/montmorillonite (MMT) nanocomposites were prepared via melt intercalation. The structure, mechanical properties, and nonisothermal crystallization kinetics of PA6/MMT nanocomposites were investigated by X‐ray diffraction (XRD), tensile and impact tests, and differential scanning calorimetry (DSC). Before melt compounding, MMT was treated with an organic surfactant agent. XRD traces showed that PA6 crystallizes exclusively in γ‐crystalline structure within the nanocomposites. Tensile measurements showed that the MMT additions are beneficial in improving the strength and the stiffness of PA6, at the expense of tensile ductility. Impact tests revealed that the impact strength of PA6/MMT nanocomposites tended to decrease with increasing MMT content. The nonisothermal crystallization DSC data were analyzed by Avrami, Ozawa, modified Avrami‐Ozawa, and Nedkov methods. The validity of these empirical equations on the nonisothermal crystallization process of PA6/MMT nanocomposites is discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2878–2891, 2004     

Viscoelastic behavior of epoxy prepolymer/organophilic montmorillonite dispersions

Dispersions of a bisphenol A‐based epoxy resin with an organophilic montmorillonite (Nanofil 919) were studied by X‐ray diffraction and oscillatory shear rheometry. X‐ray studies reveal that the clay is intercalated by the epoxy and forms stable dispersions. The viscoelastic behavior of the nanodispersions was measured as a function of the Nanofil concentration and temperature. An increase in both G′ and G″ moduli was detected as the concentration increases. Furthermore, a transition from a liquid‐like behavior, at low temperatures, to a solid‐like behavior, at higher temperatures, was observed for all the samples. This transition is accounted for the formation of a percolated structure of interconnected tactoids through hydrophobic interactions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1837–1844, 2008     

Magnetic field alignment of block copolymers and polymer nanocomposites: Scalable microstructure control in functional soft materials

Block copolymers (BCPs) offer an exciting range of structures and functions that are of potential utility in existing as well as emerging technologies. Although this is generally acknowledged, with few exceptions, viable strategies for establishing scalable and robust control of BCP microstructure are underdeveloped. Magnetic field alignment offers great potential in this regard. The physics bears much in common with electric field alignment, but the absence of dielectric breakdown concerns and the more flexible, space pervasive nature of magnetic fields make it possible to design processes for high‐throughput fabrication of well‐ordered films with appropriate materials. In this perspective, we highlight the use of magnetic fields for control of microstructure in BCPs as well as polymer nanocomposites involving anisotropic nanomaterials. A brief review of efforts to date is given. Open questions related to field‐polymer interactions and future directions for magnetic alignment of these systems are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Morphology and mechanical properties of a novel amorphous polyamide/nanoclay nanocomposite

A novel amorphous polyamide/montmorillonite nanocomposite based on poly(hexamethylene isophthalamide) was successfully prepared by melt intercalation. Wide angle X-ray diffraction and transmission electron microscopy showed that organoclay containing quaternary amine surfactants with phenyl and hydroxyl groups was delaminated in the polymer matrix resulting in well-exfoliated morphologies even at high montmorillonite content. Differential scanning calorimetry results indicated that clay platelets did not induce the formation of a crystalline phase in this amorphous polymer. Tensile tests demonstrated that the addition of nanoclay caused a dramatic increase in Young's modulus (almost twofold) and yield strength of the nanocomposites compared with the homopolymer. The nanocomposites exhibited ductile behavior up to 5 wt % of nanoclay. The improvement in Young's modulus is comparable with semicrystalline aliphatic nylon 6 nanocomposites. Both the main chain amide groups and the amorphous nature of the polyamide are responsible for enhancing the dispersion of the nanofillers, thereby, leading to improved properties of the nanocomposites. The structure-property relationship for these nanocomposites was also explored. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2605–2617, 2008     

Preparation of ZnO nanoparticle‐reinforced polyamide 6 composite by in situ‐coproduced method and their properties

Polyamide 6/ZnO nanocomposites (noted as PA6/ZnO) were prepared by an in situ co‐producing method, during which Zn₂(OH)₂CO₃ decomposed into nano‐ZnO in the process of the opening‐ring polymerization of caprolactam at high temperature. Transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry were used to analyze the size and dispersive properties of nano‐ZnO, the crystallization and melting properties, the thermal properties, and crystal structure of PA6/ZnO composite, respectively. The results showed that the nano‐ZnO derived from Zn₂(OH)₂CO₃ via in situ polymerization of PA6‐ZnO was uniformly dispersed in PA6 matrix. However, the overall nano‐ZnO crystallization rate and crystal size in the PA6 matrix were hindered by the bulky PA6 molecular chains. The mechanical properties were evaluated using universal tensile and impact testing instruments. The results revealed that PA6/ZnO composite with 0.2% nano‐ZnO content possessed excellent tensile strength, enhanced by 75% in comparison with the pure PA6. The nano‐ZnO had little influence on the impact strength of PA6. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 165–170     

X‐ray powder diffraction of polymer/layered silicate nanocomposites: Model and practice

X‐ray powder diffraction in reflection (Bragg–Brentano parafocusing geometry) is extensively used to characterize the structure of polymer/layered silicate nanocomposites (PLSNs). The large basal spacings (d₀₀₁ > 2.0 nm) necessitates the collection of data at scattering angles (2θ) of less than 10°. The calculation of an ideal scattering profile for PLSNs provides an avenue to ascertain the influence of experimental parameters and the arrangement, organization, concentration, and composition of constituents on the experimentally observed pattern. This enables better experimental technique, more complete utilization of the scattering data, insight into inconsistencies between scattering and microscopy, and minimization of incorrect interpretation or overinterpretation of data. Because of the strong θ dependence of theoretical and experimental factors at low values of 2θ, careful sample preparation and data evaluation are necessary and should be complemented by microscopic observations, especially for PLSNs with low volume fractions of organically‐modified layered silicates (OLS) that are suspected of having exfoliated morphologies. X‐ray powder diffraction in reflection alone is insufficient to completely characterize and ascribe PLSN morphology. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1590–1600, 2002     

Crystalline structure of polyamide 12 as revealed by solid‐state 13C NMR and synchrotron WAXS and SAXS

The crystalline structure of polyamide‐12 (PA12) was studied by solid‐state ¹³C nuclear magnetic resonance (NMR) as well as by synchrotron wide‐ and small‐angle X‐ray scattering (WAXS and SAXS). Isotropic and oriented PA12 showed different NMR spectra ascribed to γ‐ and γ′‐crystalline modifications, respectively. On the basis of the position of the first diffraction peak, the isotropic γ‐form and the oriented γ′‐form were shown to be with hexagonal crystalline lattice at room temperature. When heated, the two PA12 polymorphs demonstrated different behaviors. Above 140 °C, the isotropic γ‐PA12 partially transformed into α‐modification. No such transition was observed with the oriented γ′‐PA12 phase even after annealing at temperatures close to melting. A γ′–γ transition was observed here only after isotropization by melting point. Various structural parameters were extracted from the WAXS and SAXS patterns and analyzed as a function of temperature and orientation: the degree of crystallinity, the d‐spacings, the Bragg's long spacings, the average thicknesses of the crystalline (l_c) and amorphous (l_a) phases, and the linear crystallinity x_cl within the lamellar stacks. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3720–3733, 2005     

Structure Evolution upon Uniaxial Drawing Skin‐ and Core‐Layers of Injection‐Molded Isotactic Polypropylene by In Situ Synchrotron X‐ray Scattering

The structure evolution of the oriented layer (skin) and unoriented layer (core) from injection‐molded isotactic polypropylene samples upon uniaxial drawing is probed by in situ synchrotron X‐ray scattering. The X‐ray data analysis approach, called “halo method”, is used to semiquantitatively identify the transformation process of crystal phase upon uniaxial drawing. The results verify the validation of the stress‐induced crystal fragmentation and recrystallization process in the deformation of the injection‐molded samples under different temperatures. Furthermore, the end of strain softening region in the engineering stress‐strain curves explicitly corresponds to the transition point from the stress‐induced crystal fragmentation to recrystallization process. Basically, the skin and core layers of the injection‐molded parts share the similar deformation mechanism as aforementioned. The stretching temperature which dramatically affects the relative strength between the entanglement‐induced tie chains and the adjacent crystalline lamellae determines the crystal structural evolution upon drawing. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1618–1631     

A re‐examination of the sub‐Tm exotherm in polyamide 6: The roles of thermal history,water and clay

The sub‐T_m exotherms in polyamide 6 (PA6) have been carefully re‐examined by differential scanning calorimetry and X‐ray diffraction, considering the effects of processing and thermal history, addition of water and clay. The results obtained cast doubt on Khanna's proposal that sub‐T_m exotherm in PA6 comes from the release of strain energy absorbed during processing, and suggested that the origin of sub‐T_m exotherm is the γ?α transformation at the premelting temperature, namely, the less thermodynamically stable γ‐form (γ^ns) transforming into the more thermodynamically stable α‐form (α^s). The presence of water or clay in PA6 samples facilitated the formation of γ^ns at corresponding cooling rates, and enhanced the development of sub‐T_m exotherms. During the heating scan of PA6/clay composites, the initial γ^ns can be transformed into more stable (γ^s)^t and α^s at the same time, which can be thought as the origin of their sub‐T_m events. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2385–2393, 2009     

Two crystal populations with different melting/reorganization kinetics of isothermally crystallized polyamide 6

Differential scanning calorimetry and fast scanning chip calorimetry heating experiments were carried out in a wide range of rates of temperature change from 0.2 to 60,000 K s^?1 for isothermally crystallized polyamide 6. Multiple melting peaks were observed. With increasing heating rate, the highest‐temperature endotherm shifts toward lower temperatures and finally disappears due to suppression of the reorganization. The critical heating rate to suppress reorganization was 15–50 times higher than the critical cooling rate to cause complete vitrification. On heating at rates higher than the critical heating rate to suppress reorganization, there were observed two melting processes of different kinetics. Four possible assignments were considered regarding the two crystal populations. These are (i) crystals grown during primary and secondary crystallization, (ii) crystals grown in the bulk and nucleated at the surface/substrate, (iii) crystals, which are subjected to different local stress originating from heterogeneities in interlamellar regions, and (iv) the crystal/mesophase polymorphism. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2126–2138     

Morphology and Dielectric Property of Homogenous BaTiO3/PVDF Nanocomposites Prepared via the Natural Adsorption Action of Nanosized BaTiO3

Summary: The development of a novel technique for the preparation of homogeneous BaTiO₃/polyvinylidene fluoride (BT/PVDF) nanocomposites without obvious agglomeration of BaTiO₃ particles was reported in this communication. The morphology, structure, and frequency dependence of the dielectric properties of the nanocomposites were characterized. All results show that the dielectric properties of the nanocomposites in this study are desirable, and the process for preparing the nanocomposites has potential applications in the electronic industry.

TEM micrograph of dry BT/PVDF mixtures with nanosized BT particles.     

Effects of TEMED and EDTA on the structural and mechanical properties of NIPAAm/Na+MMT composite hydrogels

N‐isopropyl acrylamide (NIPAAm) hydrogels are known as thermosensitive crosslinked polymer networks. In this work, the network parameters of their composites, i.e., NIPAAm/sodium montmorillonite (NIPAAm/Na⁺MMT) hydrogels synthesized by free radical solution polymerization in the presence of two different types of accelerator (tetramethyl ethylenediamine (TEMED) and ethylenediamine tetraacetic acid (EDTA)) and initiator (potassium persulphate (K₂S₂O₈) and cerium ammonium nitrate ((NH₄)₂Ce(NO₃)₆), Ce(IV)) using five different clay content (in the range of 1.0–5.0 wt % of total monomer concentration) at 25 °C were presented and discussed. FTIR spectra, XRD patterns, SEM photographs, and network parameters of the samples indicated that the presence of COOH groups on EDTA molecules was resulted in the formation of exfoliated structures and the activity of EDTA/KPS redox pair was higher than those of TEMED/KPS and EDTA/Ce (IV) pairs. The compression moduli (G) of the hydrogels initiated with EDTA/Ce(IV) redox pair showed smooth and continual changings with increase in Na⁺MMT content (for swelling equilibrium at 25 °C) on the contrary of EDTA/KPS and TEMED/KPS pairs. It might be related to low initiator efficiency of cerium ammonium nitrate than KPS molecules, having higher effective crosslinking density with increasing clay content. On the other hand, the G moduli of NIPAAm/Na⁺MMT hydrogels (above their phase transition temperature) initiated with TEMED/KPS redox pair were higher than the others because of the more hydrophobic nature of TEMED molecules. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1256–1264, 2010     

Towards scalable production of polyamide 12/halloysite nanocomposites via water‐assisted extrusion: mechanical modeling,thermal and fire properties

In this study, polyamide 12 (PA12)/untreated halloysite nanotubes (HNTs) nanocomposites are prepared in a semi‐industrial scale extruder using a non‐traditional “one step” water‐assisted extrusion process. A morphological study is carried out using a combination of scanning electron microscopy and transmission electron microscopy analyses to evaluate the influence of water injection and filler content on the quality of clay dispersion. The use of water injection slightly improves the nanoscale dispersion at low HNTs content (<8 wt.%), while this effect is more pronounced at higher filler loading (16 wt.%). A mechanism explaining the physico‐chemical action of water during extrusion is proposed. The materials are characterized with respect to their mechanical, thermo‐mechanical, thermal and fire properties. A strong correlation is found between nanostructure and physical properties; the more uniform dispersion of the clay nanotubes, the higher mechanical reinforcement, thermal stability and fire retardancy of PA12 nanocomposites. Tensile tests results are interpreted in terms of three mechanical models: the Halpin–Tsai's model for stiffness and the interfacial strength model and the Pukanszky's equation for yield strength. Linear fits of the experimental data confirm that the superior reinforcement of nanocomposites prepared using water injection results from improved clay dispersion and better interfacial adhesion between PA12 and HNTs. In view of these promising results, the proposed direct melt compounding method could be easily scaled‐up towards the production of PA12–HNTs nanocomposites at an industrial scale. Copyright © 2013 John Wiley & Sons, Ltd.     

Deposition and characterization of Langmuir‐Blodgett films of cadmium arachidate/SWCNTs composites

The incorporation of single‐wall carbon nanotubes (SWCNTs) in cadmium arachidate film by means of the Langmuir‐Blodgett (LB) technique was investigated as a function of arachidic acid/SWCNT mass ratio at the air/water interface and in Langmuir‐Blodgett films. The behaviour at the air/water interface shows that SWCNTs act as an independent phase with respect to the cadmium arachidate. Deposition conditions are optimized when the weight ratio between the arachidic acid (AA) and SWCNTs is in the range 0.018:1 to 1:1. The general order of the LB multilayered structure was destroyed by the progressive density increase in SWCNT quantity as evidenced by X‐ray reflectivity (XRR) analysis. Scanning electron microscopy images indicated that when a multilayered structure was formed its layers consisted of SWCNT bundles stacked one over the other. Copyright © 2006 John Wiley & Sons, Ltd.     

Wide angle X‐ray diffraction and Fourier transform infrared dichroism studies of stretched‐recovery‐restretched process of polyurethane/clay nanocomposite

An intercalated polyurethane (PU) /clay nanocomposite was prepared by in situ intercalative polymerization. The PU/clay nanocomposite pellet or film samples were stretched‐recovery‐restretched, using selfmade microstretching tools. The changes of the basal spacings of clay and the orientation of polymer chain segments during the stretched‐recovery‐restretched process were studied by wide angle X‐ray diffraction (WAXD) and Fourier transform infrared (FTIR) dichoism techniques. The WAXD results show that the basal spacing of clay did not change obviously, indicating that no macromolecular chains entered or moved out of the interlayer space, and the orientations of both hard and soft segments inside the interlayer space did not change obviously, either. The FTIR dichroism tests suggest that outside the interlayer space, the orientation of the hard chain segment increased, decreased, and then increased again during the stretched‐recovery‐restretched process. However, no obvious changes of the degree of orientation of the soft segment were observed during the processes, the slightly orientation might be released during the relaxation process before the measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 654–660, 2007     

Selective localization of organoclay and effects on the morphology and mechanical properties of LDPE/PA11 blends with distributed and co‐continuous morphology

A study was made on the effect of small amounts of organically modified clay on the morphology and mechanical properties of blends of low‐density polyethylene and polyamide 11 at different compositions. The influence of the filler on the blend morphology was investigated using wide angle X‐ray diffractometry, scanning and transmission electron microscopy and selective extraction experiments. The filler was found to locate predominantly in the more hydrophilic polyamide phase. Although such uneven distribution does not have a significant effect on the onset of phase co‐continuity of the polymer components, it brings about a drastic refinement of the microstructure for the blends both with droplets/matrix and co‐continuous morphologies. In addition to the expected reinforcing action of the filler, the resulting fine microstructure plays an important role in enhancing the mechanical properties of the blends. This is essentially because of a good quality of stress transfer across the interface between the constituents, which also seems to benefit for a good interfacial adhesion promoted by the filler. Our results provide the experimental evidence for the capabilities of nanoparticles added to multiphase polymer systems to act selectively as a reinforcing agent for specific domains of the material and as a medium able to assist the refinement of the polymer phases during mixing. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 600–609, 2010     

Shrinkability of ethylene vinyl acetate/polyurethane blends and their characterization

Heat shrinkability of the polymer, which depends on the elastic memory, is being utilized in various applications, mainly in the field of encapsulation. The elastic memory is introduced into the system in the form of an elastomeric phase. Here the blends of ethylene vinyl acetate and polyurethane were studied with reference to their shrinkability, introducing crosslinking in both the phases. It is found that with increase in elastomer content the shrinkage increased to a certain level and then decreased. With increase in cure time shrinkage is decreased. It is seen that high‐temperature (HT) stretched samples showed higher shrinkage than room temperature (RT) stretched one. Generally, the crystallinity of the HT stretched sample is higher than that of low‐temperature stretched sample, which is again higher than that of original sample. From high temperature differential scanning calorimetry it is found that with increase in PU content stability towards oxygen is increased and further high temperature processing decreases the initial degradation temperature but enhances the rate of degradation. From scanning electron microscopy it is seen that an HT stretched sample is more elongated than an RT stretched one. Copyright © 2000 John Wiley & Sons, Ltd.     

Synthesis and characterization of organosoluble,thermoplastic elastomer/clay nanocomposites

We synthesized organosoluble, thermoplastic elastomer/clay nanocomposites by making a jelly like solution of ethylene vinyl acetate containing 28% vinyl acetate (EVA‐28) and blending it with organomodified montmorillonite. Sodium montmorillonite (Na⁺‐MMT) was made organophilic by the intercalation of dodecyl ammonium ions. X‐ray diffraction patterns of Na⁺‐MMT and its corresponding organomodified dodecyl ammonium ion intercalated montmorillonite (12Me‐MMT) showed an increase in the interlayer spacing from 11.94 to 15.78 Å. However, X‐ray diffraction patterns of the thermoplastic elastomer and its hybrids with organomodified clay contents up to 6 wt % exhibited the disappearance of basal reflection peaks within an angle range of 3–10°, supporting the formation of a delaminated configuration. A hybrid containing 8 wt % 12Me‐MMT revealed a small hump within an angle range of 5–6° because of the aggregation of silicate layers in the EVA‐28 matrix. A transmission electron microscopy image of the same hybrid showed 3–5‐nm 12Me‐MMT particles dispersed in the thermoplastic elastomer matrix; that is, it led to the formation of nanocomposites or molecular‐level composites with a delaminated configuration. The formation of nanocomposites was reflected through the unexpected improvement of thermal and mechanical properties; for example, the tensile strength of a nanocomposite containing only 4 wt % organophilic clay was doubled in comparison with that of pure EVA‐28, and the thermal stability of the same nanocomposite was higher by about 34 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2065–2072, 2002