Morphology and properties of ternary polyamide 6/polyamide 66/elastomer blends

The aim of the work presented is to evaluate the mechanisms and phase interactions in ternary blends based on different polyamides and functionalised elastomers, and to establish a correlation between the morphology controlled by the specific binary interactions, and physical and technological properties, respectively. The properties of the ternary system polyamide 6/polyamide 66/ elastomer depend on the specific blend morphology which is determined mainly by the differences of the surface tension of the components. A phase‐in‐phase structure was observed by microscopic study (AFM) in the ternary polyamide 6/polyamide 66/elastomer blends with maleic anhydride grafted ethene‐octene copolymer, and a “quasi” phase‐in‐phase structure in blends with maleic anhydride grafted ethene‐propene‐diene copolymer as the elastomer phase. An incorporation of polyamide inside of the elastomer particles was observed in the first case due to the difunctionality of polyamide 66. This type of morphology causes an increased elongation at break and toughness of these blends. In comparison to the binary polyamide based blends the ternary blends show an increased elastic modulus, elongation at break and yield stress as well as a high impact strength at low temperatures up to ?20 °C. Copyright © 2003 John Wiley & Sons, Ltd.     

Thermal properties of polyamide 6/polyurethane blends

Equilibrium melting temperatures and crystallization parameters of polyamide 6/polyurethane blends were investigated. Thermal properties of the crystalline phase of blends obtained from polyamide 6 and polyurethane containing 40 wt% of hard segments, are only limited influenced by the overall blend compositon. Because from separate measurements single glass transitions for all samples were estimated, so in the investigated case the blending process may occur mainly between amorphous fraction of polyamide 6 and the polyurethane or, what is more probable, the polyurethane phase is dispersed in the continuous polyamide matrix, although some interactions exist.     

Morphologies and properties of plasticized starch/polyamide compatibilized blends

A new sodium carboxymethylcellulose (CMC) compatibilized glycerol-plasticized starch/polyamide PA11 blend having improved mechanical properties was realized in a one step extrusion process. Blends were prepared in internal mixer and twin screw extruder. Mechanical properties (stress and strain at break) are improved by adding 1 wt% of CMC. Rheological characterization and scanning electron microscopy show that a co-continuous morphology is observed on a wide range of TPS amount.     

Toward a prediction of the phase behavior of polyamide blends

As we have reported recently, the application of association models has provided a theoretical basis for the calculation of the free energy changes and phase diagrams of binary polymer blends in which hydrogen bonding plays a significant role. Here we report theoretical calculations of spinodal phase diagrams of a series of polyisophthalamide-polyether blends and compare the predictions with experimental observations of the miscibility of these polymer blend systems. The general agreement between theory and experiment is very encouraging and has important ramifications to discussions of polymer-induced crystallnity, the minimum number of hydrogen bonding sites necessary to ensure significant molecular mixing, and the effect of hydrogen bonding on the breadth of “miscibility windows.”     

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     

Thermomechanical study of low-density polyethylene, polyamide 6 and its blends

By using thermomechanical analysis (TMA) multiple relaxation transitions in the amorphous part of semi-crystalline polymers and their blends can be found. These result from differences in the interaction energies between segments of macromolecules, and as a result, in molecular mobility. TMA shows essential changes in the structure of low-density polyethylene (LDPE) resulting from the grafting of a maleic anhydride (LDPE-g-MAH) onto this semi-crystalline polymer. The grafting process did not suppress the ability of polyethylene to crystallize. Essential changes were found in molecular weight distribution and relaxation transitions of the ternary blends LDPE/PA6 (polyamide 6, PA6)/LDPE-g-MAH studied. For a concentration of PA6 up to 30 wt.%, a single relaxation transition is visible, which testifies that the components are miscible in the amorphous region. For blends with 40 and 50 wt.% of PA6, this structure was transformed and two relaxation transitions are visible. From the results obtained in this study it is concluded that the introduction 5 wt.% of grafted polyethylene is sufficient to produce a PA6/LDPE blend only for PA6 concentration up to 30 wt.% which is homogenous on “molecular” level. The transformation of the structure of the ternary polymer blend was explained by the interaction of the components during the melt mixing and changes in the structure of its amorphous regions.     

Dynamic mechanical thermal analysis of polyamide 6/thermoplastic polyurethane blends

Blends obtained from polyamide 6 and polyester or polyether polyurethanes were investigated by means of DMTA. The blends were prepared by compounding in a twin-screw Brabender —Plasticorder. Changes in composition did not influence the glass temperature of the amorphous fraction of the polyamide, but also no distinct transition for separated polyurethane soft segment was visible. Therefore the blends seem to be multiphase systems, where the elastomeric polyurethane phase is dispersed in a continuous polyamide phase. From changes in the β relaxation region of the polyamide better miscibility of polyester polyurethanes comparing to polyether polyurethanes was explained by hydrogen bonding in the common amorphous phase.     

Properties of polyamide 6 and thermoplastic polyurethane blends containing modified montmorillonites

In this paper are reported some experimental data related to the influence of preparation regimes and characteristics of exfoliated graphite based sorbents produced by thermal expansion of H₂SO₄-graphite intercalation compounds (H₂SO₄-GICs) on their sorption properties. Investigations involving X-ray diffraction analyses, surface area, bulk density and oil sorption capacity measurements, have been performed. Sorption capacity was discussed as a function of bulk density, total pore volume and surface area. Some empirical correlation between studied characteristics of exfoliated graphite have been found. The differences among the obtained samples, as a consequence of synthesis conditions, were also put in evidence by thermal analysis (TG, DTG and DTA) performed after their exposure to oil sorption.It was found that thermal analysis method could provide information about the exfoliated graphite pore system related to the sorbed oil oxidation rate. The capacity for oil uptake was also discussed in the case of graphite oxide soot.     

Mechanical and barrier properties of ternary nanocomposite films based on polycarbonate/amorphous polyamide blends modified with a nanoclay

Ternary polycarbonate (PC)/amorphous polyamide–nanoclay (naPA) nanocomposite (PC/naPA) films were obtained by melt mixing and drawing, and the effects of the naPA content and the draw ratio (DR) on the structure, morphology and mechanical and barrier properties were studied. Despite the presence of nanoclay, the films exhibited a negligible roughness and the excellent optical properties of PC and amorphous polyamide (aPA). The dispersed naPA phase was pure and small, indicating compatibility. The naPA did not hinder the drawing ability of PC. At low DRs the dispersed phase was elongated and oriented along the machine direction (extrusion flow direction), but at high DRs, it fibrillated due to the higher non‐isothermal elongational flow induced by drawing. The laminar structure of the nanoclay allowed the films to be reinforced both in the machine and the transverse directions. The oxygen permeability of PC was reduced by 42% in the nanocomposite with 25% of naPA, and dropped further with the DR, which is attributed to the increased tortuosity of the oxygen path induced by fibrillation. Copyright © 2015 John Wiley & Sons, Ltd.     

Fractionated crystallization in blends of functionalized poly(tetrafluoroethylene) and polyamide

Blends of poly(tetrafluoroethylene)/polyamide (PTFE/PA) were prepared to combine the good processing properties of PA with the excellent sliding properties of PTFE. For the compatibilizing of the immiscible components the chemical reaction of functional groups of modified PTFE (micro powder produced by electron irradiation in air) and polar PA during a reactive extrusion process was used. The parameter influencing the efficiency of the in‐situ reaction between both components were varied. The crystallization and melting behaviour of the different blends was investigated by DSC. In dependence on the degree of compatibilization the phenomenon of fractionated crystallization of the dispersed PTFE component was observed. In this way a qualitative characterization of the dispersity of PTFE in dependence on the functionality of the components and the processing conditions is possible, and therefore an estimation of the efficiency of the in‐situ reaction.     

Amide-exchange reactions in mixtures of N-alkyl amides and in polyamide melt blends

The amide-exchange reactions which cause copolymer formation in polyamide melt blends were studied with mixtures of N-ethylcaproamide and N-hexylacetamide containing small concentrations of caproic acid and hexylamine as a model system for melt blends of aliphatic polyamides. Amide exchange was found to involve acidolysis and aminolysis reactions with no detectable contribution of direct reaction between amide groups. Kinetics data are consistent with formation of an anhydride intermediate in amide acidolysis. Rate constants over the range 200–275°C and activation energies for amide acidolysis and aminolysis reactions are given. Equations are given for calculating amide exchange rates in polyamide melt blends and for relating degree of amide exchange to block copolymer composition.     

Friction and wear mechanisms of polyamide 66/high density polyethylene blends

Polyamide 66 (PA66)/high density polyethylene (HDPE) blends having miscible structure were produced by compatibilization of HDPE grafted with maleic anhydride (HDPE‐g‐MAH). Mechanical and tribological properties of blends in different compositions were tested. It was found that the polymer blends greatly improved the mechanical properties of PA66 and HDPE. Blending HDPE with PA66 significantly decreased the friction coefficient of PA66; the friction coefficients of blends with different compositions were almost the same and approximately equal to that of pure HDPE; the blends with 80 vol % PA66 exhibited the best wear resistance. The transfer films, counterpart surfaces, and wear debris formed during sliding were investigated by Scanning Electron Microscopy (SEM), and Differential Scanning Calorimetry (DSC) analysis was further carried out on wear debris. These investigations indicated that the thermal control of friction model is applicable to PA66/HDPE blend, that is the friction coefficient of blend is governed by the HDPE component, which possesses a lower softening point relative to the PA66 component in this system. The wear mechanism of PA66/HDPE blend transforms from PA66 to HDPE as the HDPE content increases. PA66, as the component with higher softening point, increases the hardness of blend, enhances the ability of blend to form a transfer film on the counterface, and inhibits the formation of larger belt‐like debris of HDPE, at the same time, the presence of self‐lubricating HDPE in the system decreases the friction coefficient and the frictional heat, all of these factors are favorable for the wear resistance of PA66/HDPE blend. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2514–2523, 2005     

New clay-reinforced polyamide nanocomposite based on 4-phenylenediacrylic acid: Synthesis and properties

New type of aromatic polyamide/montmorillonite nanocomposites were produced using solution intercalation technique in N-methyl-2-pyrrolidone. High-molecular-weight amide chains were synthesized from 4,4′-diaminodiphenyl ether and 4-phenylenediacrylic acid in N-methyl-2-pyrrolidone. The resulting nanocomposite films containing 5–20 wt.% of organoclay (Cloisite® 20A) were characterized for FT-IR, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), optical transparency and water absorption measurements. The distribution of organoclay and nanostructure of the composites were investigated by (XRD) and SEM analyses. Thermogravimetric analysis indicated an increase in thermal stability of nanocomposites as compared to pristine polyamide. The percentage optical transparency and water absorption of these hybrids was found to be much reduced upon the addition of modified layered silicate indicating decreased permeability.     

New polyamide cryptand for anion binding

An anion receptor derived from a tren-based amide cryptand with pyridine spacers has been synthesized and characterized. Two crystal structures are reported: the hydrochloride salt and the fluoride complex. The cryptand shows extremely high binding with fluoride ion in DMSO-d6. Both the crystal structure and solution 19F NMR data indicate an encapsulated fluoride ion with very high symmetry.     

Facile fabrication of thermoplastic ternary copolymerized polyamide and maleated polyethylene shape memory blends

Novel thermoplastic shape memory blends of ternary copolymerized polyamide (PAM) and maleated polyethylene (PE-g-MAH) were prepared by a simple melt-blending method, which might provide a new way for the industrial production of thermoplastic shape memory materials. The new chemical bonds were generated between PAM and PE-g-MAH, which was essential for enhancement of properties. The mechanical, thermal and shape memory properties of the blends were investigated in detail. It was found that the microstructure and proportion of different constituents was vital for the shape memory properties of the blends. In PAM/PE-g-MAH blends, a crystalline region of PAM acted as a fixed domain, and the crystalline region in PE-g-MAH acted as a reversible domain. The synergistic effect of the fixed and reversible domains determined the shape memory behavior of the blends. When the blend ratio of PAM/PE-g-MAH was 30/70, the composites exhibited the best shape memory properties, with a shape fixity ratio of 95.5% and a shape recovery ratio of 79.8%.     

Influences of hyperbranched polyethylenimine on the reactive compatibilization of polycarbonate/polyamide blends

The influences of hyperbranched polyethylenimine(h PEI), which possesses many reactive amino end-groups, on the blending properties of bisphenol-A polycarbonate(PC) and amorphous polyamide(a PA) were systematically investigated. Scanning electron microscopy(SEM) and differential scanning calorimetry(DSC) were used to observe the effect of h PEI on morphologies of PC and a PA phases in bulk blends. While the interfacial fracture toughness between planar PC and a PA layers with and without h PEI was studied by using augmented double cantilever beam(ADCB) method. Results show that the compatibility in PC/a PA blends can be significantly improved by adding a small amount of h PEI, mainly due to the interchange reactions between the polymers leading to the formation of block copolymers, cross-linked polymers and molecules with other constitutions. The augmented double cantilever beam experiments showed that the reactive process drastically reinforced the interfacial adhesion between planar layers of PC and a PA. However, degradation takes place during annealing at 180 °C, which was responsible for the production of small molar mass species of PC.     

The effect of polyethylene addition on the morphology of polystyrene/polyamide blends

The effect of a small admixture of high‐density polyethylene (HDPE) with a high or low viscosity to polystyrene/polyamide (PS/PA) blends of various compositions was studied. PS/PA blends with composition near 50/50 form sheet‐like or fiber‐like morphology at mixing that passes to the cocontinuous structure during compression molding. Ternary PS/PA/HDPE blends with PS/PA ratio about 50/50 show similar behavior. Generally, neither continuity nor shape of PS and PA phases was changed qualitatively by the addition of a small amount of HDPE. In agreement with existing rules for ternary blends, HDPE particles prefer a contact with PS phase to PA phase. On the other hand, none of these rules explains why a number of small HDPE subinclusions were dispersed into PS particles instead of HDPE‐PS core‐shell structure with a lower Gibbs free energy. Quantitative evaluation of the size of PA particles in blends with PS matrix showed that the previously proposed rule stating, that the addition of a small amount of a third immiscible component leads to a strong decrease in the size of dispersed particles, was not valid for the blends studied in this work. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2158–2170, 2009     

Miscibility-structure-property correlation in blends of ethylene vinyl alcohol copolymer and polyamide 6/66

Blends of ethylene vinyl alcohol (EVOH; 44 mol% ethylene) and polyamide 6/66 (PA; 75 mol% PA 6) random copolymers were studied in the entire composition range. Specific interaction between the components was analyzed by IR spectroscopy; furthermore, coefficients related to the Flory-Huggins interaction parameter were derived from equilibrium water uptake and tensile strength. Morphology of the blends was investigated by thermal analysis (DSC), density measurements, and SEM micrographs. The two polymers form heterogeneous blends in each composition. Although the components crystallize in separate phases, the morphology and the mechanical properties are greatly affected by the association of OH and NH groups. Crystallization is restricted in the blends, and the increase of the amorphous fraction, as well as specific interaction between the components, results in essential improvement in the mechanical properties.     

Compatibilization of polyethylene/polyamide 6 blends with functionalized polyethylenes prepared with metallocene catalyst

Metallocene catalyst technology was utilized to prepare functionalized polyethylenes, which were used as compatibilizers in polyethylene/polyamide 6 (40/60) blends. Polymerization of ethylene with 10-undecen-1-ol, 10-undecenoic acid, or N-methyl-10-undecenylamine resulted in ethylene copolymers with a small amount (0.2–1.2 mol %) of functionalized side chains. The blends were prepared in a twin-screw midiextruder, and injection molded with a mini-injection molding machine. The effect of the new compatibilizers on morphology and mechanical and thermal properties was studied. Toughness as well as stiffness and strength increased significantly with an addition of 10 wt % compatibilizer. Morphology became much more uniform, and crystallization and melting behavior changed. The Molau test with FTIR analysis was used to determine that the desired reactions between the compatibilizer and polyamide had actually taken place. The results showed functionalized polyethylenes prepared with metallocene catalysts to act as effective compatibilizers in polyethylene/polyamide 6 blends. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3099–3108, 1999     

Blending and barrier properties of blends of modified polyamide and ethylene vinyl alcohol copolymer

The blending and barrier properties of the MPAEVOH blends of modified polyamide (MPA) and ethylene vinyl alcohol copolymer (EVOH) were systematically investigated in this study. After blending MPA in EVOH resin, a noticeable “negative deviation” was found on the plot of the oxygen permeation rate versus MPA content when the MPA contents present in MPAEVOH resins reach about 80 wt %. The peak temperatures associated with the main melting endotherm of MPA and EVOH reduce significantly with increasing the EVOH and MPA contents present in MPAEVOH resins, respectively. The melting endotherm and X‐ray diffraction peak associated with EVOH crystal phases disappear gradually as the MPA contents present in MPAEVOH increase. In fact, the melting endotherm and X‐ray scattering peak corresponding to EVOH crystals almost disappear as the EVOH contents present in MPAEVOH specimens are less than 20 wt %. Further Fourier‐Transform Infrared (FT‐IR) investigations indicate that the strengths of intermolecular hydrogen bonds of MPAEVOH specimens reduce significantly as the MPA contents increase, wherein the self‐associated hydroxyl‐hydroxyl bonds within EVOH resins almost disappear as the EVOH contents reduce to be less than about 20 wt %. As expected, the average sizes of the free volume holes of MPAEVOH specimens increase significantly as the MPA contents increase. However, somewhat surprisingly, a clear negative deviation was found on the plot of the numbers and fractional free volumes of free volume holes against the MPA contents as the EVOH contents are close to about 20 wt %. The interesting barrier properties of the MPA, EVOH, and MPAEVOH specimens were investigated in terms of the free volume and intermolecular interaction properties in the amorphous phases of MPAEVOH specimens described above. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 511–521, 2005