Influence of preparation methods on the structures and properties for the blends between polyamide 6co6T and polyamide 6: Melt‐mixing and in‐situ blending

Two blends between polyamide 6 (PA6) and Polyamide 6co6T (PA6co6T, a random copolymer between polyamide 6 and polyamide 6T) were fabricated by melt‐mixing on a twin‐screw extruder and the subsequent injection molding, or through the in‐situ polymerization of ε‐caprolactam in the presence of PA6co6T. As far as the former method is concerned, there exist an obvious decline of toughness and a slight increase in strength and modulus; however, for the latter, there appear a remarkable improvement in toughness and a simultaneous moderate increase in strength and modulus. A series of characterizations were carried out including scanning electron microscopy, wide‐angle X‐ray diffraction, polarized optical microscopy, differential scanning calorimetry, dynamic mechanical analysis, and Fourier transform infrared spectrometry. It is found that both blends exhibit single glass transition on DMA tan δ curves. However, contrary to that of the melt‐mixed blends, the glass transition temperature (T_g) of the in‐situ ones decreases with increasing PA6co6T content. It is suggested that different mixing levels are the main reasons. Moreover, the addition of PA6co6T containing linear rigid segments conducts remarkable refinement of spherulites for the blends. Significantly different changes in the crystallographic form, spherulite size, crystalline content and perfection due to the introduction of PA6co6T for the two blends are ascribed to their varied thermomechanical histories and the presence of interchange reaction only for the in‐situ blends. On the basis of the characterizations of the microstructures, the different trends of changes in the mechanical properties with the addition of PA6co6T for the two fabrication methods are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 201–211, 2008     

PA66/PA12/clay based nanocomposites: structure and thermal properties

In a previous paper the structure and the physical properties of melt mixed polyamide 66 (PA66)/polyamide 12 (PA12) blends characterized by different compositions have been investigated by means of morphological and physical analyses. A low amount of organically‐modified layered silicate (OMLS, 4 wt%) was introduced in order to evaluate its effect on blends structure and components miscibility. This paper completes the characterization of these materials investigating their thermal properties by means of standard and modulated differential scanning calorimetry (DSC, MDSC), dynamic‐mechanical analysis (DMA), and thermogravimetric analysis (TGA). The partial miscibility of PA66 and PA12, with phase separation depending on blend composition, has been confirmed by analyzing the glass transition temperature (T_g) dependence on composition as well as the existence of strong segmental interactions between polymer components. A compatibilizing action of OMLS has been observed because of a lowering of interfacial tension avoiding coalescence phenomena between particles during melt mixing process. Copyright © 2010 John Wiley & Sons, Ltd.     

PA66/PA12/clay based nanocomposites: morphology and physical properties

The structure and the physical properties of several polyamide 66 (PA66)/polyamide 12 (PA12) blends containing different amounts of the two polymers and obtained by melt‐blending have been investigated. A low amount of organically‐modified layered silicate (OMLS, 4 wt%) has also been introduced in order to further improve the physical properties and, in particular, to evaluate its effect on the blends' structure and components' miscibility. The microstructure and morphology of all the composites were analyzed by means of X‐Ray diffraction (WAXD), transmission electron microscopy (TEM), and high resolution scanning electron microscopy (SEM), while the macroscopic scale properties (mechanical behavior and water adsorption) were assessed in order to investigate and understand the materials' structure–properties relationships. The partial miscibility of PA66 and PA12, with phase separation depending on blend composition, has been confirmed. The results also underlined the possibility to tailor the behavior of polymer blends in terms of mechanical water adsorption properties by varying the amount of PA12, added to PA66 with and without the addition of the OLMS. The effectiveness of the clay in modifying the components' miscibility as well as its tendency to segregate preferentially within separate PA66 domains have been assessed. WAXD results showed opposite effects of PA12 and clay on the crystallization behavior of PA66, an aspect that has also been deepened in another paper by the same authors discussing the results of the complete thermal characterization. Copyright © 2010 John Wiley & Sons, Ltd.     

Reactive compatibilization of polyamide‐6 (PA 6)/polybutylene terephthalate (PBT) blends by a multifunctional epoxy resin

A multifunctional epoxy resin has been demonstrated to be an efficient reactive compatibilizer for the incompatible and immiscible blends of polyamide‐6 (PA 6) and polybutylene terephthalate (PBT). The torque measurements give indirect evidence that the reaction between PA and PBT with epoxy has an opportunity to produce an in situ formed copolymer, which can be as an effective compatibilizer to reduce and suppress the size of the disperse phase, and to greatly enhance mechanical properties of PA/PBT blends. The mechanical property improvement is more pronounced in the PA‐rich blends than that in the PBT‐rich blends. The fracture behavior of the blend with less than 0.3 phr compatibilizer is governed by a particle pullout mechanism, whereas shear yielding is dominant in the fracture behavior of the blend with more than 0.3 phr compatibilizer. As the melt and crystallization temperatures of the base polymers are so close, either PA or PBT can be regarded as a mutual nucleating agent to enhance the crystallization on the other component. The presence of compatibilizer and in situ formed copolymer in the compatibilized blends tends to interfere with the crystallization of the base polymers in various blends. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 23–33, 2000     

Effect of PPO‐g‐MA on structures and properties of PPO/PA6/short glass fiber composites

Poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6) blends were reactively compatibilized by maleic anhydride (MA) grafted PPO (PPO‐g‐MA) and reinforced by short glass fibers (SGF) via melt extrusion. An observation of the SGF‐polymer interface by scanning electronic microscope (SEM) together with etching techniques indicated that the PPO‐g‐MA played a decisive role in the adhesion of polymers to SGF. The rheological behavior was investigated by capillary rheometer, and the addition of PPO‐g‐MA, and SGF could increase the viscosity of the PPO/PA6 blends. The analysis of fiber orientation and distribution in the PPO/PA6/SGF composites showed PPO‐g‐MA favored to the random dispersion of SGF. The statistic analysis of SGF length showed that PPO‐g‐MA was helpful to maintain the fiber length during melt‐processing. For the composites at a given SGF content of 30 wt %, the addition of PPO‐g‐MA increased the tensile strength from 59.4 MPa to 97.1 MPa and increased SGF efficiency factor from 0.028 to 0.132. The experimental data were consistent with the theoretical predictions of the extension of Kelly‐Tyson model for tensile strength. The fracture toughness of the composites was investigated by single edge notch three‐point bending test. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2188–2197, 2009     

侧链液晶离聚物对PA1010/PP共混体系的增容作用

将聚酰胺（PA1010）、聚丙烯（PP）和热致型侧链液晶离聚物（SLCI）进行熔融共混，采用FTIR，SEM，DSC，WAXD研究测定了共混物中的相互作用，用形态结构，热行为和结晶行为，系统地研究了SLCI对PA101／PP共混物的增容作用。结果表明，SLCI有效地改善了PA1010／PP共混物的形态结构，增强了PA1010与PP链间的相互作用，使PA1010／PP熔点升高，结晶度提高。     

Rheology,electrical conductivity,and the phase behavior of cocontinuous PA6/ABS blends with MWNT: Correlating the aspect ratio of MWNT with the percolation threshold

Multiwalled carbon nanotubes (purified, p‐MWNT and ～ NH₂ functionalized, f‐MWNT) were melt‐mixed with 50/50 cocontinuous blends of polyamide 6 (PA6) and acrylonitrile–butadiene–styrene in a conical twin‐screw microcompounder to obtain conductive polymer blends utilizing the conceptual approach of double‐percolation. The state of dispersion of the tubes was assessed using AC electrical conductivity measurements and melt‐rheology. The rheological and the electrical percolation threshold was observed to be ～ 1–2 wt % and ～ 3–4 wt %, respectively, for blends with p‐MWNT. In case of blends with f‐MWNT, the rheological percolation threshold was observed to be higher (2–3 wt %) than p‐MWNT but the electrical percolation threshold remained almost same. However, the absolute values were significantly lower than blends with p‐MWNT. In addition, significant refinement in the cocontinuous morphology of the blends with increasing concentration of MWNT was observed in both the cases. Further, an attempt was made to understand the underlying concepts in relation to cocontinuous morphologies that how the geometrical percolation threshold which adversely suffered because of the attrition of tubes under prolonged shear contributed further in retaining the rheological percolation threshold. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1619–1631, 2008     

Effect of adding new phosphazene compounds to poly(butylene terephthalate)/polyamide blends. II: Effect of different polyamides on the properties of extruded samples

Poly(butylene terephthalate) (PBT) and a sample of polyamide have been melt processed in the presence of two new phosphazene compounds, namely 2,2-dichloro-4,4,6,6-bis[spyro(2′,2″-dioxy-1′,1″-biphenyl)]cyclotriphosphazene (2Cl-CP) and 2,2-bis(2-methoxy-4-methyleneoxy-phenoxy)-4,4,6,6-bis[spyro(2′,2″-dioxy-1′,1″-biphenyl)]cyclophosphazene (CP-2EPOX).The blends were prepared by using polyamide 6 (PA6) and polyamide 6,6 (PA66) in 25/75 and 75/25 w/w compositions by using a co-rotating twin-screw extruder.The materials have been completely characterized from a mechanical, rheological, and morphological point of view. The results indicate that the additives used cause an increase of the rupture properties and of the viscosity, especially in the PA6 rich blends containing CP-2EPOX. This result can be not only attributed to a chain extension effect on the PA phase but also to in situ formation of PA/PBT copolymers promoted by the presence of the CP compound as confirmed by NMR and MALDI-TOF analyses. The compatibilization effect fades in blends containing PA66, probably due to a thermal deactivation of the additives at higher temperature required to process this polymer.     

Reactive melt blends of thermoplastic polyolefins,MAH‐g‐PP and nylon 6

Reactive melt blends of an ethylene‐propylene‐diene terpolymer (EPDM) based thermoplastic elastomer (TPE), maleic anhydride grafted polypropylene (MAH‐g‐PP), and nylon 6 were prepared in a single screw extruder and evaluated in terms of morphological, rheological, thermal, dynamic mechanical, and mechanical properties of the blends. It was found that MAH‐g‐PP‐co‐nylon 6 copolymers were in situ formed and acted as effective compatibilizers for polypropylene (PP) and nylon 6. Phase separation of PP and EPDM in TPE increased with the addition and increasing amount of MAH‐g‐PP and nylon 6, leading to decreased glass transition temperature (T_g) of TPE and increased crystalline melting temperature (T_m) of PP. Copyright © 2004 John Wiley & Sons, Ltd.     

Phase morphology development in PP/PA6 blends induced by a maleated thermoplastic elastomer

The effects of maleated thermoplastic elastomer (TPEg) on morphological development of polypropylene (PP)/polyamide 6 (PA6) blends with a fixed PA6 content (30 wt %) were investigated. For purpose of comparison, nonmaleated thermoplastic elastomer (TPE) was also added to the above binary blends. A comparative study of FTIR spectroscopy in above both ternary blends confirmed the formation of in situ graft copolymer in the PP/PA6/TPEg blend. Dynamic mechanical analysis (DMA) indicated that un‐like TPE, the incorporation of TPEg remarkably affected both intensity and position of loss peaks of blend components. Scanning electron microscopy (SEM) demonstrated that PP/PA6/TPE blends still exhibited poor interfacial adhesion between the dispersed phase and matrix. However, the use of TPEg induced a finer dispersion and promoted interfacial adhesion. Transmission electron microscopy (TEM) for PP/PA6/TPEg blends showed that a core‐shell structure consisting of PA6 particles encapsulated by an interlayer was formed in PP matrix. With the concentration of TPEg increasing, the dispersed core‐shell particles morphology was found to transform from discrete acorn‐type particles to agglomerate with increasing degree of encapsulation. The modified Harkin's equation was applied to illustrate the evolution of morphology with TPEg concentration. “Droplet‐sandwiched experiments” further confirmed the encapsulation morphology in PP/PA6/TPEg blends. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1050–1061, 2006     

Synthesis of copolyamides based on PA 66 bearing lithium sulfonate groups and having unique thermal properties

Copolyamides of PA 66/6 lithium 5‐sulfoisophthalic acid (LiSIPA) containing up to 40 mol % of LiSIPA were prepared in a 1L‐pilot reactor operating at high pressures and high temperatures. Interestingly, the presence of lithium sulfonate moieties highly impacted the glass transition temperature of the polyamide. The T_g increased from 59 °C for PA 66 to 155 °C for a copolymer containing about 40 mol % of LiSIPA. 1,3‐Dihexylbenzenedicarboxamide and lithium p‐toluenesulfonate were synthesized as model compounds to investigate the interaction of lithium sulfonate moieties and amide functions. Infrared spectroscopy using ATR technology performed on mixture of both compounds showed that the carbonyl group of amide functions interacts with the lithium cation of lithium sulfonate moieties. Similar S? O and C? O adsorption bands were observed in copolyamides PA 66/6LiSIPA and in mixture of model compounds, which strongly suggest the formation in the copolyamides of physical cross‐linking points centered on lithium cations coordinated by carbonyl groups of amide functions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Blends of different linear polyamides with hyperbranched aromatic AB2 and A2 + B3 polyesters

To explore the possible applications of hyperbranched polymers for modifying linear polyamides, two hyperbranched aromatic polyesters characterized as high T_g polymers possessing phenolic end groups were used in melt mixing with partly aromatic polyamide and commercially available aliphatic polyamide‐6, respectively. Different amounts of both hyperbranched polyesters (from 1 wt % up to 20 wt %) were added to the polyamides, and the influence of these hyperbranched polyesters on the properties of the polyamides was investigated. The hyperbranched polyester based on an AB₂ approach was found to be the most effective modifier. A significant increase of the glass transition temperature of the final blend was detected. However, a remarkable reduction of crystallinity as well as complex melt viscosity of those blends was also observed. The use of an A₂+B₃ hyperbranched polyester as melt modifier for the polyamides was less effective for changing the thermal properties, and the complex melt viscosity of the final material increased since heterogeneous blends were formed. In contrast to that, generally, the addition of the AB₂ hyperbranched polyester to the polyamides resulted in homogeneous blends with improved T_g and processability. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3558–3572, 2009     

Poly(silylenemethylene)‐based polymer blends. III. Synthesis and properties of polymer blends containing siloxane‐crosslinked poly(silylenemethylene)s

Soft–hard binary polymer blends consisting of amorphous poly(silylene methylene)s (PSMs) and crystalline poly(diphenylsilylenemethylene) were prepared by both melt processing at 360 °C and in situ polymerization at 300 °C. Linear and siloxane‐crosslinked PSMs were used as amorphous components for the purpose of determining how the crosslinks affected the interactions between the component polymers. Differential scanning calorimetry and dynamic mechanical analysis indirectly suggested that discernable differences between the blends containing linear and crosslinked PSMs were attributable to the degree of interactions between the amorphous and crystalline components. The morphological differences between these blends were studied with transmission electron microscopy. The dispersion phase was smaller in the blends containing crosslinked PSM than that in the blends containing linear PSM. This directly indicated that a larger interaction between the amorphous and crystalline phases was obtained by the introduction of crosslinks because of the smaller viscosity difference between the phases and a larger degree of polymer chain entanglement. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 257–263, 2003     

紫外辐照官能化LLDPE及改性尼龙66的研究

尼龙66（PA66）是工程塑料的重要品种之一,具有高强度、耐磨、耐油、自润滑和使用温度范围广等优良特性,广泛应用于机械、汽车、电子电器等行业．但PA66在干态和低温下冲击强度偏低,吸水率大,尺寸稳定性差,使其应用范围受到一定的限制。     

Nanostructure and mechanical properties studied during dynamical straining of microfibrillar reinforced HDPE/PA blends

Oriented polymer blends whose major component is high‐density polyethylene (HDPE) are strained until failure. Two‐dimensional (2D) small‐angle X‐ray scattering (SAXS) patterns monitor the nanostructure evolution, which is related to the macroscopic mechanical evolution. Data evaluation methods for high‐precision determination of macroscopic and nanoscopic parameters are presented. The hardest materials exhibit a very inhomogeneous nanodomain structure. During straining, their domains appear to be wedged and inhibit transverse contraction on the nanometer scale. Further components of the blends are polyamide 6 (PA6) or polyamide 12 (PA12) (20–30%) and Yparex® 8102 (YP) as compatibilizer (0–10%). Some HDPE/PA6 blends are additionally loaded with commercial nanoclays (Nanomer® or Cloisite®), the respective amounts being 7.5% and 5% with respect to PA. Blending of HDPE with PA12 causes no synergistic effect. In the absence of nanoclay, PA6 and HDPE form a heterogeneous nanostructure with high macroscopic Young's modulus. After addition of YP a rather homogeneous scaffold structure is observed in which some of the PA6 microfibrils and HDPE crystallites appear to be rigidly connected, but the modulus has decreased. Both kinds of nanoclay induce a transition in the HDPE/PA6 blends from a structure without transverse correlation among the microfibrils into a macrolattice with 3D correlations among the HDPE domains from neighboring microfibrils. In the range of extensions between 0.7 and 3.5%, the scattering entities with 3D correlation show transverse elongation instead of transverse contraction. The process is interpreted as overcoming a correlation barrier executed by the crystallites in an evasion‐upon‐approaching mechanism. During continued straining, the 3D correlation is reduced or completely removed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 237–250, 2010     

Reactive blending of PE‐GMA/PA6 effect of composition and processing conditions

Blends of ethylene‐glycidyl methacrylate copolymer (PE‐GMA) and polyamide 6 (PA6) were prepared in a corotating twin screw extruder. Two processing temperatures were used in order to disperse PA6 in two forms: at high temperature in the molten state in molted PE‐GMA Matrix (emulsion type mixture) and at lower temperature as fillers in molted PEGMA matrix (suspension type mixture). Processed blends were analyzed by scanning electron microscopy and dynamic mechanical experiments to probe the reactivity in the extruder and the compatibilization phenomena. The dependence of the morphology and the rheological properties of PE‐GMA/PA6 blends on blend composition and screw rotational speed was also investigated and is discussed in the paper. The results show that dispersion of the two polymers in the molten state leads to a higher level of interfacial reaction. They also show that whatever the screw rotational speed and the temperature of extrusion are, the rate of interfacial reaction in PE‐GMA/PA6 blends is higher for 50/50 PE‐GMA/PA blends than for 70/30 PE‐GMA/PA blends. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of dispersion and selective localization of carbon nanotubes on rheology and electrical conductivity of polyamide 6 (PA6), Polypropylene (PP), and PA6/PP nanocomposites

Nanocomposites were prepared by adding 1–3 vol % multiwalled carbon nanotubes (MWCNTs) to polyamide 6 (PA6), polypropylene (PP), and their co‐continuous blends of 60/40 and 50/50 volume compositions. Because of the good interaction and interfacial adhesion to the PA6, nanotubes were disentangled and distributed evenly through nanocomposites containing PA6. In contrast, lack of active interactions between the matrix and the CNTs resulted in poor tube dispersion in PP. These observations were then verified by studying the rheology and electrical conductivity of their respective nanocomposites. Absence of percolated CNT clusters and possible wrapping of the tubes by PA6 resulted in low electrical conductivity of PA6/CNT nanocomposites. On the other hand, despite the weak dispersion of the tubes, electrical conductivities of PP/CNT nanocomposites were much higher than all other counterparts. This could be the result of good three‐dimensional distribution of the agglomerated bundles and secondary aggregation of tubes in PP. Adding CNTs to blends of PA6/PP (60/40 and 50/50) resulted in almost full localization of carbon nanotubes in PA6, leading to their higher effective concentration. At the same CNT loadings, the blend nanocomposites had three to seven orders of magnitude higher electrical conductivity than pure PA6. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 368–378     

Morphologies,interfacial interaction and mechanical performance of super-tough nanostructured PK/PA6 blends

Nanostructured polyketone (PK)/polyamide 6 (PA6) blends can be readily prepared via melt blending technologies and exhibit ultra-high toughness when PA6 is present as the nanoscale phase domains. When PA6 content is 30 vol%, the impact strength of the blends increases from 21.4 kJ/m² of pure PK to 103.2 kJ/m². The impact strength of the PK/PA6 blends with a 5:5 composition ratio reaches as high as 113 kJ/m². The strong intermolecular force between PK and PA6 molecular chains enables the PA6 nanophase to cavitate to dissipate a significant amount of impact energy and effectively prevents the crack propagation or even terminates the cracks. The fracture mechanism of the PK/PA6 blends was further examined by the essential work of fracture method which proves that PK/PA6 blends show improved ability to prevent crack propagation. This work may deepen the understanding of polymer blend systems with strong hydrogen bonding interaction.     

Preparation of core‐shell structured particle and its application in toughening PA6/PBT blends

Combining the excellent mechanical strengths of polyamide 6 (PA6) with the low water absorption of poly(butylene terephthalate) (PBT) was supposed to be a feasible way to prepare a high comprehensive performance material. However, the poor compatibility between PA6 and PBT resulted in low‐notched impact strength of PA6/PBT blends. Poly(n‐butyl acrylate)/poly(methyl methacrylate‐co‐methacrylic acid) (PBMMA), a core‐shell structured modifier with controlled particle sizes, was prepared by seed emulsion polymerization and confirmed by Transmission electron microscope (TEM). The PBMMA particles as toughening modifier and compatilizer were employed to toughen PA6/PBT blends. The notched impact strength of the PA6/PBT blends was significantly increased and the water absorption was reduced with the addition of PBMMA particles. With 23.0 wt% modifier loading, the notched impact strength of the blends was 25.66 kJ/m², which was 4.04 times higher than that of pure PA6/PBT. Meanwhile, the water absorption of the blends was only 1.3%, dropping 53.6% compared with pure PA6 and reducing by 26.6% than PA6/PBT. Scanning electron microscope results showed that the PBMMA particles were dispersed in the PA6/PBT blends homogeneously, and the toughening mechanism was the cavitation of rubber particles and shear yielding of the matrix. Thermo‐gravimetric analysis analysis demonstrated that the compatibility between PA6 and PBT was improved with the addition of core‐shell PBMMA particles. The core‐shell particles could be used as an effective modifier to achieve the high toughness and low water absorption for PA6/PBT blends. Copyright © 2016 John Wiley & Sons, Ltd.     

Specific properties of in situ ruthenium‐catalyzed polyamide 12/polydimethylsiloxane compatibilized blend

The main objective of this work focused on the chemical modification of polyamide 12 (PA12) properties through the reaction with a hydride‐terminated polydimethylsiloxane (PDMS‐SiH). The investigated PA12/PDMS‐SiH blend was compatibilized by ruthenium derivative catalyzed hydrosilylation reaction in molten state. This original route enhanced interfacial adhesion and avoid PDMS‐SiH leaching phenomenon between the two immiscible phases. More specifically, the size of PDMS‐SiH domains in the blend decreased from around 4 μm to 800 nm and from 30 to 1 μm after compatibilization with 10 and 20 wt % PDMS‐SiH, respectively. For the best compatibilized PA12/PDMS‐SiH blend, the introduction of PDMS lowered the surface free energy and the PA12‐based blend turned from hydrophilic to hydrophobic behavior, as evidenced by the water contact angle measurements. Gas permeability and CO₂/H₂ and CO₂/He gas selectivity were also improved with the increase in PDMS content. Besides, the mechanical properties were enhanced with 13% increase in Young's modulus after in situ compatibilization with 15 wt % PDMS‐SiH. Thermal stability was also improved after compatibilization as the initial degradation temperature of reactive blends obviously increased compared with nonreactive ones. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 978–988