Free‐volume hole properties of two kinds thermoplastic nanocomposites based on polymer blends probed by positron annihilation lifetime spectroscopy

Two type of nanocomposites—an immiscible blend, high density polyethylene/polyamide 6 (HDPE/PA‐6) with organomodified clay, and a compatibilized blend, high density polyethylene grafted with acrylic acid/PA‐6 (PEAA/PA‐6) with organomodified clay—were prepared via melt compounding. X‐ray diffraction and transmission electron microscopy results revealed that the clay was intercalated and partially exfoliated. Positron annihilation lifetime spectroscopy has been utilized to investigate the free‐volume hole properties of two type of nanocomposites. The results show a negative deviation of free‐volume size in PEAA/PA‐6 blend, and a positive deviation in HDPE/PA‐6 blend, and I₃ has a greater negative deviation in compatibilized blend than in immiscible blend due to interaction between dissimilar chains. For nanocomposites based on polymer blends, in immiscible HDPE/PA‐6/organomodified clay system, the variation of free‐volume size with clay content is not obvious and the free‐volume concentration and fraction decreased. While in the case of compatibilized PEAA/PA‐6/organomodified clay nanocomposites, complicated variation of free‐volume properties due to interactions between two phases and organomodified clay was observed. And the interaction parameter β shows the interactions between polymers and organomodified clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2463–2469, 2006     

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     

Preparation of thermoplastic elastomer nanocomposites based on polyamide‐6/polyepichlorohydrin‐co‐ethylene oxide

This work is aimed at determining the effect of nanoclay and polyepichlorohydrin‐co‐ethylene oxide (ECO) content on the microstructure and mechanical properties of PA6/ECO thermoplastic elastomers (TPEs). TPE nanocomposites were prepared in a laboratory mixer using polyamide 6 (PA6), ECO, and an organoclay by a two‐step melt mixing process. First, the PA6 was melt blended with Cloisite 30B and then mixed by ECO rubber. X‐ray diffraction results and transmission electron microscopy image showed that the nanoclay platelets were nearly exfoliated in both the phases. The SEM photomicrograph of PA6 with ECO showed that the elastomer particles are dispersed throughout the polyamide matrix and the size of rubber particles is less than 3 μm. Introduction of organoclay in the PA6 matrix increased the size of dispersed rubber particles in comparison with the unfilled but otherwise similar blends. The nanoscale dimension of the dispersed clay results in an improvement of the tensile modulus of the nanocomposites. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Polyamide‐6/high‐density polyethylene blend using recycled high‐density polyethylene as compatibilizer: Morphology,mechanical properties,and thermal stability

Blends of polyamide‐6 (PA6) or postindustry polyamide‐6 (piPA6) and high‐density polyethylene (HDPE) or recycled high‐density polyethylene (rHDPE) were processed in single and twin‐screw extruders. The use of rHDPE in the blends promotes a significant decrease of size domains and improvement in the mechanical properties. The thermal stability was also slightly improved compared with PA6 and HDPE blends. The Molau test exhibited a stable emulsion in formic acid, which can be attributed to the formation of an interfacial copolymer involving polar amino end groups of PA6 and the rHDPE, respectively. These results indicate that recycled polymers can be used in the production of polymer blends with improved properties. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers.     

Gasoline permeation behavior and mechanical properties of polyamide 6/nanoclay,polyamide 6/PE‐g‐maleic anhydride blend,and polyamide 6/PE‐g‐maleic anhydride/clay nanocomposite

In this article, polyamide 6 (PA6)/clay nanocomposites, PA6/polyethylene grafted maleic anhydride (PE‐g‐MA) blends, and PA6/PE‐g‐MA/clay nanocomposites were prepared and their gasoline permeation behavior and some mechanical properties were investigated. In PA6/clay nanocomposites, cloisite 30B was used as nanoparticles, with weight percentages of 1, 3, and 5. The blends of PA6/PE‐g‐MA were prepared with PE‐g‐MA weight percents of 10, 20, and 30. All samples were prepared via melt mixing technique using a twin screw extruder. The results showed that the lowest gasoline permeation occurred when using 3 wt % of nanoclay in PA6/clay nanocomposites, and 10 wt % of PE‐g‐MA in PA6/PE‐g‐MA blends. Therefore, a sample of PA6/PE‐g‐MA/clay nanocomposite containing 3 wt % of nanoclay and 10 wt % of PE‐g‐MA was prepared and its gasoline permeation behavior was investigated. The results showed that the permeation amount of PA6/PE‐g‐MA/nanoclay was 0.41 g m^?2 day^?1, while this value was 0.46 g m^?2 day^?1 for both of PA6/3wt % clay nanocomposite and PA6/10 wt % PE‐g‐MA blend. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40150.     

Toughening and brittle‐tough transition in polyamide 12‐organoclay/maleated styrene‐ethylene‐co‐butylene‐styrene nanocomposites

Tough nanocomposites based on polyamide 12 (PA12) can be obtained by the addition of a maleated rubber to a highly dispersed PA12‐clay nanocomposite by melt processing. The nanostructure behavior was evaluated by X‐ray diffraction and transmission electron microscopy. The results showed that the organoclay was highly dispersed and mostly located in the PA12 matrix due to the larger affinity between the polyamide and the clay, but some of the organoclay was also present in the polymer/polymer interface. The presence of organoclay slightly increased the dispersed particle size, indicating decreased compatibilization. This was attributed to a partial shielding of maleic anhydride compatibilizer by surfactant. The addition of the elastomer considerably improved the toughness of the PA12‐based nanocomposites, maintaining its stiffness; i.e., the nanocomposites with 25% rubber content showed an increase of 25‐fold of notched impact strength of the PA12 matrix, meanwhile ductility and stiffness remained constant. This allowed us to obtain toughened PA12 PNs throughout a large range of strain rate and a modulus similar to that of the unmodified PA12. The position of the brittle/tough transition in terms of rubber content, determined by the standard notched Izod test (25% mSEBS) is basically the same as that determined by the essential work of fracture procedure. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Crystal structures and their effects on the properties of polyamide 12/clay and polyamide 6–polyamide 66/clay nanocomposites

Both polyamide 12 (PA 12)/clay and polyamide 6–polyamide 66 copolymer (PA 6/6,6)/clay nanocomposites were prepared by melt intercalation. The incorporation of 4–5 wt % modified clay largely increased the strength, modulus, heat distortion temperature (HDT), and permeation resistance to methanol of the polyamides but decreased the notched impact strength. Incorporation of the clay decreased the melt viscosities of both the PA 12 and PA 6/6,6 nanocomposites. Incorporation of the clay increased the crystallinity of PA 6/6,6 but had little effect on that of PA 12, which explained why the clay obviously increased the glass‐transition temperature of PA 6/6,6 but hardly had any effect on that of PA 12. The dispersion and orientation of both the clay and the polyamide crystals were studied with transmission electron microscopy, scanning electronic microscopy, and X‐ray diffraction. The clay was exfoliated into single layers in the nanocomposites, and the exfoliated clay layers had a preferred orientation parallel to the melt flow direction. Lamellar crystals but not spherulites were initiated on the exfoliated clay surfaces, which were much more compact and orderly than spherulites, and had the same orientation with that of the clay layers. The increase in the mechanical properties, HDT, and permeation resistance was attributed to the orientated exfoliated clay layers and the lamellar crystals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4782–4794, 2006     

Effect of clay addition on the morphology and thermal behavior of polyamide 6

The nanostructure, morphology, and thermal properties of polyamide 6 (PA6)/clay nanocomposites were studied with X‐ray scattering, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). The wide‐angle X‐ray diffraction (WAXD) and TEM results indicate that the nanoclay platelets were exfoliated throughout the PA6 matrix. The crystallization behavior of PA6 was significantly influenced by the addition of clay to the polymer matrix. A clay‐induced crystal transformation from the α phase to the γ phase for PA6 was confirmed by WAXD and DSC; that is, the formation of γ‐form crystals was strongly enhanced by the presence of clay. With various clay concentrations, the degree of crystallinity and crystalline morphology (e.g., spherulite size, lamellar thickness, and long period) of PA6 and the nanocomposites changed dramatically, as evidenced by TEM and small‐angle X‐ray scattering results. The thermal behavior of the nanocomposites was investigated with DSC and compared with that of neat PA6. The possible origins of a new clay‐induced endothermic peak at high temperature are discussed, and a model is proposed to explain the complex melting behavior of the PA6/clay nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1191–1199, 2007     

The effect of zinc oxide addition on the compatibilization efficiency of maleic anhydride grafted high‐density polyethylene compatibilizer for high‐density polyethylene/polyamide 6 blends

A high‐density polyethylene with grafted maleic anhydride units has been investigated as a compatibilizer for high‐density polyethylene with polyamide 6. The material acts as an effective compatibilizer, causing a marked reduction in dispersed phase size as well as an increase in tensile strength and toughness. Compatibilizer also affects the glass‐transition temperature, crystallization kinetics, and amount of crystalline material for certain blend compositions. The addition of zinc cations, which are effective in increasing ethylene‐acid copolymer compatibilizer performance in low‐density polyethylene/polyamide blends, has little, if any, effect on compatibilizer performance in these high‐density polyethylene/polyamide blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3871–3881, 2007     

Two‐body abrasive wear behavior of particulate filled polyamide66/polypropylene nanocomposites

An experimental characterization of the abrasive wear behavior of clay and clay plus short carbon fiber filled polyamide66/polypropylene (PA66/PP) nanocomposites has been investigated. Two‐body abrasive wear studies were carried out using pin‐on‐disc wear tester under multi‐pass condition against the water proof silicon carbide abrasive paper. It was observed that the clay reinforcement is detrimental to the abrasive wear resistance of PA66/PP blend. A combination of clay and short carbon fiber in PA66/PP blend improved the abrasive wear performance than those of clay filled PA66/PP nanocomposites. Further, on the basis of microscopic observation of the worn surfaces, dominant wear mechanisms were discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Potential in situ preparation of aliphatic polyamide‐based nanocomposites: The organoclay‐polyamide salt interaction

In situ intercalative polycondensation is applied for the preparation of polyamide (PA) n,6–clay nanocomposites, namely poly(ethylene adipamide) (PA 2,6), poly(hexamethylene adipamide) (PA 6,6), and poly(dodecamethylene adipamide) (PA 12,6). For this purpose, two different polymerization routes are considered; a low‐temperature melt polymerization technique and the conventional solution‐melt one. Under the specific experimental conditions, lack of clay exfoliation is detected through XRD measurements, which is proved irreversible even when twin‐screw extrusion is attempted as an additional step. The resulting PA n,6–clay structures are found dependent on the diamine moiety length; more specifically, an intrinsic interaction between the polyamide monomer and the organoclay surfactant is indicated. An ion exchange occurs between the two competitive species, that is, diamine and surfactant cations, leading to flocculated clay structures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Morphology,thermal behavior,and mechanical properties of PA6/UHMWPE blends with HDPE‐g‐MAH as a compatibilizing agent

A functionalized high‐density polyethylene (HDPE) with maleic anhydride (MAH) was prepared using a reactive extruding method. This copolymer was used as a compatibilizer of blends of polyamide 6 (PA6) and ultrahigh molecular weight polyethylene (UHMWPE). Morphologies were examined by a scanning electron microscope. It was found that the dimension of UHMWPE and HDPE domains in the PA6 matrix decreased dramatically, compared with that of the uncompatibilized blending system. The size of the UHMWPE domains was reduced from 35 μm (PA6/UHMWPE, 80/20) to less than 4 μm (PA6/UHMWPE/HDPE‐g‐MAH, 80/20/20). The tensile strength and Izod impact strength of PA6/UHMWPE/HDPE‐g‐MAH (80/20/20) were 1.5 and 1.6 times as high as those of PA6/UHMWPE (80/20), respectively. This behavior could be attributed to chemical reactions between the anhydride groups of HDPE‐g‐MAH and the terminal amino groups of PA6 in PA6/UHMWPE/HDPE‐g‐MAH blends. Thermal analysis was performed to confirm that the above chemical reactions took place during the blending process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 232–238, 2000     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Developing laminar morphology in higher‐viscosity‐ratio polyblends by controlling flow fields in a single‐screw extruder

The morphology of high‐density polyethylene (HDPE)/polyamide‐6 (PA‐6) blends with different melt‐shear‐viscosity ratios (VRs), prepared by combining a single‐screw extruder with a convergent die was studied. Two different screw geometries, metering and mixing screws, and three screw speeds, 20, 40 and 60 rpm, were evaluated to investigate their effects on the morphology of extruded ribbons. Two mixing screws with low and high shear intensity, respectively, were used. Both the geometry and speed of screw were found to have an important role in the morphological changes of the blends. In contrast to previous studies, the results shown in this work reveal that it is possible to develop a laminar structure of PA‐6 in an HDPE matrix with a VR larger than one by controlling the flow fields, through appropriately combining the type and shear intensity of the screw with its speed. A well‐developed laminar PA‐6 phase with an aspect ratio of about 100 was obtained under the optimum combination. Copyright © 2004 Society of Chemical Industry     

Mechanical and thermal properties of toughened PA6/HDPE/SEBS‐g‐MA/Clay nanocomposite

Preparation and morphology of Polyamide 6 (PA6)/high density polyethylene (HDPE)/Styrene/Ethylene–Butylene/Styrene grafted with maleic anhydride (SEBS‐g‐MA)/Modified clay nanocomposites were studied. Mixing was performed using melting process in an extruder co‐rotating twin screw. After etching the materials with boiling toluene and THF at room temperature, the morphology of sample checked by scanning electron microscopy (SEM) analyses. X‐ray diffraction (XRD) used for evaluation of the effects of organo‐clay addition in the structure of nanocomposites. XRD traces showed that the characteristic (001) peak of the nanocomposites shifted to the lower degree region. XRD and SEM results showed more uniformly distribution and dispersion of HDPE in the PA6 matrix. Better sample morphology obtained, regarding less distance, and more uniformity between nanoparticles. The mechanical properties like tensile strength, impact strength, hardness and thermal properties of these toughened nanocomposites are discussed in terms of the nanoclay, SEBS‐g‐MA contents and morphology. Adding nanoclay improved hardness of nanocomposites product but reduced toughness and thermal properties. Meanwhile the presence of SEBS‐g‐MA as a compatibilizer improved toughness, thermal properties, hardness property, and the balance properties are achieved. POLYM. ENG. SCI., 55:29–33, 2015. © 2014 Society of Plastics Engineers     

Effects of swelling agents on the crystallization behavior and mechanical properties of polyamide 6/clay nanocomposites

Montomorillonite was organically modified with three different swelling agents: n‐dodecylamine, 12‐aminolauric acid, and 1,12‐diaminodecane. These organoclays and polyamide 6 (PA6) were blended in a formic acid solution. X‐ray diffraction analysis showed that the clay still retained its layer structure in the PA6/clay nanocomposite. Consequently, these materials were intercalated nanocomposites. The effects of the swelling agent and organoclay content on the crystallization behavior of the PA6/clay nanocomposites were studied with differential scanning calorimetry. The results showed that the position and width of the exothermic peak of the PA6/clay nanocomposites were changed during the nonisothermal crystallization process. The clay behaved as a nucleating agent and enhanced the crystallization rate of PA6.The crystallinity of PA6 decreased with an increasing clay content. Different swelling agents also affected the crystallization behavior of PA6. The effects of the type and content of the swelling agent on the tensile and flexural properties of PA6/clay nanocomposites were also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1686–1693, 2003     

OMMT对PE-HD/PA6合金的结晶性能和相容性的影响

研究了不同含量的有机蒙脱土（OMMT）对高密度聚乙烯/聚酰胺6（PE-HD/PA6）合金的结晶性能和微观结构的影响。X射线衍射和差示扫描量热仪分析表明,随着OMMT的含量的增加,PA6倾向于生成γ晶型;扫描电镜分析表明,对于PE-HD/PA6合金,PA6以球状分散在PE-HD基体中,相尺寸直径较大,为30~40 μm;添加OMMT后,PA6分子链的极性基团可以与OMMT层间表面产生强的相互作用,使得大分子链在熔融过程中进入OMMT层间,得到PE-HD/PA6/OMMT纳米复合材料。当添加3份OMMT后,复合材料中分散相PA6的相尺寸降低至10 μm,尺寸分布均匀,说明OMMT起到了相容剂的作用。同时,适量的OMMT提高了PE-HD/PA6合金对有机溶剂的阻透性。     

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

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