Compatibilized polyamide 6/polyethylene blend-clay nanocomposites: Effect of the degradation and stabilization of the clay modifier

Blends of polyamide 6 (PA6) and high-density polyethylene (HDPE) were compatibilized using an already investigated method and a sample of Cloisite 15A, a montmorillonite modified with ammonium quaternary salts was added. The blends were prepared in a twin screw extruder and characterized from a morphological, rheological and mechanical point of view. The results indicated that, despite a good morphology achieved in the filled blends and a moderate intercalation of the clay, the mechanical properties are far from being good, especially the ultimate properties.In order to investigate the possible influence of the inhibition of the crystallization and of the degradation of the organic modifier of the clay, DSC measurements and FTIR-ATR were carried out. The results confirm that the clay causes a slight decrease of the crystallization, particularly in the HDPE phase. In addition, in the preparation conditions, the clay modifier is sensitive to thermo-oxidation. Both features can, therefore, explain the bad mechanical performance, even if the degradation effects seem to be more important. In order to prevent, or at least to reduce, the thermo-oxidation, a stabilizing system was added to the filled blends. In this case, the mechanical properties are improved for the entire compatibilized blend set.     

The effects of reprocessing cycles on the structure and properties of isotactic polypropylene/cloisite 15A nanocomposites

The effects of reprocessing cycles on the structure and properties of isotactic polypropylene (PP)/Cloisite 15A (OMMT) (5 wt. %) nanocomposites was studied in presence of maleic anhydride-grafted-polypropylene (PP-g-MA) (20 wt. %) used as the compatibiliser to improve the clay dispersion in the polymer matrix. The various nanocomposite samples were prepared by direct melt intercalation in an internal mixer, and further they were subjected to 4 reprocessing cycles. For comparative purposes, the neat PP was also processed under the same conditions. The nanocomposite structure and the clay dispersion have been characterized by wide angle X-ray scattering (WAXS), transmission electron microscopy (TEM) and rheological measurements. Other characterization techniques such as Fourier transform infrared spectroscopy (FT-IR), tensile measurements, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) have also been used to evaluate the property changes induced by reprocessing. The study showed through XRD patterns that the repetitive reprocessing cycles modified the initial morphology of PP/OMMT nanocomposites by improving the formation of intercalated structure, especially after the fourth cycle. Further, the addition of PP-g-MA promoted the development of intercalated/exfoliated silicate layers in the PP matrix after the second cycle. These results are in agreement with TEM observations indicating an improved silicate dispersion in the polymer matrix with reprocessing cycles displaying a morphology with both intercalated/exfoliated structures. The initial storage modulus (G′) of the nanocomposites, which was highly improved in presence of PP-g-MA seems to be less affected by reprocessing cycles at very low frequencies exhibiting a quasi-plateau compared to pristine PP/OMMT and PP. In contrast, the complex viscosity was found to decrease for the whole samples indicating that the main effect of reprocessing was a decrease in the molecular weight. Moreover, the thermal and mechanical properties of the nanocomposites were significantly reduced after the first cycle; nevertheless they remained almost unchanged during recycling. No change in the chemical structure was observed in the FT-IR spectra for both the nanocomposites and neat PP samples after 4 cycles.     

Effect of maleic anhydride-grafted ethylene-propylene rubber on the mechanical, rheological and morphological properties of organoclay reinforced polyamide 6/polypropylene nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic modified montmorillonite (organoclay) were compatibilized with maleic anhydride-grafted ethylene-propylene rubber (EPRgMA). The blends were melt compounded in twin screw extruder followed by injection molding. The mechanical properties of PA6/PP nanocomposites were studied by tensile and flexural tests. The microstructure of the nanocomposite were assessed by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The dynamic mechanical properties of the PA6/PP blend-based nanocomposites were analyzed by using a dynamic mechanical thermal analyzer (DMTA). The rheological properties were conducted from plate/plate rheometry via dynamic frequency sweep scans. The melt viscosity in a high shear rate region was performed by using a capillary rheometer. The strength and stiffness of the PA6/PP-based nanocomposites were improved significantly with the incorporation of EPRgMA. Adding EPRgMA to the PA6/PP blends resulted in a finer dispersion of the PP phase. TEM and XRD results revealed that the organoclay was dispersed more homogeneously in the presence of EPRgMA, however, mostly in the PA6 phase of the blends. DMTA results showed that EPRgMA worked as an effective compatibilizer. The storage (G′) and loss moduli (G″) assessed by plate/plate rheometry of PA6/PP blends increased with the incorporation of EPRgMA and organoclay. Furthermore, the apparent shear viscosity of the PA6/PP blend increased significantly for the EPRgMA compatibilized PA6/PP/organoclay nanocomposite. This was traced to the formation of an interphase between PA6 and PP (via PA6-g-EPR) and effective intercalation/exfoliation of the organoclay.     

One-step water-assisted melt-compounding of polyamide 6/pristine clay nanocomposites: An efficient way to prevent matrix degradation

Polyamide 6 (PA6)/clay nanocomposites, based on organo-modified and pristine (i.e. purified but non-modified) montmorillonite, were prepared using a water-assisted extrusion process based on the injection of water during extrusion. The formation of a single PA6/water phase during extrusion (shown by High Pressure Differential Scanning Calorimetry (HPDSC)) improves the clay dispersion, decreases the PA6 melting temperature by 66 °C (so-called cryoscopic effect), and thus prevents the polymer matrix degradation during processing. This process enables the compounding of pristine clay-based nanocomposites whose dispersion state, thermal and mechanical performances are close to what is generally reported for organo-modified montmorillonite-based nanocomposites. Advantage was taken of water-assisted extrusion to optimize the clay dispersion by increasing shear rate and of the cryoscopic effect to limit the degradation by decreasing the processing temperature. Using these conditions PA6/pristine clay nanocomposites properties are similar to those of more conventional PA6/organomodified clay nanocomposites.     

Nanocomposites based on a polyamide 6/maleated styrene-butylene-co-ethylene-styrene blend: Effects of clay loading on morphology and mechanical properties

The addition of up to 6% of an OMMT to a 70/30 polyamide 6 (PA6)/maleated styrene-ethylene/butylene-styrene (mSEBS) blend led to ternary compounds where the rigidifying effect of the clay and the toughening effect of the rubber came together. In fact, in the 70/30 blend with 3% OMMT supertough behaviour was accomplished with a modulus increase of 44% with respect to the pure PA6 matrix. When the changes in morphology of the dispersed rubber phase in presence of OMMT are discussed, the slight decrease in viscosity upon clay addition does not explain the increase in rubber particle size that indicates a decrease in the compatibilization level. Interactions between the surfactant of the OMMT and the maleic anhydride groups of modified rubber are proposed as the reason for the decrease in compatibility. The maximum impact strength attained is rather independent of the clay content and the testing temperature. The increase in modulus of the blend upon clay addition was similar to that observed for the pure PA6 matrix, while maintaining the ductile nature in the ternary PN’s, which is not always present in PA6/OMMT binary materials.     

Fire behaviour of polyamide 6/multiwall carbon nanotube nanocomposites

Nanocomposites of polyamide 6 with 5 wt.% multiwall carbon nanotubes are investigated to clarify their potential as regards the fire retardancy of polymers. The nanocomposites are investigated using SEM, electrical resistivity, and oscillatory shear rheology. The pyrolysis is characterized using thermal analysis. The fire behaviour is investigated with a cone calorimeter using different external heat fluxes, by means of the limiting oxygen index and the UL 94 classification. The fire residue is characterized using SEM. The comprehensive fire behaviour characterization not only allows the materials’ potential for implementation in different fire scenarios and fire tests to be assessed, but also provides detailed insight into the active mechanisms. The increased melt viscosity of the nanocomposites and the fibre-network character of the nanofiller are the dominant mechanisms influencing fire performance. The changes are found to be adjuvant with respect to forced flaming conditions in the cone calorimeter, but also deleterious in terms of flammability.     

Preparation, characterization and water barrier properties of PS/organo-montmorillonite nanocomposites

Polystyrene/organo-montmorillonite nanocomposites were prepared via solution blending method, using CHCl₃ and CCl₄ as solvents. The clay used was organically modified by hexadecyltrimethyl-ammonium bromide (CTAB) at various surfactant loadings. Intercalated nanocomposite structure was obtained using CHCl₃ as solvent while exfoliated or partially exfoliated was probably the predominated form in the case of CCl₄, as shown by X-ray diffraction measurements. Enhancement in thermal stability and in water barrier properties was observed for PS-nanocomposites compared to that of pristine polymer as indicated by thermogravimetric analysis and water vapor transmission measurements. This increment was more prevalent for nanocomposites prepared with carbon tetrachloride as solvent.     

Preparation and characterization of PE and PE-g-MAH/montmorillonite nanocomposites

Polyethylene (PE) was chemically modified with grafting maleic anhydride (MAH) monomer on its backbone at first. Then the melt-direct intercalation method was employed to prepare two kinds of nanocomposites, polyethylene (PE)/organic montmorillonite (Org-MMT) and maleic anhydride grafted polyethylene (PE-g-MAH)/Org-MMT nanocomposites. X-ray diffractometery (XRD) was used to investigate the intercalation effect and transmission electron microscopy (TEM) to observe the dispersion of Org-MMT interlayers in matrixes. The results show that an intercalated structure would be acquired on mixing the PE and Org-MMT; and an almost exfoliated system would be obtained by mixing the PE-g-MAH and Org-MMT. Moreover, further measurements via thermogravimetric (TGA) and differential scanning calorimetry (DSC) showed that both of the nanocomposites had a higher thermal decomposition temperature and a higher crystallization temperature when compared to the original matrix. At the same time, the thermal and crystal properties for the PE-g-MAH prepared in this experiment are also discussed.     

From exfoliation to intercalation—changes in morphology of HNBR/organoclay nanocomposites

Hydrogenated nitrile rubber (HNBR)/organoclay nanocomposites (HNBR/OCNs) were prepared by mechanical mixing technique. By altering the temperature, pressure, and treatment time, respectively, the microstructural changes of HNBR/OCNs compounds under those treatments were studied by X-ray diffraction (XRD) and transmission electron microscopy (TEM) in detail. It was investigated that after the treatment, the exfoliated organoclay dispersion in untreated HNBR/organoclay compounds transformed into the co-existing of exfoliated, intercalated, and aggregated structures by de-intercalation action. Moreover, pressure, and temperature played accelerated roles in determining the final clay structures in HNBR/OCNs. It was suggested that the transformation was caused by the relaxation of HNBR chains, and it could be proceed spontaneously in thermodynamics under the treatment condition.     

Preparation and characterization of waterborne polyurethane/attapulgite nanocomposites

In this paper, waterbrone polyurethane (WPU)/attapulgite (AT) nanocomposites have been prepared by direct emulsion blending. The WPU was synthesized from poly(tetramethylene glycol), 4,4-diphenylmethane diisocyanate, dimethylol butanic acid, and neutralized by triethylamine. SEM examination of fractured surfaces showed that AT particles were irregularly dispersed in the WPU matrix. FTIR analysis suggested no major chemical structural changed in the presence of a small amount of AT. DMA results showed that the storage modulus of WPU/AT nanocomposites was increased and the glass transition temperatures of both soft and hard segments shifted to higher temperature compared to the pristine WPU. Thermal resistance of the samples measured by TGA was improved with the addition of AT. The mechanical properties of the nanocomposites, examined by tensile tests, showed higher tensile strength and elongation at break than that of the pristine WPU.     

A rheological analysis of interactions in phenoxy/organoclay nanocomposites

Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature.     

Flammability, structure and mechanical properties of PP/OMMT nanocomposites

Polypropylene/organoclay (PP/OMMT) nanocomposites were prepared in a twin-screw corotating extruder using two methods. The first method was the dilution of commercial (PP/50% Nanofil SE3000) masterbatch in PP (or PP with commercial flame retardant). The second method consists of two stages was the extrusion of maleic anhydride grafted polypropylene (PP-g-MAH) with commercially available organobentonite masterbatch in first stage and dilution of the masterbatch in PP (or PP with commercial flame retardant) in second stage. XRD results showed no intercalation in composites obtained from commercial masterbatch without compatibilizer and semi - delamination for compatibilized systems. Tensile tests revealed that nanocomposites with 5% of organoclay have a slightly higher tensile modulus and tensile strength than pristine PP, however addition of the commercial flame retardant (FR) reduces mechanical parameters to roughly the level of those for neat PP. PP/OMMT composites have approx. 25% higher oxygen index than pristine PP, and this changes slightly after the addition of FR. The cone calorimeter tests showed a decrease of a heat release rate (HRR) and a mass loss rate (MLR) after the addition of FR.     

Effects of reprocessing on the structure and properties of polyamide 6 nanocomposites

PA6 based nanocomposites (NCs) were reprocessed by repeated injection moulding to find out whether reprocessing is possible in these materials by means of the observation of the changes in the structure and mechanical properties. The studied variables were (a) the number of cycles (1-5), (b) the origin of the NC: either laboratory mixed or commercial and (c) the processing temperature (230 °C and 270 °C). Neat PA6 was also reprocessed as a reference material. In spite of the colour change, the Young's modulus, the solid state characteristics and the dispersion level were preserved upon reprocessing. The lack of change of chemical nature observed by FTIR, and the observed decreases in viscosity indicated that the main effect of reprocessing was a decrease in the molecular weight. At 230 °C the decreases in viscosity were smaller after reprocessing, and almost no change was seen in the structural parameters and properties. The decrease in the molecular weight after reprocessing at 270 °C leads to lower ductility and mainly to a decrease in the ability of the nPA6 matrix to cold draw. However, no change of the interphase conditions or agglomeration of the OMMT was detected and the NCs remained clearly ductile; thus, revealing a lack of deterioration of the interface and the ability of the NCs for recycling.     

Structure and properties of nanocomposites with a poly(trimethylene terephthalate) matrix

Poly(trimethylene terephthalate) (PTT), and three organically modified montmorillonites were mixed in the melt state obtaining widely dispersed nanocomposites. The parameters varied in this study were the type and amount of the organic modification and the clay content. A higher polarity of the surfactant made intercalation easier, but neither the nature (included polarity) nor the amount of surfactant influenced the dispersion level. The latter was shown directly by TEM and indirectly by the values of the modulus of elasticity. Upon mixing, a maximum interlayer distance was observed regardless of the initial interlayer distance and the nature and amount of the organoclay used. This finding was also observed in other matrices but does not appear to be a general rule. The decrease in the break properties is mainly attributed to the clay addition and the increases in the modulus of elasticity were large, in agreement with the high degree of dispersion obtained.     

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     

Preparation and characterization of nylon 66/montmorillonite nanocomposites with co-treated montmorillonites

In this paper, a new type of organophilic montmorillonites, co-treated by octadecylammonium and aminoundecanoic acid, were synthesized and applied to prepare nylon 66/montmorillonite nanocomposites via melt compounding in a twin extruder. WAXD and TEM characterization indicate that a disordered structure was derived and the montmorillonite platelets dispersed in nanoscale in the nylon 66 matrix. The nanocomposites with co-treated montmorillonite display comparatively higher strength and modulus compared to nylon 66 matrix.     

Photochemical stabilization of linear low-density polyethylene/clay nanocomposites: Towards durable nanocomposites

This article reports a study of the chemical modifications of LLDPE/nanoblend nanocomposites exposed to UV light in conditions of artificially accelerated ageing and natural weathering. Analysis by infrared spectroscopy of the chemical modifications produced by photoageing shows that the presence of an organo-clay leads to the decrease of the oxidation induction time of the polymer (LLDPE), which results in lower durability of the nanocomposites. Protection against photooxidation was tested with different kinds of UV stabilizers and with a metal deactivator. It is shown that the metal deactivator is very efficient in stabilizing the nanocomposite since it totally cancels the prodegradant effect of the organo-clay. This confirms the role played by iron impurities in natural clays. The use of a metal deactivator offers a new insight into the stabilization strategy for nanocomposites.     

Polymer/carbon nanotube nanocomposites: Influence of carbon nanotubes on EVA photodegradation

The influence of carbon nanotubes on the photodegradation of EVA/carbon nanotube nanocomposites was studied by irradiation under photooxidative conditions (at λ > 300 nm, at 60 °C and in the presence of oxygen). The influence of the nanotubes on both the photooxidation mechanism of EVA and the rates of oxidation of the matrix was characterized on the basis of infrared analysis. On one hand, it was shown that the carbon nanotubes act as inner filters and antioxidants, which contribute to reduction in the rate of photooxidation of the polymeric matrix. On the other hand, it was shown that light absorption could provoke an increase in the local temperature and then induce the photooxidation of the polymer. The competition between these three effects determines the global rate of photooxidation of the polymeric matrix. Several factors are involved, the concentration of the carbon nanotubes, the morphology of the nanotubes and the functionalization of the nanotube surface.     

Preparation and characterization of cellulose nanocomposite films with two different organo-micas

The mechanical properties, morphologies, and gas barriers of hybrid films of cellulose with two different organoclays are compared. Dodecyltriphenyl-phosphonium-mica (C₁₂PPh-mica) and hexadecyl-mica (C₁₆-mica) were used as reinforcing fillers in the fabrication of the cellulose hybrid films. The cellulose hybrid films were synthesized from N-methyl-morpholine-N-oxide (NMMO) solutions with the two organo-micas, and solvent-cast at room temperature under vacuum, yielding 15–20 μm thick films of cellulose hybrids with various clay contents. We found that the addition of only a small amount of organoclay is sufficient to improve the mechanical properties and gas barriers of the cellulose hybrid films. Even polymers with low organoclay contents (1–7 wt %) were found to exhibit much higher strength and modulus values than pure cellulose. The addition of C₁₂PPh-mica was more effective than that of C₁₆-mica with regards to the initial tensile modulus, whereas the addition of C₁₆-mica was more effective than that of C₁₂PPh-mica with regards to the gas barrier of the cellulose matrix. The intercalations of the polymer chains in the clays were examined with wide-angle X-ray diffraction (XRD) and electron microscopy (SEM and TEM).     

Morphology and performance of unsaturated polyester nanocomposites modified with organoclay and thermoplastic polyurethane

<正>Unsaturated polyester(UPR)/thermoplastic polyurethane(TPU)/organoclay nanocomposites were prepared by melt compounding of thermoplastic polyurethane and unsaturated polyester prepolymer,and then mixing with the hybrids of styrene monomers and organoclay at ambient temperature.The crosslinking reaction eventually occurred through the unsaturated polyester prepolymer and styrene monomer.The morphology of the composites was investigated by scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The results show that the impact strength of UPR/TPU/organoclay nanocomposites increases obviously;the cure shrinkage decreases markedly,the glass transition temperature is enhanced and an elastic response to the deformation is prominent at the temperature above 10℃.