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The non-isothermal crystallization behavior of polylactic acid (PLA) in presence of linear low-density polyethylene (LLDPE) and two different commercial-grade nanoclays, Cloisite 30B and Cloisite® 15A at different conditions were investigated using DSC and WAXS. The results showed that crystallization of neat PLA was very difficult from the melt in the non-isothermal quenching process and presence of nanoclays only improved the crystallization of PLA during heating. LLDPE as an efficient plasticizer enhanced the mobility of PLA chain segments, which led to the increased crystallization rate during heating. In PLA/LLDPE/clay hybrid, PLA component could crystallize only during heating and a fractionated crystallization of LLDPE was occurred during cooling. Cloisite® 15A as a good nucleating agent and LLDPE as an efficient plasticizer promoted the crystallization of PLA in a certain degree indicating the synergistic effects of LLDPE and nanoclays on PLA crystallization particularly at low nanoclays content.

Polylactide (PLA)/linear low-density polyethylene (LLDPE), (PLA/LLDPE), blends and nanocomposites were prepared by melt mixing process with a view to fine tune the properties. Two different commercial-grade nanoclays, Cloisite® 30B (30B) and Cloisite® 15A (15A) were used. A terpolymer of ethylene, butylacrylate (BA) and glycidylmethacrylate (GMA) was used as a reactive compatibilizer. The influence of type of clay on the morphology and mechanical properties of two PLA-rich and LLDPE-rich blend systems was studied. Morphological analysis using X-ray diffraction, transmission electron microscopy, and scanning electron microscopy revealed that the organoclay layers were dispersed largely at the interface of PLA/LLDPE. Decreasing the PLA content changed the morphology from droplet-in matrix to coarse co-continuous. In comparison with 30B, due to less affinity of 15A towards compatibilizer and PLA phase, the reduction of the size of dispersed phase was less than that of the equivalent 30B composites. The mechanical results demonstrated that the composites containing both types of organoclay exhibited higher modulus but lower elongation and tensile strength as compared to the neat blends. The injection molded nanocomposites were shown to have the sequential fracture behavior during tensile test. The tensile testing results on the neat blends and nanocomposites showed significant increase in elongation at break and decrease in the modulus as compared with the neat PLA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 749-758, 2013

Polylactic acid (PLA)/linear low density polyethylene (LLDPE) blend nanocomposites based on two different commercial-grade nanoclays, Cloisite® 30B and Cloisite® 15A, were produced via different melt mixing procedures in a counter-rotating twin screw extruder. The effects of mixing sequence and clay type on morphological and rheological behaviors as well as degradation properties of the blends were investigated. The X-ray diffraction (XRD) results showed that generally the level of exfoliation in 30B based nanocomposites was better than 15A based nanocomposites. In addition, due to difference in hydrophilicity and kind of modifiers in these two clays, the effect of 30B on refinement of dispersed phase and enhancement of biodegradability of PLA/LLDPE blend was much more remarkable than that of 15A nanoclay. Unlike the one step mixing process, preparation of nanocomposites via a two steps mixing process improved the morphology. Based on the XRD and TEM (transmission electron microscopic) results, it is found that the mixing sequence has a remarkable influence on dispersion and localization of the major part of 30B nanoclay in the PLA matrix. Owing to the induced selective localization of nanoclays in PLA phase, the nanocomposites prepared through a two steps mixing sequence exhibited extraordinary biodegradability, refiner morphology and better melt elasticity.

Multicomponent compatibilized blends of polyamide 6 (PA6) and styrene-butadiene-acrylonitrile (ABS) with co-continuous morphology are among commercial alloys with an interesting combination of properties. To further enhance the properties different amounts of nanoclay were incorporated into these blends through a one step melt mixing process. The effect of nanoclay addition on rheological, thermal stability, crystallization and morphological properties of the nanocomposites were investigated and compared with those of the neat blends. The nanoscale dispersion of the clay layers in the blends were confirmed through X-ray diffraction and transmission electron microscopy methods. Rheological investigation indicated an increased viscosity and melt elasticity for the nanocomposite systems. The viscosity of nanocomposites followed a shear thinning flow behavior and decreased with increasing shear rates. The changes in the rheological properties were accompanied by refinement of the co-continuous morphology. For thermal degradation under N2 atmosphere, the onset and maximum of degradation temperatures for the nanocomposites were as high as the neat blends, while significant improvement in thermal stability (about 60 °C by 3 wt% clay addition) was observed in the air environment. In addition agglomerated clay particles did not significantly affect thermal stability of the polymer matrix. Non-isothermal crystallization results indicated that the clay layers had a retarding effect on the crystal growth rate and facilitated the formation of α crystalline form. In addition no nucleation effect was observed during the crystallization process due to incorporation of nanoclay into the blends.

Morphological, melt rheological and dynamic mechanical properties of low-density polyethylene (LDPE)/ethylene–octene copolymer (POE)/organo-montmorillonite (OMMT) nanocomposites, prepared via melt compounding were studied. The XRD traces indicated different levels of intercalated structures for the nanocomposites. Addition of a compatibilizer (PE-g-MA) improved the intercalation process. TEM results revealed existence of clay layers in both phases but they were mainly localized in the elastomeric POE phase. Addition of 5 wt% OMMT to the LDPE/POE blend led to reduction in the size of the elastomer particles confirmed by AFM. The complex viscosity and storage modulus showed little effect of the presence of the clay when no compatibilizer was added. As the extent of exfoliation increased with addition of compatibilizer, the linear viscoelastic behavior of the composites gradually changed specially at low-frequency regions. The interfacially compatibilized nanocomposites with 5 wt% OMMT had the highest melt viscosity and modulus among all the studied nanocomposites and blends. Also, this particular composition showed the best improvement in dynamic storage modulus. The results indicated that clay dispersion and interfacial adhesion, and consequently different properties of LDPE/POE/clay nanocomposites, are greatly affected by addition of compatibilizer.

A systematic approach was adopted to study multicomponent clay-containing nanocomposites using compatibilized and non-compatibilized blends of polyamide 6 (PA6)/acrylonitrile–butadiene–styrene terpolymer (ABS) and their organoclay (OMMT) nanocomposites. For this purpose PA6/styrene–acrylonitrile copolymer (SAN) based blends and nanocomposites were selected as simple model systems. In this way the role of each component of the systems, especially the clay, compatibilizer, and polybutadiene fraction on the formation of intercalated or exfoliated OMMT structures as well as resulting dynamic mechanical properties (DMA) could be elucidated. Structural analysis of the model systems using theoretical approach, and X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and DMA revealed that the most crucial factor in controlling the morphology and achieving different levels of dispersion is the extent of interaction between clay and the polymer matrix. Morphological analysis revealed that the OMMT layers were dispersed and exfoliated largely in the PA6 phase but, some were also accumulated at the rubber particle surface which remained non-intercalated. The effect of a compatibilizer on the dispersion of OMMT was not completely clear. The SAN based nanocomposites containing PA6 showed fully exfoliated OMMT structures, whereas the ABS based nanocomposites, having an additional rubber fraction, showed a mixed exfoliated and also partly non-intercalated morphology. The OMMT did not change the general occurrence of the co-continuous structures but refined the structures and led to mechanical stiffening as indicated by the DMA results. A correlation was established between the changes in the morphological states and the DMA properties.