High-temperature X-ray diffraction studies on polyamide6/clay nanocomposites upon annealing

The influence of nanodispersed clay on the alpha crystalline structure of polyamide 6 (PA6) was examined in-situ with X-ray diffraction (XRD) between room temperature and melting. In pure PA6 upon annealing the alpha crystalline phase was substituted by an unstable pseudohexagonal phase at 150degreesC, then it transformed into a new stable crystalline structure - high temperature alpha' phase above the transition temperature. However, in PA6/clay nanocomposite (PA6CN), the alpha phase did not present crystalline phase transition on heating. The increase in the annealing temperature only led to continuous intensity variation. The different behaviors were caused by the confined spaces formed by silicate layers, which constrained the mobility of the polymer chains in-between.

Phase transition in polyamide-66/montmorillonite nanocomposites on annealing

The crystalline-phase transition in polyamide-66/montmorillonite nanocomposites before melting was investigated by in situ X-ray diffraction and is reported for the first time in this work. The phase-transition temperature in the nanocomposites was 170 degreesC, 20 degreesC lower than that in polyamide-66. The lower phase-transition temperature of the nanocomposites could be attributed to the gamma-phase-favorable environment caused by silicate layers. Meanwhile, the addition of silicate layers changed the crystal structure of the polyamide-66 matrix and influenced the phase-transition behavior.

Tensile modulus of polymer nanocomposites

Based on Takayanagi's two-phase model, a three-phase model including the matrix, interfacial region, and fillers is proposed to calculate the tensile modulus of polymer nanocomposites (E-c). In this model, fillers (sphere-, cylinder- or plate-shape) are randomly distributed in a matrix. If the particulate size is in the range of nanometers, the interfacial region will play an important role in the modulus of the composites. Important system parameters include the dispersed particle size (t), shape, thickness of the interfacial region (tau), particulate-to-matrix modulus ratio (E-d/E-m), and a parameter (k) describing a linear gradient change in modulus between the matrix and the surface of particle on the modulus of nanocomposites (E-c). The effects of these parameters are discussed using theoretical calculation and nylon 6/montmorillonite nanocomposite experiments. The former three factors exhibit dominant influence on E-c At a fixed volume fraction of the dispersed phase, smaller particles provide an increasing modulus for the resulting composite, as compared to the larger one because the interfacial region greatly affects E-c. Moreover, since the size of fillers is in the scale of micrometers, the influence of interfacial region is neglected and the deduced equation is reduced to Takayanagi's model. The curves predicted by the three-phase model are in good agreement with experimental results. The percolation concept and theory are also applied to analyze and interpret the experimental results.

Morphology and melt rheology of nylon 11/clay nanocomposites

Nylon 11 (PA11)/clay nanocomposites have been prepared by melt-blending, followed by melt-extrusion through a capillary. Transmission electron n-Licroscopy shows that the exfoliated clay morphology is dominant for low nanofiller content, while the intercalated one is prevailing for high filler loading. Melt rheological properties of PA11 nanocomposites have been studied in both linear and nonlinear viscoelastic response regions. In the linear regime, the nanocomposites exhibit much higher storage modulus (G') and loss modulus (G") values than neat PAIL The values of G' and G" increase steadily with clay loading at low concentrations, while the G' and G" for the sample with 5 wt % clay show an inverse dependence and lie between the modulus values of the samples with 1 and 2 wt % of clay. This is attributed to the alignment/orientation of nanoclay platelets in the intercalated nanocomposite induced by capillary extrusion. In the nonlinear regime, the nanocomposites show increased shear viscosities when compared with the neat resin. The dependence of the shear viscosity on clay loading has analogous trend to that of G' and G".

Mechanical and thermal properties of glass bead-filled nylon-6

The mechanical and thermal properties of glass bead-filled nylon-6 were studied by dynamic mechanical analysis (DMA), tensile testing, Izod impact, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) tests. DMA results showed that the incorporation of glass beads could lead to a substantial increase of the glass-transition temperature (T-g) of the blend, indicating that there existed strong interaction between glass beads and the nylon-6 matrix. Results of further calculation revealed that the average interaction between glass beads and the nylon-6 matrix deceased with increasing glass bead content as a result of the coalescence of glass beads. This conclusion was supported by SEM observations. Impact testing revealed that the notch Izod impact strength of nylon-6/glass bead blends substantially decreased with increasing glass bead content. Moreover, static tensile measurements implied that the Young's modulus of the nylon-6/glass bead blends increased considerably, whereas the tensile strength clearly decreased with increasing glass bead content.

Properties of compatibilized nylon 6/ABS polymer blends

Nylon 6/poly(acrylonitrile-butadiene-styrene)(ABS) blends were prepared in the molten state by a twin-screw extruder. Maleic anhydride-grafted polypropylene (MAP) and solid epoxy resin (bisphenol type-A) were used as compatibilizers for these blends. The effects of compatibilizer addition to the blends were studied via tensile, torque, impact properties and morphology tests. The results showed that the additions of epoxy and MA copolymer to nylon 6/ABS blends enhanced the compatibility between nylon 6 and ABS, and this lead to improvement of mechanical properties of their blends and in a size decrease of the ABS domains.

Isothermal crystallization studies on neodymium oxide filled nylon 6

Melt mixing of nylon 8 with neodymium oxide particles was carried out with a single-screw extruder. The crystal behaviors of plain nylon 6 and the neodymium oxide filled nylon 6 mixture were studied by means of isothermal crystallization kinetic analysis. Isothermal crystallization thermograms obtained by differential scanning calorimetry (DSC) were analyzed based on the Avrami equation. The neodymium oxide particles acted as a nucleating agent in the mixture. The overall rate of di-isothermal crystallization of the neodymium oxide filled nylon 6 mixture is higher than that of plain nylon 6. The mechanism and modes of plain nylon 6 were the same as those of neodymium oxide filled PA6 mixture.

FRACTIONATED CRYSTALLIZATION IN POLYOLEFINS-NYLON-6 BLENDS

The crystallization behavior of polyolefins-nylon 6 polymer blends was studied by differential scanning calorimetry (DSC) measurements. In these blends, the crystallization of the minor component often starts with distinctly deeper supercooling than that

The investigation of exfoliation process of organic modified montmorillonite in thermoplastic polyurethane with different molecular weights

Cloisite 30B (30B) was melt-mixed with two kinds of thermoplastic polyurethane (TPU) with different molecular weights to discern the roles of molecular diffusion and shear in the exfoliation process. The higher level of exfoliation was achieved in TPU matrix with higher molecular weight due to the appropriate viscosity. In order to have an insight into the mechanism of exfoliation, the degree of dispersion and exfoliation of 30B was characterized by wide angle X-ray diffraction and transmission electron microscopy. The layers of 30B were exfoliated via a slippage process, which was also observed in polyamide 12 nanocomposites recently.

Morphology evolutions of organically modified montmorillonite/polyamide 12 nanocomposites

Organically modified montmorillonites (OMMTs) by octadecylammonium chloride with two adsorption levels were dispersed in polyamide 12 (PA12) matrices with two molecular weights for different melt mixing times in order to investigate morphology evolutions and factors influencing fabrication of PA12 nanocomposites. Different adsorption levels of the modifier in the OMMTs provide different environments for diffusion of polymer chains and different attractions between MMT layers. Wide-angle X-ray diffraction (WAXD), transmission electron microscope (TEM) and gas permeability were used to characterize morphologies of the nanocomposites. Both OMMTs can be exfoliated in the PA12 matrix with higher molecular weight, but only OMMT with lower adsorption level can be exfoliated in the PA12 matrix with lower molecular weight. It was attributed to the differences in the levels of shear stress and molecular diffusion in the nanocomposites. The exfoliation of OMMT platelets results from a combination of molecular diffusion and shear. After intercalation of PA12 into interlayer of OMMT in the initial period of mixing, further dispersion of OMMTs in PA12 matrices is controlled by a slippage process of MMT layers during fabricating PA12 nanocomposites with exfoliated structure.

Sulfonated poly(ether ether ketone)/clay-SO3H hybrid proton exchange membranes for direct methanol fuel cells Journal of Power Sources

A new type of sulfonated clay (clay-SO3H) was prepared by the ion exchange method with the sulfanilic acid as the surfactant agent. The grafted amount of sulfanilic acid in clay-SO3H was 51.8 mequiv. (100 g)(-1), which was measured by thermogravimetric analysis (TGA). Sulfonated poly(ether ether ketone) (SPEEK)/clay-SO3H hybrid membranes which composed of SPEEK and different weight contents of clay-SO3H, were prepared by a solution casting and evaporation method. For comparison, the SPEEK/clay hybrid membranes were produced with the same method.

A strategy of fabricating exfoliated thermoplastic polyurethane/clay nanocomposites via introducing maleated polypropylene

By reducing the attraction between the platelets of octaclecylammonium chloride modified montmorillonite (OMMT-C18) via pre-intercalation of maleated polypropylene (MAPP), OMMT-C18 was exfoliated in thermoplastic polyurethane (TPU) matrix during melt-mixing. Wide angle X-ray diffraction, transmission electron microscopy and thermogravimetric analysis were used to investigate the microstructure of TPU nanocomposites. Three factors (including introducing sequence, the kind and the content of MAPP) showed important effects on the dispersion degree of OMMT-C18 in TPU matrix. The results confirmed that the pre-intercalation of MAPP was necessary for the exfoliation of OMMT-C18; however, the role of MAPP in TPU nanocomposites was different from that in polypropylene nanocomposites.

Thermal stability, crystallization, structure and morphology of syndiotactic 1,2-polybutadiene/organoclay nanocomposite

Syndiotactic 1,2-polybutadiene/organoclay nanocomposites were prepared and characterized by thermogravimetry analysis (TGA), X-ray diffraction (XRD), polarized optical microscopy (POM), and differential scanning calorimetry (DSC), respectively. The XRD shows that exfoliated nanocomposites are formed dominantly at lower clay concentrations (less than 2%), at higher clay contents intercalated nanocomposites dominate. At the same time, the XRD indicates that the crystal structures of sPB formed in the sPB/organoclay nanocomposites do not vary, only the relative intensity of the peaks corresponding to (0 1 0) and (2 0 0)/(1 1 0) crystal planes, respectively, varies. The DSC and POM indicate that organoclay layers can improve cooling crystallization temperature, crystallization rate and reducing the spherulite sizes of sPB. TGA shows that under argon flow the nanocomposites exhibit slight decrease of thermal stability, while under oxygen flow the resistance of oxidation and thermal stability of sPB/organoclay nanocomposites were significantly improved relative to pristine sPB. The primary and secondary crystallization for pristine sPB and sPB/organoclay (2%) nanocomposites were analyzed and compared based on different approaches.

Compatibilization of polyamide-6/syndiotactic polystyrene blends using styrene/glycidyl methacrylate copolymers

Blends of polyamide-6 (PA6) with syndiotactic polystyrene (sPS) were prepared using a series of styrene/glycidyl methacrylate (SG) copolymers as compatibilizers. These copolymers are miscible with sPS, and the epoxide units in SG are capable of reacting with PA6 end groups. These copolymers thus have the potential to form SG-g-PA6 graft copolymers at the PA6/sPS interface during melt processing. This study focuses on the effects of functionality and concentration of the compatibilizer on the morphological, mechanical and crystallization behaviors of the blends.. In general, SG copolymers are effective in reducing the sPS domain size and improving the interfacial adhesion. About 5 wt% glycidyl methacrylate (GMA) is the optimum content in SG copolymer that produces the best compatibilization. Both the strength and modulus of the blend have been improved on addition of the SG copolymers, accompanying a loss in toughness when higher concentration copolymer is added. Incorporation of SG compatibilizers to PA6/sPS blend has little influence on the crystallization behavior of PA6 component but resulted in a steady reduction in intensity of crystallinity peak of sPS and simultaneous crystallization of sPS with PA6 is observed.