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.

STRUCTURAL EVOLUTION AND COMPOSITION CHANGE IN THE SURFACE REGION OF POLYPROPYLENE/CLAY NANOCOMPOSITES ANNEALED AT HIGH TEMPERATURES

A model experiment was done to clear the formation mechanism of protective layers during combustion of polypropylene (PP)/organically modified montmorillonite (OMMT) nanocomposites. The investigation was focused on the effects of annealing temperature on the structural changes and protective layer formation. The decomposition of OMMT and degradation of PP/OMMT nanocomposites were characterized by means of thermogravimetric analysis (TGA). The structural evolution and composition change in the surface region of PP/OMMT nanocomposites during heating were monitored by means of X-ray photoelectron spectroscopy (XPS), ATR-FTIR and field emission scanning electron microscopy (FESEM).

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".

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.

Mechanism on flame retardancy of polystyrene/clay composites-The effect of surfactants and aggregate state of organoclay

Effects of organically modified montmorillonites (OMMTs) with different type and amount of modifiers on flame retardancy of polystyrene (PS) have been studied. The results from morphology analysis, gas chromatography-mass spectrometry and cone calorimeter have showed different mechanisms for the flame retardancy of PS/OMMTs composites, depending on surface property of OMNTrs. One is the catalysis of acid sites formed on the surface of octadecylammonium modified MMT (c-MMT) via Hoffman decomposition on the carbonization of degradation products, which promotes the formation of clay-enriched char barrier.

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.

Chemical effects of cationic surfactant and anionic surfactant used in organically modified montmorillonites on degradation and fire retardancy of polyamide 12 nanocomposites

Three kinds of organically modified Na+-montmorillonites (OMMTs), including two kinds of octadecylammonium modified montmorillonite with different contents of octadecylammonium and a kind of sodium dodecylsulfonate (SDSo) modified montmorillonite, were used to prepare polyamide 12 (PA12)/OMMT nanocomposites. Effects of the modifiers on degradation and fire retardancy of PA12/OMMT nanocomposites were investigated. Acid sites formed in cationic surfactant modified MMT via Hoffman decomposition could accelerate degradation of PA12 at high temperature. However, catalytic effect of the acid sites on carbonization of the degradation products promoted char barrier formation, which reduced heat release rate (HRR). Higher content of cationic surfactant in OMMT is beneficial to fire retardancy of PA12 nanocomposites and the dispersion states of OMMT have assistant effects. In contrast, Na+-montmorillonite (Na-MMT) and anionic surfactant modified MMT (a-MMT) could not form acid sites on the MMT layers; in this case, fire retardancy of PA12/Na-MMT appears to have no improvement and PA12/a-MMT appears to have limited improvement.

Influences of catalysis and dispersion of organically modified montmorillonite on flame retardancy of polypropylene nanocomposites

The degradation and flame retardancy of polypropylene/organically modified montmorillonite (PP/OMMT) nanocomposite were studied by means of gas chromatography-mass spectrometry and cone calorimeter. The catalysis of hydrogen proton containing montmorillonite (H-MMT) derived from thermal decomposition of (alkyl) ammonium in the OMMT on degradation of PP strongly influence carbonization behavior of PP and then flame retardancy. Bronsted acid sites on the H-MMT could catalyze degradation reaction of PP via cationic mechanism, which leads to the formation of char during combustion of PP via hydride transfer reaction. A continuous carbonaceous MMT-rich char on the surface of the burned residues, which work as a protective barrier to heat and mass transfer, results from the homogeneous dispersion of OMMT in the PP matrix and appropriate char produced.

Synthesis and characterization of polyethylene/clay-silica nanocomposites: A montmorillonite/silica-hybrid-supported catalyst and in situ polymerization

A novel approach to the preparation of polyethylene (PE) nanocomposites, with montmorillonite/silica hybrid (MT-Si) supported catalyst, was developed. MT-Si was prepared by depositing silica nanoparticles between galleries of the MT. A common zirconocene catalyst [bis(cyclopentadienyl)zirconium dichloride/methylaluminoxane] was fixed on the MT-Si surface by a simple method. After ethylene polymerization, two classes of nanofillers (clay layers and silica nanoparticles) were dispersed concurrently in the PE matrix and PE/clay-silica nanocomposites were obtained. Exfoliation of the clay layers and dispersion of the silica nanoparticles were examined with transmission electron microscopy. Physical properties of the nanocomposites were characterized by tensile tests, dynamic mechanical analysis, and DSC. The nanocomposites with a low nanofiller loading (<10 wt %) exhibited good mechanical properties. The nanocomposite powder produced with the supported catalyst had a granular morphology and a high bulk density, typical of a heterogeneous catalyst system.

Controlling dispersed state and exfoliation process of clay in polymer matrix

In the present review, the authors do not try to provide a comprehensive review of researches on polymer/clay nanocomposites (PCNs), but some examples to demonstrate different exfoliation processes of the clay in various polymer matrixes and the dispersed state of clay. Interaction between polymers and layered silicates plays an important role in adjusting the exfoliation process of layered silicates and the microstructure of polymer nanocomposites. Properties of polymer/layered silicate nanocomposites mainly depend on the dispersed state of layered silicates. The authors will also address the outline of the present research in the direction of PCNs including the discussion of technical problems and their possible solutions.

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.

The preparation of phenolic resin/montmorillonite nanocomposites by suspension condensation polymerization and their morphology

Phenolic resin/clay nanocomposites were prepared using a suspension condensation polymerization method that was suitable to both novolac and resole. Natural montmorillonite and two kinds of organic modified montmorillonite were adopted to investigate the effect of modification on the final morphology of the nanocomposites. X-ray diffraction (XRD) measurements and Transmission Electron Microscope (TEM) observations showed that clay platelets were easier to be exfoliated or intercalated in novolac than in resole because novolac usually has a linear structure. The modifier with a phenyl ring was more compatible with novolac (or resole) than the aliphatic type modifier. The influence of curing on the morphology was studied as well. An exfoliation-adsorption and in situ condensation mechanism was proposed on the formation of the nanocomposites.

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.