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).

In Situ Preparation and Luminescent Properties of CeF3 and CeF3:Tb3+ Nanoparticles and Transparent CeF3:Tb3+/PMMA Nanocomposites in the Visible Spectral Range

CeF3 and CeF3:Tb3+ nanoparticles were prepared by reverse microemulsion with a functional monomer, methyl methacrylate (MMA), as the oil phase, and CeF3:Tb3+/poly (methyl methacrylate) (PMMA) nanocomposites were obtained via polymerization of the MMA monomer. The nanoparticles and nanocomposites have been well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), low- and high-resolution transmission electron microscope (TEM), selected-area electron diffraction (SAED), thermogravimetric analysis (TGA), UV/vis transmission spectra, photoluminescence excitation, and emission spectra and luminescence decays. The well-crystallized CeF3 and CeF3:Tb3+ nanoparticles are spherical with a mean diameter of 15 nm. They show the characteristic emission of Ce3+ 5d-4f (313 nm, D-2-F-2(5/2); 323 nm, D-2-F-2(7/2)) and Tb3+ D-5(4)-F-7(J) (J = 6-3, with D-5(4)-F-7(5) green emission at 541 nm as the strongest one) transitions, respectively.

Isothermal Crystallization Behavior of Poly(L-lactic acid)/Organo-Montmorillonite Nanocomposites

The isothermal crystallization behavior of poly(L-lactic acid)/organo-montmorillonite nanocomposites (PLLA/OMMT) with different content of OMMT, using a kind of twice-functionalized organoclay (TFC), prepared by melt intercalation process has been investigated by optical depolarizer. In isothermal crystallization from melt, the induction periods (t(i)) and half times for overall PLLA crystallization (100 degrees C <= T-c <= 120 degrees C) were affected by the temperature and the content of TFC in nanocomposites. The kinetic of isothermal crystallization of PLLA/TFC nanocomposites was studied by Avrami theory. Also, polarized optical photomicrographs supplied a direct way to know the role of TFC in PLLA isothermal crystallization process. Wide angle X-ray diffraction (WAXD) patterns showed the nanostructure of PLLA/TFC material, and the PLLA crystalline integrality was changed as the presence of TFC. Adding TFC led to the decrease of equilibrium melting point of nanocomposites, indicating that the layered structure of clay restricted the full formation of crystalline structure of polymer.

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.

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".

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.

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.

Combination of Carbon Nanotubes with Ni2O3 for Simultaneously Improving the Flame Retardancy and Mechanical Properties of Polyethylene

Effects of multiwalled carbon nanotubes (MWCNTs) and Ni2O3 on the flame retardancy of linear low density polyethylene (LLDPE) have been studied. A combination of MWCNTs and Ni2O3 showed a synergistic effect in improving the flame retardancy of LLDPE compared with LLDPE composites containing MWCNTs or Ni2O3 alone. As a result, the peak value of heat release rate measured by cone calorimeter was obviously decreased in the LLDPE/MWCNTs/Ni2O3 Composites. According to the results from rheological tests, carbonization experiments, and structural characterization of residual char, the improved flame retardancy was partially attributed to the formation of a networklike structure due to the good dispersion of MWCNTs in LLDPE matrix, and partially to the carbonization of degradation products of LLDPE catalyzed by Ni catalyst originated from Ni2O3, More importantly, both viscoelastic characteristics and catalytic carbonization behavior of LLDPE/MWCNTs/Ni2O3 composites acted in concert to result in a synergistic effect in improving the flame retardancy.

In situ preparation and luminescent properties of LaPO4:Ce3+, Tb3+ nanoparticles and transparent LaPO4:Ce3+, Tb3+/PMMA nanocomposite

LaPO4:Ce3+, Tb3+ nanoparticles were prepared by the reverse microemulsion with functional monomer, methyl methacrylate (MMA) as oil phase, and LaPO4:Ce3+, Tb3+/poly(methyl methacrylate) (PMMA) nanocomposite was obtained via polymerization of MMA monomer. The nanoparticles and nanocomposite have been well characterized by XRD, SEM, TEM, UV/vis spectrum, photoluminescence excitation and emission spectra and luminescence decays. The obtained solid nanocomposite LaPO4:Ce3+, Tb3+/PMMA is highly transparent and exhibits strong green photoluminescence upon UV excitation, due to the integration of luminescent LaPO4:Ce3+, Tb3+ nanoparticles. The luminescent lifetime of Tb3+ is determined to be 1.25 ms in the nanocomposite. (C) 2009 Elsevier Inc. All rights reserved.

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.

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.