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).

Evolution of phase morphology of high impact polypropylene particles upon thermal treatment

Solvent fractionation and differential scanning calorimetry (DSC) results show that high impact polypropylene (hiPP) produced by a multistage polymerization process consists of PP homopolymer, amorphous ethylene-propylene random copolymer (EPR), and semicrystalline ethylene-propylene copolymer. For the original hiPP particles obtained right after polymerization, direct transmission electron microscopy (TEM) observation reveals a fairly homogeneous morphology of the ethylene-propylene copolymer (EP) phase regions inside, while the polyethylene-rich interfacial layer observed between the EP region and the iPP matrix supports that EP copolymers form on the subglobule surface of the original iPP particles. Compared with that in original hiPP particles, the dispersed EP domains in pellets have much smaller average size and relatively uniform size distribution, indicating homogenization of the EP domains in the hiPP by melt-compounding. Upon heat-treatment, phase reorganization occurs in hiPP, and the dispersed EP domains can form a multiple-layered core-shell structure, comprising a polyethylene-rich core, an EPR intermediate layer and an outer shell formed by EP block copolymer, which accounts to some extent for the good toughness-rigidity balance of the material.

Stabilization of metastable phase II of isotactic polybutene-1 by coated carbon

Stabilization effect on metastable phase II of isotactic polybutene-1 (iPB-1) by coated carbon has been investigated by transmission electron microscopy (TEM) and electron diffraction (ED) techniques. The results indicate that after evaporating carbon, the phase II-I crystal transformation time is greatly prolonged from 9 days for carbon-uncoated samples to 120 days for carbon-coated ones under atmospheric pressure, while under high pressure (50 bar), the phase transformation time increases from 5 min for the former to 20 min for the latter. The stabilization effect on metastable phase II of carbon coated iPB-1 is attributed to a surface fixing effect of the evaporated carbon.

Computer simulation of the damage evolution of fiber-reinforced polypropylene-matrix composites with matrix defects

The damage evolution of fiber-reinforced polypropylene-matrix composites with matrix defects was studied via a Monte Carlo technique combined with a finite element method. A finite element model was constructed to predict the effects of various matrix defect shapes on the stress distributions. The results indicated that a small matrix defect had almost no effect on fiber stress distributions other than interfacial shear stress distributions. Then, a finite element model with a statistical distribution of the fiber strength was constructed to investigate the influences of the spatial distribution and the volume fraction of matrix defects on composite failure. The results showed that it was accurate to use the shear-lag models and Green's function methods to predict the tensile strength of composites even though the axial stresses in the matrix were neglected.

The combined catalytic action of solid acids with nickel for the transformation of polypropylene into carbon nanotubes by pyrolysis

The effects of both organically modified montmorillonite (OMMT) and Ni2O3 on the carbonization of polypropylene (PP) during pyrolysis were investigated. The results from TEM and Raman spectroscopy showed that the carbonized products of PP were mainly multiwalled carbon nanotubes (MWNTs). Surprisingly, a combination of OMMT and Ni2O3 led to high-yield formation of MWNTs. X-ray powder diffraction (XRD) and GC-MS were used to investigate the mechanism of this combination for the high-yield formation of MWNTs from PP. Bronsted acid sites were created in degraded OMMT layers by thermal decomposition of the modifiers. The resultant carbenium ions play an important role in the carbonization of PP and the formation of MWNTs. The degradation of PP was induced by the presence of carbenium ions to form predominantly products with lower carbon numbers that could be easily catalyzed by the nickel catalyst for the growth of MWNTs. Furthermore, carbenium ions are active intermediates that promote the growth of MWNTs from the degradation products with higher carbon numbers through hydride-transfer reactions. The XRD measurements showed that Ni2O3 was reduced into metallic nickel (Ni) in situ to afford the active sites for the growth of MWNTs.

Polypropylene as a carbon source for the synthesis of multi-walled carbon nanotubes via catalytic combustion

Multi-walled carbon nanotubes (MWCNTs) were efficiently synthesized by catalytic combustion of polypropylene (PP) using nickel compounds (such as Ni2O3, NiO, Ni(OH)(2) and NiCO3 (.) 2Ni(OH)(2)) as catalysts in the presence of organic-modified montmorillonite (OMMT) at 630-830 degrees C. Morphologies of the sample undergoing different combustion times were observed to investigate actual process producing MWCNTs by this method. The obtained MWCNTs were characterized by X-ray diffraction (XRD), transmission electron microscope and Raman spectroscopy. The yield of MWCNTs was affected by the composition of PP mixtures with OMMT and nickel compounds and the combustion temperature. The proton acidic sites from the degraded OMMT layers due to the Hoffman reaction of the modifiers at high temperature played an important role in the catalytic degradation of PP to supply carbon sources that are easy to be catalyzed by nickel catalyst for the growth of MWCNTs. The XRD measurements demonstrated that the nickel compounds were in situ reduced into the Ni(0) state with the aid of hydrogen gas and/or hydrocarbons in the degradation products of PP, and the Ni(O) was really the active site for the growth of MWCNTs. The combination of nickel compounds with OMMT was a key factor to efficiently synthesize MWCNTs via catalytic combustion of PP.

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.

The mechanical and thermal behaviors of glass bead filled polypropylene

Notch Izod impact strength of poly(propylene) (PP)/glass bead blends was studied as a function of temperature. The results indicated that the toughness for various blends could undergo a brittle-ductile transition (BDT) with increasing temperature. The BDT temperature (T-BD) decreased with increasing glass bead content. Introducing the interparticle distance (ID) concept into the study, it was found that the critical interparticle distance (IDc) reduced with increasing test temperature correspondingly. The static tensile tests showed that the Young's modulus of the blends decreased slightly first and thereafter increased with increasing glass bead content. However, the yield stress decreased considerably with the increase in glass bead content. Dynamic mechanical analysis (DMA) measurements revealed that the heat-deflection temperature of the PP could be much improved by the incorporation of glass beads. Moreover, the glass transition temperature (T-g) increased obviously with increasing glass beads content. Differential scanning calorimetry (DSC) results implied that the addition of glass beads could change the crystallinity as well as the melting temperature of the PP slightly.

Brittle-ductile transition of polypropylene/ethyllene-propylene-diene monomer blends induced by size, temperature, and time

To study the brittle-ductile transition (BDT) of polypropylene (PP)/ethylene-propylene-diene monomer (EPDM) blends induced by size, temperature, and time, the toughness of the PP/EPDM blends was investigated over wide ranges of EPDM content, temperature, and strain rate. The toughness of the blends was determined from the tensile fracture energy of the side-edge notched samples. The concept of interparticle distance (ID) was introduced into this study to probe the size effect on the BDT of PP/EPDM blends, whereas the effect of time corresponded to that of strain rate. The BDT induced by size, temperature, and time was observed in the fracture energy versus ID, temperature, and strain rate. The critical BDT temperatures for various EPDM contents at different initial strain rates were obtained from these transitions. The critical interparticle distance (IDc) increased nonlinearly with increasing temperature, and when the initial strain rate was lower, the IDc was larger. Moreover, the variation of the reciprocal of the initial strain rate with the reciprocal of temperature followed different straight lines for various EPDM contents. These straight lines were with the same slope.

Nonisothermal crystallization behavior of glass-bead-filled polypropylene

The effects of the glass-bead content and size on the nonisothermal crystallization behavior of polypropylene (PP)/glass-bead blends were studied with differential scanning calorimetry. The degree of crystallinity decreased with the addition of glass bead, and the crystallization temperature of the blends was marginally higher than that of pure PP at various cooling rates. Furthermore, the half-time for crystallization decreased with an increase in the glass-bead content or particle size, implying the nucleating role of the glass beads. The nonisothermal crystallization data were analyzed with the methods of Avrami, Ozawa, and Mo. The validity of various kinetic models for the nonisothermal crystallization process of PP/glass-bead blends was examined. The approach developed by Mo successfully described the nonisothermal crystallization behavior of PP and PP/glass-bead blends. Finally, the activation energy for the nonisothermal crystallization of pure PP and PP/glass-bead blends based on the Kissinger method was evaluated.

Reactive blending of modified polypropylene and polyamide 12: Effects of compatibilizer content on crystallization and blend morphology

The crystallization behavior and morphology of nonreactive and reactive melt-mixed blends of polypropylene (PP) and polyamide (PA12; as the dispersed phase) were investigated. It Was found that the crystallization behavior and the size of the PA12 particles were dependent on the content of the compatibilizer (maleic anhydride-modified polypropylene) because an in situ reaction occurred between the maleic anhydride groups of the compatibilizer and the amide end groups of PA12. When the amount of compatibilizer was more than 4%, the PA12 did not crystallize at temperatures typical for bulk crystallization. These finely dispersed PA12 particles crystallized co-incidently with the 1313 phase. The changes in domain size with compatibilizer content were consistent with Wu's theory. These investigations showed that crystallization of the dispersed phase Could not be explained solely by the size of the dispersion. The interfacial tension between the polymeric components in the blends may yield information on the fractionation of crystallization.

Synergistic effect of supported nickel catalyst with intumescent flame-retardants on flame retardancy and thermal stability of polypropylene

Supported nickel catalyst (Ni-Cat) was used as a catalyst to improve the flame retarclancy of intumescent flame-retardants (IFR) systems based on ammonium polyphosphate and pentaerythritol (PETOL) in polypropylene (PP) matrix. Limited oxygen index (LOI), UL-94 rating, and thermogravimetric analysis were used to characterize the flame retardancy and thermal stability of the PP systems, and field emission scanning electron microscopy (FE-SEM) and Fourier transformed infrared spectroscopy (FTIR) were used to analyze the microstructure and composition of the chars formed during measuring LOI value and after combustion at 800 degrees C. The catalytic effect of NiCat was shown in an increase of LOI, a change in the char microstructure, and improvement of the thermal stability in the PP systems, which result from the synergistic effect of Ni-Cat and IFR. The results from FE-SEM and FTIR spectra of the char can explain how this synergistic effect happened.

Compatibilization of PP/EPDM blends by grafting acrylic acid to polypropylene and epoxidizing the diene in EPDM

In this article, ethylene-propylene-diene-rubber (EPDM) was epoxidized with an in situ formed performic acid to prepare epoxided EPDM (eEPDM). The eEPDM together with the introduction of PP-g-AA was used to compatibilize PP/EPDM blends in a Haake mixer. FTIR results showed that the EPDM had been epoxidized. The reaction between epoxy groups in the eEPDM and carboxylic acid groups in PP-g-AA had taken place, and PP-g-EPDM copolymers were formed in situ. Torque test results showed that the actual temperature and torque values for the compatibilized blends were higher than that of the uncompatibilized blends. Scanning electron microscopy (SEM) observation showed that the dispersed phase domain size of compatibilized blends and the uncompatibilized blends were 0.5 and 1.5 mu m, respectively. The eEPDM together with the introduction of PP-g-AA could compatibilize PP/EPDM blends effectively. Notched Izod impact tests showed that the formation of PP-g-EPDM copolymer improved the impact strength and yielded a tougher PP blend.

Effects of surfactant loadings on the dispersion of clays in maleated polypropylene

A series of organically modified clays (OMCs) with a surfactant loading range from 0.625 to 2.5 times the cation exchange capacity (CEC) were melt-mixed with maleated polypropylene (PPMA). Wide-angle X-ray diffraction and transmission electron microscopy results of these narrocomposites show that dispersion of clays becomes unfavorable in the PPMA matrix during melt intercalation as the surfactant loading increases in the process of modifying clays, though larger interlayer distances are obtained in their corresponding OMCs. It is even important that clays uniformly disperse at the nanoscale level in the PPMA matrix when the surfactant loadings are below the CEC, which implies that incomplete exchange of inorganic cations in the process of modifying clay benefits the dispersion of clays in the PPMA matrix.