Polyethylene nanocomposites by gas‐phase polymerization of ethylene in the presence of a nanosilica‐supported zirconocene catalyst system

BACKGROUND: Much of the current research related to the development of in situ nanocomposites of olefins by polymerizing them with metallocenes in the presence of surface‐treated fillers is carried out in the slurry phase. In slurry‐phase methods a large amount of solvent is required and there is always a need of purification of the final product due to the possibility of traces of solvents present in the product. To overcome these drawbacks, to perform solvent‐free metallocene‐catalysed polymerizations with in situ incorporation of inorganic nanoparticles, we have used a gas‐phase polymerization technique as this does not require solvents and also utilizes monomer feed stocks efficiently. RESULTS: The catalyst used for the synthesis of in situ polyethylene nanocomposites by gas‐phase polymerization was nanosilica‐supported zirconocene. The fillers used were Cloisite‐20A, kaolin and nanosilica. Three different in situ polyethylene nanocomposites, i.e. Cloisite‐20A‐filled polyethylene (CFPE), kaolin‐filled polyethylene (KFPE) and nanosilica‐filled polyethylene (SFPE), were prepared by gas‐phase polymerization. The nanocomposites were obtained in the form of fine powder. The polyethylene content in the developed nanocomposites is in the orthorhombic crystalline phase. Using our approach, it is observed that the nanofillers are completely encapsulated by a thin layer of polyethylene. Significantly higher molecular weight polyethylene was formed in the case of KFPE in comparison to CFPE and SFPE. The thermal decomposition temperature, melting temperature and enthalpy are also observed to be higher for KFPE. CONCLUSIONS: The gas‐phase polymerization technique has been successfully carried out for the synthesis of in situ polyethylene nanocomposites. Copyright © 2007 Society of Chemical Industry     

Effect of modified layered silicates on the confined crystalline morphology and thermomechanical properties of poly(ethylene oxide) nanocomposites

In this work, poly(ethylene oxide) (PEO)/organoclay nanocomposites with three different types of nanoclays (Cloisite 30B, Somasif JAD400, and Somasif JAD230) were prepared by melt mixing with a laboratory kneader followed by compression molding. The nanocomposites were characterized by atomic force microscopy and scanning electron microscopy. Their crystallization behavior on a hot stage was investigated with polarized optical microscopy. The size and regularity of the spherulites of the PEO matrix were altered significantly by the incorporation of Cloisite 30B, but there was not as much variation with the other two clays. The dynamic viscoelastic behavior of the PEO/organoclay nanocomposites was assessed with a strain‐controlled parallel‐plate rheometer. The effects of clay modification on the thermomechanical and rheological properties were addressed. The reinforcing effect of the organoclay was determined with dynamic mechanical analysis and tensile testing. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Noise reduction in synthetic aperture radar images using fuzzy logic and genetic algorithm

Synthetic aperture radar (SAR) is a self-illuminating imaging technique; it produces high resolution images in all weather conditions, day and night. SAR images are widely accepted and used by many application scientists. However, the SAR images are corrupted with speckle noise. Speckle noises are caused by random interference of electromagnetic signals scattered by the object surface within one resolution element. The amount of noise and distribution of noise corrupting the image is unpredictable. Conventional noise filters are quantitative in nature; they are not well suited for uncertainty problems. Fuzzy logic is capable of handling uncertainty. In this work, noisy pixels in the images are identified by using fuzzy rules and filtered using fuzzy weighted mean, keeping the healthy pixels unchanged. The optimum value of parameters used in defining fuzzy membership function is determined by using genetic algorithm (GA). Reducing noise and simultaneously preserving image details are the two most desirable characteristics of noise filters. Peak signal-to-noise ratio (PSNR) and edge preserving factor (EPF) are used to evaluate the performance of the proposed fuzzy filter. SAR images affected by varying amounts of speckle noise are used to evaluate the performance. It was observed that the proposed filter suppresses noise and preserves image edges.

     

Studies on polyethylene oxide and phenolic resin blends

Blends of poly(ethylene oxide) (PEO) and novolac type phenolic resin were prepared by a solution cast method using acetonitrile as a solvent. In this work, we have investigated the PEO/phenolic blends having low phenolic content (0 to 30 wt %) with the objective in mind to design a crystallizable component for a shape memory polymer system having adjustable switching temperature. The blends were characterized by Fourier transform infrared (FTIR) spectroscopy, polarized optical microscopy (POM), and differential scanning calorimetry (DSC). The rate of crystallization and crystallinity (calculated from heat of crystallization value) decrease with increase in novolac content. FTIR analysis indicates the existence of H‐bonding between hydroxyl groups of novolac and ether groups of PEO. POM studies indicate that size of Maltese cross section decreases with increase in novolac content and in the blends containing higher novolac content less regular leaf like texture was obtained. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermomechanical properties and morphology of polyethylene oxide and phenolic resole blends

Blends of poly(ethylene oxide) (PEO) and resole type phenolic resin were prepared by a solution cast method using water as a solvent. The cured blends were made by heat curing without using any catalyst. The blends were characterized by dynamic mechanical analysis (DMA), which indicated that PEO forms compatible blend with the resole. The glass transition values, read from the DMA traces, showed a positive shift as compared to the theoretical values calculated by the Fox equation. This suggests a strong H‐bonding interaction between the phenolic resole and PEO as established by Fourier transformed infrared spectroscopy. Flexural test indicated an enhanced flexibility of the blends when compared to the neat phenolic resin. The fracture surface analysis by using a scanning electron microscope (SEM) revealed an increase in plastic deformation with increasing PEO concentration in the blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Epoxy and hyperbranched polymer blends: Morphology and free volume

In this work, the phase separation of an epoxy‐functionalized hyperbranched polymer (HBP) in a blend with a conventional epoxy resin is examined. Morphology development with the advancement of curing reaction was investigated by hot‐stage polarized optical microscope, where it was found that HBP is miscible in epoxy resin solvent at 120°C and undergoes phase separation during the curing reaction, leading to a two‐phase microstructure which maintains a dispersed morphology up to 20 wt % HBP. The degree of phase separation and morphology were also investigated using differential scanning calorimetry, and the resultant microstructure was confirmed by atomic force microscopy. The epoxy/HBP blends were characterized by positron annihilation lifetime spectroscopy for their free volume characteristics where behavior typical of miscible blends was seen, likely due to chemical bonding between the two phases. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Nanocomposites of poly(ethylene oxide) and multiwall carbon nanotube prepared using an organic salt‐assisted dispersion technique

Poly (ethylene oxide) (PEO)/multiwall carbon nanotubes (MWCNT) nanocomposites were prepared by dispersion of MWCNTs in aqueous solution using half neutralized sodium salt of sebacic acid as a modifier. The physical interaction of half neutralized sodium salt of sebacic acid with MWCNT (cation‐π interaction) has been established by using Fourier transform infrared and Raman spectroscopic analyses. Such interaction helps in debundling the MWCNTs and resulted in a better dispersion in PEO matrix as confirmed by scanning electron microscopy and transmission electron microscopy. Addition of MWCNT significantly improves the storage modulus in rheological measurements as well as in dynamic mechanical thermal analysis. The crystallization behaviors of the composites made with the unmodified and modified MWCNTs were investigated. The modified MWCNT‐based composites shows large number of spherulite with smaller size compared to those observed in unmodified MWCNT‐based composite. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Studies on effect of ethyl 4-amino cinnamate functionalized multiwall carbon nanotubes (f-MWCNTs) on properties of millable polyurethane rubber (MPU) nanocomposites

Multiwall carbon nanotubes (MWCNTs) were prepared using chemical vapor deposition (CVD) technique in presence of nano Co/Mo-MgO as an efficient catalyst. Further the as-synthesized MWCNTs were functionalized using ethyl 4-amino cinnamate (f-MWCNTs) to improve its wettability or compatibility with the chains of polymer. The as-synthesized MWCNTs and f-MWCNTs were subjected to various characterization techniques Raman spectroscopy, X-ray diffraction, FTIR, FESEM and TGA to investigate its size, presence of functional groups and stability. It was observed that diameter of f-MWCNTs were found to be ~ 45 nm with thermally more stable. Further, f-MWCNTs (0 to 1 %) were reinforced in MPU rubber using two roll mill and molded on compression molding machine. The dumbbell shape specimens were then subjected to mechanical and thermal study. It was observed that both the tensile strength and % elongation at break of MPU nanocomposites increases significantly up to 0.8 wt loading and decreases thereafter. This improvement in properties was due to uniform dispersion of f-MWCNTs into the chains of MPU rubber with homogeneity in bonding, while the decrement in properties at 1wt % loading was due to agglomeration of f-MWCNTs at some places. Also the functionalization using ethyl 4-amino cinnamate increases the compatibility of MWCNTs with MPU rubber chains. Besides this, functionalization makes the surface of MWCNTs smooth with enhancement in bonding between the two surfaces that is filler as well as matrix counterpart. Significant improvement in mechanical and thermal properties are achieved due to modification MPU with functionalized MWCNT.     

Rheological properties and crystal morphology of poly(ethylene oxide)/clay nanocomposites

Poly(ethylene oxide) (PEO)/organoclay nanocomposites were prepared by a solution intercalation method. The crystallization behavior of the nanocomposites was investigated by a cross‐polarized optical microscopy (CPOM) fitted with a hot‐stage facility. A decrease in size and regularity were observed as a result of incorporation of clay into the PEO matrix. The dynamic viscoelastic behavior of PEO/organoclay nanocomposites was assessed using a strain‐controlled parallel plate rheometer. The effects of clay concentration on the rheological properties of the nanocomposites were extensively studied. A significant increase in the viscosity and storage modulus of the nanocomposites was found with increasing clay content. The reinforcing effect of the organoclay was determined by using a dynamic mechanical analyzer (DMA) and compared with the theoretically calculated values. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Rheological and thermal properties of poly(ethylene oxide)/multiwall carbon nanotube composites

Poly(ethylene oxide) (PEO) based nanocomposites were prepared by the dispersion of multiwall carbon nanotubes (MWCNTs) in aqueous solution. MWCNTs were added up to 4 wt % of the PEO matrix. The dynamic viscoelastic behavior of the PEO/MWCNT nanocomposites was assessed with a strain‐controlled parallel‐plate rheometer. Prominent increases in the shear viscosity and storage modulus of the nanocomposites were found with increasing MWCNT content. Dynamic and isothermal differential scanning calorimetry studies indicated a significant decrease in the crystallization temperature as a result of the incorporation of MWCNTs; these composites can find applications as crystallizable switching components for shape‐memory polymer systems with adjustable switching temperatures. The solid‐state, direct‐current conductivity was also enhanced by the incorporation of MWCNTs. The dispersion level of the MWCNTs was investigated with scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008