Electrolytic admicellar polymerization of pyrrole on natural rubber/clay nanocomposites

Organic–inorganic composites consisting of natural rubber (NR), polypyrrole (PPy), and sodium montmorillonite (Na‐MMT) were synthesized via electrolytic admicellar polymerization. A constant potential of 9 volts was chosen for the synthesis. The PPy concentration was fixed at 100 mM, and the clay contents were varied from 1 to 7 parts per hundred of rubber (phr). The synthesized nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy (TEM), together with thermal stability (TGA), mechanical properties, and electrical conductivity (σ_dc) studies. The FTIR spectra indicated the characteristic peaks of both PPy and MMT clay and also evidenced a slight interaction between the PPy chain and the clay layers, verifying the success of electrolytic admicellar polymerization. XRD and TEM results pointed out the good dispersion of clay platelets in the polymer matrix, suggesting an exfoliated structure. The morphology of the nanocomposites was greatly dependent on the amount of MMT clay, especially at a 7 phr loading. The initial modulus and tensile strength of the nanocomposites containing the 7 phr loading were about four and two times higher, compared with unfilled NR/PPy, respectively. Thermal stability studies revealed a slight improvement in the decomposition temperature for the PPy component by the clay layers, whereas the opposite trend was found for the NR component. More interestingly, the electrical conductivity of the admicelled rubber increased significantly (～ 19–32 times) with increasing clay contents from 1 to 7 phr, in comparison with unfilled NR/PPy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melt Rheology of Low-Density Polyethylene/Polyamide 6 using Ionomer as a Compatibilizer

Rheology of blends of polyamide 6 with low-density polyethylene compatibilized with sodium-, zinc-, and lithium-neutralized ethylene-methacrylic acid ionomers were investigated at 11, 33 and 55% neutralization of ionomer. Blends of polyamide 6 with low-density polyethylene without compatibilizer had lower shear viscosities than a mixing rule would predict. After adding compatibilizer, the shear viscosity of the blend is increased, presumably due to the formation of graft copolymer from the reaction of the primary amine with free acid groups. The increase of shear and elongational viscosity properties is less with EMAA than with the ionomers; which is consistent with mechanical property and dispersed phase size results presented in an earlier publication. For high polyamide 6 content blends, zinc-neutralized compatibilizers yielded the highest shear and elongational viscosities; while for low polyamide 6 contents, lithium-neutralized compatibilizers yielded the highest viscosities.     

Peroxide cured natural rubber/fluoroelastomer/high‐density polyethylene via dynamic vulcanization

In this work, blends of fluoroelastomer (FKM), natural rubber (NR) along with high‐density polyethylene (HDPE) by dynamic vulcanization using peroxide (DBPH, DCP) as a curing agent were prepared. HDPE was melt‐mixed with NR and FKM at different compositions (HDPE/FKM/NR i.e. 30/60/10, 30/55/15, 30/50/20, and 30/35/35%wt) using an internal mixer at 150°C and 50 rpm rotor speed. The mechanical properties and oil swelling resistances of these blends were analyzed according to ISO 37 (Type 1) and ASTM D471, respectively. The results suggest that DBPH works better as a curing agent for the dynamic vulcanization system than DCP. The optimum mechanical properties and oil resistance were revealed in 30/50/20 and 30/60/10 HDPE/FKM/NR, being dynamic vulcanized with DBPH, respectively. In addition, was found that a dispersed HDPE phase shows the percent crystallinity in the range of 53% to 55% upon increasing the NR content. The SEM micrographs reveal the NR phase is well dispersed in FKM as small particles. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers .     

TiO2/modified natural clay semiconductor as a potential electrode for natural dye-sensitized solar cell

TiO₂/modified natural bentonite clay semiconductor, as a potential electrode of dye-sensitized solar cell, having a Ti:Si molar ratio of 85:15 was, for the first time, compared with pure TiO₂ (commercial P25) electrode in terms of solar cell efficiency and characteristics. 4-Chloro-2,5-difluorobenzoic acid and 4-(chloromethyl)benzoyl chloride were added to the electrodes to increase light harvesting ability of natural dyes extracted from red cabbage, rosella, and blue pea. The results showed that the TiO₂/clay semiconductor provided a higher surface area but a slightly lower efficiency than the pure TiO₂. The best natural sensitizer was found to be the dye extracted from red cabbage. Besides, the 4-(chloromethyl)benzoyl chloride provided a higher short circuit current for the TiO₂/clay semiconductor.     

Preparation of sol–gel TiO2/purified Na-bentonite composites and their photovoltaic application for natural dye-sensitized solar cells

The sol–gel TiO₂/purified natural clay electrodes having Ti:Si molar ratios of 95:5 and 90:10 were initially prepared, sensitized with natural red cabbage dye, and compared to the sol–gel TiO₂ electrode in terms of physicochemical characteristics and solar cell efficiency. The results showed that the increase in purified Na-bentonite content greatly increased the specific surface area and total pore volume of the prepared sol–gel TiO₂/purified Na-bentonite composites because the clay platelets prevented TiO₂ particle agglomeration. The sol–gel TiO₂/5 mol% Si purified Na-bentonite and sol–gel TiO₂/10 mol% Si purified Na-bentonite composites could increase the film thickness of solar cells without cracking when they were coated as a scattering layer on the TiO₂ semiconductor-based film, leading to increasing the efficiency of the natural dye-sensitized solar cells in this work.     

Morphological study of LLDPE‐NR reactive blending with maleic anhydride

A binary blend and ternary reactive blends of 90/10 LLDPE/NR using maleic anhydride (MA) as a reactive agent with and without dicumyl peroxide (DCP) were made at 150°C in an internal mixer. The fracture surfaces of the blends were conventionally observed by TEM and atomic force microscope, revealing that the rubber domains became smaller with the addition of MA and DCP. This suggested that the in situ graft copolymer (LLDPE‐g‐NR) was formed and acted as an in situ compatibilizer to enhance interfacial adhesion. This was further supported by FTIR results. Importantly, after removal of NR phase from the blends, the remaining LLDPE part was dissolved in hot xylene, purified by precipitation in methanol, and carefully prepared by solvent casting for TEM observation. The microstructures of the solvent‐extracted LLDPE from all blends are unlike that of solvent cast‐ pure LLDPE, which shows only crystalline structure. This leads to an unambiguous way to disclose the existence of an in situ graft copolymer. The solvent‐extracted LLDPE from the blends shows mixed morphology of LLDPE crystalline structure and its in situ graft copolymer as nanofibrillar networks of the NR phase protruded from the amorphous region of the LLDPE matrix due to spinodal decomposition by the solvent removal. Adding MA makes more branches and fibril connections of the NR phase, whereas a thinner fibril network and more links of the NR and the LLDPE amorphous region are found in the reactive blend with MA and DCP, where the most compatibilized blend is obtained. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Adhesion and permeability of polyimide–clay nanocomposite films for protective coatings

A polyimide (PI)–clay nanocomposite was prepared from a solution of poly(amic acid), a precursor of 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and p‐phenylenediamine, and dodecylamine–montmorillonite. Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, and atomic absorption spectroscopy were used to verify the incorporation of the modifying agents into the clay structure and the intercalation of the modified clay into the PI matrix. Both PI and PI–clay films were subsequently prepared by solution casting. The gas permeability, resistivity, and adhesion properties were determined. In the case of gas permeability, only a 3 wt % addition of clay reduced oxygen permeability to less than half that of unfilled PI. Furthermore, this hybrid showed an improvement in electrical resistivity because of the prevention of electrical tree growth by clay particles. More importantly, adhesion between the films and silicon increased with increasing clay content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2875–2881, 2003     

Modified Porous Clay Heterostructures by Organic–Inorganic Hybrids for Nanocomposite Ethylene Scavenging/Sensor Packaging Film

Porous clay heterostructures (PCHs) were prepared by the surfactant‐directed assembly of mesostructured silica within the two‐dimensional galleries of clays. PCH is an interesting material for use as an entrapping system (for example, as an ethylene scavenger) because of its high surface area with uniform and specific pore sizes. In the present work, the PCH was synthesized within the galleries of bentonite by the polymerization of tetraethoxysilane (TEOS) in the presence of surfactant micelles. In addition, mesoporous clay was modified by an organic–inorganic hybrid material through the co‐condensation reaction of TEOS with the functional groups (methyl and thiol) designated as hybrid organic–inorganic PCH (HPCH) and mercaptopropyl functionalized PCH (MPPCH), respectively. The synthesized PCH, HPCH and MPPCH were blended with polypropylene (PP) to produce PCH/PP, HPCH/PP and MPPCH/PP for ethylene scavenging blown films. All nanocomposite films were evaluated as ethylene sensors by measuring the conductivity changes by the attachment time with the ethylene gas. According to the surface characterization, the specific surface areas of modified PCHs increased from 31 to about 500 m²/g. From the ethylene adsorption results, the PCH, HPCH and MPPCH show higher efficiency in adsorbing ethylene gas than those of bentonite because of the non‐polar property of the modified functional groups. Subsequently, the electrical conductivity of the nanocomposite films decreased when they react with the longer attachment time to the ethylene gas, and the largest conductivity drop resulted from the MPPCH/PP nanocomposite films. Copyright © 2011 John Wiley & Sons, Ltd.     

Compounding of poly(dimethyl siloxane) to reduce tack in natural rubber

Tack in natural rubber latex was reduced by compounding poly(dimethyl siloxane) (PDMS) emulsion in concentrated latex. Sheet and dipped film surfaces were examined with Fourier transform infrared spectroscopy using attenuated total reflection (FTIR–ATR) and by contact angle measurements. Autohesive tack and tensile properties were also determined. For both sheet and dipped film, FTIR–ATR showed that the PDMS concentration was higher at the glass surface than at the air surface. The contact angle of ethylene glycol on the rubber decreased with increasing PDMS content. Autohesive tack for sheet and dipped film also decreased with increasing PDMS amount; however, annealing for 1 week at 70°C in air did cause tack to rise in the sheets. The rubber surface could be made nonadhesive by addition of sufficient PDMS. PDMS caused a decrease in tensile strength for the sheet, especially after annealing; however, PDMS did not cause a substantial decrease in percentage elongation for the sheets, except at relatively high PDMS contents. The tensile strength and percentage elongation for dipped film was not affected by PDMS over the much more limited PDMS concentration range studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 519–526, 2001     

Correlation of viscosity ratio,morphology, and mechanical properties of polyamide 12/natural rubber blends via reactive compatibilization

Natural rubber (NR)-modified polyamide 12 (Nylon12/NR) was produced by melt blending Nylon12 and NR in the presence of polystyrene/maleated natural rubber (PS/MNR) copolymer as a reactive compatibilizer. The influence of compatibilizer loading on viscosity ratio, morphology, and mechanical properties of the blends was investigated. As a consequence of the reactive blend between Nylon12 and maleated NR in PS/MNR, the formation of amide and succinimide linkages was set at rubber-Nylon12 interfaces. Thus the dispersion of rubber particles was improved, and the particle coalescence was prevented so that the fine morphology with good interfacial adhesion was stabilized. This also resulted to enhance the blend viscosity and to lower viscosity ratio. The data revealed strong correlation between low viscosity ratio and fine spherical morphology of the compatibilized blends. An optimum PS/MNR compatibilizer content was at 7 phr to produce good dispersion of small rubber domains (size ≤0.3 μm) in Nylon12 matrix. Thermal properties by DSC revealed that crystallization temperature of Nylon12 was lowered by the presence of NR and crystallinity of Nylon12 was slightly affected by the PS/MNR content. An enhancement of mechanical properties, especially the impact energy was observed without suffering the tensile and flexural properties. Compared to the neat Nylon12, the compatibilized blends showed an increase in impact energy by a factor of 5. This large enhancement is successfully interpreted in term of the toughening effect by rubber phase of suitable dispersed size and the interparticle distance.