Unique microstructure analysis of ethylene-propylene copolymer synthesized using catalytic system based on α-diimine nickel complexes: a comparative study by 13C NMR technique

The microstructure of rubber-like ethylene-propylene copolymer (MN4) produced by a mixed nickel-based system (MN) containing catalysts of dibromo[N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediimine]nickel(II) n1 and dibromo[N,N′-(phenanthrene-9,10-diylidene)bis(2,6-diisopropylaniline)]nickel(II) n2 was determined by ¹³C NMR technique. Sequences distribution of ethylene (E), propylene (P), EP, inverted propylene and uninterrupted methylene and also methylene number-average sequence lengths for the copolymer (MN4) were estimated. The results obtained from the MN4 EP copolymer were compared with reported copolymers which had been synthesized using constrained geometry catalyst (CGC) and vanadium-based Ziegler-Natta catalyst. The results demonstrated that the MN4 EP copolymer had fewer alternating comonomer sequences than ethylene-propylene elastomers obtained by CGC and vanadium-based (V) catalysts. A large number of the inversion structures (66 %) and high mole percent of sequences containing a long branch (3.2 mol%) were also observed in unique microstructure of the copolymer (MN4).     

Mortality response of folate receptor-activated,PEG–functionalized TiO2 nanoparticles for doxorubicin loading with and without ultraviolet irradiation

TiO₂ nanoparticles (NPs) were synthesized by hydrothermal assisted sol–gel technique. In the next step, as-synthesized NPs were modified by poly ethylene glycol (PEG). Then, folic acid (FA) was conjugated to TiO₂–PEG. Finally, Doxorubicin (Dox) as an anticancer drug was loaded on as-prepared TiO₂–PEG–FA nanocarrier. The optimization of TiO₂ and FA concentration and the influence of ultraviolet (UV) irradiation on photocatalytic activity of nanocarrier and Dox loaded carrier were assessed by utilizing the 3-(4,5-dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide (MTT)-assay method.     

Synthesis and characterization of polyazomethine conducting polymers and oligomers

Conjugated polyazomethine polymers were prepared from the polycondensation of terephthalaldehyde with 4,4′-thiodianiline, and 4,4-thiodibenzaldehyde with 4,4′-thiodianiline, 4,4′-phenylenediamine and benzidine. The polymers showed good stability in air and were soluble in many organic solvents. The electrical conductivities of the undoped and doped (H₂SO₄ and I₂) polymers were studied. Doping the polymers markedly increased their conductivities from 10^?8 ? 10^?11 S cm^?1 (dielectric region) to 10^?3 ? 10^?5 S cm^?1 (semiconducting region). The polymers were characterized by IR spectroscopy, elemental analyses, viscosity measurements and X-ray diffraction. Furthermore, polyazomethine oligomers were prepared and a comparative study of the physical properties of the oligomers and their corresponding polymers was performed. The electrical behavior of the oligomers was studied. It was found that oligomers with a minimum of eight aromatic (Ar) rings gave almost the same electrical conductivities as long-chain polymers.     

Effect of oxide and carbide nanoparticles on tribological properties of phenolic-based nanocomposites

The phenolic-based composites and components are widely used because of their excellent thermal, tribological and mechanical behaviors. In the present study, phenolic resin composed of hexamine, novalac, furfural, and furfuryl alcohol has been used. The effects of two carbide nanoparticles (SiC and TiC) and two oxide nanoparticles (TiO₂ and ZrO₂) on the tribological properties of phenolic resin were experimentally investigated. This paper intends to identify the effects of different fillers, fraction of particles and normal load on wear rate and coefficient of friction in dry sliding wear of phenolic-based nanocomposites against hard metal. The proportions of fillers were 0.5, 1 and 2?vol% and experiments were carried out under 40, 50, 60 and 70?N loads and at 0.2?m/s speed. The fillers were mixed with phenolic resin and molded in the form of a cylinder (8.5?mm diameter?×?25?mm height). The samples were cured at 135?°C with a special heating cycle. The wear tests were performed on pin-on-disk testing apparatus at ambient temperature. The composite pins were tested in dry sliding against carbon steel disk. The worn surfaces of samples have been investigated by SEM and the effects of nanometer particles showed different wear mechanisms. Observations showed that carbide particles have better enhancing effect on tribological properties of phenolic resin as compared to the oxide particles. Nanocomposites with SiC particles showed the best tribological properties among the investigated samples. The optimal content of SiC nanoparticles were 1?vol%.     

The effect of SiO2 porosity on activity profiles and comonomer incorporation in slurry ethylene/butene‐1 polymerization by (SiO2/MgCl2/TEOS/TiCl4) catalyst system

To investigate the influence of support porosity parameters e.g., average pore volume (APV), pore diameter (PD), and pore surface area distribution (PSAD) on activity‐profile of catalyst and comonomer incorporation, a series of silica‐supports with different porosity were prepared through sol–gel method and used to synthesize corresponding (SiO₂/MgCl₂/TEOS/TiCl₄) catalysts. Polymerization of ethylene/butene‐1 showed that increasing of APV from 0.75 to 2.2 cm³ g increase initial activity from 120 to 400 (g_poly/g_cat.bar.hr) followed by appearance of secondary peaks in activity‐profile which could be attributed to the variation of PSAD. It is found that the effect of support in polymerization is a complicated issue which depends not only on the porosity parameters also on the comonomer concentration. The catalyst with PD of 300 Å gives higher comonomer incorporation and polymers with 15–20% lower crystallinity in contrast to catalyst with PD of 100 Å. Porosity effect was quantitatively studied by modifying of conventional Z‐N catalyst polymerization mechanism through introducing fragmentation term to achieve a new tool in designing and developing of polyolefin catalysts. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of a novel silicone containing vinylic macromonomer and its uses in the preparation of poly (silicone‐co‐styrene‐co‐butylacrylate) with montmorillonite nanocomposite emulsion

A new silicone containing macromonomer, 4‐(methacrylamido) phenoxy polymethylhydrosiloxane (4‐MPMHS) with a vinyl group, was successfully synthesized. Then poly (silicone‐co‐styrene‐co‐butylacrylate) with montmorillonite, P (Si‐co‐St‐co‐BA) with MMT nanocomposite emulsion was prepared by in situ intercalative emulsion polymerization of styrene (St), butyl acrylate (BA), and 4‐MPMHS, in the presence of organic modified montmorillonite (OMMT) with different OMMT contents (0, 0.5, 1.0, 1.5, and 2 wt %). Potassium persulphate (KPS) was used as an initiator and sodium lauryl sulfoacetate (SLSA) and nonyl phenol ethylene oxide—40 U (NP‐40) were used as anionic and nonionic emulsifiers, respectively. The resulting macromonomer was characterized by elemental analysis, Fourier transformer infrared (FT‐IR), proton (¹H NMR), and carbon (¹³C NMR) nuclear magnetic resonance spectroscopes. The OMMT was characterized by FT‐IR and X‐ray diffraction (XRD). The nanocomposite emulsions were characterized by using Fourier Transform infrared spectroscopy (FT‐IR), laser light scattering, and surface tension method. Thermal properties of the copolymers were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and then the effects of OMMT percent on the water absorption ratio and drying speed were examined. Results showed that OMMT could improve the properties of emulsion. In other words, the properties of nanocomposite emulsions were better when compared with those of the silicone‐acrylate emulsion. The property of nanocomposite emulsion containing 1 wt % OMMT was the best one, and the following advantages were obtained: smaller particle size, faster drying speed, smaller surface tension, and improved water resistance by the incorporation of OMMT. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of water-based polyurethane–acrylic hybrid nanocomposite emulsion based on a new silane-containing acrylic macromonomer

A new silane-containing acrylic macromonomer, maleimidedoethoxybutoxydimethylsiloxy butyl acrylate (MEBDMSBA), based on maleic anhydride (MA), ethanolamine (EA), 1,4-butanediol (BDO), dichlorodimethylsilane (DCDMS), and acrylic acid (AA) has been synthesized for formulation of waterborne polyurethane (WPU). Also a series of new silane-containing WPU, methyl methacrylate (MMA), MEBDMSBA, and montmorillonite (MMT) with organically modified montmorillonite (OMMT) content (1.25 wt%) hybrid nanocomposites have been successfully prepared by the emulsion polymerization in the presence of a WPU dispersion, using ammonium peroxodisulfate (APS) as an initiator. The WPU dispersion has been synthesized by a polyaddition reaction of isophorone diisocyanate (IPDI) on polypropylene glycol (PPG-1000) and dimethylol propionic acid (DMPA) as chain extender. The monomer was characterized by Fourier transformer infrared spectroscopy (FTIR), elemental analysis, proton (¹H NMR), and carbon (¹³C NMR) nuclear magnetic resonance spectroscopes, respectively. The nanocomposite emulsions were also characterized using Fourier transform infrared spectroscopy (FTIR) and laser light scattering. Thermal properties of the copolymers were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The OMMT was characterized by FTIR and X-ray diffraction (XRD). The morphology of copolymers was investigated by scanning electron microscopy (SEM) and transition electron microscopy (TEM), and then the effects of silane concentrations on the water absorption ratio were examined. Results showed that OMMT could improve the properties of emulsion; in other words, the properties of nanocomposite emulsion were better when compared with those of the silane–acrylate emulsion.     

Comparison of Canola and Soy Flour with Added Isocyanate as Wood Adhesives

Canola is widely grown in the northern latitudes for its vegetable oil, generating large quantities of residual, low value canola flour used as animal feed. The common wood adhesive poly(diphenylmethylene diisocyanate) (pMDI) should react with the wide variety of functional groups in proteins. Therefore, it would seem that canola flour with added pMDI could be an effective adhesive. Two main questions are addressed in this study: How do the wood adhesive properties of canola flour compare to the better-studied soy flour? How well do proteins, which contain an abundance of functional groups, cure with the very reactive pMDI? These questions were addressed using the small-scale adhesive strength test ASTM D-7998, with various adhesive formulations and bonding conditions for canola flour plus pMDI compared to soy adhesives. The more challenging wet cohesive bond strength was emphasized because the dry strengths were usually very good. Generally, soy adhesives were better than canola ones, as was the polyamidoamine-epichlorohydrin cross-linker compared to pMDI, but these generalizations can be altered by the conditions selected. Three-ply plywood tests supported the small-scale test results.     

Crystallization of P Type Amorphous Silicon (a-Si: H) by AIC Method: Effect of Aluminum Thickness

In this work, we will study the crystallization of P type hydrogenated amorphous silicon (a-Si:H) by Aluminum Induced Crystallization technique (CIA) by varying the thickness of the aluminum films. We have deposited a 100 nm thickness of p-type a-Si:H layer on Corning glass substrates using PECVD technique. An aluminum layer with thickness ranging from 10 to 400 nm was thermally evaporated on the a-Si:H surface. The thermal annealing was performed in a conventional furnace at temperature of 550 °C for 4 h in flowing N2 ambient. The study of the crystallization of the Al/a-Si:H/Glass structure according the aluminum thickness was carried out by using Raman spectroscopy, X-rays diffraction and Hall Effect measurements. Raman results reveal the presence of the peaks between 510 and 520 cm−1, which are close to the peak of crystallized Si (about 521 cm−1) proving the crystallization of all samples. The XRD measurements show the presence of the characteristic peaks of the crystalline silicon, thus the a-Si: H (p) layer was effectively crystallized by the AIC method in a short time. Through Hall measurements we found an improvement in electrical properties and an increase in dopant concentration (+ 5.3 1014 to + 2.9 1017 cm2).