Electrorheological properties of kaolinite,polyindole, and polyindole/kaolinite composite suspensions

In this study, polyindole (PIN) and polyindole/kaolinite (PIN/KAO) composite were synthesized by free radical polymerization using FeCl₃ as an initiator. Average particle sizes (d₅₀) of PIN and PIN/KAO composite were determined by dynamic light scattering (DLS) as 7.2 and 6.2 μm, respectively. The samples were characterized by FTIR, elemental analysis, DSC/TGA and SEM measurements. Suspensions of KAO, PIN, and PIN/KAO composite were prepared in silicone oil (SO) and the sedimentation stabilities were determined. Electrorheological (ER) properties of these suspensions were studied as a function of dispersed phase concentration, shear rate, shear stress, and temperature; and yield stresses and excess shear stresses determined. Further, dielectric properties of KAO, PIN, and PIN/KAO composite were investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis, characterization, and cyclopolymerization of a functional non-symmetric divinyl monomer

A non-symmetric divinyl monomer with terminal carboxylic acid functionality was readily synthesized from the reaction of ethyl α-hydroxymethylacrylate (EHMA) with maleic anhydride. The new monomer (EHMA-MA) was homopolymerized in both bulk and ethyl acetate using AIBN as an initiator to give cyclopolymers. The synthesis of the monomer and cyclopolymers were followed by ¹³C NMR, ¹H NMR, and FTIR. ¹H NMR was also utilized to obtain the degree of cyclization of the polymers, which were found to be 95% or higher in all cases. The molecular weights of the cyclopolymers were around 40-60,000 g/mol as estimated by SEC. The cyclopolymers were thermally stable up to 150 °C. Although the cyclopolymers obtained were not water-soluble; they were soluble in aqueous 1 M NaOH solution. In addition to the carboxylic acid functionality present, the cyclopolymers also had an ethyl ester and a lactone moiety. These functional groups were reacted with hexylamine to obtain a polymer with imide and amide moieties.     

Desulphiting dried apricots by exposure to hot air flow

Sulphited dried apricots were exposed to hot air flows at 40, 50 and 60 °C and the removal of SO₂ was investigated as their moisture content fell from an initial value of 193.2 g kg^?1 to a final value of 80–90 g kg^?1. A first‐order kinetic model was found for the removal of SO₂ between 40 and 60 °C. Temperature quotients (Q₁₀) for the removal of SO₂ were 2.84 between 40 and 50 °C and 4.93 between 50 and 60 °C; the activation energy (E_a) was 114.40 kJ mol^?1 between 40 and 60 °C. Analysis of the kinetic data also suggested a first‐order reaction for non‐enzymatic browning, with Q₁₀ values of 2.34 between 40 and 50 °C and 5.36 between 50 and 60 °C and an E_a value of 109.36 kJ mol^?1 between 40 and 60 °C. Exposure of dried apricots to a 60 °C air flow resulted in a rate constant for brown pigment formation that was 12 and 5 times higher than those at 40 and 50 °C respectively. © 2002 Society of Chemical Industry     

Laser Treatment of Sintered Silicon Carbide Surface for Enhanced Hydrophobicity

In this study, laser treatment of sintered SiC surfaces is carried out to enhance the surface hydrophobicity. Morphological and metallurgical changes of the treated surfaces are evaluated using optical and scanning electron microscopy, energy dispersive spectroscopy, and x-ray diffraction (XRD). Microhardness and fracture toughness are measured using indentation tests. The residual stresses present are determined using the XRD technique. The wetting characteristics of the treated surfaces are assessed through contact angle measurements. It is found that the laser-treated surfaces consist of fine grooves and pillars and that the resulting surface roughness enhances the surface hydrophobicity. The fracture toughness of the treated surface is reduced possibly because of the microhardness increase at the surface. The residual stress formed in the surface region is on the order of 1.8 GPa, and it is compressive.     

Synthesis and electrochemical,in situ spectroelectrochemical,electrical and gas sensing properties of ball-type homo- and hetero-dinuclear phthalocyanines with four [1a,8b-dihydronaphtho[b]naphthofuro[3,2-d]furan-7,10-diyl] bridges

The new mono-nuclear Fe^II 2 and ball-type homo-dinuclear Fe^II–Fe^II 3 phthalocyanines have been synthesized from the corresponding 4,4′-(1a,8b-dihydronaphtho[b]naphthofuro[3,2-d]-furan-7,10-diyl)bis(oxy)diphthalonitrile 1 while ball-type hetero-dinuclear Fe^II–Co^II phthalocyanine 4 was synthesized from 2. The compounds have been characterized by elemental analysis, UV–vis, IR and MALDI-TOF-mass spectroscopies. The redox behaviours of the complexes were identified by controlled-potential coulometry, cyclic voltammetry and differential pulse voltammetry measurements on Pt in dimethylsulfoxide containing tetrabutylammonium perchlorate. The assignments of the redox processes and the understanding of the interactions between the metal phthalocyanine units in 3 and 4 were achieved by the combined evaluation of the voltammetric and in situ spectroelectrochemical outcomes. Complex 3 showed ring-based mixed-valence behaviour as a result of the considerable interaction between the phthalocyanine rings. On the other hand, the interactions between the two metal phthalocyanine units of 4 were found to be much weaker than those in 3. The potential application of molecular organic semiconductors needs the control adjustment of conductivity. Ac and dc conductivity measurements were performed with the applied external electric filed. At high frequency, the conduction follows the universal power law and conduction mechanism can be explained by classical hopping barriers mechanism for the system.     

Synthesis and electrochemical,electrochromic and electrical properties of novel s-triazine bridged trinuclear Zn(II), Cu(II) and Lu(III) and a tris double-decker Lu(III) phthalocyanines

The new s-triazine-bridged trinuclear Zn(II) and Cu(II) phthalocyanines have been synthesized from the reaction of corresponding anhydrous metal salts, Zn(OAc)₂ and CuCl with 4,5-bis(hexylthio)-phthalonitrile and 2,4,6-tris(2-thiophthalonitrile)-s-triazine. The tris phthalonitrile derivative of s-triazine was prepared from the reaction of 4-nitrophthalonitrile and thiocyanuric acid in dry dimethylformamide as solvent using K₂CO₃ as the base. The same route was applied to prepare the trinuclear Lu(III) phthalocyanine analogue. The conversion of tris phthalonitrile into its isoindoline derivative was accomplished by bubbling ammonia gas through a solution in methanol in the presence of sodium methoxide. The cyclization of two different isoindoline derivatives and 4,5-bis(hexylhthio)-1,2-diiminoisoindoline, with lutetium (III) acetate in dimethylformamide gave trinuclear Lu(III) phthalocyanine. The reaction of this complex with octakis-hexylthio phthalocyanine led to the isolation of tris double-decker Lu(III) phthalocyanine. The structures of the target compounds were confirmed by elemental analysis, UV–vis, IR and MALDI-TOF mass spectroscopies. The d.c. and a.c. conductivities of the phthalocyanine compounds were measured as a function of temperature. The small value of pre-exponential factor suggested the conduction by localized states in the band tails and by localized states near the Fermi level. The temperature dependence of the frequency exponent showed that the conduction in these compounds is due to hopping of charge carriers. The tris double-decker phthalocyanine complex showed well-defined electrochromic behaviour with green-blue and blue-purple colour transitions.     

Electrochemical conversion of phenolic wastewater on carbon electrodes in the presence of NaCl

The electrochemical conversion of highly concentrated synthetic phenolic wastewater was studied on carbon electrodes in a batch electrochemical reactor. The effects of reaction temperature, electrolyte concentration, current density and initial phenol concentration on phenol conversion were elucidated. The wastewater was synthetically prepared and used in reactions carried out generally at 25 °C with an initial phenol concentration of 3500 mg dm^?3. Although current density increased, phenol conversion% and initial phenol conversion rate did not increase correspondingly above 35 °C and an electrolyte concentration of 90 g dm^?3. As the voltage values applied were increased, the increasing current density resulted in fast phenol conversion. Kinetic investigations denoted that overall phenol destruction kinetics was of zero order with an activation energy of 10.9 kJ mol^?1. Under appropriate conditions, phenol was completely converted within 15 min for an initial phenol concentration of 98 mg dm^?3 while 8 h was required to gain 95% conversion using 4698 mg dm^?3. Solid polymeric materials were produced at initial phenol concentrations above 500 mg dm^?3 using the appropriate current density. In the reaction medium, only mono‐, di‐ and tri‐substituted chlorophenols were formed and 100% of all species were either oxidised or contributed to the formation of a polymeric structure. Almost all of the phenol loaded to the reactor was converted into non‐passivating polymeric products, denoting a safe and easy method for the separation of phenol. © 2001 Society of Chemical Industry     

Palladium-Catalyzed Suzuki–Miyaura Reaction Using Saturated N-Heterocarbene Ligands

Recent studies have pointed to the heptamethylbenzenium cation as a prominent intermediate in the methanol to hydrocarbons (MTH) reaction. The reactions of the heptamethylbenzenium cation in a H-beta zeolite was studied at 300 °C by feeding its corresponding base (WHSV = 0.4 h^?1). The reactant was converted completely into aliphatic products, polymethylbenzenes and coke under the employed conditions. The results testify that the proposed reaction intermediate yields the same product spectrum as methanol. The composition of the material retained in the catalyst micropores after 15 min of reaction was determined by dissolving the catalyst in 15% HF. Polymethylated benzenes (predominantly pentamethylbenzene), dihydro-trimethylnaphthalenes, and hexamethylnaphthalene were the major components. The results also support the idea that the lowest naphthalene derivative is formed from the heptamethylbenzenium cation by a molecular rearrangement. Hence, the heptamethylbenzenium cation is inherently linked to both product formation and catalyst deactivation in the MTH reaction.     

Polymers,composites, and characterization of conducting polyfuran and poly(2‐bromoaniline)

Polyfuran (PFu), poly(2‐bromoaniline) (P2BrAn), and poly(2‐bromoaniline)/polyfuran (P2BrAn/PFu) composites were synthesized by coupling using various solvents and oxidants. 2‐Bromoaniline (2BrAn) was polymerized using FeCl₃ and (NH₄)₂S₂O₈ in aqueous HCl medium. PFu was synthesized using FeCl₃ and SbCl₃ in anhydrous media (CHCl₃, CH₃CN). Furan was polymerized using both salts in CHCl₃ medium, whereas it could be polymerized using only FeCl₃ in CH₃CN medium. The new electrically conducting composites were prepared by chemical oxidative polymerization using polyfuran synthesized with SbCl₃ and poly(2‐bromoaniline). The polymers and composites were characterized using conductivity, magnetic susceptibility, infrared spectra (FTIR), UV‐Vis spectra, thermal analysis (TGA), and scanning electron microscopy (SEM) measurements. It was found that PFu(SbCl₃) has the lowest thermal stability. Thus, the thermal stability of PFu was increased by preparing composites. The chemical structures of P2BrAns and composites have been found from UV‐Vis results to contain quinone‐imine units along the polymer chain. Magnetic susceptibility measurements indicated that the polymers and composites were diamagnetic or paramagnetic. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2048–2057, 2005     

Synthesis and antimicrobial activities of new water‐soluble bis‐quaternary ammonium methacrylate polymers

New methacrylate monomers containing pendant quaternary ammonium moieties based on 1,4‐diazabicyclo‐[2.2.2]‐octane (DABCO) were synthesized. The DABCO group contains either a butyl or a hexyl pendant group comprising the hydrophobic segment of the monomers and one tether group to the methacrylate moiety. The monomers were homopolymerized in water by using 2,2′‐azobis(2‐methylpropionamide) dihydrochloride (V‐50) as an initiator. The monomers and polymers were characterized by elemental analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), FTIR, and ¹³C‐NMR. The antimicrobial activities of the corresponding small molecules (bis‐quaternary ammonium monocarboxylates) and polymers were investigated against Staphylococcus aureus and Escherichia coli. Although the small molecules did not show any antimicrobial activity, the polymers were moderately effective against both Gram‐positive and Gram‐negative bacteria. The minimum inhibitory concentration (MIC) values of the polymers with butyl and hexyl hydrocarbon chains against S. aureus and E. coli were found to be 250 and 62.5 μg/mL, respectively. The minimum bactericidal concentration (MBC) value for the polymer with the butyl group was higher than 1 mg/mL, whereas the MBC value for the polymer with hexyl group was found to be 62.5 μg/mL. Thus, an increase of the alkyl chain length from 4 to 6 significantly increased the antimicrobial activity of the polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 635–642, 2004