Synthesis and characterization of chitosan‐g‐methacrylic acid and studies of its additional physicochemical properties,such as swelling,metal‐ion sorption,and flocculation behavior

The aim of this study was to examine the synthesis of a graft copolymer of chitosan and methacrylic acid (MAA) by free‐radical polymerization with a potassium peroxymonosulfate/cyclohexanone (CY) redox system in an inert atmosphere. The optimum reaction conditions affording maximum grafting ratio (%G), grafting efficiency (%E), add on (%A), and conversion (%C) were determined. The grafting parameters were found to increase with increasing concentration of MAA up to 24 × 10^?2 mol/dm³, but thereafter, these parameters decreased. With increasing concentration of peroxymonosulfate from 0.6 × 10^?2 to 1.2 × 10^?2 mol/dm³, %G, %A, and %E increased continuously. All of these grafting parameters increased with increasing concentration of CY up to 1.2 × 10^?2 mol/dm³, but beyond this concentration, the grafting parameters decreased. With various concentrations of chitosan from 0.6 to 1.4 g/dm³, the maximum %G, %A, and %E were obtained at 1.4 g/dm³. %G, %A, and %C decreased continuously with various concentrations of hydrogen ions from 2 × 10^?3 to 6 × 10^?3 mol/dm³. The grafting parameters increased with increasing temperature up to 35°C, but thereafter, these parameters decreased. With increasing time period of reaction from 60 to 180 min, %G, %A, and %E increased up to 120 min, but thereafter, these parameters decreased. The graft copolymer was characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Process modeling and optimization of industrial ethylene oxide reactor by integrating support vector regression and genetic algorithm

This article presents an artificial intelligence‐based process modeling and optimization strategies, namely support vector regression–genetic algorithm (SVR‐GA) for modeling and optimization of catalytic industrial ethylene oxide (EO) reactor. In the SVR‐GA approach, an SVR model is constructed for correlating process data comprising values of operating and performance variables. Next, model inputs describing process operating variables are optimized using Genetic Algorithm (GAs) with a view to maximize the process performance. The GA possesses certain unique advantages over the commonly used gradient‐based deterministic optimization algorithms The SVR‐GA is a new strategy for chemical process modeling and optimization. The major advantage of the strategies is that modeling and optimization can be conducted exclusively from the historic process data wherein the detailed knowledge of process phenomenology (reaction mechanism, kinetics, etc.) is not required. Using SVR‐GA strategy, a number of sets of optimized operating conditions leading to maximized EO production and catalyst selectivity were obtained. The optimized solutions when verified in actual plant resulted in a significant improvement in the EO production rate and catalyst selectivity.     

Magnetite‐loaded calcium‐alginate (MLCA) particles as potential sorbent for removal of Ni(II) from aqueous solution

This work is focused on the removal of Ni(II) from aqueous solutions by sorption onto newly developed magnetite‐loaded calcium alginate particles. The uptake of Ni(II) by these magnetite particles, with their mean geometrical diameter 84 and 508 μm, is best described by the Freundlich isotherm and the constants K_F and 1/n were found to be 3.491 mg g^?1, 0.731 and 0.793 mg g^?1 and 0.907, respectively. The mean sorption energy, as determined by Dubinin‐Radushkevich isotherm for 508‐ and 84‐μm sized particles was evaluated to be 8.9 and 8.0 kJ mol^?1, respectively, thus, suggesting the ion‐exchange mechanism for uptake process. Of the various kinetic models proposed, the kinetic Ni(II)‐uptake data were best interpreted by “Simple Elovich” and “Power function” as suggested by their higher regression values. The almost linear nature of plots of log(% sorption) versus log(time) was indicative of intraparticle diffusion. The values of intraparticle diffusion coefficients K_id were found to be 63.49 × 10^?2 and 94.35 × 10^?2 mg l^?1 min^0.5. The intraparticle diffusion was also confirmed by Bangham equation. Finally, various thermodynamic parameters were evaluated. The negative ΔG° indicated spontaneous nature of uptake process while positive ΔH° value suggested exothermic nature of the sorption process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and emission analysis of RE (Eu or Dy):Li2TiO3 ceramics

The development and photoluminescence analysis of Eu³⁺or Dy³⁺ ions in the matrix of lithium titanate (Li₂TiO₃) ceramics by using a solid state reaction method are reported. Emission spectra of Eu³⁺:Li₂TiO₃ ceramics have shown strong red emission at 611 nm (⁵D₀ → ⁷F₂) with λ_exci = 392 nm (⁷F₀ → ⁵L₆) and from the Dy³⁺:Li₂TiO₃, a blue emission at 493 nm (⁴F_9/2 → ⁶H_15/2) and also an yellow emission at 582 nm (⁴F_9/2 → ⁶H_13/2) have been observed with λ_exci = 366 nm (⁶H_15/2 → ⁶P_5/2). Both the rare-earth ions containing ceramics have displayed their brighter emission performance from their measured spectral results. In addition, X-ray diffraction (XRD), Fourier transform infra red (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) have been used to characterize the structural properties of (Eu³⁺ or Dy³⁺):Li₂TiO₃ ceramics.     

Preparation,structural and thermo-mechanical properties of lithium aluminum silicate glass–ceramics

Lithium aluminum silicate glasses of composition (wt%) 12.6Li₂O–71.7SiO₂–5.1Al₂O₃–4.9K₂O–3.2B₂O₃–2.5P₂O₅ were prepared by the melt quench technique. These glasses were converted to glass–ceramics based on DTA data. X-ray diffraction (XRD) and Fourier transform infra-red spectroscopy (FTIR) were used to discern the phases evolved in the glass–ceramics. Phase morphology was studied using scanning electron microscopy (SEM). Thermal expansion coefficient (TEC) and glass transition temperature (T_g) of all samples were measured using thermo-mechanical analyzer (TMA). It was found that 3 h dwell time at crystallization temperature yielded samples with good crystallinity with a TEC of 9.461 × 10⁻⁶ °C⁻¹. Glass–ceramic-to-metal compressive seal with SS-304 was fabricated using LAS glass–ceramic. The presence of metal housing and compressive stresses at the glass–ceramic-to-metal interface reduced average grain size and changed the overall microstructure.     

Synthesis and evaluation of micellar properties and antimicrobial activities of imidazole‐based surfactants

The synthesis of two types of imidazole‐based surfactants, [(ROCOCH₂MIm)Br] and [(RNHCOCH₂MIm)Br], of varying chain lengths (C₁₀, C₁₂ and C₁₆), was conducted in the present work. The synthesis involves an initial reaction of bromoacetic acid with fatty alcohols or fatty amines, followed by quaternization with N‐methyl imidazole. The micellar properties of all the synthesized compounds were determined using surface tensiometry and compared with [(RMIm)Br], a well‐studied alkyl‐substituted imidazole‐based surfactant. Within the same homologous series, a decrease in critical micelle concentration (cmc) was observed with increasing alkyl chain length in all three types of cationic surfactants. Introduction of an ester [(ROCOCH₂MIm)Br] or an amide group [(RNHCOCH₂MIm)Br] in the alkyl chain lowers the cmc when compared to a cationic surfactant without functional group, [(RMIm)Br]. The synthesized surfactants were also assayed for antimicrobial activities and found to possess good activities against selected strains.     

Comparison of the Effects of an Ionic Liquid and Other Salts on the Properties of Electrospun Fibers, 2 – Poly(vinyl alcohol)

Understanding the effect of conductivity in electrospinning solutions is crucial in order to improve or control the electrospinning process. In this paper the effect of adding small amounts (0.039–0.259 mol · kg^?1) of three different conductive additives to aqueous solutions of polyvinyl alcohol has been investigated. The salts were HMICl (a room temperature ionic liquid), TEBAC (a quaternary ammonium salt) and KCl. Addition of these salts caused a steady increase in the solution conductivity but the fiber diameter was typically greater than that of PVA alone, and exhibited an oscillatory trend. The oscillatory trend on the fiber diameter is attributed to fiber backbuilding and fusion that occurs prior to deposition on the collector.

     

Synthesis and properties of water soluble single‐walled carbon nanotube graft ionic polyacetylene nanocomposites

Water‐soluble single‐walled carbon nanotube‐polyacetylene [SWNT‐PA, SWNT‐P(2EPy‐MeTf)] nanocomposites have been synthesized by using the surface initiated “grafting‐from” method. The FT‐IR spectra confirmed the formation of an amide bond between the functionalized SWNTs and the initiator, 4‐(2‐Aminoethyl) pyridine, to polymerize N‐Methyl‐2‐ethynlypyridinium triflate (2EPy‐MeTf). UV‐vis spectroscopy indicated that the degree of polymerization of P(2EPy‐MeTf) in the SWNT‐polyacetylene composites is 15, based on the Lewis‐Calvin equation. The SWNT‐polyacetylene composites have been characterized by TGA, AFM, and TEM. From TGA analysis, the loading of SWNTs in the SWNT grafted ionic polyacetylenes is estimated to be 22%. AFM and TEM images clearly showed that the nanotube is wrapped with the PA. The SWNT‐polyacetylene composites displayed high water solubility (8 mg/ml). The room temperature electrical conductivity of the doped SWNT‐polyacetylene composites was found to be in the range of 10⁻³ to 10⁻⁴ S/cm, an order of magnitude of increase over neat P(2EPy‐MeTf) and a two order of magnitude increase over Dendrimer‐polyacetylen composites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Comparative study of allelopathy as exhibited byProsopis Juliflora swartz andProsopis cineraria (L) druce

The allelopathic effects ofProsopis juliflora were studied both in the laboratory and in nature and compared with that ofProsopis cineraria to understand the chemical nature of allelochemics. Both species occupy the same habitats butP. cineraria does not appear to have any toxic effect on other plants under its canopy.P. juliflora is highly allelopathic and does not allow the growth of any other species. Leaf extracts and leaf leachates ofP. juliflora were inhibitory. Decaying leaves were also inhibitory at early stages of decomposition. Live roots were not found to be inhibitory in cogermination and interplanting of seeds. Chemical investigation of the extracts showed the allelopathic compounds to be phenolic in nature in both the species. Slow decomposition and heavy accumulation of leaf litter belowP. juliflora may possibly result in accumulation of toxic substances in soil layers, inhibiting growth of other species.     

Electrochemical membrane reactor: Synthesis of quaternary ammonium hydroxide from its halide by in situ ion substitution

Electrochemical membrane reactors (EMRs) with two compartments (EMR-2: anion-exchange membrane (AEM) separated catholyte and anolyte) and three compartments (EMR-3: three compartments separated by two AEMs to avoid contact between the product and the electrodes) were developed for the synthesis of tetrabutylammonium hydroxide (TBAOH) from tetrabutylammonium bromide (TBABr) by in situ ion substitution. In house prepared AEM with good physicochemical, electrochemical properties and excellent stabilities was used. Schematic diagrams are presented for the possible synthesis of TBAOH from TBABr by in situ ion substitution in EMR-2 and EMR-3. Synthesis of TBAOH using EMR-2 and EMR-3 was achieved under different experimental conditions and process parameters (rate of synthesis, current efficiency (CE) and energy consumption) were estimated. In EMR-2, relatively slow synthesis of TBAOH with low recovery was explained due to Hofmann elimination of TBAOH in contact with the electrode. While in EMR-3, relatively faster rate of TBAOH synthesis with its high recovery and current efficiency indicated practical application of the developed process for the efficient synthesis of TBAOH without the use of any additives or reagents.