First-principles DFT study of SO2 and SO3 adsorption on 2PANI: a model for polyaniline response

Interaction of SO_x (x?=?2,3) molecules on active sites of dianiline (as a model for polyaniline, denoted here as 2PANI) was studied using density functional theory at the BLYP-D/6-31+G(d) level of theory. Natural population analysis was used to find out the charge distribution as well as the net transferred charge of SO_x upon adsorption on 2PANI and the result has been compared with Mulliken charge analysis to evaluate the sensing ability of 2PANI. The computed density of states point to the remarkable orbital hybridization between SO_x and 2PANI during the adsorption process. As a consequence, the results of UV–VIS confirm the sensing ability of 2PANI toward SO₂ and SO₃. Based on our results, it can be found that at proper configuration the SO₂ and SO₃ molecules can be adsorbed on 2PANI with adsorption energies (E_ads) of ?18.2 and ?62.9?kJ/mol (BSSE), respectively.     

Extraction of caffeine and catechins using microwave-assisted and ultrasonic extraction from green tea leaves: an optimization study by the IV-optimal design

In this research, optimal conditions for extraction of caffeine and polyphenols were established from Iranian green tea leaves. In the first step, caffeine was extracted with efficacy about 86% versed to 4.5% of EGC + EGCG. The EGCG + EGC was extracted from partially decaffeinated green tea leaves through microwave-assisted extraction (MAE) and ultrasound-assisted extraction (USE) with efficiency levels of 95 and 85%, respectively. The best results for the MAE process were obtained with 7.8 min and three number of extraction cycles and for the USE process were as followed: time 57 min, temperature 65 °C, and the number of extraction cycles 3. The total phenol content values at the best conditions of MAE and the USE processes were 125 ± 5 and 96 ± 6 mg gallic acid/g DW. The 50% inhibition (IC₅₀) on 1,1-diphenyl-2-picrylhydrazyl (DPPH) were 56 and 66 mg/g of phenol for the MAE and USE processes.     

A statistical tolerance analysis approach for over-constrained mechanism based on optimization and Monte Carlo simulation

Tolerancing decisions can profoundly impact the quality and cost of the mechanism. To evaluate the impact of tolerance on mechanism quality, designers need to simulate the influences of tolerances with respect to the functional requirements. This paper proposes a mathematical formulation of tolerance analysis which integrates the notion of quantifier: “For allacceptable deviations (deviations which are inside tolerances),there existsa gap configurationsuch asthe assembly requirements and the behavior constraints are verified” & “For allacceptable deviations (deviations which are inside tolerances), andfor alladmissible gap configurations, the assembly and functional requirements and the behavior constraints are verified”. The quantifiers provide a univocal expression of the condition corresponding to a geometrical product requirement. This opens a wide area for research in tolerance analysis. To solve the mechanical problem, an approach based on optimization is proposed. Monte Carlo simulation is implemented for the statistical analysis. The proposed approach is tested on an over-constrained mechanism.     

Natural Palm Olein Polyol as a Replacement for Polyether Polyols in Viscoelastic Polyurethane Foam

The impact of replacing three polyether polyols with different levels of a single palm olein‐based natural oil polyol (NOP) was systematically correlated with the changes in foaming reactivity, cell structure, physico‐mechanical properties, and morphology of viscoelastic (VE) foams. The data show that replacing the polyether polyols with the NOP slightly increased the rate of the foaming reactivity. Increasing the NOP content resulted in increased cell size and cells remained fully open. Increased NOP content contributed to higher load bearing properties of VE foam, which can be attributed to higher functionality of NOP compared to polyether polyols. Addition of the NOP slightly increased the resilience of the foams, however, the hysteresis which is the measure of energy absorption remained mostly unaffected. Age properties, characterized by dry and humid compression sets, were mostly unaffected by the replacement of the polyether polyol with the NOP. The addition of NOP did not impact the morphology of the VE foam polymer matrix, which appears to retain a low degree of hard and soft segment domain separation. Overall, the results demonstrate a feasibility that the NOP can be used to partially replace the polyether polyols in VE polyurethane foams without significant impact on the functional performance.     

Urethane‐forming reaction kinetics and catalysis of model palm olein polyols: Quantified impact of primary and secondary hydroxyls

Model palm olein natural oil polyols (NOPs) with varying ratios of primary to secondary hydroxyls were synthesized, characterized, and evaluated in reaction kinetics study with isocyanate in formation of polyurethanes. Reaction rate constants and activation energies associated with primary and secondary hydroxyls of NOPs were quantified. The kinetic study in toluene shows that the NOP containing primary hydroxyls have three times higher reaction rate constants in noncatalyzed reaction with 4,4′‐diphenylmethane diisocyanate (4,4′‐MDI) compared to the model NOP containing only secondary hydroxyls, which is associated with higher activation energy of secondary hydroxyls. However, the difference in reaction rate constants of primary and secondary hydroxyls in NOPs diminished in the reactions catalyzed with dibutyltin dilaurate. Bulk polymerization reaction confirms the kinetics results in toluene, showing that the model NOP containing primary hydroxyls reached gel time at a faster rate. Evaluation of elastomers from bulk polymerization shows low degree of phase separation of hard and soft segments for elastomers based on the model NOPs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42955.     

The morphology and gas‐separation performance of membranes comprising multiwalled carbon nanotubes/polysulfone–Kapton

The development of desirable chemical structures and properties in nanocomposite membranes involve steps that need to be carefully designed and controlled. This study investigates the effect of adding multiwalled nanotubes (MWNT) on a Kapton–polysulfone composite membrane on the separation of various gas pairs. Data from Fourier transform infrared spectroscopy and scanning electron microscopy confirm that some studies on the Kapton–polysulfone blends are miscible on the molecular level. In fact, the results indicate that the chemical structure of the blend components, the Kapton–polysulfone blend compositions, and the carbon nanotubes play important roles in the transport properties of the resulting membranes. The results of gas permeability tests for the synthesized membranes specify that using a higher percentage of polysulfone (PSF) in blends resulted in membranes with higher ideal selectivity and permeability. Although the addition of nanotubes can increase the permeability of gases, it decreases gas pair selectivity. Furthermore, these outcomes suggest that Kapton–PSF membranes with higher PSF are special candidates for CO₂/CH₄ separation compared to CO₂/N₂ and O₂/N₂ separation. High CH₄, CO₂, N₂, and O₂ permeabilities of 0.35, 6.2, 0.34, and 1.15 bar, respectively, are obtained for the developed Kapton–PSF membranes (25/75%) with the highest percentage of carbon nanotubes (8%), whose values are the highest among all the resultant membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43839.     

Identification of cell‐nucleation mechanism in foam injection molding with gas‐counter pressure via mold visualization

The mechanisms of cell nucleation and growth are investigated in foam injection molding (FIM) using gas‐counter pressure (GCP). An in‐situ mold visualization technique is employed. The application of GCP suppresses cell nucleation, and prevents the blowing agent from escaping during mold‐filling. The inherent structural heterogeneity in the regular FIM can be improved because of the uniform cavity pressure when employing GCP. The cavity pressure profiles show much faster pressure‐drop rates using GCP, because the single‐phase polymer/gas mixture has a lower compressibility than the two‐phase polymer/bubble mixture. Therefore, both the cell nucleation and growth rates are significantly increased through a higher pressure‐drop rate on the removal of the GCP. The effect of GCP magnitude on the cell morphology is explored. When the GCP is lower than the solubility pressure, bimodal foaming occurs. As the GCP increases above the solubility pressure, the cell density increases because of the higher pressure‐drop rate. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4035–4046, 2016     

Electro-osmosis treatment techniques and their effect on dewatering of soils,sediments, and sludge: A review

Electro-osmosis is an established method of dewatering fine soils, sediments, and sludge (SSS). The efficiency of electro-osmotic treatment is controlled by the electrical resistance of the system. Due to an increase in SSS resistance during treatment, its cost efficiency is reduced, limiting the widespread use of this technique. The aim of this paper is to discuss the main reasons for the increase in SSS resistance during treatment and then to analyze the most recent and widely spread modifications to classical electro-osmotic treatment that attempt to combat these issues and improve the efficiency of the technique. These modifications to electro-osmotic treatment are polarity reversal, an intermittent current, the injection of chemical solutions at the electrodes, and the use of geo-synthetics. The paper discusses the relevant research on the above adaptations, and the advantages and disadvantages of each are evaluated and compared using the available laboratory and field tests in the literature on electro-osmotic dewatering research. All four methods of modification are shown to provide significant improvements and can be successfully translated to the field for greater use. However, the improvements they bring about may not be sufficient to warrant their general use in geotechnical applications.     

Synthesis of modified catalyst and stabilization of CuO/NH4‐ZSM‐5 for conversion of methanol to gasoline

In this article, the catalytic conversion of methanol to gasoline range hydrocarbons has been studied over CuO/ NH₄‐ZSM‐5(3,5,7,9%) catalysts prepared via sono‐chemistry methods. In order to improve, copper oxide can be used as a booster on NH₄‐ZSM‐5 this catalyst property. Accordingly, the conversion process of Methanol to Gasoline (MTG) was conducted under a pressure of 1 atm and temperature of 400°C by a fixed‐bed reactor on copper oxide catalysts which were prepared based on synthetic NH₄‐ZSM‐5. The synthetic catalyst was investigated by such analyses as BET, XRD, FT‐IR, and SEM. Formation of copper oxide phase and proper distribution of copper oxide were proven on the basic level of using XRD analysis. BET analysis showed the reduction in catalyst level and SEM images depicted the proper distribution of particles. The present investigation is to study the effect of CuO loading on NH4‐ZSM‐5 support for conversion of methanol to gasoline range hydrocarbons. A series of CuO/ NH4‐ZSM‐5 catalysts were prepared, characterized, and experimented for their performance on methanol conversion and hydrocarbon yield.     

Novel conductive magnetic nanocomposite based on poly (indole-co-thiophene) as a hemoglobin diagnostic biosensor: Synthesis,characterization and physical properties

The novel conductive nanocomposite has been successfully prepared by emulsion polymerization. First, magnetite nanoparticles were synthesized via coprecipitation reaction. Then, poly (indole-co-thiophene)@Fe₃O₄ nanocomposite was prepared via emulsion copolymerization of indole and thiophene monomers using sodium dodecyl sulfate as an emulsifier and ammonium persulfate as an oxidant in the presence of Fe₃O₄ nanoparticles. Characterization of the synthesized copolymer, Poly (In-co-T), and its magnetic nanocomposite were studied by Fourier transform infrared spectra, X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis, differential scanning calorimetric, UV-vis spectrophotometer, and vibrating sample magnetometer. Also, the electrical conductivity of copolymer and nanocomposite were determined by four-probe instrument. Results showed a synergic effect in thermal stability by good interaction between polymer chain and magnetic nanoparticles. The conductivity of the nanocomposite was higher than bare copolymer, and increase of nanoparticles content caused an increment in the conductivity of the nanocomposites. The applicable properties of proposed conductive nanocomposite as a base at electrochemical biosensing have been investigated.