Evolution of vinyl chloride conversion below critical micelle concentration: A response surface analysis

Utilizing response surface methodology, the conversion of vinyl chloride monomer (VCM) was monitored when the polymerization temperature, the type of surfactant, and the weight ratio of water‐to‐monomer (W/M) were taken as the emulsion polymerization variables. Because the homogeneous nucleation was found to be the dominant mechanism in VCM emulsion polymerization, irrespective of the surfactant concentration, the whole experiments have been carried out below critical micelle concentration of the used surfactants. Among all the studied variables, the polymerization temperature appeared as the most effective parameter; moreover, its interactive effect with W/M caused different trends in the alteration of final conversion being observed. Also, depending on the reaction temperature, the VCM conversion would be affected by the type of the surfactant used. Contrarily, simultaneous change in the type of surfactant and W/M revealed an insignificant effect on the evolution of VCM conversion. The optimization of final conversion of VCM was also accessible through contour plots of response surface methodology. It is worth noting that, taking a conventional approach into consideration, the alteration of VCM conversion seemed to be a monotonic function of temperature. J. VINYL ADDIT. TECHNOL., 21:157–165, 2015. © 2014 Society of Plastics Engineers     

Synthesis,Characterization, and Bioactivity Evaluation of Amorphous and Crystallized 58S Bioglass Nanopowders

The aim of this work was synthesis and characterization of amorphous and crystallized 58S nanopowders produced via sol‐gel method. According to the thermal analysis, the nanopowders were heat‐treated at 600°C and 1100°C. X‐ray diffraction results revealed that the phases of Wollastonite and tricalcium phosphate were formed at 1100°C. The in vitro tests showed that hydroxyl carbonate apatite was precipitated on both crystallized and amorphous nanopowders, while amorphous nanopowder showed a higher bioactivity than that of crystallized nanopowder. In contrast, mechanical properties of crystallized specimen were higher than those of amorphous specimen.     

Effect of different modified nanoclays on the kinetics of preparation and properties of polymer-based nanocomposites

Polymer-clay nanocomposites have been prepared by free radical and RAFT polymerizations. To investigate the effects of nanoclay content and its modification system on the kinetics of polymerization, two different commercial grades of clay including Na-MMT and Cloisite 30B have been used and a method has been developed for further modification of Na-MMT with two commercial modifiers containing either a long organic chain or a vinyl group. Also, kinetics of free radical and RAFT polymerizations of both styrene and methyl methacrylate in the presence of these nanoclays was studied. Morphology of the nanocomposites has been studied by XRD and the results have been assessed with TEM observations. Exfoliated structure was obtained for the nanocomposites with 1?wt.% of vinyl-containing clays. Thermogravimetric behavior of the nanocomposites has been studied by TGA. Incorporation of clays has resulted in an evident increase in thermal stability of both polymers.     

Microwave Synthesis and Characterization of Spinel-type Zinc Aluminate Nanoparticles

In the present work, ZnAl₂O₄ nanoparticles have been synthesized with the aid of Zn(OAc)₂·2H₂O and Al(NO₃)₃·9H₂O as starting reagents in the presence of microwave irradiation. Besides, the effect of preparation parameters such as microwave power and irradiation time on the morphology and particle size of products was studied by SEM images. The as-prepared ZnAl₂O₄ nanoparticles were characterized extensively by techniques like XRD, TEM, SEM, FT-IR, PL, and EDS. Photoluminescence studies of the ZnAl₂O₄ nanoparticles displayed quantum confinement behavior with band gap of 3.2 eV. The XRD studies showed that pure orthorhombic ZnAl₂O₄ nanoparticles have been produced after calcination.     

Crystallization conditions effect on molecular weight of solid-state polymerized poly(ethylene terephthalate)

Number-average molecular weight ( $ \overline{M}_{n} $ ) variation of polyethylene terephthalate with respect to crystallization temperature and time, and solid-state polymerization (SSP) time were studied using response surface experimental design method. All experiments were conducted in a fluidized bed reactor. $ \overline{M}_{n} $ values were calculated by Mark?CHouwink equation upon determining intrinsic viscosity (IV) of samples. Two suitable models were proposed for $ \overline{M}_{n} $ and IV, based on the regression coefficient. It was observed that $ \overline{M}_{n} $ increases with decrease in crystallization temperature and increase in crystallization time and SSP time. It was shown that SSP time is the most important parameter based on statistical calculations. Crystallization time, crystallization temperature and SSP time were determined 60?min, 160?°C and 8?h, respectively, in order to achieve maximum $ \overline{M}_{n} $ . Density measurements were applied to study the overall crystallinity of samples. Based on density results it was revealed that percent of crystallinity is not the only factor that affects the $ \overline{M}_{n} $ of polymer. Differential scanning calorimeter was used to analyze thermal properties of the samples. All samples showed two melting peaks. It was observed that the lower melting temperature peak is related to the isothermal crystallization process temperature. Polarized light microscopy was used to study spherulitic structures of polymer films after crystallization process. It was shown that the sample with smallest spherulite size had the maximum $ \overline{M}_{n} $ equal to 26,000?g/mol.     

Thermal degradation behavior and kinetic studies of polyacrylamide gel in TiO2 nanoparticles synthesis

Polyacrylamide gel (PAMG) method is a simple, fast and cheap method used for the synthesis of a wide variety of nanopowders. However, no adequate results have been reported on the thermal degradation behavior of PAMG which can be very effective on the final product properties. In this work, thermal degradation behavior of PAMG in the presence of TiCl₄ as a precursor salt for synthesis of TiO₂ nanoparticles was examined in comparison with linear polyacrylamide (LPAM) and pure PAMG by thermogravimetry/differential thermal analysis. Their thermal degradation kinetics was investigated, as well. The results showed that thermal degradation of all samples occurred in two stages at different onset temperatures. Despite the high thermal stability of pure PAMG compared to LPAM, the presence of TiCl₄ as a mineral material in PAMG structure decreases the thermal degradation onset temperature, considerably. Furthermore for LPAM and PAMG, majority of weight loss occurs in the second stage, but in PAMG with TiCl₄ the weight loss occurs mainly at the first stage. For more detailed investigation, residual materials were characterized by Fourier transform infrared spectroscopy and X-ray diffraction (XRD) techniques, attributing this trend to the presence of mineral materials in PAMG structure. XRD and transmission electron microscopy were also applied to confirm anatase crystalline structure and nanoscale distribution of the TiO₂ particles synthesized via PAMG method.     

A study on the properties of PMMA/silica nanocomposites prepared via RAFT polymerization

A number of batch polymerizations were performed to study the effect of pristine nanoparticle loading on the properties of PMMA/silica nanocomposites prepared via RAFT polymerization. In order to improve the dispersion of silica nanoparticles in PMMA matrix, the silanol groups of the silica are functionalized with methyl methacrylate groups and modified nanoparticles were used to synthesize PMMA/modified silica nanocomposites via RAFT polymerization. Prepared samples were characterized by thermogravimetric analysis (TGA), dynamic light scattering (DLS), dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). According to results, introduction of modified nanoparticles results in better thermal and mechanical properties than those of pristine nanoparticles. Also, surface modification and increasing silica nanoparticles result in variation of thermal degradation behavior of nanocomposites. The best improvement of mechanical and thermophysical properties is achieved for nanocomposites containing 7 wt. % silica nanoparticles.     

Electrocatalytic oxidation of methanol on the nickel–cobalt modified glassy carbon electrode in alkaline medium

In this work, Ni–Co alloy coating on the surface of glassy carbon (GC) electrode was performed by cyclic voltammetry. The results showed that the deposition of Ni–Co is an anomalous process. The deposition bath was prepared according to the metal ion Ni/Co ratio of 4:1 using NiSO₄·7H₂O and CoSO₄·8H₂O, and the total concentration of all solutions was 40.0 mM. The pH of the bath solution was adjusted at 2.0 using boric acid at room temperature. The modified electrode was conditioned by potential recycling in a potential range of 100–700 mV (vs. Ag/AgCl) by cyclic voltammetric method in an alkaline solution. The Ni–Co modified electrode showed a higher activity towards methanol oxidation in the Ni (III) and Co (IV) oxidation states. Cyclic voltammetry was used for the electrochemical characterization of the Ni–Co modified electrode and the mechanism of methanol oxidation is proposed. The result of double steps chronoamperometry shows that the methanol electrooxidation is an irreversible reaction. Moreover, the effects of various parameters such as mole ratio of Ni–Co in the alloy in modification step, potential scan rate, methanol concentration and solution temperature on the electro-oxidation of methanol have also been investigated.     

Highly efficient supported AlCl3-based cationic catalysts to produce polyα-olefin oil base stocks

The main aim of this research is to decrease the amount of AlCl₃ content that is very corrosive and hazardous in the catalytic system, required for the α-olefin oligomerization without substantial change of final oil features. This was successfully achieved by supporting AlCl₃ on different carriers. More precisely, a series of supported bimetallic catalysts was synthesized by immobilization of AlCl₃ and TiCl₄ onto Al₂O₃, SiO₂, and mixed supports, that is, Al₂O₃/FeCl₃ and SiO₂/FeCl₃. It was found that silica and alumina-based catalysts had higher catalytic activities compared to support free AlCl₃; however, this enhancement for silica-based supports was more significant. According to gel permeation chromatography (GPC) results, the use of single supports, that is, Al₂O₃ and SiO₂, increased oligomer's molecular weight, while the application of mixed supports resulted in the decrease of molecular weight of the oligomers. Viscosity characteristics of the synthesized oligomers have also been studied at two different temperatures of 40 and 100°C (KV⁴⁰ and KV¹⁰⁰). The viscosity index (VI) values, derived from KV⁴⁰ and KV¹⁰⁰, of the prepared oligomers were in the range of 126–145. The molecular weight and termination mechanisms of the oligomers were studied by ¹H-NMR spectroscopy. The obtained results disclosed that the employed reaction conditions led to the production of oligomer chains with various structures including vinylidene (Vd), and di and three-substituted vinylene (2Vn, 3Vn) structures.