Electrochemical studies of pyrite oxidation and reduction using freshly-fractured electrodes and rotating ring-disc electrodes

Oxidation and reduction processes on coal- and mineral-pyrite surfaces have been investigated to better understand the reactions that control the hydrophobicity and flotation behavior of pyrite. The incipient oxidation and reduction reactions were studied using fresh surfaces of pyrite that were created by in situ fracturing electrodes potentiostated at a predetermined potential. Chronoamperometry immediately after fracture and subsequent cyclic voltammetry have established that fresh fracture surfaces of pyrite instantaneously assume a unique potential (referred to as the “stable” potential) at which neither oxidation nor reduction takes place. For Peruvian and Chinese pyrites, the stable potential is −0.28 V (standard hydrogen electrode, SHE) at pH 9.2 and 0 V at pH 4.6. The initial oxidation of pyrite begins at potentials slightly positive of the stable potential and is believed to produce a hydrophobic sulfur-rich species, most likely a polysulfide or metal-deficient sulfide. A rotating ring-disc electrode (RRDE) was employed to study the kinetics and mechanisms of surface reactions on pyrite over moderate potential ranges. Two distinct soluble reduction products (ferrous hydroxide and HS⁻) and one distinct soluble oxidation product (ferrous hydroxide) were observed on pyrite in alkaline solutions. It is concluded that the initial oxidation of pyrite and the oxidation of ferrous to ferric hydroxide occur in a similar potential range. When the electrode is oxidized, e.g. by polishing, prior to experiments, the initial oxidation of pyrite is masked by the oxidation of ferrous hydroxide, making it difficult to study the oxidation of pyrite itself.     

Syntheses of new black dyes for ink-jet inks

Drop-on-demand ink-jet inks made from dyes generally show poor light and wet fastness. A number of studies have been carried out previously to improve the fastness of such inks by introducing novel dyes and new additives. Based on the research results, use of fast dyes could give ink-jet inks with good properties. This study describes new black dyes for aqueous ink-jet inks, which show better light and wet fastness and print quality, compared to an analogous ink formulated from CI Food Black 2.     

Temperature-dependent transparency of poly(HPMA-co-DMA) hydrogels: effect of synthesis parameters

The acrylic comonomers hydroxypropyl methacrylate (HPMA) and N,N-dimethylaminoethyl methacrylate (DMA) have been used in several earlier studies to produce pH-responsive hydrogels. However, these same monomers can also be used to prepare hydrogels that are highly responsive to temperature. One manifestation of this temperature sensitivity is a sharp decrease in hydrogel optical transparency that occurs when the temperature exceeds a critical transition value. For example, a hydrogel that exhibits a swelling transition at the physiological pH value of 7.4 has a transition temperature of about 45 °C when the environmental salt concentration is 0.15 M. The value of the transparency transition temperature is shown to depend on hydrogel synthesis parameters such as comonomer mole ratio, crosslinker mole ratio, and even initiator concentration. By reducing the mole ratio of the crosslinker tetraethylene glycol dimethacrylate (TEGDMA), the transition temperature can be lowered by as much as 15 °C. Environmental salt concentration and solvent polarity are also shown to influence the transition temperature.     

Effect of polycyclopentene on crystallization of isotactic polypropylene

The application of some polymers as nucleating agents for polypropylene has been examined. Among various polymeric nucleating agents, polycyclopentene was found to be a superior nucleating agent to typical organic nucleating agents. When polycyclopentene was added to polypropylene, the crystallization temperature and the degree of crystallinity of polypropylene increased. In addition, the crystallization rate and the number of spherulites increased whereas the size of spherulites decreased remarkably. As a result of polycyclopentene addition, the transparency of polypropylene film could be improved considerably. © 1994 John Wiley & Sons, Inc.     

Comparison of YAG: Eu phosphors synthesized by supercritical water in batch and continuous reactors

Luminescent yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) nanoparticles doped with Eu (10 at%) were synthesized in batch-type and continuous-type supercritical water (SCW) reactors. In the case of the continuous-type SCW method, the particles of YAG: Eu phosphors were much smaller and demonstrated a uniform spherical-like shape. Inversely, in the case of the batch-type SCW method, a needle-like or elliptical-like shape was formed because a finite amount of time was required to reach SCW conditions from ambient conditions. However, the emission intensity of YAG: Eu phosphors synthesized by using the batch-type SCW method was stronger. Therefore, it is concluded that the continuous-type SCW method is superior to the batch-type SCW method from the viewpoint of the particle size and shape, but the luminescence property of phosphors in the continuous-type SCW method needs to be improved. In addition, a calcination process slightly improved the luminescence intensities of YAG: Eu phosphors generated by using either the batch-type or continuous-type SCW methods.     

Synthesis of biodegradable PU/PEGDA IPNs having micro-separated morphology for enhanced blood compatibility

Summary New biodegradable hydrophobic polyurethane (PU)/hydrophilic poly (ethylene glycol) diacrylate (PEGDA) IPN was simultaneously synthesized with changing the molecular weight of PEGDA to investigate the effect of crosslinking density on the degree of phase separation. PU was modified using biodegradable poly(-caprolactone)diol and the hydroxy group of PEG was substituted to crosslinkable acrylate group having double bond, which induce photo-polymerization. The sturucture of PEGDA was confirmed by NMR. Because the reaction rate of PEGDA was faster than that of PU, the continuous matrix of the micro-separated PU/PEGDA IPNs having amphiphilic character was made of hydrophilic PEGDA-rich phase. All IPNs have sea-island morphology resulting from the suppressed phase separation. The effect of the degree of phase separation on blood compatibility was investigated.     

Selective conversion of propane to propene by the catalytic oxidative dehydrogenation over cobalt and magnesium molybdates

Catalytic performances of various metal molybdates were tested in the oxidative dehydrogenation of propane to propene with molecular oxygen under an atmospheric pressure. Most of the molybdates tested promoted the selective oxidative conversion of propane to propene and among them cobalt and magnesium molybdates were found highest in the activity and selectivity. It was also found that their catalytic activities were highly sensitive to the catalyst composition, and it turned out that Co_0.95MoO _x and Mg_0.95MoO _x catalysts which have slightly excess molybdenum showed the highest activity in the oxidative dehydrogenation of propane. Under the optimized reaction conditions, higher reaction temperatures and lower partial pressures of oxygen, these catalysts gave 60% selectivity to propene at 20% conversion of propane. Since the molybdates having the surface enriched with molybdenum oxide tended to show high activity for the propane oxidation, surface molybdenum oxide clusters supported on metal molybdate matrix seem to be the active sites for the selective oxidative dehydrogenation of propane.     

Synthesis and non‐isothermal crystallization behavior of poly(ethylene phthalate‐co‐terephthalate)s

A series of poly(ethylene phthalate‐co‐terephthalate)s were synthesized by melt polycondensation of ethylene glycol (EG) with dimethyl phthalate (DMP) and dimethyl terephthalate (DMT) in various proportions. The DMT‐rich polymers were obtained with reasonably high molecular weights, whereas the DMP‐rich polymers were synthesized with relatively low molecular weights due to steric effects associated with the highly kinked DMP monomer. The compositions and thermal properties of the polymers were determined. The copolymers containing DMP in amounts of ≤ 21 mol% were crystallizable, whereas the other polymers were not. All the polymers exhibited a single glass transition temperature. Analysis of the measured glass transition temperatures and crystal melting temperatures confirmed that the DMT‐rich copolymers are random copolymers. The non‐isothermal crystallization behaviors of the DMT‐rich copolymers were investigated by calorimetry and modified Avrami analysis. The Avrami exponents n were found to range from 2.7 to 3.8, suggesting that the copolymers crystallize via a heterogeneous nucleation and spherulitic growth mechanism; that is, the incorporation of DMP units as the minor component does not change the growth mechanism of the copolymers. In addition, the activation energies of the crystallizations of the copolymers were determined; the copolymers were found to have higher activation energies than the PET homopolymer. Polym. Eng. Sci. 44:1682–1691, 2004. © 2004 Society of Plastics Engineers.     

Preparation and swelling behavior of biodegradable hydrogels based on α,β‐poly(N‐2‐hydroxyethyl‐DL‐aspartamide)

Biodegradable polymers and the hydrogels have been increasingly applied in a variety of biomedical fields and pharmaceutics. α,β‐Poly(N‐2‐hydroxyethyl‐DL ‐aspartamide), PHEA, one of poly(amino acid)s with hydroxyethyl pendants, are known to be biodegradable and biocompatible, and has been studied as an useful biomaterial, especially for drug delivery, via appropriate structural modification. In this work, hydrogels based on PHEA were prepared by two‐step reaction, that is, the crosslinking of polysuccinimide, the precursor polymer, with oligomeric PEG or PEI‐diamines and the following nucleophilic ring‐opening reaction by ethanolamine. Soft hydrogels possessing varying degrees of gel strength could be prepared easily, depending on the amount of different crosslinking reagents. The swelling degrees, which were in the range of 10–40 g–water/dry gel, increased somewhat at higher temperature, and also at alkaline pH of aqueous solution. A typical hydrogel remained almost unchanged for 1 week, at 37°C in phosphate buffer of pH 7.4, and then seemed to degrade slowly as time. A porous scaffold could be fabricated by the freeze drying of water‐swollen gel. The PHEA‐based hydrogels have potential for useful biomaterial applications including current drug delivery system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3741–3746, 2003     

Oxidative coupling of methane over Na+-ZrO2-C1-/Al2O3 catalysts

Oxidative coupling of methane (OCM) was carried out over Na⁺-ZrO₂-Cl /A1[₂O₃ catalysts in a temperature range from 1023 to 1123 K. The catalysts were prepared by impregnating the α- or γ-Al₂O₃ supports with sodium carbonate and/or zirconyl chloride. The OCM activity was examined using the catalysts prepared by three different preparation procedures. The best catalyst was the one prepared by subsequent impregnation of sodium carbonate-preimpregnated γ-Al₂O₃ with a mixed solution of sodium carbonate and zirconyl chloride. It was found that preimpregnated sodium played an important role in reducing the combustion activity of the γ-Al₂O₃. The catalyst with an optimal composition showed the highest C₂ selectivity and yield of 40.8% and 15.1%, respectively. From the X-ray diffraction analysis it was found that tetragonal ZrO₂ was formed and that NaCl existed in the catalysts with relatively high sodium contents.