有机电沉积涂料的新动向

阴极电沉积涂料是 2 0世纪 70年代以来发展起来的一种新的涂装方法 ,具有挥发性有机物 (VOCs)和有害空气污染物(HAPs)含量低、防蚀能力强、漆膜质量好、涂料利用率高、适合涂装结构复杂的构件和设备等特点。介绍了近年来阴极电沉积涂料研发的新动向。它们主要集中在有机双层电涂和高分子 聚电解质 /低聚物电解质复合物多层电涂体系 ,这些新的电涂体系在涂料的稳定性以及涂层的物理化学性质和力学性能方面具有明显的改进。     

Rejection of endocrine disrupters contained in biologically treated sewage by nanofiltration

Two commercial nanofiltration membranes, NF-1 (low salt rejection) and NF-3 (medium salt rejection), were used for basic experiments on the rejection of endocrine disrupters of 17βestradiol,p-nonylphenol, bisphenol A and their mixed solution. Nanofiltration membrane experiments were carried out under low trans-membrane pressure of 0.5 MPa as the operating condition. For the two nanofiltration membranes, the rejection factor was high when the pH of each feed solution was not adjusted. Based on the results of the nanofiltration membrane experiments, four commercial nanofiltration membranes-NF-1, NF-2 (medium salt rejection), NF-3 and NF-4 (high salt rejection)-were used for the rejection of endocrine disrupters contained in biologically treated sewage. The biologically treated sewage concentration of 0.039–0.055 μg/Las 17Βestradiol equivalent was reduced by each nanofiltration membrane to 0.026 μg/ L(NF-1), 0.025 μg/L(NF-2), 0.003 μg/L(NF-3) and 0.009 μg/L(NF-4), as 17βestradiol equivalent, respectively. The rejection efficiency of endocrine disrupters showed the same tendency as the TOC rejection efficiency. The permeate flux of nanofiltration membranes was high in the order of NF-1, NF-3, NF-2 and NF-4.     

Low VOC, low viscosity UV cationic radiation-cured ink-jet ink system

Ink-jet inks need to be very low in viscosity to transport the ink through the jet nozzle as well as for drop formation and integrity. The objective of this project was to demonstrate UV-cured systems for ink-jet inks and coatings with zero volatile organic compounds and very low viscosity. Cycloaliphatic epoxy systems were selected as binders of choice for this project due to their low viscosity and ability to be cured using UV-cationic photoinitiators. UV-curable coatings and inks with zero VOC and less than 10 cPs viscosities were formulated using exempt solvent acetone and vinyl cyclohexene diepoxide. UV-curable inks with up to 10% black dye were formulated. Rapid cure was achieved through the use of aryl sulfonium salts of hexafluorophosphoric acid. The presence of dye inhibited the reaction, but adequate cure of dyed formulations was achieved by increasing the concentration of the photoinitiator. Coatings Research Institute, 430 W. Forest Avenue, Ypsilanti, MI 48197.     

高级氧化技术降解双酚A的研究进展

对高级氧化技术降解污水中一种内分泌干扰物双酚A（BPA）的作用机理和研究现状进行了综合评述。针对高级氧化技术中最重要的5种技术,即芬顿氧化及光-芬顿氧化、电化学氧化、光分解及光氧化、超声辐射和光催化氧化,详述了各种氧化技术的作用机理、降解效果以及影响因素等。还对这5种高级氧化技术今后可能的发展方向做了初步展望,鉴于各种高级氧化技术降解BPA的条件不同,通过合理设计多种高级氧化技术复合作用并建立优化模型,开发低能耗、高效率以及广泛适用于内分泌干扰物及持久性有机污染物的处理技术。     

Reformulation of fire retardant coatings

Fire retardant coatings currently in use contain a number of ingredients which are either considered to be ‘toxic’ heavy metals or on the hazardous air pollutants (HAPs) list. In addition, there is concern that the use of halogenated chemicals in these coatings and other products will be banned in the future. This paper contains the details of two reformulations programs. The first is a reformulation of a low volatile organic compound (VOC) chlorinated alkyd coating and the second is a reformulation of a chlorinated emulsion system. Both programs successfully reduced the heavy metals and lowered the HAPs to an acceptable level. Preliminary results of the development of non-halogenated fire retardant coatings systems will be presented.     

Porous Electrospun PES/PEG Ultrafine Fibers for the Removal of Endocrine Disruptors

In this work, porous polyethersulfone (PES)/polyethylene glycol (PEG) ultrafine fibers were prepared via electrospinning technique, and then were used to removing endocrine disrupters from their aqueous solutions. The surface and the internal structures of PES/PEG ultrafine fibers were characterized by scanning electron microscopy (SEM) and the result showed that they were both porous. The porous electrospun PES/PEG ultrafine fibers can remove endocrine disrupters such as biphenyl A (BPA) and biphenyl (BP) effectively. Compared with pure PES ultrafine fibers, PES/PEG ultrafine fibers showed larger adsorption capacity and faster kinetics of uptaking target species. The hydrophilic properties and the porosity of porous PES/PEG ultrafine fibers can be controlled by adding hydrophilic materials such as polyethylene glycol (PEG), which can improve the adsorption properties of porous PES/PEG ultrafine fibers significantly. The results showed that porous electrospun PES/PEG ultrafine fibers had the potential to be used in environmental application and water treatment.     

绿色环保溶剂在涂料工业中的应用与展望

介绍了国内外涂料行业关于VOC和HAPs控制排放现状,分析了丙二醇醚、酯类、碳酸二甲酯、DBE、生物溶剂、活性单体等绿色环保溶剂作为传统有毒有害溶剂替代产品在涂料工业中的应用进展。     

Current efficiency and kinetics of cobalt electrodeposition in acid chloride solutions. Part I: The influence of current density,pH and temperature

In the electrodeposition of cobalt in chloride electrolytes the evolution of hydrogen is a parasitic reaction. On a rotating platinum disc electrode the current efficiency was calculated as the charge used for anodic dissolution of cobalt at a potential where no other reactions were taking place, divided by the total cathodic charge used for cobalt deposition. The results show that the current efficiency could be measured accurately in this way. In part I the current efficiency and deposition potential are studied as a function of current density and pH. The results show an increase in current efficiency with increasing current density, pH and temperature. The results also indicate a change in the reaction mechanism for electrodeposition when the pH is changed.     

新型阴极电泳涂料的研究进展

概述了无铅型、低VOC型、UV固化型、薄层型、自分层型及边角耐蚀型等新型阴极电泳涂料的最新研究进展,指出新一代的阴极电泳涂料正向着环保、节能、低成本、高性能化方向发展.     

Theoretical studies of displacement deposition of nickel into porous silicon with ultrahigh aspect ratio

A model is developed to address the uniformity of displacement deposition of nickel inside porous silicon with an ultrahigh aspect ratio as high as 200. The nickel distribution is treated as a current distribution issue as in electrodeposition. It is shown that the deposition distribution along the pore depth exhibits a strong dependence on a polarization parameter ξ. High values of ξ correspond to mass transport limitations and lead to non-uniform distributions, whereas small ξ values, representing interfacial reaction control, produce uniform distributions. Non-uniform deposition primarily occurs at an initial stage in which the reaction is dominated by mass transfer. As the deposition process continues, the deposition rate drops to a low value, and the deposition uniformity shifts from Ni²⁺ mass transport limitations to its interfacial reaction control, leading to uniform Ni²⁺ concentration and deposition rate distributions. It is predicted that the non-uniformity at the initial stage could be remedied by increasing the bulk concentration of the nickel ions and decreasing the plating bath pH. In addition, the uniformity of the deposition distribution can be significantly improved by introducing inhibiting additive coumarin to the plating solution.     

分子内敏化鎓盐的合成及光敏性研究

二芳基碘鎓盐和三芳基硫鎓盐是阳离子聚合的光引发剂和光敏产酸物,但他们在300nm以上的光吸收很低,限制了对紫外光的利用效率。为解决此问题,本文合成了一些新的碘鎓盐和硫鎓盐,并用凝胶时间方法考察了它们的光引发效率。实验结果表明,2-苯硫基甲基,2′,4′-二甲基二苯碘鎓盐和9-蒽丙基,二苯基硫鎓盐具有特别高的光引发效率,这归之于光照时这些鎓盐发生了分子内电荷转移反应,即发生了分子内敏化。9-蒽丙基二苯硫鎓盐分子中的蒽基(An)是电子给体也是敏化基团,光照时可发生如下反应:     

Lead electrodeposition from very alkaline media

The electrodeposition of lead from very alkaline media has been studied by cyclic voltammetry, chronoamperometry under stationary and convective conditions. Experimental parameters like lead concentration and temperature have been varied. From NaOH 6 M the metal deposition takes place at about −0.90 V versus SCE far from the hydrogen evolution reaction (HER) which is seen at −1.30 V, but both processes are favoured by the lead content increase and the NaOH concentration decrease. The analyses of the chronoamperometric responses support the view of a 3D growth and suggest a substantial influence of lead concentration on the type of nucleation. Progressive nucleation is observed for the deposition from solutions with low content in lead but as this concentration increases a tendency towards instantaneous nucleation is revealed. The voltammetry with the rotating platinum disc electrode has confirmed that the lead electrodeposition is a mass transfer controlled process, and also allowed the estimation of diffusion coefficients.     

Reversible crosslinking in cellulose. VI. Formation of sulfonium derivatives by the reaction of cellulose β-mercaptoethylaminocarboxylate with methyl iodide

The reaction of methyl iodide with cellulose β-mercaptoethylaminocarboxylate (RDTC) made from cotton was investigated. The product was found to contain dimethyl sulfonium groups in addition to S-methyl groups, with accompanying hydrolytic cleavage of some of urethane linkages. The iodide counterions could be easily exchanged with hydroxide and chloride ions. The dyeabilty of RDTC and its sulfonium derivatives toward Direct Sky Blue A was studied. The equilibrium uptake of the dye by RDTC decreased with increasing sulfur content, while the uptake by the sulfonium derivatives was higher than that of control cotton and increased with increasing sulfonium content. The counterions did not affect the dyeability. The dye adsorbed onto the sulfonium derivatives was very fast against solvent extraction, and could be extracted only with Cadoxen containing 0.5% sodium hydroxide. The equilibrium uptake of the dye was much more than the amount calculated on basis of the 1 : 1 ionic bonding between the sulfonic acid group in the dye molecule and the sulfonium group in the modified cotton. The spatial effect in the dye–sulfonium bonding is discussed.     

Electrodeposition of zinc-cobalt alloy from a complexing alkaline glycinate bath

The influence of cobalt on the electrodeposition of zinc onto AISI 1018 steel was studied in weakly alkaline glycine solutions. Thermodynamic calculations were performed to construct predominance-zone diagrams to identify the stability of the zinc and cobalt glycine complexes, and experimental studies of electrochemical behavior and deposit properties were conducted. When zinc is present, cobalt deposition shifts to more negative potentials, producing ZnCo alloys. Two main reduction steps were observed for electrodeposition from the ZnCo bath: the first at low potentials was due to ZnCo electrodeposition. In the second, at more negative potentials, cobalt content in the deposit increased forming a range of intermediate phases, and the hydrogen-evolution reaction became significant. The presence of Co(II) in the bath modified the morphology of the deposits as well as reducing the faradaic metal-deposition efficiency. ZnCo-deposit morphology was modified by the applied current density as well as the metal composition of the coating. X-ray diffraction studies revealed that cobalt oxide or hydroxide is formed during ZnCo electrodeposition, indicating that an elevation of the interfacial pH plays a role in the alloy deposition process.     

On the specificity of allene oxide cyclase

Jasmonic acid is a carbocyclic fatty acid that is biosynthesized from α-linolenic acid in several steps. The formation of the ring structure of jasmonic acid is catalyzed by the enzyme allene oxide cyclase (EC 5.3.99.6) and involves the cyclization of an unstable allene oxide into the cyclopentenone 12-oxo-10,15(Z)-phytodienoic acid. In this study, a number of allene oxides were generated, and their enzymatic and nonenzymatic cyclization into cyclopentenones was investigated. Nonenzymatic cyclization was observed with allene oxides having one pair of conjugated double bonds and an additional isolated double bond in the β,γ position relative to the epoxide group, i.e., the partial structure 4,5-epoxy-1,3,7-octatriene. Enzymatic cyclization took place provided that this structural element was inserted in the fatty acid chain with its epoxide group in the n−6,7 position and the isolated double bond in the n−3 position. A number of oxygenated fatty acids having structural features in common with the natural allene oxides were tested as inhibitors of allene oxide cyclase. Fatty acids having an allene oxide structure in the n−6,7 position but lacking the double bond in the n−3 position, as well as fatty acids having a saturated epoxide group in the n−6,7 position, served as competitive inhibitors of the enzyme. Data on the substrate specificity of allene oxide synthase (EC 4.2.1.92) from corn seeds indicated that fatty acid hydroperoxides with a double bond at n−3 and with the hydroperoxide function at n−6 exhibit the highest affinity but the slowest reaction velocity.     

Activation of porous Ni cathodes towards hydrogen evolution by electrodeposition of Ir nuclei

Porous Ni electrodes were modified by electrodeposition of Ir nuclei from H₂IrCl₆ solutions at 70 °C, with the aim of activating them towards the hydrogen evolution reaction and comparing their performance with those of porous Ni electrodes activated by spontaneous deposition of noble metals (Ir and Ru). The current efficiency of Ir deposition was found to be very low (1% or lower, decreasing upon increasing deposition current density). Ir deposits characterised by SEM-EDX and XRD consisted of nanocrystals decorating the Ni dendrites forming the porous layers. Ir electrodeposition led to a strong activation of the hydrogen evolution reaction from aqueous 1 M NaOH. The electrocatalytic activity of the cathodes was independent of the Ir deposition charge above the minimum explored value of 1  C cm^?2. This charge is estimated to correspond to the deposition of ca. 2.5 10^?8 Ir moles cm^?2. The kinetic parameters for hydrogen evolution were similar for porous Ni electrodes modified by either spontaneous deposition (studied in a previous work) or electrodeposition of Ir.     

Predicting the migration of endocrine disrupters from rigid plastics

Previous studies of the diffusion of gases and organic vapors at low concentrations in glassy polymers have established the applicability of Fickian kinetics, the correlation of diffusion coefficients with the dimensions of the diffusing molecules, and the impracticality of experimentally measuring the diffusivities of molecules larger than C₆ hydrocarbons. The diffusivities of the suspected endocrine disrupters, p-nonyl phenol, bisphenol-A, and tetrachlorodioxin, have been estimated by extrapolation of the established correlations of diffusivity with mean molecular diameter. Estimated diffusivities of these substances in glassy polystyrene, poly(vinyl chloride), and poly(methyl methacrylate) at 30°C range from 10^?17 to 10^?26 cm²/sec. Calculations of desorption rates, based on Fick's law, show that it would take from several hundred to millions of years for even 1% of the initial content of an endocrine disrupter to migrate from a glassy polymer sheet 1 mm thick. It therefore seems that migration from rigid polymer products should not be considered a significant source of endocrine disrupters in the environment.     

Catalytic oxidation of naphthalene using a Pt/Al2O3 catalyst

Polycylic aromatic hydrocarbons (PAHs) are listed as carcinogenic and mutagenic priority pollutants, belonging to the environmental endocrine disrupters. Most PAHs in the environment stem from the atmospheric deposition and diesel emission. Consequently, the elimination of PAHs in the off-gases is one of the priority and emerging challenges. Catalytic oxidation has been widely used in the destruction of organic compounds due to its high efficiency (or conversion of reactants), its economic benefits and good applicability.

This study investigates the application of the catalytic oxidation using Pt/γ-Al₂O₃ catalysts to decompose PAHs and taking naphthalene (the simplest and least toxic PAH) as a target compound. It studies the relationships between conversion, operating parameters and relevant factors such as treatment temperatures, catalyst sizes and space velocities. Also, a related reaction kinetic expression is proposed to provide a simplified expression of the relevant kinetic parameters.

The results indicate that the Pt/γ-Al₂O₃ catalyst used accelerates the reaction rate of the decomposition of naphthalene and decreases the reaction temperature. A high conversion (over 95%) can be achieved at a moderate reaction temperature of 480 K and space velocity below 35,000 h⁻¹. Non-catalytic (thermal) oxidation achieves the same conversion at a temperature beyond 1000 K. The results also indicate that Rideal–Eley mechanism and Arrhenius equation can be reasonably applied to describe the data by using the pseudo-first-order reaction kinetic equation with activation energy of 149.97 kJ/mol and frequency factor equal to 3.26 × 10¹⁷ s⁻¹.     

Electrodeposited Palladium Nanoflowers for Electrocatalytic Applications

Palladium was electrodeposited on an electrochemically activated carbon black substrate using potentiostatic technique, with and without the addition of polyethylene glycol (PEG‐6000) as an additive. Scanning electron micrographs showed change in morphology of Pd from spherical to flower, with increasing additive concentration. As an electrocatalyst for oxygen reduction reaction (ORR), formic acid oxidation and CO stripping, Pd nanoflowers displayed three‐ to fourfold increase in electrocatalytic activity in comparison to the spherical Pd deposits in terms of electrochemical surface area (ESA) and mass specific current density. X‐ray diffraction (XRD) patterns showed, the introduction of additive with varying concentration effect the direction of Pd growth thereby changing the morphology from spherical to flower. The result demonstrates an increase in efficiency of Pd utilization achieved with the addition of PEG during electrodeposition, which could also be applicable to other precious metal electrocatalysts. A scheme for the change in Pd morphology during electrodeposition with additive is also proposed.     

Electrodeposition of catalytically active nickel for the oxygen evolution reaction — effects of anionic composition

Nickel electrodes were prepared by electrodeposition in electrolytes of various anionic compositions. The deposition conditions and bath types were evaluated with special emphasis on the electrocatalytic properties for the oxygen evolution reaction (OER). Electrochemical characterizations in a 5 mol/L KOH solution at 25°C showed that the electrode deposited from the chloride bath, having a low Tafel slope of 50 mV/dec and an overpotential of 396 mV at 100 mA/cm², is the most catalytically active among electrodes prepared in electrolytes of various anionic compositions. The electrode activity for the OER is related to the real surface areas, which depend on the anion compositions in the deposition bath and the deposition conditions.