Application of electrochemical techniques to study the effect on the anticorrosive properties of the addition of ytterbium and erbium triflates as catalysts on a powder epoxy network

New low curing temperature epoxy powder coatings cured with o-tolylbiguanide and catalyzed by the use of erbium(III) and ytterbium(III) trifluoromethanesulfonates have been formulated. Their curing kinetics and anticorrosive properties have been studied and compared with a system commonly used in industry (o-tolylbiguanide/epoxy resin). Three different tests for measuring anticorrosive properties (EIS, AC/DC/AC, and salt fog spray) have been used together with an adherence test, in order to establish the ideal system. Results show that a system using 1 phr of ytterbium triflate presents good anticorrosive properties. The technique AC/DC/AC has shown its ability to evaluate properly and much faster than other techniques the anticorrosive properties of powder coatings with similar results.     

Anticorrosive properties of an epoxy-Meldrum acid cured system catalyzed by erbium III trifluromethanesulfonate

New low curing temperature powder epoxy coatings cured with Meldrum's acid and catalyzed by the use of erbium III trifluoromethanesulfonate have been formulated. Their curing kinetics and anticorrosive properties have been studied and compared with a system commonly used in industry (o-tolylbiguanide/epoxy resin) and with an epoxy powder coating homopolymerized by erbium III trifluoromethanesulfonate. Three different tests of anticorrosive properties (EIS, AC/DC/AC and salt fog spray) have been used together with an adherence test, in order to establish the best system. Results show that systems crosslinked with Meldrum's acid and catalyzed with erbium triflate present very fast curing kinetics and very good anticorrosive properties. The technique AC/DC/AC has shown its ability to evaluate properly and much faster than other techniques the anticorrosive properties of powder coatings.     

Investigation of corrosion protection properties of an epoxy nanocomposite loaded with polysiloxane surface modified nanosilica particles on the steel substrate

In this study, it has been aimed to investigate the corrosion protection properties of an epoxy/polyamide coating loaded with different concentrations (ranged from 3 to 6% (w/w)) of the polysiloxane surface modified silica nanoparticles (nano-SiO₂). The nanocomposites were applied on the steel substrates. Field emission scanning electron microscope (FE-SEM) and UV–vis techniques were utilized in order to investigate the nanoparticles dispersion in the coating matrix. The effects of addition of nanoparticles on the corrosion resistance of the coating were studied by an electrochemical impedance spectroscopy (EIS) and salt spray test. The coating surface degradation was studied by optical microscope and Fourier transform infrared radiation (FT-IR) spectroscopy. Results obtained from UV–vis and FE-SEM analyses revealed proper and uniform distribution of surface modified nanoparticles in the epoxy coating matrix. It was shown that the coating corrosion protection properties were significantly enhanced in the presence of 5 wt% silica nanoparticles. Less degradation occurred on the surface of the coatings loaded with 5 wt% nanoparticles.     

Optimization of deposition voltage of cataphoretic automotive primers assessed by EIS and AC/DC/AC

The dependence of the anticorrosive properties of a cataphoretic paint with the applied deposition voltage was studied by the so-called EIS tests; an accelerated cyclic test used in the automotive industry; and a rapid electrochemical test (AC/DC/AC) which combines EIS measurements with cathodic polarizations. DSC and TGA were employed for the coating characterisation. The traditional accelerated cyclic test was unable to distinguish the influence of the deposition voltage on the anticorrosive properties while electrochemical tests found an optimal range of deposition voltage between 270 and 320 V. The AC/DC/AC test obtained the same results as EIS tests but in only 24 h instead of months of evaluation. The technique AC/DC/AC is suggested as an accelerated technique able to determine the optimum range of deposition voltages to obtain the higher anticorrosive properties of an epoxy cataphoretic primer.     

硼酸喷雾包覆改性镍钴铝酸锂的制备及其电化学性能研究

针对镍钴铝酸锂（NCA）三元正极材料普遍存在的循环寿命差、浆料容易凝胶等缺点进行了硼酸喷雾包覆的改性。采用X 射线衍射仪（XRD）、扫描电镜（SEM）、透射电镜（TEM）及电化学测试等方法对硼酸包覆改性前后的材料性能进行了对比表征和分析。结果表明：喷雾包覆后可以在NCA正极材料表面形成一层保护层,改性后的NCA三元正极材料循环寿命有明显提升,特别是高温（45 ℃）1C/1C倍率下循环50次容量保持率由改性前的88.0%提升至改性后的95.2%,提升近7%;硼酸包覆可以改善NCA表面特性,使正极浆料稳定性大大提高。改性后的NCA正极浆料可以稳定放置168 h（7 d）,解决了NCA正极材料容易凝胶的问题。     

Impedance studies of poly(methylmethacrylate-co-acrylic acid) doped polyaniline films on aluminum alloy

Films of polyaniline doped with poly(methylmethacrylate-co-acrylic acid) – PAni-PMMA-co-AA – were prepared on AA3104-H19 alloy, an aluminum alloy used in the Brazilian can industry, by immersion of the pre-treated surfaces into a PAni-PMMA-co-AA saturated ethyl acetate solution.     

Determination of the adhesion properties of an alkyd pigmented coating by electrochemical impedance spectroscopy

One of the most modern methods of characterizing the electrical properties of coatings is by electrochemical impedance spectroscopy (EIS). EIS can provide useful information about the transport of water and corrosive species through a coating. In this study, impedance measurements were performed in different frequency ranges at open circuit potential for an alkyd coating with TiO₂ as a mineral pigment in 3% NaCl. The most probable impedance equivalent circuit method (MPI) was considered for data analysis. The interpretation of the impedance spectra permitted the determination of water permeation, the formation of blisters, swelling of the coating, and the loss of adhesion.     

无机固体酸催化合成氯乙酸正丁酯

在五水四氯化锡存在下,由氯乙酸和正丁醇合成氯乙酸正丁酯。研究了反应中的影响因素。当氯乙酸、正丁醇和四氯化锡物质的量的比为1∶1.5∶0.029,回流分水90 min时,氯乙酸正丁酯收率为91.3%。     

磺酸型固体催化剂催化合成乙酸乙酯

苯乙烯/丙烯磺酸共聚物(St-c-AS)作为一种高效、无污染、可重复利用的固体酸催化剂被用于乙酸和乙醇的酯化反应中。实验结果表明,该催化剂具有较高的催化活性,催化剂不需分离可重复使用10次,酯化产率达到90%以上。与传统的硫酸催化剂相比,St-c-AS为催化剂所得的产品无需除酸,后处理简单,对环境无污染,是一条合成乙酸乙酯的绿色途径。     

磷钨酸/二氧化钛催化合成甲基丙烯酸丁酯的研究

采用浸渍法制备了磷钨酸／二氧化钛催化剂，用于催化合成甲基丙烯酸丁酯，其性能优于硫酸，在酸醇物质的量的比为1：1．15，催化剂用量为甲基丙烯酸质量的1．3％，酯化温度为120℃，反应时间75min的条件下，酯化率达91．7％，产品质量分数大于98％，并且催化剂可以使用多次。     

超声协同TiO_2光催化降解酸性大红染料的研究

选取酸性大红染料为降解目标物,研究了在二氧化钛催化剂存在下的光催化氧化法与超声作用的协同反应,重点考察了超声辐射功率、初始溶液pH值、染料初始浓度、催化剂用量以及Fe3+等的添加对降解效率的影响。实验结果表明,溶液pH值为1.0,超声辐射功率400 W,染料初始浓度为40 mg/L,催化剂浓度为4 g/L,对酸性大红染料溶液降解75 m in,降解率可达90%以上。     

Studies on the synthesis and thermal properties of copoly(L‐lactic acid/glycolic acid) by direct melt polycondensation

A two‐step direct copolymerization process of L ‐lactic acid (L ‐LA)/glycolic acid (GA) was developed. The first step was to produce an oligomer of L ‐LA/GA and then the oligomer was polymerized with binary catalyst tin chloride dihydrate/p‐toluenesulfonic acid. In this way, the copoly(L ‐LA/GA) (PLGA), without any organic solvent, was synthesized directly. The thermal properties and solubility in chloroform of PLGA were studied by DSC and NMR. The results showed that the melting point of PLGA decreases with increasing mole fraction of GA units in copolymer. In addition, the melting point of polymer also decreased with increasing degree of racemization of polymer. The solubility of PLGA in chloroform decreased with the increase of the average lengths of the glycolic acid units. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2163–2168, 2004     

Behavior of phenolic antioxidants in a partitioned medium: Focus on linoleic acid peroxidation induced by iron/ascorbic acid system

The peroxidation of linoleic acid was induced by the Fe²⁺/ascorbic acid system in a micellar medium, and the kinetics of the produced conjugated dienes to a weak level (0.7 μM) in order to initiate only the sequential oxidative reactions without superimposed antioxidant activity. Other conditions were established to obtain a simple kinetic profile. With a linoleic acid/Fe²⁺ ratio of 10 and an Fe²/ascorbic acid ratio of 23 in the medium emulsified by Tween and saturated in oxygen, no limiting effect of substrates was observed for several hours. Fe²⁺ disappeared in less than 5 min, while a linear propagation rate was reached after 1 h for up to 15 h. Two parameters were chosen to quantify the level of the oxidation: the slope of the linear phase, and the extrapolated absorbance of this step at zero time. These two parameters were used in order to compare the antioxidant power of different phenolic compounds in this partitioned medium.     

丁酸在含氯化钙双水相体系中的有效分离(英文)

One of the bottlenecks for bioproduction of butyric acid as bulk chemical is the difficulty in separating butyric acid from the fermentation broth,compared with the petroleum-based chemical synthesis method.In the present work,a novel separation methodology was developed based on an aqueous two-phase system with inor-ganic salts.Calcium chloride was screened out for effective separation of butyric acid from butyric acid-water-salt systems.Within appropriate concentration range of butyric acid and salt,butyric acid was enriched in the upper phase and most of calcium ions remained in the lower phase.This"salting out"effect is very efficient to separate butyric acid from the simulated butyrate fermentation broth,which consists of butyric acid and acetic acid with concentration ratio of 4︰1,so that the final ratio of butyric acid/acetic acid in the upper phase is improved to 9.87. The aqueous two-phase system was used to separate butyric acid from the actual fermentation broth with satisfac-tory result.     

Blends of poly(L‐lactic acid) with poly(ω‐pentadecalactone) synthesized by enzyme‐catalyzed polymerization

Poly(ω‐pentadecalactone) (PPDL) was synthesized by enzyme‐catalyzed polymerization. The molecular weight of the PPDL was about 35,000. Opaque poly(L ‐lactic acid) (PLLA)/PPDL blend films were created by the solvent casting technique. The addition of PPDL led to PLLA crystallization. Furthermore, the addition of PPDL with PLLA increased both the Young's modulus [pure PLLA : 0.67 GPa, PLLA/PPDL (70/30 wt %) : 1.01 GPa] and the PLLA glass transition temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of poly(L‐lactic acid) scaffolds by thermally induced phase separation from a ternary polymer–solvent system

Poly(L ‐lactic acid) (PLLA) foams for tissue engineering were prepared via thermally induced phase separation of a ternary system PLLA/dioxane/tetrahydrofuran (THF) followed by double solvent exchange (water and ethyl alcohol) and drying. An extension to solidification from solution of a previously developed method for solidification from the melt was adopted. The technique is based on a continuous cooling transformation (CCT) approach, consisting in recording the thermal history experienced by rapidly cooled samples and then analyzing the resulting sample morphology. Different foams were produced by changing the relative amount of dioxane and THF in the starting solution while the amount of polymer was kept constant. Results show that the final morphology and crystallinity (measured by DSC) depend on solvent power, which in its turn was determined by the ratio dioxane/THF, and a minimum of pore size, optimum final crystallinity and crystallization rate were achieved for a system containing 70 % of dioxane. Under this condition, a higher bulk density (evaluated by Hg intrusion porosimetry) and a larger specific surface area (measured by BET N₂ sorption technique) was achieved. Copyright © 2004 Society of Chemical Industry