铜及其合金的表面钝化-涂装抗蚀性能的电化学测试

表面钝化与涂装工艺相结合可显著提高铜及其合金的防腐性能.采用电化学工作站对涂层腐蚀电流进行定量测量,其结果显示,常规的涂装试样,在3% NaCl盐水溶液中浸泡1天,测得腐蚀电阻(Rc)为3.56×105Ω.钝化处理后再涂装的试样测试结果为无穷大.盐水浸泡5天后,前者95%表面受到不同程度的腐蚀,后者仍然正常.后者浸泡15天的腐蚀电阻为2.31×106Ω,仍高于前者浸泡1天的数据.钝化涂装工艺可用于室外及抗腐蚀性能要求较高的铜及其合金制品的表面防护装饰.     

苯骈三氮唑对碳钢在溴化锂溶液中的缓蚀作用

用静态挂片法研究了苯骈三氮唑(BTA)对碳钢在溴化锂溶液中缓蚀作用，并通过极化曲线探讨其缓蚀作用的机理，用扫描电镜观察形成的表面膜形态，用红外光谱探讨表面膜的组成。实验表明苯骈三氮唑对碳钢在溴化锂溶液中有一定的缓蚀作用，其中添加0．020mol／L苯骈三氮唑和0．20mol／L氢氧化锂显著抑制溴化锂溶液对碳钢的腐蚀，分析可能是在碳钢表面形成一层Fe-BTA吸附膜，对阳极反应和阴极反应起一定阻滞作用。     

Computer simulation of the corrosion inhibition of copper in acidic solution by alkyl esters of 5-carboxybenzotriazole

A series of alkyl esters (methyl, butyl, hexyl, and octyl) synthesised from a mixture of 4- and 5-carboxybenzotriazole (4-CBTAH and 5-CBTAH) inhibited copper corrosion in aerated solution (pH∼0). Inhibition efficiency (IE%) of the protonated esters (CBTAH₂⁺-R) increased with hydrocarbon chain length and this is attributed to chemisorption (through azole ring N) and increased physical adsorption as more methyl groups are introduced. A modelling package employing molecular mechanics and molecular dynamics has been used to simulate the docking of a single protonated species (5-CBTAH₂⁺-R) onto a clean copper (1 1 0) surface. A decrease in potential energy was associated with the flattening of the ester ring system onto the surface and further decreases in energy were associated with the extension of the aliphatic chain onto the surface. The crude binding energy (E_bind) of each ester with the surface was estimated and this energy also increased regularly with carbon chain length. The study suggests that molecular modelling and calculation of E_bind of a single molecule on a specified metallic surface can be used to predict the inhibition performance of compounds whose structures change in a regular way.     

Polar pollutants in municipal wastewater and the water cycle: Occurrence and removal of benzotriazoles

1H-benzo-1,2,3-triazole (BTri) and its methylated analogues (tolyltriazole, TTri) are corrosion inhibitors used in many industrial applications, but also in households in dishwashing agents and in deicing fluids at airports and elsewhere. BTri and one of the TTri-isomers (4-TTri) are typical examples of polar and poorly degradable trace pollutants. Benzotriazole elimination in four wastewater treatment plants (WWTP) in Berlin ranged from 20 to 70% for 5-TTRi over 30 to 55% for BTri to insignificant for 4-TTri. WWTP effluent concentrations were in the range of 7-18 μg/L of BTri, 1-5 μg/L of 4-TTri and 0.8-1.2 μg/L of 5-TTri. BTri and 4-TTri proved to be omnipresent in surface waters of the rivers Rhine and Elbe with concentrations increasing from <0.05 μg/L to around 0.5 μg/L of BTri and 0.2-0.5 μg/L of 4-TTri over 600-700 km. Bank filtration is an important process to generate raw water for drinking water production from surface waters. Even after residence times of several months BTri and 4-TTri were determined in concentrations of a few hundred ng/L in bank filtration water. Isotherm data from batch experiments indicate that activated carbon filtration should be suitable to avoid intrusion of TTri into drinking water in partially closed water cycles. For BTri, however, sorption to activated carbon appears to be too weak and ozonation may be mandatory to remove it from raw waters.     

Effect of organic additives on hydrogen permeation into an iron membrane studied by frequency analysis techniques

The effects of thiourea and benzotriazole on the hydrogen permeation into iron were studied using a Devanathan-Stachurski electrochemical double cell equipped with a thin iron membrane. Hydrogen was cathodically generated on the entry side and fully oxidized on the exit side. The spectral analysis of both the electrochemical impedance on the entry side and the permeation transfer function between the ac current signals on the two faces of the membrane were recorded according to a method recently proposed. The modifications of the impedance diagrams and the transfer function diagrams induced by the presence of the organic additives were interpreted at the light of the mechanistic model of the transfer function which was recently derived. It is concluded that both additives inhibit the hydrogen evolution reaction, but thiourea promotes hydrogen penetration by inhibiting the recombination reaction, whereas benzotriazole adsorption inhibits the formation of the H_ads and therefore their penetration into the metal matrix.     

Is the analysis of molecular electronic structure of corrosion inhibitors sufficient to predict the trend of their inhibition performance

The often used approach in the corrosion inhibition studies employing quantum chemical calculations that relies on the correlation between molecular electronic structure parameters and inhibition effectiveness is critically examined. It is shown that the inhibition performance of three selected triazole-based corrosion inhibitors for copper - 3-amino-1,2,4-triazole (ATA), benzotriazole (BTAH), and 1-hydroxybenzotriazole (BTAOH) - cannot be explained on this basis in a sound manner. As the effectiveness of inhibitors is due to several phenomena, the outcome depends on the interplay between them and although molecular electronic parameters may provide many necessary elements, the involved effects can be estimated only approximately which may not always suffice. This supports the proposition that in general molecular electronic properties cannot be directly related to inhibition effectiveness - the actual relation is more involved - thus emphasizing the importance of a rigorous modeling of the inhibitor-surface interaction in the corrosion inhibition studies.     

Occurrence, distribution and fluxes of benzotriazoles along the German large river basins into the North Sea

Benzotriazole (BT) and tolyltriazole (TT) are high production volume chemicals which are used in various industrial and household applications. In this study, the distribution of benzotriazoles in the estuaries of different rivers of central Europe and in the North Sea was analyzed by solid-phase extraction (SPE) and liquid chromatography-mass spectrometry (HPLC-MS/MS). BT as well as TT was detected in all water samples. The concentrations for total benzotriazoles (BTs) ranged from 1.7 to 40 ng/L in the North Sea in costal areas. Concentrations in rivers are from 200 to 1250 ng/L, respectively. The mass flux of total benzotriazoles from the major rivers of central Europe into the North Sea was calculated to 78 t/a, dominated by the Rhine with an individual flux of 57 t/a of BTs. The analysis of the distribution profile in the North Sea showed that the decrease of the concentration was mostly caused by dilution and that the benzotriazoles are poorly degradable in the North Sea. This paper presents the first report of benzotriazoles in the marine environment.     

Electrochemical pitting corrosion behaviour of α-brass in LiBr containing solutions

The potentiodynamic anodic polarization curve of α-brass (70% Cu-30% Zn) in 1 M LiBr solution showed an initial active region of the alloy dissolution followed by two well defined anodic current peaks then a narrow passivation region before the pitting potential (E_pit) is reached. The initial active anodic region exhibited Tafel slope with 90 mV dec⁻¹ attributed to the formation of CuBr₂⁻ complexes. The anodic current peaks were attributed to the formation of CuBr and Cu²⁺ ions, respectively. The change of pH values of LiBr solution did not affect the anodic polarization curves of α-brass. Increasing the solution temperature from 30 to 90 °C changed the corrosion type from pitting to general one. The addition of 10⁻² M benzotriazole (BTAH) to 1 M LiBr solution is completely inhibited the pitting corrosion at 30 °C while it did not inhibit the pitting at 90 °C. The inhibition effect was attributed to the adsorption of BTAH molecules on the alloy surface, which obeys Langmuir isotherm. The presence or absence of pitting corrosion was confirmed by using SEM.     

苯并三唑类紫外线吸收剂的研究进展

论述了应用最广泛的紫外线吸收剂苯并三唑类化合物在提高消光系数、引入可聚合基团以及和其它光稳定剂如受阻胺光稳定剂的协同作用等方面的研究进展。     

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L⁻¹ H₂SO₄ solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA]_n polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases in solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L⁻¹ H₂SO₄ in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper.