Effect of benzotriazole (BTA) addition on Polypyrrole film formation on copper and its corrosion protection

Benzotriazole (BTA) was added in a conducting Polypyrrole (PPy) film prepared on copper in oxalic acid aqueous solution containing pyrrole monomer to improve corrosion protection by the PPy film and reduce copper corrosion. When BTA was added in the preparation solution, the copper surface was covered by a BTA–Cu complex layer before the anodic polymerization of PPy was started. On the copper surface with the BTA layer, the initial dissolution of copper was inhibited and the PPy polymerization-deposition was started immediately after the anodic current was imposed. The PPy film thus formed was doped with oxalic ions and ionized BTA and was homogeneous in thickness and strongly adhesive. The PPy film containing BTA protected the copper from corrosion in 3.5 wt.% NaCl solution. In 400 h of immersion, copper dissolution was inhibited with 80% protection efficiency relative to that of bare copper.     

原子力显微镜研究苯并三氮唑对铜的缓蚀作用

铜以及铜合金由于其优良的抗腐蚀性能,广泛用在冷却水系统中,苯并三氮唑(BTA)常常作为铜的缓蚀剂。将传统电化学方法和原子力显微镜(AFM)测试技术相结合,对人造海水中BTA作用于铜电极的缓蚀行为进行了研究。结果表明,BTA能够有效减缓铜在海水中的腐蚀,且随着缓蚀剂浓度的增加,缓蚀效果越明显,100 mg/L的BTA就能够高效的保护铜。电化学结果表明,BTA能够在铜的表面形成致密的保护膜[CuBTA]n;AFM测试表明,随着时间的进行,保护膜越来越致密,保护性能也越好。     

含能配合物M(BTA)(bpy)_m·nH_2O的合成及液相生成反应热动力学研究

室温下合成了6种未见报道的固态含能配合物M(BTA)(bpy)m.nH2O(M=Mn,m=1,n=1;M=Co,m=2,n=5;M=Ni,m=2,n=6;M=Cu,m=2,n=0;M=Zn,m=2,n=1;M=Pb,m=1,n=0;BTA=N,N’-二四唑胺离子,bpy=2,2’-联吡啶),对它们进行了组成、红外光谱、密度等表征。测定了298.15 K下各配合物的液相生成反应焓变△rHmθ,改变液相反应温度,在实验和计算基础上,得到了液相生成反应的热力学参数(活化焓△Hθ≠、活化熵△S≠θ和活化自由能△Gθ≠)、速率常数k和动力学参数(表现活化能E、频率因子ln[A/s]和反应级数n)。     

Chemical mechanical planarization of copper in alkaline slurry with uric acid as inhibitor

Chemical mechanical planarization of copper disks in hydrogen peroxide and l-arginine based alkaline slurry was investigated. Various commonly proposed inhibitors were screened by static etch rate experiments and only BTA and uric acid were found to be effective in the alkaline pH range, while potassium sorbate was moderately effective. The combination of arginine, hydrogen peroxide and uric acid leads to a more robust polish rate than can be achieved with glycine, hydrogen peroxide and BTA based slurries. The dissolution in presence of uric acid was further studied by potentiodynamic and cyclic polarization experiments which indicate formation of a passivation layer on the copper surface. Silicon dioxide wafers were polished to determine the Cu/silicon dioxide polish rate selectivity in alkaline pH range and a high selectivity (>100) was observed. These results indicate that it is possible to conduct a robust copper CMP with alkaline slurries while maintaining an excellent Cu/silicon dioxide polish rate selectivity.     

用扫描隧道显微镜研究铜表面苯并三氮唑吸附膜的结构形态

It is observed by scanning tunneling microscopy (STM) that the adsorbed Benzotriazole (BTA) on copper is long in shape and has an irregular rectangle.The growth of BTA on copper is in the from of polymeric chain and mainly in one dimension rather than two dimensions.The copper surface covered by BTA becomes flatter,smoother and the roughness was smaller than that of bare copper,so the corrosion is largely decreased.However,many grooves can be seen between BTA polymeric chains in which corrosion may exist to a degrees.     

苯并三氮唑及其衍生物对铜的协同缓蚀效应

以苯并三氮唑(BTA)和溴代正丁烷为原料,采用一步法合成了N-丁基苯并三氮唑(N-BBTA),研究了BTA、N-BBTA以及N-BBTA与BTA的复配体系对铜在3％(质量分数)NaC1溶液中的缓蚀行为.结果表明,单一N-BBTA和BTA对铜均具有一定的缓蚀能力.当N-BBTA、BTA浓度为10 mmol/L时,缓蚀率分...     

A quartz crystal microbalance study of the kinetics of interaction of benzotriazole with copper

The kinetics of interaction of benzotriazole (C₆H₅N₃, BTAH) with the surface of copper in salt water were studied using an electrochemical quartz crystal microbalance and X-ray photoelectron spectroscopy (XPS). Upon injecting BTAH into the electrolyte, three regions appear in the time response of the microbalance. Region I (at short time of few minutes), exhibits rapid linear growth of mass with time, which is attributed to the formation of a protective Cu(I)BTA complex. Region II reveals attachment of BTAH at a slower rate onto the inner Cu(I)BTA complex. Region III is a plateau indicating that the BTAH film attains an equilibrium mass and thickness, which increase with the concentration of BTAH. The intensity of the N1s peak in the XPS spectra increases with the time of immersion, indicating more BTAH on the surface. The results suggest a duplex inhibitor film composed of an inner thin layer of Cu(I)BTA and an outer layer of physically adsorbed BTAH which increases in thickness with time and BTAH concentration. They also offer an explanation for the much documented findings of simultaneous increase of the polarization resistance and decrease of double layer capacity with inhibitor concentration and time of immersion.     

An electrochemical and Raman spectroscopic investigation of synergetic effects in the corrosion inhibition of copper

The synergetic inhibition of copper corrosion by benzotriazole (BTA) and benzylamine (BZA) in chloride and cyanide media is assessed by voltammetric and ac impedance measurements. BZA enhances the performance of the strong inhibitor BTA by accelerating the growth of a protective surface layer; used alone, BZA is ineffective as an inhibitor. The competitive adsorption of aggressive anions and inhibitors is studied by surface enhanced Raman scattering (SERS). The dramatic increase in corrosion caused by low concentrations of cyanide ions is shown to be due to the displacement of BTA from the copper electrode surface; comparisons are made with the behaviour of mercaptobenzoxazole (MBO).     

Inhibition of Aluminium Alloy AA2024-T3 pitting corrosion by copper complexing compounds

A scanning vibrating electrode technique (SVET) is used to quantify the influence of a range of copper complexing/precipitating reagents on the kinetics of pitting corrosion affecting AA2024-T3 immersed in 5% aqueous sodium chloride (NaCl). It is shown that organic anions such as 2,5 dimercapto, 1,3,4 thiadiazolate (DMTD), benzotriazolate (BTA) and N,N- diethyl, dithiocarbamate (DEDTC), and inorganic ions such as ferrocyanide effectively inhibit pitting corrosion by film formation on Cu rich intermetallic particles (IMPs) and/or precipitation of aqueous copper cations. Inhibitor efficiency increases in the order ferrocyanide < BTA < DEDTC ≈ DMDT. In contrast, the presence of ethylenediamminetetraacetic acid (EDTA) is shown to prevent copper (Cu) replating, but does not lead to any decrease in localised corrosion currents. This supports the idea that that ample cathodic activity can be maintained on Cu-rich IMPs in the absence of any copper replating to sustain stable pitting on AA2024.     

The synergetic effect of benzylamine on the corrosion inhibition of copper by benzotriazole

Passivating films, formed by the anodization of copper in alkaline benzotriazole (BTA) solutions, have been investigated. Addition of benzylamine to the anodizing solutions was found to lead to much faster passivation and greater corrosion resistance in aqueous chloride. These passivating films appear to consist mainly of a [Cu(II)BTA₂]_n polymeric network.     

Adsorption-desorption study of benzotriazole in a phosphate-based electrolyte for Cu electrochemical mechanical planarization

In this article, the adsorption-desorption behavior of benzotriazole (BTA) in a phosphate-based electrolyte developed for Cu electrochemical mechanical planarization (ECMP) is studied. The formation of a continuous BTA passive film adsorbed on the Cu surface has been characterized by atomic force microscopy (AFM). Additionally, the adsorption behavior of BTA was found to be mass-transfer-controlled at lower operating potentials (≤0.7 V vs. Ag/AgCl). Using a microfluidic electrochemical device and electrochemical impedance spectrum (EIS), it was also observed that at low BTA concentrations (≤0.002 M), more time was necessary to form an effective passive film on the Cu surface. Furthermore, the desorption time obtained from a potentiometric response to the removal of BTA from the electrolyte increases with increasing BTA concentration or decreasing applied potential. It is critical to expand the operating potential window and to reduce the usage of inhibitors in the proposed ECMP process to enhance the removal rate and the reduction of organic residues. Therefore, the combined microfluidic and electrochemical methodology is proven useful in finding suitable BTA concentrations and a wider potential window.     

The effect of benzotriazole on mass transfer in the corrosion of a copper rotating disk electrode

The effect of benzotriazole, BTA, on mass transfer in dissolution-corrosion of the copper rotating disk electrode in 0.02 M Fe(III)–0.5 M H₂SO₄ has been studied by means of atomic absorption spectrometry. The mass transfer coefficient, K, was determined from the slope of ln(C ₀/C)_Fe(III) vs. time plots. In the absence of BTA the corrosion process can be described by the correlation Sh = KR/D = 4.47Re ^0.5. The difference in values between Sh and Sh _Levich, and the change in slope in the Arrenhius plot points to mixed control for the cathodic process Fe³⁺ + 1e^– Fe ²⁺ and charge transfer control for the anodic process, Cu Cu²⁺ + 2e. The average activation energies were 7.7 kJ mol^–1 and 19.5 kJ mol^–1 at (500–1500) and (2000–3000) rpm, respectively. At low concentration of BTA the inhibiting action of BTA increases with concentration and with rotation speed. For [BTA] 5 × 10^–3 M, the K value, 10^–4 cm s^–1, remains constant and is independent of rotation rate. The morphology of the copper rotating disk after corrosion in the absence and presence of BTA was examined using scanning electron microscopy (SEM).     

铜在硝酸介质苯并三唑抛光液中化学-机械抛光时的电化学行为

用电化学测试技术研究了硝酸、苯并三唑及H2O2浓度对铜表面的成膜及铜抛光过程的影响.测试了各种体系中铜的交流阻抗及其影响因素，探讨了腐蚀电流密度与抛光压力、抛光转速的关系，考察了化学-机械抛光过程中腐蚀电位及极化曲线的变化规律. 用腐蚀电流密度及腐蚀电位等电化学变量的变化解释了抛光过程的电化学机理，证明在硝酸溶液介质中，以苯并三唑为成膜剂、H2O2为助剂、纳米g -Al2O3为磨粒的抛光液配方是可行的.     

Long-term stability of Cu/Pd nanoparticles and their feasibility for electroless copper deposition

Poly-vinylpyrrodione (PVP) protected Cu/Pd nanoparticles synthesized with citric complexing agent were developed as activator for electroless copper deposition in printed-circuit boards (PCBs) industry. Cu/Pd nanoparticles in different molar ratio were employed in electroless copper deposition and found that the catalytic activity was influenced not only by the amount of Pd content or particle size but also by the surface protected PVP layer. From the time-resolved electroless copper deposition, we suggested that the catalytic efficiency should be evaluated by both initial activity and the structure of deposited copper film. As a result, the Cu/Pd nanoparticles of molar ratio = 1/2 was found to have best catalytic activity which was comparable to traditional Pd/Sn or pure Pd activator. In regard to the most concerned stability issue of Cu-content system, a surprising slow galvanic corrosion of Cu was found when Cu/Pd nanoparticles were exposed to the open air. Besides, slightly oxidation of Pd was found after air-exposure. Surprisingly, these Cu/Pd colloids maintain part of activity and well suspension even after 6-month exposure, suggesting well long-term stability as activator. In short, Cu/Pd nanoparticles synthesized with citric complexing agent with high catalytic activity and long-term stability was a promising activator for electroless copper deposition.     

铜钨钼硅多元取代多金属含氧簇合物的合成、性质及催化作用

合成了一个系列的铜钨钼硅多元取代多金属含氧簇合物 :K4H2 [Cu( OH2 ) Si Mo11-n Wn O39].x H2 O　 ( n=2 ,5 ,7,9;x=2 1～ 2 3 ) ,通过 IR,UV,XPS,TG- DTA,XRD对其性能进行了表征 ,并以H2 O2 的反应体系 ,考察了合成的簇合物对 H2 O2 的催化分解作用     

Benzotriazole as inhibitor for copper with and without corrosion products in aqueous polyethylene glycol

Electrochemical methods, including polarization experiments and impedance spectroscopy, were used to evaluate the effectiveness of benzotriazole (BTA) in an aqueous solution of polyethylene glycol (PEG) in protecting polished archaeological copper or archaeological copper covered with corrosion products. The adsorption of PEG on the polished copper significantly limited the corrosion current. The presence of benzotriazole enhanced the protection of the polished copper, giving maximum protection at a concentration of 10^–2moll^–1 of BTA in 20 vol% PEG 400 solution. On the other hand, PEG solutions caused degradation of the corrosion products of the copper. This degradation increased with time. When BTA was added, the corrosion products were preserved and, the higher the BTA concentration, the more the corrosion current decreased. In PEG 400 solution protection of the corrosion products of the copper by BTA improved over time.     

高浓度氯离子环境中铜合金缓蚀的电化学研究

应用线性电位扫描(LSV)和Tafel实验等电化学测试技术,研究了苯并三氮唑(BTA)浓度、缓蚀剂的复配、温度对铜合金在高浓度氯离子(25%氯化钙溶液)环境中腐蚀行为的影响。结果表明:缓蚀剂浓度改变将引起缓蚀效果的变化,BTA浓度较低时,铜合金腐蚀电位随缓蚀剂浓度增大而升高,腐蚀速率降低;BTA浓度超过0.2%后,铜合金腐蚀电位和腐蚀速率趋于稳定;NaNO2、Na2MoO4、(NH4)2MoO4等缓蚀剂与BTA复配,对改善缓蚀效果有一定作用;温度对缓蚀效果有重要影响,铜合金在高浓度氯离子溶液中的腐蚀速率随温度的升高而加快,缓蚀剂的缓蚀效果随温度的升高而降低。     

以氢键组装的铜(Ⅱ)、锌(Ⅱ)卟啉超分子构象

考察了 5 -对 - (间羰基苯甲酸 ) -氨基苯基 - 1 0 ,1 5 ,2 0 -三苯基卟啉锌 ( )配合物 ( Zn( m-CPTPP) )、铜 ( )配合物 ( Cu( m- CPTPP) )及 ( Zn( m- CPTPP) )与 5 -对 - (对羰基苯甲酸 ) -氨基苯基 -1 0 ,1 5 ,2 0 -三苯基卟啉铜 ( ) ( Cu( p- CPTPP) )通过氢键的超分子自组装行为。上述两体系都通过氢键自组装成超分子。 Zn( m- CPTPP) - Cu( m- CPTPP)体系存在卟啉环间的π-π堆积作用     

Copper electrodeposition in sulphate solutions in the presence of benzotriazole

DC and pulse plating of copper in acidic sulphate solutions containing benzotriazole (BTA) has been studied. When BTA is the only additive present, it generally has a stronger effect than the plating mode and significantly enhances deposit morphology and surface brightness over that produced in additive-free solutions. XPS and voltammetry analyses indicate that BTA is present at the surface of the deposit, but not through the entire coating, and does not become depleted within the solution over the course of plating. This may help explain why the initial surface smoothness and brightness is maintained as the coating grows beyond 5 μm thick. Plating mode does have a strong effect on deposit morphology under specific conditions. Pulse current plating at low frequency (50 Hz) and low duty cycle (20%) produces deposits with poorer quality than that obtained by DC plating. Pulse reverse plating yields very coarse and dull coatings when the frequency is low enough for metal dissolution to occur during the reverse time. Regardless of the plating mode, the addition of Cl⁻ eliminates most of the beneficial effects of BTA and leads to very rough and dull deposits. The observed effects are discussed in light of previous research on the electrodeposition and corrosion of the Cu–BTA and Cu–BTA–Cl systems.     

钝化工艺对HEDP镀铜层耐蚀性的影响

采用盐水浸泡试验、硝酸点滴试验以及电化学测试方法,研究了苯并三氮唑、苯并三氮唑与Cr(Ⅲ)复配、苯并三氮唑与铈盐复配、Cr(Ⅵ)以及HAD无铬钝化工艺对HEDP镀铜层耐蚀性的影响。结果表明,经苯并三氮唑复配钝化液钝化处理后,钝化膜耐蚀性较单一的苯并三氮唑钝化稍有提高,但均不及Cr(Ⅵ)钝化处理,而经HAD无铬钝化处理后,钝化膜耐硝酸点滴时间最长,在3.5%Na Cl溶液中的Rct最大,icorr最小,耐蚀性明显优于Cr(Ⅵ)钝化处理。