Influence of the interaction between chloride and thiourea on copper electrodeposition

The interaction between chloride and thiourea in copper electrodeposition in a sulfate-plating bath was investigated. The sole addition of thiourea to the bath increased the polarization of the electrode potential during copper deposition, leading to very fine and smoothly structured deposit but with microscopic nodules distributed over the surface. When chloride was added to a plating solution containing thiourea, the copper deposition mechanism was changed, showing a depolarization of the electrode potential, and the copper deposits were found to have a relatively rougher microstructure, but without the formation of microscopic nodules. However, rough deposit surfaces having no distinct pattern were formed at the macroscopic scale. Observations of roughening evolution show that the rough surface was initiated from small holes formed across the deposit surface during the initial stage of deposition that eventually developed into visibly rough deposits. The copper deposition inside these holes and at other areas was expected to undergo different deposition mechanisms. Copper deposition in the areas that ultimately developed into holes was almost totally inhibited by the thiourea–Cu(I)–chloride complex film, not just in the grain growth process, but over practically the entire electrodeposition process. Conversely, copper deposition occurred in other areas under conditions where nucleation proceeded, but grain growth was inhibited to produce a fine, homogeneous microstructure. An uneven deposit surface that had different microscopic structures in different areas was then formed. The structure of the thiourea–Cu(I)–chloride film was strongly affected by the current density and appeared to break down completely if sufficiently high current density was applied to yield a fine and homogeneous microstructure that was also macroscopically smooth.     

Interaction of BSA protein with copper evaluated by electrochemical impedance spectroscopy and quartz crystal microbalance

The interaction of bovine serum albumin (BSA) protein with copper in phosphate buffer solution has been studied by a combination of electrochemical impedance spectroscopy (EIS) close to the open circuit potential, with simultaneous monitoring by the electrochemical quartz crystal microbalance (EQCM), in order to throw light on BSA adsorption. Copper films were electroplated onto gold quartz crystals and mounted in the EQCM. Experiments were conducted in the presence and absence of dissolved oxygen and of BSA and the results show the influence of O₂ on the protein/metal interaction and also show specific interactions between BSA and copper. The good reproducibility obtained in these experiments suggests future application to other systems and which should lead to a better understanding of the use of such types of protein as corrosion inhibitors.     

Application of the electrochemical quartz crystal microbalance technique to copper sonoelectrochemistry: Part 1. Sulfate-based electrolytes

The applicability of the electrochemical quartz crystal microbalance technique in an ultrasonic field created by an ultrasound probe is demonstrated for the electrodeposition of copper. Cyclic voltammetry and potentiostatic depositions in acidic sulfate-based copper electrolytes were performed at different ultrasonic intensities. The electrochemical quartz crystal microbalance was operated in ultrasonic fields with intensities up to 30 W cm⁻². For cyclic voltammetry, potential resolved and averaged (apparent) current efficiencies were calculated from mass and charge data in function of the amplitude of the ultrasonic horn. Ultrasound slightly affected the current efficiencies during copper deposition in cyclic voltammetry, but did not change the efficiencies during dissolution. During potentiostatic depositions the current efficiency increased from 84% to almost 100% upon application of ultrasound. Morphology of deposits prepared by potentiostatic depositions was analyzed by scanning electron microscopy, and found to be different at high ultrasonic intensities.     

Quantitative characterization of protective films grown on copper in the presence of different triazole derivative inhibitors

The protective films developed on copper by anodic polarization in a borate-buffered solution containing benzotriazole (BTAH), 1-hydroxybenzotriazole (BTAOH) or 3-amino 1, 2, 4-triazole (ATA) have been characterized using coulometric experiments and an electrochemical quartz crystal microbalance (EQCM). The combination of these two techniques has allowed the CuO and Cu₂O layers and the cuprous-organic layer to be analyzed quantitatively. In the presence of BTAOH, the oxide layers were very similar to those formed in inhibitor-free solution and BTAOH appeared to be adsorbed on the oxide film. In the presence of BTAH, a thick Cu₂O film was covered by a Cu-BTA film containing 8% Cu⁺ ions. Cupric oxide appeared on Cu₂O areas uncovered by Cu-BTA. In the presence of ATA, the Cu₂O layer was very thin and the greater part of Cu⁺ ions (75%) was involved in a thick Cu-ATA film.     

EQCM study of the electrodeposition of manganese in the presence of ammonium thiocyanate in chloride-based acidic solutions

The influence of ammonium thiocyanate (NH₄SCN) on the mechanism of manganese electrodeposition from a chloride-based acidic solution was investigated by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). The EQCM data were represented as plots dΔm dt⁻¹ versus E, known as massograms. Because massograms are not affected by interference from the hydrogen evolution reaction, they clearly show the manganese reduction and oxidation processes. By comparing the voltammograms with their corresponding massograms, it was possible to differentiate mass changes due to faradaic processes from those due to non-faradaic processes. Morphology, chemical composition and structure of the manganese deposits formed in different potential ranges were analyzed by scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), and X-ray diffraction (XRD). The results showed that in the absence of NH₄SCN, Mn(OH)_2(s) is formed in the potential range −1.1 to −0.9 V due to the hydrogen evolution reaction in this region. At more cathodic potentials, the deposition of β-manganese and the inclusion of Mn(OH)_2(s) into the deposit occur; both of these species underwent dissolution by non-faradaic processes during the anodic scan. In the presence of NH₄SCN, the formation of α- and γ-manganese was observed. When the potential was ≤−1.8 V and [NH₄SCN] exceeded 0.3 M, the α-manganese phase was favored.     

Passive films on stainless steels—chemistry, structure and growth

The outstanding corrosion resistance of stainless steels results from the presence of a thin oxide—‘passive’—film on the metal surface, typically 1-3 nm thick. The characterisation of the composition and structure of such thin films and the study of their interaction with corrosive environments requires a combination of sophisticated experimental techniques. This paper reviews progress in the characterisation and understanding of passive films on stainless steels achieved over the past two decades. During this period, ex situ surface analysis methods have made substantial progress and new in situ methods for the study of passive films with atomic resolution have been introduced, giving real time information on film chemistry and growth. It has been found that whereas passive film growth occurs in seconds or minutes, long range film ordering is a considerably slower process that takes several hours. In situ investigations indicate that at short times, charge transfer at the metal/film or the film/solution interface limits the rate of film growth on stainless steels. In situ estimates of film composition confirm previous data obtained with ex situ techniques.     

碘酸钾对电镀铬过程的作用

本文研究了碘酸钾对镀铬阴极过程的影响。加入碘酸钾后,可使含有机添加剂的镀铬溶液稳定性最高,并使阴极电流效率及沉积速度提高。同时使镀液的覆盖能力和分散能力得到改善。测定了加入碘酸钾前后的镀铬阴极化曲线,利用ＸＰＳ方法对镀层表面及深度分析表明,碘酸钾不与铬发生共沉积。     

Electrochemical behavior of thin polycrystalline rhodium layers studied by cyclic voltammetry and quartz crystal microbalance

Electrochemical behavior of thin polycrystalline Rh layers has been studied in 0.5 M H₂SO₄ solution by cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). The properties of surface oxide formed on freshly electrodeposited Rh are different than on electrochemically aged Rh. The analysis of frequency changes in both hydrogen and oxygen regions is presented. It is suggested that hydrogen desorption occurs simultaneously with the adsorption of HSO₄⁻ ions, whose maximum surface coverage reaches ca. 8%. The EQCM results indicate that RhO is the main species formed during Rh surface oxidation. Metal dissolution proceeds during electrode cycling to sufficiently high potentials. The amount of dissolved metal increases with an increase in potential and a decrease in scan rate.     

Electrodeposition of CdS from acidic aqueous thiosulfate solution—Invesitigation of the mechanism by electrochemical quartz microbalance technique

Electrochemical quartz crystal microbalance was used to study mechanism of cathodic electrodeposition of CdS from acidic aqueous solutions containing 0.01 M Cd(ClO₄)₂ and 0.1 M Na₂S₂O₃ as a source of sulfur. Experiments were performed by means of cyclic voltammetry and potentiostatic method. A comparison of gravimetric and current responses at pH 3 and 4 allowed for determination of the potential range in which side reactions of reduction of SO₃²⁻ and H⁺ ions compete most strongly with formation of CdS. The film thickness was determined by means of two methods: from AFM profiles and EQCM measurements.     

Correlation between conductance and mass changes during p-doping of 2-methoxynaphthalene films

The redox response of 2-methoxynaphthalene films electrosynthesized in two different organic solvents, acetonitrile (ACN) and nitrobenzene (NB) has been studied by different in situ electrochemical techniques: the in situ conductance technique, electrochemical quartz crystal microbalance (EQCM) and electrochemical voltage spectroscopy (EVS). In situ measurements of conductance as a function of the potential during p-doping of 2-methoxynaphthalene films, electrosynthesized in TBAPF₆-ACN and TBAPF₆-NB, show that the conductance properties are strongly dependent on the solvent used during electrosynthesis, resulting in higher conductance values for films electrosynthesized in NB solutions. The EQCM technique has been used to correlate the frequency changes (mass changes) at the electrode surface with conductance changes during p-doping of the different films. The molar mass of the species involved in the charging-discharging reactions has been estimated from the EQCM results. For the determination of the electrochemical bandgap of the two different films, cyclic voltammetry (CV) and EVS were applied. Films electrosynthesized in NB solutions have a lower value of the bandgap (1.34 eV) than films electrosynthesized in ACN solutions (2.00 eV).     

有机添加剂作用下锌镍合金电沉积机理

运用循环伏安、交流阻抗和电势阶跃等电化学方法研究了酸性电解液中苄叉丙酮、香草醛和OP-10 3种有机添加剂对锌镍合金电沉积的作用机理.结果表明,加入有机添加剂后均能使锌镍合金电沉积电位负移,当苄叉丙酮和OP-10联合作用时,锌镍电沉积阴极超电势最大,并能有效阻化氢气析出,更有利于得到光亮锌镍合金镀层.同时伏安图上出现一...     

Influence of polyethoxylated additives on zinc electrodeposition from acidic solutions

The influence of several ethoxylated additives (ethyleneglycol and polyethyleneglycol polymers of different molecular weights) on the nucleation, growth mechanism and morphology of zinc electrodeposited from an acidic chloride bath is reported. The electrochemical study was carried out using cyclic voltammetry, inversion potential and chronoamperometric techniques. The dimensionless graphs model was applied to analyse the nucleation process and the results showed that the studied additives have a blocking effect on the electrodeposition of zinc. This effect occurs in the first stages of the nucleation process and is dependent on the molecular weight of the additive. Changes induced by the presence of additives in the morphology and grain size of the deposits were observed using SEM analysis. Results show that the presence of additives modifies the nucleation process and determines the final properties of the deposits.     

Mechanism of copper electrodeposition in the presence of picolinic acid

The influence of picolinic acid (PA) on copper deposition from a slightly acidic sodium sulphate electrolyte has been studied over a wide range of concentration and pH by cyclic voltammetry. The mechanism by which the copper electrodeposition process in the presence of PA takes place, depends on the chemistry and electrochemistry characteristics of the additive. Depending on the PA concentration and pH of the solution, five different cathodic current peaks are obtained, which are assigned to different steps involving copper deposition from free-Cu²⁺ ions and [Cu(PA)_n]²⁺ complex species as well as H⁺ ions electroeduction. Fine-grained, highly adherent and bright copper deposits were obtained.     

Growth of multiwalled carbon nanotubes during the initial stages of aerosol-assisted CCVD

We report a study of the initial stages of growth of aligned multiwalled carbon nanotubes (MWNT) synthesised by catalytic chemical vapour deposition (CCVD) of liquid aerosol obtained from toluene/ferrocene solution. A special experimental procedure has been developed to stop the process after short durations (30 s to 2 min). Two different pyrolysis temperatures are considered: 800 and 850 °C. Both scanning and transmission electron microscopy (SEM, TEM) coupled to energy-dispersive X-ray (EDX) analyses are used in order to determine the location of catalyst particles and to examine their chemical nature, morphology and size distribution when nanotubes start to grow. During the early stages (30 s), we observe the formation of a layer of catalyst particles on silicon substrates before the growth of nanotubes. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements indicate the occurrence of iron oxide (γ-Fe₂O₃ or Fe₃O₄). In addition, XPS analysis reveals the formation of graphite-like carbon, demonstrating that iron oxide particles catalyse the decomposition of toluene vapour. SEM and TEM observations show that these particles are most often located at the nanotube root, suggesting a base growth mechanism responsible for the formation of aligned nanotube when prolonging growth time (2 min).     

Effect of naturally formed oxide films and other variables in the early stages of Mg-alloy corrosion in NaCl solution

The influence of initial surface conditions on the subsequent corrosion behaviour of AZ31 and AZ61 magnesium alloys in 0.6 M NaCl solution has been studied using electrochemical impedance spectroscopy. For obtaining the different surface conditions, some of the specimens were immersion tested with the surface in the as-received condition, while others were tested immediately after mechanical polishing, and part of the polished specimens after six months of exposure to the laboratory atmosphere. Considering the evolution of the high-frequency capacitive arc of the Nyquist diagram, whose diameter is related to the corrosion process, a clear effect of the initial surface conditions is observed only in the early stages of testing. This effect is especially significant for the freshly polished specimens.     

Electrochemical copolymerisation of luminol with aniline: A new route for the preparation of self-doped polyanilines

Electrochemical copolymerisation of luminol and aniline from acidic aqueous medium onto gold electrodes has been investigated. Cyclic voltammetry in combination with electrochemical quartz crystal microbalance (EQCM) have been used to study both the in situ growth and redox switching process. In monomer free solution, the deposited polymers are stable and electrochemically active but distinct behaviour is shown by poly(luminol-aniline) films obtained from solutions with different monomers concentration ratio. In acidic medium, the current-voltage profiles range from a polyluminol (one pair of redox couple) to a polyaniline like redox conversion (three redox couples) as the aniline concentration increases. Unlike polyaniline, all prepared copolymers display well expressed electroactivity in sodium carbonate medium (pH 8), which also extends with the aniline content. The self-doping role assured by luminol moiety in the copolymer is also retrieved from the simultaneously recorded EQCM data.     

Studies of the morphology, composition and reactivity of osmium nanodeposits on platinum single crystal electrodes

In the present work, the morphology and composition of osmium deposits formed in submonolayer amount on Pt(1 0 0) and Pt(1 1 1) single crystal surfaces either by spontaneous deposition or by electrolysis at 50 mV in different deposition times (t_dep), were studied. The cyclic voltammetric curves for Pt(1 0 0)/Os and Pt(1 1 1)/Os were recorded in the potential range where the oxidation of deposited osmium species occurs, which suggests that the chemical composition of the deposits is a mixture of metallic Os and OsO₂. The ratio of each species deposited depends directly on the deposition potential, as well as the surface structure characteristics. The composition of the modified platinum single crystal surfaces has also been estimated by X-ray photoelectron spectroscopy (XPS), whose results agree with those obtained by CV, about the amount of osmium oxide on Pt(1 1 1) to be higher than on Pt(1 0 0). This feature of the Pt(1 1 1)/Os becomes its surface more active for ethanol oxidation at lower potentials than that observed for Pt(1 0 0)/Os, although at high potentials the high presence of OsO₂ is prejudicial to the catalytic activity of the electrode. The Pt-Os surfaces were also explored by use of the scanning tunneling microscopy (STM) technique in order to image the features of osmium deposits on platinum, after a short and a long deposition time. It was found, by using spontaneous deposition procedure, that the dimensions of osmium deposits islands do not grow with the increase of degree of coverage of osmium on the surface, as well as they keep the monoatomic thickness.     

Self-assembly on copper surface by using imidazole derivative for corrosion protection

This paper presents the self-assembly of 1-(3-aminopropyl) imidazole (API) monolayer on the copper surface to study the inhibition effect of the API against copper corrosion in 3% NaCl solution. The optimum concentration and assembling time for the assembly of API on copper were ascertained using electrochemical impedance spectroscopy (EIS). It was found that the API self-assembled monolayer (SAM) was formed with the concentration of 1.0 mM of API at 24 h assembling time and the maximum inhibition efficiency that could be achieved was 93.10%. The API SAM on copper was characterized by Fourier transform infrared spectroscopy (FT-IR), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle measurement (WCA). The presence of N and C signals in the XPS and EDX, show that the API molecules successfully anchor on the copper surface which demonstrates formation of API SAM on the copper surface. Corrosion protection capability of the copper modified with API was evaluated by the electrochemical polarization study (EPS) and scanning electron microscopy (SEM). The results of electrochemical and SEM analysis revealed that the API modified copper showed better corrosion protection in 3% NaCl solution.     

某些有机添加剂对硫酸-酒石酸盐溶液中电沉积Cu-Zn合金的作用

研究了以酒石酸钾钠、柠檬酸三钠作为络合剂的酸性硫酸盐溶液中的Cu-Zn合金镀层。探讨了电流密度、pH、温度对镀液分散能力和镀层组成的影响。在本实验条件下,添加剂的加入可以使镀液具有较好的分散能力和较高的电流效率。实验发现,在所研究的各种添加剂中,糖精、苯酚是加速剂,而硫脲、甘油是阻化剂。采用动电位极化和电化学阻抗谱方法,测定了Cu-Zn合金镀层在NaCl(φ=3.5%)溶液中的耐蚀性能。采用扫描电镜研究了添加剂对控制沉积质量的微妙作用。X-射线衍射分析表明,合金镀层的相结构是正交晶。在上述研究的基础上,提出了Cu-Zn合金电沉积的最佳组成和工艺控制参数。     

Influence of ultrasound irradiation on the adsorption of bovine serum albumin on copper

The effect of irradiation by power ultrasound on the adsorption of proteins on copper has been investigated, using bovine serum albumin (BSA) as a model protein in pH 7 phosphate buffer solution. Open circuit potential measurements, cyclic voltammetry and electrochemical impedance spectroscopy were used to characterise the copper/solution interface. Electrochemical impedance measurements at potentials close to the open circuit potential showed that pulsed ultrasound irradiation removes the naturally formed copper oxide films in phosphate buffer solution, and that their re-formation can lead to an oxide film with different electrical characteristics. Adsorption of BSA blocks the surface, decreasing or increasing the interfacial resistance, depending on the applied potential and the oxide characteristics, as well as changing the interfacial capacitance. This study augurs well for application of the combination of electrochemical impedance plus ultrasound to other systems. Special issue dedicated to Prof. Tony Wragg.