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 additives on Cu electrodeposition mechanisms in acid solution: direct current study supported by non-electrochemical measurements

The effect of polyethylene glycol (PEG) and chloride ions on copper electrodeposits is investigated by electrochemical measurements (cyclic voltammetry, current and potential pulses) coupled with an ellipsometric study at open circuit. When PEG is added to the Cu²⁺ solution, the modifications of the copper electrodeposition mechanism can be explained by a polymer-electrode interaction instead of a complex formation in solution. Since ellipsometry has shown no PEG adsorption at least at open circuit, that adsorption is assumed to be potential dependent. Moreover, the efficiency of PEG alone in solution, seems to be decreased when the deposit grows. With Cl⁻ alone, an activation of copper deposition is performed. The simultaneous addition of the two additives induces a blocking effect of the copper reduction that continues on with time. X-ray diffraction, optical microscopy and atomic force microscopy (AFM) carried out complementary results, on bulk deposits obtained from solution with and without these additives. It has been found that a bright, compact and homogeneous coating is only obtained in presence of both additives. In that case, the texture of the deposit is modified and the roughness is significantly decreased to 0.5 μm.     

脒基硫脲对酸性硫酸盐溶液中铜电沉积过程影响的研究

研究添加剂对电沉积的作用机理及添加剂用量对镀层结构的影响,有利于开发一种更好效果的添加剂。为了获得良好的镀层,硫脲及其衍生物作为添加剂已经广泛应用于电镀工业中,脒基硫脲(GTU)作为电镀添加剂,采用循环伏安法(CV)和电化学石英晶体微天平(EQCM)技术,考察GTU在酸性溶液中对铜沉积机理的影响。CV结果表明,脒基硫脲对铜电沉积有抑制作用;QCM分析表明,当镀液中含有GTU时,铜阴极沉积和阳极溶出过程的M/n分别为61.50,64.12 g/mol,表明电极反应过程中,Pt/Cu电极表面的铜离子沉积从二电子过程过渡到单电子过程,添加剂的最佳浓度为10 mmol/L。     

The effect of thiourea,LIX65N and chloride ion on the morphology of electrowon copper

The effect of thiourea, LIX65N (a common organic extractant for copper) and chloride ion on the morphology of electrodeposited copper under different conditions is reported. The deposit morphology was assessed by optical microscopy techniques, scanning electron microscopy and X-ray diffraction measurements. The importance of controlling the concentration of these additives in electrowinning copper from electrolytes obtained from a solvent extraction separation process is indicated.     

连续电解精炼阴极铜过程中添加剂的作用

采用循环伏安法研究了浓度不同的几种添加剂(硫脲、聚丙烯酰胺、明胶和骨胶)对铜电解精炼过程的影响。结果发现,与未加添加剂的空白电解液相比,加入单一添加剂后铜沉积电流峰值明显提高,表明单一添加剂的加入会促进阴极铜的沉积。当在电解液中加入3.0 mg/L硫脲和2.4 mg/L聚丙烯酰胺作为复合添加剂时,铜沉积电流峰值与加入单一硫脲与聚丙烯酰胺时相比分别提高了31.2%与5.1%,表明二者有协同作用。结合扫描电镜(SEM)、能谱(EDS)和X射线衍射(XRD)对阴极铜的微观形貌、元素组成与物相进行表征,发现使用上述复合添加剂时,阴极铜的表面形貌与纯度最理想。     

Galvanostatic and microscopic studies of nodulation during copper electrolysis

The galvanostatic technique on a laboratory scale has been shown to be a useful tool in detecting the presence of nodules on the cathode during copper electrodeposition by using the value of the starting electrolytic potential and by the presence of a cathodic polarization peak on the potential–time curve. Studying the morphology of the deposit with a scanning electron microscope at various magnifications confirmed the galvanostatic results. It is postulated that inappropriate concentrations and/or ratios of the additives (thiourea, gelatin and chloride ions) are associated with a certain current density that generates intergranular microcracks due to adsorption of the additives and leads to the formation of nodules at the macroscale.     

Electrodeposition of copper: the nucleation mechanisms

The nucleation mechanisms of copper during electrodeposition of thin films from sulfate solutions were studied by utilizing the electrochemical techniques (cyclic voltammetry and chronoamperometry) and atomic force microscopy (AFM). Near atomically smooth glassy carbon was used as the deposition substrate (electrode). The copper nucleation mechanisms were examined as a function of solution pH, copper concentration, deposition potential, temperature, and background electrolyte. It was found that with pH and copper concentration increase, the nuclei size increased, while the nuclei population density decreased. An increase of deposition potential produced smaller nuclei and higher nuclei population density. Temperature affected the morphology of deposited copper. The presence of background electrolyte also influenced the morphology and population density of copper nuclei. The nucleation mechanisms were examined by fitting the experimental data (chronoamperometry) into the Scharifker-Hills nucleation models. It was found that at pH 1, in the absence of background electrolyte, copper nucleation was instantaneous. At pH 2 and 3, the mechanism was inconclusive. In the presence of background electrolyte, the mechanism at pH 1 and 2 was mixed, while at pH 3, the mechanism was progressive nucleation.     

Copper electrodeposition from an acidic plating bath containing accelerating and inhibiting organic additives

Copper electrodeposition on copper from still plating solutions of different compositions was investigated utilising electrochemical impedance spectroscopy (EIS), cyclic voltammetry, and scanning electron microscopy (SEM). An acid copper sulphate plating base solution was employed either with or without sodium chloride in the presence of a single additive, either polyethylene glycol (PEG) or 3-mercapto-2-propanesulphonic acid (MPSA), and their mixture. Thallium underpotential deposition/anodic stripping was employed to determine the adsorption capability of additives on copper. In the absence of chloride ions, MPSA shows a moderate adsorption on copper, whereas PEG is slightly adsorbed. At low cathodic overpotentials, the simultaneous presence of MPSA and chloride ions accelerates copper electrodeposition through the formation of an MPSA-chloride ion complex in the solution, particularly for about 220 μM sodium chloride. The reverse effect occurs in PEG-sodium chloride plating solutions. In this case, from EIS data the formation of a film that interferes with copper electrodeposition can be inferred. At higher cathodic overpotentials, when copper electrodeposition is under mass transport control, the cathode coverage by a PEG-copper chloride-mediated film becomes either partially or completely detached as the concentration of chloride ions at the negatively charged copper surface diminishes. The copper cathode grain topography at the μm scale depends on the cathodic overpotential, plating solution composition and average current density. Available data about the solution constituents and their adsorption on copper make it possible to propose a likely complex mechanism to understand copper electrodeposition from these media, including the accelerating effect of MPSA and the dynamics of PEG-copper chloride complex adsorbate interfering with the surface mobility of depositing copper ad-ions/ad-atoms.     

Palladium electrodeposition on polyaniline films

The electrochemical nucleation and growth of palladium particles onto polyaniline (PAni) films have been investigated by chronoamperometry and topographic and phase-mode atomic force microscopy (AFM). The films were synthesized under different potentiodynamic conditions in order to obtain polymer layers with comparable electroactivity but distinctly different morphology/porosity. The analysis of the current transients obtained for the initial stages of the Pd deposition indicates a 3D nucleative formation regime. A detailed Pd electrodeposition study onto the polymer matrix, using different deposition times, suggests that a constant number of critical nuclei is formed in the superficial part of the polymer porous matrix in the time scale between ca. 5 and 15 s.     

化学置换镀铜的研究

用电化学方法和扫描电子显微镜研究了钢铁置换镀铜反应及镀层形貌,结果表明,钢铁表面的置换铜镀层总是多孔的。加入增大铜,铁阴阳极极化的有机添加剂可以使镀层致密,减少孔隙总面积,有利于提高铜镀层与基体的结合强度。     

The use of electrochemical noise measurements to detect bad copper electrorefining conditions

Additives like thiourea, gelatin and chloride are used during copper electrorefining to promote a smooth deposit. However, additives can also facilitate nodule formation when their ratios and/or concentrations are inadequate. A preliminary investigation was conducted to determine if electrochemical noise (EN) measurements could be used to monitor and detect inefficient copper electrorefining conditions due to improper ratios and/or concentrations of additives. EN measurements were carried out in the laboratory under simulated industrial conditions. Galvanostatic experiments were conducted using a synthetic electrolyte containing different concentrations of additives. A 316L SS cathode and industrial copper anodes were used. The effects of three different data acquisition frequencies were also investigated. EN signals obtained as potential time record series were studied using statistical analyses and frequency domain transforms. The different calculated parameters gave similar results for all conditions studied except when additives present in the electrolyte led to nodule formation. Results also showed that the data acquisition frequency must be at least 10 Hz to detect improper ratios and/or concentrations of additives.     

Corrosion of cyanide copper deposits on zinc diecastings in acid solutions

The corrosion potential and morphology of copper films deposited from a cyanide solution on zinc diecast were studied in acid solutions similar to those employed in industry for the deposition of a second copper layer. Open circuit potential measurements and gravimetric methods were employed to determine the influence of the copper electrodeposition variables on the corrosion potential. The influence of variables such as the presence or absence of additives, the current density and the copper or cyanide concentrations were studied. The corrosion potential decreased with increasing copper film thickness. Less protection was obtained when a thin copper layer was electrodeposited from a solution without additives. Higher protection for the same thickness was obtained from a solution with high cyanide content. This result is related to the strong interaction between cyanides and the metal surface during the electrodeposition. A smooth surface structure was observed by SEM under these conditions.     

梯度电流密度下电沉积制备铜-镍-钼合金电极及其性能研究

采用梯度电沉积法制备铜基Cu–Ni–Mo合金电极,电流密度参数为:10 mA/cm^2×5 min+30 mA/cm^2×40 min+50 mA/cm^2×5 min。通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)分析了Cu–Ni–Mo合金镀层的表面形貌、元素组成、相结构和各元素的化学价态,并通过线性扫描伏安曲线(LSV)、电化学阻抗谱(EIS)和计时电流法对比了Cu–Ni和Cu–Ni–Mo合金电极在1 mol/L KOH溶液中的析氢性能和稳定性。结果表明,所得Cu–Ni–Mo合金镀层是呈花椰菜多孔形貌的非晶态结构。与Cu–Ni合金电极相比,Cu–Ni–Mo合金电极具有更大的比表面积,可为析氢反应提供更多活性位点,表现出更好的析氢性能,稳定性也更好。     

Comparative study of copper electrodeposition from sulphate acidic electrolytes in the presence of IT-85 and of its components

The effect of a new additive (IT-85) representing a mixture of triethyl-benzyl-ammonium chloride (TEBA) and hydroxyethylated-2-butyne-l,4-diol (Ferasine) on the kinetics of copper electrodeposition from sulphate acidic electrolytes, as well as on the morphology and structure of copper deposits was investigated and compared with those exerted by its two components, TEBA and Ferasine. Quasi-steady state hydrodynamic voltammetry at a rotating-disc electrode and electrochemical impedance spectroscopy were performed in order to obtain information about the kinetics of the cathodic process. SEM and X-ray diffraction analysis were used to examine the morphology and the structure of copper deposits. The kinetic parameters (_c, k₀) obtained by both Tafel and Koutecky-Levich interpretations showed that all tested organic additives have an inhibiting effect on copper electrodeposition. Unlike IT-85 or Ferasine, TEBA acts only as a blocking agent in the copper discharge process, without changing the reaction pathway corresponding to the absence of additives. Comparison of the inhibiting effects exerted by IT-85 and its components on the electrodeposition process pointed to the existence of a beneficial complementarity of TEBA and Ferasine when they are used in mixture.     

Effect of thiourea and saccharin on the roughness of electrodeposited ultrathin nickel and cobalt layers

Ni and Co films were produced by electrodeposition from plating baths containing either thiourea or saccharin. The effect of the organic additives on surface roughness was studied for the Ni-thiourea, Ni-saccharin, Co-thiourea and Co-saccharin systems. Layer thicknesses were varied from 1 to 10 nm and the additive concentration was varied from about 1 M to 1 mM. Contact mode atomic force microscopy was used to measure both the root mean square (RMS) peak height (nm) and the areal peak density (m^–2) of each film. Although the RMS peak height and areal density were both influenced by film thickness and by additive concentration, the two roughness measures provide complementary information on the layer morphology and growth mechanisms. The four systems studied responded differently to changes in the concentration of the added organic. For example, for films 8 nm thick, addition of 1.22 × 10^–3 thiourea reduced the Ni peak density about 80%; in contrast, the Co peak density was increased over 180% by addition of 1.25 × 10^–3 thiourea. Use of peak height and peak density data to infer growth mechanisms for ultrathin films is discussed.     

Zinc deposited polymer coatings for copper protection

Polypyrrole (PPy) and polyaniline (PAni) coatings were electrosynthesized on copper, by using cyclic voltammetry technique. Then, these coatings were modified with the deposition of zinc particles from aqueous zinc sulphate solution. The electrodeposition of zinc was achieved at a constant potential value of −1.20 V, in the amount of ∼0.75 mg/cm². The corrosion performance of zinc modified polymer coatings were investigated in 3.5% NaCl solution; by using the electrochemical impedance spectroscopy (EIS), and anodic polarization curves. The zinc particles improved the barrier property of polymer films, thanks to formation of voluminous zinc corrosion products within the pores of polymer coating. Also, the zinc particles provided cathodic protection to the substrate, where the polymer film played the role of conductance between zinc particles and copper.     

Amperometric determination of thiourea in alkaline media on a copper oxide–copper electrode

A copper oxide–copper electrode was tested in alkaline media for the anodic electrochemical detection of thiourea (TU). The correlation between the history of the electrode and potential range for optimum sensing of the particular susceptible species was analysed by electrochemical and surface layer techniques. The chemical composition and morphology of surface layers were examined using the SEM/EDX technique. Electrochemical data were obtained by cyclic voltammetry (CV) and chronoamperometry (CA). The linear calibration plots for an amperometric detection of TU in a delimited potential range, using CV and CA, were obtained for the 1–8 mM concentration range. Some considerations on the correlation between TU, electrode formation and polarization conditions are proposed. A copper oxide–copper electrode can be used as an inexpensive alternative for amperometric determination of TU in alkaline media without fouling the electrode surface.     

双向脉冲电镀纳米级镍镀层耐腐蚀性能研究

用直流电沉积法制备了普通光亮镍镀层,同时用双向脉冲电镀制备了纳米级镍镀层。用X射线衍射(XRD)、扫描电镜(SEM)等方法研究了镀层的晶粒尺寸、组织结构和表面形貌,通过孔隙率测定、盐雾试验、静态浸泡腐蚀失重试验和电化学方法等测试了镀层的耐蚀性能。结果表明,采用双向脉冲电流制备的纳米级镍镀层的耐蚀性明显优于普通直流镍镀层。     

酸性镀铜研究进展

将至今所使用的酸性镀铜添加剂分成六类进行了归纳叙述;简述近年来的各种物理因素例如脉冲技术、超声波技术、激光技术等在酸性镀铜中的应用现状及其对镀层质量的影响;总结应用阴极极化曲线、交流阻抗、微分电容等测试方法研究添加剂电化学行为和用扫描电镜、X-射线衍射、原子力显微镜等研究镀层结构来探讨酸性镀铜的沉积机理的一般方法。     

Influence of pulse plating parameters on the synthesis and preferred orientation of nanocrystalline zinc from zinc sulfate electrolytes

The influence of pulse electrodeposition parameters (current on-time T_on, current off-time T_off, and pulse current density J_p) was investigated on the surface morphology and grain size of zinc electrodeposited from a sulfate bath containing polyacrylamide and thiourea additives. The grain size and surface morphology of zinc deposits were studied by field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM), and the preferred orientation of the deposits was studied by X-ray diffraction. At constant current off-time and pulse current density, the grain size decreased asymptotically with increasing current on-time. In contrast, increase in the current off-time at constant current on-time and pulse current density resulted in grain growth. A progressive decrease of the grain size was observed with increasing pulse current density at constant current on-time and off-time. Nanocrystalline zinc with an average grain size of 38 nm was obtained at a pulse current density of 1200 mA/cm². The crystallographic orientations developed were correlated with the change in the cathodic overpotential, the angle between the preferred oriented plane and the lowest energy of formation plane (0 0 0 2), and the pulse electrodeposition parameters.