Electrodeposition of silver from nitrate solution: Part II. Mechanism of the effect of phosphate ions

The mechanism of compact Ag-film formation by electrolysis from nitrate solution with addition of small amounts of phosphate ions is elucidated. It is shown that the phosphate ions exert their effect by lowering the exchange current density. Consequently, the radii of nucleation exclusion zones also diminishes, thus producing conditions stimulating electrodeposition of continuous thin Ag-film.     

电沉积铁氰化镍薄膜的电控离子交换性能

采用电沉积方法在不同导电基体上制备出具有电化学控制离子交换(ESIX)性能的电活性NiHCF(nickel hexacyanoferrate)薄膜.在1 mol•L^-1 KNO₃溶液中采用电势循环可逆地置入与释放碱金属离子,比较了铂、铝和石墨基体上薄膜的电活性、离子交换容量及再生能力;在1 mol•L^-1(KNO₃+CsNO₃)混合溶液中测定了不同浓度下薄膜的伏安特性曲线和电化学交流阻抗谱,分析了薄膜对Cs/K离子的选择性.重点考察了制膜液组成对薄膜电化学性能的影响,通过EDS测定薄膜组成并结合循环伏安曲线分析了薄膜组成和结构与其电化学特性之间的关系.实验表明,3种基体材料上均能制得性能稳定的NiHCF膜,铝和石墨基体上的NiHCF薄膜同样具有良好的ESIX性能;控制制膜液组成可得到不同组分占优的膜,由此可筛选较为理想的ESIX膜材料.     

颗粒掺杂对Al基β-PbO_2复合材料性能的影响

在Al/Pb/α-PbO2-WC表面恒电流电沉积制备了β-PbO2-WC(Co3O4)复合沉积层,获得了Al/Pb/α-PbO2-WC/β-PbO2-WC(Co3O4)复合材料.考察了WC、Co3O4颗粒掺杂对β-PbO2复合材料物理性能及其在锌电积模拟体系中的耐蚀性、析氧电催化活性、交流阻抗特性的影响.结果表明:WC与Co3O4颗粒在β-PbO2中的掺杂,提高了复合材料的显微硬度,降低了电阻率及锌电积模拟体系中的析氧过电位,增强了锌电积模拟体系中的耐腐蚀性能.     

电沉积非晶态合金镀层磁性的控制

磁性元件薄膜化促进了磁性镀层的开发与应用。综述了镀液及镀层成分、电沉积工艺、镀层厚度及热处理对电沉积非晶态镀层性能的影响，以便在实际应用中控制非晶态合金镀层的磁性。     

On the observation of inductive high-frequency impedance behaviour during the electrodeposition of Au—Sn alloys

Inductive high-frequency impedance behaviour is often observed in metal electrodeposition systems. This behaviour is typically attributed to equipment limitations or non-idealities in the cell set-up and electrical connections. Such instrumental artefacts would nevertheless be relevant to a frequency range which is expected to be well above that in which inductive behaviour is in fact observed (down to a few tens of Hz). In this paper some results on an acidic Au—Sn electrodeposition system are reported. Electrochemical impedance and potentiostatic transients were measured. These results suggest that the high-frequency inductive behaviour may be related to metal nucleation processes. A correlation is proposed between the pseudo-inductive potentiostatic nucleation transients and the pseudo-inductive behaviour of the impedance spectra.     

Electrodeposition, composition and structure of Zn—Cr alloys

The effect of polyethylene glycol (PEG 1500) as additive and of deposition conditions on Zn—Cr alloy electrodeposition from an acidic sulfate electrolyte at room temperature, without agitation was investigated. PEG polarizes the overall cathodic reaction and inhibits Zn deposition. Cr codeposition with Zn starts at a cathodic potential of about –1,95 V vs Hg/Hg₂SO₄, which is reached at current density of about 20 A dm^–2 in galvanostatic conditions. Zn—Cr alloy coatings containing up to 28 at % Cr were obtained depending on the plating conditions. SEM observations showed an island-like structure, formed by the local growth of crystals, which covered the surface during further deposition. In the first stages of electrodeposition the powder diffraction spectra contain lines of b.c.c. -(Zn,Cr) phase (a 3.02 Å). After 30 s deposition time weak lines of Zn-based phase (a 2.67 Å, c 4.90 Å) appear, and become clearly visible in coatings deposited for 90 s. The average Cr content in the alloy coatings decreases with advancing deposition. The as-plated surface contains C in organic compounds and Zn(OH)₂. After 50 min sputtering, Zn and a mixture of Cr, Cr₂O₃ and Cr₇C₃ were found. The presence of organic C and O, probably from inclusions of PEG, were also detected.     

Influence of charged tail groups of self-assembled monolayers on electrodeposition of polyaniline

Self-assembled monolayers (SAMs) of thiols with three different tail groups, −COOH, −SO₃Na, and −NH₂, were used to modify the Au substrates for electrodepositing polyaniline (PANI). Electrochemical quartz crystal microbalance (EQCM) results indicated a slower rate of deposition of PANI on a SAM surface consisting of positively charged amine groups compared to polymerization on bare gold and on a SAM of carboxyl acid groups. The properties of the SAM layers are dependent on the pH value of the solutions, and are effective only at very low pH values (pH < 2). A layer of the positively charged amino groups in acidic solution acted as a barrier for electron transfer in electro-oxidation of aniline monomer. The positively charged SAM of amine groups also increased repulsion between the coupled aniline species and the electrode surface and in this way hindered electrodeposition. Modification of the surface with pre-patterned SAMs have been demonstrated to be a convenient and practical way to fabricate selectively deposited thin films of polyaniline.     

Electrochemical investigations of copper behaviour in different cupric complex solutions: Voltammetric study

The electrochemical behaviour of copper has been investigated in different cupric complex solutions by cyclic voltammetry. In pyridinic and picolinic solutions the reduction of cupric complex occurred in two stages leading to Cu(I) and Cu(0), respectively. The electrodeposited copper is oxidized in two steps leading to Cu(I) and Cu(II) as in ammoniacal cupric complex solutions. In glycine, alanine, sulfamic acid and ethylenediamine solutions, the cuprous complex is an intermediate in the cupric complex reduction but it is not detected during the oxidation of the electrodeposited copper in these solutions. In EDTA and triethanolamine solutions, the cuprous complex is not observed. The rate of copper etching was determined in pyridinic and ammoniacal cupric solutions and was shown to be faster in ammoniacal cupric solutions than in the pyridinic solutions.     

Effect of electrolysis conditions on the deposition of silver–bismuth alloys

The electrochemical deposition and dissolution of silver, bismuth and silver–bismuth alloy from a cyanide–tartrate electrolyte were studied by means of cyclic voltammetry. The influence of the electrolyte composition on the electrochemical reactions is discussed. The deposition potentials of the two metals could be maintained close to each other by means of appropriate complex forming agents, leading to their codeposition. Silver deposition is the predominant reaction in the electrolyte studied and the bismuth content in the coating increases with increased current density. The dissolution potentials of the two metals are quite distinct; they differ by more than 0.5 V. In the presence of a free complex forming agent, both the deposition and the dissolution potentials of silver can be shifted in the negative direction. Depending on the type and amount of the complex forming agent, they can become more negative than the deposition and dissolution potentials of bismuth. Predominant deposition of bismuth is realized in this case and the codeposition of silver is enhanced at higher current densities. By varying the amount of the complex forming agent, silver–bismuth coatings of any desired composition can be obtained.     

微电解-生物膜复合工艺净化含重金属离子的有机废水

A complex process of micro electrolysis and biofilm was developed to continuously treat organic wastew-aters containing heavy metal ions such as Cu^2 and Cr^3 ,and the relevant purifying mechanism was also addressed. In detail,organic materials in wastewater could be consumed as nutritious source by biofilm composed of aerobes and anaerobes,However,for heavy metal ions (Cu^2 ,Cr^3 ),part was removed by electrodeposition,and some was adorbed on biofilm.In order to compare with the combined process of micro electrolysis and biofilm,the experimental data of micro electrolysis process (intermittent )or biofilm process (continuous)were provided,and the kinetic data of C6H12O6(glucose)biodegradation by cultured microbes or acclimated microbes were also obtained,These experimental results indicated that for wastewater initially consisted of C6H12O6(500 mg.L^-1),Cu^2 and Cr^3 (10mg.L6-1),after treatment,its concentrations of C6H12O6,Cu^2 and Cr^3 were lowered to the leve of 55-65 mg.L^-1),after treatment,its concentrations of C6H12O6,Cu^2 and Cr^3 were lowered to the level of 55-65 mg.L^-1,and less than 1mg.L^-1,respectively,And the industrial reused water standards could be met by treated wastewater.