Electrodeposited Ni-B alloy coatings: Structure, corrosion resistance and mechanical properties

Ni-B alloy coatings with different boron content ranging from 4 to approximately 28 at.% were prepared by electrodeposition in a nickel-plating bath containing sodium decahydroclovodecaborate as a boron source. The influence of the boron concentration in the coatings on their structure, morphology, electrochemical and corrosion behavior, physico-mechanical and electrical properties was investigated using X-ray diffractometry (XRD), scanning electron microscopy (SEM), potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and other methods. It was found that the electrodeposited Ni-B coatings with relatively low boron content (≤8 at.%) are nanocrystalline and comprise a solid solution of boron in f.c.c. Ni lattice having a mixed substituted-interstitial type. Further increase in the boron content (up to 10-15 at.%) leads to the appearance of heterogeneous amorphous-nanocrystalline structure, and the coatings with a high boron content (20 at.% and above) are X-ray amorphous. Polarization measurements in neutral NaCl solutions showed that the Ni-B coatings with relatively low boron content demonstrate a potential region of low anodic currents associated with the passive film formation at the alloy surface. The anodic current in this potential region increases significantly with increasing the boron content above 10 at.%, suggesting the non-protective nature of the anodic film formed on the amorphous Ni-B alloys. Immersion tests monitored by EIS measurements revealed a significantly better corrosion performance of the Ni-B coatings with low boron content (4 at.%) in comparison with that of the amorphous coatings. The microhardness and wear resistance of the Ni-B coatings essentially increases with increasing the boron content. Maximum microhardness and wear resistance were found for the coatings containing 8 at.% B.     

Magnetic properties of nanocrystalline iron group thin film alloys electrodeposited from sulfate and chloride baths

Systematic studies of iron group binary (NiCo and CoFe) and ternary (CoNiFe) thin film alloys relating their magnetic properties with film composition, grain size and the corresponding crystal structure were investigated. Anions influence current efficiencies, magnetic properties, surface morphology and phases of electrodeposited films. Higher current efficiencies in chloride baths compared to sulfate baths were observed for CoFe, NiCo and CoNiFe alloys. The higher deposition current efficiencies in chloride baths were attributed to a catalytic effect. Anion types in CoFe and CoNiFe thin film alloys influenced the microstructures and the resulting magnetic properties (coercivity and squareness). The microstructures of NiCo alloys depend on the deposit Co contents rather than anion types. The surface morphologies of CoFe, NiCo and CoNiFe thin films were independent of anion types. CoFe deposits exhibited relatively smooth surface morphology and turned into fine crystallites with increasing solution Fe⁺² concentration. NiCo deposits showed very smooth surface morphology. CoNiFe deposits had the surface morphology of polyhedral crystallites. The deposit Fe content in CoFe electrodeposits linearly increased with increasing solution Fe⁺² concentration for both chloride and sulfate baths. Similar linear behavior of deposit Co contents was observed in NiCo electrodeposits.     

Electrochemical corrosion performance in 3.5% NaCl of the electrodeposited nanocrystalline Ni films with and without dispersions of Cr nanoparticles

Nanocrystalline (nc) Ni films with and without dispersions of Cr nanoparticles were electrodeposited from a nickel sulfate bath. The grain size of the nc-Ni films was reduced with increasing in the co-deposition content of Cr nanoparticles. Potentiodynamic polarization tests showed that increasing in the co-deposition content resulted in an enlarged passive region of the nc-Ni in 3.5% NaCl through reducing the corrosion potential and increasing the breakdown potential. Scanning electron microscopy (SEM) observation indicated that the polarized pure nc-Ni film exhibited numerous large and deep pits. However, they became smaller and shallower when 4.5 wt.% Cr nanoparticles were co-deposited, and almost disappeared when 10.9 wt.% Cr were co-deposited. X-ray photoelectron spectroscopy (XPS) analysis showed that the different electrochemical corrosion performance was associated with the ability of the Cr nanoparticles co-deposited nc-Ni film to form a continuous Cr-oxide passive film.     

Electrochemical investigation of electrodeposited Fe-Pd alloy thin films

In the present study, the electrodeposition of Fe, Pd and Fe-Pd alloys, in alkaline solutions, has been investigated. Using ammonium hydroxide and trisodium citrate as the complexing agents, it has been shown that the co-deposition of Fe and Pd is achieved due to diminishing the difference between the reduction potentials of these two metals. Cyclic voltammetry results clearly show that the electrodeposition processes are diffusion-controlled and the diffusion coefficients of Fe²⁺ and Pd²⁺ are 1.11 × 10⁻⁶ and 2.19 × 10⁻⁵ cm² s⁻¹, respectively. The step potential experiments reveal that nucleation mechanism is instantaneous with a typical three-dimensional (3D) growth. At low overpotentials, addition of Pd²⁺ to Fe²⁺ solution leads to a dramatic reduction in the number of nucleation sites, due to this fact that at such overpotentials, the electrodeposition behavior of Pd²⁺ governs on the overall process. The analysis of chemical composition of the electrodeposited films and the number of nucleation sites indicate that at higher overpotential, Fe²⁺ is deposited preferentially, thus the electrodeposition of iron-palladium alloys was classified as an anomalous co-deposition.     

Electrodeposition of nanocrystalline CdSe thin films from dimethyl sulfoxide solution: Nucleation and growth mechanism, structural and optical studies

Cadmium selenide (CdSe) nanocrystalline semiconductor thin films have been synthesized by electrodeposition at controlled potential based in the electrochemical reduction process of molecular selenium in dimethyl sulfoxide (DMSO) solution. The nucleation and growth mechanism of this process has been studied. The XRD pattern shows a characteristic polycrystalline hexagonal wurtzite structure with a slight (1 0 1 0) crystallographic preferred orientation. The crystallite size of nanocrystalline CdSe thin films can be simply controlled by the electrodeposition potential. A quantum size effect is deduced from the correlation between the band gap energy and the crystallite size.     

Phase structure of electrodeposited alloys

By electrodeposition it is possible to obtain alloy phases of metastable structure; these phases may be different from those reported for metallurgical equilibrium conditions or may have different compositions for the solubility limits, in some cases with very important enlargement. Typical cases are examined, discussing published results and presenting new findings. To understand the general behaviour, free energy versus composition g/x diagrams were calculated and are presented for the alloys examined in equilibrium conditions and after modification to obtain composition limits for the electrodeposited phases in stable and metastable state.The first reported case is Ni-Sn alloy, where the well known metastable phase NiSn is obtained. The second case is the electrodeposition of IB-Sn alloys from non-cyanide electrolytes. Phase structure of Zn-rich electrodeposited Zn-Ni alloys is also discussed as representative of grain size effect on phase stability.From the different cases examined, the occurrence of electrodeposited intermediate phases can be interpreted according to a local thermodynamic equilibrium, whilst long range order is difficult to observe in as-deposited layers. These phases depend on bath composition and operation conditions (temperature, stirring, direct or pulse current density) giving phases of different grain size which in turn can influence their stability.     

化学镀Ni-B非晶箔性能的研究

介绍一种利用化学镀制备非晶箔方法,用x射线对非晶特性检测,DSC测定非晶晶化温度,扫描电镜、透射电镜对其结构、显微组织进行研究.     

非晶态镍-硼合金柱撑膨润土催化剂的制备及其加氢性能的研究

采用浸渍-化学还原法制备了非晶态镍-硼合金柱撑膨润土催化剂,考察了催化剂不同制备条件对其催化硝基苯加氢制苯胺反应性能的影响;并对催化剂的晶相、形貌和比表面积等方面进行了表征。结果表明,非晶态镍-硼合金柱撑膨润土催化剂具有较大的比表面积,非晶态镍-硼在柱撑膨润土孔道中分散性较好,具有较好的催化加氢性能和稳定性。非晶态镍-硼柱撑膨润土催化剂在加氢反应的初始压力为2.0 MPa、温度为110 ℃、反应时间为2 h条件下,催化硝基苯加氢制苯胺的转化率和选择性分别达到92.6%和96.1%,并且催化剂在连续使用6次后硝基苯的转化率和苯胺的选择性分别为88.9%和93.8%。     

Corrosion behavior of electrodeposited Wo3 thin films

In this study, nanostructured tungsten trioxide (WO₃) thin films were deposited on Indium tin oxide (ITO)-coated glass substrate using electrochemical deposition (ECD). After deposition, the films were annealed at 450 °C for 2 h in an air atmosphere. X-ray diffraction (XRD) analysis confirmed that the prepared WO₃ thin films have crystalline phases. According to the absorption measurements, the optical bandgap of the WO₃ film was calculated as Eg 2.80 eV. Based on the scanning electron microscopy (SEM) images, the surface morphology of the thin films was influenced by deposition conditions. Raman spectroscopy analysis was also used to further examine the structure and chemical compositions of the thin films. The nature of the nanostructured WO₃ thin films was studied with Electrochemical Impedance Spectroscopy (EIS) and Tafel. Nyquist, open circuit potential and Bode analysis were used to evaluate structural changing and corrosion behavior of the prepared WO₃ thin films. With the help of these measurements and analyzes, the parameters such as solution resistance (Rs), polarization resistance (Rpo), a constant phase element (CPE) and a CPE exponent (n) were calculated as 43.43 Ω cm², 2.67 × 10⁶ Ω cm², 18.45 × 10⁻⁶ Ω⁻¹ s cm⁻², 0.958, respectively. Also, the corrosion features of the WO₃ thin films were investigated with the help of tafel measurements and the corrosion potential and current values were calculated as −0.583 V and 5.09 × 10⁻¹⁵ A, respectively. It is thought that the prepared thin film might have the potential to be used industrially with these features.     

Wettability of nanocrystalline diamond films

The wettability of nanocrystalline CVD diamond films grown in a microwave plasma using Ar/CH₄/H₂ mixtures with tin melt (250–850 °C) and water was studied by the sessile-drop method. The films showed the highest contact angles θ of 168 ± 3° for tin among all carbon materials. The surface hydrogenation and oxidation allow tailoring of the θ value for water from 106 ± 3° (comparable to polymers) to 5° in a much wider range compared to microcrystalline diamond films. Doping with nitrogen by adding N₂ in plasma strongly affects the wetting presumably due to an increase of sp²-carbon fraction in the films and formation of C–N radicals.     

Morphological, structural, microhardness and electrochemical characterisations of electrodeposited Cr and Ni-W coatings

This study examines the corrosion of electrodeposited Cr and of two electrodeposited Ni-W coatings in 0.1 mol L⁻¹ NaCl solution, as well as the influence of heat treatment on the crystallographic structure and microhardness properties of these coatings. Physical characterisation is carried out using scanning electron microscopy, X-ray diffraction, and energy dispersive X-ray analysis. Electrochemical characterisation is carried out using both the potentiodynamic linear polarization technique and open circuit measurements during long-term immersion tests. The corrosion products on the coating surfaces are characterised by ex situ Raman spectroscopy. As-electrodeposited Ni-W samples do not present defects, and the surface evolves from fine globular grains to rough polycrystalline morphology with decreasing electrodeposition current density. All the studied coatings corrode in the chloride medium and the corrosion is non-uniform for the Ni-W coatings. Raman analyses carried out after the immersion tests reveal Cr₂O₃ and Cr(OH)₂ corrosion products on the Cr coating surface, and Ni(OH)₂, NiO and WO₃ corrosion products on the Ni-W coating surfaces. Ni, Ni₄W and Ni-W phases are formed after heat treatment of the Ni₈₆W₁₄ coating at 600 °C. Although all the annealed Ni-W layers are cracked, their microhardness increases as the annealing temperature increases, suggesting that Ni-W coatings are potential substitutes for chromium in industrial applications in which good microhardness properties and stability at temperatures higher than 100 °C are required.     

Effects of photo-assisted electrodeposited on CuInSe2 thin films

Photo-assisted one-step electrodeposition has been applied to help in forming smooth and dense CuInSe₂ films. The difference in surface morphology and crystalline quality between CuInSe₂ films with various photo-assistance has been investigated. In the photo-assisted electrodeposition process, the many kinds of lamps providing maximum light intensity at about 380 to 620 nm were used as light source to be irradiated onto the surface of Mo-coated soda-lime glass substrates. The results suggested effects of photo-assistance including activating surface diffusion and growing high-crystalline quality films with reduced defects during electrodeposition.     

Formation of intermediate intermetallic layers on interaction of electrodeposited Sn,Ni-Fe,Ni-B coatings with different metallic substrata

The structure of layers and formation of intermetallic phases after thermal treatment in the system of thin electrodeposited Sn, Ni-Fe and sputtered Cu, Fe-Ni layers (thickness 0.1-2.0 μm) and thick electrodeposited Sn (thickness 6-10 μm) and Fe-Ni and Ni-B layers (thickness 2 μm) have been investigated by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and by metallographic and X-ray diffraction (XRD) techniques. The formation of intermetallic phases NiSn₃, Ni₃Sn₂, FeSn₂ and considerable reduction in the formation of brittle layers Ni₃Sn₄, Cu₆Sn₅, Cu₃Sn are determined by the structure and purity of electrodeposited tin [C (0.5-5) x 10-²; N (1-5) x 10-²; Fe, Cu, Bi, Pb (0.15-5.0) x 10^-2 wt%] in the system Sn/Fe-Ni/Cu. Electrodeposited Fe-Ni (80% Ni) as barrier layer in the system Sn/Fe-Ni/sputtered Cu completely prevents formation of Cu₆Sn₅, Cu₃Sn as a result of thermal treatment at 170°C up to 75 h. An amorphous Ni-B layer [B 4-8; C (3-7) x 10^-2 wt%] prevents formation of Ni₃Sn₄ and Cu₆Sn₅ in the system Sn/Ni-B/Cu (or Cu-Zn alloy) as a result of thermal treatment at 130°C (200 h) and 170°C (150 h).     

Electrodeposition of amorphous/nanocrystalline and polycrystalline Ni-Mo alloys from pyrophosphate baths

Pyrophosphate plating bath was found to be a good alternative to citrate bath for deposition of Ni-Mo amorphous alloys. The addition of wetting agents such as 2-butyne-1,4-diol and rokafenol N-10 to the pyrophosphate bath resulted in the removal of bumps, spheres and cracks from the Ni-Mo alloy surface. The plated alloy layers adhered well to Cu-Zn brass and steel, were of thickness from a fraction to tens of micrometers and the molybdenum content was independent of the distance from the support. An increase in the concentration of the molybdate ion in the bath leads to an increase in the amount of Mo in the alloys up to 33-35 at.% and to a decrease in the deposition rate. These changes and the influence of pH are discussed in the paper. The atom arrangement in the alloys changes from (2 2 0) preferred for pure-nickel deposition to (1 1 1) for content of Mo higher than 15 at.%. For 20 and more at.% of Mo the structure of the alloy is amorphous like. An analysis of SEM and STM micrographs obtained indicates that contrary to the Ni-W alloy the “amorphous” phase is made of circa 10-50 nm in diameter objects and not by long needles perpendicular to the substrate.     

Electrochemical and sorption characteristics and thermal stability of epoxy coatings electrodeposited on steel modified by Zn–Co alloy

The corrosion behaviour, transport properties and thermal stability of epoxy coatings electrodeposited on steel and steel modified by Zn–Co alloys were investigated during exposure to 3% NaCl solution. The electrochemical impedance spectroscopy (EIS), gravimetric liquid sorption measurements and thermogravimetric analysis (TGA) were used. Zn–Co alloys were electrodeposited on steel from chloride and sulphate baths, by different current densities. From the time dependence of pore resistance and coating capacitance of epoxy coating, diffusion coefficient of water through epoxy coating and thermal stability it was shown that Zn–Co sublayer obtained from chloride solution significantly improves the corrosion stability of the protective system based on epoxy coating. Almost unchanged values of pore resistance were obtained over the long period of exposure time, indicating the great stability of this protective system, due to the existence of a passive layer consisting of basic salts.     

Mechanical properties of nanocrystalline diamond/amorphous carbon composite films prepared by microwave plasma chemical vapour deposition

Nanocrystalline diamond films (NCD) have been deposited by microwave plasma chemical vapour deposition from CH₄/N₂ mixtures with varying methane content. They consist of diamond nanocrystallites with sizes of 3–5 nm embedded in an amorphous matrix with grain boundary widths of 1–1.5 nm. The CH₄ content in the gas phase has almost no influence on the microscopic structure but a strong effect on the macroscopic structure and morphology. The mechanical and tribological properties of these films have been investigated by nanoindentation, nano tribo tests, and nano scratch tests. The hardness of a 4-μm-thick film deposited with 17% methane was about 40 GPa, the indentation modulus 387 GPa, and the elastic recovery 75%. Ball-on-disk tests against an Al₂O₃ ball revealed, after initially higher values, a friction coefficient of ≤0.1. Tribo tests and scratch tests proved a strong adhesion and a protective effect on silicon substrates. Finally, the correlations between the macroscopic structure of the films and their mechanical and tribological properties are discussed.     

非晶态Ni-B合金在催化苯丙酮酸胺化加氢反应中活性寿命的研究

通过化学还原法制备了非晶态Ni-B合金催化剂,考察了催化剂在苯丙酮酸胺化加氢制备苯丙氨酸反应中的活性寿命。结果表明,非晶态Ni-B合金催化剂表现出比传统催化剂如雷尼镍和漆原镍等更为优异的活性与寿命。Ni-B合金催化剂经过简单的过滤回收步骤,重复使用5次后,催化活性没有明显大幅度下降,而雷尼镍和漆原镍分别循环使用3次和2次后,催化活性显著降低。结合XRD、DSC和TEM等手段,针对新鲜和使用回收后的催化剂进行了表征,发现非晶态结构在苯丙酮酸加氢反应环境中没有出现明显晶化现象,而小尺寸纳米颗粒的团聚和部分镍的氧化可能是导致催化剂活性降低的主要原因     

Effects of electrodeposition potential on the corrosion properties of bis-1,2-[triethoxysilyl] ethane films on aluminum alloy

Bis-1,2-[triethoxysilyl] ethane (BTSE) films were prepared on 2024-T3 alloys by using potentiostatic method for corrosion protection. This work mainly investigated the effects of electrodeposition potential on the corrosion properties of silane films. Films prepared at cathodic potentials display an improvement in corrosion inhibition properties, while those prepared at anodic potentials present the deterioration of protectiveness. In the case of cathodic deposition, when the potential shifts negatively from the open-circuit potential (OCP), corrosion protection of the obtained films initially increases and then decreases, with the optimal deposition potential at −0.8 V/SCE. As indicated in scanning electron microscopy (SEM) images, films deposited at the optimum potential present the most uniform and compact morphologies. In addition, steady-state polarization and current-time curves have been also recorded on Al alloys in BTSE solutions during the deposition, respectively.     

硼氢化钠对滑轮用铸钢板化学镀Ni-B合金薄膜性能的影响

在滑轮用铸钢板上化学镀Ni-B合金薄膜,并研究了硼氢化钠的质量浓度对化学镀Ni-B合金薄膜性能的影响。结果表明:适当增加硼氢化钠的质量浓度,有利于增大化学镀Ni-B合金薄膜的厚度及硼的质量分数,从而提高化学镀Ni-B合金薄膜的硬度。当硼氢化钠的质量浓度大于1.2 g/L时,硼氢化钠的水解速率加快及剧烈的析氢反应,导致化学镀Ni-B合金薄膜的厚度及硬度有所降低。当硼氢化钠的质量浓度为1.2 g/L时,化学镀Ni-B合金薄膜表面"胞状"颗粒均匀、致密,摩擦因数和磨损率最低,具有最佳的耐磨性。     

Electrochemical corrosion behavior of nanocrystalline Co coatings explained by higher grain boundary density

In this paper, nanocrystalline Co coatings were prepared using pulse reverse electrodeposition method. The electrochemical corrosion behavior of nanocrystalline (NC) Co compared with coarse-grained Co (CG) coatings in different corrosion media were characterized using potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). Results showed that in the NaOH or NaCl solutions, the NC Co exhibited improved corrosion resistance when compared with CG Co coatings, which is due to the higher grain boundary density in NC materials to quickly form a stable and protective passive film. In the case of NC Co coatings in HCl or H₂SO₄ solutions, since no obviously passive process can be observed, high grain boundary density in NC Co will accelerate corrosion by providing high-density of active sites for preferential attack. The controversial experimental results on NC Co coatings in different corrosion media can be reasonably explained by the positive or negative effect of high-density network of grain boundaries in NC materials.