Tribological and electrochemical behavior of thick Cr-C alloy coatings electrodeposited in trivalent chromium bath as an alternative to conventional Cr coatings

Alternative process to hexavalent chromium plating, substitute materials and new designs are urgently needed owing to the requirement of “clean” manufacture. This comparative study was conducted to systematically investigate the tribological and electrochemical behavior of the Cr-C alloy coatings electrodeposited from a trivalent chromium bath and the hard Cr coatings electrodeposited from conventional hexavalent chromium bath, using reciprocating ball-on-disc tribometer and electrochemical analyzer. The electroplated Cr-C alloy coatings with thickness of 50 μm and acceptable quality that can be used for wear resistance as well as corrosion resistance purposes were produced successfully. The results show that the as-deposited Cr-C alloy coatings exhibited crack-free surface and amorphous/microcrystalline structure. The following heat treatment resulted in the cracked surface and the increase in hardness for the electroplated Cr-C alloy coatings. In contrast, the conventional Cr coatings exhibited cracked surface and their hardness decreased with the increase in annealing temperature. The electroplated Cr-C alloy coatings after heat treatment at 200 °C for 1 h exhibited better wear resistance than the conventional Cr coatings. In regard to the electrochemical behavior, the as-deposited Cr-C alloy coatings exhibited better corrosion resistance than the conventional Cr coatings. Therefore, the electroplated Cr-C alloy coatings are environmentally acceptable candidates to replace the conventional Cr coatings.     

锌-三氧化二铬复合镀层的特性

采用由氧化锌12g/L、氢氧化钠94 g/L、2-氨基-3-羧基吡啶4.2 g/L、四乙烯五胺17g/L、三乙醇胺2g/L、专利表面活性剂0.5 g/L及碳三氧化二铬(粒径2μm)0～ 11 g/L组成的镀液,于温度50℃、pH 6.5和电流密度4A/dm2的条件下,在低碳钢上电镀Zn-Cr2O3复合镀层.其显微硬度采...     

Properties and preparation of amorphous chromium carbide electroplates

The electrochemical and corrosion behavior of chromium electroplates formed in sulfuric acid solutions of Cr(III) in the presence of oxalates was studied by measuring steady-state polarization curves in 0.5 M H₂SO₄ solution. These electroplates demonstrate no active dissolution region and their open-circuit potentials are located in the passivity region, i.e. shifted substantially in the positive direction as compared with those of metallurgical chromium and electroplates from standard chrome-plating baths. The results of X-ray photoelectron spectroscopy (XPS) studies evidence that the passive metal surface layer several nanometers thick consists of chromium oxides with incorporated carbides formed during electroplating. It is supposed that the peculiarities of the corrosion and electrochemical behavior of the deposits under study can be attributed to the presence in them of chromium carbides, which operate as cathodic agents. At the same time, the formation of these carbide compounds during the cathodic deposition of chromium electroplates from sulfuric acid Cr(III) solutions in the presence of sodium oxalate is a result of electrocatalytic activity of metal chromium. The latter assumption is confirmed by XPS analysis of surface layers formed during the exposure of chromium to sulfuric acid solutions containing organic substances.     

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.     

Evaluation of the effects of surface treatments on the cathodic delamination and anticorrosion performance of an epoxy-nanocomposite on steel substrate

The St-37 type steel substrates were pretreated with Cr(VI) and Cr(III) conversion coatings where the latter was then post-treated with Co(II) and Ni(II) chemical treatments. The epoxy coatings containing 3.5 wt% nano-sized ZnO particles were applied over the chemically treated steel samples. The corrosion resistance of the samples was studied by a DC polarization technique. A scanning electron microscope (SEM) was utilized to investigate the morphology of the pretreated and post-treated samples. Electrochemical impedance spectroscopy (EIS) was utilized to investigate the corrosion resistance of the epoxy nanocomposites for different immersion times in 3.5 wt% NaCl solution. The adhesion strengths of the coatings were measured before and after 120 days of immersion in the corrosive electrolyte using a pull-off test. The cathodic delamination (CD) of the painted samples was also investigated. Results showed that conversion coatings can significantly increase the corrosion resistance and adhesion strength of the epoxy coating on the steel, and also reduce the rate of CD in comparison with an untreated sample. The adhesion strength and corrosion resistance of the epoxy coating on the Cr(III) pretreated samples were significantly greater than on the Cr(VI) sample. The increase in adhesion strength and corrosion resistance was more pronounced on the samples that were post-treated with Co(II) and Ni(II) chemical treatments. The cathodic disbonded areas of the Cr(III)–Co(II) and Cr(III)–Ni(II) post-treated samples were significantly lower than the Cr(III) and Cr(VI) pretreated samples. Results showed that Cr(III)-based conversion coatings can improve the anticorrosion performance and reduce CD compared with those with Cr(VI).     

脉冲电沉积Ni-W-P-SiC复合电镀的研究

研究了脉冲电沉积Ni-W-P-SiC复合电镀工艺.研究表明:Ni-W-P-SiC镀层的脉冲电沉积速率比直流电沉积的大,脉冲镀层的耐蚀性和硬度都优于直流镀层,耐蚀性还优于1Cr18Ni9Ti不锈钢;脉冲频率和占空比对镀层的沉积速率、镀层成分以及镀层的性能都有很大的影响.SEM观察表明,脉冲镀层比直流镀层的结晶更细密,表面更光滑平整.     

Electroless deposited Ni–P alloys: corrosion resistance mechanism

Electroless Ni–P alloys are produced as coatings on a broad variety of substrates. They exhibit a corrosion resistance that is superior to pure nickel but do not form a NiO oxide film (passive film) as pure nickel does. Despite the fact that many mechanisms have been proposed to explain this superior corrosion behaviour, no consensus has yet been reached. In this work electrochemical and XPS surface analytical methods have been combined in order to gain a deeper insight into the mechanisms underlying the corrosion resistance of electroless deposited Ni–P alloys with phosphorus content between 18 and 22 at.%. The anodic polarization curves in acidic and neutral solutions confirm a broad current plateau followed by a region with increasing current density. During potentiostatic polarization in the plateau region the current decays according to a power law with exponent ca. −0.5 indicating diffusion-limited dissolution of nickel. XPS/XAES measurements performed after potentiostatic polarization show that phosphorus is present in three different chemical environments. Based on the Auger parameter concept and on the chemical state plot, the three phosphorus states were assigned to phosphorus in the bulk alloy, phosphates and an intermediate phosphorus compound attributed to elemental phosphorus. Angle-resolved XPS analysis has shown that the elemental phosphorus is enriched at the interface between the alloy and the outermost surface in contact with the corrosive solution. These results suggest the following conclusions: the high corrosion resistance of electroless deposited Ni–P alloys can be explained by a strong enrichment of elemental phosphorus at the interface which limits the dissolution of nickel via a diffusion mechanism. A complementary explanation––not yet advanced––for the high corrosion resistance may lie in the electronic state of nickel in the Ni–P alloys.     

Improved electrochemical performance of trivalent-chrome coating on Al 6063 alloy via urea and thiourea addition

This project aims at improving the electrochemical performance of trivalent-chrome coating through urea and thiourea addition. The electrochemical behaviors of coatings formed with different concentrations of urea and thiourea were investigated in 3.5 wt.% NaCl solution at 25 °C, using potentiodynamic polarization curves and EIS. The corrosion resistance of coatings is improved greatly by adding a small amount of inhibitors, whereas the excessive addition deteriorates the corrosion resistance. Thiourea addition presents better effect than urea. To explain the EIS results of the coatings, a simple equivalent circuit was designed. The EIS parameters were obtained by fitting the EIS plots. The results of the polarization curves and EIS show that the inhibitor-containing coatings present better corrosion resistance than the coating without inhibitor. The morphology and composition and valence state of the conversion coatings were examined by SEM and EDS and XPS, respectively. The results indicated that the trivalent chromium coating was developed on Al 6063 alloy, urea and thiourea inhibitors were also deposited on the substrates, respectively. A noticeable chemical shift was also observed.     

Anti-corrosive properties of waterborne polyurethane/poly(o-toluidine)-ZnO coatings in NaCl solution

The aim of this research was to prepare waterborne polyurethane (WPU) coating blended with a series of poly(o-toluidine)-nano ZnO composites and study its anti-corrosion performance after its application over carbon steel. The synthesized composites were characterized by X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The corrosion resistance of coatings with and without nano ZnO were studied in 3.5% NaCl solution at a temperature of 25?°C, by electro-chemical techniques such as potentiodynamic polarization measurements and electrochemical impedance spectroscopy (EIS). It was observed that the composite coating containing 7% poly(o-toluidine)-nano ZnO composite had higher corrosion resistance than poly(o-toluidine) and 14% poly(o-toluidine)-nano ZnO composite. The presence of appropriate amount of ZnO significantly improved the corrosion resistance, due to the formation of passive layer on steel surface and the synergistic effects of poly(o-toluidine) along with a suitable amount of nano-ZnO reduced the porosity of the coating surface.     

Development of HA-CNTs composite coating on AZ31 Magnesium alloy by cathodic electrodeposition. Part 2: Electrochemical and in-vitro behavior

The carbon nano-tubes (CNTs) reinforced hydroxyapatite (HA), with various functionalized CNTs concentration ranging from 0 to 1.5?wt%, were deposited on AZ31 magnesium alloy by direct and pulse cathodic electrodeposition methods. The corrosion resistance of the coatings was tested in simulated body fluid (SBF) using different electrochemical methods such as open circuit potential, polarization and electrochemical impedance spectroscopy. The in-vitro behavior, changes in solution pH as well as the amount of evolved hydrogen of these coatings were also evaluated during five days immersion in SBF. The results indicated that the pulse deposited HA having 1% CNTs coating was the optimum condition which decreased the corrosion current density of AZ31 magnesium alloy from 44.25?µA/cm² to 0.72?µA/cm². Moreover, it stabilized the alkalization behavior of AZ31 alloy and caused a tenfold decrease in the amount of hydrogen generation in SBF. Additionally, the formation of new hydroxyapatite layer on the surface of the pre-exist coatings after five days immersion in SBF was confirmed by SEM characterization.     

黑Cr-C纳米复合电沉积工艺中电流密度的确定

研究了电流密度对黑Cr-C纳米复合镀层组织及性能的影响.通过扫描电镜(SEM)观察复合镀层的表面形貌,并测定了镀层的显微硬度.结果表明,黑Cr-C纳米复合镀层显微硬度最高达10.5 GPa,镀层中微粒的体积分数最高达8.12%,电沉积复合电镀最佳电流密度为100 A/dm2.     

Effect of phytic acid on the microstructure and corrosion resistance of Ni coating

In this work, the pure Ni coatings were synthesized on Q235 steel by using reverse pulsed electrodeposition technique in sulphate-based baths with 0, 0.1, 0.2 and 0.3 g/L phytic acid additive. The effect of phytic acid on the microstructure and micro-morphology of the sample was observed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. And the effect of phytic acid on the corrosion resistance of the sample was studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results demonstrated that the addition of phytic acid was in favor of the growth of nano-scale twins (NT) in the interior of grains, which was due to the lowered stacking fault energies of Ni during the electrodeposition, and the typical morphology of pyramidal islands on the surface. The results also demonstrated that the effect of phytic acid was not monotonous with increasing concentration: the passive current density i_p was minimum and the charge transfer resistance R_t was maximum for the sample obtained from the bath with 0.2 g/L phytic acid, indicating that the sample obtained from the bath with 0.2 g/L phytic acid showed the best corrosion resistance.     

多弧离子镀(Ti,Cr)N镀层耐蚀性研究

采用多弧离子镀技术在高速钢表面制备了(Ti,Cr)N镀层,通过电化学工作站对镀层的塔菲尔曲线进行测试,分析镀层的耐腐蚀性,并采用质量变化法对电化学测试结果进行了验证。利用扫描电子显微镜观察了(Ti,Cr)N镀层腐蚀前后的微观形貌。结果表明,随电流比例ICr/ITi的增大,(Ti,Cr)N镀层表面晶粒尺寸逐渐减小。当ICr/ITi为90 A/60 A时,基体的自腐蚀电位由-0.750 V正移至-0.534 V,基体的腐蚀速率降低85.67%,耐蚀性提高。基体的腐蚀主要为点蚀和均匀腐蚀,(Ti,Cr)N镀层主要为小孔腐蚀。     

阴极电弧离子镀ZrN梯度膜和Zr/ZrN多层膜的腐蚀特性

采用阴极电弧离子镀技术在1Cr13不锈钢表面制备了ZrN梯度层和Zr/ZrN多层膜,并用电化学腐蚀方法和中性盐雾法检测了1Cr13基体、ZrN梯度层和Zr/ZrN多层膜的耐腐蚀性能.结果表明:Zr/ZrN多层膜和ZrN梯度层均能提高1Cr13基体的抗腐蚀能力,而Zr/ZrN多层膜的效果更明显:镀层的内部缺陷(如微孔)和液滴导致薄膜发生孔蚀、隙缝腐蚀和电偶腐蚀;镀层保护的实质是物理屏障作用,细化晶粒、减少膜层中的液滴及针孔等缺陷能显著提高薄膜的抗腐蚀性能.     

钛和铈对热浸锌镀层组织与耐蚀性能的影响

为了获得厚度适中、耐蚀性能好的热浸镀锌层,在锌浴中添加微量的Ti和Ce,分别在Zn-0.04%Ti、Zn-0.02%Ce和Zn-0.04%Ti-0.02%Ce镀浴中制得热浸锌合金镀层.采用金相显微分析以及电化学阻抗谱、电化学极化测试、中性盐雾试验,研究了Ti和Ce对镀层组织和耐蚀性能的影响.结果表明:在锌浴中添加0.0...     

Effect of WC on electrodeposition and corrosion behaviour of chromium coatings

To study the effect of WC particles on corrosion behaviour of chromium coating steel samples were plated in Cr(VI) baths with various concentrations of WC. XPS, EPM and XRD were used to study the chemical composition, morphology and texture of the coatings. The corrosion behaviour was studied at different exposure times in solution containing 0.01 mol L^–1 H₂SO₄ + 0.5 mol L^–1 Na₂SO₄ using cyclic voltammetry and impedance spectroscopy. Cyclic polarization measurements suggest that WC particles slow down the processes of passive film dissolution and penetration of aggressive ions to the substrate. Electrochemical impedance spectroscopy (EIS) was used to reveal the details of the corrosion process at the solution/electrode interface. The simulation of EIS data with a proposed equivalent circuit model made it possible to obtain quantitative valuation of the Y₀ (Q_c), Y₀ (Q_s) and R_pore parameters, reflecting corrosion behaviour of samples at the solution/electrode interface. Samples plated in a Cr(VI) bath with WC provided better resistance to corrosion than those plated in a bath without WC. Analysis of the data obtained suggests that WC particles enhance corrosion resistance due to the microstructural features of the coatings.     

(Ni-W-P)-SiC复合镀层的脉冲电沉积及其耐蚀性

研究了(Ni—W—P)—SiC复合镀层的脉冲电沉积工艺及耐蚀性。结果表明：(Ni—W—P)—SiC复合镀层的脉冲电沉积速率比直流电沉积大,脉冲镀层的耐蚀性优于直流镀层和1Cr18Ni9Ti不锈钢;脉冲频率和占空比对镀层的沉积速率、镀层成分以及镀层的耐蚀性都有较大的影响。     

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.     

Electrospun protective self‐healing coatings for light alloys: A better understanding of the intrinsic potential of the technology

Polymeric coating systems exhibit high potentiality to provide an effective barrier against corrosion of metallic surfaces. However, these coatings can lose their protective characteristics because of their high susceptibility to damage. Thus, the addition of corrosion inhibitors is desirable and considered as an alternative route for active corrosion protection. In the present work, eco‐friendly electrospun coatings of poly(vinyl alcohol) (PVA) loaded with cerium salts have been deposited onto aluminium 6082 alloy. Two different precursors of cerium (III) (i.e., cerium nitrate and cerium acetylacetonate) were added to the electrospinning solutions and the effectiveness of the resulting nanofibrous coatings was evaluated for the healing of generated defects. The microstructural features of the electrospun coatings have been investigated by scanning electron microscopy, infraredspectroscopy, and thermal analysis. Tensile tests were performed to assess the mechanical properties of the different fibrous coatings. The electrochemical behavior of both intact and damaged coatings was evaluated in 3 wt % NaCl solution by means of electrochemical impedance spectroscopy. All the deposited PVA coatings loaded with cerium(III) salts showed remarkable corrosion resistance. In the case of artificially damaged coatings, a self‐healing effect, which stops the development of the corrosion process and provides a significant recovery of the corrosion resistance, has been observed only for coatings loaded with cerium III acetylacetonate. The release of cerium from damaged PVA fibers has been demonstrated by means of inductively coupled plasma mass spectrometry. The observed self‐healing effect has been ascribed to the formation of cerium hydroxide on the defective zone, which hindered the corrosion process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42728.     

Effect of alternating voltage passivation on the corrosion resistance of duplex stainless steel

Potentiodynamic polarization and E _corr versus t curves were obtained, together with electrochemical impedance spectroscopy (EIS) measurements, in order to understand the effects of alternating voltage (AV) passivation on the corrosion resistance of duplex stainless steel (DSS). SEM, EDS and XPS were employed to further investigate the influence of AV passivation on the properties of the passive film. The results of the electrochemical measurements showed that AV passivation significantly improved the corrosion resistance of DSS. SEM images indicated that the surface exhibited a unique morphology after AV passivation treatment, and XPS results suggested that AV passivation greatly increased the thickness of the passive film. Furthermore, significant chromium enrichment and a higher ratio of Fe³⁺/Fe²⁺ were observed in the passive film after AV passivation. Mott–Schottky results confirmed that AV passivation had a strong influence on the semiconducting properties of the passive film.