Investigation on corrosion and wear resistance of MgO-Al2O3 composite coating prepared by plasma electrolytic oxidation

Ceramic coatings were prepared on 6061 Al alloy in a mixed electrolyte with/without MgO powders at different treatment durations. The results of energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) showed that MgO powder was incorporated into the coatings, and Mg species gradually aggregated into coating inside as prolonging the oxidation time. Scanning electron microscopy (SEM) showed that MgO additive had a certain effect on the microstructures and coating thickness. The corrosion behavior tests evaluated by potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS) in 3.5 wt% NaCl solution suggested that at the same treatment time, the addition of MgO powders can improve the corrosion resistance of the coating, and the Mg-rich layer can affect the corrosion resistance of the coating. The tests of mechanical properties showed that the addition of MgO powders improved the stability and hardness of the coating.     

Influence of ionic substitution in improving the biological property of carbon nanotubes reinforced hydroxyapatite composite coating on titanium for orthopedic applications

The present work is aimed for the development of carbon nanotubes (CNTs) reinforced single mineral (Sr, Mg, Zn) as well as multi minerals (Sr+Mg+Zn) substituted hydroxyapatite composite (M-HAP) coatings on titanium (Ti). The effect of different mineral ions substitution and CNTs reinforcement in HAP composite coating is discussed in detail. Fourier Transform Infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped with energy dispersive X-ray analysis (EDX), and high resolution transmission electron microscopy (HRTEM) were used to characterize the structural and morphological behavior of the composite coatings. The corrosion resistance of the composite coatings in simulated body fluid (SBF) solution was evaluated by the potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies. In addition, the biocompatibility of the composite coatings was evaluated by in vitro culture of human osteoblast MG63 cells on the composite coated Ti. All these results essentially suggest that CNTs/M-HAP composite coated Ti can be a potential candidate for orthopedic applications.     

片状玻璃对水性复合锌铝合金涂层耐蚀性的影响

为了改善水性锌铝合金涂层的耐蚀性能,在硅烷钝化液中加入玻璃粉制备了玻璃/水性锌铝涂层,采用中性盐雾试验、电化学阻抗谱、极化曲线等方法研究了玻璃粉用量对 Q235 钢表面该涂层耐蚀性能的影响,利用扫描电镜、能谱、X 射线衍射等技术分析了涂层的形貌、组成以及元素分布状况。结果表明,添加片状玻璃粉可以提高涂层的耐蚀性能。玻璃粉与金属粉以平行叠加的方式排列在锌铝合金涂层中,部分玻璃粉包覆在涂层的外围形成致密的网状结构。当玻璃粉的添加量为 20 g/L时,涂层的耐蚀性能最好,耐中性盐雾试验时间为 3 100 h,是不添加玻璃粉涂层的 5 倍。     

Preparation and characterization of a double-layer coating on magnesium alloy AZ91D

A double-layer coating was prepared on AZ91D alloy by plasma electrolytic oxidation (PEO) plus electroless plating (EP). The plasma eletrolytic oxidation film was prepared in a silicate bath as an inner layer of the coating. Electroless plated Ni-P layer grew from the pores of the PEO film in a nickelous acetate bath and formed as the outer layer of the coating. The microstructure and crystallographic structure was observed with FESEM and XRD. The corrosion resistance of the double-layer coating was evaluated by means of chronopotentiometric (E-t), potentiodynamic polarization (E-i), neutral salt spray test and electrochemical impedance spectroscopy (EIS) test. Compared with the data of as-cast AZ91D magnesium, the open circuit potential of the double-layer coated AZ91D alloy increased by 1.1815 V, while the self-corrosion current density decreased by two orders of magnitude. E-i, EIS result showed that the corrosion resistance of magnesium alloy AZ91D was improved by the double-layer coating. The salt spray test and polarization test results show that the pitting corrosion resistance of AZ91D alloy was improved greatly. An equivalent circuit was proposed to fit the impedance diagrams of AZ91D alloy with the coating.     

[V10O28]6-柱撑纳米水滑石在AZ31镁合金有机防腐涂层中的应用

研制了一种以钒酸盐阴离子([V10O28]6-)柱撑纳米水滑石防腐颜料替代铬酸盐,用于AZ31镁合金腐蚀防护的有机涂层.研究了水滑石在不同浓度的NaCl溶液里的吸附和离子交换性能,以及钒酸盐缓蚀剂的极化曲线:考察了该水滑石防腐颜料的添加比例对镁合金环氧防腐涂层性能的影响,并通过电化学交流阻抗(EIS)测试技术对各试样进行了性能检测.结果表明,添加了20%(质量分数)水滑石的环氧涂层对镁合金具有较好的防腐作用.     

Corrosion behaviors of Zn/Al-Mn alloy composite coatings deposited on magnesium alloy AZ31B (Mg-Al-Zn)

After being pre-plated a zinc layer, an amorphous Al-Mn alloy coating was applied onto the surface of AZ31B magnesium alloy with a bath of molten salts. Then the corrosion performance of the coated magnesium alloy was examined in 3.5% NaCl solution by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the single Zn layer was active in the test solution with a high corrosion rate while the Al-Mn alloy coating could effectively protect AZ31B magnesium alloy from corrosion in the solution. The high corrosion resistance of Al-Mn alloy coating was ascribed to an intact and stable passive film formed on the coating. The performances of the passive film on Al-Mn alloy were further investigated by Mott-Schottky curve and X-ray photoelectron spectroscopy (XPS) analysis. It was confirmed that the passive film exhibited n-type semiconducting behavior in 3.5% NaCl solution with a carrier density two orders of magnitude less than that formed on pure aluminum electrode. The XPS analysis indicated that the passive film was mainly composed of AlO(OH) after immersion for long time and the content of Mn was negligible in the outer part of the passive film. Based on the EIS measurement, electronic structure and composition analysis of the passive film, a double-layer structure, with a compact inner oxide and a porous outer layer, of the film was proposed for understanding the corrosion process of passive film, with which the experimental observations might be satisfactorily interpreted.     

Enhancement of the Ti-6Al-4V alloy corrosion resistance by applying CrN/CrAlN multilayer coating via Arc-PVD method

In this study, the Ti-6Al-4V substrate was coated by CrN-CrN/TiN-TiN and CrN/CrAlN multilayer coatings using the cathodic arc physical vapor deposition (Arc-PVD) method. The results of potentiodynamic polarization (PDP) have shown the lowest and highest corrosion current density belong to the double-layer (0.16 µA/Cm²) and TiN (0.51 µA/Cm²) samples, indicating the higher corrosion resistance of the double-layer coating. The field emission electron microscope (FESEM), X-ray diffraction pattern (XRD), open circuit potential (OCP), PDP, and electrochemical impedance spectroscopy (EIS) analysis were employed in order to characterize the coatings and evaluate their corrosion behavior. Finally, applying the double-layer coating resulted in the significant improvement of the protective behavior of the Ti-6Al-4V alloy, as compared to the sample coated with TiN in corrosive environments.     

Effects of carbon nanotube content on adhesion strength and wear and corrosion resistance of epoxy composite coatings on AA2024-T3

The effects of multiwalled carbon nanotube (MWCNT) content on the adhesion strength and wear and corrosion resistance of the epoxy composite coatings prepared on aluminum alloy (AA) 2024-T3 substrates were evaluated using atomic force microscopy (AFM), blister test, ball-on-disk micro-tribological test and electrochemical impedance spectroscopy (EIS). The adhesion strength of the epoxy composite coatings improved with increasing MWCNT content. Increased MWCNT content also decreased the friction coefficient and increased the wear resistance of the epoxy composite coatings due to improved solid lubricating and rolling effects of the MWCNTs and the improved load bearing capacity of the composite coatings. Finally, EIS indicated that increased MWCNT content increased the coating pore resistance due to a decreased porosity density, which resulted in an increase in the total impedance of the coated samples.     

Electrochemical corrosion behavior of composite coatings of sealed MAO film on magnesium alloy AZ91D

Protective composite coatings were prepared on magnesium alloy AZ91D by micro-arc oxidation (MAO) treatment plus a top coating with sealing agent using multi-immersion technique under low-pressure conditions. The corrosion resistance of AZ91D alloy with composite coatings was superior evidently to that with merely MAO film. SEM observations revealed that the sealing agent was integrated with MAO film by physically interlocking; therewith covered uniformly the surface as well as penetrated into pores and micro-cracks of MAO film. The anti-corrosion properties in 3.5% NaCl solution of the composite coatings were evaluated by using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. Based on the results of chronopotentiometric (E ∼ t) and EIS measurements for long time immersion in 3.5% NaCl solution, appropriate equivalent circuits for the composite coatings system were proposed. It follows that due to the blocking effect of the sealing agent in pores and cracks in MAO film, the composite coatings can suppress the corrosion process by holding back the transfer or diffusion of electrolyte and corrosion products between the composite coatings and solution during immersion.     

Designing of corrosion resistant epoxy coatings embedded with polypyrrole/SiO2 composite

Polypyrrole/SiO₂ composite was synthesized by chemical oxidative polymerization of pyrrole using FeCl₃. The synthesized polymer composite was loaded in epoxy resin to develop coatings for mild steel substrates using powder coating technique. SEM and TEM images reveal homogenous dispersion of SiO₂ particles in polypyrrole matrix. TGA analysis confirms good thermal stability of the polymer composite. Tafel polarization and electrochemical impedance spectroscopy (EIS) results exhibit remarkably high corrosion protection efficiency of epoxy coatings with polymer composite in 3.5% NaCl solution. Corrosion studies of coatings with an artificial defect reveal the passivation of defect by the polymer composite present in the epoxy coatings. Salt spray test results revealed superior corrosion resistance offered by the polymer composite.     

Effect of pH and carbon nanotube content on the corrosion behavior of electrophoretically deposited chitosan–hydroxyapatite–carbon nanotube composite coatings

In the first stage, chitosan (CH)–hydroxyapatite (HA)-multiwalled carbon nanotube (MWCNT) composite coatings were synthesized by electrophoretic deposition technique (EPD) on 316L stainless steel substrates at different levels of pH and characterized by X-ray diffraction (XRD), Raman spectroscopy, FTIR and field emission scanning electron microscopy (FESEM). A smooth distribution of HA and MWCNT particles in a chitosan matrix with strong interfacial bonding was obtained. In the next stage, effects of pH and MWCNT content of the suspension on the corrosion behavior and deposition mechanism were studied. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) curves revealed that increasing pH level of the suspension increases the corrosion protection properties of the deposited composite coating in simulated body fluid (SBF). Furthermore, Nyquist plots showed that increasing MWCNT content of the suspension resulted in higher amounts of R_p, but because of the capillary properties of MWCNTs and degradability of the chitosan matrix, corrosion protection level of the coatings containing HA–CH–MWCNT was lower than those of coatings containing solely HA–CH. Amperometric curves in different pH levels of the suspension revealed that the system is diffusion controlled at elevated pH values.     

Hydroxyapatite-carboxymethyl cellulose-graphene composite coating development on AZ31 magnesium alloy: Corrosion behavior and mechanical properties

In this study, hydroxyapatite (HA) coatings containing carboxymethyl cellulose (CMC) and graphene (Gr) were developed on AZ31 magnesium alloy through two-step electrophoretic deposition method. The morphology and chemical bonding of coatings were characterized and also the phase identification was done using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction, respectively. Moreover, the corrosion behavior of the applied coatings was compared with the bare AZ31 Mg alloy substrate in the simulated body fluid by the means of potentiodynamic polarization test and electrochemical impedance spectroscopy. Obtained results revealed that the novel HA-CMC-Gr coating possesses the highest corrosion resistance compared to the HA, HA-CMC, and HA-Gr coatings due to its uniform and compact structure. To investigate the mechanical properties and to elucidate the effect of CMC on the adhesion of coating-alloy interface, pull-off test was employed, where results demonstrated that the addition of CMC increases the adhesion force from 1.06 MPa to 1.62 MPa. Besides, the modulus of elasticity and the hardness of HA and HA-Gr composite coatings were compared by applying nanoindentation test. Interestingly, it is detected that the presence of Gr has considerably increased the elastic modulus of the coating by approximately 30% in comparison to the pure HA coating.     

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.     

3种溶液体系中镁合金微弧氧化研究第一部分——氧化膜的相组成及其耐蚀性

利用直流脉冲方法在3种溶液体系中于AZ91D镁合金表面制得了微弧氧化陶瓷膜,分析了各膜层的厚度、显微硬度、相组成和耐蚀性能。结果表明,不同体系中的膜层增厚速率不同,形成膜层的相关成分也不同。通过比较微弧氧化前后镁合金的动电位极化曲线和交流阻抗发现,处理后的AZ91D镁合金的耐蚀性得到了明显改善。     

Zn-Fe合金镀层黑色钝化工艺研究Ⅱ--工艺条件的优化及钝化膜耐蚀性能的研究

在钝化膜组成成分研究的基础上，详细研究了工艺条件对Zn-Fe合金钝化膜耐蚀性的影响，从而得到了最佳的工艺条件。对Zn-Fe合金钝化膜性能进行了测试，并采用5％NaCl中性溶液浸泡试验对Zn镀层、Zn-Fe合金镀层及Zn-Fe-TiO2复合镀层黑色钝化膜的耐蚀性进行了比较。结果表明，经黑色钝化后，Zn-Fe合金镀层及Zn-Fe-TiO2复合镀层的耐蚀性都有很大的提高；Zn-Fe合金镀层的耐蚀性是纯锌镀层的3倍多，而Zn-Fe-TiO2复合镀层的耐蚀性是Zn-Fe合金镀层的2倍多，是纯锌镀层的5倍左右。     

铝合金表面电解沉积稀土转化膜工艺研究

研究了一种通过电解沉积方法在防锈铝LF21表面上生成铈盐转化膜的工艺,应用正交实验研究了有关因素对成膜过程的影响并获得了最佳的技术参数用极化曲线、交流阻抗和中性盐雾试验等方法测试了该工艺形成膜层的耐蚀性能及其组成一结果表明：经过电解沉积稀土转化膜处理后,防锈铝的阳极腐蚀过程受到了阻滞,自然腐蚀电位负移;与经过化学转化膜处理后相比,其耐蚀性能有显著提高,可通过400h的中性盐雾实验,亲水性能亦有明显提高。     

Pulsed electrodeposition of carbon nanotubes-hydroxyapatite nanocomposites for carbon/carbon composites

Carbon nanotubes-hydroxyapatite (CNTs-HA) composite coatings, which behaved like single composites, were synthesized by a combined method composed of electrophoretic deposition and pulsed electrodeposition. The phase compositions and the microstructure of the composite coatings were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared spectrometry (FTIR). Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies showed that the CNTs-HA composite coatings protected the bare carbon/carbon composites from corrosion in simulated body fluid (SBF) solution. The adhesion strength of CNTs-HA composite coating prepared by the combined method is 14.57±1.06 MPa achieved at the CNTs EPD time of 10 min. Compared to the other CNTs-HA composite coatings with different content of CNTs, the CNT-HA composite coating with the electrophoretic deposition of 10 min showed the best corrosion resistance. The morphology of CNTs-HA composite coatings immersed in SBF solution rendered the formation of HA crystallites. In addition, in vitro cellular responses to the CNTs-HA composite coatings were assessed to investigate the proliferation and morphology of mouse cells 3T3 cell line.     

Mica/polypyrrole (doped) composite containing coatings for the corrosion protection of cold rolled steel

Micas/polypyrroles (PPys) doped with molybdate, p-toluene sulfonate, dodecyl benzene sulfonate, and 2-naphthalene sulfonate composite pigments were synthesized by chemical oxidative polymerization and characterized in coatings for corrosion protection on cold rolled steel substrate by various electrochemical techniques. Synthesized composite pigments were characterized for morphology by scanning electron microscopy, which indicated physical formation of PPy on the surface of mica. Chemical composition of the composite pigments was analyzed by X-ray photoelectron spectroscopy which chemically confirmed doped PPy formation on the mica surface. Coatings were formulated at 20% pigment volume concentration (composite pigments or as-received mica pigment) and were applied on cold rolled steel substrate. Coatings were exposed to salt spray test conditions (ASTM B117) for 30 days and were periodically assessed for corrosion with electrochemical impedance spectroscopy (EIS), open circuit potential (OCP), and potentiodynamic polarization. EIS and circuit modeling results demonstrated higher coating resistance (R _c) for mica/PPy (doped) composite coatings as compared to as-received mica pigment containing coating after 30 days of salt spray exposure. Lower current density and more positive corrosion potential values were observed for mica/PPy (doped) composite coatings as compared to mica pigment-based coating in potentiodynamic polarization measurements, indicating improved corrosion protection for cold rolled steel substrate. OCP measurements revealed more positive values for mica/PPy (doped) composite coatings as compared to mica pigment-based coating suggesting superior corrosion protection for mica/PPy (doped) composites.     

Corrosion protection of Mg alloys by cathodic electrodeposition coating pretreated with silane

The corrosion resistance characteristics of three coatings on magnesium alloy AZ31—conventional paint with phosphate film, cathodic electrodeposition coating (E-coating), and E-coating pretreated with silane (Mg/silane/E-coating)—have been studied by means of electrochemical impedance spectroscopy (EIS) in a 3.5 wt% NaCl neutral aqueous solution and salt spray test using ASTM B117. Silane film was obtained by dipping AZ31 specimens in diluted hydroalcoholic silanic solutions and successively curing. It was found that the corrosion resistance of the Mg alloy with E-coating was superior to conventional paint and could be further enhanced with silane pretreatment as an interfacial film. The results of water volume fraction (Φ_saturation) and diffusion coefficient (D) also indicated that the Mg/silane/E-coating possessed excellent compactness and corrosion resistance. A model of the corrosion mechanism for Mg/silane/E-coating has been presented through EIS analysis.     

Evaluation of corrosion resistance of polypyrrole/functionalized multi-walled carbon nanotubes composite coatings on 60Cu–40Zn brass alloy

Polypyrrole/multi-walled carbon nanotubes (PPy/MWCNT) and its carboxylic functionalized (PPy/MWCNT-COO⁻) composite films were successfully electropolymerized by cyclic voltammetry as protective coating against corrosion on 60Cu–40Zn brass alloy surface. It yielded to strongly adherent and smooth nanocomposite films. Kinetics of the corrosion protection was investigated in 3.5 wt% NaCl solutions by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests. The results showed that the presence of MWCNT in PPy coat considerably reduces the corrosion rate of 60Cu–40Zn brass alloy. The enhanced inhibition is most likely due to interaction between MWCNT and PPy. This in turn, improves the alloy passivation improvement and alters the permselectivity of the coating from anionic selectivity to the cationic selectivity. Moreover, PPy/MWCNT-COO⁻ functionalized nanocomposite provided higher corrosion resistance coating than PPy/MWCNT alone.