Enhancement of corrosion resistance of Mg-9 wt.% Al-1 wt.% Zn alloy by a calcite (CaCO3) conversion hard coating

A calcite (CaCO₃) coating on Mg alloy, formed by chemical conversion treatment, was investigated. Aqueous with Ca²⁺ concentration of ∼220 ppm was employed in the chemical conversion treatment. Cross-sectional microstructures of the coated sample after 2 h of treatment revealed a two-layer coating structure. The corrosion current density (I_corr) of the coated sample was approximately two orders of magnitude lower than that of the untreated sample. Electrochemical impedance spectroscopy (EIS) and an appropriate equivalent circuit suggested that each of the layers of the two-layer coating effectively protects Mg alloy against corrosion.     

Effect of fluxing chemical: An option for Zn-5wt.%Al alloy coating on wire surface by single hot dip process

The corrosion of wire is one of the primary causes for premature failure. The ideal way to overcome this problem is to provide corrosion protection right at the time of manufacturing. It is well established fact that Zn-5 wt.% Al alloy coating on steel surface provides much better protection against corrosion than the conventional pure Zn coating. Conventional fluxing operation is done on wire surface using zinc and ammonium chloride mixture before dipping in molten zinc bath. Galvanization bath temperature of about 415 °C for Zn-5 wt.% Al alloy coating on wire surface develops black spots of AlCl₃ when conventional flux is used. Double dip process is being followed for Zn alloy coating on wire surface due to non availability of suitable flux. An effort has been made to develop a suitable flux to obtain Zn-5 wt.% Al alloy coating on wire surface by single hot dip process. A salt mixture (containing zinc, ammonium, sodium, potassium, cobalt and lead chloride) was formulated based on the decomposition temperature of individual chloride salts. Differential thermal and thermo gravimetric analysis indicate the temperatures for complete decomposition of conventional and formulated flux are 445 and 410 °C, respectively. The lower decomposition temperature of formulated flux is ensured black spot free Zn-5 wt.% Al alloy coating. Alloy coated wire consists of alternative layers of zinc rich and aluminium rich phases. The performance of alloy coated wires has been evaluated by salt spray and Tafel tests. The alloy coated wire shows around 4 times improvement of corrosion performance against aggressive chloride environment compared to pure zinc coated wire. This can be attributed to the fact that aluminium rich phase prevents dissolution of zinc rich phase.     

Influence of oxygen ion irradiation on the corrosion aspects of Ti-5%Ta-2%Nb alloy and oxide coated titanium

The corrosion resistance of Ti-5%Ta-2%Nb alloy and DOCTOR (double oxide coating on titanium for reconditioning) coated titanium by O⁵⁺ ion irradiation were compared and investigated for their corrosion behaviour. O⁵⁺ ion irradiations were carried out at a dose rate of 1 × 10¹⁷, 1 × 10¹⁸ and 1 × 10¹⁹ ions/m² at 116 MeV. The surface properties and corrosion resistance were evaluated by using scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray (EDX), glancing-angle X-ray diffraction (GXRD) and electrochemical testing methods. The results of electrochemical investigations in 11.5 N HNO₃ indicated that the open circuit potential (OCP) of DOCTOR coated titanium is nobler than Ti-5%Ta-2%Nb alloy. The potentiodynamic polarization study of Ti-5%Ta-2%Nb alloy and DOCTOR coated specimen indicated decrease in passive current density with increase in ion doses (1 × 10¹⁷ to 1 × 10¹⁹ ions/m²) indicating decrease in anodic dissolution. Nyquist arc behaviour in the electrochemical impedance study substantiated the enhancement in oxide layer stability by O⁵⁺ ion irradiation. AFM results revealed that the DOCTOR coated Ti surface was dense without gross voids, and the surface roughness decreased by O⁵⁺ ion irradiation, but increased after corrosion test. EDX and GXRD patterns of DOCTOR coated Ti sample indicated that the coating was mainly composed of rutile TiO₂. Based on the above results, the O⁵⁺ ion irradiation effect on corrosion behavior of Ti-5%Ta-2%Nb alloy and DOCTOR coated titanium are discussed in this paper.     

Electrochemical properties of microarc oxidation films on a magnesium alloy modified by high-intensity pulsed ion beam

Microarc oxidation (MAO) films on AZ31 magnesium alloy were treated by high-intensity pulsed ion beam (HIPIB) irradiation with ion energy of 300 keV at ion current density of 200 A/cm². A remelted layer of a few micrometers was produced on irradiated MAO films. The corrosion resistance of MAO films was characterized by potentiodynamic electrochemical test in 3.5% NaCl solution. The anodic polarization behavior of MAO samples exhibited a transition from the active anodic dissolution for the original one to the passivation-pitting breakdown for the modified films. The passivation-pitting breakdown voltage of modified films increased with multi-shot irradiation, i.e. from a value of − 1420 mV(SCE) at 1 shot to − 800 mV(SCE) at 5 shots, and the corresponding passivation current density decreased by two orders of magnitude. The irradiated MAO films have a higher corrosion potential than the original one, reaching a maximal value of − 1350 mV(SCE) at 5 shots from the original − 1580 mV(SCE). The electrochemical impedance spectrum (EIS) of modified MAO films was measured with varying the immersion time in 3.5% NaCl solution. The Nyquist impedance plots from modified films may show only a capacitive loop at the immersion time of 5 h, and the inductive loop occur at longer immersion time, whereas original films presenting both capacitive and inductive loops at all the immersion time. Bode plots of MAO films before and after irradiation were obviously distinguished in shape at low frequency range, especially at short immersion time. The evolution of Nyquist and Bode plots with immersion time was discussed in association with the processes of electrolyte penetration into the MAO structure and resultant reaction at the film-substrate interface. It is concluded that the improvement in the continuity and compaction of MAO films accounts for the enhanced corrosion resistance of the films irradiated by HIPIB.     

微弧氧化处理对AZ91D镁合金腐蚀行为的影响

采用碱性硅酸盐溶液,在AZ91D镁合金试样表面制得微弧氧化膜,并利用电化学阻抗方法对镁合金及微弧氧化处理试样在3.5%NaCl溶液中的腐蚀行为进行比较研究.结果表明,镁合金经微弧氧化处理后,腐蚀电位和膜层阻抗均有一定程度的提高.但在浸泡过程中,微弧氧化处理试样的电化学参数呈现出不同的变化规律,初期波动较大,后期则逐渐降低,趋向稳定.     

Influence of pH on the deterioration of plasma electrolytic oxidation coated AM50 magnesium alloy in NaCl solutions

The corrosion deterioration process of plasma electrolytic oxidation (PEO) coatings on AM50 magnesium alloy prepared from two different based electrolytes, i.e., an alkaline phosphate electrolyte and an acidic fluozirconate electrolyte, were investigated using electrochemical impedance spectroscopy (EIS) in a 0.1 M NaCl solution with pH of 3, 7 and 11, respectively. It was found that the PEO coating formed in alkaline phosphate electrolyte, which was composed mainly of MgO, suffered from rapid chemical dissolution and lost its protection capability very quickly in acidic NaCl solution (pH 3). The chemical dissolution of this PEO coating was retarded in neutral NaCl solution (pH 7) and the corrosion damage was localized in this environment. On the other hand, in the alkaline NaCl solution (pH 11), the MgO coating underwent only slight degradation. The PEO coating produced in acidic fluozirconate electrolyte, the failure was marked by the flaking-off of the large areas of coating in acidic NaCl solution (pH 3). However, in the neutral and alkaline NaCl solutions, the coating underwent only a slight degradation without any observable corrosion damage in the 50 h test. The results showed that the deterioration process of PEO coated magnesium alloy was governed mostly by the pH of NaCl solution and it was also strongly related to the microstructure and composition of the PEO coatings.     

Hot dip fine Zn and Zn-Al alloy double coating for corrosion resistance at coastal area

A new hot dip Zn-7Al alloy coating was performed on a structural steel by double coating of fine Zn and Zn-7 wt.% Al alloy, to prevent severe corrosion in coastal area. The alloy-coated steels were exposed to seaside, quasi-industrial, and rural districts to compare with conventional Zn coating. Double coating was significantly effective in preventing corrosion, particularly in a seaside. It was estimated from the exposure test for 10 years that the life of the Zn-7Al alloy-coated steel would be almost four times that of the Zn-coated steel in the seaside. A bending test showed that no exfoliation occurred at the interface between the coated alloy and substrate steel. TEM observation revealed that the excellent adhesiveness of the doubly coated fine Zn and Zn-7Al alloy to the steel substrate was due to formation of the interface region consisting of heterogeneous fine phase mixture of zinc, aluminium and iron.     

Corrosion characterization of Mg-8Li alloy in NaCl solution

The corrosion mechanism of Mg-8Li alloy in NaCl solution was investigated by electrochemical testing and SEM observation. The electrochemical results indicated that the corrosion resistance of Mg-8Li alloy in 0.1 M NaCl solution gradually deteriorated with increasing of immersion time expect for 2 h immersion, which was consistent with the SEM observation of corrosion morphology. Mg-8Li alloy exhibited filiform type of attack under significant anodic control of magnesium solution reaction. The cathodic reaction was driven by hydrogen evolution reaction. The presence of filiform corrosion also proved a resistant oxide film naturally formed on the surface of Mg-8Li alloy.     

Effect of Micro Arc Oxidation Coatings on Corrosion Resistance of 6061-Al Alloy

In the present study, the corrosion behavior of micro arc oxidation (MAO) coatings deposited at two current densities on 6061-Al alloy has been investigated. Corrosion in particular, simple immersion, and potentiodynamic polarization tests have been carried out in 3.5% NaCl in order to evaluate the corrosion resistance of MAO coatings. The long duration (up to 600 h) immersion tests of coated samples illustrated negligible change in weight as compared to uncoated alloy. The anodic polarization curves were found to exhibit substantially lower corrosion current and more positive corrosion potential for MAO-coated specimens as compared to the uncoated alloy. The electrochemical response was also compared with SS-316 and the hard anodized coatings. The results indicate that the overall corrosion resistance of the MAO coatings is significantly superior as compared to SS316 and comparable to hard anodized coating deposited on 6061 Al alloy.     

Effect of sintering temperatures on corrosion and wear properties of sol-gel alumina coatings on surface pre-treated mild steel

Sol-gel alumina coatings were developed on the surface pre-treated (zinc-phosphated) mild steel substrate and subsequently sintered at 300 °C, 400 °C and 500 °C. The alumina sol was synthesised using aluminium iso-propoxide as a precursor material. FTIR of the boehmite (AlOOH) gel sintered at above-mentioned temperatures was employed to identify the presence of various functional groups. The microstructural features and the phase analysis of the sol-gel coated specimens were carried out using SEM and XRD respectively. The corrosion resistance of the sol-gel alumina coatings was evaluated by electrochemical measurement in 3.5% NaCl solution at room temperature. The abrasive wear behaviour of the sol-gel coated specimens was measured in two body (high stress) conditions. The experimental results revealed that the sol-gel coated specimen sintered at 400 °C has superior wear and corrosion resistance properties as compared to the sol-gel coated specimen sintered at 300 °C. However, the sol-gel coated specimen sintered at 500 °C has exhibited a very poor corrosion and wear resistance properties. Poor performance of the sol-gel coatings sintered at 500 °C could be explained to be due to (i) the presence of numerous cracks (ii) absence of organic groups in the coating.     

Porous TiO2 film prepared by micro-arc oxidation and its electrochemical behaviors in Hank's solution

Porous titanium oxide film was prepared by micro-arc oxidation (MAO) method on the surface of titanium alloy in electrolyte containing Ca and P. Surface characterizations of the film were carried out using X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) before and after immersion in Hank's solution. Electrochemical behaviors and corrosion resistance were studied by electrochemical techniques. The film was mainly composed of titania, α-tricalcium phosphate (α-TCP) and amorphous Ca-P compounds. α-TCP and amorphous compounds could transformed into hydroxyapatite (HA) when immersed in Hank's solution. MAO film showed higher corrosion potential and lower corrosion current than the titanium alloy and its chemical stability was slightly changed after formation of HA. Fitted electrochemical impedance spectroscopy (EIS) data indicated that after immersion for 2 weeks the MAO film kept good corrosion resistance. Porous TiO₂ film on titanium alloy by MAO method showed good chemical stability in Hank's solution and the transformation of Ca-P compounds into HA indicated that MAO was an effective method for preparing titanium alloys as bioactive artificial bone substitute even when Ca and P in the tissue environment were not abundant.     

Corrosion behaviour of die-cast AZ91D magnesium alloy in aqueous sulphate solutions

The corrosion behaviour of die-cast AZ91D magnesium alloys in sulphate solutions was investigated by SEM, FTIR and polarization measurements. For immersion times less than 48 h, no pitting corrosion occurred and only generalized corrosion was apparent. According to the polarization curves, the corrosion rate order of the die-cast AZ91D Mg alloy in three aqueous solutions was: NaCl > MgSO₄ > Na₂SO₄. The main corrosion products were Mg(OH)₂ and MgAl₂(SO₄)₄·22H₂O in the sulphate solutions and the product film was compact. Precipitation of MgAl₂(SO₄)₄·22H₂O required a threshold immersion time.     

Microstructure and corrosion performance of a cold sprayed aluminium coating on AZ91D magnesium alloy

A pure Al coating was deposited on AZ91D magnesium alloy through cold spray (CS) technique. The microstructure of the coating was characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that the grain interfaces and subgrains formed close to the particle/particle boundaries. Electrochemical tests revealed that the cold sprayed pure Al coating had better pitting corrosion resistance than bulk pure Al with similar purity in neutral 3.5 wt.% NaCl solution. In addition, a mass-transfer step was found to be involved in the corrosion during 10 days immersion.     

The relation between microstructure and corrosion behavior of AZ80 Mg alloy following different extrusion temperatures

Cast AZ80 alloy was subjected to conventional extrusion pressing at 250 °C, 300 °C, and 350 °C. In order to characterize the changes in their microstructure a thorough study was done through various microscopy analyses including Optical Microscope, SEM, and TEM.Corrosion performance of each condition was investigated in 3.5% NaCl solution saturated with Mg(OH)₂ (pH ≈ 10.5) using immersion and AC and DC polarization tests. The local potential difference on the surface resulting from different compositions of second phase particles to the matrix was investigated using scanning Kelvin probe force microscopy (SKPFM) technique.The results show grain refinement by a factor of about 15-20 and obvious evidence of dynamic recrystallization were identified leading to the formation of nano-sized grains after the extrusion process.The corrosion resistance of cast AZ80 alloy drastically decreases after the thermo-mechanical processes and the main factor is high dependence on different phase rearrangements before and after the extrusion process, especially β phase. For the extrusion conditions, different corrosion resistances are attributable especially to dislocation rearrangement results by grain growth after dynamic recrystallization.     

PREPARATION OF MICROARC OXIDATION COATING ON (Al2O3-SiO2)sf/AZ91D MAGNESIUM MATRIX COMPOSITE AND ITS ELECTROCHEMICAL IMPEDANCE SPECTROSCOPIC ANALYSIS\par

在硅酸盐电解液体系中, 采用交流微弧氧化方法在增强体体积分数为33%的 (Al₂O₃-SiO₂)_sf/AZ91D镁基复合材料表面制备出完整的保护性氧化膜. 利用SEM, EDS和XRD分析了氧化膜的形貌、成分和相组成, 测量了膜层的显微硬度分布. 采用电化学阻抗谱(EIS)评价了微弧氧化表面处理前后复合材料的电化学腐蚀性能, 确立了不同浸泡时间对应的等效电路. 结果表明, 微弧氧化膜主要由MgO和Mg₂SiO₄相组成, 最大硬度达到1017 HV. 氧化膜电化学阻抗模值|Z|与镁合金基体相比大幅度提高, 耐腐蚀性能明显高于基体. 在3.5%NaCl溶液里浸泡96 h后, EIS出现感抗弧, 显示膜内部开始出现点蚀破坏. 氧化膜耐蚀性由膜内致密层特性所决定.     

An electrochemical study of the effect of Li on the corrosion behavior of Ni3Al intermetallic alloy in molten (Li + K) carbonate

A study of the effect of lithium content (1, 3 and 5 wt.%) and heat treatment (400 °C during 144 h) on the corrosion behavior of Ni₃Al alloy has been carried out in a 62 mol.%Li₂CO₃-38 mol.%K₂CO₃ mixture at 650 °C using electrochemical techniques. Employed electrochemical techniques included potentiodynamic polarization curves, linear polarization resistance, LPR, electrochemical impedance spectroscopy, EIS, and electrochemical noise, measurements EN. Results have shown that the alloys exhibited an active-passive behavior regardless of the heat treatment. For alloys without heat treatment, the most corrosion resistant was the Ni₃Al base alloy, but when they were heat treated, the most corrosion resistant was the alloy containing 3%Li. EIS results showed that for short immersion tests, the corrosion process was under diffusion control, but for longer exposure times, the presence of a protective scale was evident. All the alloys were highly susceptible to a localized type of corrosion according to EN measurements and supported by SEM micrographs.     

Effects of alternating current on corrosion of a coated pipeline steel in a chloride-containing carbonate/bicarbonate solution

In this work, the alternating current (AC)-induced corrosion of a coated pipeline steel was studied in a chloride-containing, concentrated carbonate/bicarbonate solution, which simulated the trapped high pH electrolyte under coating, by potentiodynamic polarization measurements, immersion tests and surface characterization technique. It was found that an application of AC resulted in a negative shift of corrosion potential of the steel, caused an oscillation of anodic current density, and degraded the steel passivity developed in the solution. With the increase of AC current density, the corrosion rate of the steel increased. At a low AC current density, a uniform corrosion occurred, while at a high AC current density, pitting corrosion occurred extensively on the steel electrode surface. At individual applied AC, there was a higher electrochemical dissolution activity of the coated steel electrode containing a 1 mm defect than that of the electrode containing a 10 mm defect.     

Effect of plasma electrolytic oxidation coating on the stress corrosion cracking behaviour of wrought AZ61 magnesium alloy

An attempt was made to understand the effect of silicate based plasma electrolytic oxidation (PEO) coating on the stress corrosion cracking (SCC) behaviour of an AZ61 wrought magnesium alloy. The SCC behaviour of untreated and PEO coated specimens was assessed using slow strain rate tensile tests at two different nominal strain rates, viz. 1 × 10⁻⁶ s⁻¹ and 1 × 10⁻⁷ s⁻¹, in ASTM D1384 test solution at ambient conditions. The PEO coating was found to improve the general corrosion resistance to a significant extent; however, the improvement in the resistance to stress corrosion cracking was only marginal.     

Chemistry of corrosion products on Zn-Al-Mg alloy coated steel

Zn-Al-Mg alloy (ZM) coating provides a decisively enhanced corrosion resistance in a salt spray test according to DIN EN ISO 9227 (NSS) compared to conventional hot-dip galvanised zinc (Z) coating because of its ability to form a very stable, well adherent protecting layer of zinc aluminium carbonate hydroxide, Zn₆Al₂(CO₃)(OH)₁₆·4H₂O on the steel substrate. This protecting layer is the main reason for the enhanced corrosion resistance of the ZM coating. Surface corrosion products on ZM coated steel consist mainly of Zn₅(OH)₆(CO₃)₂, ZnCO₃ and Zn(OH)₂ with additions of Zn₅(OH)₈Cl₂ · H₂O and a carbonate-containing magnesium species.     

Corrosion resistance of lamellar aluminium pigments coated by SiO2 by sol–gel method

The aluminium pigments were coated with SiO₂ by sol–gel method to improve their stability. The effects of formulation factors, such as medium of reaction, adding sequence of catalyst and number of coating, were investigated. The stability of the coated aluminium pigments in acid was examined by measuring the hydrogen generation amount. It was found that the coating layer formation is due to the condensation of tetraethyl orthosilicate (TEOS) to form a dense 3D cross-linked layer on the surface of aluminium. The optimized sequence of adding catalysts would be hydrochloride first, then ammonia. Stability tests confirmed that the aluminium pigments have better corrosion resistance after coating with SiO₂.