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Corrosion and Corrosion Protection for Light Metals/Alloys

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Corrosion".

Deadline for manuscript submissions: closed (30 June 2020) | Viewed by 38062

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Prof. Takahiro Ishizaki

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Shibaura Institute of Technology, Tokyo, Japan

Special Issue Information

Dear Colleagues,

Light metals, including aluminum and magnesium, and so on, and their alloys, offer excellent mechanical properties, such as high specific strength and good ductility. Therefore, they are expected to be used as stractural materials for transportation parts in order to mitigate CO₂ emissions. However, their low corrosion resistance has restricted their application in corrosive environments. Up to now, various surface treatments such as anodization and chemical conversion have been developed. However, there is still plenty of room to improve them. There is a need, therefore, for a novel corrotion protection or coating technology that is capable of improving the corrosion resistance of the light metals.

Great importance in corrosion protection is enabling of uniform formation of film and its higher chemical stability in corrosive environments. This can be achieved by surface pre-treatment or modificaion of microstructure of substrate. Thus, this Special Issue focuses on not only a novel corrotion protection or coating technology to improve corrosion resitance of the light metals but also corrosion mechanism of light metals responsible for improvement of corrision resistance and for the effect of corrosion protection by surface pre-treatment or modificaion of microstructure of substrate.

Prof. Takahiro Ishizaki
Guest Editor

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Keywords

Light metals
Corrosion Protection
Coating
Corrosion Resistance
Corrosion
Microstructure

Published Papers (12 papers)

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Research

26 pages, 11053 KiB

Open AccessArticle

Atmospheric and Marine Corrosion of PEO and Composite Coatings Obtained on Al-Cu-Mg Aluminum Alloy

by Vladimir S. Egorkin, Ivan M. Medvedev, Sergey L. Sinebryukhov, Igor E. Vyaliy, Andrey S. Gnedenkov, Konstantine V. Nadaraia, Nikolaj V. Izotov, Dmitriy V. Mashtalyar and Sergey V. Gnedenkov

Materials 2020, 13(12), 2739; https://doi.org/10.3390/ma13122739 - 17 Jun 2020

Cited by 31 | Viewed by 2837

Abstract

Wrought Al-Cu-Mg aluminum alloy (D16) was treated by bipolar plasma electrolytic oxidation to create a base plasma electrolytic oxidation (PEO)-coating with corrosion protection and mechanical properties superior to bare alloy’s natural oxide layer. Additional protection was provided by the application of polymer, thus creating a composite coating. Electrochemical and scratch tests, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction studies were performed. Degradation of coatings in the marine atmosphere and seawater was evaluated. The composite polymer-containing coating provided better corrosion protection of aluminum alloy compared to the PEO-coating, although seawater affected both. During the atmospheric exposure, the PEO-coating provided reasonably good protection, and the composite coating showed excellent performance. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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13 pages, 8382 KiB

Open AccessArticle

Effect of Hydrogen and Absence of Passive Layer on Corrosive Properties of Aluminum Alloys

by Paweł P. Włodarczyk and Barbara Włodarczyk

Materials 2020, 13(7), 1580; https://doi.org/10.3390/ma13071580 - 30 Mar 2020

Cited by 6 | Viewed by 2183

Abstract

This paper reports the results of research on the effect of hydrogen permeation and the absence of passive layers on the variations in the corrosive properties of aluminum alloys. The study demonstrated that such variations contribute to the deterioration of corrosive properties, which in turn contributes to shortening the reliability time associated with the operation of aluminum alloy structures. The analysis involved structural aluminum alloys: EN AW-1050A, EN AW-5754, and EN AW-6060. It was demonstrated that the absorption of hydrogen by the analyzed alloys led to the shift of the electrode potential to the negative side. The built hydrogen corrosion cells demonstrate in each case the formation of electromotive force (EMF) cells. The initial EMF value of the cell and its duration depends on the duration of hydrogenation. As a result of removing the passive layers, the electrode potential also changes to the negative side. Following the removal of the passive layer from one of the electrodes, the cells also generated a galvanic (metal) cell. The duration of such a cell is equivalent to the time of restoration of the passive layer. The formation of such hydrogen and metal galvanic cells changes the electrochemical properties of aluminum alloys, therefore deteriorates the corrosive properties of aluminum alloys. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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17 pages, 4930 KiB

Open AccessArticle

Improvement of AZ91 Alloy Corrosion Properties by Duplex NI-P Coating Deposition

by Jaromír Wasserbauer, Martin Buchtík, Jakub Tkacz, Stanislava Fintová, Jozef Minda and Leoš Doskočil

Materials 2020, 13(6), 1357; https://doi.org/10.3390/ma13061357 - 17 Mar 2020

Cited by 21 | Viewed by 2595

Abstract

The corrosion behavior of duplex Ni-P coatings deposited on AZ91 magnesium alloy was studied. The electroless deposition process of duplex Ni-P coating consisted in the preparation of low-phosphorus Ni-P coating (5.7 wt.% of P), which served as a bond coating and high-phosphorus Ni-P coating (11.5 wt.% of P) deposited on it. The duplex Ni-P coatings with the thickness of 25, 50, 75 and 100 µm were deposited on AZ91 magnesium alloy. The electrochemical corrosion behavior of coated AZ91 magnesium alloy was investigated by electrochemical impedance spectroscopy and potentiodynamic polarization method in 0.1 M NaCl. Obtained results showed a significant improvement in the corrosion resistance of coated specimens when compared to uncoated AZ91 magnesium alloy. From the results of the immersion tests in 3.5 wt.% NaCl, 10% solution of HCl and NaOH and 5% neutral salt spray, a noticeable increase in the corrosion resistance with the increasing thickness of the Ni-P coating was observed. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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15 pages, 7167 KiB

Open AccessArticle

The Effect of Vanadate, Phosphate, Fluoride Compounds on the Aqueous Corrosion of Magnesium Alloy AZ31 in Dilute Chloride Solutions

by Zhiyuan Feng, Jichao Li, Zi Yang and Rudolph Buchheit

Materials 2020, 13(6), 1325; https://doi.org/10.3390/ma13061325 - 14 Mar 2020

Cited by 18 | Viewed by 2808

Abstract

The anodic polarization response of magnesium alloy AZ31 was first characterized during exposure to aerated 0.1 M NaCl solutions with millimolar additions of NaVO₃, Na₃PO₄, Na₂HPO₄, NaF and various pairings to assess their ability to inhibit corrosion kinetics and retard localized corrosion. Each of the candidate inhibitors reduced the corrosion rate of the alloy to some degree. A Na₃PO₄–NaVO₃ pair produced a good inhibiting effect decreasing the corrosion rate to about 10⁻⁷ A/cm², which was two orders of magnitude lower than the uninhibited control case. A Bliss Independence assessment indicated that this inhibitor pair acted synergistically. A Na₂HPO₄–NaVO₃ pair reduced the corrosion rate to 10⁻⁶ A/cm² but was not assessed to be acting synergistically. The NaVO₃–NaF pair did not reduce the corrosion rate significantly compared to the control case and was an antagonistic pairing. SEM imaging showed film formation due to exposure, which appears to be the origin of the observed inhibition. The resistance to localized corrosion was assessed as the difference in the breakdown potential and the corrosion potential, with larger values indicating a lower probability of localized corrosion during free corrosion exposures. The effects of the inhibitors on this characteristic were mixed, but each of the inhibitor pairs yielded potential differences in excess of 100 mV. A conceptual conversion coating process based on a mixture of vanadate and phosphate compounds were demonstrated. A fluoride-bearing formulation produced coatings whose total impedance was increased by a factor of two compared to an uncoated control. A fluoride-free formulation produced coatings whose corrosion resistance was increased by more than a factor of three. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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12 pages, 5869 KiB

Open AccessArticle

In Situ Scanning Electron Microscopy Observation of Crack Initiation and Propagation in Hydroxide Films Formed by Steam Coating on Aluminum-Alloy Sheets

by Hongmei Li, Naoki Takata, Makoto Kobashi and Ai Serizawa

Materials 2020, 13(5), 1238; https://doi.org/10.3390/ma13051238 - 09 Mar 2020

Cited by 4 | Viewed by 2876

Abstract

Hydroxide film was formed on 6061 Al-alloy (Al-1.00Mg-0.62Si(wt.%)) sheets by steam coating with the temperature of 220 °C for 24 h. During bending test of the coated specimens, the crack initiation and propagation processes in the hydroxide film were investigated using in situ SEM observations. The hydroxide film formed exhibited a dual-layer structure composed of an inner amorphous layer and an outer polycrystalline γ-AlO(OH)-phase layer. On the compressively strained surface, lateral cracks are preferentially initiated inside the inner amorphous layer, and propagate either inside this layer or on its interface with the outer γ-AlO(OH) layer. Digital image correlation analyses of the in situ observed SEM images suggested that the concentrated tensile strain along the surface normal localized at some parts of the amorphous layer could contribute to the crack initiation. On the tensile-strained surface, a number of cracks were initiated inside the inner amorphous layer along the surface normal and propagate into the outer γ-AlO(OH) layer. No cracks were found along the interface of the amorphous layer with the Al-alloy substrate. As a result, the anticorrosion hydroxide film adhered on the Al sheet after bending deformation. Such strong adhesion contributes to the excellent corrosion resistance of the Al-alloy parts provided by the steam coating. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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14 pages, 3030 KiB

Open AccessArticle

Erosion Corrosion Behavior of Aluminum in Flowing Deionized Water at Various Temperatures

by Liangshou Hao, Feng Zheng, Xiaoping Chen, Jiayang Li, Shengping Wang and Youping Fan

Materials 2020, 13(3), 779; https://doi.org/10.3390/ma13030779 - 08 Feb 2020

Cited by 8 | Viewed by 2648

Abstract

To optimize the operating temperature and flow velocity of cooling water in a high voltage direct current (HVDC) thyristor valve cooling system, the erosion corrosion characteristics of aluminum electrodes in deionized water at various temperatures were studied. With increasing water temperature, the corrosion current of the aluminum electrode gradually increases and the charge transfer impedance gradually decreases, thus, the corrosion of aluminum tends to become serious. The aluminum electrode in 50 °C deionized water has the most negative corrosion potential (−0.930 V), the maximum corrosion current (1.115 × 10⁻⁶ A cm⁻²) and the minimum charge transfer impedance (8.828 × 10⁻⁶ Ω), thus, the aluminum corrosion at this temperature is the most serious. When the temperature of deionized water increases, the thermodynamic activity of the ions and dissolved oxygen in the deionized water increases, and the mass transfer process accelerates. Therefore, the electrochemical corrosion reaction of the aluminum surface will be accelerated. The corrosion products covering the aluminum electrode surface are mainly Al(OH)₃. With increasing water temperature, the number of pits and grooves formed by corrosion on the aluminum surface increased. In this paper, the molar activation energy Ea and the equilibrium constant K of the aluminum corrosion reaction with various temperatures are calculated. This clarifies the effect of temperature on the aluminum corrosion reaction, which provides a basis for protecting aluminum from corrosion. The results of this study will contribute to research that is focused on the improvement of production techniques used for HVDC thyristor valve cooling systems. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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19 pages, 2925 KiB

Open AccessArticle

Guar Gum as an Eco-Friendly Corrosion Inhibitor for Pure Aluminium in 1-M HCl Solution

by Gaetano Palumbo, Katarzyna Berent, Edyta Proniewicz and Jacek Banaś

Materials 2019, 12(16), 2620; https://doi.org/10.3390/ma12162620 - 16 Aug 2019

Cited by 44 | Viewed by 5220

Abstract

Guar gum (GG) was investigated as a possible eco-friendly corrosion inhibitor for pure aluminium in a 1-M HCl solution at different temperatures and immersion times using gravimetric and electrochemical techniques. The results showed that GG was a good corrosion inhibitor for pure aluminium in the studied environment. The inhibition efficiency of GG increased with increasing inhibitor concentration and immersion time but decreased with increasing temperature. Polarisation measurements revealed that GG was a mixed type inhibitor with a higher influence on the cathodic reaction. The adsorption behaviour of the investigated inhibitor was found to obey the Temkin adsorption isotherm and the calculated values of the standard free adsorption energy indicate mixed-type adsorption, with the physical adsorption being more dominant. The associated activation energy (E_a) and the heat of adsorption (Q_a) supported the physical adsorption nature of the inhibitor. Fourier-transform infrared spectroscopy (FTIR) and Raman/SERS were used to explain the adsorption interaction between the inhibitor with the surface of the metal. The results suggested that most inhibition action of GG is due to its adsorption of the metal surface via H-bond formation. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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17 pages, 11453 KiB

Open AccessFeature PaperArticle

Effect of Microstructure on the Corrosion Resistance of TIG Welded 1579 Alloy

by Andrey S. Gnedenkov, Sergey L. Sinebryukhov, Dmitry V. Mashtalyar, Igor M. Imshinetskiy, Igor E. Vyaliy and Sergey V. Gnedenkov

Materials 2019, 12(16), 2615; https://doi.org/10.3390/ma12162615 - 16 Aug 2019

Cited by 31 | Viewed by 2875

Abstract

The paper studies microstructure, chemical composition and corrosion activity of the tungsten inert gas welded joint of the Al-Mg-Sc alloy. An intensive corrosion attack of the heat affected zone (HAZ) was found due to precipitation of secondary phases at recrystallized grain boundaries. The ccorrosion process initiated along the boundary of α-Al grains, where a high concentration of anodic (Mg₂Si and Mg₂Al₃) and cathodic phases ((MnFe)Al₆) was observed. Increased temperatures during welding led to coalescence of the anodic phases in HAZ. Additionally, HAZ was found to be enriched with hard intermetallic compounds (Mg₂Si and (MnFe)Al₆). This area had a higher microhardness (930 MPa) compared to base metal (BM, 895 MPa) and fusion zone (FZ, 810 MPa). The volume fraction of secondary phases was 26% in BM, 28% in FZ and 38% in HAZ. The average grain size increased in the following order: (9 ± 3) µm (BM) < (16 ± 3) µm (HAZ) < (21 ± 5) µm (FZ). A plasma electrolytic oxidation (PEO) coating of aluminum-based material was applied to protect the weld from oxidation. The PEO-coating provided a high corrosion protection in the aggressive Cl⁻-containing environment. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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15 pages, 9697 KiB

Open AccessArticle

Effect of Sn Addition on Microstructure and Corrosion Behavior of As-Extruded Mg–5Zn–4Al Alloy

by Jian Ding, Xin Liu, Yujiang Wang, Wei Huang, Bo Wang, Shicheng Wei, Xingchuan Xia, Yi Liang, Xianhua Chen, Fusheng Pan and Binshi Xu

Materials 2019, 12(13), 2069; https://doi.org/10.3390/ma12132069 - 27 Jun 2019

Cited by 17 | Viewed by 2504

Abstract

The effect of Sn addition on the microstructure and corrosion behavior of extruded Mg–5Zn–4Al–xSn (0, 0.5, 1, 2, and 3 wt %) alloys was investigated by optical microscopy (OM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electrochemical measurements, and immersion tests. Microstructural results showed that the average grain size decreased to some degree and the amount of precipitates increased with the increasing amount of Sn. The extruded Mg–5Zn–4Al–xSn alloy mainly consisted of α-Mg, Mg₃₂(Al,Zn)₄₉, and Mg₂Sn phases as the content of Sn was above 1 wt %. Electrochemical measurements indicated that the extruded Mg–5Zn–4Al–1Sn (ZAT541) alloy presented the best corrosion performances, with corrosion potential (E_corr) and corrosion current density (I_corr) values of −1.3309 V and 6.707 × 10⁻⁶ A·cm⁻², respectively. Furthermore, the corrosion mechanism of Sn is discussed in detail. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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14 pages, 5353 KiB

Open AccessArticle

Effect of Al Content in the Mg-Based Alloys on the Composition and Corrosion Resistance of Composite Hydroxide Films Formed by Steam Coating

by Takahiro Ishizaki, Tomohiro Miyashita, Momo Inamura, Yuma Nagashima and Ai Serizawa

Materials 2019, 12(7), 1188; https://doi.org/10.3390/ma12071188 - 11 Apr 2019

Cited by 11 | Viewed by 3292

Abstract

Mg alloys are expected to be used in fields of the transportation industry because of their lightweight property, however, they show low corrosion resistance. To improve the corrosion resistance, preparation of the protective film on Mg alloys is essential. In this study, composite hydroxide films were prepared on three types of Mg alloys with different aluminum contents—that is, AZ31, AZ61, and AZ91D—by steam coating to investigate the relationship between the Mg-Al layered double hydroxide (LDH) content in the film and the Al content in the Mg alloys. Scanning electron microscopy (SEM) observation demonstrated that films were formed densely on all Mg alloy surfaces. X-ray diffraction (XRD) analyses revealed that all films prepared on AZ61 and AZ91D were composed of Mg(OH)₂, AlOOH, and Mg-Al LDH, while the film containing Mg(OH)₂ and Mg-Al LDH were formed only on AZ31. The Mg-Al LDH content in the film prepared on AZ61 was relatively higher than those prepared on AZ31 and AZ91D. The content of AlOOH in the film increased with an increase in the Al content in the Mg alloys. The film thickness changed depending on the treatment time and type of Mg alloy. Polarization curve measurements in 5 mass% NaCl solution demonstrated that the film prepared on the AZ61 showed complete passive behavior within the potential range of −1.0 to −0.64 V. In addition, immersion tests in 5 mass% NaCl aqueous solution for 480 h demonstrated that the film on the AZ61 had superior durability against 5 mass% NaCl aqueous solution. These results indicated that the film on the AZ61 had the most superior corrosion resistance among all samples. The results obtained in this study suggest that the LDH content in the film could be related to the corrosion resistance of the film. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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12 pages, 4487 KiB

Open AccessArticle

Corrosion Resistance of 2060 Aluminum–Lithium Alloy LBW Welds Filled with Al-5.6Cu Wire

by Fencheng Liu, Xiaoguang Wang, Baosheng Zhou, Chunping Huang and Feiyue Lyu

Materials 2018, 11(10), 1988; https://doi.org/10.3390/ma11101988 - 15 Oct 2018

Cited by 15 | Viewed by 3578

Abstract

Alloy sheets of type 2060 aluminum–lithium were welded by laser beam welding (LBW) filled with ER2319 Al-5.6Cu wire. Microstructural observations showed the uneven distribution of columnar grains, equiaxed grains and equiaxed dendrite grains in the weld. The θ′(Al₂Cu) phase and other phases precipitated in the weld. The θ′(Al₂Cu) phase centrally distributed at the grain boundaries. During the immersion corrosion, the pitting corrosion first occurred and then gradually expanded and transformed to intergranular corrosion and exfoliation corrosion. The electrochemical corrosion test showed a higher corrosion tendency of the base metal and heat-affected zone for the lower corrosion potential, but the corrosion current density of the weld was relatively larger. The segregation of Cu, Mg and other elements at the grain boundary aggravated the occurrence of intergranular corrosion. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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11 pages, 11138 KiB

Open AccessFeature PaperArticle

Effect of Vapor Pressure During the Steam Coating Treatment on Structure and Corrosion Resistance of the Mg(OH)₂/Mg-Al LDH Composite Film Formed on Mg Alloy AZ61

by Kae Nakamura, Yuta Shimada, Tomohiro Miyashita, Ai Serizawa and Takahiro Ishizaki

Materials 2018, 11(9), 1659; https://doi.org/10.3390/ma11091659 - 08 Sep 2018

Cited by 14 | Viewed by 3506

Abstract

Corrosion resistant films with almost the same film thickness were prepared on the magnesium alloy AZ61 by steam coating at different vapor pressure and treatment times. The effect of the vapor pressure on the structures and the corrosion resistance of the films was investigated by using FE-SEM, SEM-EDX, GAXRD, and potentiodynamic polarization curve measurements in a 3.5 mass percentage NaCl aqueous solution. These studies clarified that the interlayers of Mg-Al Layered Double Hydroxide (LDHs) increased and its structure became non-uniform with an increase in the vapor pressure. The corrosion current density slightly increased with an increase in the vapor pressure during the treatment, but pitting corrosion occurred at both low and high vapor pressures. These results indicate that water molecules were pushed into an interlayer of Mg-Al LDHs by high vapor pressure. Consequently, the interlayer distance of Mg-Al LDH was widened and the cracks were generated in the anti-corrosive film. On the other hand, the Mg-Al LDH with an insufficiently large interlayer distance could not fill the cracks in the Mg(OH)₂ crystallites and caused pitting corrosion when the vapor pressure was low. Full article

(This article belongs to the Special Issue Corrosion and Corrosion Protection for Light Metals/Alloys)

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