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Corrosion Prevention of Magnesium Alloys
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Magnesium (Mg) alloys are receiving increasing attention due to their abundance, light weight, castability, formability, mechanical properties and corrosion performance. By selecting the appropriate combination of materials, coatings and surface modifications, their corrosion resistance can be greatly enhanced. Corrosion prevention of magnesium alloys is a comprehensive guide to the effective prevention of corrosion in these important light metals.
Part one discusses alloying, inhibition and prevention strategies for magnesium alloys as well as corrosion and prevention principles. Part two reviews surface treatment and conversion. Beginning with an overview of surface cleaning and pre-conditioning, the book goes on to discuss the use of surface processing and alloying, laser treatments, chemical conversion and electrochemical anodization to improve the corrosion resistance of magnesium alloys. Coatings are then the focus of part three, including varied plating techniques, cold spray coatings, gel and electroless electrophoresis coatings. Finally, the book concludes in part four with a selection of case studies investigating the application of preventative techniques for both automotive and medical applications.
With its distinguished editor and international team of expert contributors, Corrosion prevention of magnesium alloys is a key reference tool for all those working with magnesium and its alloys, including scientists, engineers, metallurgists, aerospace and automotive professionals, and academics interested in this field. Chapters provide an overview of surface cleaning and pre-conditioning Examines processes to improve the corrosion resistance of magnesium alloys, including laser treatments and chemical conversion and electrochemical anodization Discusses cold spray, sol-gel and electrophoretic coatings
Part one discusses alloying, inhibition and prevention strategies for magnesium alloys as well as corrosion and prevention principles. Part two reviews surface treatment and conversion. Beginning with an overview of surface cleaning and pre-conditioning, the book goes on to discuss the use of surface processing and alloying, laser treatments, chemical conversion and electrochemical anodization to improve the corrosion resistance of magnesium alloys. Coatings are then the focus of part three, including varied plating techniques, cold spray coatings, gel and electroless electrophoresis coatings. Finally, the book concludes in part four with a selection of case studies investigating the application of preventative techniques for both automotive and medical applications.
With its distinguished editor and international team of expert contributors, Corrosion prevention of magnesium alloys is a key reference tool for all those working with magnesium and its alloys, including scientists, engineers, metallurgists, aerospace and automotive professionals, and academics interested in this field. Chapters provide an overview of surface cleaning and pre-conditioning Examines processes to improve the corrosion resistance of magnesium alloys, including laser treatments and chemical conversion and electrochemical anodization Discusses cold spray, sol-gel and electrophoretic coatings
Azioni libro
Inizia a leggereInformazioni sul libro
Corrosion Prevention of Magnesium Alloys
Descrizione
Magnesium (Mg) alloys are receiving increasing attention due to their abundance, light weight, castability, formability, mechanical properties and corrosion performance. By selecting the appropriate combination of materials, coatings and surface modifications, their corrosion resistance can be greatly enhanced. Corrosion prevention of magnesium alloys is a comprehensive guide to the effective prevention of corrosion in these important light metals.
Part one discusses alloying, inhibition and prevention strategies for magnesium alloys as well as corrosion and prevention principles. Part two reviews surface treatment and conversion. Beginning with an overview of surface cleaning and pre-conditioning, the book goes on to discuss the use of surface processing and alloying, laser treatments, chemical conversion and electrochemical anodization to improve the corrosion resistance of magnesium alloys. Coatings are then the focus of part three, including varied plating techniques, cold spray coatings, gel and electroless electrophoresis coatings. Finally, the book concludes in part four with a selection of case studies investigating the application of preventative techniques for both automotive and medical applications.
With its distinguished editor and international team of expert contributors, Corrosion prevention of magnesium alloys is a key reference tool for all those working with magnesium and its alloys, including scientists, engineers, metallurgists, aerospace and automotive professionals, and academics interested in this field. Chapters provide an overview of surface cleaning and pre-conditioning Examines processes to improve the corrosion resistance of magnesium alloys, including laser treatments and chemical conversion and electrochemical anodization Discusses cold spray, sol-gel and electrophoretic coatings
Part one discusses alloying, inhibition and prevention strategies for magnesium alloys as well as corrosion and prevention principles. Part two reviews surface treatment and conversion. Beginning with an overview of surface cleaning and pre-conditioning, the book goes on to discuss the use of surface processing and alloying, laser treatments, chemical conversion and electrochemical anodization to improve the corrosion resistance of magnesium alloys. Coatings are then the focus of part three, including varied plating techniques, cold spray coatings, gel and electroless electrophoresis coatings. Finally, the book concludes in part four with a selection of case studies investigating the application of preventative techniques for both automotive and medical applications.
With its distinguished editor and international team of expert contributors, Corrosion prevention of magnesium alloys is a key reference tool for all those working with magnesium and its alloys, including scientists, engineers, metallurgists, aerospace and automotive professionals, and academics interested in this field. Chapters provide an overview of surface cleaning and pre-conditioning Examines processes to improve the corrosion resistance of magnesium alloys, including laser treatments and chemical conversion and electrochemical anodization Discusses cold spray, sol-gel and electrophoretic coatings
Anteprima del libro
Corrosion Prevention of Magnesium Alloys
diligently.
Part I
Alloying and inhibition
1
Corrosion behavior and prevention strategies for magnesium (Mg) alloys
G.-L. Song, General Motors Corporation, USA
Abstract:
Magnesium (Mg) alloys have low corrosion resistance and exhibit unusual corrosion behavior in aqueous environments. Because of this unique corrosion performance, some special corrosion prevention techniques have to be employed for Mg alloys in their applications. This chapter briefly summarizes the corrosion characteristics of Mg alloys, and also presents a strategy and methodologies to mitigate the corrosion damage of Mg alloys in applications.
Key words
magnesium
corrosion
protection
1.1 Introduction
Note: This chapter is a revised and expanded version of Chapter 1 ‘Corrosion behaviour of magnesium alloys and protection techniques’ by G.-L. Song, originally published in Surface engineering of light alloys: aluminium, magnesium and titanium alloys, ed. Hanshan Dong, Woodhead Publishing Limited, 2010, ISBN: 978-1-84569-537-8.
Magnesium and its alloys have a high strength/density ratio and have found many successful applications, particularly in the automotive and aerospace industries (Makar and Kruger, 1993; Polmear, 1996; Aghion and Bronfin, 2000; Bettles et al., 2003; Song, 2005b, 2006). However, the poor corrosion resistance of existing magnesium alloys in some service environments has limited the further expansion of their application. Existing investigations have clearly suggested that the corrosion behavior of Mg alloys is very different from that of a convention metal, such as steel (Song, 2004a, 2005b, 2006, 2009a, 2009c; Winzer et al., 2005, 2007, 2008; Wan et al, 2006; Song and Atrens, 2007; Wang et al, 2007). For more successful applications of Mg alloys, it is important to understand their characteristic corrosion phenomena and have a practical corrosion prevention strategy.
1.2 Corrosion characteristics and implications in protection
The corrosion characteristics of Mg alloys critically concern their applications. Only if the corrosion behavior is comprehensively understood, can a Mg alloy be correctly used in suitable applications, and also the most effective protection be selected for this alloy.
1.2.1 Electrochemical corrosion mechanism
Mg alloys follow a corrosion mechanism different from other engineering metallic materials. On pure Mg or a Mg alloy, the overall corrosion reaction can be written as (Makar and Kruger, 1993; Song and Atrens, 1999; Song, 2005b, 2006):
[1.1]
or
[1.2]
This overall corrosion can be decomposed into anodic and cathodic reactions. The cathodic process is (Song, 2005b, 2006):
[1.3]
or
[1.4]
and the anodic process (Song, 2005b, 2006):
[1.5]
[1.6]
y is the ratio of further anodic reaction over hydrogen production reactions. The detailed anodic and cathodic reactions under a steady corrosion condition have been illustrated previously (Song et al, 1997a, 1997b; Song and Atrens, 1999, 2003; Song, 2005b). In general the anodic dissolution occurs mainly in a film-free area, while in a film-covered area the anodic dissolution is negligible. The cathodic reaction, which is mainly a hydrogen evolution process, can take place in both film-free and film-covered areas, and the reaction rate in a film-free area is much faster than the rate on a film-covered surface, particularly if impurity particles are present there.
Both the anodic and cathodic reactions occur simultaneously on Mg. In fact, more detailed reaction steps can be involved in the anodic and cathodic processes, which have been demonstrated by Song (2011) and are schematically illustrated in Fig. 1.1.
1.1 Schematic illustration of anodic and cathodic reactions involved in the self-corrosion of Mg.
Based on this corrosion model, the subsequent corrosion phenomena and behavior can be predicted. Correspondingly, what these corrosion characteristics imply can also be understood.
1.2.2 Hydrogen evolution
The overall corrosion reactions [1.1] and [1.2] suggest that the dissolution of Mg is always accompanied by hydrogen evolution. This corrosion-related hydrogen evolution is also applicable to Mg alloys in aqueous solutions (Song et al, 1998, 2001, 2005a; Song and Atrens, 1998, 2003; Song and St John, 2002), including engine coolants (Song and St John, 2004, 2005) and simulated body fluids (SBF) (Song and Song, 2006, 2007; Song, 2007b). In a severe corrosion process, Mg particle undermining may take place (Mg particle falling into solution due to the surrounding material becoming completely corroded). However, this process has been shown to have no influence upon either reaction [1.1] or [1.2] (Song et al., 1997b). Therefore, for Mg and Mg alloys in an aqueous solution, the hydrogen evolution phenomenon is one of the most important features and includes cathodic hydrogen evolution (CHE) and anodic hydrogen evolution (AHE).
Having realized that hydrogen evolution is closely associated with the corrosion of Mg and its alloys, a simple hydrogen evolution measurement technique was first employed by Song et al. (1997b) to estimate the corrosion rate of Mg. Following further illustration of the theory and analysis of possible errors inherent to this method (Song et al., 2001; Song, 2005b, 2006), it has also been widely used on many Mg alloys (Krishnamurthy et al, 1988; Hallopeau et al., 1999; Bonora et al.; 2000; Eliezer et al., 2000; Mathieu et al., 2000; Song and St John, 2002; Song, 2005a; Pu et al, 2012; Song and Xu, 2012).
According to reaction [1.1] or [1.2], dissolution of one Mg atom always corresponds to the generation of one hydrogen gas molecule. In other words, if there is one mole of hydrogen evolved, then there must be one mole of magnesium dissolved (Song et al, 2001; Song, 2005b, 2006). Measuring the volume of hydrogen evolved is equivalent to measuring the weight-loss of a corroding Mg alloy, and the measured hydrogen evolution rate is equal to the weight-loss rate if they are both converted into the same unit (e.g. mole per minute).
The experimental set-up for measuring hydrogen evolution is straightforward (Song et al, 2001) and can simply consist of a burette, a funnel and a beaker (see Fig. 1.2a). This set-up can also be combined into an electrolytic cell for electrochemical measurements (see Fig. 1.2b) (Song and St John, 2002). The overall theoretical error of this technique is less than 10% (Song et al.; 2001). In practice, the corrosion rates of various Mg alloy specimens measured by the hydrogen evolution method have been found to be in very good agreement with those measured by weight-loss (Song et al., 2001). Furthermore, the hydrogen evolution measurement has several advantages over the traditional weight-loss measurement (Song, 2005b, 2006):
1.2 Schematic illustration of the set-up used to measure the volume of hydrogen evolved. (a) Simple set-up for short-term corrosion measurements (Song et al., 1997b). (b) Combination of hydrogen evolution and electrochemical measurements (according to Song and St John, 2002).
1. smaller theoretical and experimental errors;
2. easy to set-up and operate;
3. suitable for corrosion monitoring of magnesium and its alloys; and
4. no need to remove corrosion products.
While hydrogen evolution is an important corrosion characteristic and can even be employed to reliably monitor the corrosion of Mg and its alloys, its detrimental effect on the corrosion prevention/protection performance should not be overlooked. First, the hydrogen evolution from a corroding area will disturb the solution, which will to a great degree eliminate concentration difference and diffusion effect in the adjacent solution. Without a limited diffusion current density controlling the process, the corrosion rate can continuously increase to a very high level. Second, owing to the hydrogen evolution, corrosion products are unlikely to precipitate in a corroded area and the corrosion product film which forms is very loose and porous. Since the naturally formed surface film on Mg is not protective, the self-limitation effect caused by the products during corrosion is weak. Third, the hydrogen evolution resulting from corrosion can cause damage to an externally applied coating/plating and explains why blistering phenomena are especially common for a Mg alloy coated in an organic coating.
1.2.3 Alkalization
A relationship between the dissolution of Mg and the generation of OH‒ or consumption of H+ during the corrosion of Mg alloys is also given by either reaction [1.1] or [1.2]. Similar to hydrogen evolution in an acidic solution, the production of OH‒ or consumption of H+ always accompanies the corrosion of Mg and its alloys in a neutral or alkaline environment, which can result in an increased pH value for the solution. However, the pH increase levels out at ~10.5 even though the corrosion will continue at this pH value. This is a result of the deposition of Mg(OH)2 (Song, 2005b, 2006): the additional hydroxyls generated at this pH level are consumed by dissolved Mg² + through deposition of Mg(OH)2, which stabilizes the pH value of the solution at approximately ~10.5.
The surface of a corroding Mg alloy always experiences an alkalization process because either hydroxyls are generated or protons are consumed directly in the corroding area. It has been estimated that the local pH value of the solution adjacent to a Mg surface can be around 10.5 even if the bulk solution is acidic (Nazarrov and Mikhailovskii, 1990; Song, 2005b, 2006). The alkalization effect varies slightly with Mg alloy. Figure 1.3 shows the variation of solution pH value with time after different Mg alloys are immersed in the solution (Song and Liu, 2011).
1.3 Variation of pH value of Mg alloys (10 cm x 7 cm x 1 mm coupons) immersed in a diluted HCl solution (100 mL; initial pH = 3.5) with immersion time (Song and Liu, 2011).
The alkalization effect can be affected by the ratio of the surface area of a Mg alloy to the volume of the solution it is exposed to. A more significant alkalization effect is likely with a larger Mg alloy specimen in a smaller volume of solution. For example, under an atmospheric corrosion condition, only a thin aqueous film stays on the surface of a Mg alloy. This is a case of a large specimen with a small volume of solution which can easily result in a strong alkalization effect. Hence, the corrosion of a Mg alloy in an atmospheric environment is normally less severe than under immersion conditions (Song et al., 2004b, 2006b; Wan et al., 2006).
The alkalization effect has also been utilized to monitor the corrosion rate of a Mg alloy. For example, Hur et al. (1996) and Weiss et al. (1997) tried to measure the change in pH value or concentration of H+ of the solution in order to monitor the corrosion process of a Mg alloy. The pH method may be convenient in monitoring the corrosion of Mg alloys in a neutral solution in the initial stage. However, it is not as reliable as the hydrogen evolution technique. Firstly, the alkalization is dependent on the volume of the testing solution which can vary in different experiments; it is difficult to compare corrosion rates measured at different ratios of surface/volume. Secondly, in the later stages of corrosion, as considerable Mg has been dissolved and the solution has become Mg(OH)2 saturated, the pH value of the testing solution will be stable at 10.5 and will not increase further, even though the corrosion rate may still be high. Thirdly, the dissolution of atmospheric carbon dioxide could influence the pH value of the testing solution and result in a faulty corrosion indication. Lastly, in a strongly acidic or basic solution the variation of the pH value is not sufficiently sensitive to reflect the change of proton or hydroxyl concentration.
As some organic polymers dislike alkalinity and degrade quickly in an alkaline environment, the Mg surface alkalization effect hinders the application of some organic coatings on Mg alloy surfaces. However, for those organics that are by nature resistant to alkalinity, the surface alkalization effect can be utilized to enhance the coating formation and performance. Electroless E-coating is an example of such an organic coating resulting from the Mg surface alkalization effect (Song, 2009c, 2009d, 2009e, 2010a, 2011a; Song and Liu, 2011).
1.2.4 Macro-galvanic corrosion
Mg has the highest chemical activity of the engineering metals. Because the standard equilibrium potential of Mg/Mg² + is as negative as − 2.4 V ~ NHE (Perrault, 1978; Song, 2005b), Mg and its alloys normally have a very negative open-circuit (or corrosion) potential (around − 1.5 V ~ NHE) in a neutral aqueous environment. This means that Mg alloys are always the anode when in contact with other engineering metals.
Macro-galvanic corrosion is an anodic dissolution process of an anode accelerated by the cathodic reactions on a cathode that is in electrical contact with the anode. In theory, the galvanic corrosion rate (ig) is determined by (Song et al, 2004b):
[1.7]
where Ec and Ea are the open-circuit (corrosion) potentials of cathode and anode respectively in a given electrolyte; Rc and Ra are the cathode and anode polarization resistances; and Rs and Rm are the solution and electronic resistances between the anode and cathode, respectively.
The corrosion potential difference (Ec–Ea) between the anode and cathode is the first critical variable determining the galvanic corrosion rate ig. The corrosion potential of Mg in a NaCl solution is the least noble among those engineering metals and in fact, is over 600 mV more negative than zinc which is second in the galvanic series. Based on corrosion potentials, engineering metals exposed to seawater can be ranked in a galvanic series from active (negative) to passive (noble) (Hack, 1995):
Magnesium → magnesium alloys → zinc → galvanized steel → aluminum1100 → aluminum 6053 → Al clad → cadmium → aluminum2024 → mild steel → wrought iron → cast iron → 13% Cr stainless steel, type 410 (active) → 18–8 stainless steel, type 304 (active) → 18-12-3 stainless steel, type 316 (active) → lead-tin solders → lead → tin → muntz metal → manganese bronze → naval brass → nickel (active) → 76Ni-6Cr-7Fe alloy (active) → 60Ni-30Mo-6Fe-1Mn → yellow brass → admiralty brass → aluminum brass → red brass → copper → silicon bronze → 70:30 cupro nickel → G-Bronze → Silver solder → Nickel (passive) → 76Ni-16Cr-7Fe alloy (passive) → 13% Cr stainless steel, type 410 (passive) → titanium → 18-8 stainless steel, type 304 (passive) → 18-12-3 stainless steel, type 316 (passive) → silver → graphite → gold → platinum.
Mg and its alloys always act as anodes if in contact with other engineering metals. Because of the large difference between their corrosion potentials (Ec–Ea), the galvanic corrosion tendency is always significant between a Mg alloy and another engineering metal. Equation [1.7] also suggests that the galvanic corrosion is determined by the anodic and cathodic polarization resistances (Ra and Rc). Mg and its alloys normally have a low anodic polarization resistance (Song et al., 1997a, 1997b, 2004a; Song, 2004b, 2009b) while the cathodic polarization resistance of other metals in a neutral solution resulting from diffusion controlled oxygen reduction is relatively large. For a specific Mg alloy in a given solution whose corrosion potential and anodic resistance are fixed, the corrosion potential and the cathodic polarization resistance of a cathode metal will have a decisive influence on the galvanic corrosion of the Mg alloy (Song et al, 2004b). A metal with a noble potential and relatively low cathodic polarization resistance will severely accelerate the corrosion of a Mg alloy. It is well known that Fe, Co, Ni, Cu, W, Ag and Au metals are much nobler than Mg alloys in an aqueous solution (Table 1.1) and have relatively low hydrogen evolution over-potentials (lower than 500 mV, i.e. low cathodic polarization resistance). Thus, these metals in contact with a Mg alloy can form galvanic corrosion couples and result in serious galvanic corrosion damage to Mg alloys. This type of galvanic couple should be avoided. Unfortunately, aluminum, steel and galvanized steel are widely used engineering materials and are quite often used together with Mg alloys. In this case, steel is the most detrimental and Al the least harmful to Mg alloys (Avedesian and Baker, 1999; Song et al., 2004b).
Table 1.1
Standard equilibrium potentials of typical metals in aqueous solution
Source: Bard and Faulkner, 1980.
In Equation [1.7], Rm can also significantly affect the galvanic corrosion current. If it is large enough, for example, where the anode and cathode are separated by an insulator, then the galvanic corrosion will stop. Unfortunately, the anode and cathode are normally electrically connected and thus Rm = 0 in practice. Therefore, Rm is not seriously considered in many galvanic corrosion studies.
The parameters involved in Equation [1.7] can determine the overall galvanic corrosion current, ig, which represents the overall galvanic corrosion of an anode (Song, 2010). As long as all the parameters of Equation [1.7] are measured, the overall galvanic corrosion damage can be estimated. Many applied studies have tried to estimate the compatibility of various materials (including fasteners) with Mg alloy parts using this equation (Hawke, 1987; Skar, 1999, Gao et al., 2000; Senf et al., 2000; Starostin et al., 2000; Boese, et al., 2001).
However, in many practical applications, the distribution of galvanic current density, ig, over a Mg alloy component surface is of greater concern as it cannot simply be predicted by Equation [1.7]. The distribution of galvanic current density is closely associated with parameter Rs which is dependent on the geometric configuration of the solution path for the galvanic current between the anode and cathode. For a simple one-dimensional galvanic couple consisting of a Mg alloy and another metal, an analytical prediction of the galvanic current density distribution is possible (Waber and Rosenbluth, 1955; Kennard and Waber, 1970; Gal-Or et al, 1973; McCafferty, 1976, 1977; Melville, 1979, 1980). It has been reported that the galvanic current density has an exponential distribution (Song et al., 2004b; Song, 2010). This can be confirmed experimentally by direct measurement of the distribution of galvanic current density of a Mg alloy in contact with another metal under a standard salt spray condition (Song et al., 2004b).
A specially designed ‘sandwich’-like galvanic probe (see Fig. 1.4) (Song et al., 2004b; Song, 2010) can be used for these measurements. The measured galvanic current density exponentially decreases with the thickness of an insulating spacer which implies that the galvanic corrosion can still be significant even when the thickness of the insulating spacer between a Mg alloy and steel is as large as 9 cm under a salt spray condition (Song et al., 2004b; Song, 2005b. 2006). It seems that insertion of an insulating spacer may reduce but cannot eliminate galvanic corrosion. The reason is that the insulating spacer does not completely block the ionic current path.
1.4 Configuration of a ‘sandwich’ like probe used to measure the galvanic current (Song et al., 2006b).
When the geometry of a galvanic couple becomes complicated, experimental measurement of the galvanic corrosion rate using such a ‘sandwich’ galvanic probe will be difficult. In this case, computer modeling is an option (Klingert et al, 1964; Doig and Flewitt, 1979; Sautebin et al, 1980; Helle et al, 1981; Fu, 1982; Munn, 1982; Kasper and April, 1983; Munn and Devereux, 1991a, 1991b; Miyaska et al, 1990; Aoki and Kishimoto, 1991; Hack, 1997). There are already a few successful studies of the galvanic corrosion of Mg alloys by computer modeling (Jia et al, 2004, 2005a, 2005b, 2006, 2007). Nevertheless, experimental measurement of the polarization curves of the coupling metals is still important in numerical analysis and computer modeling. Polarization curves are required as boundary conditions in computer modeling. Due to the negative difference effect, alkalization effect, ‘poisoning’ effect, ‘short-circuit’ effect, etc. (Song et al., 2004b; Song, 2005b, 2006), current computer modeling techniques cannot at this time comprehensively simulate a practical macro-galvanic process and quite often there are significant deviations between computer-modeled data and measured galvanic corrosion results.
The most important conclusion regarding macro-galvanic corrosion is that galvanic effect is responsible for most corrosion problems with practical Mg components, as the contact with other metals cannot be avoided in industry. An isolation spacer in theory cannot completely eliminate the galvanic effect, but can significantly reduce the corrosion intensity. The most cost-effective way of mitigating galvanic corrosion is to disconnect the electronic circuit between the anode and cathode in design, but this is impractical. In industry, an insulating coating layer separating the anode or cathode or both from contacting the electrolyte may be a practical approach. An insulating spacer between the anode and cathode is also usually adopted under atmospheric conditions.
1.2.5 Micro-galvanic effect
The surface of Mg or a Mg alloy cannot be perfectly uniform and as such it is impossible for anodic and cathodic reactions to occur uniformly throughout the entire surface. Due to the non-uniformity in terms of the composition, microstructure and even crystal orientation, galvanic couples can be formed within a Mg alloy (see Fig. 1.5). These micro-galvanic cells dominate the corrosion of the alloy. Within the Mg alloy, the Mg matrix always acts as a micro-anode and is preferentially corroded (Song, 2005b, 2006, 2007a). Micro-cathodes include:
1.5 Schematic illustration of the non-uniformity within a Mg alloy that can result in various micro-galvanic cells. AEH and CHE refer to anodic hydrogen evolution and cathodic hydrogen evolution, respectively; ig is galvanic current caused by the differences in the Mg alloy.
• grains with different orientations and areas with significantly different solid solution concentrations of alloying elements within the matrix phase;
• secondary phases along grain boundaries; and/or
• impurity containing particles.
An important implication of the non-uniformity is that Mg and Mg alloys will be corroded unevenly. Localized corrosion will be the dominating damage. Localized corrosion will be the main threat to Mg alloy components that we need to battle against in practice. In some cases, the non-uniformity may diminish as corrosion proceeds. For example, the difference between the matrix and secondary phases and that of different alloying element segregation zones can become smaller after the easily corroded zones or phases have been dissolved. In some other cases, the factors causing the non-uniformity remain unchanged with time in corrosion. For example, when the galvanic corrosion is caused by different grain orientations, before the grains are corroded completely, this kind of difference remains.
Because of the non-uniformity, the practical corrosion of Mg and its alloys becomes unpredictable or can significantly deviate from a theoretical model. Thus, computer modeling of a corrosion process of Mg and its alloys poses a great challenge in corrosion science. The unpredictable localized corrosion attack also complicates the selection of the corrosion prevention/protection techniques. More importantly, the non-uniformity can interfere with a film or coating formation process. If surface treatments or coatings are employed to prevent the corrosion of a Mg alloy component, the heredity of the non-uniformity from the substrate to the surface layer/coating will lead to a premature failure. In the following sections, the non-uniformity resulting from the microstructure of the substrate will be discussed further.
1.2.6 Corrosion of matrix phase
In a magnesium alloy, the matrix phase is a major constituent and its corrosion performance is crucial to the alloy. The corrosion of the matrix phase is responsible for the corrosion behavior of the alloy. Therefore, the corrosion of a magnesium alloy is actually a problem of the matrix phase. In the matrix, which is a solid solution, its solute has an important influence on its corrosion behavior. For an Al-containing Mg alloy, the matrix phase is a Mg-Al single phase which becomes less active as the Al content increases (Song et al, 1998, 1999, 2004a, Song, 2005a). More importantly, the difference in solid solution concentration can result in differences in corrosion potential and anodic/cathodic activity (Song et al, 1998, 2004a).These differences can lead to formation of a micro-galvanic cell within a grain because the Al content is higher along the grain boundary than the grain interior for a cast Mg-Al alloy. The Al content in the solid solution can vary from 1.5 wt.% in the grain centre to about 12 wt.% along the grain boundary (Dargusch et al, 1998). Therefore, the difference in electrochemical activity and corrosion resistance can be significant even within the same grain of a Mg-Al alloy. Experimental evidence for the differences between the grain center and boundary comes from the corrosion morphology of an AZ91E alloy (Song, 2005a). The corrosion occurred in the interior areas of α grains and the grain boundary areas were much less corroded.
In the group of non-Al containing alloys, the matrix typically contains Zr as a grain refiner. The role of Zr in corrosion is remarkable and is as important as Al is for the Al-containing alloys. For example, in the Zr-containing alloy MEZ, the central areas of many grains remain uncorroded while the grain boundaries had been severely corroded which is converse to the corrosion morphology of Al-containing Mg alloys. It was found (Song and St John, 2002; Song, 2005a) that the distribution of Zr in the grain is not uniform. The grain centre is rich in Zr which may stabilize Mg through forming a more protective Zr-containing surface film.
In high purity Mg (in which there is no micro-galvanic effect caused by impurities or different solid solution concentrations), different exposed crystal planes, that have different crystal orientations, can still produce different electrochemical activities. Different Mg grains have different depths of corrosion after immersion in an acidic solution (Liu et al, 2008). The corrosion depths of different crystal planes were compared and it was found that the corrosion rates on the basal plane were more stable than the prismatic planes (Liu et al, 2008).
The different corrosion rates of individual grains can be ascribed to their unique orientation or the unique crystal plane exposed to the corrosive solution. The corrosion rate of a metal can to some extent be correlated to its surface energy (Buck and Henry, 1957; Weininger and Breiter, 1963; Ashton and Hepworth, 1968; Abayarathna et al, 1991; Konig and Davepon, 2001) which in turn, is associated with its atomic density. It is well known that pure Mg has a hexagonal crystallographic cell with axes: a = b = 0.3202 nm, c = 0.5200 nm and angles: α = β = 90°, γ = 120°. The atomic densities of the three lowest index planes can be calculated (Konig and Davepon, 2001) to be 1.13 × 10¹⁵, 6.94 × 10¹⁴ and 5.99 × 10¹⁴, respectively (see Fig. 1.6). Different crystal planes have different electrochemical activities when they are exposed to an aqueous solution. The atoms in the lower surface energy planes are more difficult to dissolve or corrode away. Therefore, the lowest index plane (0001) has the lowest energy and should be dissolved more slowly than the other surfaces. This has been evidenced by the dependence of corrosion resistance of a crystal plane on its atomic density (Liu et al., 2008).
1.6 Corrosion resistance of the basal and prismatic planes (according to Liu et al., 2008).
Recently, the grain orientation-dependent anisotropic corrosion behavior has been further verified with Mg alloy AZ31B (Song and Xu, 2010, 2012; Song et al, 2010). The basal dominated rolling surface of this alloy is much more corrosion resistant than the cross-section surface which is mainly composed of the prismatic planes. In fact, the grain orientation influences the formation and protection performance of the surface corrosion product film, and thus affects the corrosion behavior of Mg (Song and Xu, 2012a). The important lesson from the effect of the matrix on corrosion suggests that successful passivation of the matrix phase is a critical prerequisite for gaining high corrosion resistance of a Mg alloy. Alloying, surface conversion and anodization that can enhance the matrix passivity will lead to significantly improved corrosion performance of Mg alloys.
1.2.7 Influence of secondary phase
Almost all the Mg intermetallic phases are nobler than the magnesium matrix itself and many of them exist in commercial magnesium alloys as secondary phases (Nisancioglu et al, 1990; Song et al, 1998, 1999; Song and St John, 2002). These phases are cathodic to the matrix phase and can act as micro-galvanic cathodes to accelerate the corrosion of the matrix. For example, the β phase not only has a corrosion potential about 400 mV more positive but also a cathodic current density much larger than the a matrix phase, suggesting that the β phase is an active cathode to the matrix phase. Therefore, in a magnesium alloy the matrix can be subjected to micro-galvanic corrosion attack caused by the β phase.
It is well known that the galvanic corrosion current density of a galvanic couple increases with cathode electrode surface area. Due to the galvanic effect of the secondary phase, a Mg alloy is expected to be subjected to increasingly severe corrosion with an increasing amount of the secondary phase in the alloy. This has been verified by some experimental results. It was found (Song, 2005b, 2006; Shi et al., 2005) that the corrosion rate of a Mg-Al alloy first increased and then decreased as the amount of the secondary phase β increased. The corrosion rate increasing with the amount of the β phase before the maximum corrosion rate suggests that the micro-galvanic effect was dominating the corrosion of the alloy. However, it has also been widely reported (Nisancioglu et al, 1990; Lunder et al, 1993, 1995, 1989; Ambat et al, 2000; Uzan et al, 2000; Yim and Shin, 2001) that the corrosion rate of a Mg alloy decreases as the volume fraction of the β phase increases. Even within the same alloy sample, some areas with a large amount of the secondary phase can display higher corrosion resistance than other areas having only a small amount of the secondary phase. For example, a cold-chamber die-cast AZ91D has different microstructures in its interior and surface layer. The surface layer has a larger amount of the finely and continuously distributed β-phase than the interior, and the corrosion rate of the surface layer is about 10 times lower than the interior under the same salt solution (Song and Atrens, 1998; Song et al, 1999; Song, 2005b). In this case, the galvanic effect of the secondary phase does not appear to be responsible for the corrosion behavior.
In fact, the secondary phase can also play another important role within a Mg alloy as a barrier against corrosion. It has been found that the secondary phase in Mg alloys is much more stable than the magnesium matrix (Song et al;, 1998; 2007; Song and Atrens, 2003). In AZ alloys, the β-phase is normally not corroded if exposed to an NaCl solution (Song et al., 1998; Zhao et al., 2008a, 2008c) and in the corroded areas where the matrix phase has been severely corroded, the β-phase is still intact. Similarly, the secondary phase in a Mg-RE alloy is also superior to the matrix in terms of corrosion resistance (Song and St John, 2002).
The high corrosion resistance of the secondary phase in a Mg alloy can retard the corrosion of the alloy though a barrier mechanism. A piece of direct evidence is that the corrosion within the matrix phase stops upon reaching the β phase in an AZ Mg alloy (Song, 2005a). The same barrier effect from the secondary phase of a non-aluminum containing alloy has also been found in a Mg-RE-Zr alloy (Song and St John, 2002). The barrier effect and the micro-galvanic effect are two different aspects of the role that the secondary phase plays in corrosion. In other words, the secondary phase has a dual-role in the corrosion (Song and Atrens, 1998; 2003; Song et al, 1999, 2004a; Song, 2005). Whether the barrier effect or the galvanic effect of the secondary phase dominates the corrosion of a Mg alloy depends on the continuity and amount of the secondary phase. If the amount of the secondary phase is small and the distribution is discontinuous, then the galvanic effect will govern the corrosion of an alloy. On the contrary, the secondary phase will effectively separate grains and thus act as a barrier to retard the corrosion development from grain to grain (Song and Atrens, 1999; Song et al, 1999; Song and St John, 2000, 2002; Song, 2005b). Figure 1.7 schematically summarizes the dual-role of the secondary phase in corrosion of a Mg alloy.
1.7 Schematic illustration of the dual-role (galvanic effect and barrier effect) of the secondary phase in corrosion of a Mg alloy.
The dual-role model can explain many corrosion phenomena of Mg alloys. For example, the higher corrosion rate of Mg-5%Al can be attributed to the galvanic effect of the β phase in a discontinuous distribution; whereas for Mg-10%Al, there is sufficient β phase continuously distributed along the grain boundaries to stop corrosion from progressing across grain boundaries, and hence its corrosion rate is lower than that of Mg-5%Al.
Based on the dual-role model, the corrosion resistance of a Mg alloy can be enhanced through decreasing the galvanic effect and increasing the barrier effect. Increasing the alloying level is a straightforward approach of producing more continuous network of the secondary phase to retard the corrosion development. In practice, alloying the surface with a passivating element or selective dissolution of the matrix phase in the surface layer is a cost-effective way.
1.2.8 Detrimental effect of impurities
A very small amount of Fe, Ni, Co or Cu addition can dramatically increase the corrosion rate of Mg through a micro-galvanic effect (Hanawalt et al, 1942; Nisancioglu et al., 1990; Lunder et al., 1995). Currently, Fe, Cu and Ni, which are likely to be contained in Mg alloys, are defined as Mg alloy impurities. It is well known that the over-voltages for hydrogen evolution on Fe, Co, Ni, Cu, etc., are less than 0.7 V. This means that Fe, C, Ni and Cu are very active under cathodic polarization and that hydrogen evolution from them is easy and fast. Moreover, they are cathodic to Mg in most aqueous solutions. If these impurities are present in Mg alloys as separate phases, they will be effective micro-galvanic cathodes and can significantly accelerate the corrosion of the matrix phase.
A very small amount of impurity present in Mg or its alloys can result in strikingly deteriorated corrosion performance. For each impurity in Mg and its alloys, there is a critical concentration, also known as the impurity tolerance limit, above which the corrosion rate increases significantly. Corrosion rates are considerably higher and can be accelerated by a factor of 10 to 100 when the concentrations of the impurities Fe, Ni and Cu are increased above their tolerance limits (Hillis and Murray, 1987). If the impurity levels are lower than their tolerance limits, the corrosion rates are low and the impurities have an insignificant influence on the corrosion rates. A higher level of the impurity can lead to lower corrosion resistance for Mg and most Mg alloys (Emley, 1966, Hillis, 1983, Busk, 1987b, Avedesian and Baker, 1999). Studies (Aune, 1983; Hillis, 1983; Frey and Albright, 1984) have shown that dramatic improvement of corrosion resistance can be realized through controlling impurity levels in a Mg alloy. For this reason, Dow has recommended that the following specific impurity tolerance limits should be used to ensure optimum salt water corrosion performance for AZ91: Fe < 50 ppm, Ni < 5 ppm, Cu < 300 ppm (Hillis,
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