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Scripta Materialia 63 (2010) 12011204 www.elsevier.com/locate/scriptamat

Revealing the relationship between grain size and corrosion rate of metals
K.D. Ralston, N. Birbilis and C.H.J. Davies
ARC Centre of Excellence for Design in Light Metals, Department of Materials Engineering, Monash University, Victoria 3800, Australia
Received 29 July 2010; revised 18 August 2010; accepted 18 August 2010 Available online 24 August 2010

A denitive understanding of how grain size aects the corrosion rate and passivity of dierent metallic alloys has not been developed to date. A review of the pertinent literature, combined with the authors works, reveals that a relationship exists between corrosion rate and grain size. This phenomenon correlates with total grain boundary length and reveals an important fundamental relationship that can be exploited for material durability and design. 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Corrosion; Grain boundaries; Grain rening; HallPetch eect; Severe plastic deformation

Grain boundaries have distinct properties relative to bulk material in terms of atomic coordination, reactivity and diusion rates. Consequently, it is not unreasonable to expect surfaces with relatively high grain boundary densities to exhibit dierent electrochemical behaviour (namely corrosion rates) than coarser grained surfaces with lower grain boundary densities. The HallPetch relation reveals that yield strength is inversely proportional to grain size [1,2]. However, an analogous relationship between grain size and corrosion rate has yet to be determined, and is the prime focus of this work. There have been a number of studies on different materials that involve grain size variation and corrosion performance, but, as detailed in a recent review, there is little consensus as to an all-encompassing eect applicable across dierent materials or even within similar alloy classes (readers are directed towards the review by Ralston and Birbilis [3] for more details and a current summary of the state of the eld). This lack of consensus is not surprising for at least three reasons, the rst two of which do not relate to scientic aspects. First, authors have not previously presented corrosion rates as a function of grain size raised to a selection of powers. Secondly, most works to date have only studied coarse and ne grained alloys (and not a spectrum of grain sizes), making any general relationship dicult

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to extract. Lastly, studies of grain size eects on corrosion are inherently dicult because any processing and or alloy additions used to achieve grain renement may impart physical or chemical changes to the material in addition to the intentional grain size modication. Such secondary consequences from thermo-mechanical processing include the development of texture, internal stresses and segregation of alloying additions to grain boundaries, each of which may have an impact on corrosion response, in addition to the role of the test electrolyte or environment. Of studies that that considered grain size when interpreting corrosion, many have suggested that as grain size decreases corrosion rate decreases (i.e. corrosion resistance improves). Improved resistance generally is attributed to an ability of high grain boundary density surfaces to passivate more readily or to the physical breakdown of second phase intermetallic particles [47], but such claims are rarely substantiated within the said papers. Such studies have deployed dierent processing paths to achieve grain-rened microstructures, which include rolling operations and severe plastic deformation (SPD) techniques, such as surface mechanical attrition (SMAT) [8,9] and equal channel angular pressing (ECAP) [10,11]. The ECAP and SMAT processes have been noted to both increase [5,1218] and decrease [1921] corrosion resistance. A better representation of the overall impact of grain size upon corrosion for all known relevant references is given in Figure 1. The corrosion rate data presented in this gure were

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Figure 1. The eect of grain size on corrosion rate (expressed as A cm2) for dierent materials and environments. Data were obtained from: Afshari [24] for Fe in 10 wt.% NaOH; Liu and Duh [25] for Ni50.5Al49.5 in 0.9 wt.% NaCl; Ghosh et al. [26] for NiCu in deaerated 3 wt.% NaCl; Mishra and Balasubramaniam [27] for Ni in 1 M H2SO4; Song et al. [20] for Mg (99.9%) in 3.5 wt.% NaCl; Mahmoud [28] for AA6063 in 1 M HCl; Hamu et al. [29] for AZ31 Mg in 3.5% NaCl saturated with Mg(OH)2 at pH 10.5; Lin et al. [30] for alloy 600 in boiling ferritic sulfate (31.25 g l1)50% H2SO4; opt Hoog et al. [16] for Mg (99.9%) in 0.1 M NaCl; Ralston et al. [22] for Al (99.999%) in 0.1 M NaCl; Birbilis et al. [15] for Mg (99.9%) in 0.1 M NaCl.

originally determined using a variety of methods, including Tafel extrapolation on potentio-dynamic polarisation curves, mass loss and linear polarisations; within this manuscript icorr values have been standardised to be given as A cm2. This gure only includes data where at least three dierent grain sizes existed (as studies with only one coarse and one ne grained specimen are not subsequently amenable to linearisation of the data). Figure 1 reveals that the literature data spans several orders of magnitude of corrosion rate, necessitating (only for this representation) a log scale on the y-axis. This representation is important, because it shows that the data in the literature can be separated into two classes, including a range of materialenvironment combinations that show low to passive corrosion rates (610 lA cm2) and those which display corrosion rates of several tens to hundreds of lA cm2. This dierentiation is also signicant because the specic eect that grain size has on corrosion varies depending on whether a material exhibits active corrosion or low to passive dissolution rates. If the data with corrosion rates 610 lA cm2 are isolated, then a relation becomes apparent when such data are plotted as corrosion rate versus grain size0.5, as shown in Figure 2 (the signicance of the reciprocal square root dependence is discussed further below). Figure 2 illustrates how linear regression (Origin 8) can be used to determine a relationship between corrosion rate and grain size. To our knowledge, such a relationship has not been previously reported. Figure 2a shows the results from two studies for magnesium specimens that had been grain rened by various SPD processes, Figure 2b shows results from a NiAl and a NiCu alloy, and Figure 2c shows results from a systematic study on rened aluminium. The relationship observed in all cases is:

Figure 2. The relationship between corrosion rate and grain size for low to passive current densities. Data were obtained from: Birbilis et al. [15]; opt Hoog et al. [16]; Liu and Duh [25]; Ghosh et al. [26]; Ralston et al. [22].

icorr A Bgs0:5

where the constant A is likely to be a function of the environment (since, conceivably, the same material may have a dierent corrosion rate in dierent electrolytes for a given grain size) and B represents a material constant, which will dier according to composition or impurity level. In Birbilis et al. [15], opt Hoog et al. [16,17] and Ralston et al. [22] the authors were diligent

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about using material from the same ingot as the test material. Such a linear correlation is not only interesting to note, but also an important mechanistic revelation. In examinations of systems where low rates of corrosion occur or systems that exhibit some level of passivity (where by denition an oxide is present on the metal surface) corrosion rates decreased with grain size reduction. This, therefore, allows us to link this nding to emerging work in the literature, including our own, whereby grain renement is posited to allow dierent rates of oxide growth. This is in line with pure grain renement being principally conned to controlling the rate of anodic reactions and having little role in altering the rate at which cathodic reactions can be sustained (presumably because cathodic reactions rely on electronic more than ionic conduction, with increased grain boundary density being important for the latter). This is in agreement with the detailed experiments of Lee and White [23], who elegantly revealed that small increases in oxide lm ion conduction are associated with grain boundaries when comparing polycrystalline Al with single crystals, which is wholly in line with the observations herein. The presentation of a relationship such as that proposed by Eq. (1) would, therefore, require rationalisation of the 0.5 dependence. Based on a hypothesis of grain boundary conduction and reactivity, icorr should vary with grain boundary length. A general expression for grain boundary length (gbl) can be presented as: gbl C Dgsa ; 0:5 6 a 6 1 2

corrosion resistant. In the absence of an oxide lm, such as when dissolution rates are >10 lA cm2, increased grain boundary densities will likely enhance overall surface reactivity and, consequently, the corrosion rate. This is indeed seen, as reported in Figure 4. The apparent discrepancy between the results of Song et al. [20] (Fig. 4) and those of opt Hoog et al. [16] and Birbilis et al. [15] (Fig. 2a) for compositionally similar Mg is likely due to electrolyte potency; Song et al. tested in 3.5 wt.% NaCl ($0.6 M) while opt Hoog et al. and Birbilis et al. used 0.1 M NaCl. In terms of corrosion resistance, the reported phenomena can be considered analogous to the bounds of the classical HallPetch relationship (albeit for dierent mechanistic reasons). Whereas HallPetch is conned to the yield behaviour of a material, the utility of grain renement for reduction in corrosion rates as described herein is conned to materials when an oxide/passivity exists. Specic details regarding the processing and testing which relates to the results herein are given in the respective papers, however, it is apparent that grain size alteration oers the engineer latitude in tailoring microstructures for enhanced corrosion resistance or

where the constant C is an area term and D is a scale term. For the ideal case of perfectly equiaxed grains (phenomenologically shown in Fig. 3a) a = 1. However, simulation of random grain structures (with a distributed variation in shape and size) and subsequent evaluation of skeleton length (via Fovea Pro) yields a dispersed relationship closer to a = 0.5. Such a grain structure is seen in Figure 3b. Hence, in the more realistic case of the metals tested in Figure 2, a approaches 0.5, giving Eq. (1) the corresponding dependence. If grain boundary density dictates the oxide lm conduction rate on surfaces with low to passive corrosion rates, then ne grain structures are expected to be more

Figure 4. The relationship between corrosion rate and grain size for high current densities. Data were obtained from: Mahmoud [28]; Lin et al. [30]; Song et al. [20].

Figure 3. Simulated grain structures illustrating an (a) ideal and (b) random structure with a values of approximately 1 and 0.5, respectively.

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designing materials with the same bulk chemistry to have varied corrosion rates, and is thence clear that the same bulk material can have dierent corrosion rates owing to non-chemical structural changes alone. This revelation has important ramications for alloy design and functional materials. Financial support from the Australian Research Council (Centre of Excellence for Design in Light Metals) and Victorian State Government for the establishment of the Victorian Facility for Light Metals Surface Technology are gratefully acknowledged.
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