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Wang 2013
Wang 2013
Intermetallics
journal homepage: www.elsevier.com/locate/intermet
a r t i c l e i n f o a b s t r a c t
Article history: The effect of shear bands on pitting corrosion of a pre-deformed Zr-based bulk metallic glass was studied
Received 3 April 2013 through immersion test in 1 M HCl solution. It was found that pitting always preferentially occurred at
Accepted 14 May 2013 the offsets of the shear bands, but this selective corrosion behavior disappeared when the shear offsets
Available online
were polished, although shear bands did exist at the same locations. This demonstrates that the shear
offsets, rather than the structural changes in the shear bands, is the dominant factor for the pitting
Keywords:
initiation.
B. Glasses, metallic
Ó 2013 Elsevier Ltd. All rights reserved.
B. Corrosion
D. Microstructure
0966-9795/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.intermet.2013.05.006
108 Y.M. Wang et al. / Intermetallics 42 (2013) 107e111
Fig. 1. (a) SEM image of the shear bands after three-point-bending test of (Zr62Cu23Fe5Al10)97Ag3 BMG and the distribution of pits after being immersed in 1 M HCl for 1 h, all
the corrosion pits were formed at the shear bands; (b) a magnified pit shown in (a); (c) a 3D profile showing a pit on a shear band; (d) SEM image of a polished sample
after being immersed in 1 M HCl for 2 h at the same position and the insert is the enlargement of a portion in (d), showing several pits stochastically distributed on the polished
surface.
Y.M. Wang et al. / Intermetallics 42 (2013) 107e111 109
shear bands do exist at the same places, even though the offsets corrosion pits were found on the sample surface even prolonging
were removed, it is suggested that the shear offsets, but not shear the immersion time to 4 h (see Fig. 2(b)). Considering that a heavy
bands themselves, play a crucial role in the initiation of pits in structural change (i.e., significant intake of free volume in this case)
BMGs in corrosive solution. It is true that structural changes, e.g. the really occurred in the shear band, the disappearance of selective
accumulation of free volume, the formation of nanovoids or even pitting after elimination of the shear offset indicates that the
nanocrystals, can occur in the shear bands [5e7]. However, the structural changes in the shear bands have little effect on pit
present results imply that the change in structure may not be the initiation.
dominant factor for the initiation of pits on the shear bands. To To better understand the role of shear offsets in the preferential
further clarify this issue, a compressive test was conducted on a formation of pits, a mechanical scratch was intentionally made by a
BMG rod (f 2 4 mm) to form a single shear band under a needle on a mirror-finish BMG surface to form a sharp offset. The
controlled loading (see Ref. [5] for the detailed loading process), offset had a height of around 4.3 mm (see Fig. 3(a)), which is roughly
and the sample was subsequently immersed in 1 M HCl solution for in the same level as the shear offset formed by three-point-bending
1 h. The merit of using a single shear band is that severe plastic test (see Fig. 1(c)). Fig. 3(b) shows the SEM image of the scratched
deformation is constrained into a short region, leading to a drastic sample after immersion in 1 M HCl solution for 1 h. Many corrosion
structural change in the shear band, so that the effect of structural pits were formed on the sharp edges of the offset, while no pits
changes on corrosion, if any, could be enlarged. Our previous work were observed on the bed of the scratch where it is relatively
[5] revealed that a huge increase of 1.4% of free volume was smooth. It is noted that plastic deformation could take place not
introduced in the single shear band due to the constrained and only on the edges but also on the bed when a scratch was made.
severe plastic deformation. This caused a 35% reduction in hardness However the pits only existed at the edges but not on the bed,
in the band, which is almost 3 times lower than that in multiple which again confirms that the offset plays a dominant role in the
shear bands [15,16]. Fig. 2(a) shows that almost all the pits are initiation of pits.
formed on the sharp shear offset after being exposed in HCl solu- The question arises as to how and why the shear offsets of the
tion for 1 h. However, once the shear offset was removed, no shear bands promote pitting initiation on the deformed BMG. To
Fig. 2. (a) SEM image of pits on a single shear band after being immersed in 1 M HCl
for 1 h, the inset is the shear band morphology of the deformed sample after im- Fig. 3. (a) SEM image of the scratch induced by a needle, the inset is the line profile of
mersion; (b) SEM image of the sample after polishing the shear offset and immersion the scratch, showing a height of 4.3 mm of the offset; (b) SEM image of the scratched
in 1 M HCl for 4 h, and the inset is a cross-sectional view of the sample with a single sample after being immersed in 1 M HCl for 1 h, showing that all the pits were formed
shear band. at the edges of the scratch.
110 Y.M. Wang et al. / Intermetallics 42 (2013) 107e111
answer the questions, we have to understand where the passive the film there is usually weak and could be preferential broken, and
film on BMG surface is preferentially broken and how the galvanic become the possible sites for pitting. However, to make pitting
cells are formed. For an alloy containing metallic elements, passive proceed galvanic cells must be established, otherwise the broken
film could be spontaneously formed by the oxidation of the active film can be recovered by the consecutive oxidation reaction. As a
elements once it is immersed in corrosive solution. Actually, the matter of fact, the shear offsets on BMG surface with smaller cur-
formation of passive film is a dynamic process, i.e., dissolution and vature radius should have lower potential as compared with the
growth of the film simultaneously proceed [17]. The dynamic smooth region nearby. Therefore, the galvanic cell could be easily
equilibrium of the two processes could lead to the formation of formed between the shear offsets and nearby smooth surface.
stable passive film on the alloy surface, and protect the alloy from Combining the Kelvin’s equation [20], ln(P/P0) ¼ 2sM/rrRT, which
corrosion. However, the surface of the alloy is not completely correlates the surface vapor pressure (P) and the curvature radius
prefect and homogenous. The equilibrium of dissolving and (r) and the Nernst equation [21], E ¼ E4 ðRT=nFÞln ððP=P0 Þ=aMnþ Þ,
growing process may be dilapidated in the regions where defects or which correlates the electrode potential (E) and surface vapor
stress concentration exist. In these regions, the dissolution can pressure (P), we can drive the relationship between the electrode
prevail over the growth of the film, and eventually causes the potential and the surface curvature radius, as being simplified as
breakdown of the passive film [18,19]. In the present case, the shear
offsets on the BMG surface, originating from shear banding, are the
places where great tension stress and defects existed (see Fig. 4(a)),
1
Ef (1)
r
The parameters in the above equations are defined as: P0 is the
vapor pressure of a metal surface with infinite curvature radius, s is
the surface tension, M and r are the molecular mass and density of
the metal, Ef is the standard electrode potential, n is the number of
electrons transferred in the reaction, F is the Faraday constant and
anþ
M is the activity of metal ion, which is a constant for a certain
metal in the same electrolyte, R and T are the gas constant and
temperature, respectively.
The equation (1) reflects clearly that the difference in curvature
radius r results in the difference in electrode potential E, which
means that the regions with smaller curvature radius exhibit lower
electrode potentials, vice versa. The theory can well explain the
preferential pitting at the shear offset in the present work. The peak
regions can have a lower electrode potential due to the smaller
radius r, and metals in these regions are more active, thus release
more easily electrons [22] with respect to the relatively smooth
regions nearby (see Fig. 4(b)). Therefore the peak regions (shear
offsets) can serve as anodes, while the valleys nearby serve as the
cathodes, leading to the formation of galvanic cells. Once the pas-
sive film ruptures at the peak regions, these galvanic cells start to
work via the exchange of ions and electrons, causing the initiation
of pitting [23], as show in Fig. 4(c). This phenomenon was actually
observed, especially on the specimen with a surface scratch, where
all the pits were only formed at the edges of the scratch (see
Fig. 3(b)).
Structural changes can occur in shear bands during plastic
deformation, including the increase of free volume due to shear
dilatation, and sometimes nanovoids formation and even crystal-
lization when the plastic deformation is very severe. Based on our
previous work, the intake of free volume is only the form of
structural change during the deformation and a maximum 1.4% of
free volume was introduced in the shear band. The increase in free
volume does not change the amorphous feature or the composi-
tion of the BMG, and thus cannot alter the chemical potential in
the shear bands. Therefore, selective corrosion could not take
place only by the increase of free volume. The formation of
nanocrystals or nanovoids may change the structure and compo-
sition of the BMG, causing alteration of the chemical potential in
the shear bands. However, a shear band usually has the width of
several tens nanometers (e.g. 10e20 nm [7,24]), meaning that the
structural change, if any, should be localized in such a narrow
Fig. 4. Schematic illustration of pitting corrosion in a BMG with shear offset: (a) failure region. This region with severe structural change, may alter locally
of the passive film caused by interfacial tension in the peak region; (b) electrons at the chemical potential of the shear band, but cannot induce the
sharp peak escape more easily than those in the flat area, lowering the potential of the
peak region; (c) the peak with a lower potential acts as an anode, while the region in
formation of a stable pit, as a stable pit usually has a size of larger
the flat area, with a higher potential, acts as a cathode, thus forming an electro- than ten micrometers, otherwise the pit can die by surface
chemical cell. repassivation [25].
Y.M. Wang et al. / Intermetallics 42 (2013) 107e111 111
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