Electrochimica Acta 87 (2013) 283–293
Contents lists available at SciVerse ScienceDirect
Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
Potentiometric scanning electrochemical microscopy for the local
characterization of the electrochemical behaviour of magnesium-based materials
Javier Izquierdo a,b , Lívia Nagy c , István Bitter d , Ricardo M. Souto a,b,∗ , Géza Nagy c,∗∗
a
Department of Physical Chemistry, University of La Laguna, E-38200 La Laguna, Tenerife, Canary Islands, Spain
Instituto Universitario de Materiales y Nanotecnologías, University of La Laguna, E-38200 La Laguna, Tenerife, Canary Islands, Spain
Department of General and Physical Chemistry, Faculty of Sciences, University of Pécs, 7624 Pécs, Ifjúság útja 6, Hungary
d
Budapest University of Technology and Economics, Budafoki u. 8, 1111 Budapest, Hungary
b
c
a r t i c l e
i n f o
Article history:
Received 4 June 2012
Received in revised form
10 September 2012
Accepted 11 September 2012
Available online xxx
Keywords:
Potentiometric SECM
Magnesium
pH
Ion selective micropipettes
Antimony electrode
a b s t r a c t
The applicability of scanning electrochemical microscopy for the local detection and quantification
of relevant species participating in the corrosion of magnesium-based materials is presented. The
iron–magnesium galvanic pair exposed to aqueous NaCl solution was adopted as model system for this
purpose. Mg2+ ion concentration and pH profiles were investigated using ion selective electrodes, containing a liquid membrane and Sb/Sb2 O3 as sensor elements, respectively. Oxygen consumption at the
substrate related to the cathodic reaction was also monitored with the antimony-based electrode though
operated amperometrically. Data show a major production of hydroxyl anions at the cathodic sites as
result of the oxygen reduction half-reaction, whereas in the vicinity of the magnesium surface pH is
greatly affected by the anodic dissolution process instead. The later produces the release of metal cations
accompanied by hydrogen evolution.
© 2012 Elsevier Ltd. All rights reserved.
1. Introduction
Electrochemical corrosion is one major cause of economic
losses in the industrialized countries [1]. Despite their attractive mechanical properties, most metals and alloys spontaneously
undergo corrosion if certain conditions occur, especially in aqueous environments. Particularly, due to its high strength-to-weight
ratio, magnesium and its alloys are attractive materials for several applications in the automotive, aerospace, electronics and
energy-production industries [2–5]. And they are often found in
unavoidable contact with other metals such as aluminum or steel
[5]. However, these materials lack stability against corrosion and
usually require additional protection. In fact, thanks to its tendency
to degrade in aqueous environments, it has been considered as a
potential biodegradable and biocompatible material for non permanent implants [6–9]. Moreover, its position in the galvanic series
has allowed magnesium to be evaluated for the protection of other
metals by acting as sacrificial anode, either as a component of a
∗ Corresponding author at: Department of Physical Chemistry, University of La
Laguna, E-38200 La Laguna, Tenerife, Canary Islands, Spain. Tel.: +34 922318067;
fax: +34 922318002.
∗∗ Corresponding author.
E-mail addresses: rsouto@ull.es (R.M. Souto), G-nagy@gamma.ttk.pte.hu
(G. Nagy).
0013-4686/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.09.029
protective coating, or via direct galvanic connection [10–14].
Besides, several Mg-containing alloys like those aluminum-based
ones, tend to suffer from preferential dissolution of this component,
usually the most active in the material [5,15,16].
Local microcells are originated in a metallic material subjected to corrosion, with the subsequent spatial distributions of
anodes and cathodes on its surface when left at its open circuit potential (OCP). In this way, dissolution occurs as result of
metal oxidation at the anodes, whereas this process is maintained by the reduction of some species from the environment at
the cathodes, usually oxygen in neutral and moderately alkaline
media, or protons in acidic solutions. Since these local cells are
originally formed within the range of micrometers and nanometers, a comprehensive understanding of the mechanistic aspects
of corrosion requires the synthesis of data in those scales. Unfortunately, conventional electrochemical techniques lack spatial
resolution and provide little information on behavior at sites of
corrosion initiation or at defects. The recent advent of a variety of
local probe techniques is greatly contributing to overcome these
limitations when applied to the investigation of corrosion processes in situ. Following this trend, researchers are exploring a
wide variety of methods to characterize local electrochemical processes, which range from the design of microelectrochemical cells
and setups, to the use of scanning probe techniques [17]. Among
the later scanning electrochemical microscopy (SECM) has become
one of the most powerful local techniques for corrosion research
284
J. Izquierdo et al. / Electrochimica Acta 87 (2013) 283–293
due to the wide variety of operation modes which contribute to
give a great versatility to the technique [18–20].
The corrosion of metals produces local changes in the concentrations of ionic and molecular species present in the adjacent
liquid phase. Thus, the Mz+ ions produced at the anodic sites
are transferred under diffusion control to the bulk, and the system can be studied by amperometric SECM [21]. This feature has
been exploited to image the generation of specific metal cations
in several studies that include visualization of metastable pits on
austenitic steel in situ by SECM at the open-circuit potential [22], to
the detection of metal dissolution either from inclusions in alloys
[23–25] or from defects in polymer-coated metals [10,26,27]. On
the other hand, in a neutral aqueous medium, the reaction of
dissolved oxygen from the electrolyte at the cathodic areas may
be analyzed through monitoring of the subsequent depletion of
oxygen content in the solution volume adjacent to the cathodic
sites [28–32]. However, for the detection of concentration distributions in certain corroding samples, especially for metals with
sufficiently negative redox potentials in aqueous environments,
the use of Pt microelectrodes is limited by the onset of oxygen
reduction and hydrogen evolution reactions [10,27,31]. Thus, for
effective amperometric operation of the SECM, it becomes necessary to either purge out oxygen and to use modified electrodes to
avoid early evolution of hydrogen gas [33,34]. Yet, more robust and
selective procedures are to be developed for the analysis of these
metal cations in order to gain a better understanding of the mechanisms involved in corrosion and passivation. As it is well known,
corrosion processes are dramatically affected by pH too. Furthermore, both corrosion half-cell reactions may lead to local changes
in pH of the surrounding environment. On one hand, alkalinization
always occurs in the cathodic sites due to either H+ consumption
or OH− release, depending on nature of sample and electrolyte,
and it may facilitate the formation of passive films. On the other
hand, some corrosion-produced metal ions may undergo hydrolysis at the anodic sites, and consequently reduce the local pH, a
feature that usually accelerates the corrosive attack. Though the
extent of pH variation associated with the hydrolysis of metal ions
mainly depends on the equilibrium constant for their hydrolysis
process [35], thus greatly varying from one metal to another, it
may become a major feature affecting the onset of local corrosion
microcells. Therefore, the measurement of the local alterations of
pH in the vicinity of a corroding system and their time evolution is
a matter of major interest.
In contrast, though rather scarcely applied, these physicochemical parameters may be studied using ion-selective electrodes (ISEs)
as tips. In this case, the SECM is operated in the potentiometric
mode [36–38], which gives greater chemical selectivity. The applicability of Zn2+ ion-selective microelectrodes (ISMEs) for the study
of model corrosion systems with SECM [39,40] has been recently
demonstrated, similarly to what has already been achieved with
the Scanning Ion Electrode Technique (SIET) [41]. In studies applying SIET, a variety of ion-selective systems have been investigated
[42–50], including Mg2+ species released during corrosion of the
buried metal from defects operated on coated magnesium alloys
[42,45,48]. Yet investigations of magnesium substrates with SECM
have only been carried out in amperometric mode [51,52] or for
measurements of the electrolyte resistance between the tip and
the substrate [53], using always Pt microelectrodes as the probe.
In those studies, visualization of active regions in the surface was
accomplished, however selective potentiometric detection of the
local concentration of the corrosion produced Mg2+ ions was not
attempted.
Most often liquid type microelectrodes have been employed for
studying pH distributions above corroding metal surfaces [42–50].
Nevertheless, for corrosion purposes using SECM, it would be
preferable to use microelectrodes based on the characteristics of
certain oxides of transition metals such as antimony [54–56] and
iridum [57]. These solid state microelectrodes are much more
robust than ion selective micropipettes. Furthermore they have the
ability to behave as double function electrodes. This means that
while in potentiometric mode they detect local pH, they can also
function as amperometric SECM tip to detect electroactive species.
In this work, we report preliminary results on the characterization of a model corrosion system formed by an iron–magnesium
galvanic couple which were obtained from SECM measurements
using antimony and Mg2+ -ion selective electrodes as the tips. The
concentration distributions of dissolved oxygen and Mg2+ ions, as
well as the pH distributions that result of the galvanic corrosion
process, were measured and analyzed in terms of the reactions
occurring in the system.
2. Experimental
2.1. Chemicals and solutions
High purity antimony in powder presentation (Aldrich) was
employed for the fabrication of the antimony electrode. Solutions
were prepared from Millipore deionized water and analytical grade
chemicals. The inner reference solution employed in the lumen
of the Mg2+ -ISE was 10 mM MgCl2 + 0.25 M KCl. Different concentrations of the same magnesium salt, dissolved in 10 mM NaCl
solution, were employed for calibration of the ISE.
The ionophore employed in the fabrication of the Mg2+ ISE
was bis-N,N-dychlohexyl-malonamide, which was synthesized
following the method described in reference [58]. The composition of the ion selective cocktail was the following: 2.1 wt.%
ionophore, 34.0 wt.% high molecular weight poly(vinyl-chloride),
and 63.9 wt.% o-nitrophenyl-octyl-ether. 70 mol.% potassium
tetrakis(p-chloro-phenyl) borate was subsequently added. All
the components in the ionophore membrane were supplied by
Sigma–Aldrich. Ion-selective microelectrodes were prepared using
micropipettes pulled from borosilicate glass capillaries B200-11610 (Sutter, Novato, CA, USA). The inner wall of the pipette tips were
hydophobized exposing them to a solution of dimethyldichlorosilane in carbon tetrachloride.
2.2. Samples and instruments
The galvanic Fe–Mg couple employed for this study consisted
on one sheet of each metal immobilized in Epofix resin (Struers,
Ballerup, Denmark). Iron was cut from 1 mm thick sheet of 99.99%
purity purchased from Goodfellow Materials Ltd. (Cambridge, UK),
in order to obtain a 1 mm × 2 mm strip. For the magnesium surface,
metal ribbon of 99% purity supplied by Panreac (Barcelona, Spain),
with a cross section of 200 m × 3 mm, was employed. The metal
was not analyzed, but typical impurity levels (in ppm) were cited by
the supplier as: Cu 5, Fe 50, Ni 5, Pb 5, Zn 20. Both metal strips were
fixed vertically in the resin, facing up their rectangle cross sections
as the active surfaces to be analyzed. The separation between the
two metals was ca. 5 mm, which was assumed to be enough distance to avoid alterations in either of the active metal areas due to
the reactions taking place on the other one for the duration of the
tests performed in this study. The resulting mount with the embedded metals had a circular top surface of 3 cm diameter. The surface
of the specimen was flat ground with abrasive SiC paper up to 4000
grit, rinsed with ethanol, dried in air, and finally wrapped around
laterally by sellotape that reached over the mount surface for about
6 mm. Thus a small container of approximately 5 ml of electrolyte
was created for the microelectrochemical measurements.
The antimony electrode employed in SECM for combined
amperometric/potentiometric operation was fabricated following
J. Izquierdo et al. / Electrochimica Acta 87 (2013) 283–293
285
Fig. 1. Sketches of the two types of potentiometric tips employed in the SECM measurements: (A) antimony electrode, and (B) micropipette-based Mg2+ -ISE (containing
10−2 M MgCl2 + 0.25 M KCl as the internal solution).
the procedure described elsewhere [55]. In brief, the fabrication
was initiated by heating the antimony powder in a melting pot
with a gas flame. When antimony melted, it was introduced in
a thick glass Pyrex capillary using syringe suction. The resulting,
antimony filled capillary was then pulled manually with standard
glass blowers technique using metallic tweezers. This resulted in
a small diameter glass fiber filled with antimony. A pipette with
500 m tip diameter was prepared from borosilicate glass capillary and a section of the previously prepared antimony fiber was
inserted in its lumen with the tip reaching out for about 15 mm,
whereas ca. 20 mm long staying in the lumen. Mercury metal and a
copper wire were then inserted into the lumen of the thicker capillary to provide electrical contact resulting in the assembly shown
in Fig. 1A. Loctite® adhesive was used to seal both ends. The final
microelectrode had an antimony disk of 175 m with an RG value of
2.9. The electrochemical response of the antimony microelectrode
for amperometric operation was tested in two electrolytes, namely
aerated 10 mM NaCl, and deaerated 5 mM [Ru(NH3 )6 ]Cl3 + 0.1 M
NaCl solutions. Potentiometric operation was directed to monitor
the effect of pH on the potential of the electrode. Calibration was
performed using 9 buffer solutions covering the range 4 ≤ pH ≤ 12.
A linear relationship between the potential of the antimony tip and
the solution pH was observed between 4 and 11, and the slope of
the calibration plot amounted 42.3 mV/pH unit.
Potentiometric ion-selective operation was performed using
a conventional micropipette type Mg2+ -ISE, that was prepared
with liquid internal filling solution and a silver chloride coated
silver wire of 250 m diameter, as internal reference electrode.
Schematic drawing of the micropipette electrode is shown in
Fig. 1B. It was fabricated according to well established procedures
[59,60]. In brief, two micropipettes were first pulled from one
glass capillary, and subsequently silanized by introducing inside a
few microliters of 5 vol.% dimethyldichlorosilane solution in carbon
tetrachloride. The hydrophobic layer was obtained by keeping the
micropipettes at 80 ◦ C in an oven for about 30 min. The ionophore
cocktail was then filled into the micropipette by applying vacuum
from the back side with an attached syringe. Finally, the internal
solution was backfilled with the assistance of a very thin capillary
attached to a syringe, and the Ag/AgCl was placed and fixed with
Loctite® adhesive. Due to the relatively big size of the metal samples employed in this study, micropipettes with about 180 m tip
diameter were prepared and used. As it is well known micropipette
ISE’s can be easily prepared with submicron diameter, however it
was not justified to use so small tips in this work, because they
present bigger resistance and high noise picking up character.
2.3. Instruments
Measurements were performed in an SECM equipment built
by Sensolytics (Bochum, Germany), controlled with a personal
computer. The electrochemical interface employed in the amperometric operation was an Autolab bipotentiostat provided with
a frequency response analyzer (Metrohm, Herisau, Switzerland).
In this case, the electrochemical cell was completed with an
Ag/AgCl/KCl (3 M) electrode as reference, and a Pt wire as counter
electrode. Alternating current (AC) mode was also performed using
these instrument and cell configurations. AC voltage signals of
10 mVpp amplitude around the open circuit potential of the tip in
the electrolyte were applied. A total of 26 frequency values in the
351–55,493 Hz frequency range were used, and the values spaced
logarithmically. The same SECM instrument was employed for
the potentiometric measurements using ion selective electrodes,
though in this case a home made voltage follower based on a
1012 input impedance operational amplifier was interconnected
between the cell and the potentiometric input of the system.
3. Results
3.1. Mg2+ distribution over the magnesium surface
In order to study the distribution of Mg2+ concentration in the
electrolyte from metal corrosion, SECM in potentiometric operation was employed with a Mg2+ -ISE as probe. The metal sample was
placed at the bottom of the small electrochemical cell, and the Mg
ISE tip was fastened onto the tip holder. Before the test electrolyte
was introduced in the cell, the tip was placed over the center of Mg
metal surface using the X, Y motors of the instrument. A video camera was employed to assist the process. Next, the tip was carefully
moved towards the metal surface by means of the Z motor until ca.
75 m vertical tip–substrate distance was reached. At this stage,
the test solution was added to the measuring cell, the reference
electrode was introduced, and the two metals in the sample were
J. Izquierdo et al. / Electrochimica Acta 87 (2013) 283–293
286
4
3.2
3
pMg
pMg
2.4
2
1.6
Retreat, galvanic connection
Approach, galvanic connection
Retreat, electrically disconnected
Galvanic connection
Disconnected
0
1
0
1
2
3
4
5
d/a
Fig. 2. Distribution of Mg2+ ion concentration above the magnesium strip measured
with the Mg2+ -ISE as the height of the tip is changed. The iron–magnesium sample
was immersed in 10 mM NaCl solution, whereas the two metals were either connected electrically (i.e. galvanic coupling) or disconnected. Both the direction of the
tip movement and the electrical condition of the metal are given in the graph. d/a is
the dimensionless distance between the sample and the tip. Scan rate: 5 m s−1 .
electrically connected at the rear of the sample by means of a copper
wire. The evolution of the e.m.f. of the cell was monitored with the
elapse of time. After a few minutes, a steady voltage was attained.
Then the tip was slowly removed from the metal surface, at a speed
of 5 m/s moved upward, while recording the electrode potential at the ISE. Once the chosen maximum tip–substrate distance
was reached, the tip–substrate distance was kept constant for two
minutes, and subsequently the tip was moved down at the same
rate, 5 m/s, to approach the Mg metal surface again. The electrode potential vs. tip–substrate distance curves could be converted
into pMg2+ –tip–substrate distance plots using the calibration curve
of the electrode. Normalized tip–substrate distances were used by
determining the ratio between the tip radius, a, and the vertical
tip–substrate distance, d. The pMg2+ –d/a curves measured during
the initial withdraw (black curve) and the subsequent approach
(red curve) steps are shown in Fig. 2. Next, the electric connection
between the Fe and Mg metals was removed, and a new retreat
pMg2+ –d/a curve was registered for the electrically-disconnected
magnesium metal (cf. the blue curve in Fig. 2).
As it was expected, the Mg2+ ion concentration was higher
when the tip was placed closer to the substrate. Nevertheless,
the approaching (black) and the withdrawing (red) experimental
curves for the galvanically-coupled metals are quite different. This
difference can be attributed to unavoidable convection in the electrolyte produced by the motion of the tip. That is, as the tip is moved,
it displaces some electrolyte from the Mg2+ -rich surroundings of
the metal to the bulk solution, resulting in the measurement of bigger values for ion concentration during the retreat movement. And
the opposite behavior is observed when recording the approach
curve.
Higher pMg2+ data were determined when the two metals were
disconnected. This indicates that magnesium dissolves less vigorously in the environment when it is not acting as sacrificial anode
for iron. From the plots given in Fig. 2, it is also obvious that when
magnesium was galvanically-coupled to iron, the curves were
rougher than the one determined over the unconnected metal. The
origin of this fact could be explained with the assistance of the video
camera, because gas evolution occurred on the surface of magnesium when the two metals were electrically connected. That is,
gas evolution was not exclusively restricted to the iron strip, but
500
1000
Distance along X axis, m
Fig. 3. Potentiometric SECM scan lines measured above the magnesium strip in
the iron–magnesium sample during immersion in 10 mM NaCl. The metals were:
(– –) with, and (– –) without galvanic connection. Vertical tip–substrate distance: 75 m; scan rate: 5 m/s.
it was even more vigorous over magnesium. It is known from basic
chemistry that the gas evolving at the magnesium–water interface
must be hydrogen resulting from the reaction between this metal
and water. Interestingly the magnesium acts as an anode in the
Mg–Fe couple, but hydrogen is reduced during its corrosion protecting function, a distinctive feature for this metal and its alloys
[5].
The electric connection of the two metals originates the development of a high negative potential on the iron metal. It was
observed to be more negative than −1.60 V vs. Ag/AgCl/KCl (3 M)
at all times. These potential values lay outside the stability range
of water. And hydrogen gas evolution is also occurring at the iron
surface.
Concentration profiles of Mg2+ ions were also determined by
rastering the ISE parallel to the surface. Line scans were measured
along the 200 m cross section of the Mg area, both with (red curve)
and without (black curve) galvanic connection between the two
metals. Results are given in Fig. 3 for single scan lines determined
when the tip was maintained at ca. 75 m vertical distance from
the surface. As it was observed before, the signal registered near
the corroding metal indicated higher Mg2+ concentration when
the metal was acting as sacrificial anode in the iron–magnesium
galvanic pair, than those measured when the two metals were disconnected. The maximum dissolution of magnesium was detected
when the tip passed over the central position of the metal strip,
which supports that the whole area was behaving anodically. Conversely, this maximum over the center of the Mg strip surface was
not observed when the metals were not in electrical contact. In
this case, the shape of the concentration profile was not symmetric
over the metal, and a separation between the portion acting as the
anode (at the left side of the line scan), and the area functioning as
hydrogen-reducing cathode (right side), could be noticed.
Additionally, several concentration profiles were measured at
different locations over the Mg strip while the metal was under galvanic connection. In this way, heterogeneities in the location of the
corrosion process over the metal could be detected. Fig. 4 depicts six
concentration profiles measured when the tip was moved along the
X axis at different Y positions, covering a total length of 100 m in
the Y axis, whereas keeping the same scan direction used to record
Fig. 3. That is, scanned X lines correspond to several of the cross
sections taken in the 200 m width direction of the magnesium
area, which were measured over a central region of the larger 3 mm
side. Despite the fact that the tip is actually too large to spatially
J. Izquierdo et al. / Electrochimica Acta 87 (2013) 283–293
287
1.0
3.0
pMg
2.0
1.5
0.8
0.6
i / i lim
Y=0 m
Y = 20 m
Y = 40 m
Y = 60 m
Y = 80 m
Y = 100 m
2.5
0.4
1.0
0.5
Dis
t
100
80
0
an
ce
a
60
40
500
lon
g
XA
xis
,
1000
m
20
0
ea
nc
sta
i
D
gY
lo n
Ax
is,
0.2
above resin, disconnected
above Fe, disconnected
above Fe, galvanic connection
m
Fig. 4. Potentiometric SECM scan lines measured when the tip crossed (X direction) over the magnesium strip in the iron–magnesium galvanic pair immersed in
10 mM NaCl, taken in a plane parallel to the surface of the metal. The different curves
were obtained after shifting the tip in the Y direction in 20 m steps. Tip–substrate
distance: 75 m; scan rate: 5 m/s.
resolve the system in these dimensions, the concentration profile
measured for Y = 20 m shows the higher values, indicating a region
in the anodic surface of the metal displaying greater electrochemical activity. Further studies would be necessary to determine the
actual heterogeneity of the whole system and its possible relationship to any microstructural features as the nucleation sites for the
eventual generation of corrosion pits as result of it.
3.2. Oxygen consumption
When a sacrifice anode is used for corrosion protection, oxygen
consumption occurs at the cathodic sites of the protected metal surface if these metals are placed in non-acidic environments. In order
to study the oxygen concentration profile over the protected iron
surface, an antimony microelectrode was employed as the SECM
measuring tip while the technique operated in the amperometric
mode. Since the SECM was operated in the amperometric mode, the
tip–substrate distance could be adjusted using the negative feedback effect when approaching a zone of the resin sleeve located
between the two metals. Furthermore, variations in the local oxygen concentration could also be visualized. For this purpose, the
electrode was placed as close to the surface of the iron strip as
possible with the assistance of a video camera, and subsequently
retracted 1000 m in the Z direction. Next, the tip was shifted horizontally 1.5 mm to be located above the resin sleeve. After the test
electrolyte was added to the system, and while the two metals were
kept electrically disconnected, the Z-approach curve was recorded.
A constant potential of −0.70 V vs. Ag/AgCl/KCl (3 M) was applied
to the tip, a potential value at which oxygen reduction occurs. The
closest tip–substrate distance in Z-approach curve shown in Fig. 5
occurs for a negative feedback of ca. 60% (black curve). This reduction in the faradic current measured at the tip corresponds to a
height of 85 m over the surface if we consider the electrode to be
a microelectrode of 175 m diameter with RG = 2.9 [61]. After this
curve was recorded, the tip was lifted up, and moved parallel to
the surface to a position located just above the center line of the
iron strip to record the corresponding Z-approach curve. The same
scan parameters were employed as before, still without galvanic
connection between the two metals. The corresponding approach
plot is also given in Fig. 5 (blue curve). Though it could be expected
that the corrosion of the disconnected iron should result in some
oxygen consumption, the negative feedback effect actually seemed
0.0
0
1
2
3
4
5
6
7
d/a
Fig. 5. Normalized Z-approach curves measured with the antimony electrode in
amperometric SECM operation using oxygen reduction at the tip as redox mediator
reaction. The plots were measured above the resin sleeve or the iron strip as indicated in the graph. The iron and the magnesium strips were either disconnected,
or connected electrically during the experiments, as indicated in the legend. Test
electrolyte: 10 mM NaCl. Tip potential: −0.70 V vs. Ag/AgCl/KCl (3 M); scan rate:
10 m/s; tip diameter: 175 m; RG = 2.9. i/ilim is the dimensionless tip current, and
d/a is the dimensionless distance between the sample and the tip.
to be smaller on iron than above the resin. This apparent discrepancy could be explained by considering differential polishing on the
resin and the metal piece. That is, due to the difference in hardness
between the materials, the metal sample can be expected to protrude above the surrounding resin holder. Indeed, the Z-approach
curve measured above the iron strip could be superimposed over
that obtained on the resin by slightly shifting the curve along the X
axis. In the forecoming, this observed distance difference was taken
into account in order to establish the actual tip–substrate distance.
On the other hand, the fact that the Z-approach curves measured
both on the resin and on the iron strip could be superimposed, indicates that the extent of iron corrosion in this environment does not
lead to a significant depletion of the oxygen concentration at early
exposures.
On the other hand, the red curve in Fig. 5 shows the Z-approach
curve measured above the same location on iron strip that was
measured after the two metals were electrically connected. In this
case, local depletion of oxygen is readily observed in the plot. Thus,
the corrosion of Mg drives a very intensive electrochemical oxygen
reduction at the iron surface. And oxygen diffusion from the bulk
electrolyte could not compensate its consumption at the metal.
Two dimensional images of oxygen consumption were obtained
when the antimony tip scanned the surface in an X–Y plane set at
175 m vertical tip–substrate distance, and they are shown in Fig. 6.
Image A was recorded when the two metals were disconnected,
while image B was achieved when they were galvanically-coupled.
In Fig. 6A, the image of the iron substrate shows up among the surrounding resin areas. Above the iron surface smaller current values
were registered, showing smaller oxygen concentrations could be
obtained. We can conclude that the SECM image shows the corrosion of iron in this environment. On the other hand, the image
of the iron strip shown in Fig. 6B is much sharper. In this case, tip
currents close to 0 nA were measured over the metal, thus showing
that oxygen was absent from the thin electrolyte volume comprised between the tip and the iron strip. The dimensions of the
area showing the lowest current values in the image closely match
the dimensions of the iron surface (1 mm × 2 mm). This proves that
the whole metal is behaving as a cathode. Therefore, the iron strip
J. Izquierdo et al. / Electrochimica Acta 87 (2013) 283–293
288
Fig. 6. Amperometric SECM images depicting the absolute current measured at the antimony tip travelling over the iron strip when the iron–magnesium sample was
immersed in 10 mM NaCl. The metals were: (A) without, and (B) with galvanic connection. Tip potential: −0.70 V vs. Ag/AgCl/KCl (3 M); tip diameter: 175 m; RG = 2.9;
tip–substrate distance: 175 m; scan rate: 30 m/s. The figures represent an area of 2500 m × 3000 m in X and Y directions.
is effectively protected from corrosion through its connection with
the sacrificial anode of magnesium.
3.3. pH distributions
The antimony electrode was also employed to image pH distributions over the substrate during the corrosion reaction. Though
the electrode was usually placed as close as possible to the investigated surface with the assistance of a video camera, the possibility
to more precisely establish the tip-to-substrate distance by applying an alternating potential to the tip was investigated. In this way,
the tip could remain unbiased, provided a sufficiently small excitation AC signal was employed. The rationale for not polarizing
the antimony tip was to avoid the chemical modification of the
Sb/Sb2 O3 surface of the electrode. AC operation of the SECM was
employed, and the magnitude of the current and its phase shift with
respect to the applied AC potential modulation were recorded as
impedance values. The near-field interaction between the SECM tip
and the surface could be employed to obtain AC Z-approach curves
within the frequency range. A location above the insulating resin,
approximately equidistant from both metal specimens, was chosen
for the determination of the tip–substrate distance, and the result
is given in Fig. 7. The plots depict the variation of the normalized
modulus (Fig. 7A), and the phase shift (Fig. 7B) of the impedance as
the tip approached the substrate for a selection of frequencies of the
A
1.6
B
50
55.0 kHz
23.1 kHz
9.68 kHz
4.06 kHz
1.70 kHz
715 Hz
300 Hz
Phase, degrees
Normalized modulus
2.0
AC perturbation. Modulus values have been normalized by dividing the value recorded at each point by that measured in the bulk
solution (e.g., sufficiently far from the substrate to give a stationary
value). The higher impedance observed at the end of the curve for
every frequency and the decrease in phase angle, are indications
of the greater resistance offered to ionic current flow when the tip
approached the insulating surface due to the smaller electrolyte
volume, though the extent of this blocking effect greatly depends
on the frequency of the AC excitation signal. Greater contrast was
observed in the low-frequency range, whereas the system became
very noisy at 55 kHz.
Once the very close tip–substrate distance was established with
AC mode of SECM, the antimony tip was removed to a height of
80 m, and subsequently positioned over the center of the magnesium sample, or the iron strip, by moving the tip in the X–Y
plane. Then, the potentiometric operation mode was set in order to
monitor pH distributions over the metals. Vertical pH profiles were
determined over the center line of each of the metals, both when
they were disconnected, and when galvanic contact was established between them. In these experiments the following protocol
was followed: first, the pH-sensitive ISE was removed from the surface to a distance of 600 m. After 10 s waiting time at this height,
the tip was moved down towards the surface until a tip–substrate
distance of 0.5 normalized (d/a) units. After 10 s waiting time, the
tip was removed again from the surface of the metal to the bulk.
1.2
40
30
20
10
0.8
0
1
2
3
4
d/a
5
6
7
0
0
1
2
3
4
5
6
7
d/a
Fig. 7. Normalized AC Z-approach curves towards the resin sleeve at a position located between the iron and the magnesium strips when the sample was immersed in
10 mM NaCl with the 175 m antimony electrode. The tip was left at its spontaneous open-circuit potential in the electrolyte (namely + 0.44 V vs. Ag/AgCl/KCl (3 M)). The
excitation signal amplitude was 10 mVpp , and frequencies are indicated in the figure. (A) Normalized magnitude, and (B) phase of the impedance measured at the tip. d/a is
the dimensionless distance between the sample and the tip.
J. Izquierdo et al. / Electrochimica Acta 87 (2013) 283–293
11
11
B
10
10
9
9
8
8
pH
pH
A
7
6
5
5
0.5
1.0
1.5
2.0
2.5
3.0
Retreat
Approach
7
Retreat
Approach
6
0.0
289
3.5
0.0
0.5
1.0
d/a
1.5
2.0
2.5
3.0
3.5
d/a
Fig. 8. pH distributions above the magnesium strip measured with the antimony tip as its height was changed relative to the surface. The iron–magnesium sample was
immersed in 10 mM NaCl, whereas the two metals were (A) disconnected, and (B) galvanically-coupled. The direction of the tip movement is indicated in the figures; scan
rate: 5 m/s. d/a is the dimensionless distance between the sample and the tip.
8.5
8.0
7.5
pH
7.0
6.5
6.0
5.5
0
500
1000
Distance along X axis, m
Fig. 9. pH distribution during a scan line recorded with the antimony electrode over
the magnesium strip. The iron–magnesium galvanic pair was immersed in 10 mM
NaCl. Tip–substrate distance: 80 m; scan rate: 5 m/s.
15
Retreat
Approach
14
pH
The potential of the ISE was continuously recorded during all the
duration of the experiment. Tip movement in the vertical direction
was always performed at the speed of 5 m/s. In this way, vertical pH profiles could be obtained as a function of the normalized
tip–substrate distance for both the approach and the retreat steps.
The same protocol was employed while the two metals were electrically disconnected, and when they were galvanically coupled.
Fig. 8 shows the mentioned vertical pH profiles measured above Mg
surface. As it can be seen, in the case of the free-corroding magnesium sample, higher alkalinity is detected in the vicinity of the Mg
surface (see Fig. 8A), which indicates that the cathodic half-reaction
takes place on some regions of the metal due to its free corrosion.
The pH values determined at the largest distances were close to the
corresponding value for the bulk solution, which was measured to
be 8.76 when registered with a conventional pH-meter. Though the
approach and retreat curves exhibit a similar behavior, they could
not be overlapped, and they showed the biggest gap for normalized distances smaller than 1.5. This fact can be attributed to the
forced convection effect produced by the tip during its movement
to and from the surface. Higher pH values were measured during the retracting process in the major part of the displacement,
because the electrode was departing from a portion of the electrolyte more concentrated in hydroxyl anions during its movement
from the surface towards the bulk of the solution.
The opposite trend was observed when galvanic connection was
ensured (cf. Fig. 8B). The pH of electrolyte adjacent to the magnesium surface became lower, than the pH of the bulk. Close to the
metal surface, pH values as low as 5.5 could be detected. This shift
to the acidic direction occurred despite hydrogen evolution could
be observed with the video camera, and thus a source of alkalinization was still somehow active at the metal. However, the higher
presence of protons is more difficult to evaluate due to the greater
diffusion rate of this species and, in this specific case, also due to the
noise in the system provoked by the evolution of hydrogen gas. The
same effect was observed when the tip was moved parallel to the
surface to record the scan line given in Fig. 9. This latest measurement shows a clear pH decrease in a section of ca. 200 m, which
corresponds with the actual X portion of the magnesium strip used
as target. It must be noticed that the onset of acidification could be
detected at larger distances as a result of the diffusion of H+ and
Mg2+ ions.
Finally, Fig. 10 displays pH–vertical d/a plots obtained above
iron surface when the two metals were connected. In both plots,
namely approach and retreat curves, the alkalinization observed
near the cathode is extensive, even at distances as large as 2 mm. It is
13
12
11
10
0
2
4
6
8
10
12
d/a
Fig. 10. pH distributions above the iron strip measured with the antimony tip as
its height was changed relative to the metal surface. The iron–magnesium galvanic
pair was immersed in 10 mM NaCl. The direction of the tip movement is indicated
in the figures; scan rate: 5 m/s.
J. Izquierdo et al. / Electrochimica Acta 87 (2013) 283–293
290
interesting to compare this result with the amperometric curve
recorded for oxygen detection, previously shown in Fig. 6B, when
the limiting current was attained at d/a values of ca. 5. That is,
constant oxygen concentration in the electrolyte close to the bulk
solution value could already be found at a tip–substrate distance of
900 m. Certainly, the corrosion process originates an increase in
the solution pH here through the reduction of oxygen. But in combination with the amperometric observations, if that was the only
source of this effect, OH− concentration should decrease down to
the values in bulk solution at much smaller tip–substrate distances
than those found in Fig. 10. Then, hydrogen evolution, probably
resulting from the highly negative OCP experienced by the electrically connected system, is likely to be the additional factor that
leads to this high pH in the proximity of the iron strip. It must be
noted that pH values shown in Fig. 10 for the volume of electrolyte
in the vicinity of the iron surface are far beyond the dynamic measuring range of the antimony electrode. Therefore no quantitative
information can be extracted from these curves.
4. Discussion
We report here that potentiometric operation of the SECM can
be employed to locally measure concentration distributions of key
species involved in the corrosion of magnesium in aqueous solution. This metal is very reactive in water, thus making difficult to
design accurate experiments to study its corrosion mechanism. At
present, despite the rather extensive literature on the corrosion of
this metal and its alloys, the origin of the corrosion process is still
obscure and subjected a big controversy, and a number of experimental observations are regarded by some researcher as dubious.
Even experimental techniques are often put to their limits when
investigating the electrochemical behaviour of magnesium in aqueous solutions due to joint operation of several features, namely:
(1) The high dissolution rate of the metal in contact with an aqueous environment often leads to portions of the material being
physically detached from the matrix. It also makes difficult
the safe removal of corrosion products from the uncorroded
material. As a result, weight-loss measurements may bear
big experimental errors. Furthermore, they are average measurements that give no information on the dynamics of the
corrosion reactions.
(2) The corrosion of the magnesium is accompanied by vigorous hydrogen evolution [3,4]. A “strange hydrogen evolution
behaviour” has been described [5]. That is, more hydrogen is
evolved when the anodic overvoltage is increased or a higher
anodic current density is imposed, conversely to what happens
with the other metals. This phenomenon is called the negative
difference effect (NDE). Hydrogen evolution can greatly affect
the efficiency of electrochemical probes either by blocking their
surface or even modifying their surface state. Additionally, it
causes convection effects in the electrolyte solution that affect
the current distribution in the electrochemical cell. Conversely,
experimental methods have been developed for the quantification of hydrogen evolving during the corrosion of magnesium
and its alloys [62]. Though they may be regarded highly efficient techniques, and procedures have been designed to follow
the variation with time of hydrogen evolution, they cannot distinguish whether the gas evolves from anodic or cathodic sites.
(3) Magnesium hydrolysis is basically non-acidic. The equilibrium
constant associated with the first deprotonation step of its
aquo-complexes [M(H2 O)x ]2+ , has pKa1 = 11.4 [63]. The acidification caused by hydrolysis of Mg2+ can be calculated for given
concentrations of the metal ion using the equation:
pH = − log
K1a [Mg2+ ]
(1)
(4) Using [Mg2+ ] = 0.0001 and 0.1 M, the expected pH values would
be 7.0 and 6.2, respectively [41]. That is, oxidation of magnesium is not capable of significantly changing the pH of a
neutral corrosion medium. Conversely, either oxygen or proton
electroreduction during the cathodic half-cell reaction produce
strong alkaline environments. Strong alkaline environments
are usually reported around corroding magnesium and magnesium alloys [5].
(5) The formation of a passive film of magnesium hydroxide that
exhibits some corrosion protection characteristics is considered
to be formed on magnesium and its alloys, especially at high pH
[64]. This passive film is unstable, and the onset of corrosion on
magnesium is regarded to occur at film-free areas on the surface
of the metal [5,53,65]. Indeed, the open circuit potential of fresh
polished samples immersed in aqueous environments usually
evolves towards more noble potentials [5,53], until a “pitting
potential” is attained at which breakdown of the surface film
occurs [3,66,67]. Though pitting potential and pit nucleation are
terms frequently employed in the literature related to the corrosion of this metal, stable pit growth has not been described for
magnesium and magnesium alloys [35]. Conversely, retrieved
samples show that the entire exposed surface has been corroded [35].
Scanning electrochemical microscopy was selected as the
experimental technique for this work as to gain new spatiallyresolved information concerning the chemical reactions responsible for the corrosion of CP magnesium. A special concern was
taken in relation to identify if alkalinization occurred at both the
anodic and cathodic microcells formed on the metal, or whether
diffusion of the high concentration of hydroxyl ions formed in the
cathodes were responsible for the alkalinization of the electrolyte.
Though a small electrolyte volume is typically employed in SECM
experiments, the choice of a small magnesium strip insulated in
a much bigger resin mount was considered to allow enough dilution of the formed OH− species as to detect the source of these
ions at least for the early stages of metal corrosion. Additionally,
the mount contained also an iron strip, thus allowing some experiments to be conducted with galvanic coupling of the two metals,
which could be simply attained by electrically connecting the two
strips at the back of the mount. In this way, separation of the anodic
and cathodic sites could be achieved if the two metal strips were
separated enough in the mount, though at the cost of both an
increase of the corrosion rate of magnesium and a greater ohmic
loss in the electrolyte. Though the latter might be regarded to drive
a fraction of the hydrogen evolution reaction from the iron to the
magnesium strip in order to minimize the separation between both
half-cell reactions, this would result in local alkalinization around
those cathodic sites on magnesium. But no evidence of any local
alkalinization around magnesium has been observed in the course
of these experiments. Yet, additional experiments are currently
undertaken in order to completely rule out any eventual effects on
the localization of the hydrogen evolution reaction directly related
to the significant losses occurring in the electrochemical cell. Variations in both the distance comprised between the two metals in the
holder and the ionic strength of the electrolyte are thus considered.
Figs. 2 and 3 show significantly smaller pMg values in a thin
electrolyte layer above the magnesium strip following the galvanic
coupling of this metal to iron. That is, the use of a Mg2+ ISE allowed
for concentration distributions of the dissolved metal to be measured. It must also be noticed that despite the enhancement of
magnesium dissolution due to the galvanic-coupling to iron, the
dimensions of the magnesium strip were sufficient for the amount
of dissolved magnesium never to saturate the detection limit of
the ISE (see Supplementary material). That is, the microelectrode
J. Izquierdo et al. / Electrochimica Acta 87 (2013) 283–293
probe was sensitive to changes in the concentrations of Mg2+ for
the duration of the experiments, contrary to the expectations made
by other authors [5]. Another important outcome from our work is
obtained from inspection of Fig. 4. Though the magnesium strip
was working as the anode in the Fe–Mg galvanic pair, dissolution of the metal does not occur simultaneously over the entire
exposed surface. Indeed, it has been observed from a sequence of
SECM measurements passing over the same scan lines (not shown),
that the locations of high Mg2+ concentrations are shifted over the
exposed magnesium strip. Our experiments, still of some preliminary nature, agree thus well with the previous observations made
using SVET by Williams and McMurray [35]. We are currently working on the fabrication of more robust ion-selective electrodes with
smaller internal resistances, that will allow higher scan rates to be
used with SECM, thus allowing maps instead of selected scan lines
to be recorded.
Another important outcome of this work was the observation
of oxygen consumption when magnesium was galvanically connected to iron. This dissolved species in the solution was consumed
in the thin electrolyte volume located over the iron strip when
acting as the cathode during the corrosion of magnesium. Indeed,
the amperometric SECM images in Fig. 6 clearly demonstrate that
the enhanced corrosion rate of magnesium when galvanicallycoupled to iron directly corresponds to an enhancement in the
consumption of oxygen, despite the occurrence of hydrogen evolution on the metal. Simultaneously, the pH in the thin electrolyte
volume located above the magnesium strip becomes slightly acidic,
attaining values between 5.5 and 6. These values are only slightly
more acidic than those predicted by application of Eq. (1) considering the hydrolysis of Mg2+ ions in the electrolyte. Values as low
as 5.3 have already been reported from SIET measurements on
corroding AZ31 magnesium alloy, which was ascribed to the codissolution and hydrolysis of Al along with Mg, since this alloy
contains ca. 3% aluminum. In the case of CP magnesium, the possible contribution of minute amounts of iron, even in small amounts
in the order of ppm [68], may justify the more acidic values found
in our work. Since the pKa1 of Fe is more than two units smaller
than that of Al (2.2 and 4.5, respectively) [63], a 0.0001 M Fe2+ solution produces almost the same pH decrease than another 0.1 M in
Al3+ [41]. Not only the pH values can be justified on the basis of
the physicochemical response of CP magnesium, but they are well
inside the linear response of the antimony microelectrode with pH
[56]. Again the design of the experiment has satisfactorily served
for pH monitoring of magnesium corrosion in an aqueous solution,
without meeting the warnings raised in ref. [5]. This feature is very
important when considering that no alkalinization was observed
around the anodic sites in any of the experiments described in
our work. And alkalinization is a requirement for the occurrence
of the chemical reaction suggested to account for the NDE [65,69].
In this model, formation of Mg+ species and their direct reaction
with water, is proposed:
2H+ + 2e− → H2 ↑
2Mg → 2Mg + e
+
−
2Mg + 2H2 O → 2Mg
+
(cathodicpartialreaction)
(2)
(anodicpartialreaction)
(3)
2+
+ 2OH + H2 ↑
−
(chemicalreaction) (4)
From Eq. (4), both the consumption of protons and the production of OH− are expected at the anodic sites on corroding
magnesium. Another implication is that hydrogen gas evolution
should occur at those sites. Yet, evolution of hydrogen gas from
the corroding magnesium sample can be explained by taking in
account the previous observations by Williams and McMurray [35].
In their work on the corrosion of magnesium in concentrated chloride solution investigated by SVET, they observed that the anodic
sites occupy only a (small) fraction of the area exposed to the
electrolyte, and that local cathodes can develop in very near
291
proximity to them on the previously corroded surface. Therefore,
hydrogen evolution do not necessarily must occur at the actual
anodic microcell sites, but could occur on the surrounding cathodic
area. The results reported in this work could be well described using
the same interpretation. This explanation may hold even in the case
of magnesium galvanically-coupled to iron. Though the major part
of the cathodic reaction occurs on the separated iron strip, some
cathodic areas might still develop on the magnesium sample in the
close proximity to the corroding anodic sites. The development of
such minute cathodic sites in the otherwise anodic metal in a galvanic couple has been recently observed in our laboratory using a
combination of scanning microelectrochemical techniques for the
Fe–Zn galvanic system [70]. This interpretation also accounts for
the electrolyte resistance SECM images given in Ref. [53], in which
the anodic activity on a free corroding magnesium sample occurred
only on a small portion of the exposed surface.
5. Conclusion
The applicability of the Mg2+ -ISE to characterize magnesiumbased materials by SECM has been demonstrated. The results show
that anodic dissolution of magnesium anodes takes place preferentially in certain most active sites. The increase in Mg2+ ion
concentration occurring in the vicinity of the magnesium strip, was
found to be two orders of magnitude bigger when the nature of the
degradation process changed from spontaneous self-corrosion to
galvanic corrosion. Imaging of oxygen concentration distribution
and pH detection were carried out with the antimony electrode, and
it was possible to clearly distinguish anodic and cathodic behaviors
occurring simultaneously on the same surface. Thus, the combination of measurements and electrodes presented here allowed to
identify and to quantify the different reactions taking place during
the corrosion process. Additionally, the results open a promising
new route to the elucidation of certain characteristics of the mechanism involved in the corrosion and passivation of magnesium,
which result from greatly localized reactions.
Acknowledgements
The authors are grateful to the Spanish Ministry of Science
and Innovation (MICINN, Madrid, Acción Integrada No. HH20080011) and to the National Office for Research and Technology
(NKTH, Budapest, research grant ES-25/2008 TeT) for the grant of a
Collaborative Research Programme between Hungary and Spain.
J.I. and R.M.S. are grateful for financial support by the MICINN
and the European Regional Development Fund (Brussels, Belgium)
under Project No. CTQ2009-12459. A Research Training Grant
awarded to J.I. by the MICINN (Programa de Formación de Personal
Investigador) is gratefully acknowledged. L.N. and G.N. acknowledge support from “Developing Competitiveness of Universities in
the South Transdanubian Region (SROP-4.2.1.B-10/2/KONV-20100002)”. The Authors acknowledge valuable discussions with Dr.
Nick Birbilis during the preparation of the manuscript.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.electacta.2012.09.029.
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