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Development of Solid Contact

Micropipette Zn-Ion Selective Electrode
for Corrosion Studies
a a b c
Ágnes Varga , Lívia Nagy , Javier Izquierdo , István Bitter ,
b b
Ricardo M. Souto & Géza Nagy
a
Department of General and Physical Chemistry, University of Pécs,
Pécs, Hungary
b
Department of Physical Chemistry, University of La Laguna, La
Laguna, Tenerife, Spain
c
Budapest University of Technology and Economics, Budapest,
Hungary
Version of record first published: 06 Dec 2011.

To cite this article: Ágnes Varga , Lívia Nagy , Javier Izquierdo , István Bitter , Ricardo M. Souto &
Géza Nagy (2011): Development of Solid Contact Micropipette Zn-Ion Selective Electrode for Corrosion
Studies, Analytical Letters, 44:18, 2876-2886

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 Analytical Letters, 44: 2876–2886, 2011
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DOI: 10.1080/00032719.2011.582545

Electrochemistry

DEVELOPMENT OF SOLID CONTACT MICROPIPETTE

Zn-ION SELECTIVE ELECTRODE FOR CORROSION
STUDIES
Downloaded by [Universidad Nacional Colombia] at 09:06 11 February 2013

Ágnes Varga,1 Lı́via Nagy,1 Javier Izquierdo,2 István Bitter,3

Ricardo M. Souto,2 and Géza Nagy2
1
Department of General and Physical Chemistry, University of Pécs,
Pécs, Hungary
2
Department of Physical Chemistry, University of La Laguna,
La Laguna, Tenerife, Spain
3
Budapest University of Technology and Economics, Budapest, Hungary

Micron-size ion selective micropipettes can be used in scanning electrochemical microscopy

(SECM). They can provide excellent spatial resolution. Unfortunately the resistance of
these small sensors is high. Their application needs special shielding and slow scanning
rates. Usually their lifetime hardly exceeds a few days.
Zinc layer or dispersed zinc particles containing films are often used for providing
cathodic protection against corrosion in case of metal surfaces. Therefore, in corrosion stu-
dies, measurements of local zinc ion concentration can give important information about the
nature of the process. For corrosion studies we needed SECM measuring tips for imaging
concentration profiles of Zn2þions involved in surface processes. Based on our earlier
experience, solid contact micropipettes for selective measurements of Zn2þion concen-
tration were prepared with a tip size of a few micrometers. The properties of the micro-
pipettes were investigated. They were also used in SECM imaging. In this paper, details
of Zn2þion selective microelectrode preparation are described. Data about their properties,
lifetime, resistance, and ion activity response are shown. Preliminary findings in SECM
imaging of zinc ion concentration profiles are shown. The improvement of the scanning rate
achieved by lowering tip resistance is a main advantage in potentiometric SECM.

Keywords: Corrosion; SECM; Zinc ion selective electrode

Received 15 July 2010; accepted 3 November 2010.

This paper was presented at the International Conference on Analytical and Nanoanalytical
Methods for Biomedical and Environmental Sciences (IC-ANMBES 2010), held in Brasov, Romania,
18–20 June 2010.
The authors acknowledge the financial support from the grant of a Hungarian-Spanish Inter-
governmental S&T Cooperation Program awarded by the National Office for Research and Technology
(NKTH, Budapest, research grant ES-25=2008 TeT) and the Ministry for Research (MICINN, Madrid,
Acción Integrada No. HH2008-0011).
Address correspondence to Géza Nagy, University of Pécs, Department of General and Physical
Chemistry, Ifjúság u. 6, 7624 Pécs, Hungary. E-mail: G-nagy@ttk.pte.hu

2876
 SOLID CONTACT MICROPIPETTE ION SELECTIVE ELECTRODE 2877

INTRODUCTION
Zinc is a transition metal that has important roles in living organisms as well as
in human technology. The functions of zinc in living objects are mainly related to
enzymatic processes and DNA replication. In particular, the human hormone insulin
contains zinc, and the human body contains a relatively high amount of zinc (ca.
2.3 g). Zinc is an important trace metal in human dietary. On the other hand, zinc
is also contained in many technological applications including paints, batteries,
pharmaceuticals, and other industrial products. And, zinc-containing pollutants
are often found in environmental samples. Therefore, analytical methods are needed
for assessment of zinc concentrations in dietary, environmental, industrial, or bio-
logical samples. Numerous methods developed for the analysis of zinc in various
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samples are available. Among them, atom spectroscopic methods seem most popu-
lar. Zinc ion can be reduced on different electrodes; therefore, voltammetric methods
have also been successfully employed.
Due to the simplicity and cost effectiveness of potentiometry, several attempts
have been made to develop zinc ion selective electrodes (ISE). A zinc ISE made of plas-
ticized PVC membrane containing 5,6-benzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicy-
clo[8,8,8]hexacos-5-ene (BHDE) cryptandionophore has been reported (Zamani,
Ganjali, and Pooyamanesh 2006). This electrode was used for end-point detection
in complexometric titration as well as in the monitoring of zinc ion occurrence in
industrial wastewaters resulting from zinc electroplating processes. Another zinc elec-
trode was fabricated using a porphyrin-based ionophore incorporated into a PVC
matrix (Gupta et al. 2003). Up to now, most research groups working on the develop-
ment of ion selective zinc electrodes focused on the environmental, clinical, or dietary
analyses as potential application fields for their new sensors. But, due to the com-
plexity and low zinc concentration of these matrices, it has been a difficult task to find
appropriate ionophores to produce zinc ISEs that will function well for those samples.
Therefore, further work is still needed in this area in order to improve the selectivity
and dynamic range of analysis properties of the resulting zinc-selective electrodes.
An emerging field for the application of zinc ion selective electrodes is found in
corrosion science (Lamaka, Souto, and Ferreira 2010). Zinc layers or films contain-
ing dispersed zinc particles are often used to provide cathodic protection against cor-
rosion in the case of metal surfaces. Indeed, spatially-resolved investigations of the
corrosion processes, occurring when iron and zinc surfaces are put in galvanic con-
tact, have already been performed using the scanning vibrating electrode technique
(SVET, Ogle, Morel, and Jacquet 2006; Souto et al. 2007; Simões et al. 2009) and the
scanning electrochemical microscope (SECM, Simões et al. 2007). By carrying out
experiments in different ionic solutions, consistent results were obtained for the cor-
rosion of iron, but significant differences were observed concerning the detection of
zinc corrosion. This arises from the low over-potential for oxygen reduction and
water decomposition exhibited by the materials used as tips in SECM, and these
reactions overlap the amperometric reduction of zinc ions (González-Garcı́a 2007).
It is thus expected that the use of a selective zinc concentration detecting tip could
be very helpful in these corrosion studies.
Scanning electrochemical microscopy (SECM) is a powerful technique for
the local investigation of reactions occurring at surfaces for factors responsible for
 2878 Á. VARGA ET AL.

corrosion (Pust, Maier, and Wittstock 2008; Niu et al. 2009; González-Garcı́a 2010;
Souto, Lamaka, and González 2010). The technique is based on the combined
application of high-resolution measurement tip positioning devices, appropriate
computer controlled measurement and data collection routines, and computerized
image formation or evaluation software. The SECM can provide high-resolution
images containing chemical information on surface processes (González-Garcı́a
et al. 2004; Santana et al. 2010; Souto et al. 2010) and concentration profiles of dif-
ferent species in the liquid phase in close vicinity to interfaces (Bastos et al. 2004;
Gabrielli et al. 2005; Volker Inchauspe, and Calvo 2006). Thus far, most of the
SECM studies employ a voltammetric ultramicroelectrode as the data collecting
measuring tip while the electrochemical system operates in amperometric mode.
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However, in many cases, an ion selective electrode measuring tip and operation of
the SECM in the potentiometric mode would be a better choice. The local concen-
tration of a species presenting no electroactivity in the accessible potential window
can be measured with the appropriate ion selective electrode. And, its greater selec-
tivity, which is superior to amperometry, is also often required. In an earlier work
(Wei et al. 1995), images displaying zinc ion concentration profiles over small size
zinc ion diffusion sources, as well as over electrochemical zinc ion sinks, were
recorded with a micropipette type zinc ISE. Very recently, a new Zn2þ-selective
microelectrode developed for the determination of the Zn2þ species released in the
course of corrosion processes has been described (Bastos et al. 2010).
Ion selective micropipette electrodes are well-known sensors and are used
broad scale in experimental life sciences (Messerli, Collis, and Smith 2009a,
2009b). Their main advantage is that they can be made with a very small measure-
ment tip with a diameter often in the nm range. Their preparation procedure is quite
universal and, depending on the composition of the measurement ‘‘cocktail,’’ several
types of electrodes can be prepared by the same procedure. Unfortunately, the ion
selective micropipettes are very fragile devices sensitive to mechanical effects and
electric shocks. Their lifetime is seldom longer than a few days. They need special
care during handling and noise filtering during measurements. Furthermore, their
very high electrical resistance severely hinders usage in SECM. In this technique,
the measuring probe travels stepwise at a programmed scan rate over the surface
under study. At each location it takes a signal, reflecting the ion activity there.
The higher the resistance, the longer the time needed for achieving steady signal at
each place. Slower scanning rates are thus needed to attain reliable images when
the resistance is higher. Additionally, bigger resistances result in more electric noise
disturbing the measurements. For the interested reader, a detailed discussion con-
cerning the problems and difficulties of ion selective SECM can be found elsewhere
(Denuault, Nagy, and Toth 2001).
On the other hand, a novel type of micropipette ion selective electrode has been
recently developed in the authors’ laboratory at Pécs (Gyetvai et al. 2007; Gyetvai
et al. 2009). In this electrode, the internal reference electrode was replaced by a thin
carbon fiber coated by a conductive polymer film, which is dipped into the
ion-selective cocktail. In this way, the resistance of the electrode was greatly reduced
at the same time that its lifetime was dramatically improved. The properties of these
novel ammonium (Gyetvai et al. 2007) and potassium (Gyetvai et al. 2009) selective
micropipettes and their application in SECM were reported. These new micropipette
 SOLID CONTACT MICROPIPETTE ION SELECTIVE ELECTRODE 2879

ISEs may be considered for the use of potentiometric SECM in the investigation of
processes of interest in corrosion science. In this paper the description of the prep-
aration of ion selective zinc micropipettes provided with solid contact, together with
the results obtained during the investigation of their properties is provided. Prelimi-
nary data on the corrosion of zinc obtained with the SECM technique using these
zinc ion selective electrode tips are also given.

EXPERIMENTAL
Materials, Instruments, and Methods
Chemicals used in this work were used as received, namely: high molecular
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weight poly(vinyl chloride), potassium tetrakis(4-chlorophenyl)borate (KTFPB),

and 2-nitrophenyl octyl ether (OPOE) from Fluka; tris(hydroxymethyl)amino-
methane buffer from Merck; tetrahydrofuran from Interkemia. The conductive
polymer used to coat the carbon fiber was produced from the monomer, 3,4-ethyle-
nedioxythiophene (EDOT) supplied by H.C. Starck. The electropolymerization pro-
cess was carried out in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM
PF6
) ionic liquid solvent from Solvent Innovation. The other chemicals not
mentioned here were of analytical grade. The N-phenyliminodiacetic acid bis-N’,
N’-dicyclohexylamide zinc ionophore used in the ISMEs was synthesized as
described elsewhere (Lindner et al. 1992). All solutions were prepared using
deionized water.
The 33 mm diameter carbon fibers were a generous gift of Specialty Materials
(Massachusetts, USA), and borosilicate glass capillaries (types: B100-50-10 and
B200-116-10) were purchased from Sutter Instrument (Novato, CA, USA).
A battery-powered voltage follower based on TL082 operational amplifier was
used for all potentiometric measurements. Its output was connected to a digital mul-
timeter (METEX M-3630D Digital Multimeter). The cell voltage data were collected
with a PC through a multimeter using the commercial program supplied for the
METEX. A home built scanning electrochemical microscope was employed (Csóka,
Kovács, and Nagy 2003). It is based on a 3D positioning device driven by precision
step motors with 75 nm minimal step size. The distance between the ISME and the
substrate was established by allowing the probe to gently rest on the sample, and,
subsequently, the probe was retracted to the chosen operation distance with the
aid of the Z-positioning motor.
Ag=AgCl reference electrodes in quasi-reference configuration were employed
in the polymerization, potentiometric, and SECM experiments, whereas a platinum
wire was used as the auxiliary electrode during the preparation of the electropoly-
merized coating for the carbon fiber.

Preparation of the Micropipette Electrodes

The micropipette electrodes were made of two parts as shown in Figure 1. The
glass pipette with broader internal diameter holds the cocktail, and the thinner one is
inserted into the lumen of the first. The carbon fiber that provides the internal con-
tact is inside at the tip of the thinner pipette, whereas a thin copper wire is inserted
 2880 Á. VARGA ET AL.
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Figure 1. The structure of the micropipette electrode. (Figure available in color online.)

into the lumen. Mercury or silver epoxy paste provides electric contact between the
carbon fiber and the copper wire. The internal part of the electrode assembly is
reusable, that is, it can be inserted into a new outer part when the previously used
gets damaged.
In preparation of the micropipette electrodes, borosilicate glass capillaries of
two different internal diameters (types: B100-50-10 and B200-116-10, Sutter Instru-
ments) were selected and checked for fit. The capillaries were soaked in a ‘‘piranha
solution’’ of concentrated sulfuric acid: hydrogen peroxide (30%) 1:1 volume. Next,
they were thoroughly washed with double deionized water and ethanol, and dried in
oven at 105 C. Micropipettes were pulled from both sizes of capillaries by using a
pipette puller (Sutter Instruments, type P-30, Novato, CA, USA). The 33 mm diam-
eter carbon fiber was inserted in the lumen of the thinner capillary with the fiber
reaching out for about 15 mm and about 20 mm long in the lumen. Loctite adhesive
was used for sealing. Mercury metal or Amepox silver epoxy paste (Amepox
Microelectronics, Ltd. Poland) and the copper wire were then inserted into the lumen
of the thin pipettes as shown in Figure 1. At this point the inner section of the
electrode assembly was ready for the electropolymerization of EDOT over the
portion of the carbon fiber reaching out from the tip.
The tip of the larger diameter pipette was provided with a hydrophobic layer
using dichlorodimethylsilane (Fluka) by using a simple procedure. Namely, the tip
of the micropipette is introduced into a small amount quantity of 5% solution of
dichlorodimethylsilane in carbon tetrachloride into the tip of the micropipettes,
and they were subsequently kept in an oven (80 C) for approximately half an hour
inside a closed Petri dish. The finished pipettes were stored in the Petri dish at room
 SOLID CONTACT MICROPIPETTE ION SELECTIVE ELECTRODE 2881

temperature until use. The zinc ion selective cocktail can be backfilled into the tip
shortly before the assembly of the electrodes in the measuring device. In this way,
a 5–10 mm long cocktail column is formed at the tip end of the pipettes.
The zinc ion selective cocktail was made having the following composition: 5%
zinc ionophore, 1.8% K-tetrakis (4-chlorophenyl) borate hydrophobic additive, 13%
PVC matrix, 80% 2-nitrophenyloctylether (OPOE) plasticizer solvent, and 0.2% tet-
rahydrofurane diluting solvent. Mechanical stability was attained with further addi-
tions of PVC in the case of bigger pipette orifices.

RESULTS AND DISCUSSION

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The voltage divider method was used to measure the internal resistance (Ri) of
the cell containing the zinc micropipettes. A high ohmic resistance resistor (Rk,
100 MX) was selected for these studies, and the emf of the cell containing the quasi-
reference and the zinc ion selective electrodes was recorded. After attaining a steady
reading, resistance Rk was switched in as a load, and the transient of the voltage
drop,
DU ¼ emf
Uk

was determined. Assuming that Rk and Ri are much bigger than any other resistances
in the circuit, Equation (1):
DU  Rk
Ri ¼
Uk

can be used to calculate Ri, where Uk is the steady voltage value established after
switching in the resistor Rk. The average of three DU=Uk data pairs was used in every
case. Values in the range of 40.9 MX=mm were found for the resistance Ri, and they
depended on the tip diameter of the electrode. As it was observed earlier with pot-
assium (Gyetvai et al. 2009) and ammonium (Gyetvai et al. 2007) micropipettes,
the resistance of the solid contact micropipettes were just a fraction of those
exhibited by micropipettes of the same size fabricated using the ‘‘conventional’’ pro-
cedures. In this work, the new Zn ion selective electrodes were fabricated using the
optimized design for minimum internal resistance developed in the authors’ previous
work (Gyetvai et al. 2007).
Figure 2 shows a typical recording obtained during the resistance measure-
ments for an ISE electrode presenting a tip diameter of about 3 mm. When the
resistor was connected in parallel to the cell, it is indicated by ‘‘on’’ in the figure,
whereas the instant when it was disconnected has been indicated by ‘‘off.’’ The shape
of the curve corresponds to the initial purely resistive response of the system,
whereas a non-linear behavior is observed from the transport characteristics of the
membrane when the external resistor was switched off. This behavior was also
observed for the potassium (Gyetvai et al. 2009) and ammonium (Gyetvai et al.
2007) selective electrodes and corresponds to one of the two situations described
in the pioneer work by Amman et al. (1985).
The concentration dependence of the electrode potential was checked using
solutions of varying concentration. The obtained calibration curve is shown in
 2882 Á. VARGA ET AL.
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Figure 2. Cell voltage vs. time recording obtained during the measurement of the electrode resistance.

Figure 3. As it can be seen, the response exhibits close Nernstian slope in the concen-
tration range of 10
4 to 10
1 M. In order to investigate the potential stability of the
zinc micropipettes, the freshly made electrodes were inserted in the measurement cell
containing 0.1 M tris(hydroxymethyl)aminomethane buffer with the different zinc
ion concentrations. By monitoring the cell potential, the electric noise sensitivity
and the potential stability were also observed. When the measurements were made
outside the Faraday cage, the electric noise sensitivity was checked. The drift was
then determined as the slope DE=Dt of the electrode potential-time dependence.
Usually a 0.05–0.08 mV=min drift was observed for the freshly prepared electrodes

Figure 3. Plot of the electrode potential vs. log zinc concentration obtained with a solid contact zinc ion
selective electrode (electrode tip diameter 7 mm, slope in the 10
4 to 10
1 range is 27.7 mV=decade).
 SOLID CONTACT MICROPIPETTE ION SELECTIVE ELECTRODE 2883

when measured after a few minutes of their introduction in the solutions for zinc
concentrations between 0.1–10 mM.
The applicability of the zinc micropipettes in SECM studies was checked after
a small size zinc ion source was prepared and introduced through a hole in the bot-
tom of the SECM measurement cell. This was prepared from a glass micropipette,
the tip of which was blocked by an agar gel plug. The pipette was filled with
0.1 M ZnSO4 solution and the measuring cell was filled with a 0.1 M KCl supporting
electrolyte solution. The zinc ion selective tip was moved upward and downward in
relation to the investigated sample and also parallel to the surface both above and in
the vicinity of the diffusion zinc source. In this way, the local electrode potential
values were recorded at different locations. The variation of the electrode potential
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with the tip-substrate distance recorded above the center of the source in case of tip
traveling in vertical direction can be seen in Figure 4. At 0 mm distance the tip almost
touched the source plug. Calibration curve was used for transforming the electrode
potential readings to concentration values. The corresponding zinc ion concentration
vs. distance plot is depicted in Figure 4 as well.
Analogously, Figure 5 shows the electrode potential recorded when an ISE tip
(about 7 mm diameter) was scanned at the constant height of 150 mm above a 50 mm
diameter source disc acting as the source for zinc ions. Though the potential curve
shows some broadening beyond the limits of the ion source due to the smaller size
of the probe compared to the active area of the metal, the actual location of the
source is satisfactorily imaged, and it is sensed at the rather large distance between
the measuring tip and the surface employed.
The low resistance ion selective measuring tip was developed for application in
corrosion studies. Currently, experiments are in progress concerning the investi-
gation of the galvanic corrosion of iron and zinc samples immersed in different ionic
media. In those studies SECM images are recorded over electrically connected as

Figure 4. Effect of the tip-substrate distance on the electrode potential and the corresponding Zn ion
concentration when a zinc ion selective measuring tip (diameter 7 mm) was scanned above the center of
a disc-shaped diffusing zinc source.
 2884 Á. VARGA ET AL.
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Figure 5. Electrode potential versus lateral distance plot recorded with a zinc ion selective measuring tip
(diameter 7 mm) scanned over a disc shaped diffusion zinc source of 50–100 mm. Scan rate: 5 mm=s. (Figure
available in color online.)

well as insulated iron and zinc surfaces. A one-dimension zinc electrode potential-
horizontal distance image is shown in Figure 6. This curve was recorded when the
electrode was scanned over a flat surface containing a small size zinc disc in direct
electric contact with an iron surface disc, both inserted in an epoxy resin holder.
Electric contact was established at the back of the sample. The detection of Zn ionic
species is clearly detected when the ISE tip passed above the zinc disc, whereas no
signal could be measured either above the surrounding epoxy resin or the iron disc.
The relevance of this observation toward further use of SECM in corrosion investi-
gations can be understood when it is considered that previous studies, based on the
amperometric operation of the SECM, only allowed for the detection of the cathodic

Figure 6. Horizontal line scan displaying the variation of the zinc concentration obtained by evaluating
electrode potential values measured at the ISE tip when travelling above an Fe-Zn galvanic couple
immersed in 0.1 M KCl. Scan rate: 5 mm=s.
 SOLID CONTACT MICROPIPETTE ION SELECTIVE ELECTRODE 2885

half reaction occurring over the iron sample measured as the local depletion of
dissolved oxygen in the vicinity of the metal (Simões et al. 2007).

CONCLUSION
Low resistance zinc ion selective micropipette electrodes were prepared for
corrosion studies. The electrodes contain electrochemically prepared PEDOT con-
ductive polymer coated carbon fiber as solid contact. Using this design the electrode
resistance could be significantly lowered, which allows faster scanning rates to be
used in SECM applications. From the previous experience gained with similar pot-
assium and ammonium selective electrodes it is expected that the operation and stor-
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age stability of these newly developed zinc electrodes will be much higher than that
of the ‘‘conventional’’ micropipettes. These electrodes can be prepared with tip sizes
of a few micrometers. The preliminary results obtained in studying their analytical
properties and their use as probes in potentiometric SECM operation proved their
applicability.

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