Surface & Coatings Technology 397 (2020) 126060

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Surface & Coatings Technology

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Electropolishing of two kinds of bronze in a deep eutectic solvent (Ethaline) T

a,⁎ a a b b c
A.A. Kityk , F.I. Danilov , V.S. Protsenko , V. Pavlik , M. Boča , Y. Halahovets
a
Ukrainian State University of Chemical Technology, Gagarin St., 8, Dnipro 49005, Ukraine
b
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská St., 9, 845 36 Bratislava 45, Slovak Republic
c
Institute of Physics, Slovak Academy of Sciences, Dúbravská St., 9, 845 11 Bratislava 45, Slovak Republic

ARTICLE INFO ABSTRACT

Keywords: Electropolishing of bronze was investigated in this work in an electrolyte based on a deep eutectic solvent,
Deep eutectic solvent Ethaline (a eutectic mixture of choline chloride and ethylene glycol in a 1:2 M ratio, respectively). Two kinds of
Anodic treatment bronzes were used: AMPCO® 22 alloy (containing Al and Fe as alloying components) and AMPCO® 712 alloy
Bronze (containing Sn, Ni, Pb and Zn as alloying components). Electrochemical responses of bronze in Ethaline were
Surface roughness
studied by cyclic voltammetry technique. It was established that the electropolishing of both bronzes can be
Corrosion resistance
performed at the temperature of 25 °C and anode electrode potential of 2.5 V (vs. Ag pseudo-reference elec-
trode). The surface leveling and dissolution of microdefects were confirmed by atomic force microscopy and
scanning electron microscopy. The electrochemical polishing of the surfaces of AMPCO® 22 and AMPCO® 712
bronzes was shown to result in an improvement in their corrosion resistance. Electrolytes based on deep eutectic
solvents seem to be a promising replacement for traditional corrosive and environmentally hazardous acid
aqueous solutions for electropolishing of copper alloys.

1. Introduction It should be noted that electropolishing of copper and Cu-based

alloys has been studied > 80 years [2,3], but still the most common
The industrial importance of copper in 21st century has been ex- electrolytes imply the use of highly concentrated H3PO4 solutions
tended by the ease with which it combines with other metals. Tin and [4–15]. For a long time, all modifications of the electrolytes and elec-
zinc are and always have been the principal alloying elements, but tropolishing procedures just came to the attempts to select some new
many others, such as aluminium, nickel, chromium, cadmium, etc., additives (predominantly organic surfactants) and optimize operating
form alloys with copper yielding unique combinations of mechanical conditions. It was observed in the above previous works that high
properties and good corrosion and wear resistances. These attributes concentrations of an acid in the electrolyte and the presence of some
have contributed towards copper and its alloys being the materials of additives ensure the formation of a viscous layer near the electrode
choice for building construction (e.g., plumbing, wiring and roofing), surface consisting of the products of anodic reaction. This provides a
but have also led to the use in many demanding engineering applica- diffusion control of a polishing process and results in a surface leveling.
tions in the marine, automotive, chemical, and electronics industries As recently became known, electropolishing of different metals and
[1]. However, the excellent results of using copper and its alloys in alloys can be successfully performed using a new type of ionic liquids,
various industries is mainly determined by surface quality and therefore the so-called deep eutectic solvents (DESs), as an alternative to con-
by preliminary preparation of the surface of these materials. During ventional aqueous electrolytes [16–28]. The deep eutectic solvents
fabrication, copper alloys may become coated with lubricating oils, demonstrate definite advantages over both common organic solvents
drawing compounds, dirt, oxides, metallic particles, etc., which must be and aqueous solutions with respect to their potential industrial appli-
removed by mechanical, chemical, chemical-mechanical or electro- cation. For instance, DESs are characterized by the availability of
chemical cleaning (polishing). Chemical and chemical-mechanical electrolyte components, ease of synthesis, thermal and chemical stabi-
polishing imparts a finish similar to that obtained by electropolishing, lity, low saturated vapor pressure (which ensures safe working condi-
but electropolished surfaces are usually smother and brighter. More- tions), low corrosivity towards the equipment, biodegradability and the
over, electropolishing is a much simpler process, which can be per- possibility of recycling (extraction of unwanted components and reuse)
formed on large surface areas. [16–18].

⁎
Corresponding author.
E-mail address: [email protected] (A.A. Kityk).

https://doi.org/10.1016/j.surfcoat.2020.126060
Received 6 May 2020; Received in revised form 8 June 2020; Accepted 9 June 2020
Available online 11 June 2020
0257-8972/ © 2020 Elsevier B.V. All rights reserved.
A.A. Kityk, et al. Surface & Coatings Technology 397 (2020) 126060

It was shown that deep eutectic solvents due to the unique combi-
nation of physicochemical properties and environmental safety can be
widely used as a medium for electrodeposition of different metals, al-
loys and composite coatings [29–34]. The possibility of efficient elec-
trodeposition of metals and alloys from DESs can be considered as the
basis for the future purification of electrolytes after electropolishing
and the possibility of their reuse.
It is worth-mentioning that a relatively high viscosity of DESs and
slow diffusion in them are the main prerequisites for the formation of a
viscous layer and the implementation of electropolishing process under
diffusion control. It's well known, that implementation of electro-
polishing under diffusion control provides an excellent result of leveling
and brightening the surface. Earlier, DESs-based electrolytes were used
for electropolishing of various steels [19–21], Ag [22], Ni and Co
[23,24], and Al [25]. To the best of our knowledge, only few works
have dealt with anodic processing of pure copper and CueSn alloy in
DESs [26,35,36] and no papers have reported the electropolishing of
bronzes with Al, Fe, Ni, Pb, Zn alloying elements.
In order to develop novel and high-efficient procedure for the
electropolishing of some bronzes, we considered in the present study
the use of a deep eutectic solvent, Ethaline, for the electrochemical
polishing of two types of commercial bronzes: bronze AMPCO® 22 (it
contains Al and Fe as alloying components) and AMPCO® 712 (it con-
tains Sn, Ni, Pb and Zn as alloying components). We revealed the fea-
tures of electrodissolution processes and the effects of the electro-
polishing on surface morphology and topography, surface composition
and anticorrosive properties of two kinds of bronzes under considera-
tion.

2. Materials and methods

Ethaline was prepared by mixing choline chloride (Sigma-Aldrich,

≈99%) and ethylene glycol (Sigma-Aldrich, ≈99.5%) in a 1:2 M ratio,
respectively. This eutectic mixture was heated and stirred at around
70 °C until a homogeneous and colorless liquid had formed. As pre-
viously shown [37–39], it is very important to prevent prolonged
contact of Ethaline with air, which may result in water absorption and Fig. 1. Cyclic voltammograms of AMPCO® 22 (a) and AMPCO® 712 (b) bronze
unwanted changes in electrolyte composition. Therefore, Ethaline after samples recorded in Ethaline at the scan rate of 5 mV s−1 and the temperature
preparation and between uses was stored in a closed desiccator. The of 25 °C.
content of absorbed moisture was controlled by the Fischer method
before all experiments; the content of hygroscopic water did not exceed
implemented by means of a built-in compensator of the potentiostat.
1 wt%.
In order to determine the main corrosion characteristics of bronzes
The working electrodes (bronze AMPCO® 22 and AMPCO® 712)
in 10 wt% NaCl solution, linear polarization resistance (LPR) method
were produced by AMPCO METAL S.A. (Switzerland). The alloys
was used. LPR measurements were conducted using a common three-
compositions are presented in Table 1. Prior to the electrochemical
electrode cell and the same potentiostat. In the study of corrosion be-
measurements, the surface of electrodes was polished mechanically
havior, the bronze samples AMPCO® 22 and AMPCO® 712 (electro-
using magnesium oxide, then etched in HCl solution (1:1) for 30 s,
polished and untreated) were working electrodes, a saturated silver
thoroughly rinsed with distillate water and finally dried in hot air flow.
chloride electrode was a pseudo-reference electrode and platinum grid
All electrochemical measurements were carried out in a thermo-
served as a counter electrode. The LPR was measured at the scan rate of
stated (25 °C) three-electrode glass cell using potentiostat Metrohm
1 mV s−1 and the temperature of 25 °C.
Autolab PGSTAT302N (Netherlands) controlled by a personal computer
To characterize the electrode surface, the atomic-force microscopy
with Autolab NOVA software. To study the electropolishing process,
(AFM) (Bruker, Dimension Edge) was applied. AFM investigations were
bronze samples were used as working electrodes, platinum grid was
performed in tapping mode using etched silicon probes (Bruker, RTESPA-
served as an auxiliary electrode and silver wire was used as a pseudo-
300). Root mean squared roughness (Rq) was calculated from AFM data.
reference electrode. The scan rate was equal to 5 mV s−1. In all elec-
Eq. (1) used for calculation of the roughness parameter (Rq) implies that
trochemical measurements, an automated IR-compensation was
the roughness profile has been filtered from the raw profile data and the
mean line has been calculated. The roughness profile contains n ordered,
Table 1
equally spaced points along the trace, and yi is the vertical distance from
Chemical composition of AMPCO bronzes according to the materials quality
the mean line to the ith data point. Height is assumed to be positive in the
certificate.
up direction, away from the bulk material [40].
Bronze Element content (wt%)
n
1
Cu Al Sn Fe Ni Pb Zn Rq = × yi2
n i=1 (1)
AMPCO® 22 The remainder 14.1 – 4.7 – – –
AMPCO® 712 The remainder – 12 – ≤2 ≤1 ≤1 The surface morphology of the samples before and after electro-
chemical treatment was estimated by scanning electron microscopy

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A.A. Kityk, et al. Surface & Coatings Technology 397 (2020) 126060

Fig. 2. SEM images of AMPCO® 22 (a and b) and AMPCO® 712 (c and d) bronze samples before (a and c) and after (b and d) electropolishing in Ethaline.
Electropolishing was performed at the electrode potential of +2.5 V, the temperature of 25 °C and the duration of 20 min.

(Zeiss EVO 40XVP). The chemical composition of the surface was es- dissolution as in the case of electropolishing of Cu and Cu-based alloys
timated by energy dispersive X-ray spectroscopy (EDX, calibrated with in H3PO4 solutions [4].
respect to Cu) coupled with SEM microscope (Oxford INCA Energy On the contrary, there is only one peak of anodic dissolution in the
350). anodic region of the CV corresponding to the AMPCO® 712 sample (at
The bronze samples after electropolishing in Ethaline and before about +0.45 V). Also, a current plateau can be observed in voltam-
further testing (SEM, AFM, EDX, and LPR) were thoroughly washed metry curve. Let us note that CV for AMPCO® 712 bronze looks very
with bidistilled water and then dried in air flow. similar to those which were reported for electropolishing of Cu and Cu-
All quantitative results were taken as an average of five parallel based alloys in concentrated acidic solutions [4–7].
measurements. We suppose that the first dissolution peak for AMPCO® 22 (at about
+0.45 V) and the sole anodic peak for AMPCO® 712 (at the same
3. Results and discussion electrode potentials) can be mainly associated with electrochemical
dissolution of Cu [26]. Abbot et al. [41] showed that an initial as-
3.1. Electrochemical study cending section of the polarization curve of Cu-electrode dissolution in
Ethaline is most likely due to the formation of a CuI species, e.g.
Cyclic voltammograms (CVs) of AMPCO® 22 and AMPCO® 712 [CuCl2]−. In such a case, the near-electrode layer becomes enriched in
bronze samples in Ethaline are shown in Fig. 1. The voltammetric CuI species, which has a low solubility as compared with CuII in this
curves were recorded starting from the open circuit potential (−0.25 V solvent [42]. This can provide the formation of a porous layer of in-
vs. pseudo-reference Ag-wire electrode) in the anodic direction. After soluble dissolution products in this potential region. It was also de-
achieving the potential of +4 V, the sweep was reversed into the monstrated [43] that the CuI/II redox couple in Ethaline appears at
cathodic direction (up to –0.75 V). Finally, the potential sweep was +0.45 V. Thus, the first dissolution current peak for alloys AMPCO® 22
once again reversed to return the initial value of the open circuit po- and AMPCO® 712 corresponds to the dissolution of copper that yields
tential. the accumulation of CuI ions in the near-electrode layer and a further
As can be seen from Fig. 1, the voltammograms of these two kinds of formation of CuII species. Taking into account the high content of Cl−
bronze exhibit significant differences. Two anodic dissolution peaks are anions in Ethaline, it can be assumed the formation of [CuCl4]2−
observed for AMPCO® 22 bronze at ~0.45 V and ~1.2 V. At higher complexes under these conditions. Earlier by using UV–vis. analysis and
anodic potentials, the CV curve shows a current plateau, which can be EXAFS methods, Karim et al. [36] established that the dissolution of
attributed to a diffusion-controlled process of electrochemical copper in Ethaline occurs with formation of [CuCl4]2− complex ions.

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(caption on next page)

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A.A. Kityk, et al. Surface & Coatings Technology 397 (2020) 126060

Fig. 3. EDX analysis of surface elemental compositions of AMPCO® 22 bronze (a) and AMPCO® 712 bronze (b) before (1) and after electropolishing in Ethaline (2).
Electropolishing was performed at the electrode potential of +2.5 V, the temperature of 25 °C and the duration of 20 min.

Table 2 plateau was chosen for electropolishing of bronze AMPCO® 22 and

The surface chemical composition of AMPCO® 22 bronze before and after AMPCO® 712 in all further experiments.
electropolishing in Ethaline according to the results of EDX analysis.
State of the sample Element content (wt%) 3.2. SEM, EDX and AFM studies
Cu Al Fe C O
The results of SEM analysis (Fig. 2) showed that the anodic po-
Unpolished 72.41 10.05 4.21 3.51 9.82 tentiostatic treatment of both kinds of bronze leads to a noticeable le-
Electropolished 81.87 8.97 4.23 2.51 2.42 veling of the surfaces: the amount of surface defects noticeably de-
creases, deep scratches of the rolling disappear, and the surface
morphology becomes smoother and more uniform.
Table 3
Results of EDX analysis of surface elemental composition of bronze
The surface chemical composition of AMPCO® 712 bronze before and after
samples before and after electropolishing treatment are shown in Fig. 3
electropolishing in Ethaline according to the results of EDX analysis.
and Tables 2 and 3. The differences between chemical compositions
State of the sample Element content (wt%) given in materials quality certificate (Table 1) and determined by EDX
analysis (Tables 2 and 3) are naturally due to the fact that EDX method
Cu Sn Zn Ni Pb O
yields the content of chemical elements in a surface layer where some
Unpolished 81.83 12.35 1.49 1.39 0.52 2.42 oxide films can be formed.
Electropolished 83.04 8.58 1.65 1.58 0.56 4.59 It is clearly seen that electropolishing affects chemical composition
of the surface of bronze samples. An appreciably reduced content of
aluminium in AMPCO® 22 bronze before anodic treatment as compared
with the value given in material certificate (Table 1) is probably due to
The emergence of the peak of current of Cu dissolution and a current the surface oxidation of this electronegative components induced by
plateau at higher electrode potentials can be explained by the slow contact with atmospheric oxygen. Electropolishing of AMPCO® 22
diffusion and the limited solubility of the products of the electro- bronze results in a decrease in the surface content of Al and O which
chemical reaction, which can lead to the formation of a viscous layer indicates a partial removal of aluminium oxide from the surface. Elec-
near the surface of the electrode. tropolishing treatment of AMPCO® 22 bronze also causes a decrease in
We think that the anodic peak at about +0.45 V for AMPCO® 712 carbon content and enrichment of a surface layer with copper, the
bronze corresponds not only to the electrochemical dissolution of surface content of iron being practically unchanged.
copper as a main and dominant component of the alloy, but also to the On the contrary, electropolishing of AMPCO® 712 bronze in
dissolution of tin component. Seemingly, anodic oxidation of metallic Ethaline leads to some accumulation of Zn, Ni and Pb in a surface layer.
copper and tin occurs practically at the same potential region. Copper Apparently, these components are present on the surface in the form of
and tin are anodically dissolved as a single phase [4], thereby yielding a respective oxides, therefore the content of oxygen also increases after
sole anodic current peak. anodic treatment. A leaching of Sn is also observed after electro-
As far as the second anodic dissolution peak for AMPCO® 22 bronze polishing of AMPCO® 712 bronze. Similarly to AMPCO® 22 bronze,
is concerned, Abbot et al. showed [35] that this potential region electropolishing of AMPCO® 712 alloy causes an increase in the content
(~1.2 V) can be associated with an electrochemical reaction of dis- of copper in a surface layer.
solution of iron: Fe0 → Fe2++2e−. Considering a high concentration of The AFM method was applied to characterize the changes in surface
chloride anions in the solution, we can assume that the formation of topography and estimate the surface roughness of bronze samples
[FeCl4]2− complexes occurs in this segment of CV. It should be noted under consideration subjected to electrochemical polishing in Ethaline.
that a contact with atmospheric oxygen with time can cause a chemical AFM images clearly showed (Fig. 4) that the surface defects, including
oxidation of [FeCl4]2− yielding more stable complexes [FeCl4]−. traces of shaping and scratches, of the unpolished bronze AMPCO® 22
It should be noted that there is an appreciable difference in the and AMPCO® 712 disappeared after anodic treatment. Thus, an ap-
values of plateau currents for these two kinds of bronze. The plateau preciable surface leveling is observed. The calculated values of Rq
current of AMPCO® 712 bronze is much higher than that of AMPCO® 22 parameter confirm this conclusion: Rq diminishes substantially after
bronze. This can be explained by a possible dissolution of other alloying electropolishing in Ethaline both for AMPCO® 22 and AMPCO® 712
elements of AMPCO® 712 alloy. The AMPCO® 22 bronze contains a bronzes (Table 4). This indicates a decrease in surface roughness.
noticeable amount of aluminium (Table 1), the electrochemical dis- Changes in surface appearance seen by the naked eye were also
solution of which in Ethaline starts at the electrode potentials of above detected: the surface of both kinds of bronze became bright and uni-
2 V [25]. Thus, the total current of the electrode processes corre- form after anodic treatment (see Graphical abstract). Hence, the elec-
sponding to the plateau region of CV includes also the fraction of anodic tropolishing of the surfaces of AMPCO® 22 and AMPCO® 712 bronzes
dissolution of aluminium. can be successfully performed in environmentally safe electrolyte based
To complete the discussion of the recorded CVs, it should be ob- on a deep eutectic solvent (Ethaline).
served that their cathodic regions (Fig. 1) can be attributed to the The effectiveness of electropolishing should be evaluated in terms of
electroreduction of the products which were formed during anodic comparison of the roughness coefficients (Rq) for the untreated and
potential scan. The cathodic current peak at about −0.1…–0.2 V for electropolished states of the surface. In our case, the surfaces of
both alloys may correspond to the reaction Cu2++2e− → Cu0. The unpolished commercial bronzes were initially rough enough (Table 4),
cathodic current peak at about 0.9 V for AMPCO® 22 bronze can be however the polishing procedure ensured a noticeable decrease in
associated with the reaction Fe2++2e− → Fe0. roughness: the surface roughness diminished by about 60% and almost
It is known that the surface leveling in electropolishing processes is 80% as compared with the initial value for AMPCO® 712 and AMPCO®
achieved when an electrochemical dissolution of metal is governed by a 22 bronzes, respectively. Such results are not only comparable, but also
slow mass transfer (in other words, under diffusion control) [44,45]. even superior to those reported earlier for many acidic water electro-
According to this, a potential of +2.5 V on the middle of current lytes [8,9,11].

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Fig. 4. AFM images of the surface of AMPCO® 22 (a and b) and AMPCO® 712 (c and d) bronze samples before (a and c) and after (b and d) electropolishing in
Ethaline. Electropolishing was performed at the electrode potential of +2.5 V, the temperature of 25 °C and the duration of 20 min.
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Table 4 3.3. Effect of electropolishing on corrosion resistance

Calculated values of surface roughness (Rq) determined by AFM analysis.
Bronze Rq (nm) Earlier, it was reported [25,46] that electrochemical polishing by
using DES-based electrolyte allows favorably affecting various proper-
Before electropolishing After electropolishing ties of metal surfaces, including corrosion resistance. It is interesting to
estimate how the electropolishing of AMPCO® 22 and AMPCO® 712
AMPCO® 22 626.8 135.3
AMPCO® 712 454.0 179.4 bronzes influences their corrosion behavior. To this end, electro-
chemical characteristics of unpolished and polished samples in 10 wt%
NaCl water solution were investigated.
The measurements of the open circuit potentials (OCPs) for unpol-
ished and electropolished bronze samples in 10 wt% NaCl showed that
electrochemical surface treatment in Ethaline contributes to the shift of
the OCPs towards more positive potentials for both kinds of bronze
samples under consideration. For bronze AMPCO® 22, the OCP shifted
from −320 mV (unpolished sample) to −240 mV (electropolished
sample). Similarly, for bronze AMPCO® 712, the OCP shifted from
−230 mV (unpolished sample) to −210 mV (electropolished sample).
It is usually thought that the shift of the OCP to the region of more
positive values indicates an increase in the corrosion resistance. It
should also be noted that the OCPs for all bronze samples quickly
reached (during few seconds) a certain constant value and then re-
mained unchanged.
The LPR measurements showed that the electrochemical anodic
treatment of both kinds of bronzes in Ethaline leads to a noticeable shift
of all segments of polarization curves (including Tafel regions) towards
more positive values of electrode potential (Fig. 5). Parameters char-
acterizing corrosion process were calculated from the recorded vol-
tammetric curves (Table 5). It can be seen that the electrochemical
polishing causes both an increase in the value of corrosion potential
(Ecorr) and a decrease in both the corrosion current density (icorr) and the
corrosion rate (CR). Reduction of corrosion rate after anodic electro-
polishing in Ethaline may be due to the influence of few factors: a
change in surface composition, a decrease in the amount of surface
defects and the reduction of effective surface area resulted from the
surface smoothing.
Table 5 also presents Tafel slopes, |ba| and |bc|, which can be used
to characterize the corrosion surface properties of bronzes samples
before and after electrochemical processing. The values of Tafel slopes
for the anodic and cathodic reactions were determined from the Tafel
regions in the obtained polarization curves (Fig. 5). It is well known
that the coefficients |ba| and |bc| depend not only on the nature of the
metal or alloy, but also on the state of their surfaces. Commonly, the
constant ba, that directly characterizes the kinetics of anodic metal
dissolution in a corrosion process, decreases when the surface becomes
rougher or partially coated with some passivating layers. In our case
(Table 5), the electropolishing of both AMPCO® 22 and AMPCO® 712
alloys leads to an increase in the parameter ba, which may be due to
Fig. 5. Polarization curves characterizing corrosion behavior of unpolished (1) both a decrease in roughness and the removal of oxide layers on the
and electropolished (2) AMPCO® 22 (a) and AMPCO® 712 (b) bronze samples polished surface of the Cu-based alloys.
recorded in 10 wt% NaCl water solution at 25 °C. Electropolishing of the
bronzes was performed in Ethaline at the electrode potential of +2.5 V, the 4. Conclusions
temperature of 25 °C and the duration of 20 min.
The possibility of using a deep eutectic solvent, Ethaline, for

Table 5
Corrosion parameters of AMPCO® 22 and AMPCO® 712 bronzes in 10 wt% NaCl solution calculated from polarization measurements.
Alloy Corrosion parameter

Ecorr (V) |ba| (V dec−1) |bc| (V dec−1) icorr (A cm−2) CR (mm year−1)

AMPCO® 22 Unpolished −0.304 0.064 0.134 1.176 × 10−5 0.1635

Electropolished −0.241 0.067 0.137 8.447 × 10−6 0.1174
AMPCO® 712 Unpolished −0.226 0.051 0.076 1.396 × 10−5 0.1699
Electropolished −0.204 0.061 0.131 1.295 × 10−5 0.1576

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