Applied Surface Science 256 (2010) 4370–4375

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Removal of tarnishing and roughness of copper surface

by electropolishing treatment
A.M. Awad a,∗ , N.A. Abdel Ghany b , T.M. Dahy c
a
Chemical Engineering and Pilot Plant Dept., National Research Centre, Dokki, Giza, Egypt
b
Physical Chemistry Dept., National Research Centre, Dokki, Giza, Egypt
c
Electron Microscope and Thin Films Dept., National Research Centre, Dokki, Giza, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Tarnishing and roughness of copper surface can be removed by electropolishing treatment (EP) imparting
Received 14 September 2009 a bright and smooth surface at suitable conditions, e.g. current density, time, temperature, and viscosity.
Received in revised form 9 February 2010 It was carried out by using an electrolytic cell containing phosphoric acid 55% as the electrolytic solution.
Accepted 9 February 2010
Both copper working electrode and lead counter electrode, and reference electrode (SCE) were connected
Available online 16 February 2010
to a Potentiostat/Galvanostat to allow an electric current to pass through the solution. Some additives
such as soluble starch, ethylene glycol, and methanol were added to reduce defects formed on the copper
Keywords:
surface during EP process. The results showed that the highest gloss value was obtained by applying
Electropolishing
Anodic oxidation
electric potential 1.5 V at the passive region of polarization curve. The surface was investigated after EP
Tarnishing treatment, where SEM and EDX showed lower roughness in case of addition of both soluble starch and
Brightness ethylene glycol more than methanol. Moreover, AFM analysis showed the lowest roughness in case of
Roughness soluble starch more than other additives.
Leveling © 2010 Elsevier B.V. All rights reserved.

1. Introduction Electropolishing technique (EP) is a highly efficient method for

Chemical, physical and mechanical properties of copper make it
the world third most widely used metal after iron and aluminum. It
is used in very essential fields such as electrical applications, build-
ing construction, industrial machinery, equipment, transportation,
and consumer products [1].
Copper surface seems rough and complex under microscopic
investigation, due to the presence of macro and micro scales of
humps and depressions. The enhancement of surface smoothness
requires removal of more than one micron of scratches (level-
ing), while production of both smooth and bright surface requires
removal of less than one micron of scratches, and then, a highly
reflective surface is obtained [2].
Rough surface including humps and depressions allow contami-
nants to be formed as traces of micro grams imparting a tarnish and
matt appearance. Natural deposits lead to the tarnishing of copper
surface, particularly, metal sulfide and carbonyl sulfide. Tarnishing
of copper is formed by chemical reactions or adsorption of the envi-
ronmental contaminations. It is highly influenced by the location
of copper sheets and the environment, where the regions of sev-
eral factories or crowded with transportation tools showed more
tarnishing [3,4].
∗ Corresponding author. Tel.: +20 238951623; fax: +20 233370931.
E-mail address: awadx1@yahoo.com (A.M. Awad).
cleaning and brightening of metals and alloys. It has received much
attention due to its practical and academic interests, some work-
ers tried to attain bright and smooth surface of copper, aluminum,
stainless steel, and other alloys by applying EP method [5–8].
For instance, Edson studied the brightening of copper, silver and
gold by using an electrolytic solution composed mainly of thiourea
and some additives such as polysaccharides as reducing materials
and mineral acids as conductivity improvers. Also, Mayer explained
the necessity to separate between anode and cathode by non-
conductive slit to prevent the gas bubbles transfer to the anode
surface and enhance the homogeneous distribution of electric cur-
rent [9,10].
The process is diffusion controlled, depending on the concen-
tration gradient forming a selective electrochemical dissolution
and improving planarization efficiency of Cu surface, where the
down and up thickness differences are eliminated [11,12]. It typi-
cally occurs at the mass transfer limiting current at highly anodic
potentials, where the metal surface is smoothed out. Simultane-
ously, during EP process, some defects and pitting over the surface
can be formed due to high evolution of oxygen gases adjacent to
the surface at higher electric potential [13–15].
The limiting current value that determines the polishing effi-
ciency depends on the rate of mass transfer of Cu2+ ions from the
diffusion layer to the bulk of the solution. The rate of mass transfer
depends on the relative ionic movement, geometry of the anode,
temperature, the type and physical properties of the electrolyte.

0169-4332/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2010.02.033
 A.M. Awad et al. / Applied Surface Science 256 (2010) 4370–4375
Fig. 1. A schematic diagram of experimental set up (1) working electrode, (2)
counter electrode, (3) reference electrode (SCE), (4) electrolytic solution + additives,
(5) glass electrolytic cell, (6) Potentiostat/Galvanostat, (7) magnetic stirrer and (8)
magnet.
Additionally, others studied using of different concentrations of
acids such as phosphoric acid, sulfuric acid, acetic acids, and citric
acid to maintain the best mixture ratio achieving a highly lustrous
and smooth surface [16,17].
The novelty of the present work is to eliminate the tarnishing
layer covering copper surface. Also, the attempts are extended to
reduce the roughness of the surface by reducing etched pits and
defects formed over the surface, consequently, the surface smooth-
ness and brightness could be increased. To prevent the severely
etched pits on the polished surface, some additives were added to
overcome the oxygen evolution adjacent to the anode during EP
treatment.
2. Experimental
2.1. Materials and apparatus
Copper sheet 99.99% distorted by a tarnish layer was cut into
small samples with a dimension 4 cm × 2.5 cm and each sample
was degreased before treatment by rinsing with acetone, tap water,
then distilled water.
The experimental work was carried out in two stages: (a)
Two electrodes system, where sample was fixed as working
electrode and lead plate as counter electrode into a glass cell
15 cm × 7.5 cm × 8 cm using GW Lab DC Power Supply GPR-3030.
In this system, the effect of different additives was studied at
the same conditions by measuring gloss values and surface anal-
ysis. (b) Three electrodes system, where in addition to the above
system, saturated calomel electrode (SCE) was used as reference
electrode. Each electrode was fixed well into the same glass cell
and connected to EG&G Potentiostat/Galvanostat (Applied Prince-
ton Research) Model 273A, driven by software M352/252 Corrosion
as shown in Fig. 1. In this system, the relation between electric
potential and current density was studied and represented by the
polarization curve.
Fig. 2. Flow chart shows the sequence steps of EP process.
4371
Fig. 3. Effect of applied electric potential on both current density and measured
gloss value (G) of copper samples at constant time (10 min), concentration (55%),
and temperature (25 ◦ C).
Electrolytic solution was prepared using 55% H3 PO4 and
some additives were added such as E1: prepared solu-
ble starch solution 5% (w/v) (R&D use), E2: ethylene glycol
extra pure (1.11 g/ml), and E3: methanol 99.8% (0.79 g/ml).
Viscosity of each type of electrolytes was measured at
constant 100 rpm and 20 ◦ C by using BROOCKFIELD Model
DV.II + Viscometer.
A magnetic stirrer (PMC-BARNSTEAD/THERMOLYNE-USA) was
used for agitation of the electrolytic solution, where the electrolytic
solution was mixed well for 5 min to have a homogenous solution,
and then agitation was stopped before starting EP in a stagnant
solution.
Copper sample was taken out, and rinsed with tap water then
distilled water. All the samples were dried at 105 ◦ C for 15 min,
then the average of gloss value (G) of the surface (five positions)
was measured after 10 min ( G/i, i = 5).
All samples were stored well in a desiccator from 1 to 15 days
before the surface analysis. Then, they were taken as a group for
the same type of analysis either by EDX, SEM, or AFM to obtain
comparable results.
2.2. Surface characterization
- Brightness of the surface was obtained by measuring gloss value
(G) by using ERICHSEN PICOGLOSS 503 Glossmeter.
- SEM and EDX analysis were measured by using JEOL, JXA-840
A: ELECTRON PROB MICROANALYZER Dimension 3100 Scanning
Probe Microscope (SPM).
- Surface roughness (Ra ) and statistical data were obtained by using
Atomic Force Microscopy (AFM) Model-VEECO.
The flow chart in Fig. 2 shows the different steps of EP process.
4372 A.M. Awad et al. / Applied Surface Science 256 (2010) 4370–4375
Fig. 4. Effect of time on the gloss value of copper samples at different current den-
sities and constant concentration (55%) and temperature (25 ◦ C).
3. Results and discussion
3.1. Effect of operating conditions
Improvement of both brightness and smoothness of copper sur-
face by EP is highly dependent on the applied conditions such
as current density, time, temperature and viscosity of electrolytic
solution.
The effect of applied electric potential on both current den-
sity and brightness (gloss value) of copper samples was studied
at constant time 10 min, concentration of H3 PO4 55%, and tem-
perature 25 ◦ C. As shown in Fig. 3, the measured gloss value of
copper surface after EP process was increased from 600 to 1300
by increasing electric potential from 0.5 to 1.5 V, and the current
density was increased from 5.5 to 12 A/dm2 ; while with continu-
ous increase of electric potential to 2.5 V, the current density was
highly increased to 20 A/dm2 leading to a dramatic decrease of gloss
value (G = 650).
These results indicate that a highly bright and smooth surface
can be obtained at electric potential around 1.5 V, where the region
of polishing conditions is present, but at high potential (E > 1.5 V),
more defects and excess of pitting were formed due to a huge evo-
lution of oxygen bubbles at high current density. As a result of EP
treatment in suitable intervals of applied electric potential, the matt
and rough surface of copper was converted into a highly bright and
smooth one.
One can observe the continuous increase of gloss value with
the increase of duration time of EP at low applied current density
5 A/dm2 as shown in Fig. 4, where gloss value of tarnished surface
was raised from 150 to 775 by increasing time from 5 to 20 min.
This indicates that the applied conditions were in the potential
range of polishing region according to polarization curve, but the
time of treatment is not sufficient. While, at high current density
10 A/dm2 , gloss value was increased rapidly to 1200 after 10 and
15 min, but decreased to 900 after 20 min, this indicates that the
potential exceeded the polishing region to the high irregular disso-
lution (HID) region, where a distortion and roughing of the surface
is predominant.
So, due to these aggressive conditions, the surface was distorted
and roughness was increased leading to worse brightness and lower
gloss value.
Thus, the applied electric potential governs the values of limit-
ing current, where the region according to the polarization curve
determines the efficiency of treatment; consequently it limits the
degree of the surface improvement.
Fig. 5. Polarization curve of the EP treatment of copper in a range from 0 to 1800 mV.
3.2. Mechanism
The mechanism of EP process for different metals and alloys was
investigated by some workers, where they showed that each metal
or alloy has a distinct behavior during EP [18,19].
In the present study during EP of copper under the applied
electric potential, it was observed that a dark layer was firstly
formed over the surface. Then, after a few minutes, it was decom-
posed, where a homogenous and regular removal of dark layer has
occurred, leaving a shiny and smooth surface.
As shown in Fig. 5, the polarization curve tracked EP treatment
of copper with the increase of electric potential passing through
the following steps:
• Activation step (a–b): where the current was sharply increased
due to both anodic oxidation of outer surface and ionization of
water molecules (Eq. (1) and (2)).
Cu → Cu2+ + 2e− (1)
6H2 O → 4H3 O+ + O2 ↑ + 4e− (2)
• Neutralization step (b–c): is characterized by the decrease of cur-
rent and total covering of the surface by oxide/hydroxide film (Eq.
(3)).
Cu2+ + 2OH− → Cu(OH)2 (3)
• Stripping step (c–d): is accompanied by slight increase of elec-
tric current, where a slowly electrochemical decomposition of
oxide/hydroxide film (dark layer) occurred regularly leaving a
bright copper surface (Eq. (4)).
Cu(OH)2 → Cu2+ + 2OH− (4)
• Polishing step (d–e): is characterized by the stability of electric
current and a stagnant plateau due to the presence of two equal
opposite reactions, namely, (a) filling up of the surface cavities
and depressions (Eq. (3)), and (b) decomposition of the surface
humps and peaks accompanying by oxygen gas evolution (Eq.
(4)).
• High dissolution region (e–f): is characterized by an increase of
electric current density where an aggressive oxidation reaction
and high loss of copper surface takes place.
3.3. Surface analysis
For the enhancement of EP applications, some additives were
selected from materials containing poly hydroxyl group, e.g. soluble
starch, bi-hydroxyl group, e.g. ethylene glycol, and mono hydroxyl
group, e.g. methanol. Each type was examined to improve both
brightness and smoothness of copper surface by EP.
 A.M. Awad et al. / Applied Surface Science 256 (2010) 4370–4375 4373

Table 1
Concentrations of different contaminants over copper surface detected by EDX
analysis.

Elements

C O Na Al Si P S Ca Fe Cu Zn

Weight % 44 31 6 1 4 1 2 5 2 48 3
Atomic % 52 27 4 0.6 2 0.4 1 2 0.4 11 1

3.3.1. EDX analysis

EDX analysis of copper surface before EP treatment showed high
tarnishing of copper surface by the deposition of different ions like,
Zn, Na, Fe, K, P, Ca, Mg, Si, Al, sulfur and carbon, Table 1 shows the
Fig. 7. SEM image of copper surfaces. (a) Before EP, (b) after EP with soluble starch
concentration of each element.
added, (c) after EP with ethylene glycol added, (d) after EP with methanol added.
As shown in Fig. 6a, EDX analysis showed that several types
of tarnishing elements were detected over the surface leading
to dense roughness (Ra ), and matt surface with low gloss val-
ues (G ≤ 150, Ra = 117.82 nm). After EP treatments, EDX analysis
revealed the abatement of tarnishing deposits and the presence

Fig. 6. EDX analysis of copper surface. (a) Before EP, (b) after EP with soluble starch added, (c) after EP with ethylene glycol added, (d) after EP with methanol added.
4374 A.M. Awad et al. / Applied Surface Science 256 (2010) 4370–4375

Fig. 8. AFM analysis of copper surfaces. (a) Before EP, (b) after EP without addition, (c) after EP with soluble starch added, (d) after EP with ethylene glycol added, (e) after
EP with methanol added.

only of copper peaks where all peaks of tarnishing materials Table 2

Measured roughness (Ra ) of copper samples.
were totally ceased, imparting a highly bright and smooth surface
(G = 1000, Ra = 21.88 nm). Sample EP conditions Ra (nm) RMS (nm)
These aspects can be clearly observed after EP treatment by a Before EP 118 156
human eyes, where the tarnish layer was totally removed after the b After EP without addition 67 85
regular elimination of the whole humps and homogenous filling of c After EP + SS 22 35
the whole depressions. d After EP + EG 40 50
e After EP + Me OH 61 77
On the other hand, after EP treatment of samples in a bath
composition containing starch and ethylene glycol (Fig. 6b and
c) revealed a highly sharp and height peaks of copper more than The values of roughness indicated that EP of copper surface is
methanol (Fig. 6d). more effective in case of addition of starch more than both ethylene
glycol and methanol.
Moreover, the image statistics showed also, that the root mean
3.3.2. SEM analysis
square (RMS) decreased from 155.6 to 34.49 nm after EP in the case
After EP, the surface was also investigated by SEM to explore
of starch addition.
and compare the development of surface morphology. Fig. 7a–d
These results were ascertained by measuring gloss values of the
shows a comparison between samples before and after EP with the
surface after EP treatment. The increase in gloss value was clearly
addition of starch, ethylene glycol, and methanol, they revealed the
observed, where it was increased to 1150, 900, 700, 600 in case
enhancement of surface uniformity, where small scratches were
of starch, ethylene glycol, methanol and without addition, respec-
eliminated and deep cavities were filled up.
tively.
These results were ascertained by measuring gloss values of the
Furthermore, the conductivity () of electrolytic solution is
surface after EP treatment. The increase of gloss value was clearly
highly influenced by the difference of viscosity () of each type of
observed, where the surface gloss value before EP was ≈150. After
additives according to the equation:
EP by addition of starch, ethylene glycol, and methanol, gloss values
increased to ≈1150, 1000, and 700 respectively. const
=
Specifically, the inspection of SEM images and measurements of 
gloss values after EP treatment showed that the brightness and uni-
The case of starch addition to the electrolytic solution com-
formity of the surface in case of soluble starch addition was better
posed of phosphoric acid (55%, w/w) showed a high viscosity more
than both ethylene glycol and methanol.
than the case of both ethylene glycol and methanol addition, where
the addition of soluble starch leads to the increase in viscosity to
18 mPa s; while the measured viscosity was 8.2, 6.8, and 7 mPa s in
3.3.3. AFM analysis
case of ethylene glycol, methanol addition and without any addi-
Surface topography was investigated after EP treatment by
tion, respectively (Table 3).
Atomic Force Microscope (AFM), it was used to explore the micro
This phenomenon demonstrates the enhancement of smooth-
burrs and scratches of the surface. Also, a comparison of the sur-
ness and brightness of copper surface by addition of soluble starch
face roughness obtained after EP by each type of additives can be
more than ethylene glycol and methanol, where the increase in
elucidated.
As shown in Fig. 8a–e, AFM images of copper surfaces before
and after EP in the absence of additives and in the presence of Table 3
soluble starch, ethylene glycol, and methanol, it revealed that the Effect of additives on the gloss value after electropolishing process.

roughness obviously decreased after EP, where Ra decreased from Sample Electrolyte type Type of additives Viscosity (m Pa s) Gloss value
117.82 nm to 66.49 nm without addition of any materials. Before EP 150
On the other hand, Ra was decreased from 117.82 nm to After EP E No additives 7.0 600
21.88 nm by addition of starch and decreased to 39.71 nm by addi- After EP E1 Soluble starch 18 1150
tion of ethylene glycol, while it was decreased to 76.17 nm by After EP E2 Ethylene glycol 8.2 900
After EP E3 Methanol 6.8 700
addition of methanol (Table 2).
 A.M. Awad et al. / Applied Surface Science 256 (2010) 4370–4375
viscosity of electrolytic solution leads to the increase in electric
resistance to the high velocity of ionic motion through the diffu-
sion layer. Consequently, the aggressive attack of ionic species is
decreased, reducing pitting and defects formed over the surface
and also reducing the oxygen bubbles evolution adjacent to the
copper surface.
Accordingly, the improvement in the surface smoothness and
brightness gave the order of the additive type as:
Soluble starch (SS) > ethylene glycol (EG) > methanol (MeOH).
By investigation of the chemical composition of each type of addi-
tives, one can observe the density difference of the hydroxyl groups
in the chemical structure of each type. Starch contains several
groups and ethylene glycol contains two, while methanol contains
only one hydroxyl group.
According to the results obtained, the addition of soluble starch
to the electrolytic solution improved the level of brightness and
smoothness of the surface more than other additives; the interpre-
tation of that phenomenon may be attributed to:
• Hydroxyl groups reduce the hydrogen embrittlement at the
anode surface.
• High viscosity reduces the electric conductivity and the aggres-
sive attack of ions towards copper electrode.
• High densities of OH− groups reduce the random anodic dissolu-
tion of copper.
• Hydroxyl groups with negative charges reduce the evolution
of oxygen adjacent to the surface of copper during EP treat-
ment which may cause some defects and pitting over the
surface.
• Starch containing high density of OH− groups increases the vis-
cosity of the electrolytic solution, giving the advantage to retard
the aggressive attack of ions and the high dissolution of working
electrode.
So, the tarnishing of copper can be eliminated by EP at
the electric potential 1.5 V in a cell containing H3 PO4 , where
the polishing region is present according to polarization
curve. High brightness and smoothness can be achieved by
using starch or ethylene glycol as additives to the elec-
trolytic solution, while addition of methanol showed lower
effect. This method can be considered as a promised tech-
nique for the improvement of surface morphology of copper
sheets.
4375
4. Conclusion
EP treatment of copper surface is influenced by the applied con-
ditions such as current density, time, temperature and viscosity.
The enhancement of the surface morphology and topography was
achieved by addition of some materials such as, soluble starch,
ethylene glycol or methanol to the electrolytic solution. These addi-
tives played an essential role to reduce pitting and defects formed
by oxygen evolution. According to SEM, EDX, AFM analysis and
measured gloss values, addition of starch to the electrolytic solution
was highly effective to enhance brightness and to remove tarnish-
ing more than ethylene glycol and methanol.
Acknowledgements
The authors would like to thank Dr. Ehab Abdel Rahman, Lab-
oratory of Physics, American University (Cairo—AUC) for his help
and using analysis of AFM for copper samples. Also, thanks to the
central laboratory for services (National research Centre, Giza) for
analysis of SEM and EDX.
References
[1] U.S. Congress, Office of Technology Assessment, Copper: Technology and Com-
petitiveness, OTA-E-367, U.S. Government Printing Office, Washington, DC,
September 1988.
[2] W.J. McG Tegart, The Electrolytic and Chemical Polishing of Metals in Research
and Industry, Pergamon Press Ltd., 1956.
[3] A. Kratschmer, I.O. Wallinder, C. Leygraf, Corros. Sci. 44 (2002) 425.
[4] M.C. Bernard, E. Dauvergne, M. Evesque, M. Keddam, H. Takenouti, Corros. Sci.
47 (2005) 663.
[5] Bing Dua, Ian Ivar Suni, J. Electrochem. Soc. 151 (2004) 6.
[6] V. Vignal, J.C. Roux, S. Flandrois, A. Fevrier, Corros. Sci. 42 (2000) 1041.
[7] D. Sazou, Electrochim. Acta 42 (4) (1997) 621.
[8] G.L. Wynick, C.J. Boehlert, Mater. Characterization 55 (2005) 190.
[9] G.I. Edson, US4,663,005 (1987).
[10] S.T. Mayer, R.J. Contolini, A.F. Bernhardt, US5,096,550 (1992).
[11] J. Edwards, J. Electrochem. Soc. 100 (1953) 139.
[12] G.M. El-Subruiti, A.M. Ahmed, Portug. Electrochim. Acta 20 (2002) 151.
[13] D. Landoldt, Electrochim. Acta 32 (1987) 1.
[14] S.C. Chang, Electrochem. Solid-State Lett. 5–6 (2003) G72–G74.
[15] M.H. Tsai, International Electron Devices Meeting, Washington, DC, 2001, p. 80.
[16] S.H. Glarum, J.H. Marshall, J. Electrochem. Soc. 132 (1985) 2872.
[17] M. Buhlert, Ph.D., Elektropolieren und Elecktrostrukturieren von Edelsthl,
Messing und Aluminium, Bremen Uni., 2000.
[18] M. Buhlert, M. Gartner, M. Modreanu, A. Jitianu, R. Gavrila, A. Awad, P.J. Plath,
Galvanotechnik 95 (7) (2004) 1629.
[19] A.M. Awad, Ph.D., Optical characterization of spectrally selective anodically
coated electrolytically colored and polished aluminum surfaces, Ain Shams
Uni., 2004.