Surface and Coatings Technology, 64 (1994 ) 75-80 75

Concept of microsmoothing in the electropolishing process

Tadeusz Hryniewicz
Technical University of Kos zalin, Raclawicka 15-17, PL75-620 Koszalin (Poland)

(Received March 5,1993; accepted in final form October 6.1993)

Abstract

Electropolishing of metals and numerous alloys can provide smooth, bright and reflective surfaces that exhibit superior corrosion
resistance compared with untreated materials. These features are achieved mainly after electropolishing pure metals and single-phase
alloys. Earlier researchers have indicated that, in comparison with other treatments (mechanical polishing, chemical etching), electro-
polishing produces a much thinner surface layer with changed and specific properties. This implies a difference in the solid surface
chemistry which is valuable from the viewpoint of the technical usefulness of such surfaces.
Experimental investigations carried out on various metals and alloys have proved that both electrochemical and hydrodynami c
conditions are responsible for the positive results obtained in the process. The aim of the present work is to provide a new concept of
electropolishing covering transport phenomena such as diffusion and adsorption as wellas the hydrodynamic conditions.

1. Introduction 2. Theoretical analysis

A lot of previous investigations on electropolishing
have been carried out in the relatively simple and well-
known system of copper-phosphoric acid solution. In
this electrochemical system the classical form of the
polarization curve has been defined . This curve includes
a region of low polarization, giving anodic etching, a
plateau of high polarization where polishing occurs, and
a more depolarized zone of oxygen evolution at higher
potentials [1-6]. Many other works, both theoretical
and experimental, have generally considered only the
diffusional aspect of the process. The diffusional
approach led to formulation of the diffusion equations
[7J and then to their solution [8 , 9J , taking into account
diffusion, natural and forced convection, and solid film
formation during the process .
The phenomena accompanying the process of electro-
polishing are quite complex. The set of factors affecting
the process and the experimental results are presented
in Fig. 1 [9].
The purpose of the present work is to reveal a new
concept of electropolishing followed by an outline of the
theory of the process . The new concept of microsmooth-
ing is developed taking into account all the elementary
stages and acts, as well as the cyclic kinetics of the
process, the phenomena observed in the experiment.
Some significant conclusions of practical importance
are derived.
Beginning from the early work of Faust [lJ and
others [3, 9J , Kojima [4], Hryniewicz et al. [10],
Landolt [l1J and many others all focused their efforts
on only the diffusional phenomena as playing the main
part in the electropolishing process. Moreover, studies
by Kirchheim et al. [7] seemed to conclude the diffu-
sional theory of electropolishing and, although some of
their solutions happened to be misleading, surprisingly
the conclusions drawn there were right.
To analyse the close-to-anode phenomena, let us
consider the case with a rotating disc electrode (RDE).
"Sticky" layer formation on the anode surface under
natural convection is presented in Fig.2. Taking into
account diffusion, convection and the solid film forma-
tion during electropolishing, the concentration c at the
anode surface changes with consecutive lapses of time t
as follows:
cc
x L (limn) siu{mnxl<5) exp(- t/'r:m)
111=1
where
'r m =c? Jm2n2D
with the current density i given by
2
i =-io(tslt)o.5
n
Parameters in the formulae are presented in Figs. 2 and

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SSDI 0257-8972(93)02218 -2
 76 T. Hryniewicz / Concept of microsmoothing in electropolishing

Y, Change of surface
,--
r=
x, Composition and type
,....
<E---

ｾ
roughness parameters, Ra,Rz ｾ of bath, pH m
iii
Y2 Variance of profile slope
m
ｾＭ x" Dynamic viscosity
ｾ
ｾ
{standard deviation cr)

Y3 Surface gloss
Y4 Change of microhardness
ｾ
;l
g.
"0 ...e
5" ...
<C
'0
0
e
r
m
o
-I
ｾＭ

.---
x12 Bath density
x'3 Conductivity V ｾ

-
l1> ｾ
ｾ

ｾ
o0
r::;
2:

ｾ
n' '0 :0
x2 Voltage (U) Q. 1l
Ya Change of stress state s, '"
iil 0 0 <E---
or c-;

ｩｾ
.!2: g:
Ya Change of shape
Y7 Change of workpiece dimensions
jA - .... --
OJ
I
"'0
0
r
CIl
ｾ
(l)

0
<E--- x3 Current Intensity (I)
x4 ECPtime
ｾ
l1>

ｲＭｾ
ｾ
s:m
m ::J x g Intensity of ｳｴｩｲｮｾ or n:j
o :r Cii I-- electrolyte flow ve ocity
'" I-- Xs
z g. *
OJ
:J:l
.!!!.

rV
Heating or cooling ｾ

ｾ Gl OJ
<:to Distance A - C /I
"'0 0
I+- x7
ｾＮ :=!
0 :0
" 0
ｾ r--
e o
I-- 0, Workpiece - anode
ｾ o
ｾ
;::;:' m
!!' CIl
'<: I-- °2 Cathode 0
ｾ
CIl
"
Ya Increase of electrolyte
temperature

Yg Change of electrolyte properties

ｾ ｾ
ｾ
I--
Os Geometry of electrolyzer
°4 Electrolyte tank capacity V '--
S
a

'nr.
'--
Y,o Decrease of workpiece mass r-
,
K' Local changes of temperature 0

L-:---
ｾＮ
l:
'--
11:2 Convection a-
K:, Progressive contamination
of electrolyte ｾ "'o"
l1>
III

Fig. 1, Visual presentation of the parameters, interferences and final results of electropolishing [9].

c C ELECTROLYTE ] [
Cs
Cob
" ELECTROLYTE c:
0
, .... DIFFUSION ZONE '£
.... l[
.... , .... l:
o
Ql
>
, Ｎｾ
l:
8 C!!.:'
" '0

CJJ
.... c: Ql
o l:
' ..... t......".i:JO o
... .... ｾ
0
u,
....
... ... ;3
.... z'"
.... , -, x=o
x=8
ｾ
....
'.... x=os
.... ｾ Ｌ
" I,
Distancefrom anode x

Fig. 2. Schematic of sticky layer formation and change in concen- Distance from anode x
tration during electropolishing under natural convection for consecu- Fig. 3. Sticky layer formation during electropolishing under forced
tive moments 1,,=0,11,12 , ... , I-->CO. convection.

3. However, some more factors should be taken into

account for microsmoothing and brightening to occur. and brightening is the variable thickness of the effective
Also the number of factors affecting the process is diffusional layer ON [9]. Interrelation of factors affecting
increased when forced convection is considered (Fig. 3). the process of electropolishing shows adsorption as one
As is shown below, this is of great importance when the of the essential physical properties, which additionally
initial stage of electropolishing is started with a new changes with time. Thus the theory of electropolishing
solution, where the amount of dissolved ions is grow- should cover the mechanism of adsorption and/or chemi-
ing rapidly. sorption for the process. Coming out of the diffusion
In accordance with the diffusional concept of electro- and adsorption theory of electropolishing, the way of
polishing to date, the main reason for microsmoothing controlling the process may be rendered more efficient.
 T. Hryniewicz / Concept of microsmoothing in electropolishing
3. Experimental details
The experiments on electropolishing were carried out
on both (i) a stationary electrode with natural and
forced convection [3J and (ii) an RDE system [9, 10].
The materials used for samples were: metals (copper,
aluminium, pure iron, Armco iron) and alloys (brass,
carbon steels, low alloy steels, stainless steels).
All the experiments were carried out in solutions of
orthophosphoric and sulphuric acids, with the addition
of Cr03 for carbon and low alloy steels and/or lactic
acid for electropolishing stainless steels.
The main part of the experiments were concerned
with various kinds of ferrous alloys and so are the results
and conclusions presented here.
The experiments with the RDE were carried out under
potentiostatic and/or galvanostatic control. The active
anode surface area was 2.834 cnr', the samples being
round in shape. All the experiments were repeated three
times. The cathode was made from a round stainless
steel sheet fitted into the bottom of a beaker with a
surface 45 times larger than the anode area.
The samples were ground with a 240-grit wet-grinding
paper before a run and then rinsed with running water
and dried in air to obtain, generally, a single value of
initial roughness. Microscopic observations of the anode
surfaces under magnifications of 6 x and 40 x were
performed after washing and drying.
4. Results and discussion
Some examples of results of the investigations carried
out are presented in this section. A typical anodic
polarization curve was obtained for copper with quite a
long plateau region and, as this is classical in shape, it
is not presented here. For all steels treated under electro-
polishing conditions these plateaux were much shorter,
and dependent on the type of steel used; there were cases
where this plateau could be hardly noticed, e.g. for tool
steels H13 and 01 [9, 10]. This might be the reason
why Faust [IJ stated that there is no plateau for steels
at all. However, some more observations worthy of note
were made during the electropolishing of steels.
Changes of impedance (Fig. 4) measured during elec-
tropolishing of both stainless steels and cast steels [10,
12J and carbon steels and low alloy steels show that
three stages of dissolution may be distinguished. Dur-
ing continuous electropolishing of steels in the phos-
phoric-sulphuric aqueous solutions the impedance
decreased in the initial stage, up to about 4 A h dm - 3
(section a, curves 1 and 2 in Fig. 4), and then monotoni-
cally increased until a full saturation of the electrolyte
solution with metal ions was reached (section b, curves
3 and 4 in Fig. 4). There was a corresponding sharp
77
130
110
4
N
E
ｾ 90
ｾ
Ｎｾ 70
c
"c
ｾ 50
ｾ
8 30
10
o 1 357 9
Voltage applied (V)
Fig. 4. Change of impedance during electropolishing of steels in freshly
prepared solution: section a, decrease in the initial stage (zero to
4 A h dm -3); section b, monotonic increase. Curves obtained with
increasing contamination of the H 3P04-H2S04 aqueous solution were
as follows: curve 1, at zero; curve 2, at about 4 A h dm - 3; curve 3, at
about 50 A h dm -3; curve 4, at about 240 A h dm -3.
deterioration in the surface quality at about 200 to
240 A h dm- 3 .
The first stage of the process (Fig.4, section a) is
characteristic of an uneven dissolution and in fact cannot
be recognized as proper electropolishing (Fig. 5). In
Fig. 5 projections are visible in the centre of the sample
surface. These appeared in the initial stage of electro-
polishing with the freshly prepared electrolyte solution
and occurred on different materials [9, 10]. After
some period of "working out" of the solution (about
4 A h dm -3) such spots no longer appeared and instead
some spirals were visible on the surface (Fig. 6).
In the second stage of treatment (section b in Fig. 4),
the observed irregularities of dissolution vanished and
bright and specular surfaces were obtained.
Potentiostatic polarization Curves obtained for carbon
steels electropolished in phosphoric-sulphuric-chromic
aqueous solution for two temperatures, 343 and 363 K,
are presented in Fig. 7. Here the increasing electrolyte
contamination is shown to decrease the extent of barely
occurring plateau. The effect of this is a decrease in
current efficiency and a monotonic increase of the imped-
ance up to the value corresponding to curve 4 in Fig. 4,
at which the process of electropolishing is distorted.
The effect of rotation speed and overpotential on the
surface finish during electropolishing using the RDE
system is presented in Fig. 8. A spatial graph shows the
areas of a good and bright finish, depending on the
rotation speed and voltage applied.
It is often repeated that to produce satisfactory electro-
polishing results the current density at each point of the
electropolished surface should be at least on the plateau
of the polarization curve. In practice, however, a higher
voltage than that derived from the polarization curve
must usually be applied. A further conclusion resulting
78 T. Hryniewicz ! Concept of microsmoothing in electropolishing

Fig. 5. Spot in the specimen centre after electropolishing with the RDE system [10J (magnification, 6 x) (aqueous phosphoric-sulphuric-chromic
solution, 341 K, 500 rev min -1: (a) 1028 carbon steel, 3 V, 10 min; (b) 4141 low alloy steel, 2 V, 5 min (potentiostatic control).

100

ｾ
"'
"'
o
0> 50
.'">"
'"
0;
a:

4 5
ESe E (V)

Fig. 6. Micrograph of the sample surface obtained after electropol-

ishing on the RDE system (magnification, 40 x). The electrolyte was
as in Fig. 4; other parameters were 339 K and 1500 rev min -1; the
material was pure iron (99.91% purity) [10J.
Fig. 8. Dependence of surface reflectivity on the rotation speed OJ and
applied potential E in electropolishing of 1040 carbon steel with the
RDE system [10].

20 r----------:-----..
from this study is that, even at a very high rotation
speed (high Reynolds number), electropolishing condi-
tions can be found. This finding may mean that it is
sufficient to generate a thin solid film on a surface,
conditioning the process, with a very thin stagnant layer
(or maybe none at all), for electropolishing to occur.

o 1 2
£SHE (V) 5. Effect of adsorption
Fig. 7. Polarization curves for a carbon steel electropolished in the
electrolyte as in Fig. 4 at 343 K (curve 1) and 363 K (curve 2). Arrows The effects of surface-active agents [2, 9, 13, 14] are
indicate increasing saturation. very promising. These substances usually serve to
 T. Hryniewicz / Concept of microsmoothing in electropolishing
improve microsmoothing through an increase in activa-
tion energy of the electrode under dissolution (Fig. 9).
By analogy to electrolytic plating one may assume
that the action of surface-active substances proceeds in
several elementary stages [9,13]. Such a substance must
first diffuse to the surface of the electrode or anode and
then take part in the process of electro-oxidation.
Without going deeply into the details of these elementary
acts one may state that the substance itself may undergo
electro-oxidation and be incorporated in microrecesses
of the anode surface, which causes an increase in the
activation energy.
It is known [13] that adsorption of such organic
substances takes place over a determined range of poten-
tials, dependent on the point of zero charge: anions
undergo adsorption mainly on surfaces of positive
charge, and cations undergo adsorption close to the
potentials of zero charge [14]. However, the adsorption
of neutral particles and organic ions is not possible on
a surface with a large charge.
The problem is [14], however, that one cannot make
use of these, because the surface of metals and alloys, in
particular of polycrystalline ones, has various lattice
defects, microcracks etc., and its surface energy is not
uniform over the whole geometrical surface. Moreover,
there are crystallite phase boundaries and, inevitably in
practice, contaminations, often situated just at the grain
boundaries.
6. Mechanism of electropolishing
The mechanism of the process of electropolishing may
be described as follows. Under the influence of the
applied voltage an essential part of the electric charge
will accumulate on the points of projections of the
surface roughness. From the very beginning the "edges"
will be undergoing a dissolution. The accumulating ions
coming from the dissolved metal will face a barrier in
the form of a stagnant layer adjacent to the anode. A
f'136
o The mechanism presented embraces a considerable
E
ｾ 102
>-
e>
Ql
sc 68
o and the ions of the dissolved metal are subject to a
Ｎｾ
> partial oxidation and change their position due to
ｾ 34
o 1 2 3 4 5
o3
Concentration of surface-ectlve agent (g dm
Fig. 9. Effect of carboxymethylocellulosis addition on the activation
energy during electropolishing of a carbon steel in ｈＳｐｏＮＭＲｓＰＴｾ
H 20 solution, according to ref. 2.
79
supersaturated solution will be formed in the vicinity.
In consequence, a part of these ions will move into the
roughness recesses, masking them and considerably
inhibiting the rate of their dissolution.
The surface-active agent sometimes added to the
solution in a very similar way, although with a greater
intensity, will behave. It will inhibit the metal dissolution,
leading in consequence to smoothing the "edges" of
roughness. However, bearing in mind the fact that the
electropolishing solution itself has a high viscosity [2J,
the amount of the surface-active agent has to be chosen
very carefully, and in many cases it is even superfluous.
The products of the anode dissolution play that role
instead. The adsorbed particles on the metal surface
may significantly prolong and/or limit the process of
electropolishing under a given voltage. This also
decreases the anode efficiency.
7. Outline of the diffusion and adsorption theory of
microsmoothing in the process of electropolishing
It appears that the hitherto existing views of the solely
diffusional character of electropolishing resulting from
the variable thickness ON of the effective diffusion layer
[2, 13J need to be supplemented. Not to negate or deny
the essential influence of the variable thickness ON on
the surface profile, one should take into account the
contribution of adsorption in the mechanism of the
process. This mechanism may rely on the following
elementary acts: (1) establishing the primary current
distribution according to the diagram of current lines
and equipotential lines [15]; (2) in the case where no
use of surface-active substances is made, accumulating
the dissolved metal ions in the vicinity of the surface,
directing them to the microrecesses and then masking
those places on the anode; (3) in the case where surface-
active substances are used, adsorption of the substance
particles together with the dissolved ions of the polished
metal in the microrecesses; (4) directing the current lines
to the microelevations on account of the partial masking
of microrecesses.
simplification and does not take into account the cyclic
kinetics which can be outlined in the following way.
In the microrecesses both the surface-active substance
diffusion, whereas the new ions and the surface-active
substance are transported all the time in accordance
with the diffusion laws. Some confirmation of the cyclic
) character of the process is the potential oscillation during
microsmoothing, i.e. after some tens of seconds of elec-
tropolishing.
Finally it should be mentioned that a big rate of
80 T. Hryniewicz / Concept q{microsmoothing in electropolishing
adsorption is not a necessary attribute of microsmooth-
ing. A very high affinity of the surface-active agents for
the substrate may result in filling the anode surface
within a broader range of current density and causing
more difficult desorption which may, in turn, disturb the
cyclic mechanism and disadvantageously affect the
microsmoothing.
8. Conclusions
Based on the investigations carried out, the following
conclusions may be drawn:
(1) The process of electropolishing may be well
described by an open model (Table 1) for a group
analysis of factors affecting it.
(2) Change of impedance indicates three stages which
may be distinguished in the whole process after the new
solution is prepared: the first one with a quick metal
removal rate and disturbances in the dissolution which
cannot be considered as electropolishing; the second
stage with appropriate electropolishing; and the third
one pointing to rejection of the solution. For steels
treated in the phosphorus-sulphuric and/or chromic
solutions the stages last about 4 A h dm -3 and
240 A h dm -3 consecutively.
(3) The meaning of polarization curves, although
essential in a search for the anodic film formation in
electropolishing, cannot be overestimated. The presence
of a current plateau, associated with the anodic film, is
not a sufficient criterion for microsmoothing to occur
but it is rather a necessary condition for the mass-
transport-controlled reaction rate. In consequence, the
plateau region in electropolishing steels is not the range
of "the best electropolishing" in contrast to what is
stated in numerous references on electropolishing.
(4) Apart from diffusion, the concept of electropol-
ishing must comply with the changing adsorption-chem-
isorption during the process. The following conclusions
may be useful for practical purposes: for the selection
and use of surface-active agents, the adsorption charac-
teristics in the practical range of current densities have
to be respected; and a reasonable moderation must be
observed when intensifying the electropolishing pro-
cess-too high a current density may cause a decrease
in the microfinish as there is no preferential adsorption.
References
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Engineering Handbook, Reinhold, Princeton, NJ, 1971.
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edn., Masinostroenie, Leningradskoe otdelenie, Leningrad, 1987.
3 T. Hryniewicz, Wybrane zagadnienia polerowania elektrolitycz-
nego, Ph.D. Thesis, Institute of Machine Building Technology,
Wroc!aw Polytechnic, Wroc!aw, 1978.
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Materials and Molecular Research Division, Lawrence Berkeley
Laboratory, University of California, Berkeley, CA, 1981.
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431-434.
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