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Electrochimica Acta 53 (2008) 3356–3363

Electropolishing of 304 stainless steel: Surface roughness control using

experimental design strategies and a summarized electropolishing model
Chi-Cheng Lin b , Chi-Chang Hu a,∗,1
a Department of Chemical Engineering, National Tsing Hua University, Section 2, 101 Kuang Fu Road, Hsin-Chu 30013, Taiwan
b Department of Chemical Engineering, National Chung Cheng University, Chia-Yi 621, Taiwan

Received 3 August 2007; received in revised form 15 November 2007; accepted 24 November 2007
Available online 14 January 2008

Abstract
The electropolishing (EP) settings for obtaining 304 stainless steel (304SS) with variable surface roughness factors (Ra) in a mixture containing
phosphoric acid, sulfuric acid, and glycerol were achieved using experimental design strategies, including the fractional factorial design (FFD)
coupled with the response surface methodology (RSM) and the path of the steepest ascent. The bath temperature and polishing time were found
to be the strongest factors affecting Ra of 304SS in the FFD study. The glycerol content and polishing current density involved strong interactions
with the bath temperature although both factors only showed marginal significant effects. The effects of bath temperature and polishing time on
Ra of 304SS were examined in the study of the steepest ascent path for controlling the surface roughness. The results showed that Ra of 304SS is
decreased with decreasing the bath temperature and polishing time but increased when the temperature was lower than 20 ◦ C. A summarized model
with a new idea on the molecular interactions in the polishing bath is proposed to elucidate the phenomena found in this work. The morphologies
and Ra of 304SS electropolished under various conditions were examined by means of the SEM photographs and AFM analyses.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Electropolishing; Anodic dissolution; 304 stainless steel; Surface roughness factor; Experimental design

1. Introduction ohmic (primary current distribution), activation (secondary), and

Electropolishing (EP) is one of the anodic methods widely
employed in the industry for the surface finishing of metals or
alloys to obtain the fine surface brightness and stress-free surface
[1]. The proposal of EP as an industrial surface finishing process
is usually attributed to the work by Jacquet who took a patent in
1930 [2]. However, the first recorded publication dealing with
EP goes back even further [3].
The surface phenomena of EP are generally classified into
two processes: anodic levelling and anodic brightening. Anodic
levelling results from a difference in the dissolution rate between
peaks and valleys on a rough metal/alloy surface depending
on the current distribution or mass-transport conditions [4–11].
It is usually associated with a decrease of roughness in the
micrometer or larger range [12] and can be achieved under the
∗ of stainless steels in industries is usually performed in a mix-
Corresponding author. Tel.: +886 3 5736027; fax: +886 3 5715408.
E-mail address: cchu@che.nthu.edu.tw (C.-C. Hu).
1 ISE member.
mass-transport (tertiary)-controlled metal dissolution reactions
[13,14]. Anodic brightening, on the other hand, is associated
with the suppression of the influence of the metal microstructure
on the dissolution rate. It can be achieved only under the condi-
tions in which the metal dissolution is mass-transport-controlled
and the formation of a precipitated salt layer at the electrode sur-
face is possible. The presence of a salt layer can suppress the
influence of crystallographic orientation and surface defects on
the dissolution process [13–16]. This phenomenon will lead to
microfinishing in the sub-micrometer scale and specular reflec-
tivity of metals/alloys can be obtained. Accordingly, a fine
electropolished surface of metals/alloys, which appears bright to
the naked eye, generally results from an effective combination
of levelling and brightening.
The use of an appropriate electrolyte and operating conditions
in an EP process will produce smooth and bright surfaces that
are free of defects, stress, and contamination. Electropolishing
ture containing concentrated phosphoric and sulfuric acid [17],
and similar processes may lead to micro-finishing in concen-

0013-4686/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.11.075
 C.-C. Lin, C.-C. Hu / Electrochimica Acta 53 (2008) 3356–3363
trated acid solutions under EP conditions [11]. Gabe measured
the anodic polarization curves of mild steel in phosphoric acid
and phosphoric–sulfuric acid mixtures [18]. Passivation was
observed in these solutions and the passive current density was
found to depend on the electrolyte composition. In addition, a
phosphoric acid solution containing sulfuric acid gave a bet-
ter surface finish than a pure phosphoric acid. Similar results
were also obtained by Ponto et al. [19] who studied the anodic
behavior of different stainless steels in mixtures of phosphoric
and sulfuric acids. Well-polished surfaces can be obtained at or
above a limiting current density, which means that EP takes place
in the transpassive region under mass-transport control. The
impedance study [17] and the temperature effect on the appear-
ance of metals/alloys through EP in the phosphoric–sulfuric acid
system [11,20] have also been done. Furthermore, addition of
glycerol into this system was adopted [21,22]. In this glycerol-
containing system, the limiting polishing current was found to
slightly depend on the flow rate [21] and a concept for mini-
mizing agitation of the electrolyte was proposed to eliminate
the cost of pumping concentrated acids [22]. Based on these
studies, several mechanisms have been proposed successively
for the process of anodic dissolution: (i) salt film (dissolution
products) mechanism [12]; (ii) acceptor mechanism [12]; (iii)
preferential adsorption of shielding molecules [23,24]; and (iv)
formation of solid oxide film for aluminum [25]. However, due
to the complicated interactions involving in the EP processes,
a model, effectively controlling and predicting Ra, should be
established on the basis of the experimental design strategy.
The experimental design strategy is a sequential procedure
to reach the optimal/robust operation conditions of interest
[26–31]. Based on this strategy, the response variable(s) (e.g.,
roughness factor of 304SS) is expressed as a function of
the quantitative control variables. Since there may be several
key factors influencing the response(s), the fractional factorial
design (FFD) is usually employed to efficiently find these key
variables [26–28]. After the FFD experiment, the methodology
of the steepest ascent path is often used to extend the experi-
mental window for robust/optimal conditions.
The purpose of this work is to identify the key variables of
EP to construct a mathematic model for roughness factor (Ra)
against the key EP variables in order to control and predict Ra of
304SS. The key variables affecting Ra of 304SS were screened
out in the FFD study. These variables were examined in the
study of the steepest ascent path to confirm the trend of Ra vari-
ation. Finally, a model integrated from the mechanisms found
in the literature with introducing a new concept of molecular
interactions between adsorbed solution molecules, is proposed
to interpret the results.
2. Experimental details
Electropolishing was performed on 304SS sheets covered
with a Teflon coating with an exposed area of 1 cm × 1 cm. The
test sheets were used directly without any pretreatment. The
304SS sheet was totally immersed into the center of a cylin-
drical cell with 50 ml EP solution, which was surrounded by
an isothermally circulated water system (Haake DC3 and K20).
3357
Fig. 1. The potential–time responses for the EP experiment conducted in the
solution containing: (1) H3 PO4 :H2 SO4 = 2:1 (75 vol.%) and 25 vol.% glycerol
at 80 ◦ C and 0.5 A cm−2 for 5 min; (2) H3 PO4 :H2 SO4 = 2:1 (75 vol.%) and
25 vol.% glycerol at 30 ◦ C and 0.5 A cm−2 for 5 min.
The cathode, which was a stainless steel mesh with an area of
4 cm × 12 cm, was also totally immersed into the solution and
surround the test sheet. The EP solution was composed of co-
acid and glycerol (Merck, GR) with two volume ratios, 75:25
and 65:35. Co-acid was premixed by concentrated phosphoric
acid (85%, Riedel-deHaen, GR) and concentrated sulfuric acid
(97%, Merck, GR) with two volume ratios, 3:2 and 2:1, prior to
use. The EP experiment was conducted by a direct current (dc)
power supply (AMB 6030D). The polishing potentials generally
reach a steady-state value after the current is applied for 200 s
(see Fig. 1). After the EP treatment (under various conditions
designed in the FFD and the path of steepest ascent studies), the
test sheet was rinsed in deionized water in an ultrasonic oscilla-
tion bath (Branson 2201) for 10 min followed by drying process.
The average surface roughness factor (Ra) was measured at
two points near the centers of the test sheet with an area of
40 ␮m × 40 ␮m by an atomic force microscope (AFM, Hitachi
S2300). The maximum error for such repeated measurements is
about 4.8 nm (see run 6 in Table 2). Finally, the morphologies of
the test sheets were measured through means of a field-emission
scanning electron microscope (FE-SEM, Hitachi S4800).
3. Results and discussion
3.1. Fractional factorial design
In order to find the key variables affecting Ra of 304SS, the
fractional factorial design (FFD) is introduced to screen out these
key variables. Based on the literature review, the following EP
variables were investigated in the FFD study: (A) volume ratio
of phosphoric acid and sulfuric acid; (B) volume content of glyc-
erol (vol.%); (C) temperature of the EP solution (◦ C); (D) EP
current density (A cm−2 ); and (E) EP time (min). The fixed lev-
els of these five variables are listed in Table 1 meanwhile the
25−1 design matrix with the experimental data were given in
Table 2. In this work, effects of the electrolyte flow rate are
ignored and a mild stirring condition (10 rpm) was employed
for all the experiments because the limiting polishing current
3358 C.-C. Lin, C.-C. Hu / Electrochimica Acta 53 (2008) 3356–3363

Table 1 Table 3
Factors and levels for the 25−1 fractional factorial design in the electropolishing Analysis of variance for Ra from the 25−1 fractional factorial design
of 304SS
Source SS d.f. MS F*
Factor Level
B 15.92 1 15.92 4.31
− + C 95.06 1 95.06 25.72
E 39.21 1 39.21 10.61
(A) H3 PO4 :H2 SO4 (volume ratio) 3:2 2:1 BC 108.37 1 108.37 29.32
(B) Amount of glycerol (by vol.%) 25 35 BD 14.67 1 14.67 3.97
(C) Temperature (◦ C) 30 70 CD 61.94 1 61.94 16.75
(D) Current density (A cm−2 ) 0.5 1
(E) Electropolishing time (min) 5 10 Error 33.27 9
Total 368.43 15

Remark: F0.05 (1, 9) = 5.12; R2 = 1 − (SSE/SST) = 0.91.

was found to depend weakly on the flow rate in the glycerol-
containing system [21]. In addition, it is better to minimize the
agitation of electrolytes in order to eliminate the cost of pumping dom for factor (or interaction) i and errors, respectively. The
concentrated acids for this system [22]. test statistics, F*, defined as MSi /MSE, are employed to test the
In Table 2, the low and high levels of A–E were denoted as “−” statistical significance of each factor and the two-factor inter-
and “+”, respectively. The contrast coefficients of factor E (i.e., actions. If the calculated value of F* is greater than that in the
column 6 in Table 2) is generated from the contrast coefficients F table at a specific probability level (e.g., α = 0.05), the null
of factors A–D through Eq. (1) [27,28]. hypothesis that factor i has no effect on the surface roughness
of 304SS has to be rejected, revealing a statistically significant
E = EI = EABCDE = ABCDE2 = ABCD (1)
factor. After the test, only factors C, E and interactions BC, CD
From an examination of the results in Table 2, Ra of 304SS exhibit statistically significant effects on Ra of 304SS if α = 0.05.
varies from 7.3 to 26.6 nm, indicating that certain factors and/or Factor B and interaction BD show marginal significance (i.e.,
interactions should show significant effects on the surface rough- their effects are not as obvious as those of C, E, BC, and CD)
ness. Hence, analysis of variance (ANOVA) was carried out since their calculated F-values are somewhat lower than the criti-
on the basis of the data shown in Table 2 and the results of cal value, F0.05 (1, 9) = 5.12. The multiple correlation coefficient,
statistical analyses are summarized in Table 3. Since the pro- R2 = 1 − (SSE/SST), is the proportion of SST (sum of squares of
cedure of ANOVA completely followed our previous studies total variances) reasonably explained by the fitted equation. An
[29–31], the descriptions for employing the ANOVA method- R2 -value close to 1 means a good fit to the experiment data. In
ology are ignored here. In Table 3, SSi indicates the sum of this work, R2 = 0.91 when factors B, C, E and interactions BC,
square corresponding to factor (or interaction) i. The quantities BD, CD are considered to be significant and the other effects
MSi = SSi /d.f.i and MSE = SSE/d.f.error are defined as the mean (including factors A, D and the other two-factor interactions)
squares of factor (or interaction) i and the mean square of errors, should be pooled into the error. However, the main effect of cer-
respectively. The d.f.i and d.f.error indicate the degrees of free- tain factors which may be not significant in the F-test cannot
be classified as a null effect directly because the effect of these
Table 2
singular factors may be levelled off by their interaction effects;
The design matrix, experimental data of Ra, and errors of Ra in the repeated factors B (volume content of glycerol) and D (current density)
measurements for a 25−1 fractional factorial design with the defining relation are good examples of this case. Factor B is considered as a fac-
I = ABCDE tor with marginal significance but it involves in the significant
Run Factor Ra (nm) (error in nm) interaction of BC, which cannot be ignored simply. Similarly,
factor D should not be considered to show a null effect due to the
A B C D E
strong interaction between C and D. Accordingly, factors B–E
1 − − − − + 8.1 (1.0) are considered in the realistically experimental manipulation.
2 + − − − − 7.3 (2.2) Calculation of the estimates for factors and two-factor inter-
3 − + − − − 17.0 (0.2)
4 + + − − + 19.1 (3.8)
actions completely follows the procedure recommended by
5 − − + − − 19.4 (3.3) Box et al. [28]. The estimates of all factors A–E and interac-
6 + − + − + 26.6 (4.8) tions with (marginal) significance are shown in Fig. 2. From
7 − + + − + 23.2 (4.0) Table 3 and Fig. 2, it is very clear that the sequence of fac-
8 + + + − − 17.6 (1.7) tors/interactions with respect to decreasing the influence is
9 − − − + − 13.3 (0.6)
10 + − − + + 15.1 (1.7)
BC > C > CD > E > B > BD although the last two terms show the
11 − + − + + 19.7 (0.4) marginal significance. From Fig. 2a, factor A shows no signif-
12 + + − + − 16.8 (0.9) icant effect without any significant interactions, indicating the
13 − − + + + 21.8 (4.0) robust operation window of the volume ratio of phosphoric acid
14 + − + + − 16.4 (1.8) and sulfuric acid from 3:2 to 2:1. This fact suggests that the
15 − + + + − 15.6 (2.3)
16 + + + + + 14.9 (3.5)
interaction forces among these acid molecules are not signifi-
cantly changed by varying their volume ratio in the operation
 C.-C. Lin, C.-C. Hu / Electrochimica Acta 53 (2008) 3356–3363 3359

following:

y = 16.98 + xB + 2.44xC + 1.57xE − 2.6xB xC

− 0.96xB xD − 1.97xC xD (2)

where xi are the coded variables for factor i (i.e., B–E). Since
the definition of coded variables, xi , were clearly described pre-
viously [26–31], its corresponding description is ignored here.
Note that when xB , xC , xD , and xE are equal to −1 (i.e., factors
B–E are in the low level), the predicted value of y (i.e., the Ra
of 304SS) is only 7.3 nm (a very low Ra value).
The contour plots for the dependence of Ra on factors C
and E were constructed by using the regression model (i.e., Eq.
(2)) and a typical contour diagram is shown in Fig. 3. Based on
this figure, the surface roughness is predicted to increase with
the simultaneous increase in the polishing temperature and the
polishing time from ca. 7 to 23 nm in the investigated range. This
prediction, generally obeying the trend of the regression model
and contour diagram to a certain extent, has to be confirmed in
order to gain an understanding on the ability of the fitted model
(see next section).

3.2. The steepest ascent path

The main purpose of the steepest ascent (or decent) path is

to test the ability of the model established in the FFD study.
In addition, it is possible to approach the vicinity of optimal
conditions (e.g., the minimum or maximum Ra in this work)
through this study, which may be far from the investigation
Fig. 2. Effects of (a) factors (A) H3 PO4 :H2 SO4 (by volume), (B) amount of points of the FFD case. The design steps with the correspond-
glycerol (by volume), (C) temperature of the bath (◦ C), (D) current density
(A cm−2 ), and (E) EP time (min); and (b) interactions BC, CD and BD on Ra,
ing results in the steepest ascent study are shown in Table 4,
where (+) and (−) indicate the high and low levels of factors, respectively. which follow the direction shown in Fig. 4 (derived from the
BC interaction, see Fig. 2b). Based on Fig. 4, it is very clear
that under the low level of the glycerol content, a sharp varia-
range. For factor E, an increase in the EP time will increase Ra tion of Ra in the investigation range should be obtained. Note
of 304SS. This effect, however, is conflict to the general con-
cept of anodic dissolution, probably due to the strong adsorption
of the aggregates consisting of acids and glycerol molecules
(see below). Hence, peaks and valleys grow continuously with
the EP time, enhancing Ra. Note that factor C shows a very
strong effect on Ra, implying the importance of the competition
between molecular interactions and thermal motion of molecules
on the polishing mechanism (see below). This statement is fur-
ther supported by the complicated interactions among factors
B–D, clearly found in Fig. 2b. For example, an increase in the
glycerol content leads to an obvious decrease in Ra of 304SS
when the temperature of EP solutions is high (70 ◦ C, thermal
motion dominates). However, when this factor is under the low
level (30 ◦ C), an opposite result is observed (adsorption of large
molecular aggregates dominated by molecular interactions). The
above phenomena reveal the existence of an interaction between
factors B (glycerol content) and C (temperature). Similar phe-
nomena are also clearly found for interactions CD and BD.
From the analysis of variance and regression analysis of the
results shown in Table 2, a fitted polynomial model can be gen-
erated. This model, quantitatively elucidating the effects of all
EP variables with statistical significance, is expressed in the Fig. 3. A contour plot for constant Ra against temperature and EP time.
3360 C.-C. Lin, C.-C. Hu / Electrochimica Acta 53 (2008) 3356–3363

Table 4 that factors A and D are set as the high and low levels, respec-
Experiments of the steepest ascent path with adjusting EP temperature and time tively to obtain possible synergistic effects and the step sizes
simultaneously
of the polishing temperature and time are 15 ◦ C and 1.25 min,
Run Factor Ra (nm) (error in nm) respectively. Also note that the polishing conditions of run 5 in
C (T, ◦ C) E (t, min) Table 4 and run 2 in Table 2 are identical. Since the difference
in Ra between these two independent, replicated measurements
1 80 10 44.7 (0.6)
2 65 8.75 34.4 (1.2)
is only 0.7 nm (with the maximum error of repeated measure-
3 50 7.5 13.6 (3.5) ments = 2.2 nm), the reproducibility of electropolishing in terms
4 35 6.25 11.4 (2.7) of Ra in this work is excellent. Moreover, the results in Table 4
5 30 5 8.0 (1.0) confirm the variation of Ra in the steepest ascent direction fol-
6 20 5 12.7 (2.6) lowing the prediction of the regression model, in which the
7 5 3.75 13.5 (3.8)
surface roughness increases up to a Ra value of 44.7 nm. On
the other hand, the lowest Ra value is limited to be 8.0 nm,
which is very close to the minimum Ra obtained in the FFD
study.

3.3. A summarized model describing the electropolishing

process

From the literature, several mechanisms were proposed suc-

cessively for the process of electropolishing, including (i) the
salt film mechanism (the salt film limiting the mass-transport of
metal ions) [12]; (ii) the acceptor mechanism (the diffusion of
acceptor limiting the dissolution rate) [12]; and (iii) the pref-
erential adsorption of shielding molecules [23,24]. Moreover,
the formation of a solid oxide film for aluminum may provide
additional information in explaining the anodic dissolution phe-
nomena under electropolishing [25]. Furthermore, a duplex salt
film model, according to the salt film mechanism, was proposed
by Grimm et al. [32], attempting to characterize the role of com-
pact and porous layers in the frequency response of complicated
precipitated films. On the other hand, based on the concept of
acceptor mechanism, the adsorbate acceptor model was pro-
posed by Matlosz et al. [33], which examined the influences of
adsorbed intermediates and the transport of acceptor molecules
on the electropolishing behavior in the absence of salt films. The
impedance studies were also performed for the duplex salt film
[32,34] and adsorbate acceptor models [33,34]. Unfortunately,
Fig. 4. Prediction of variance of Ra by adjusting temperature with different
amount of glycerol.
all the above mechanisms alone cannot reasonably explain the
results obtained in this work, suggesting that an integration of

Fig. 5. (a) A schematic model for the anodic dissolution with arrows (1) the moving direction of acceptors and (2) the moving direction of metal ions. (b) Surface
morphologies of 304SS dominated by the microstructure/coverage of the adsorbed shielding molecules with a (1) small/weak and (2) large/strong polymeric structure.
 C.-C. Lin, C.-C. Hu / Electrochimica Acta 53 (2008) 3356–3363
the above concepts with an additional viewpoint considering the
molecular interactions among the strongly adsorbed molecules
formed on the electrode surface is needed (see the schematic
model shown in Fig. 5a). The top layer (layer A) indicates
the bulk polishing solution containing acceptors (i.e., water
molecules which can coordinate to metal ions), acids, and glyc-
erol. Layer B is considered as a relatively compact film mainly
consisting of the preferential adsorption molecules, including
acceptors (mechanism for the preferential adsorption of shield-
ing molecules [23,24]), layer C is a salt solution formed by
electrolyte and metal ions diffusing from layers B and D, respec-
tively. Layer D is attributed to the accumulation of metal ions
generated by the dissolution of metal or alloy substrates (layer
E), which may be precipitated as a compact metal salt film in the
salt film mechanism [12,32] or as a metal oxide film [25]. Note
that metal ions will diffuse from layer D to layer A due to the con-
centration gradient and electrostatic repulsion force. In addition,
a concentration gradient of water molecules (i.e., the acceptor
which is easier to coordinate/solvate metal ions) should be found
in layer B, due to the continuous consumption of water molecules
at the interface between layers B and C (acceptor mechanism
[12,33]). Note that the dissolution of substrates (layer E) and the
mass-transport of the dissolved metals ions will be dominated
by the microstructures of layers B, C, and D, which are mainly
determined by the solution employed in the EP process (see
below).
If the EP process obeys the salt film mechanism, the diffu-
sion of dissolved metal ions from the anode surface into the
bulk solution (i.e., dissolution of metal/alloy) will be deter-
mined by the microstructures of layers C and D [12,34]. Under
such an EP environment, the influence of layer B on the EP
process is minor and negligible. In such a case, layer D is
a compact metal salt film due to the precipitation of phos-
phates and/or sulfates (in our EP solution), meanwhile layer
C is considered as liquid film with the concentration of metal
salts approaching saturation [12,34]. On the other hand, if the
EP process follows the acceptor mechanism [12,33,34], dif-
fusion of acceptors (toward the anode) and solvated/complex
metal ions (away from the anode) should occur simultaneously
in layer B. Hence, the microstructure of layer B will domi-
nate the mass-transport of the whole EP process. In such a
case, layer D should disappear and layer C can be considered
as a liquid film with a relatively dilute concentration of metal
salts (partially) covered onto the substrate (layer E). Based on
the above viewpoints, the acceptor mechanism should domi-
nate the system containing a small quantity of acceptors. For
example, the EP process of Fe–5Cr in a concentrated solu-
tion of H3 PO4 and H2 SO4 generally follows this model, which
only contains a little water (i.e., the acceptor) [32,34]. Since
the system studied here is very similar to the Fe–5Cr case,
the EP process is believed to follow the acceptor mechanism
and layer B is expected to play an important role in this study.
However, large molecules with poly special functional groups
(i.e., glycerol in our case, which has three OH groups, lead-
ing to strong hydrogen bonding between each other) may be
concentrated to form a polymeric structure or aggregates in
layer B. This property will enhance the hindering effect on the
3361
diffusion of acceptors and metal ions (hydrated metal ions or
complex ones) toward and away from the anode, respectively.
In addition, the polymeric structure of layer B will become
more compact and denser with a large coverage area when
stronger interactions among these molecules exist. Hence, the
formation of peak indicates a less dissolution rate of 304SS,
probably due to the relatively strong hindrance of the large, con-
centrated, and compact layer B (aggregates consisting of more
molecules). On the other hand, a less compact nature of layer
B with a relatively weaker hindrance effect, presumably due to
thermal motions of molecules which randomly lead to weaker
molecular interactions and favor the diffusion of acceptors and
dissolved products through these weaker points, reasonably
ascribes the evolution of valleys. Accordingly, Fig. 5b schemat-
ically shows the morphologies resulting from the coverage of
weak and strong aggregates of the polymeric structure. The
presence of peaks and valleys is attributed to the localized
difference in the dissolution rate of 304SS. The more the dif-
ference in the dissolution rate, the rougher the surface will
be.
Since factor A in the FFD study shows no significant main
and interactive effects, the volume ratio of phosphoric acid and
sulfuric acid is believed to have no significant influence on
the structure of layer B. The complicated influences of polish-
ing temperature (factor C) on Ra (including the largest main
effect and the two significant interactions) are understandable
from the model proposed in Fig. 5. The compact structure of
layer B should become looser with rising the temperature due
to the competition between molecular interactions (e.g., hydro-
gen bonding) and thermal motions. Therefore, the diffusion and
migration rates of ions and acceptors will increase, especially
at the less compact regions, thus leading to rougher surface.
In the cases of interactions BC and CD, when the system is
under a higher temperature, an increase of the glycerol content
(factor B) or the current density (factor D) may strengthen the
compact structure of adsorbed molecules, leading to a flatter
surface. As the system is under lower temperature, the large
aggregates may be so compact (by raising the glycerol content
or the current density) that most species will diffuse or migrate
at the boundaries of aggregates (interrupting the relatively weak
points in the compact, polymeric aggregates because of the high
current density of EP). Furthermore, this phenomenon may be
caused by Joule heating of the electrolyte, which is enhanced
by increasing the potential drop across layer B. The potential
drop across layer B is relatively high when the EP tempera-
ture is low, due to the compact nature of layer B resulting from
the strong interactions among adsorbed molecules. When the
glycerol content and current density are increased at a lower tem-
perature, the potential drop will be increased, which enhances
the effect of Joule heating to a certain extent. This will decrease
the molecular interactions among adsorbed molecules at the
boundaries/weak points of aggregates, resulting in the destruc-
tion of the compact film and leading to a higher Ra value.
The above statements also explain the increase in Ra when
the temperature is lower than 20 ◦ C (see Table 4, runs 6 and
7) although there is no direct evidence supporting the above
speculations.
3362 C.-C. Lin, C.-C. Hu / Electrochimica Acta 53 (2008) 3356–3363
Fig. 6. (a, c, e and g) SEM photographs and (b, d, f and h) AFM results of 304 stainless steel electropolished in a solution containing (a and b) H3 PO4 :H2 SO4 = 2:1
(75 vol.%) and 25 vol.% glycerol at 80 ◦ C and 0.5 A cm−2 for 10 min; (c and d) H3 PO4 :H2 SO4 = 2:1 (75 vol.%) and 25 vol.% glycerol at 30 ◦ C and 0.5 A cm−2 for
5 min; (e and f) H3 PO4 :H2 SO4 = 2:1 at 35 ◦ C and 0.5 A cm−2 for 6.25 min; (g and h) raw 304SS without polishing (40 ␮m × 40 ␮m for AFM analyses).
3.4. Morphologies of 304SS
The morphologies of 304SS with electropolishing under var-
ious conditions are shown in Fig. 6. The morphologies of the
raw material are also shown in Fig. 6 for a comparison pur-
pose. Fig. 6a and b shows the morphology of a 304SS sheet
with a high Ra value of 44.7 nm, which was polished at a
high temperature (80 ◦ C) for a relatively long time (10 min).
As found in Fig. 6b, peaks and valleys are observed very clearly,
which conform to the mechanism of our model due to the par-
tially stronger coverage of layer B, and a long EP time will
enhance the difference (for the case of Fig. 5b-1). Oppositely,
the 304SS with a low Ra value of 7.3 nm (see Fig. 6c and d) was
obtained under a low temperature (30 ◦ C) for a relatively short
time (5 min). The surface is very flat due to a uniform dissolu-
tion everywhere. This result is attributed to the whole coverage
of layer B and a short polishing time depresses the increase
in Ra (for the case of Fig. 5b-2). Fig. 6e and f represents the
result obtained from the solution of phosphoric acid and sul-
furic acid without glycerol at 35 ◦ C. Its morphology is similar
to that of a raw sheet (see Fig. 6g and h) with very close Ra
values. This result is similar to that obtained from the literature
in which the extent of EP treatment in such a temperature and
solution containing phosphoric acid and sulfuric acid (without
glycerol) is relatively minor in comparison with the case pol-
ished under a high temperature [11]. However, the surface of
this sheet is somewhat polished under the conditions mentioned
in the figure caption, leading to a brighter and cleaner appear-
ance, too. Note that the sample with a high Ra value shown in
Fig. 6a and b also exhibits a bright and clean surface because
EP still works at whole surface including the peaks and val-
leys. From all the above results and discussion, the structure
and coverage of layer B under EP in the solution containing
phosphoric acid, sulfuric acid, and glycerol should be very dif-
ferent from the case containing phosphoric acid and sulfuric
acid only. Hence, their corresponding surface morphologies are
mainly determined by the microstructure and/or coverage of
layer B.
4. Conclusions
Using the sequential experiment strategies (i.e., the fractional
factorial design and the study of the steepest ascent path), the
key factors and interactions for the EP process of 304SS with the
roughness factor (Ra) varying from ca. 7 to 45 nm are clearly
demonstrated. The EP time is one of the key factors promot-
ing Ra of 304SS, which does not involve in any interactions
with other polishing variables. Although the effects of glycerol
content and current density are marginal significant in the FFD
study, they involve very strong interactions with the polishing
temperature, a significant factor. Hence, the glycerol content,
the EP temperature, the current density, and the EP time are
simultaneously considered as important factors in the realistic
experimental manipulation. In the path of the steepest ascent
study, Ra reaches a maximum value of 44.7 nm precisely pre-
dicted by the model equation established in the FFD study. A
modified model, integrating several important concepts for elec-
tropolishing of metals/alloys from the literature with a new idea
on the molecular interactions among the shielding molecules,
is proposed to elucidate the phenomena and results obtained
in this work. The SEM morphologies and AFM analyses also
support this model although a further study on the molecular
interactions of the shielding molecules is needed, which is under
investigation.
Acknowledgment
The financial support of this work, by the National Science
Council of the Republic of China, is gratefully acknowledged.
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