Journal of Materials Processing Technology 140 (2003) 255–259

Optimization of electrochemical polishing of stainless

steel by grey relational analysis
P.S. Kao, H. Hocheng∗
Department of Power Mechanical Engineering, National Tsing Hua University, Hsinchu, Taiwan

Abstract

Grey relational analysis is useful for the multi-input, discrete data and uncertain experimental study. Developed in this paper is the appli-
cation of the grey relational analysis for optimizing the electropolishing of 316L stainless steel with multiple performance characteristics.
The processing parameters (temperature, current density, and electrolyte composition) are optimized with considerations of the multiple
performance characteristics (surface roughness and passivation strength). The conducted experiments approve the effectiveness of the grey
relational analysis.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Electropolishing; ECM; Grey relational analysis; 316 steel

1. Introduction development lag and to tighten the quality control, which

The electrochemical machining (ECM) based on the
principle of anode metal dissolution in the electrolyte was
introduced in 1929 and found particularly advantageous for
high-strength and high-melting point alloys. Industrial ap-
plications have been extended to electrochemical drilling,
electrochemical deburring, electrochemical grinding and
electrochemical polishing [1]. Fine surface brightness and
stress-free surface can be obtained by electropolishing [2].
The effects of electropolishing of workpiece im-
mersed in an electrolyte tank are shown in threefold: (A)
micropolishing—the removal of the bulge on the surface
of about 0.01 mm in size makes the surface more reflec-
tive and bright, while the smoothness of the surface might
not get improved; (B) macropolishing—the removal of the
bulge larger than 0.1mm in size makes the surface smooth,
while the brightness of the surface is not guaranteed; (C)
passivation—it produces a chemically passivated layer (par-
ticularly suitable for stainless steel and copper), that other
mechanical polishing processes cannot produce [3,4].
In semiconductor industry, the 316L stainless steel tubes
are used to deliver corrosive gas needed for wafer processing.
The inner surface of the tubes must be highly smooth and
passivated to ensure no leakage occurs. To achieve this goal,
the inner surface of the tubes is often eletropolished. The
optimization of this process is desired to save the process
∗ Corresponding author. Tel.: +886-3-5715131-3748.
E-mail address: hocheng@pme.nthu.edu.tw (H. Hocheng).
are crucial for the semiconductor industry.
To optimize the process based on the experimental data,
the traditional statistical regression requires a large amount
of data, that causes the difficulty in treating the typical nor-
mal distribution of data and the lack of variant factors. In
the grey system theory, the grey relational analysis is a mea-
surement method to analyze the relationship between se-
quences using less data and multi-factor, which is considered
more advantageous to the statistical regression analysis. This
method is proposed for electropolishing in the current paper.
2. Experiment
2.1. Passivation processing
The experimental setup is composed of the power supply,
current meter, voltage meter, stainless steel container, work-
piece, reference electrode, thermometer, fan, and stirring
heating apparatus. A schematic diagram of the experimental
setup is shown in Fig. 1.
The power supply provides the direct current of maxi-
mum 180 A. The stainless steel container avoids the ferro-
magnetism. The experimental sample is 316L stainless steel
of 30 mm in length, 1 mm in thickness and 20 mm in width.
The reference electrode uses Cu–CuSO4 half battery. Before
the experiment proceeds, the phosphoric acid, sulfuric acid,
glycerin, and water are added to the designed ratio. The elec-
trolyte is stirred and heated to the experimental temperature

0924-0136/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0924-0136(03)00747-7
256 P.S. Kao, H. Hocheng / Journal of Materials Processing Technology 140 (2003) 255–259

Workpiece Reference electrode Table 2

Experimental layout using L9 orthogonal array
Thermometer
Voltage meter No. Temperature Current density Electrolyte
V
Fan 1 1 1 1
Power
supply 2 1 2 2
A 3 1 3 3
4 2 1 2
Current meter
5 2 2 3
Electrolyte cup 6 2 3 1
7 3 1 3
8 3 2 1
Span heater 9 3 3 2

Fig. 1. Sketch of experimental setup of surface passivation.

number of comparisons between process parameters needed
Seal rubber to optimize the parameters. In the present study, there are
six degrees of freedom owing to the three-level polishing
Workpiece parameters, while the interaction between the parameters is
Workpiece holder neglected.
FeCl3 solution
Once the degree of freedom is known, the next step is to
select an appropriate orthogonal array. The degree of free-
Beaker dom for the orthogonal array should be greater than or at
least equal to those of the process parameters. In this study,
an L9 orthogonal array is used because it has eight degrees
of freedom in the polishing parameters. Each polishing pa-
rameter is assigned to a column and nine polishing parame-
Heater ters. There are hence nine experiments needed to study the
Fig. 2. Sketch of experimental setup of corrosion test. entire polishing parameter space by using the L9 orthogonal
array. The experimental layout for the polishing parameters
using the L9 orthogonal array is shown in Table 2. In addi-
with stirring. The workpiece is immersed into the electrolyte tion, each experimental set is tested three times.
20 mm deep and connected to the electrical current. The surface roughness ratio and the passivation strength
ratio are the performance characteristics defined as follows:
2.2. Corrosion test
The surface roughness ratio (%)
The method of the corrosion test conforms to ASTM G48. final surface roughness
It tells the passivation level between different passivation = × 100 (1)
initial surface roughness
layers and is considered suitable for assessing the effects of
the processing parameters in the experiment. The passivation strength ratio (%)
Fig. 2 shows the experimental setup of corrosion test. The
workpiece is put into the FeCl3 solution 20 mm deep. The number of pitting dots of unpassivated sample
container is then sealed, and the temperature is controlled at −number of pitting dots of passivated sample
= × 100
50 ◦ C for 72 h. number of pitting dots of unpassivated sample
(2)
2.3. Experimental design
3. Grey relational analysis
The experiment includes three polishing parameters (tem-
perature, current density, and electrolyte composition), as
3.1. Experimental results
shown in Table 1. The degree of freedom is defined as the
The grey relational theory provides an efficient manage-
Table 1
ment upon the uncertainty, multi-input and discrete data. On
Polishing parameters the other hand, the grey relational analysis reveals the nec-
essary information of the interactions among parameters.
Level 1 Level 2 Level 3
The first step of parameter design is to switch the quality
Temperature (◦ C) 75 85 95 characteristic to S/N ratio (signal-to-noise ratio). There are
Current density (A/cm2 ) 0.5 1.0 1.5 three categories of performance characteristics in the anal-
Electrolyte composition (H2 SO4 :H3 PO4 ) 5:5 4:6 3:7
ysis of the S/N ratio, that is, the lower the better, the higher
 P.S. Kao, H. Hocheng / Journal of Materials Processing Technology 140 (2003) 255–259 257

Table 3 Table 5
Experimental results of surface roughness ratio (SRR) and corresponding Results of grey relational generation
S/N ratio
No. SRR PSR
No. SRR (%) S/N (dB)
Ideal 1 1
1 50 6.02 1 0.052724 0.770382
2 5.25 25.597 2 0.959739 1
3 45 6.936 3 0.095163 0
4 4.75 26.466 4 1 1
5 41 7.744 5 0.132598 0.770382
6 56 5.036 6 0.007135 0
7 7 23.098 7 0.843958 1
8 43 7.33 8 0.113417 0.527864
9 57 4.882 9 0 0.770382

the better, and the nominal the better. To obtain the optimal 3.2. Grey relational generation
electropolishing performance, the minimum surface rough-
ness and the maximum passivation strength are desired. The In the grey relational analysis, when the range of the
first criterion selects the-smaller-the-better characteristic of sequence is large or the standard value is enormous, the
the surface roughness. The calculation of the S/N ratio ηij function of factors is neglected. However, if the factors
for the ith experiment at the jth test is as follows: goals and directions are different, the grey relational analy-
  sis might also produce incorrect results. Therefore, one has
n

1 to preprocess the data which are related to a group of se-
ηij = −10 log  yij2  (3) quences, which is called “grey theory relational generation”
n
j=1 [5,6].
A linear data preprocessing method for the S/N ratio is
where yij is the ith experiment at the jth test and n is the
(0) (0)
number of tests. xi (k) − mink xi (k)
xi∗ (k) = (0) (0)
(5)
The second criterion selects the-large-the-better charac- maxk xi (k) − mink xi (k)
teristic for the passivation strength. The equation of the S/N
ratio is as follows: where xi∗ (k) is the value after the grey relational generation;
(0) (0) (0)
  mink xi (k) the smallest value of xi (k); maxk xi (k) the
n (0)
1 1 largest value of xi (k).
ηij = −10 log   (4)
n y 2 Based on Tables 3 and 4, the experimental results of
j=1 ij
the grey relational generation using the experimental layout
(Table 2) are shown in Table 5.
Table 3 shows the results of the surface roughness and
signal-to-noise rate. Table 4 shows the results of the passi-
3.3. Grey relational grade
vation strength and signal-to-noise rate. To consider the two
different performance characteristics, the S/N ratios corre-
In the grey relational analysis, the grey relational grade
sponding to the surface roughness and passivation strength
is used to show the relationship among the series. Let (X,
are processed by the grey relational analysis.
Γ ) be a grey relational space, X stand for the collection of
the collection of grey relational factors, xi be the compared
series, and x0 be the reference series:
Table 4
Experimental results of passivation strength ratio (PSR) and corresponding xi = (xi (1), xi (2), . . . , xi (n)), xi ∈ X, i = 1, 2, . . . , m
S/N ratio
(6)
No. PSR (%) S/N (dB)

1 95 −0.445 x0 = (x0 (1), x0 (2), . . . , x0 (n)), x0 ∈ X (7)

2 100 0
3 80 −1.938 The grey relational coefficient is
4 100 0
∆min + ζ∆max
5 95 −0.445 γ(x0 (k), xi (k)) = (8)
6 80 −1.938 ∆0i (k) + ζ∆max
7 100 0
8 90 −0.915 where
9 95 −0.445
∆0i (k) = |x0 (k) − xi (k)| (9)
258 P.S. Kao, H. Hocheng / Journal of Materials Processing Technology 140 (2003) 255–259

Table 6
grey relational grade

0.8
Grey relational grade and orders
0.6
No. Grey relational grade Order
0.4
1 0.4651 6
0.2
2 0.7638 2
3 0.4006 7 0
A1 A2 A3 B1 B2 B3 C1 C2 C3
4 0.7989 1
parameter level
5 0.5037 4
6 0.3576 9 Fig. 3. Influence of electropolishing parameters on multiple performance.
7 0.7122 3
8 0.4932 5
9 0.3853 8
4. Analysis of variance

∆max = max max∆0i (k) (10) The purpose of the analysis of variance (ANOVA) is to re-
i k
veal the process parameters that significantly affect the per-
∆min = min min∆0i (k) (11) formance characteristics. The traditional statistic technique
i k
can only obtain one parameter in a single sequence, one has
ζ ∈ [0, 1] (12) to do the analysis repeatedly to obtain other factors for the
The grey relational grade is obtained: experiment [7]. Using the experimental design module in the
n Statistica software, one obtains the results of two parameter
1 sets, as shown in Table 8.
γ(x0 , xi ) = γ(x0 (k), xi (k)) (13)
n In Table 8(a), the electrolyte is the only parameter show-
k=1
ing the P-value under 0.05, namely the electrolyte is the
Table 6 shows the experimental results of the grey relational only noticeable factor for the surface roughness. Table 8(b)
grade using the experimental layout (Table 2). shows that all the three factors influence the passivation
strength significantly based on the P-values. After identify-
3.4. Factor effects ing the significant parameters, one picks the middle level
for the-smaller-the-better surface roughness and considers
Since the experimental design is orthogonal, it is then the-larger-the-better passivation strength of the results. Con-
possible to separate the effects of each polishing parameter sequently, No. 2 and No. 4 in Table 2 are considered the
at different levels. For example, the mean of grey relational optimum in the experiment.
grade for the workpiece pulse-on time at level 1, 2 and 3
can be calculated by taking the average of the grey rela-
tional grade for the experiments 1–3, 4–6 and 7–9, respec- 5. Verification test
tively (Table 2). The mean of the grey relational grade for
each level of other machining parameters can be computed Once the optimal level of the process parameters is iden-
in the similar manner. The mean of the relational grade for tified, the following step is to verify the improvement of the
each level of the combining parameters is summarized in the performance characteristic using this optimal level. The es-
multi-response performance index table (Table 7). In addi- timated S/N ratio η̃ is calculated as
tion, the total mean of the grey relational grade of the eight
α

experiments is also calculated, as shown in Table 7. Fig. 3
shows the grey relational grade. The dash line shows the η̃ = ηm + (η̂i − ηm ) (14)
i=1
value of the total mean of grey relational grade. Basically,
the larger the grey relation grade is, the closer will be the where ηm is the total mean of the grey relational grade, η̂i the
product quality to the ideal value. Thus the larger grey rela- mean of the grey relational grade at the optimal level, and α
tional grade is desired. the number of the process parameter that significantly affect
the multiple performance characteristics. Based on Eq. (14),
Table 7 the estimated grey relational grade can be obtained.
Influence of electropolishing parameters on grey relational grade Table 9 shows the results of the confirmation experiment
Grey relational grade using the optimal electropolishing parameters. As shown in
Table 10, the surface roughness ratio is reduced from 50 to
Level 1 Level 2 Level 3 Max−min
4.75%, the passivation strength ratio is increased from 95 to
Temperature 0.543 0.553 0.530 0.023 100%. The comparison of the S/N ratios between the initial
Current density 0.659 0.587 0.381 0.278 and the optimal parameters is also shown in Table 10. It is
Electrolyte composition 0.439 0.649 0.539 0.21
clear that the surface roughness and passivation strength are
Mean value of the grey relational grade = 0.543
considerably improved through this study.
 P.S. Kao, H. Hocheng / Journal of Materials Processing Technology 140 (2003) 255–259 259

Table 8
Results of ANOVA
SS d.f. MS F P

(a) Surface roughness

Temperature 8.166667 2 8.166667 0.674312 0.497861
Current density 0.666667 2 0.666667 0.055046 0.836337
Electrolyte composition 266.6667 2 266.6667 22.01835 0.04254
Error 24.22222 2 12.11111
Total SS 431.5556 8
(b) Passivation strength
Temperature 15.04487 2 7.522433 4605.571 0.000217
Current density 15.4574 2 7.7287 4731.857 0.000211
Electrolyte composition 15.39247 2 7.696233 4711.98 0.000212
Error 0.003267 2 0.001633
Total SS 45.898 8

Table 9 analysis of the multiple performance characteristics has been

Comparison between initial level and optimal level performed by grey relational grade. As a result, the target
Raw data Optimal electropolishing performance characteristics, i.e. surface roughness and pas-
parameters sivation strength, can be improved through this method. The
Prediction Experiment effectiveness of this approach is verified by experiment and
analysis of variance.
Setting level A 1 B1 C1 A2 B1 C2 A2 B1 C2
Surface roughness ratio (%) 50 4.75
Passivation strength ratio (%) 95 100
Grey relational grade 0.4651 0.7053 0.7989 References
Improvement of grey relational grade = 0.3338
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[3] O.L. Riggo, C.E. ad Locke, Anodic Protection, Plenum Press, New
SRR PSR
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Optimal parameters (A2 B1 C2 ) 26.466 0 1971, pp. 79–161.
Improvement of S/N ratio 20.446 0.445 [5] J. Deng, A Course on Grey System Theory, HUST Press, Wnhan,
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ishing of stainless steel by the grey relational analysis. The